S.O. Pillai - Solid State Physics-New Age International (P) LTD., Publishers (2005)

Revised Sixth Edition
•
' .•
(NEW REVISED SIXTH EDITION)
s.o. Pillai
B.Sc. (Hons.), M.Sc., Ph.D.
Professor of Physics (RetJL)
Anna University, Chennai
India
•
•
Nf;WAOE
TECHNO
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CONTENTS
Preface to rhe Sixth Edition vii

Preface to First Edition tx
A cbiowledgements i
An academic experience witfl Prof A. PJ . Abdul Kalani xi
Some Views.... xiii
INTRODUC (TON
REVIEW OF ATOMIC STRUCTURE
I : TheRulhErfordAlodeLoLthc A irnp
II Conclusion o f Rutherford's Theory
III Drawbacks of Rutherford Model of the Atom
Bohr Model of Atom
Bohr's Theory o f Hydrogen Atom
T o u t Energy o f the Electron in the Stationary Orbits
Calculation o f r; and E* for Hydrogen Atom
V III Bohr's Interpretation o f Hydrogen Spectrum
Spectral Series o f Hydrogen
Shortcomings o f Bohr's Theory
Sommerfeld's Relativistic Atom M odel
Elliptical Orbits for Hydrogen Atom
Total Energy, o f an Electron tn an Elliptical Orbit
X IV Sommerfeld's Relativistic Correction
Fine Structure o f ty, Line
Drawbacks o f Bohr-Su i i i i i crfeld Atom Model
XY11 Vector Atom Model
XY1I1 The Charactensiic Quantum Numbers
Pauli’s Exclusion Principle
Application o f Pauli's Exclusion Principle
Electron Configuration
X X II The Periodic Table
XXJ1I Wave-Mechanical Concept o f the Atom
IMTERAT C FORCES AND BONDING IN SOLIDS

I : Introduction 42
H : Force Between Atoms 42
xvi Contents
B K B B K £ fc
Cohesion of Atoms and Cohesive Energy
Calculation of Cohesive Energy
Bonding in Solids
Ionic Bonding
Bond Energy of NaCl Molecule
Calculation of Lattice Energy of Ionic Crystals
Calculation of Made hi ng Constant of Ionic Crystals
Calculation of Repulsive Exponent from

Compress!bility Data
The Born-Haber Cycle
Properties of Ionic Solids
Examples of look Solids
XIV Covalent Bond

XV Saturation in Covalent Bonds
XVI Direction^ Nalurc.uf a C.Qvuli:nt Bond

XYU Hybridization
XY11I Properties of Covalent Compounds
XIX Mdallifi-Bcnd
Properties of Metallic Crystals
1 nterniolcuular Bonds
xxn Dispersion Bonds
xxm Dipok Bonds

XXIV Hydrogen Bonds
CRYSTAL PHYSICS
(8 S 1 S E S B G 3
1 s Introduction
H : Lattice Points and Space Lattice
Hl : The Basis and Crystal Structure

IV : Unit Cells and Lattice Parameters
V : Unit Cell versus Primitive Cell
VI : Crystal Systems
VII : Crystal Symmetry (Symmetry Elements in Crystals)

VIII : The Twenty Three Symmetry Elements in a Cubic
Crystal
8
IX : To Show ih^fiviToldKotaiimAxis isntx

S
Com patible with a La ft i ce

8
X : Combination of Symmetry Elements

XI : Rquuoh: Inversion Axis
XII : Translation Symmetry Elements
Contents xvii
XIII : Space Groups
XL¥ : The Bravais Space Lattices

XV : Metallic Cry ^:i I Structures
XVI : Relation Between the Density of Crystal Material and Lattice Constant in
a Cubic Lattice
XYH : Other Cubic Structurcs

XVIII : Directions, Planes and Milter Indices
XIX : Important Features of Miller Indices of Crystal Planes
XX : Important Planes and Directions in a Cubic crystal

XXI : Distribution of Atoms in the Atomic Planes of a Simple Cubic Crystal
XXII : Separation between Lattice Planes in a Cubic Crystal

XXIII : Allotropy and Polymorphism
XXIV : Imperfections in Crystals
XXV : Reciprocal Lattice
1___ WAVE NATURE OF MATTER AND X-RAY DIFFRACTION

I iluction
II The de Broglie Hypothesis
Hl Relativistic Correction
IV Experimental Study of Matter Waves
V TheDavisson-Germ erExpen ment

VI Hei senderg’s Uncertarnty Principle
VII X-ray Diffraction

VU1 Bragg*s Law
Bragg's X-ray Spccirameter

X Powder Crystal Method
XI Rotating Crystal Method
Correction for Bragg's Equad on
ELECTRICALPRQPXRTIESJ}FÎETa I
I Introduction
H Classical Free Electron Theory of Metals
in Drawbacks of Classical Theory
Relaxation Time, Collision Time and Mean Free Path

V Quantum TL.ory of Free Electrons
Classical Wave Equation

VII Schrodinger Wave Equation
V1H SchrOdin ger Equa lion for Stationary Stales
IX Importance of Schrodinger Equation

xviii Contents
Physical Significance of the Wave Function y
Limitation s on y j nd Norm ah sat ion of Wave Function

The Quantum Mechanics of Simple Problems
Panicles tn a Box with Impenetrable Walls
XIV Fermi-Dirac Statistics and Electronics Distribution in Solids

Density of Energy States and Fermi Energy
i:ul eimi DuiribuhoaEimGiion
xvu Heat Capacity of the Electron Gas
XVIII Mean Energy of Eteccron Gas at Absolute Zero
Effect of Temperature of Fermi Distribution Function

Elec th c al Conductivity from Quantyn i Mechanical Cons iderations
XXI Electron Scattering and Sources of Resistance

in Metals
XXH : Electron-Scattering Mechanisms and Variation
of Resistivity with Temperature
XXIII : Resistivity of Alloys

XXIV : Variation of Resistivity with Pressure
XXV : Thermal Conductivityin Metals

XXVI * Thermal Expansion
XXVII Mechanical Effects on Electrical Resistance
XXVIII Conductivity at High Frequencies
XXIX : Joule's Law
XXX : Effect of ihe Magnetic Fields

XXXI : Thermionic Emission
XXXU : Schottky Effect

XXXm : Magnetism in Metals
XXXIV ; A Note on Selection of Electrical Engineering

Materials
xxxv Failure of Sommerfeld's Free Electron Theory
XXXVI Band Theory of Solids
XXX Vil Electron in a Periodic Field of a Crystal
(The Kronig-Pcnny Model)
XXXVUI Brillouin Zones
XXXIX Number of Possible Wave Functions in n Band
xxxx Monon of Electrons m a OneJJimcnsmnalJ •VtT<

iodic
* Potential
XXXX1 Distinction Between Metals. Insulators and Intrinsic
Semieundueiurs
Contents ma
7. THERMAL PR0PERT1ESDF SOUDS

I______
Introduction
n Lattice Specific Heat
in Classical Theory (Dtdong and Petit Law)

fV Einstein's Theory of Specific Heat
V ___ Debye’s Theory
8. SVPERGONPUCTIMTY
1 HistaricaL 1 nlroduc ti on
11 A Survey of Superconductivity
IB An Account of the Mechanism o ~ Superconductors
IY Effects of Magnetic Field

V A-C. Resistivity
Cntical Currents
Huz Eiclusiani The Meissner Effect
YUI Thermal Properties

The Energy Gap
X IsotopeEffect
Mechanical EHeuG
The Penetration Depth
I ype I and Type H Superconductors

XIV London Equations: Elcctrodynamics
Superconductors in A.C. Fields
Xii rhermodynamics of Superconductors

XVH A Survey of B.C3. Theory
XY1II BCS Theory
Quantum Tunneling
Josephson's Tunneling
Theory of DC Josephson Effect
XXII New Superconductors
xx] n Applications of Superconductivity in Early Days
and their Limitations
XXIV Potential Applications of Superconductivity
XXY Power Applications of Superconductors
9. MAGNETIC PROPERTIES OF MATERIALS

ilFrtT* AiEimn
II : Magnetic Permeability
III: Magnetization
xx Contents
IV Electric Current in Atoms — Bohr Magneton 432
V Electron Spin and Magnetic Moment 434
VI Magnetic Moment Due to Nuclear Spin 435

VII More about the origin of Magnetism 435
YUI Theory of magnetism in EJecttor» 436

IX Diamagnetism 441
X Summary 446
XI Paramagnetism 446
XU Weiss Theory of Paramagnetism 456
XIII Paramagnetic Susceptibility of a Solid Substances 457
Quantum Theory of Paramagnetism
XV Coohng by Adiabatic Demagnetization 467

XVI Determination of Susceptibilities of Para and
Diamagnetic Materials
XVII HundRulcs
xvni Summary
XIX Ferromagnetism
XX Spontaneous Magnetization in Ferromagnetism Materials
Quantum Theory of Ferromagnetism
xxn Weiss Molecular Field
Behaviour of Ferromagnetic Mate lafcFor

T> Oj - (Curie-Weiss Ljaw)
XXIV Temperature Dependence of Spontaneous Magnetism

XXV The internal Fidd And Exchange Interaction
XXVI Fenonugnctic Domains
XXVII The Domain Model

xxvin Domain Theory
XXIX Experimental Demonstration of the Domain Structure
XXX Explanation of Hysteresis
XXXI Antiferromagnetism
XXXII Ferrimagnetism (Ferrites)
XXXUI Structure nf Ferrites
XXXIV Magnetic Materials
10f. JM.YS1CSOFSEMICONDUCTORS
1_______ :___ Introduction
H_____ ;__ The Band Structure of Semiconductors
III__________ ScinieonducLors
Contents xxi
IV Intrinsic Semiconductor^
Y Conductivity And Tempera :ure

¥1 Statistics of.Electrons And. Holes in Intrinsic Semtamduetora
¥11 Electrical Conductivity
vm Impurity Semiconductors or Extrinsic Semiconductors
ix Statistics of Extrinsic Semi

iilLvIiP.factors
x Mechanism of Current Conduction in Semiconductors
XI Generation And Recombination
XII Mobility of Current Canjm
XIH Genera I Study of Excess Carrier Movement
XV Advantages of Semiconductor Devices
XVI The p-n Junction
XVU The Potential Barrier at The pn Junction

XVIII Width of Depletion Layer of The p-n Junction
XIX Volt-Ampere Characteristics of The p-n Junction
XX Application of Voltage Across A p-n Junction
XXI Rectifier Equation
XXII Continuity Equation

XXIII SomeSpecialp-nJunctionDiodes
11. DI ELECTRICS AND RELATED PROPERTIES

I Introduction
1A Review of Basic F Mil
II The Microscopic Concept of Polarization
ni Langevin's Theory of Polarisation in Polar Dielectrics

F
IV Internal-Field or Local Field in Liquids and Solids
v C Laus lus-Ml so tii Rclaiioii
VI The Static Dielectric Constants of Solids and Liquids
YU Ferroelectricity
Piezoelectricity
IX Properties of Dielectrics in Alternating Fields
X The Complex Dielectric Constant and Dielectric Loss
XI Dielectrics tn Alternating Fields
XII Ionic Polarizability as a Function of Frequency
XIII Complex Dielectric Constant of Non-Polar Solids 673
XIV Dipolar Relaxation 675
XV Absorption of Energy and Dielectric Losses 678

xxii Contents
XV] : Effects
■ of Dielectrics 681
XVH ; Important Requirements of Good Insulating Materials 685

XVIII : Some Important Insulating Materials 6K5
li___ OPTICAL PROPERTIES OF SOLIDS

I IlftOlUL’tlQD
11 Cl apical Mlidel — Prude Model

[Il lumdCondu-cnon
IV Optical Refractive Index and Relative Dielectric Constant
Optical Absorption in Metals, Insulators and Semiconductors
VI Colour Centres
Excitons
Yin Limtnescence
IX Maser and Laser
X
XI Application of Lasers
XII Physics of Optical Fibres
13, M ISC ELI A NEOUS TOPICS

I : Insulating Materials and Their Properties
II: Composite Materials
LL___ SOME USEFUL INFORMATION

I: Special Tables
I : Metric Prefixes
111 : Derived S I Units having Special Names and Symbols
IV; Advantages of S | Units
V: Some common Differentials and Integrals
Appendices
Answers jq Objective Questions
Anmigrj .to Problems
Bibliography
CHAPTER 1
INTRODUCTION
Ever since Adam and £W felt a need for some sort of apparel in the Garden Of Eden, mankind has been
concerned with problems of materials. While Adam and Eve and (heir immediate descendants had only rel
atively simple materials problems such as clothing and the construct sen of shelter, we in our modem civili
zation have far more numerous problems. We still have the age-old needs for clothing and shelter, but in our
modem life, we have become extremely dependent of a great variety of materials, In fact, materials provide
the ffameuoric plus the: sinews and ligaments that hold our civilization together. As a small example, con
sider the 747 ‘Jumbv Jet1 which serves as part of the international transportation system. 1 his air
craft is approximately 1% fibre glass. 4% titanium, 13% steel* and 82% aluminium.
For several centuries the few metals and alloys (such as iron, copper, tin and brass), the few ceramics
(such as pottery), and the natural poly mm (such as wool, cotton, asbestos, and cellulose j were sufficient to
meet most human needs. The new age of materials took its birth in the late nineteenth and early twentieth
centuries. Imperceptible progress had been made for centuries, but now new materials are being developed
ai a rate hitherto unachieved.
The tremendous increase in the number of materials available and their varying physical properties,
coupled with demands from new applications and more severe service requirements, have brought about
many changes in attitudes and view points. Advances in fundamental science have led to the development of
a new technical area which we might call a unrtied science end technology of materials.
The range of materials and their properties to the engineer today is vast The traditional materials like
glass, rubber, limber, copper and germanium, are all used by engineers today also, but in character and
properties they are completely different from the past ones. Within one group of materials, properties may
range from a soft and easily deformed metal such as lead to tool steels which are hard and tough. Every
engineer is concerned with materials and he has to select the most suitable material for the job in hand, be it
for civil engineering structure, or a power plant, or perhaps for an electronic component
There is one thing which all materials have in common, and that is they are all composed of atoms.
Hie atoms themselves may differ from one another, but the atoms of alt the known elements arc composed
of the same three kinds of basic particles, the proion, the neutron and the electron. The nature and final
properties of the bulk engineering materials we use every day involve the atomic and molecular structure,
{he degree of order and perfection in these structures, and the forces and energies associated with 1hem.
Revent developments in materials science lead towards a new understanding of rhe nature of materials and
suggest a more basic approach to their application, Techniques are available for describing the properties of
existing materials and are becoming available for prcdicung properties of new materials, in terms of their
atomic and molecular structures The behavioural response to fabrication methods and environments can
also be related to these factors. Consequently, an understanding of the fundamentals of materials technology
is becoming a prerequisite to their engineering applications.
2 Solid Slate Physics
Atoms are made up of three types of elementary particles. These are the proton, the neutron and the
electron, The proton is a panicle which has a positive electrical charge and a mass of 1.672 x 10 kg, The
neutron has an almost identical mass (1.675x l(Tn kg)+ but has no electrical charge. The third particle, the
electron, has an electrical charge which is equal and opposite to (hat of proton but has a mass only 1/1836 of
’hh;ir of the proton. The atom as a whole is electrically neutral since it contains protom and electrons in equal
number. The number of neutrons in the atom is often the same as, or greater than, the number of protons.
Each of the hundred and odd known ekments is characterised by a different number of protons in the
nucleus The number of protons contained in the micieus is termed the atomic number, Z. In an electrically
neutral atom, there must be equal number of electrons. The nucleus is normally composed of the two kind of
pan teles: protons and neutrons, and they make up the mass of the atom. The atomic mass number, or otomn?
weight. Ma. indicates the total numbers of protons and neutrons in the nucleus for the simplest atom, hydro-
gen: Z ~ L MA - 1, so that the nucleus has just one proton. For oxygen, 2 - 8, MA = 16, so that the nucleus
contains 8 protons and 8 neutrons. The quoted atomic weights of atoms arc not all whole numbers. The
atomic weight of hydrogen is I 008.
If Afx represents the atomic weight of an element, MA gm of the element is called one gram atomic
weight (at wt) and \tA kg is I kg at wt. If fallows from Avogadro’s hypothesis that J kg at wt samples of
.di elements have the same number of atoms, now known to be 6.0225 x IQ26. This is called Avogadro**
number and represented by NAz b’A molecules of a gaseous subsuncc constitute 1 kg mol of the substance.
The solid state of matter is quite different from cither the gaseous or the liquid state, mainly because
the atomic panicles are packed closely together in some orderly three-dimensional network in space. The
kinetic energies are lowered to the extent that movements are restricted to regular vibrations about fixed
mean positions and diffusion rates are extremely slow Nevertheless, diffusion processes in solid materials
are of great significance since many engineering phenomena depend upon the rales of diffusion of ihc van-
ous atoms within the metal
Many electrical engineering materials are solids, and since ail solids are made of up atoms,
molecules, other atomic particles, the study of solid state must logically begin at the level of atomic
siHKiurc.
C opyri g hi ed ifn aleri a1

CHAPTER 2
REVIEW OF ATOMIC STRUCTURE
I. THE RUTHERFORD MODEL OF THE ATOM

The first exploration of the structure of the atom was made by Rutherford in 1911 making use of
ct particles, He bombarded a thin gold foil with a panicle (helium nucleit which are positively charged
particles with an atomic mass number of 4) and found that very many (^particles passed through rhe gold
foil without being deflected, but some of them were deflected through large angle. The inference was that
much of the atom was void space allowing most of the a-panicles io pass straight through, but with some
particles being deflected owing to their passing close to, or colliding with, a central mass (nucleus) of very
small dimensions, The effective diameter of the gold atom is 03 nm and the diameter of the nucleus is about
1/KXOOO of this size
The first postulation about electrons was that they are in orbit Mound the central nucleus just as plan
ets round the sun. To rn^srporate these findings and the discovery of the electron, Rutherford proposed the
following model of the atom:
This postulates a tiny, massive, and positively charged nucleus around which orbit the negative elec
trons.
In Fig. 2.1. an electron is revolving in a circular orbit of radius, r, with a constant velocity, v; The
system is now subjected to two forces. Acting inwards wiU be electrostatic attraction given by
law:
* 4nEQ?
Here is the permittivity offree space. The other one is the centrifugal force, ff acting outwards. The
value of this force is
where m is the mass of the electron and (v’fr) is its radial acceleration^ The condition for orbit stability is
Thus
mV2 Ze2
(2.1)
r
Copyrighted material
4 Sahel Stale Physics
i
II. CONCLUSION OF RUTHERFORD S

THEORY
The atom consists of a positively charged heavy nucleus

surrounded by revolving negatively charged extremely
light panicles called electrons, like the planets round the
sun. at such a speed that the mechanical centrifugal force
would just balance the net excess of electrostatic attrac
tion and in consequence stability of the atom could be
secured:
Fig, 2.1 Circular orbit of on electron in jh alum.
III. DRAWBACKS OF THE RUTHERFORD MODEL OF THE ATOM
A logical place for an electrical engineer ora physicist to begin his study of solid stale physics is with the
rudiments of quantum mechanics. Quantum mechanics was developed because classical mechanics failed to
explain the behaviour of atoms. As an example, consider the hydrogen atom consisting of one electron and
one proton with an attractive Coulomb potential between ihem. Newton’s laws of motion would allow the
electron any value of energy in its orbit about the proton as long as the Coulomb attractive force which
varies inversely as the square of the distance between the proton and electron is balanced by the outward
centrifugal force of the electron. However, experiments on the hydrogen atom inform us that the electron
appears to have only very specific or discrete values of energy. A further problem arises in regard to some
other classical equations cl physics (Maxwell's equations) which have to do with moving charges and
electromagnetic fields These equations predict that the negatively charged electron whirling around the
proton would continuously radiate energy (in the form of light) and gradually be drawn into the proton as it
slowed down. This is contrary to the fact that hydrogen atoms can exist in nature without continuously
emitting light. After much trial and error, quantum mechanics was developed in 1926 and explained these
discrepancies, I'll us the laws of physics that are valid in the macroscopic world do not hold g 33?i in the case
of microscopic particles such as electrons. Rutherford model also failed to explain the emission of radiations
as light, x-rays, etc. from the atoms of different substances under certain conditions.
IV. BOHR MODEL OF ATOM

Hydrogen, the simplest of al J elements, was investigated most extensively both experimentally and theoretic
call y, As long ago ax 1885t Burner succeeded m obtaining a rimpte relationship among the wave numbers
of the lines in the visible region of the hydrogen spectrum. The first quantitatively correct derivation of the
Balmer formula on the basis of an atomic model was given by Bohr (1913), in his theory of the hydrogen
atom. This theory has played such an important role in the development of atomic physics that, even though
it has been modified and extended by the later developments tn quantum mechanics, it will be worthwhile to
present the original simplified theory.
In 1913, Niels Bohr proposed a model for the hydrogen atom which retained the earlier nuclear model
of Rutherford but made f urther stipulations as to the behaviour of the electron. A dramatic explanation of the
Rydberg spectral expression resulted. Many modern ideas about atomic and molecular structure stem from
this model.
Bohr suggested the following postulates to explain the electron motion in an atom and the observed
spectral lines:
CoDVikihied material
flmew ofAtomic Structure 5
(i) An deetron in an atom moves in a circular orbit about the nucleus tinder the influence of Coulomb
force of attraction between the electron and nucleus The Coulombian force of attraction is bal
anced by Newtonian centrifugal farce Thus we have
(Ze)(e) mv2
4neBrJ r
iii) An electron cannot revolve round the nucleus in all possible orbits as suggested b> the classical
theory. It can revolve only in a few widely separated permitted orbits While moving along these
oibih round the nucleus, an electron docs mH radiau- energy. These non-radiating orbits arc called
stationary orbits.
fiii) The permissible orbits of an electron revolving round J nucleus are those for which rhe angular
momentum of the electron is an integral multiple ot ftfln, where k is Pian-ck*s constant. Thus for
any permitted orbit*
j V* ft ':
or
mr V - <2.2}
where m and r+ are the mass and veloc ity of (he electron* the radius of the orbit and n is a positive
integer, called the quantum number The above equation is called Boftr's quantum condition.
(iv) An atom radiates energy only when an electron jumps from a stationary orbit of higher energy to
another of lower energy* Thus if the electron jumps from an initial orbit of energy Er io a final orbit
of energy £z (E, > Ef), the frequency v of the radiation emitted is given by the relationship,
h v » E. - Et
where ft re Planck a- constant. This equation is called Bahr s frequency condition.
V. BOHR’S THEORY OF HYDROGEN ATOM

Let us now apply these postulates to the classical model of the atom with a nucleus of charge iZe). From
Bohr's first postulate, we have
(2.î
r« 4rt€0r,J
m v.: = . (2.4)
4?l€0
where Z - I for hydrogen atom*

Rom Bohr’s third postulate, the angular momentum of the electron in a permitted orbit must be an
integral multiple of From equation (2.2). have
Copy ri g hi ed rn aleri $ I
6 Solid State Physta
(2J5)
(2.6)
Substituting this value of vM in equation (24). we get

nh f Ze2
(mrj - --------- = 7-------
•'[ZKflir.J 4K€g
n1*’ —... ....

Z<** ---- -
<fc€e
Thus the radius of n* permissible orbit for electron in hydrogen is given by
r.“ ^mZe\ (2.7)
Hence, the radii of different st ary orbits are directly

proportional 60 square of n (called principal quantum
number). Velocity of electron in the stationary orbits can
lined by substituting this value of rt in equation
(Z6),
nh nmZe1
2xmJ n2h2
Ft#. 2.2 Bohr's model of hydrogen atom *
Ze1
v J
(2.8)
• 2»A€o
It is now clear that the velocity of the electron it inversely proportional to the principal quantum
number n Thus electron moves at a lower speed in higher orbits and vice-versa.
The orbital frequency of an electron in the stationary orbits is calculated as follows:
Thus
Ze2 ttmZe1
2nh e J[n2AJ6D
wZV4
4e2 n1*3 (2.9)
Coovriidhled material
Review of Atomic Structure 7
i.e.
VL TOTAL ENERGY OF THE ELECTRON IN THE STATIONARY ORBITS

The electron revolving round the nucleus has both potential energy (due to its position with respect to the
nucleus) and kinetic energy (due to its motion). The iai energy of the electron is considered to be zero
when it is at infinite distance from the nucleus, Potential energy of An electron in an orbit is given by the
work done tn taking the electron from the distance r to infinity against the electrostatic attraction between
the nucleus and the electron. This is obtained by integrating the electrostatic force of attraction between the
nucleus and the electron from the limit to r>
Thus PE. of the electron = Ffr)dr
f Ze*dr
PE~ 1 4lt£0r;
Thai is,
Zr2
P-E«
4neur„
Similarly K.E of the electron -r-iwvj
Substituting the value of Imv* from equation (2>4h we get
Thus the total energy of the electron in the n* orbit is
E^PE^KE
Ze* Ze1 * Ze*
4ke0fh
Substituting the value of ra from equation (2.7)
(240)
The negative sign of the energy expression shows that the electron is bound to the nucleus and some
work must be done to pull jt away. It further follows from equation (2.10) that as n increases, £„ becomes
H Solid State Phyxii r
le^-% negative and hence its algebraical value increases. I'he electron. therefore has minimum energy when it
is in its innermost orbit, fl = L The stale of the atom with the electron revolving in the innermost orbit is
called the ground or normal state and u obviously the most stable state of the atom.
VIL CALCULATION OF rn AND En FOR HYDROGEN ATOM

■ " ■■' .. I
nV .
r - —------ ; with 2 - i {Refer equation (2.7)]
it fliZe
n 6.626 x l0~w)?(8.854x IO'11)

*“ n(9.109 x 1G*)(1.602 x KT'-f
I
I
r, - («’) (0.529 x 10' '*) metre (2.11)

t
Thus radius of the first orbit of hydrogen, r - 0.529 x 10rf° m.
This is called the Bohr radius (r#).
Thus f; = = 0.0529 nm
I
rj = 2 >.
and r, = rtV,
The energy of the electron in the orbit is

tnZê*
Efl *------- 2~"j t with = 1 [Refer equation (2.10)|
8 £* ft n
_ 8 me*
E* A; where 8 *—=—? (2.12)
* n1 8ejh2
Thus e - tory ;
* n!x8(8.354x 1 fl-11)’(6.626 X 10M)2
k
„ 2.179XI0'1*. .
=------------ j------ joule
2.179x IO-11
'^1.602 x IO-1*)” ।
4—(2.13)
fl*
when A - 1
E;*-13.6 eV
Jfevfrw ofAtomic Structure 9
This corresponds to the ground state energy of the aiom, and is called the ionirarion potential of
hydrogen atom. Similarly, the energy of the atom with the electron in the second otbit is
and that with ihe electron in the third orbit

13.6
* a -L511 eV and so on.
VIII. BOHR'S INTERPRETATION OF HYDROGEN SPECTRUM

If an electron jumps from an outer initial orbit n, of higher energy to an inner f inal orbit of lower energy,
the frequency of the radiation emitted is given by
Hence
mZ1** U
8€jfcJL"?
mA‘[ 1 I 5
(2.14)
«e}*4«i «s.
c /nZ:e4 i l
>- 8ejh!L«:J
i mzv ur
X 8eJcAJtni "1-
The reciprocal ol the wavelength is called the wave number.

Thus
(2.151
mZ’e4
w'ithZ = I is called Rydberg Constant for hydri'gen IHu; Thus
86} cA’
(9.109 x 10~>;) (1,602 x 10'7____
S.8.854x 10 b;)‘(3x 10'} (6.626 x 10 '7
Rh - 1.0961 x 10’ tif'

An atom is said to be excited, if the electron ts raised to an orbit of higher energy. The electron can be
completely freed from the influence of the nucleus by supphinp sufficient energy and the minimum energy
needed for this is called ionisation energy. For hydrogen
I0 Solid Suu tr Physics
me*Z2 I 1
with Z «I
SejA’Ll -
Thus E = 13 6 eV (2.16)
As long as the electron remains in its orbit, no energy is radiated, but whenever an electron jumps
from an outer orbit to an inner orbit, energy is emitted in the form of radiation. When the hydrogen atom is
subjected to an external source of energy, the electron jumps from lower energy state to higher energy state.
The atom is said to be excited, The excited state is not stable and hence the electron returns to its ground
stare in about IQ ’ second. The excess of energy is now emitted in the form of radiations of different
wavelengths. In a hydrogen discharge lube there are very large number of hydrogen atoms which arc
excited, and radiate energy. In some atoms the electrons may jump from the second orbit to the first orbit in
some others from the third to the second or first and so on. The different wavelengths due to different
transitions of the elections constitute spectral series which are characteristics of the atom emitting them.
X SPECTRAL SERIES OF HYDROGEN
Lyman series
When electrons jump from second, third, .« etc. orbits io the first orbit* the spectral lines are in the ultra
violet region. Here, n] - i and n3 = J, 3,4...
Thus
-8 - f15
Vi = g and u, - /tJ — and soon.
This is identified as Lyman series.
Belmer Series
When electrons jump from outer orbits to the second orbit (n, - 2, n2 - 3.4,
we get lines of Balmer series
i.e. with n. - 3,4,5,".
This series is called Balmer series and Lies in the visible region of the spectrum, The first line in the
series = 3} is called Ha line, the second line (n2 = 4) is called and so an.
Re i'iw of A tomic Structure 11
Fig. 2.3 Quantum jynips giving rise to diflercm spectral series of hydrogen
Paschen series
Paschen series lines in the infrared region are due to the transition of electrons from outer orbits to the third
orbit
Thus with n2 - 4,5,....
Brackett series
If «| ■ 4 and « 5,5.7.,., we get Brackett series lines.
with «3 = 5,6,7, ft,, ii .etc.
Pfund series
If «. =s5 and «2 ~ 6,7,8...,we get the Pfund series lines. Fur this series,
r J.
o ~RH
s2 with 7, ft,
Brackett and Pfund series he in the far infrared region of the hydrogen spectrum. By putting
«, = (fl| + 1) in each one of the series, we get the longest wavelength of the series. Similarly by putting
nt = «• in each one of the scries, we get rhe shortest wavelength of the series (or series limit).
n;a>(E+l3 6)
6 (13 2)
5 (13-1)
4 (12-8)
3 (12-1)
2 (10 2)
1 (0)
Fig. 2.4 Energy level diagram of hydiogert.
X. SHORTCOMINGS OF BOHR’S THEORY

Bohr's theory, based on circular electron orbits, was able to explain successfully a number of experimentally
observed facts and has correctly predicted the spectral tines of neutral hydrogen atom and singly ionized
helium atom in terms of the principal quantum number n However, the theory fails to explain the following
facts:
(i > It Codd not account the spectra of atoms more complex than hydrogen.
(ii) H fails to give any information regarding the distribution and unangetnem of electrons in
atoms.
(Hl I It does not explain the ex pen mentally observed variations er intensity of the spectral lines of
an element.
(iv) It fails to explain the transitions of electrons from one level to archer, the rate al which they
occur or the ieêt7ww rules which apply to them.
(v) it fails to account the/me ffw/wre of spectral lines Actually, it was found that when spectral
fines emitted by an atom are examined, each line is composed of several lines closely packed
together Bohr's theory does ixn Throw any hghi on it.
(vi) The theory cannot be used for the quantitative study of chemical bonding.
(vii) It was found that when electric or magnetic field is applied to the atom, each spectral hoe
splits into several lines. The former one is called Stark effect whiki the later Zee^w« effect.
Bohr's theory fails to explain these effects.
XI. SOMMERFELD’S RELATIVISTIC ATOM MODEL

According to Bohr the lines of hydrogen-like spectrum should each have a well-defined wavelength. Care
ful spectroscopic examination showed that the and lines in the hydrogen spectrum are not single
Each spectra! line actually consisted of several very close lines packed together. Michelson found (hat under
high resolution. H.f line can be resolved into two close components, with a wavelength separation 0.D13 nm
This is called the fine structure of the spectral lines. Bohr's theory could not explain this fine structure.
Sommerfeld succeeded partially in explaining the observed fine structure of spectral lines by intro
ducing the following main modifications in Bohr s theory:
(i) Sommerfeld suggested that the path of an electron around the nucleus in general, is an ellipse
with (he nucleus at one of the foci The circular orbits of Bohr are a special case of this.
(ii) The velocity of the electron moving in an elliptical orbit varies considerably ai different parts
of the orbit This causes relativistic variation in the mass of the moving electron. Therefore
Sommerfeld took into account the relativistic variation of the mass of rhe electron with
velocity. Hence this model of the atom is called the rehmwtic aia/n mode/.
XII. ELLIPTICAL ORBITS FOR HYDROGEN

An electron moving in the field of ihe nucleus describes elliptical orbits* with ihe nucleus at one focus Cir
cular orbits arc only special cases of ellipses. When the electron moves along a circular orbit, the angular
coordinate is sufficient to describe its motion In □□ elliptical orbit, the position of the electron at my time
instant is fixed by two coordinates namely the angular coordinate (0) and the radial coordinate (ri Here r is
the radius vector and o is the angle which the radius vector makes with the major axis of the ellipse.
Consider an electron of mass m and linear tangential
velocity v revolving in the elliptical orbit. TTiis tangential t
velocity of the electron can he resolved into two components: |
one along ihc radius vector called radial velocity and the other >***"^*^
perpendicular to the radius vector called the transverse vefoc- b fI
tty. Corresponding to these velocities, the electron has two r 0 gf X
momenta: one along the radius vector called radial momentum \ J
and the other perpendicular to the radius vector known as azi-
muthal momentum or angular momentum. So in the case of
elliptic motion, both the angle © and the radius vector r vary
periodically, as shown in Fig.2.5, Fig. 2.$ Sommcrfdd’i model of the atom.
Thus U« momenta associated with both these coordinates (0 and r) may be quantized in accordartce
with Bohr’s quantum condition. The two quantisation cordilions. are
(2.17)
ptdr = nfi (2.18)

14 Solid State Physics
where and arc the two quantum numbers introduced by Sommerfeld. Since they stand for one periodic
system, -4. Here n, is known as radial quantum number and rq as angular or azimuthal quantum
number, n is known as principal quantum number.
We have now to quantize the momenta associated with both the radial and angular coordinates. The
two equations are
J P/T0 ■ V
and
The integrals arc taken over one complete cycle of variation of the respective coordinates* Both n*
and nf are integers- Furthermore, the sum of nt and a, is equal io the principal quantum number n.
The force on the electron is due to the electrostatic a I traction to the nucleus and acts along the radius
vector There is no force at right angles to this radius vector, so the transverse component of the acceleration
& zero ihroughoui the atom. Hence
iszrw.
r^L dt „
Therefore r I dr
i must be a constant.
Equation (2 J 7) can be easily evaluated* Thus,
<2-19)
This equation shows that the angular momentum of the electron is an integral multiple of —
2n
St ts considerably difficult to evaluate the integral in equation (2J8X However, an attempt is made
here. The polar equation to the ellipse is
1 1 + ECO3<>
(2.20)
where «is the semrmajor axis and £ the eccentricity. Thus differentiating this equation with respect to we
get
Esmjfr
C»(i ~eJ)
re sin$
(2.21)
<1(1-t,>
Substituting the value of /-from equation (2.20). we get
CoDvriohltKl in alerial
Review qfAtomic Sfnature 15
llW a(l-e*) esit>0

.(1 +fcos$)J a(l -e3)
11 dr | esin0
Thus rl^J (1 + ecos0) (2.22)
Referring to equation (X13)
id* 1 dr
Substituting for mr — (= pj and -—-from equation (2,22), wc get
al raQ
d^ = n,A
ecos0.
Referring to equation (2.19)
Esini>
cty - nrh
J + ECOS$.
21W Li i-ECOS^J ffr (2.23)
1
put w -tsin^ arj^ v
1 -FECOS0
The above equation may now be written as
«0- ^JJo 1+ecos*
I rÊCOSfrfo
2/tJJo I +ecos$
I
-1 rf0*=n, (214)
J + E COS0
Sofutrofl of the inu^raL*
P.nns/rinhitirl m ntt^ri a
16 .Wirf Sfui e Pfry
Jo 1+ECOS$
Hint: Proper^ of def inite integral
f */(*>&-2 C/UM* if/f2^x)=/Cx)

Jo Jo
In the integral
Jo l+ecos^
I+ ecos^
1 +ECOS(2rt-Q) = 1 + £COS$
c* tf® f" d$
Jo (1 +ecos<!>) Jo l+ecoa^
I he MsJutjon of this integral is obtained as follows:
Let
When <b ■ 0,r “0 and when 0 “-«j
2^ = = 2dt
sec1- 1+ten3* l+r
I-tan*- j„f2
and cos$=x---------- J^TTj
f+tan*; 1+/
Substituting these values, the integral becomes
M ______
2 - - which becomes
Jti 1+ECOS0
Copyrighted inriEilerial
Review af Atomic Structure 17
(225)
(2.26)
For an ebipsc (1 * f2) = where a and hare the semi * major and semi-minor axes respectively-
Thus.
(2.27)
Equations (2 25) and (2.27) are (he conditions that determine the allowed elliptical orbits The allowed
elliptical orbits are those to which the ratio of major to minor axes is that of two integers. When - nf
b « a and £ = 0. the orbit becomes circular, n, cannot be zero, since the ellipse would then degenerate into a
straight line passing through the nucleus. Also ne cannot be greater than m since b is always Im than n.
Hence for a given value of n. n4 can assume only n different values, which means that there can be only n
elliptical orbits of different eccentricities.
Cppy ri g hi ed rn aleri $ I
[8 Solid Stare Physics
XIIL TOTAL ENERGY OF AN ELECTRON IN AN ELLIPTICAL ORBIT

The tangential velocity of the electron at any instant can be resolved into two components: one along the
radius vector called the radial velocity and the other at right angle to the radius vector called the franr -
wmeve/otiry r -
Thus, the radial momentum, (2.28)
the orbital angular momentum. (2.39)
The kinetic energy of the revolving electron is given by
(230)
Again
dr' _ dr '
n df j j \ dt
Thus from equation i2 29)
□nd
Substituting these values in equation (230), we get
I
I
Copyrighted! material
Review of A tomic Structu re 19
Thus inc total energy of the electron
I dr Ze1
(Wl)
2m r L
41 ‘
J—
(idr ze
or
ne0
ImÊ. mrZe2
(2.32)
Lrd$.
From equation (2.21)

1 [dr? E^sin’^ €V(i - cosJ$)
(232a)
A4*J [afl-E2)] [«(1 -e3)]
if*? (E^-^COS^) (233)

2ld*J La(l
The term (e3 - ^cos3^) of this equation can be further simplified by referring to equation (2.20)
(1 +ecos|) =
ecos$ «
(ecos0)3-
Substituting this in equation (2.32a) we get
1 dr 2
~rdfy^
‘Ur? 2^(1 -e3)

— —— !
.rd<>.
1 dr
fldr? 2r
c2(l^)3 afl-E3)
1 dr 2
(2^M)
,rd^
Equating the coefficients of r and r in equations (2.34) and (232), we get
_ 1
(235)
p,; a\i-c*>
, fflZ? _ 2
a 2neop; <a(l—f2) (2.36)
Thus equation (235) becomes

g.______ *L_.
(2-37)
Sma’U-e1)
Substituting the value of (1-r * from equation (2.36} in equation (2.37). we get
pZ amZe2
£■ -—LL.. —------- --
2m<rl_4EeoP^
Ze*
(238)
fin £j e ri
Again substituting for « from equation (236)t we get
Substituting for (He1) and pj from equations (235) arni (2.19) respectively, we get
mZe 2rt
mZV _ 1
(239)
which is identical with the expression for the energy of the electron in a circular orbit of quantum number n.
Thus the introduction of elliptical orbits does not result in the production of new energy terms; hence no new
spectral lines are to be expected because of this multiplicity of orbits. Thus the introduction of elliptical
orbits gives no new energy levels hence no new transition. Hence Sommerfeld's attempt to explain the
fine structure of spectra! lines failed. Eut soon, on the basis of variation of mass of the electron with
velocity, Sommerfeld was able to find a solution to the problem of fine structure of spectral lines. Here it is
worthwhile; to mention that experimental results and quantum mechanical predictions confirm that also
assumes a value of zero, So corresponding to n, n* assumes 0,1,2.,.,(«-!) values; Le., a total of n possibili*
ties In wave mechanics azimuthal quantum number n+ is denoted by t

The magnitude of the semi-major axis a is obtained as follows:
Equation (2.33) is
Ze1 -Ze2
E *-------------- and a = -——
" 8ne*<r 8n€e£, -
CoDvriahled in alerial
Jftfvfew of A iomic Structure 21
Substituting for En from equation (2.39)

Ze1 l[8eÂJn 2
ft r* ^0
or -- ;■ or (2.40)
8n e oJ . J* itmZe2 L Z J
where r*-—v = 0,0529 nm is the Bohr radius Referring to ifc theory of ellipse,
lune'
we write
b -a — [Refer equLit»on(2.27t[
(2,41)
Equations (2.40) and (2.41 > show that the length of the semi-major axis is determined safety by (he principal
quantum number n, while (he length of (he sc mi-minor axis depends upon the n/imutlul quantum number
as well as n. For a given value of the possible values of n* are 0. J t 2 n. while the corresponding values of
nr are n, In-IK.O. When n* = 0. the ellipse reduces to a straight line and the electron then passes through the
nucleus traversing the orbit This leads to the collapse of the atom The value of n* - 0 is, therefore forbidden
and for a given value is permitted to take only w values, 1. 2, 3,.„n, with tt, taking the corresponding
values (n-l)r (fl — 2)^,0,
For the first orbit,« = 1: since (n, + = I and * 0T«4 = I Thus with n = n# and nr = 0, the first orbit
is a circle as seen from equation (2,27), All the rr -orbits resulting from the n possible values of n, will have
the same energy £, given by equation (239), With n - 2. may have the values I and 2, so that there arc
two possible orbits for ft = 2, One is n = 2, and = 1 - an diipsc and the other is fl = 2 and n* = 2 - a circle;
all these orbits ha\e the Mime energy E2 goen by equation < 2.39). Similarly \ulh n - 3, /ta will have values 1,
2 and 3, and the three possible orbits are - two ellipses with (n - 3, = 1 and n = 3, = 2) and one circle
with n - = 3; all these orbits have the same energy Es Usually the allowed orbits are described by
giving values of w and rc*. The three orbits for n = 3 are represented by symbols 3P 3^ and 3(» the subscript
being the azimuthal quantum number (ra4). In another notation used, the value of azimuthal quantum number
is described by the letters d,/, etc, The values of corresponding to these letters are L 2,3, 4 etc.,
respectively. In this notation, the orbit determined by n - 3 and = I is represented by 3s. Similarly 4d will
represent theorbn n = 4 and = 3. These orbits are represented in Fig. 2-6,
'The transitions between the orbits n - 3 and a - 2 giving line can now take place in six differoit
ways. However, all these transiiions hive the same energy Ey - Ej and hence give rise to a single frequency
for the H, fine, according to the frequency condition No new lines, which would explain rhe fine structure
are therefore predicted.
22 S&tid State Physics
Fig. 2.6 Elliptical Bohr-Sommerfeld oibiU for hydrogen.
XIV. SOMMERFELD’S RELATIVISTIC CORRECTION

The velocity of an electron mevmg in an elliptical orhii vanes from point to point in the orbit, being a max
imum when the electron is nearest to the nucleus and a minimum when it U farther Away from the
nucleus Furthermore, this velocity is quite large , According to the theory of relativity, the variation of velocity
means variation of mass of the electron

Sommerfeld. including the relativistic correction in the treatment of elliptical orbits, showed that
equation of the psith of the electron was not simply that for an ellipse but waj of the form
i
1 IVEcOSyp
r" o(l ’E*)
where y is given by
This is the equation of an ellipse which precesses, i.e., the

major axis turns slowly about the focus (the nucleus) in
the plane of the ellipse. The path of the electron ist there*
fore, a rosette.
It can be shown that rhe total energy with a prime i

pal quantum number n in the relativistic theory is
mZ:c‘ ni7.:e‘u' n 3 )
HejAW 8ej?rlH* 4Jn4 (2.42J
where 0 ~ - —- ■ - ---•■ . a is a di mens tontess quantity and

2eoc/t 137
FiS- 2.7 Rosette path of the electron about the
is called thc/inr structure constant. nucleus
/teview of 4 tomic Structure 23
The first term on the right hand side is the energy of (he electron in the orbit with the principal quan
tum number n according to Bohr's theory and the second term is Sommerfeld's relativity correction arising
from the rosette motion of the electron orbit with principal quantum number n and azimuthal quantum
number The dependence of the total energy of the electron in its orbit as given by the equation (2.42)
results in a splining of energy levels in the atom. For a given value of n, there will be n components corre
sponding to the n permitted values of Hence multtpltcity of spectral lines snould appear in hydrogen
atom.
XV. FINE STRUCTURE OF Ha UNE

Une is due to the transition from n = 3 state to n = 2 state of hydrogen atom. For n - 3t there are three
possible energy levels corresponding to the three values of - L 2 and 3. Similarly, there are two possible
levels for n = 2. Therefore, theoretically six transitions are possible:
and these transitions are shown in Fig. 2.8. Actually, the line has only three components. To make
experiment and theory agree, some of the transitions have to be ruled out by some selection rule. The selec
tion rule is that /i, can change only by 4-1 or -L i.e.t Art, = ±L
Fig. 2.8 Transitions and forbidden lines.
XVI. DRAWBACKS OF BOHR-SOMMERFELD ATOM MODEL

(i) Borhr’s theory failed to explain the fine structure of spectral lines even in the simplest
hydrogen atom.
(it) In the case of complex atoms Bohr-Sommerfeld theory failed to calculate the energy of
the system and frequencies of radiation emitted.
fiii) Sommerfeld's modification. though gave a theoretical background of the splitting of indi
vidual spectral lines of hydrogen, still it could not predict the correct number of observed
fine structure lines.
(iv) Both the models could not explain the distribution and arrangement of electrons in atoms,
(vi Both the models do not throw any light on (he intensities of (he spectral lines.
24 Serfid State Ph vs toj
* (vi) Both the models could not explain anomalous Zeeman effect and Stark effect.
In order to provide a satisfactory explanation of the above, the vector model of the atom was formu
lated, this being based partly on experiments, partly on an analogy and parity on empirical methods.
XVIL VECTOR ATOM MODEL

For explaining the complex spectra of atom and their relation to atomic structure, the vector atom model was
introduced. The two distinct features of the vector atom model are: (i) the conception of spatial quantize
rsffn. and (n) the spinning electron hypothesis.
(I) Spatial quantization or quantization of direction

According to Bohr's theory. the orbits are quantised as regards their magnitude [i.e^ their size and shape)
only. Finding this theory yet inadequate to explain further experimental observations viz., the Zeimari and
StarJt effects in which the spectral lines could be split up under the influence of magnetic and electric fields,
the idea of orientation of the orbit tn space naming it 'the space quantization* was introduced; Le.> the
direction or orientation of the orbits in space also should be quantized. To specify the orientation of the
electron orbit in space, we need a fixed reference axis. This reference line is chosen as the direction of an
external magnetic field that is applied to (he atom, The different permitted orientations of an electron orbit
are determined by the fact that the projections of the quantized orbits on the field direction must themselves
be quantized. The idea of space quantization leads to an explanation of Zeeman effect The Stcm-<3er1ach
experiment provided an excellent proof of the space quantization of atom. The quantum number associated
with the space quantization is called 'magnetic orbital quantum number1 and is represented by
(H) Spinning electron

To account for further hyperfine details in th© atomic spectra of multi-electron atoms, Uhlenbeck and
Goudsmit (1925) showed that the remaining difficulties could be resolved by assuming (hat the electrons
were spinning about their Own axes like a top, while traversing their orbits thus resulting in slight changes of
energy. The spin of the electron is analogous to the spinning of a planet about its own axis as it moves in an
elliptical orbit around the sun, In other words, the electron is endowed with a spin motion over and above
the orbital mot ton. According to the quantum theory, the spin motion like the orbital motion, is to be quan
tized which will therefore introduce a new quantum number called the magnetic spin quantum number.
denoted by mt.
XVI[I. THE CHARACTERISTIC QUANTUM NUMBERS

The slate of ihe electron around the nucleus in terms of its location relative to the nucleus and rhe energy
associated with it is described by a set of quantum numbers. Each electron is characterised by tour impor-
tant quantum numbers called the total or principal quantum number, the orbital or azimuthal quantum
number, the magnetic orbital quantum number and the magnetic spin quantum number. 'The significance of
these quantum numbers in terms of size, shape, orientation of orbitals in space and spin around the nucleus
is now described briefly,
(!) The total or principal quantum number (n)

This is identical wish the one used in Bohr-Sommerfeld^ theory. It can take values 1, 2t 3. 4 . .«■. This
specifies the major axis of the ellipse with which the energy of the electron is associated and hence pertains
to the main energy level or shell These energy levels having values of n = L 2,3,4, etc. as we go away from
the nucleus are denoted by symbols K. L. M .V. etc. The energy (jE) is inversely proportional to «2. That is,
/feview of Atomic Structure 25
(ii) The orbital quantum number (I)

This quantum number is an integer and for a given value of n, it can take any of the >t values OJ* 2, 3, 4.,..
(fl-1). By comparing these values with the values of the azimuthal quantum number of Sommerfeld s
theory, it is seen that / is nothing but (n0 - J) J specifies the minor axis of the ellipse and is equal to (a - l)
when the orbit is circular. h also divides the main shell into n slightly different energy levels or subshells so
that the number of sub-shells in a main shell is given by its principal quantum number. Thus the shell with
principal quantum number n - I or Af-shel 1 has only one sub-shell designated as s-sub*shell and in that case
I = 0. This quantum number specifies the mechanical angular momentum of the electron and hence it is also
called the angular momentum quantum number The orbital angular momentum pt associated v ith different
orbits are
= > where/-0J, 2,,.. etc.
According To quantum mechanical results, the value of orbital angular momentum p( is dot equal to
. h . .
/ — hut given by
2n
/1 ?
fl = M + D
2n
The second principal shell or the L-shell will have two sub-shells having values of / = 0 and / - I.
They are designated as j- and p-sub-shells. Similarly, the Af principal shell has three sub shells with
values of / = 0„ 1, and 2, and they are named ass-/?- and d- sub shells respectively. Thus the nsub shells of
the nVl principal shell have rhe / values of 0, 1, 2i). It may further be noted that s-sub-shell ri /oner in
energy than p sub shell and the latter is lower in energy than the d-sub shell and so on.
(Hi) Magnetic orbital quantum number (mJ

This quantum number specifies the orientation of the
election in an externa! magnetic field; i.e, this quantum
number specifies the space orientation of the electron’s
plane elliptical orbit but has no effect on energy levels. It
originated in the evidences of slight differences between
almost identical energy levels obtained from the Zeeman
effect; Le., the splitting of spectral lines when a light
source is placed in a strong magnetic field and from the
corresponding Stark effect produced by the application of
an intense electric field. In these cases, the electrons
because of their magnetic moments will experience
torques tending to orient them so that the spin and the
angular momentum vectors will take up definite positions
in space with respect to the magnetic field thus introduc
ing fresh levels. These extra sub shells are denoted by the Fig. Z9 Projection of orbital quantum vecior m
magnetic orbital quantum number For a given value ot the direction of the magnetic fidd
the orbital quantum number A m, can take any of the
Copy ri g hi ed rn ateri a I
26 Solid Stale Physics
(21 + I) values t (/-!), (/ - 2)..... 0,-1, -2.........-L This means that can assume (2fe-1) values or the vector
£ can have (2? + 1) orientations. For example if I- I, the permitted orientations of I are 3 for which mf has the
values 4-1,0, -1. This is illustrated in Fig. 2 A for f -1 The angle 9 iwrween I and B is pw by 1 cos 9 = m,.
The permuted orientations of the I vector relative to the Held direction B ia (2/ + I) For example. if I = 3, the
permitted orienuikrns of I are 7, for which 3,2, lt 0, **i, -2, —3, Hence the I vector can take only the
seven directions shown in Fig, 2.9. / cannot be inclined to B at any other angle< This is called spatial
quantiztition,
(iv) The magnetic spin quantum number (mJ

This quantum number specifies the ortenurion of the electron spin axis relative to the same frame of refer
ence as used for mi+ The angular momentum can assume only two possible positions with respect to the
magnetic field, clockwise or anticlockwise, that is, it may be parallel or antiparaHd to ilt viz* oppositely
directed to it Its projection along the direction of the magnetic field is denoted by m, which is
called the magnenc spin quantum number and can have only the values + j or as illustrated in Fig, 2.10r so
that the difference in the spin qiuntum numbers for two electrons in any orbit is unity, The spin angular
momentum of the electron is given by
p = $— where r --
*1 2n 2
According to wave mechanics, the spin angular momentum p, of the electron is given by
p, = Vj(» + 1) f
Thus rhe four quantum numbers specified above define completely the state of any electron in a given
atom
XIX. THE PAULI’S EXCLUSION PRINCIPLE

The generalised principle that governs the electronic configuration of atoms having more then one electron
has been summarised in the exclusion principle, which was suggested by Wolfgang Pauli in 1925.
According to this principle, hw electrons in an Iso
lated atom can exist in the same quantum stare. This
principle is empirical and cannot be directly verified.
But its universal acceptance rests on the fact that all the
deductions which have been made from it have been
either subjected to experimental verification or fit into
a logical account of the theoretical physics of the struts
tore of the atom. Pauli's principle implies that no two
electrons in the same atom can have the same values of
the four quantum numbers nt t ftt4. At least one
quantum number must be different To illustrate this
principle, lei us take the case of helium atom which has
(Wo electrons The^t electrons occupy h = 1 orbit or
K-shelL Clearly for n - L I - 0 and therefore, fftr« 0.
Fig, 2*10 Projection of the spin vector j tn the direc
tion of the magnetic field showing the two possible
values of m,
C.opyriQtiied material
Butm, can have two values* namely, 4- - and Hence, one electron hasn “ 1J -O./n( -0Tws -4 -and
the other electrons has n = IJ = 0, mf = Quantum representation of the electrons in the K-she 11 is illus
trated in Fig 2,11.
Quantum state Electron Pictorial representation

Configuration
(a) a - 1J “0(m, = 0,m, = +- J?
(b) n = 1J *=0,mr*0tmf = -^
1?
(c) n = 1J =>0*m, =0.mr = ±^

1?
Fig. 2.11 Quantum representation of electrons in A’-shelL
XX. APPLICATION OF PAULI’S EXCLUSION PRINCIPLE

U) Find the maximum number of electrons that n - 2 orbit can accomodate according to Pauli's exclusion
principle.
ForL• shell
n=2
i -0J
- 0,+L-1
Hence, the possible different combinations of the four quantum numbers are:
n 2222222 2
I 0 0 111111
M* 0 0-1-1 1 1 0 0
1 1 1 | 1 1 1
m’ 222 “2 2222
1: can now be seen that in no two vertical columns, all the four values of quantum numbers are identical.
This means that the maximum number of electrons that can exist tn L-shell is 8.
(ii) Maximum number of electrons in orbitals or sub shells

Consider an orbit with principal quantum numbers and orbital quantum number I For finding the number of
electrons in any orbital* it is clear that the values of a and / are fixed. Only the values of and ni, can
change. Now
rnf — -1 to + / including zero.
Thus fi?r & given value of /, there are {2i + 1) values of mr Now for each value of mr can have only two
. i 1 1
values, namely: + •
Hence. there can be only 2(21 + I) different combinations of (n< /, rty, Thus the maximum number
of electrons in any sub-shell with orbital quantum number / = 2(2/ + 1). For example:
j-sub shell (/ = 0) can have a maximum of 2(2/ +1) =2 electrons, p*sub shell (/ - 1) can have a maximum of
2(2/ +1) - 6 electrons and so on.
(ill) Maximum number of electrons in main shells

The main shell consists of a number of sub-shells. called &rbitols< According to Pauli* s exclusion principle
the maximum number of electrons in an orbit with principal quantum number n is equal to W. This can be
proved as under"
Consider an orbit with principal quantum number n and orbital quantum number L It has already been
shown that the maximum number of electrons in an orbital is equal to 2(2/ +1) with I = 0< L 2t,„ (w-1),
Thus the total number of electrons with principal quantum number n is given by
S 2(2/+1)
fMfl
2n(ji * 1)
1-0 i =c J (2.42a)
Table 2» A The distnbuiton of electrons in the various stales
8 / «/ "',±1 Number of electrons in Number of

a/, 2 H ta +o sub-sMH eletirrms in
main shells
1 0 0 +1/2 2 1? 2(K)
I 0 0 -1/2
r 2 2
0
0
0
0
+1/2
-1/2
2 2?
2 ) -1 +1/2
2 1 —1 -1/2 8(L)
2 1 0 + 1/2
2 1 a -1/2 6
2 1 t + 1/2
2 1 1 -J/2
3 0 0 + 1/2 2 3?
3 0 0 -j/2
(Co/ud,)
Copyriatiied material
Rivriwo* AikmuMuMI M
_______________ - - •------------------------- -• - - -*-**--+ —
Table 2.1 The distribution ol electrons in the various stales
n / = 0,l,2, m, = -1 to + I Number of electrons
:
Number of electrons In subshells
s’
I 04
...» (n-1) In main shells (in2)
-
1 0 0 + 1/2 2 is2 2(K)
1 0 0 - 1/2
2 0 0 +1/2 . 2 2?
2 0 0 - 1/2
•
2 1 -1 + 1/2
2 1 -1 -1/2 ■
2 1 0 + 1/2
-
2 1 0 -1/2 6 . 2/ 8(£)
. 2 1 1 + 1/2
2 1 1 - 1/2
3 - 0 0 + 1/2 2 3s2
- 3 0 ■ 0 -1/2
1 -1 + 1/2 -
3
3 1 -1 -1/2
3 1 0 . +1/2 >
3 1 0 -1/2 6 3p6
•
3 1 1 +1/2
3 1 1 - 1/2 V - •
3 2 -2 + 1/2
3 2 -2 -1/2
3 2 -1 + 1/2
3 2 ~ -4 - 1/2 -
3. . 2 ?- 0 + 1/2 10 3J10 18(Af)

3 2 0 -1/2 ■
3 2 1 + 1/2 .
3 2 * 1 -1/2
3 2 2. + 1/2
3 2 2 -1/2
Hence the maximum number of electrons in an orbit is 2n2. This formula is applicable only to
closed shells. The outermost shell cannot have more than eight electrons.
The distribution of electrons in the various shells generally follows the rules given below.
(f) The maximum number of electrons possible in a main shell is 2n where n is the principal
quantum number for the shell. ,

(ii) The outermost main shell cannot contain more ectrons
(iii) The “last but one” main shell cannot contain more than' elSh^ ec^
(iv) The last shell cannot contain more than two electrons c°ntain
more than nine electrons until the “last but two” shells has its full capacity of electrons.
Some Examples of Electron Configuration
Hydrogen (Z = 1) £4, „ , „ „
The hydrogen atom has only one electron occupying the r-subshell of the K-shell for which
n = 1. This shell can have a maximum of two electrons. Since the shell is incomplete hydrogen is
chemically very active and forms new compounds on chemical reaction wit suitable elements. This
single electron exists either in the m, = + | state or m,=-1 state. Symbolically, the electron configuration
of hydrogen is represented as Is1.
Helium (Z = 2)
This atom has two electrons which fill the first orbit or AT-shell. The two electrons in this shell
are in the m = +— state and m = --7 state (having opposite spins).

2 15 2
The shell is complete and hence helium is inert element.
The electronic configuration of helium is represented as k2. The number 4 refers to the principal
quantum number 1. The symbol s refers to the subshell I = 0. The number of electrons 2 is fixed at the
top of 5.
Carbon (Z = 6)
Carbon atom has 6 electrons. Two electrons fill the first main shell. The other four electrons are
in the second main shell. Of these four electrons, two are in the s-subshell and the other two are in the
p-subshell. The electronic configuration is represented as lx2 2s2 2p2.
Neon (Z = 10)
Two electrons fill the first main shell. Eight electrons fill the second main shell. This is another
inert element.
Mendelyeev, a Russian scientist in 1869 showed that the elements when arranged according to the
magnitude of atomic weights, displayed marked periodicity in their properties. Elements were also
found to exhibit periodicity in various physical properties such as atomic volume, expansion coefficient,
electrical conductivity and melting point. Based on these observations, the law of periodic table states
that the properties of the elements are periodic functions of their atomic weights.
Mendelyeev arranged all the elements in the order of their increasing atomic weights in horizontal
rows in such a way that the elements having similar properties come directly under one another in the
Table 2.2 Electronic configuration of elements
Atomic Name of Symbol Atomic Distribution of electrons within the shells Number of
numbeir element weight neutrons
K L M N 0 P Q
• J spspdspdfspd f s p d s
1 2 4 5 6 ,7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23
1 Hydrogen H 1.008 1
2 Helium He 4.003 2 2
3 Lithium Li 6.939 2 1 4
4 Beryllium Be 9.012 2 2 5
5 Boron B 10.81 2 2 1 6
6 Carbon C 12.01 2 2 2 6
7 Nitrogen N 14.01 2 2 3 7
8 Oxygen 0 16.00 2 2 4 8
9 Fluorine F 19.00 2 2 5 10
IP Neon Ne 20.18 2 2 6 10
11 Sodium Na 22.99 2 2 6 1 12
12 Magnesium Mg 24.31 2 2 6 2 12
13 Aluminium Al 26.98 2 2 6 2'1 14
14 Silicon Si 28.09 2 2 6 2 2’ 14
15 Phosphorus P 30.99 2 2 6 2 3 16
16 Sulphur S 32.06 2 2 6 2 4 16
17 Chlorine Cl 35.45 2 2 6 2 5 18
18 Argon Ar 39.95 2 2 6 2 6 22
19 Potassium K 39.10 2 2 6 2 6 -1 20
20 Calcium Ca 40.08 2 2 6 2 6 -2 ________________________ 20
21 Scandium Sc 44.96 2 2 6 2 6 1 2 24
22 Titanium Ti 47.90 2 2 6 2 6 2 2 26
23 Vanadium V 50.94 2 2 6 2 6 3 2 28
24 Chromium Cr 52.00 2 2 6 2 6 5 1 28
25 Manganese Mn 54.94 2 2 6 2 6 5 2 30
(Contd,)
CHAPTER 2
32
Table 2, B (ComdJ
Atomic Atame of Symbol Atomic Distribution of Electrons within the shells Number of
Number Element weight neutrons
KL M N O P Q
sspspdspdf spdf s p d •
S o lid Sim e Physics
J___________ 2 3_________ 4_________ 5 6 7 8 9 10 11 12 13 14 15 16 17 jg 19 20 21 22 23

26 Iron Ke 55.85 2262662 30
27 Cobalt Co 58.93 2 2 6 2 6 7 2 32
28 Nickel N: 58.71 2262682 30
29 Copper Cu 63.54 2 2 6 2 6 10 1 34
30 Zinc Za 65.37 2 2 6 2 6 10 2 34
31 Gallium Ga 69.72 2 2 6 2 6 10 2 1 38
32 Germanium Ge 72.59 2 2 6 2 6 10 2 2 42
33 Arsenic As 7492 22626 10 23 42
34 Selenium Se 7896 226 2 6 10 24 46
35 Bromine Br 79.91 2 2 6 2 6 16 2 5 44
36 Krypton Kr 83.80 22626 10 26 48
37 Rubidium Rb 83.47 22626 10 2 6 - - t 48
38 Svomtum Sr 87,62 2 2 6 2 6 10 2 6 - - 2 50
39 Yttrium Y 88 91 22626 10 261-2 50
40 Zirconium Zr 91.22 22626 !0 2 6 2 - 2 50
41 Niobium Nb 92.9! 22626 10 264-1 52
42 Molybdenum Mo 95.94 2 2 6 2 6 10 2 6 5-1 56
43 Technetium Tc* (99) 2 2 6 2 6 10 2 6 6 - 1 (54)
44 Ruthenium Ru 101.1 22626 10 267-1 < 58
45 Rhodium Rh 102.9 22626 10 268-1 58
46 Palladium Pd 106.4 2 2 6 2 6 10 2 6 10 -- 60
47 Silver Ag 107.9 22626 10 26 10 - 1 60
48 Cadmium Cd 112.4 2 2 6 2 6 10 2 6 10 - 2 66
49 Indium In 114.8 22626 10 26 10 - 21 64
50 Tin Sa 118.7 22626 10 26 10 - 22 70
C opyrighted pi alerial
Table 2.2 (Contd.)
Atomic Name of Symbol Atomic s Distribution of electrons within the shells Number of
, number element weight neutrons
■ ■ -------- >........................................................ -i • ‘ 1; .. \v' - ’ -S. _ .7 ■
■ K , • 0 P Q
v . s ■ , s ■■ ■ p''’f-’S.::'''. p '-r'd '■■■<s f p dfs.pd f s p d s
1 .... 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23
51 Antimony Sb 121.8 2 ; 2 6 2 6 10 2 6 10 - 2 3 70
52 Tellurium Te 127.6 2 2 6 2 6 10 2 6 10 - 2 4 78
53 Iodine I 126.9 2 2 6 2 6 10 2 6 10- 2 5 74
54 Xenon Xe 131.3 2 2 6 2 6 10 2 6 10 - 2 6 78
55 Caesium Cs 132.9 2.2 6 2: 6 10 2 6 10 - 2 6 - - 1 78
56 Barium Ba 137.3 2 2 6 2 6 10 2 6 10 - 2 6 - - 2 82
57 Lanthanum La 138.9 2 2 6 2 6 10 2 6 10 - 2 6 1 - 2 82
58 Cerium Ce 140.1 2 2 6 2 6 10 2 6 ■ 10 2 2 6 - - 2 82
59 Praseodymium Pr 140.9 2 2 6 2 6 10 2 6 10 3 2 6 - - 2 82
60 Neodymium Nd 144.2 2 2 6 2 6 10 2 6 10 4 2 6 - - 2 82
’ . 1 .
61 PromethiumPm* - (145) 2 2 6 2 6 10 2 6 10 .5 2 6 - - 2 (84)
62 Samarium Sm 150.4 2 2 6, 2 610 2 6 10 6 2 6 - - 2 90
63 Europium Eu 152.0 2 2 6 2 610 2 6 10 7,2 6 - - 2 90
64 Gadolinium Gd 157.3 2 2 6 2 6 10 2 6 10 7 2 6 1 - 2 94
65 Terbium Tb 158.9 2 2 6 2 6 10 2 6 10 9 2 6 - - 2 94
66 Dysprosium Dy 162.5 2,2 6 2 6 10 2 6 , 10 10 2 6 — — 2 98

67 Holmium Ho 164.9 2 2 6 2; 6 10 2 6. 10 11 2 6 -. - 2 98
68 Erbium Er 167.3 2 2 6 2■ 6 10 2 6 10 12 2 6 - - 2 98
69 Thulium Tm 168.9 2 2 6 2 6 10 2 6 10 13 2 6 - - 2 100
70 Yetierbium Yb 173.0 2 2 6 2 6 10 2 6 10 14 2 6 - - 2 104
71 Lutetium Lu 175.0 22626 10 26 10 14 2 <6 1 — 2 104

72 Hafnium Hf 178.5 2 2 6 2 6 10 2 6 10 14 2V 6 2,-2 108
73 Tantalum Ta 180.9 2 2 6 2 6 10 2 6 10 14 2 6 3 - 2 108
74 Tungsten W 183.9 2 2 6 2 6 10 2 6 10 14 2 6 4 - 2 110
75 Rhenium Re 186.2 226 26 10 26 10 14 265 — 2 110
(Contd.)
T CHAPTER 2
pi]O g
TlbteZB (CtaoL)
Atomic Mjpic <j/ Atomic qfEtec/nm Mif/nn /Ac sAr/A MonAer r/

d
dumberr £/«menf Jif j/frpflf

K L M N 0 P Q
s s P s P d s P d f s p <1 f s P d s
1 2 3 4 5 6 7 « 9 10 IJ 12 13 14 15 16 17 18 19 20 21 22 23
76 Osftnuin Os 190.2 2 2 6 2 6 2 6 14 2 >w
10 10 6 6 2 116
77 Indium lr 19X2 2 2 6 2 6 10 2 6 10 14 2 6 9 116
78 Plauntim Pi 195.1 2 2 6 2 6 10 2 6 10 14 2 —
6 9 1 1)6
79 197 0 MC
Gold Au 2 2 6 2 6 10 2 6 10 !4 2 6 10 1 118
80 Mercury Hg 200.6 2 2 6 2 6 io 2 6 10 14 2 6 10 2 122
SI Thallium 77 204.4 2 2 6 2 6 10 2 6 10 14 2 6 10 — 2 1 124
Lead Pb 2Q7.2 2 2 6 2 6 10 2 6 10 14 2 6 10 2 2 126
S3 Bismuth Bi 209.0 2 2 6 2 10 2 6 io 14 2 —
6 6 10 2 126
84 Polonium Po* (209) 2 2 6 2 6 10 2 6 10 14 2 6 10 2 4 (125)
85 Astatine At* (210) 2 2 6 2 6 10 2 6 10 14 2 6 10 w 2 5 (125)
86 Radon Rn* (222) 2 2 6 2 6 10 2 10 14 2 —■
6 6 10 2 6 (136)
87 I'r annum ft* (223) 2 2 6 2 6 10 2 6 14 2 — 2 —
10 6 10 6 1 (136)
88 Radium Ra* (226} 2 2 6 2 6 10 2 - ■»
6 10 14 2 6 10 2 6 2 (138)
89 Actinium Ac* (227) 2 2 6 2 6 10 2 6 10 14 2 6 10 — 2 6 1 2 (138)
90 Tbttt ium Tha* 232 2 2 6 2 6 10 2 6 10 14 2 6 10 2 6 2 2 142
91 Protactinium Pa* (231) 2 2 6 2 6 10 2 6 10 14 2 6 10 2 2 I 2 (140)
92 Urmium U* 238 2 2 6 2 6 10 2 6 10 14 2 6 10 3 2 6 1 2 146
93 Neptunium Np» (237) 2 2 6 2 6 10 2 6 10 14 2 6 10 4 2 6 1 2 (144)
94 Pl uranium Pu* (244) 2 2 6 2 6 10 2 6 10 14 2 6 10 6 2 6 - 2 (150)
95 Americium Am* (243) 2 2 6 2 6 10 2 6 10 14 2 6 10 7 2 6 - 2 (148)
9(i Curium Cm* (247) 2 2 6 2 6 10 2 6 10 14 2 6 10 7 2 6 I 2 <151)
97 Berkelium Bk* (247) 2 2 6 2 6 10 2 6 10 14 2 6 10 8 2 6 1 2 (150)
9S Californium CP (251) 2 2 6 2 6 10 2 6 10 14 2 6 10 *■
10 2 6 2 (153)
99 Ei nsiet nium Es* (254) 2 2 6 2 10 2 14 2 *
6 6 10 6 10 11 2 6 2 (155)
100 Fermium Fm* (253) 2 2 6 2 6 10 2 6 10 14 2 6 10 12 2 6 2 (153)
Table IB (CrmttL )
Ahwia Name of Atomic Distribution of Electrons within the shells Member fi/
MimZvx Element weight neutrons
K L M N o P Q
s s p s p d 5 P d f S p <i f s P d s
1 2 3 4 5 6 7 S 9 10 n 12 13 14 15 16 17 18 19 20 21 22 23
101 Mendelevium Mv* (256) 2 2 6 2 6 10 2 6 10 14 2 6 10 13 2 6 * 2 (155)
102 Nobelium No* (253) 2 2 6 2 6 10 2 6 10 14 2 6 10 14 2 6 * 2 (151)
103 Lawter-lium Lw* (257) 2 2 6 2 6 10 2 6 10 14 2 6 10 14 2 6 J 2 (154)
104 Kurchatovium Ku 2 2 6 2 6 10 2 6 10 14 2 6 10 14 2 6 2 2
J05 Hahnium Ha 2 2 6 2 6 JO 2 6 to 14 2 6 10 14 2 6 3 2
Note: L Elements marked *are unstable.

2 The elements whose atomic weights are given in parenthesis do not occur in nature, hit have been prepared artificially in nuclear reactions.
3 , The number of neutrons in these cases is calculated for the most commonly found isotope.
Review
o f A to m ic S tructure
35
cn
si'
5
Table X C Periodic Table
Period Group
1 II m [V V VI Vjl vm
I 2
SoUd State Physics
!
H He
100797 4.0026
2 3 4 s 6 7 8 9 10
U Be B N O F Nc
&939 9.0122 huh 12 0112 14.0067 15.9994 19.9984 20.179
3 11 12 13 14 15 16 17 18
Ni MS Al Si P S Cl Ae
22.9® 24305 269815 2K096 30.9738 32,064 35.453 39,948
4 19 3Q 21 22 23 24 2.5 26 27 28 29 30 31 32 33 34 3$ 36
K Ci Sc "Pt V Cr Mn fie Co Hi Cu Zn Ga Ge As Se Be Kr
39402 4om 44.956 47.90 50.942 61,996 $4,938 53,847 58.933 58 <71 6354 65 37 69.72 7159 74,992 78.96 79.909 83.%)
5 17 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
Rb Sc Y Zr Mb Mo Tc Ru Rh Pd Ag C*d Tn Sn Sb Te I Xt
85.47 87.62 88.905 9L2J 92.906 95 94 (99) 101,07 102905 1064 107.870 112.40 114.82 118.69 121.75 127.60 126.904 13130
6 55 56 57-71 72 73 74 75 76 77 78 79 80 >1 82 S3 84 S5 86
Cs Ba • Hf Tl W Re u Er Pl Au Hs Ti Pb Bi Pc At Rn
132.905 13734 17849 180.948 183,85 186.2 190.2 I92J 195.05 I%%7 200,59 20437 207 f9 2OS9fi €2J0h (210) (222)
7 87 88 89403
fir Ra «
(223) (226)
*Raie ^7 58 $9 60 61 62 63 64 65 66 67 68 69 70 7i
Earths Cfe Pr Nd Pm S/n £u Gd Tb Dy Er Tm Yb Lu
1* ■ 138.91 140.12 140.907 144,24 (147) 150.35 151.96 157.25 158.924 162.50 164,930 167.26 168.934 173 04 174.97
••Acti- 89 90 91 92 93 94 95 % 97 98 99 100 101 102 103

Hides Ac Th Pa u Np Pu Am Cm Bk Cf Ea Pm Md Na Lw
(227} 232.038 (231) 238.03 (237) (244) (243} (247) (247) (252) (254) (253) (257) (355) (356)
C opyrighted (notorial
vertical columns (or grour^Trh table’<he,B were seven hon/ontaJ rows (°r periods) and eight
study of elements, yet it could nou^plidn tteX'iC ) peri°dic lable was of si«nifKim“
but having different atomic weights arc called^ °> 7'°'’" (deme"ls havin« alo""c "umbCT
with higher atomic weight came first and el™ / "i', CaS“' " was found that
this, it was felt that the atomic weight canno t'lT lo“er a'°™c wei«h' came la“ As a
g annot be taken as the basis for the classifications of elements.
Modem Periodic Table

In 1913, Mosely suggested that the properties of elements are periodic functions of their atomic numbers
CHAPTER 2
and not atomic weights. We know that, no two elements can have the same atomic number, and hence
atomic number is more a fundamental property than the atomic weight. Mosely proposed a periodic
table in which the elements are arranged in the order of their increasing atomic numbers.
The periodic table proposed by Mosely was later modified by Bohr which is now popularly
known as Modem periodic table. In this table, elements are arranged in the order of their increasing
atomic number. There is a marked periodicity in properties. Each vertical column within this table is
numbered from one to eight and is called a group, while each of the seven horizontal rows is known as
a period. The periodic table can be conveniently divided into four distinct zones as shown in Fig. 2.12.
1. Non-metals 2. Light metals
3. Transition metals 4. Soft metals.
The non-metals are the extreme right-hand groups of the elements in the table and include the
inert gases (He, Ne, Ar, etc.). Silicon, arsenic and tellurium belong to the subgroup known as the half
metals since they exhibit some of the properties of metals and some of the properties of non-metals. The
light metals occupy the two groups on the extreme left of the table and are characterised by low densities,
low melting points, high reactivity in chemical reactions and a tendency to form ionic compounds. This
zone is made up of alkali metals and the alkaline earths having valencies of +1 and +2 respectively.
The transition metals occupy the central position of the table and P"he ^genera!
characteristics that distinguish them as a group. They are all high me ting poin , y orm
coloured compounds and most of the traditional engineering meta s come pm e table,
and they all possess relatively high densities.

The soft metals fall between the transition metals and the non-metals, and the properties of some
of them grade out into those of these two classes of metals. Generally speaking, the metals of this zone
are comparatively soft and unreactive and possess low melting point.
The properties of elements change in a systematic way through a period. From left to right in the
periodic table, and from bottom to top, the elements become more electronegative. This means that
their electron affinity increases. Inversely, from right to left and from top to bottom of the periodic table
the elements become more electropositive. The electron affinity is defined as the energy that is given
out when an electron is added to an atom to form a negative ion. On the other hand, the energy necessary
to remove the most loosely bound electron from an atom is called the ionisation potential. In general
the ionisation potential increases on going from left to right in the table.
The first element in the table is hydrogen, which has one electron. According to the rules, this
electron normally occupies one of the two Is states, since these have the lowest energy. The helium
atom (Z = 2) has two electrons, both contained in the Is state, which can accommodate two electrons
provided they have opposite spins. The first main shell (n =1) is now full, and therefore the third
electron forming lithium (Z = 3) must go into the lowest subshell of the second shell; i.e., the 2s level.
Thus, with the lithium a new shell begins to form and a new row of periodic table commences. The
elements in this row add their electrons to the second shell until it is completely filled at neon. The order
of filling may be completely understood by examining Table 2.2. It is also found that when a new shell
begins to form in the structure of the atom, the element in question commences a new row in the
periodic table.
An important effect occurs in the elements immediately following argon. To complete the third
shell, 10 more electrons are required to occupy the 3d states. For these elements, however, 4s energy
level is slightly lower than the 3d, and so fourth shell begins to form before the third shell is filled. Thus
a new period commences with an alkali metal, potassium, and an alkaline earth metal, calcium. In the
following series of elements, extending to copper, the 3d states become increasingly occupied. Hence,
there is a large group in this period with only one or two electrons in the outermost shell. All these
elements are metals, and those in which the third shell is expanding from 8 to 18 electrons are known
as transition metals.
The same sort of behaviour is found in the subsequent rows of the periodic table. The 5s states
are occupied before the 4d and 6s states before the 5d. As a result, two additional groups of transition
metals are obtained. In the final long period, the situation is completed by the fact that during filling of
the 5d states in the last group of transition metals, the 4/ states begin to be occupied. This results in a
group of elements known as the rare earths.
There have been important developments since the Bohr-Sommerfeld theory. These developments have
proposed treatments entirely foreign to the Bohr-Sommerfeld picture and these have led to even more
38 Solid Sfa/e Ph v v /rv
shell begins to form and a new row of periodic table continences- The elements in this row add Eheir elec
trons to ihe second shell until ft is completely filled at neon The order of filling may be completely under
sold by examining Tables 2B. It is also found that when a new shell begins to form in the structure of the
atom, the element in question commences a new row in the periodic table.
An important effect occurs in the elements immediately following argon To complete the third shell
10 more electrons are required to occupy the 3d states* For these elements, however, 4j energy level is
slightly lower than the 3d, and so fourth shell begins to form before the third shell is filled. Thus a new
period commences with an alkali metal* potassium, and an alkaline earth metal, calcium. In the following
scries of elements, extending to copper, the 3d states become increasingly occupied. Hence, there is a large
group in this period with only one or two electrons in the outermost shell All these elements are metals, and
those in which the third shell is expanding from 8 to 13 electrons arc known as transition metals.
The same sort of behaviour is found in the subsequent rows of the periodic table. The 5j states are
occupied before the 4^ and fn states before the 5d. As a result, (wo additional groups of transition metals are
obtained In the final long period, the situation is completed by the fact that during filling of the 5d states in
(he hist group of transition metals, the 4/states begin to be occupied. This results in a group of elements
known as the rare earths.
XXIH. WAVE-MECHANICAL CONCEPT OF THE ATOM

There have been important developments since the Bohr-Sommerfeld theory, These developments have
proposed treatments entirely foreign to the Bohr-Sommerfeld picture and these have led to even more satis
factory results from an analytical point of view. The modifications were started when de Broglie proposed
that panicles, such as electrons, possessed many properties of waves, He concluded theoretically that a
panicle of mass m now moving with a velocity v would behave as a wave having a wavelength
x-— !
This w,bc-mechanic a I treatment of the atom ilium mates

many of the odd ad hoc assumptions made in the pre*
vjous sections* Instead of assuming (he ejectron to be
moving in a fixed stationary orbit it was imagined to
generate a series of waves as it revolved round the
nucleus in any permissible orbit*
In order that the waves should not cancel each
other by interference in any permissible orbit, the elec
tron must move in such a manner as hi produce a stand
ing wave in Che orbit* This will happen only if the
electron wavefront fills the circumference as in Fig. 2.13
\Jiciethere jit an nik-gral number of uas e lengths Thus
the circumference must contain an integral number of
waves Fig. 2 T13 De Brog lie’s st ationary wave q lm n tizcd
orbits.
Thus 2^* ttX where t js the radius of the permitted orbit and n ari integer. Substituting ■■■ fui A. vse gel
tnv
Copy rig hied material

fteview of Atomic Structure 39
j=ji —
mv (243)
h
mvr -fl—
2n
But mvr is the angular momentum of the electron regarded as a particle, Thus we see that the wave
mechanical picture leads to Bohr*s postulate regarding the quantization of orbits-that the only permitted
orbits are ttuxse angular momenta wre equal to an integral multiple of --♦
211
OBJECTIVE QUESTIONS
1 Iffj and are the frequencies of the electron in the first and second orbits of hydrogen atom respec*
lively, then is
(a) 8 (b) 2
(c) 4 (d) I
2 The total energy of the electron in the orbit of hydrogen atom is
(a) *------- (b)--------t—- e1

4s €0 r, 4n ee r’n
.» e1
(t) ------ (d) «------
8it r. 8« «o r,
1 The kinetic energy of an electron in an atom to
(a) half of its potential energy
(b) twice Its potential energy
(c) equal to its potential energy
(d) thrice its potential energy
4. if the radius of the first orbit in hydrogen atom is 0.05 nm, the radius of the first orbit in helium
atom is
(a) 0.025 nm (b) 0.05 nm
(c) 1 nm (d) none of these

5. The numerical value of the radius of the fiisl orbit of hydrogen is
(a) 0.529 nm fb> 0.0529 A
(c) 5.29 A (d) 0.0529 nm
6. The total energy of the electron in hydrogen atom is
(a) -G3,6/n)eV (b) (B.6/n)eV

(c) - (13.6/n1)eV (d) (13.6/a’)eV
7. The ratio of frequencies of the first hne <4 the Lyman scrips and the first line of Balmer series is
(a) 27/5 (b) 27/8
(c) 8/27 (d) 4/27

8. When an electron jumps from the fourth orbit to the second orbit, one gets
(a) the first lineof pfund series
3. The kinetic energy of an electron in an atom is
(a) half of its potential energy (&) twice of its potential energy
(c) equal to its potential energy (d) thrice of its potential energy
4 If the radius of the first orbit in hydrogen atom is 0.05 nm, the radius of the first orbit in helium atom is
(a) 0.025 nm (*) 0 05 nm

(c) 1 nm GO none of these
5. The numerical value of the radius of the first orbit of hydrogen is
(a) 0.529 nm (fc) °-0529
(c) 5.29 A (d) 0.0529 nm
& The total energy of the electron in hydrogen atom is
(a) - ( 13.6/n ) eV (&) ( 13-6/n ) eV
(c) - (13.6/n2) eV . GO ( 13.6/n2 ) eV
7, The ratio of frequencies of the first line of the Lyman series and the first line of Balmer series is
(a) 27/5 (b)27/8

' (c) 8/27 (4)4/27
& When an electron jumps from the fourth orbit to the second orbit, one gets
(a) the first line of Pfund series (b) second line of Lyman series
(c) second lineof Paschen series (d) second line of Balmer series
ft. The ionisation energy of hydrogen atom is
(a) 0.52 eV (h) 13.6 eV
(c) -13.6 eV (4)-0.52 eV
1ft. When an electron in an atom shifts from an excited state to a lower state, a quantum of energy is always
radiated:
(a) Yes (h) No
11. The third subshell of an atom can have a maximum of
(a) 2 electrons . (£>) 14 electrons
(c) 10 electrons . , (J) 6 electrons
IX The range of frequencies of the lines of visible region in hydrogen spectrum is
(a) 6000 x 1014 s1 (b) 600 x 1014 s1
(c) 60x 1014s-1 (d)6xl014s-1
If v is the velocity of the electron in a stationary orbit of radius r, the orbital frequency of the electron is
(a) v/2wr (b) v/r
(c)v!nr (d)2nr!v
14 The root mean square velocity c of helium atom at T degree kelvin satisfies the relation
(a) c « Vr (b) c oe 1/Vf
(c) C « r . (d) c °C UT
15. The Rydberg constant for hydrogen is
(a) 1.0961 x IO"7 m-1 (t) 1.0961 xl06m’
(c) 1.0961 x 107m-‘ (4) L0961 x IO-6 m-1
16. The expression for the total energy with the principal quantum number n in the relativistic model of the
atom is
2
. a n 3 2
a 3
w-£. 1+7 V
n + n v*—
n
a a 3
(c)En 1 + "<>
n2
n2 n„
CHAPTER 2
where a = e^/2 eQch
17. The maximum number of electrons in a subshell with orbital quantum number / is
(a) (2/ + 1) (b) (2/ -1)
(c) 2(2/ +1) (d) 2(2/ - 1)
18. The electronic configuration of the element iron is
(a) Is2 2s22p6 3s2 3p6 3d8 4s° (b) Is2 2s2 2p6 3s2 3p6 3d1 4s1
(c) Is2 2s2 2p6 3s2 3p6 3d14s° (d) ls22s22p63s23p63(fiAs2
19. The shortest wavelength of Balmer series in hydrogen spectrum is given by the equation
(a) 1/1 = Rh (1/4 - 1/9) (b) 1/1 = Rh (1/2 - IM
(C) 1/1 = Rh (1 - l/oo) _. (J) ]/X = Rh (1/4 - l/oo)
where RH is the Rydberg constant for hydrogen.
2ft. Which of the following transition is ruled out?
1 '2
J2 1
21. One Bohr magneton is approximately
(a) 1023 Am2 (b) IO"23 Am2
(c) 1010Am2 (d) IO"10 Am2
22. If Ma and p are the atomic weight and density of a metal respectively and NA is the Avogadro’s number,
then the number of atoms present in unit volume is calculated using the relation
(a) MA/NAp {b)NAp!MA
(c) MAp/NA (d) NA!MAp
23k The longest wavelength of the Lyman series in hydrogen spectrum is obtained using the relation
(a) 1/1 = Rh (l/l2 - 1/22) (h) 1/1 = Rh (l/l2- IM)
(c) 1/1 = Rg (1/22 - IM) " - (d) 1/1 = Rh (l/l2 -1/32)

«
where Rg is Rydberg constant for hydrogen.
M The magnetic moment associated with the first orbit in hydrogen atom is given by
(a) hJAwne (Z>) AltmJhe
(c) eh!Awn (d) ehmJAlt

25. The length of the semimajor axis of an electron in an elliptical orbit is determined
(a) solely by the principal quantum number (b) solely by the azimuthal quantum number
(c) both by principal quantum number and azimuthal quantum number
26. When the azimuthal quantum number n. is zero

(a) the ellipse reduces to a straight line (h) the ellipse reduces into a circle
(c) none of these

27. If n. and n for an electron in an elliptical orbit are 1 and 2 respectively, then the ratio of semimajor axis and
semiminor axis is
(a) 2 (t) 0.5
(c) 1 (J) 2
28. 4 electron volt is

(a) 2 x IO-’9 joule (b) 6.4 x 10-19joule
(c) 3.2 x 10-19 joule (d) 6.4 x 1019 joule
29. If the principal quantum number and the azimuthal quantum number in the relativistic model of the atom
are 3 and 1 respectively, then the magnitude of the semiminor axis b in terms of the semimajor axis a is
given by
(a)b = a!3 (b)b = 2a/3
(c)b = a!2 (d)b = a
1. Discuss the drawbacks of Rutherford’s classical theory of the atom.
2. Give the important features of Bohr’s model of atomic structure.

V
3. Give the postulates of Bohr to explain the structure of atom.
4. What are the various quantum numbers used to describe the electronic energy levels in an atom?
5. What do the symbols 5, p, d9f stand for? ' ' '
6. Show that the circumference of an electron orbit in a hydrogen atom is an integral multiple of the de Broglie
wavelength of the electron in orbit.
7. Find the energy required to remove the electron from the normal hydrogen atom.
8. How do you explain the origin of spectral lines in hydrogen?
9. How is the fine structure of spectral lines accounted?
10. Compute the limit of the Balmer series in hydrogen spectrum.

11. Give the expression for Rydberg constant for hydrogen. How does this constant differ for singly ionised
helium?
12. Outline the nature of the relativistic hydrogen orbit.
13. Explain the fine structure of Ha line of the Balmer series.

42 Solid Stare Physics
27. If nt and n for an electron in an elliptical orbit are ! and 2 respectively, then the ratio of semi-major
axis and semi-minor axis is
(a) 2 (b) 0.5
(c) 1 (d) 2
28. 4 electron voh is
(a) 2xJ0\jcmle (to 64 #1 or1* joule

(c) 3.2 x HF1* joule (d) 6.4xi 0s* joule
29. If the principal quantum number and the azimuthal quantum number in the relativistic model of the
atom are 3 u nd 1 respectively, then the magnitude of the semi-tn mor axis b in terms of the semi-major
axis a is given by
(a) b = a/3 (b) b=2aft

(cj b = a/2 (d) b =a
SHORT QUESTIONS
I Discuss the drawbacks of Rutherford^ classical theory of the atom.
2. Give the important features of Bohr’s model of atomic structure.
3. Give the postulates of Bohr to explain the structure of atom.
4 What are the various quantum numbers used to describe the electronic energy levels in an atom?
5* What do the symbols pt d,/...stand foe?
6. Show that the circumference Of an electron orbit in a hydrogen atom is an integral multiple of the de
Broglie wavelength of the electron in oitil
7. Find the energy required to remove the elec tron from the normal hydrogen atom*
8. How do you explain the origin of spectral lines in hydrogen?
9. How is the fine structure of spectral lines accounted?
10 Compute the limit of the Balmer series in hydrogen spectrum,
11. Give (he expression for Rydberg constant for hydrogen. How does this constant differ for singly
ionised helium?
12* Outline the nature of the relativistic hydrogen orbit
13. Explain the fine structure of Ho Une of the Balmer scries.
14. Calculate the time taken by the electron to traverse the first Bohr’s orbit in hydrogen spectrum.
15. What is the frequency of radiation when the electron jumps from the third orbit to the second?
16. The energy of the electron in the permitted orbits of hydrogen atom is given by the equation -(fi/n1)
with B = 2479* KF1* joule. Give the significance of the negative sign
17* The first member of Balmer series of hydrogen has a wavelength 656*3 nm. Calculate the wavelength
of the second member.
18. What are the sal ient features of B ohr so mme rfe Id ato m mode I ?
19. Write down Sommerfeld4 s expression for the energy of the electron applying relativistic correction.
Discuss the significance of this expression with that of Bohri
20 Explain spatial quantization and spinning of electron
21. Discuss briefly vector atom model.
22. What da you understand by ionisation energy? On w hat factors does it depend?
Itao ofrtftwE Slum ft
23. Explain Pauli’s exclusion principle as applied to electrons in atoms.
24. Give the electron configuration of the elements sodium and copper.
25. Explain why newi is an inert gas.
26. Discuss briefly the wave-mechanical concept of the atom.
REVIEW QUESTIONS
1. Give an account of Rutherford's model of the atom. What are the major deficiencies in Rutherford's
nuclear model? How are they overcome by Bohr?
2, Derive the mathematical expression for energy of the electron in hydrogen atom. Give the interpreta
tion of the negative sign.
3. Discuss Bohr's theory of hydrogen atom and derive an expression for the radius of the first Bohr orbit
for the normal hydrogen atom.
4. Slate Bohr's fundamental postulates to explain the structure of hydrogen atom. Obtain the generat
expression for the radii of the Bohf s orbits and orbital frequencies of the electrons occupying them.
5* Give an account of Bohr's theory of hydrogen spectra and obtain expressions for the spectral series of
hydrogen.
6. Discuss the postulates of Bohr's theory of hydrogen atom and denve an expression for the wave
number of Balmer lines of hydrogen spectrum.
7. Outline Bohr's theory of hydrogen atom and show how it accounts for the observed spectrum of
hydrogen.
8. Based on Bohr’s assumptions obtain the expression for the orbital energy of an electron in the hydro
gen atom. Also account for the different series of spectral lines of the hydrogen atom.
9. Obtain a general expression for the radii of the Bohr orbits and for the orbital frequencies.
Explain Hspcctrum on the basis of Bohr's theory.
10. Describe Bohr's atom model. Assuming that the nucleus is infinitely heavy and the electron has mass
m and charge e, find out the energy of the electrons moving in the orbit.
Calculate the ionisation potential of hydrogen atom.
IL Describe the Bohr's theory of hydrogen atom. How is it successful in explaining the spectrum of
hydrogen atom?
12. What is meant by a spectral series? Give the formula and show how the spectral series of hydrogen
arise. Illustrate with energy level diagrams.
13, Give the theory of the elliptical orbits relating to the hydrogen atom. Explain the fine structure of the
Hq line of the Balmer series.
14. Outline the nature of the relativistic hydrogen orbit. Explain the fine structure of the Ha line due to
relativity correction.
15. Give an account of Bohr-Sommerfeld model of elliptical electron orbits of hydrogen atom.
How does it account for the fine structure of hydrogen atom?
16. What do you mean by fine structure of spectral lines? Give an account of Bohr-Sommerfeld atom
model Explain how could it explain the observed spectral lines.
17. Explain spatial quantization and spinning of electrons. State and explain the significance of the four
quantum numbers. How are they inter-related?
18. Discuss briefly vector atom model. State Pauli’s exclusion principle and explain how it helped in fix
ing up the electronic configuration of the elements in the periodic table.
11. Describe the Bohr's theory of hydrogen atom. How is it successful in explaining the spectrum of hydroo*
_ ©^0
atom?
12. What is meant by a spectral series? Give the formula and show how the spectral series of hydrogen arise
Illustrate with energy level diagrams.
13. Give the theory of the elliptical orbits relating to the hydrogen atom. Explain the fine structure of the U
line of the Balmer series. a
t
14. Outline the nature of the relativistic hydrogen orbit. Explain the fine structure of the Ha line due to relativity
correction.
15. Give an account of Bohr-Sommerfeld model of elliptical electron orbits of hydrogen atom. How does it
account for the fine structure of hydrogen atom?
M. What do you mean by fine structure of spectral lines? Give an account of Bohr-Sommerfeld atom model
Explain bow could it explain the observed spectral lines.
17. Explain spatial quantisation and spinning of electrons. State and explain the significance of the four quantum
numbers. How are they inter-related?
IS. Discuss briefly vector atom model. State Pauli’s exclusion principle and explain how it helped in fixing up
the electronic configuration of the elements in the periodic table.
W. What are the four quantum numbers assigned to an electron in an atom? What are the significances of
these quantum numbers?
2*. State Pauli’s exclusion principle. Explain the structure of the periodic table on the basis of Pauli’s exclusion
principle.
2L How are electrons distributed in the various subshells for n = 3? Give the quantum numbers for the
electrons in the first subshell.
- - - ♦
22. What is Pauli’s exclusion principle? How does this principle help in the interpretation of the periodic
system of the elements?
23. Write a detailed note on vector atom model. State and explain Pauli’s exclusion principle.
24. Discuss the applications of Pauli’s exclusion principle. Write a short note on the general usefulness of the
periodic table in reference to atomic structure.
25. What do you understand by ionisation energy? On what factors does it depend? Why would more energy
he required in the removal of an electron from the A'-shell than an L-shell?
24 Explain Pauli’s exclusion principle as applied to electrons in atoms. Describe how this principle assists in
the interpretation of the periodic system of the elements.
27. Prove that if n be the principle quantum number of a shell, it can accommodate 2n2 electrons. Indicate the
possible (n, I, mt, mt) values of electrons in the first three shells of an atom. The symbols have their usual
significance.
2S. Explain the quantum numbers associated with vector model of the atom. State and explain Pauli’s exclusion
principle. Give with examples the arrangements of electrons in an atom.
29. Give the electronic configuration of the following elements:
(a) Sodium (11) (b) Chlorine (17)
(c) Copper (29) (d) Germanium (32)

30. State Pauli s exclusion principle and explain how it helped in fixing up the electronic configuration of the
elements in the periodic table.
Give the electronic configuration of the elements with atomic numbers (a) 11 and (b) 26.
31. Explain the various quantum numbers that are used to specify an electron in an atom. Hence discuss the
periodic classification of elements.
32. State and explain the Pauli’s exclusion principle. Give the theory of elliptical orbits relating to the hydrogen
atom. Explain the fine structure of Ha line of the Balmer series.
33. Describe Bohr atom. What are the various quantum numbers by which an electron in an atom is designated?
CHAPTER 2
Explain why neon is an inert gas.
34. What are the various quantum numbers associated with an electron in an atom? State Pauli’s exclusion
principle and explain how it is helpful in obtaining the arrangement of electrons in the ground state of an
atom. Give the arrangement of electrons in the ground state of neon atom.
35. Describe the vector model of the atom and explain different quantum numbers associated with it Write
down the electronic configuration of copper (29) employing modem symbolism and explain.
36. . Show that the circumference of an electron orbit in a hydrogen atom is an integral multiple of the de
.- Broglie wavelengths of the electron in the orbit. -
1. Calculate for the hydrogen atom (z) velocity of the electron in the ground state, (z'z) radius of the orbit of
the electron in the ground state, (zzz) time taken for the electron to traverse the first Bohr orbit.
2. At what speed must the electron revolve round the nucleus of the hydrogen in its ground state in order that
it may not be pulled into the nucleus by electrostatic attraction (Given: Radius of first Bohr orbit is
0.052 nm).
3. Electrons of energies 10.2 eV and 12.09 eV can cause radiation to be emitted from hydrogen atoms.
Calculate in each case, the principal quantum number of the orbit to which an electron in the hydrogen
atom is raised and the wavelength of the radiation emitted if it drops back to the ground state.
4. The critical potential of hydrogen is 13.05 eV. Calculate the wavelength of the radiations emitted by
hydrogen atom bombarded by an electron of corresponding energy.
5. Show that for large values of principal quantum number, the frequency of an electron rotating in adjacent
energy levels of hydrogen atom and the radiated frequencies for a transition between these levels, all
approach the same value.
6. How many revolutions does an electron in the n = 2 state of a hydrogen atom make before dropping to the
n = 1 state? (The average life time of an excited state is about 10~8 s).
7. A single electron revolves around a stationary nucleus of charge +Ze. It requires 47.2 eV to excite the
electron from the second Bohr orbit to the third Bohr orbit. Calculate (z) the value of Z, (ii) the energy
required to excite the electron form third to fourth Bohr orbit, (Ui) the wavelength of the electromagnetic
radiation required to remove the electron from the first Bohr orbit to infinity, (iv) the radius of the first
Bohr orbit, (v) the kinetic energy, potential energy and the angular momentum of the electron in the first
Bohr orbit.
PROBLEMS
1. Calculate for rhv hydrogen atom i r) velocity of the electron in the ground slate r ti । radius of the orbit
of the electron in the ground state, (iii) lime taken for the electron to traverse the first Bohr orbit*
2. At what speed must the electron revolve round the nucleus of thv hydrogen in its ground state in order
that it may not be pulled into the nucleus by electrostatic attraction (Given; radius of first Bohr orbit is
0.052 nm)*
3. Electrons of energies 10 2 uV and 12.09 eV can cause radiation to be emitted from hydrogen atoms*
Calculate in each case. the principal quantum number of fhe orbit to which an electron in the hydro
gen atom is raised aM the wavelength of the radiation emitted if it drops back to the ground state.
4. The critical potential of hydrogen is J 3.05 eV. Calculate the wavelength of the radiations emitted by
hydrogen atom bombarded by an electron of corresponding energy.
1 Show that for large values of principal quantum number. (he frequency of an electron rotating in
adjacent energy levels of hydrogen atom and the radiated frequecies for a transition between these
levels, all approach the same value,
6 . How many revolutions does an electron in the n = 2 stale of a hydrogen atom make before dropping to
then = 1 state? (The average lifetime of an excited state is about 10“*s).
7> A single electron revolves around a stationary nucleus of charge +Ze. h requires 47.2 eV to excite the
electron from the second B^hr orbit to the third Bohr orbit Calculate (i) the value of Z(it) the energy
required to excite the electron from third to fourth Bohr orbit (iii) the wavelength of the electromag
netic radiation required to remove the electron from the first Bohr orbit to infinity (tv) the radius of
the first Bohr orbit (v) the kinetic energy > potential energy and (he angular momentum of the electron
in the first Bohr orbit.
8 Calculate the frequency of radiation, and also the wave number, when the electron jumps from the
third orbit to the second orbit of hydrogen atom.
9 The first member of the Burner series of hydrogen has a wavelength 6553 nm. Calculate the wave
length of its second member
ilk Calculate the kmisaiion potential of hydrogen from the first principle*
11. Calculate rhe shortest wavelength of the Balmer series (limit of Balmer series) and the largest wave
length of Lyman series.
12. Neglecting reduced mass correction, show that (i) the short-wavelength limit of the Lyman series
(ft = 1) of hydrogen is the same as that of Balmer series fo = 2) of ionised hehum and (ii) that the
wavelength of the first line of this helium series is I 35 limes the wavelength of the first line of the
Lyman series.
13 Ths lowest two excited states of hydrogen atom are 10.2 and 12.0 eV above the ground state; calcu
late ihe wavelength of radiation that could be produced by transition between these states and the
ground state.
M Calculate the magnetic moment associated w uh the first nrbit of Bohr in the case of hydrogen.
15. Give the electronic configurations of H, Li, C and Si*
16. The atomic weights and densities of aluminium and copper are 26.98 and 63.54 and 2700 kgftn3 and
8960 kg/n? respectively. Calculate the number of atoms present in unit volume of aluminium and
copper ,
17. Calculate the magnetic moment due to orhiial motion of the electron
B ..
18. Energy in a Bohr orbit is given by —; where B = 2 I79x JO ' .1.
a"
46 Solid State Phytics
Calculate the frequency of radiation and also the wave number, when the electron jumps from the
third orbit to the second.
19, Give a quick estimation of the binding energies of the hydrogen atom from de Broglie's hypothesis,
20, How much energy is required to raise the hydrogen atom from the ground state n » I to the first
excited state ji = 2? What is the wavelength of the line emitted if the atom returned to the ground state
from the enticed state?
CHAPTER 3
INTERATOMIC FORCES AND

BONDINGS IN SOLIDS
I. INTRODUCTION
Many solids arc aggregates of atoms. The arrangement of atoms in any solid material is determined by the
character strength and directionality of the binding forces, cohesive forces or chemical bonds* The bonds
are made of attractive and repulsive forces that tend to hold the adjacent atoms or atomic units at a particular
spacing such that the opposite forces just balance; and the process of holding them together is known as
bonding. Since the particular type of bonding within a material plays a major role in determining the physi
cal, chemical and electrical properties of material, the materials engineer must possess a sound working
knowledge of the types of bonding in materials.
II. FORCES BETWEEN ATOMS

The main problem now is to account for the origin of binding forces which bind the atoms in a molecule and
also the forces which bind the molecules tn a solid. Electrical forces are responsible in binding the atoms and
molecules giving different solid structures. Magnetic forces have only a weak effect in cohesion, and gravi
tational farces are negligible, A crystal of NaCl is more stable than a collection of free Na and Cl atoms*
Similarly, a germanium crystal is more stable than a collection of germanium atoms* This implies that
germanium atoms attract each other when they get close to each other; i.e*, an attractive interatomic force
exists which holds the atoms together* This is the force responsible for crystal formation* This also means
that the energy of the crystal is lower than that of the free atoms by an amount equal to the energy required
to pull the crystal apart into a set of free atoms. This is called the binding energy (also the cofajive energy of
the crystal L
The forces between atoms can be of two kinds: attractive forces which keep the atoms together* and
repulsive forces which come into play when the solid is compressed. The potential, or stored internal energy
of a material is the sum of the individual energies of the atoms plus their interaction energy* When the atoms
are all in the ground state and infinitely far apart so that they do not interact with each other to form a solid,
the potential energy is zero, since this is inversely proportional to some power of the distance of separation*
Assuming that the atoms consist of moving electric charges, one of the following two things can happen as
the atoms approach each other, Either they attract or repel each other. The potential energy due to the
attraction is negative, since the atoms do the work of attraction. The repulsive energy is positive since
external work must be done to bring the atoms together and it is inversely proportional to some power of the
48 State Physics
interatomic separation r. The net p ■ Uential energy is the sum of both terms.
This may be illustrated by considering the following model: Suppose two atoms A nnd B exert attrac
tive and rvpulsivc forces on each other such chat the btrna in finer F, between the atoms may be represented
as
F(r) wilhN > M

r r (ID
where r is the centre to centre spacing between the atom$ and A, R, M and .V are constants characteristic of
the molecule. The first temi represents the attractive force arid theMScund term the repulsive force. Near rhe
equilibrium position rhe second term must increase more rapidly for diminishing values of r than does rhe
first and N is necessarily greater than M Since the attractive forces in interatomic bonds are largely elec-
rnistauc. M is usually 2 as pet Coulomb’s law and the value of V is usually 7 to It).
The equilibrium spacing, of the
given system is obtained as follows:
% A B
At rhe equilibrium spacing
F(r} = 0 when r-rp
A B
Thus —r
r0 r£i
r(i
X1 Variation of interatomic force with

interatomic spacing
(12)
Hi. COHESION OF ATOMS ANO COHESIVE ENERGY

The potential energy reprcscntmg the interaction between the two atoms varies greatly with the interatomic
spacing and is obtained by integrating equal ion (3.1), Thus
interatomic Farces and Bondings in Solids 49
Ar1* Br'" „
1-M
a b
M
where a m.... * -1 md ««AF-L
Setting U * 0 when r we find C “ 0 and
(34)
Here r is the distance between the centres of the atoms; n and m are positive number^ a is a positive constant
which determines the strength of the attractive force and b is a positive constant which determines the
strength of the repulsive force.
The condition under which the par-

tictes form a stable lattice is that the func*
tiou f/fr) exhibits a minimum for a finite
value of r ai shown in Fig. 3.2, If this
minimiHn exists, then the two atoms form a
stable lattice, say a molecule.
Let r9 be the distance between the

atoms for this minimum tZ(r) to occur. This
spacing r0 is known as equilibrium spacing
of the system. This minimum energy at
r « r0 to negative and hence the energy
needed to dissociate the molecule then
equals the positive quantity of The
minimum for £7(r) occurs only if m and n
satisfy the condition, Fig. 3-2 Variation of pcrtcti (ial energy with s paci ng
(35}
Condition (3,5) implies that the attractive force should vary more slowly with r than the repulsive
force. This is obvious from the curves for attractive and repulsive forces shown in FigT IL The above said
condition may be established ma them a tic a Uy as follows:
I/(r) exhibits a minimum for r * r0
Thus
Solid State Physics
Hence from equation (3.4)
Thus
At the same time
r0'" + 2Z>n (n + 1) - am (m + l)/0', + 2 >0
i.e., r™ bn (n + 1) > am (m + 1) r0"
bn(n + 1) > am (m + 1 )r0'' m
Substituting for rQ from equation (3.6), we get
i.e., bn (n + 1) > am (m + (3.6a)
n>m
The forces acting between the atoms are mostly electrostatic in nature and are determined
essentially by the extent to which the wave functions of the outer electrons are perturbed by the presence
of other atoms at close proximity.
Wil
The energy corresponding to the equilibrium position (r = , denoted by t/(r„) is called the bonding
energy or the energy of cohesion of the molecule. This is the energy required to dissociate the two atoms
of the molecule (AB) into an infinite separation. This energy is also known as the energy of dissociation.
It is obtained as follows:
Equation (3.4) is
U(r) will be minimum when r = r0.

Interat&nic Forces and Bondings in Solids 51
Thus =-* (3.7)
dU
Hence =0
q
Thus 0
a fo
Thus substituting this m equation (3 J)* we gel
ri
U H.Jbi —
171 a
y =-
(3.8)
In conclusion, it may thus be said that the forces of repulsion are the result of interpenetration of outer
electronic shells between atoms, ions and molecules when they approach one another each in interatomic or
iftiermolecuiar distances The forces of attraction are due to interaction between outer electrons* of the two
atoms, resulting in the formation of a sufficiently stable aggregate which can be considered as an indepen
dent molecular species. Thus all stable arrangements of atoms in solids we such that the potential energy is a
minimum. This is one way of ex plaining the cohesion of atoms in solid aggregates. Dissociation may occur
as a result of strong electric fields and mechanical strains or at high temperature. For example. 4.4 eV of
energy is required to break one (H-Cl) bond, or 420 x 101 kJ/k mol.
V. BONDING IN SOLIDS
From experience one knows that solids are usually moderately strong and slightly elastic structures. Thus
the individual atoms must be held together in solids by interatomic forces or bonds However, in addition to
these attractive forces there must be a repulsive force because solids are not easily compressed The attrac
tive forces between the constituent particles in solids are basically electrostatic in origin and the classifica
tion of the different types of bonding is strongly dependent on the electronic structure of the atoms
concerned, and hence directly related to the periodic lable.
A solid is composed of billions of atoms packed closely together and the characteristic properties of
this state of matter can be accounted for by their proximity and the forces of attractions that hold the atoms
together. The importance of these attractions is evident when we consider a piece of copper wire of which
each gram contains (6.025 x 10*^)763,54 atoms under normal conditions; the forces of attraction that bind
these atoms are very strong If thU is not true, the atoms will easily disintegrate or crumble or the metal will
deform under small loads.
According to the strength and directionality, chemical bonds are grouped into primary and srrandary.
Copy ri g hi ed fn aleri $ I
52 Solid Stare Physics
Primary bonds by virtue of their nature arc interatomic bonds, whereas secondary bonds are mrermolecular
bonds. The attractive forces in primary bonds are directly associated with rhe valence electrons. The outer
shell, which contains rhe valence electrons, is in a high energy state and hence relatively unstable. If it can
acquire more electrons to bring the total upto eight or lose all its electrons to another, it become stable. This
is how atomic or primary bonds are formed- In fact, each bond is a direct consequence of the exchange or
sharing of valence electrons.
The study of the solid structure reveals that there are three strong principal types of primary bonds:
ionict covalent and metallic. These bonds are distinguished on the basis of the positions assumed by the
bond electrons during the formation of the bond ran der WWr and hydrogen bonds are typical examples of
secondary bonds and they result from inter molecular attracnon. The bonding energy or the cohesive energy
is defined as the energy of formation of one kmol of a substance from its atoms nr ions. It is equal but
opposite in sign to the energy of dissociation of the substance. The bond energy can be calculated as the
energy of the atoms or urns at the equilibrium spacing in the crystal structure, using the state of infinite sep
aration of the atoms or ions as the zero potential. The strength of a bond is best measured by the energy
required to break it, that is, the amount of heat which must be supplied to vaporize the solid (infinite
separation) and hence separate the constituent atoms. The melting points and the boiling points of the ele
ments are dependent on the strength of the bond. Generally, the stronger the bond, the higher are the melting
arul boiling points.
VI. IONIC BONDING

Perhaps ionic or heteropolar bonding is the simplest type of chemical bonding to visualize since it is almost
totally electrostatic in nature. It occurs between electropositive elements (metals; i.e. those elements on the
left side of the periodic table) and electronegative elements (non-metals; i.e,, those on the right side of the
periodic table), NaCI ami MgO are examples of solids in which ionic bonding dominated
The criterion for ionic bonding is the difference in electronegativity (the tendency to acquire elec
trons). An ionic bond is really the attractive force existing between a positive and a negative ion when they
axe brought into close proximity, Theê ions, of course, are formed when the atoms involved lose or gain
electrons in order to stabilise their outer shell electron configuration.
A typical example of an Ionic bond is the bond between ihe positive sodium ton and the negative
chlorine ion in sodium chlonde. The white soft metal Na has the following electron configuration;
K(2)Lt8)M(l), This atom has a low ionisation energy and hence easily loses an electron; the other atom
chlorine [K(2)L(8)M(7)J< has a high electron affinity and strongly tends to acquire an electron. Suppose a
chlorine atom and a sodium atom approach each other. This occurs when sodium bums in an atmosphere of
chlorine. The sodium gives up its valence electron to the chlorine, each of the resulting ions then has a stable
filled shell of outer electrons, and a strong electrostatic attraction is set up that bonds the Na" cation and the
O anion into a very stable molecule (NaCI) at the equilibrium spacing. The reaction is represented by
Na+CL^Na*+CT-*NaCI
Since chlorine exists as molecules, the chemical reaction must be written as
2Na + CU -* 2Na* + 2CT -> 2NaCl
To release the valence electrons, a kmd of free sodium atoms requires an expenditure of energy,
/ - 496 x IO3 kJ (this quantity is the first ionisation energy per kmol of Na atoms). Acquisition of the elec
trons by a kmoi of free chlorine atoms results in a release of energy, * 549 x ICPkL Thus, to initiate a
Interatomic
To release the valence electrons, a kmol of free sodium atoms requires an expenditure of energy,
I = 496 x 103 kJ (this quantity is the first ionisation energy per kmol of Na atoms). Acquisition of the
electrons by a kmol of free chlorine atoms results in a release of energy, Ea = 349 x 103 kJ. Thus, to
initiate a reaction between a kmol of free neutral sodium atoms and a kmol of free neutral chlorine
atoms requires a net expenditure of (/ - E() = (496 - 349) x 103 = 147 x 103 kJ. Once started, the
reaction proceeds vigorously with the evolution of light and heat because of the sizeable energy decrease
resulting from ionic bonding. The final product usually is a large number of salt crystallites. Other
examples of ionic crystals are
2 Mg + O2---------- > 2 Mg+++ 2 O—---------- > 2 MgO
Mg + Cl2---------- > Mg++ + 2 Cl"---------- > MgCl2
The different steps showing energy absorption and liberation in the formation of NaCl is given
in Table 3.1. The total energy on the right side is much greater than that on the left side and hence a
considerable amount of energy is given out during the formation of NaCi crystal. This appears as heat
and light during the chemical reaction.
Table 3.1 Energy absorbed and energy released in the formation of NaCl
CHAPTER 3
to
> Energy absorbed in the formation of NaCl Energy released in the formation of NaCl
1. Separation of chlorine atoms of the diatomic Completion of Af-shell of chlorine
CL molecule •
2. Separation of sodium atoms of solid sodium Lattice energy of sodium chloride
•
3. Separation of electron from sodium atom —
NaCl is one of the best examples of ionic compound and let the sodium and chlorine atoms be free at
infinite distance of separation. The energy required to remove the outer electron from the Na atom
- (ionisation energy of sodium atom), leaving it as an Na+ ion is 5.1 eV. That is
Na + 5.1 eV---------- > Na+ + e~
The electron affinity of chlorine is 3.6 eV. Thus, when the removed electron from sodium atom
is added to chlorine atom, 3.6 eV of energy is released and the chlorine atom becomes negatively
charged. Hence
Cl + «r---------- > Cl"+ 3.6 eV
Thus a net energy of (5.1 - 3.6) = 1.5 eV is spent in creating a positive sodium ion and a negative
chlorine ion at infinity. Thus
Na + Cl + 1.5 eV---------- > Na+ + Cl"

What happens when the .electrostatic attraction between Na+ and Cl- ions brings them together
to the equilibrium spacing r0 = 0.24 nm? At the equilibrium position, the potential energy will be
minimum and the energy released in the formation of NaCl molecule is called the bond energy ol the
molecule and it is obtained as follows:
54 S&lid Slate Physics
(c) Ionic molecule

Fifl. 3.3 Schcmaiic representation of the formation of an Ionic molecule of sodium chloride.
(3.9)
(1.602x10 ”)
_(47t)(8.85x 10"ls}(2.4x 10’’°),
________ (1.602X 1O~‘V________

eV
.4n(8.85x 10’2:x 2.4)(1.602 x IO1’).
*-6eV
Thus the energy released in the formation of NaCl molecuk starting from neutral Na and Ct atoms having
zero potential energies is (5- i - 3,6 - 6) ~ - 45 eV+ Schematically
Na+ + CF Na + Cl + 4J eV -> NaO

<—0,24 run—>
This is the energy released. Thus the entire process evolves an energy of 6 15 45 eV. This means that to
dissociate a NaCI molecule into Na and Cl iorw, ft requires an energy of 4,5 eV,
Bond lengths and bond energies of some diatomic tonic molecules arc given in Tabic 3,B.
Interatomic Forces and Bondings in Solids 55
Bond lenglhs and bond energies of some diatomic ionic molecules
Molecule Bond length (nnj Bond energy (in eV)

KC1 0.267 4.4
UH 0360 2.5
NaF 0i£5 4.7
NaCl 0236 4.3
Nai 0 271 3.1
NaBr 0250 3J
VIII. CALCULATION OF LATTICE ENERGY OF IONIC CRYSTALS

The lattice energy of an ionic solid will differ from the bond energy of diatomic ionic molecules since, in rhe
former case there will be interactions between more than two ions* The coAeu've energy of an ionic crystal is
rhe energy that would be liberated by the formation of the crystal from individual neutral atoms. Cohesive
energy is usually expressed in eV/atom, or eV/molecute or in kJ/kmol The bond energy of a molecule held
together by an ionic bond is not the same as the coterfw energy of the crystal, because in rhe crystal each
ion interacts with all the other ions present and not just with one. two or three of the opposite sign* Some*
times rhe lattice energy, rather than the cohesive energy, is presented; the lattice energy is that energy
evolved when a crystal is formed from individual ions, rather than from individual atoms.
Let us now consider the case of NaCl which is one of the best examples of an ionk campmind. Ionic
crystals are strongly bound w ith binding energies (cohesive energies) of about 5-10 eV per molecule This
is the energy required to dissociate the lattice into positive and negative ions at infinite separation. Two
common types of structures found in ionic crystals are NaCl structure which is face-centred cubic and CsCI
which is body-centred cubic* The calculation of binding energy of ionic crystals generally requires a
knowledge of forces acting between the constituent particles.
In the classical Bom Madelung theory of ionic crystals. it is assumed that the electrons are transferred
from electropositive atoms (Na. Ca, K, Mg) to electronegative atoms (0, F, Cl). The stability of an ionic
crystal depends un the balancing of alleast three forces; the electrostatic, or Coulomb forces between the
iem which give a resultant attraction falling off with the square of the distance; van def Waals forces of
attraction diminishing according to the seventh power of the distance (usually neglected); and the interionic
repulsive forces falling off still more rapidly with distance. The resultant of the attractive and repulsive
forces is to lead to an equilibrium position of minimum potential energy; i.e.; of greatest stability as shown
tn Fig. 3*4.
Z&e2
Far two ions of charges Z/ and Zjg separated by a distance r, the attractive energy is ~ 4.n e \ and there-
fore this energy is - —----- - if both rhe atoms are respectively mmo valent, divalent and
4n r
trivalcnt. For the whole crystal, the Coulomb potential energy may be written as - . This term represents
the net Coulomb potential energy of any one ion due to the presence of all other similar and dissimilar ions
present in the crystal The minus sign shows that the irci Coulomb energy is attractive. The constant A is
known as Madelung constant.
_ —/-1 r -. This tcnn represents the net Coulomb potential energy ol any one ion due in ,L
4* fA r ‘ 'he
presence of all other similar and dissimilar ions present in the crystal. The minus sign shows that the net
coulomb energy is attractive. The constant A is known as Madelung constant.
Rg. 3.4 Schematic representation of lattice energy of NaCI as a function of interatomic spacing
To prevent the lattice from collapsing, there must also be repulsive forces between the ions.
These repulsive forces become more noticeable when the electron shells of neighbouring ions begin to
overlap, and they increase strongly in this region with decreasing values of r, That is, this repulsive
force arises from the interaction of the electron clouds surroundings an atom. Bom, in his early work,
made the simple assumption that the repulsive energy due to the overlap of the outer electron shells
between two ions is inversely proportional to some power of the distance r or equal to btf1. Focusing
our attention again on one particular ion, we may thus write for the repulsive energy of this ion, due to
the presence of all other ions in the crystal as, Bld*. n is called repulsive exponent.
Now the total energy of one ion due to the presence of all others, is given by
AZiZ2e2 B
U(r) = - (3.10)
47teor r"
For the univalent alkali halides
Ae2 W
U(r) = - ----------- n (3.11)
4n e0 r
The total energy per kmol of the crystal is
£ Ae2
U(r) = N n (3.12)
4n e0 r
The P.E. will be minimum at the equilibrium spacing r0.
(KT , A£ Bn
Thus -N =0 (3.13)
. dr, A 4tt e r2 +l
L4TC eo r0
Ae2 Btl
or
4k e0 r2 ~
fo
r» Ae2
Ae2^'1
. (3.14)
4ne0 n
Substituting this value of H in equation (3.12) and putting r = rt). we get the total equilibrium
energy per kmol °f *hc crystal.
Thus lU]rsru=U() = - ÂAel + NÂe2r<>~1
4neor(J 47t£on<
i.e., U0 = -Ux + U2 (3.15)
where (7j and t/2 represent the net Coulomb attractive energy and repulsive potential.
Ae^N, F 1 rj-1
Thus
CHAPTER 3
47te0 Lr0 nro/o’'
4e2/V, T, 11
4n e0 r0 L n_
P
(3.16)
This equilibrium energy t/0 is called the lattice energy. This is defined as the energy released in
the process when the constituent ions are placed in their respective positions in the crystal lattice or this
is the amount of energy which is spent to separate the solid ionic crystal into its constituent ions. It is
experimentally measured from the Born-Haber cycle data. The comparison of the two values will enable
us to assess the merits of the above theory of ionic lattices.
The binding energy or cohesive energy per molecule of the ionic crystal NaCl is 7.95 eV. Similarly
in NaCl the energy U} due to Coulomb attraction is 8.94 eV with rQ = 0.282 nm and the Madelung
constant = 1.75. Substituting Uo = -766 x 106 joule/kmol in equation (3.16), we get n = 9.
Madelung constant represents the effect of a specific geometrical array of ions on the electrostatic
potential energy. It is a property of the crystal structure and depends on the lattice parameters, anion
cation distances, or molecular volume of the crystal. Before considering a three-dimensional crystal
lattice, we shall discuss the calculations of Madelung constants in a linear chain of ions of alternate
signs as in Fig. 3.5.

Let us pick up a positive ion for reference, and let r0 be the shortest distance between adjacent
ions. This ion has two negative ions as its neighbours on either side at a distance r0. Now the attractive
Coulomb energy due to the nearest neighbours is
—I--------------1--------------- 1--------------- 1--------------- 1--------------- 1--------------- I-
-3tq -2r0 —F q 0 Tq 2tq 3tq
Fig. 3.5 A hypothetical one-dimensional NaCl lattice
Similarly the repulsive energy due to the two positive ions at a distance of 2r0 is--------------- an(j
e0 2r0
2e2
the attractive Coulomb energy due to the two next neighbours at a distance (3r0) is------------------- and so
4K£0(3r0)
on. Thus the total energy due to all the ions in the linear array is
2e2
4tc e0 r0
4k e0 r0
4k En
—- ------- [21og(l +1)]
rn
= ----------- [2log 2], (3.17)

4k£0t0
Thus (2 log 2) is the Madelung constant per molecule of the

ionic solid. Hence (2 NA log 2) is the Madelung constant per kmol of
the ionic solid.
In three dimensions the series does present greater difficulty

and it is not possible to sum the series conveniently as in the case of
one-dimensional lattice. For definiteness let us consider the lattice of
the NaCl structure represented in Fig. 3.6.
The total potential energy is obtained by adding all the attractive

and repulsive energies between all the ions. The sodium ion Na+ at the
point A is coordinated by 6 Cl" ions at a distance r(). Therefore, the • Na*
attractive potential energy of the sodium ion at 4 due to these 6 Cl~ o cr
6e2 Fig. 3.6 NaCl structure
ions is------------- .
4k e0 r0
Interatomic Forces and Bondings in Solids 59
6e \
energy of the sodium ion at £ due to these 6 C! ions is
4n s q r0
12ra J
Similarly 12 Na+ ions at ^2r0 and 6 Na* ions al 2r0 respectively contribute ----------- t=— and—--------
4it€0V2rt 4tcg0^
respectively. Thus the Coulomb energy of this Na4 ion at A in the field of all other ions is
6eJ I2el Jte1 6eJ

4ne0 r0+4it e0^2r0"4n €«^+4« eo2r0
For a kmol of the crystal, the total Coulomb energy is
.Vxe3 C 12 8 6
U - - --—------ 6—
4rt e0 r9[_ V2 >f3 W
Nte*A
U^--------- (3J8)
4n r0
The constant A is called Madelung constant and A - L75 for NaCI structure. Note that in equation (3.1®)
(Zê) (Zje) must be used for and the quantity Z^ is one for monova Jem alkali halides such as sodium
chlorde. The minus sign indicates that the average influence of all other ions on one ion under consider
ation is of an attractive nature.
Crystal structure Madelung constant

Sodium chloride L747558
Caesium chloride L762670
Zinc blende L63M
X. CALCULATION OF REPULSIVE EXPONENT FROM

COMPRESSIBILITY DATA
Barn obtained the unknot n repalsive exponent (fl) from measurements of the compressibility of the crystal
as follows:
The bulk modulus of the solid at absolute zero is given by
Thut compressibility is at 0 K
1K _lf^K
v[dP (3.19)
60 So/id Stare Physic5
From the first law of thermodynamics
If the solid expands by dV against a pressure P due to the supply of dQ amount of heat, then
dW = PdV
dQ^dU + PdV
Neglecting the thermal effects (dQ -0 at very- low temperatures). we write
dU + PdV&O
and hence compressibility at 0 K is given by

d2U
(3 20)
dV'
In sodium chloride structure the nearest neighbour distance r - ra f = a/2 and the volume per molecule is
a1/4. Therefore the volume of a kmol of the solid is
5. Qr^lNj
(3.21)
dV
(or) (3.21a)
dr dV 36tf>4
dU dU
and
rfV dr
d_( dU_ r dr dry d I dU

Thus
MdV drjdvldV dV<dv[ J7
dU
dV2 dr dV1 dV dr\ dr dV
(3.22)
dV7 dr dr1
dU
At the equilibrium spacing r =r0 and -j*“0 (because U is minimum)
and V = Vo = 2N^ (Refer cqn. (321)}
Thus equation (3.22) becomes

dÛ __ T dr"2(dty'
dV2 \.dV,^drii
Interatomic Forces and Bondings in ids 61
Tbeequahon (320) becomes

'd!u}
'■H
i r 2/yjirdV
P |_36N;,*y Jr1. (3.220)
from equation (3.12)

[ N4Ae* nNAB
^drj 4n€ar* r***
Ai the equilibrium spacing, r - r0 (refer equation 3.14) and
d2{/" _ [ ~2A<r} n(n + 1)3

Now .dr2],.,/ 4*«e0^ rj*2 .
-2A<?2 + n(n + 1)
4s €0 ra r«'t 411 €» *
KAe1 pn + l)
4k eL tu »
a 3 jc j i4
4n Ge rl 4s e<, r»3
Equation (3.22<j) is
2^r’ dlU
. ^y0_
I r y fiÂe1
1 Xg^ -1)
B 72s e0 r# (3.23)
72rt €a r£
Thus («-!) =
/u’p
(3.24)
(>2 Sr did Slate Phy or 5
The experimentally determined cohesive energy of NaCl crystal is 766 x IO3 kJ/kmob or 7.95 eV/moiecule,
The energy (f/j) due to Coulomb attraction is 8.95 eV, taking re = 0,281 nm tor NaCL Substituting these
vaides in equation (335), v,e find n = 9. L
the compressibility data for sodium chloride was measured by Slater at low temperatures and the
extrapolated value at absolute zero was found to be 3 3 x IO’11 nrZN* Substituting this value of 0 in equation
(3.24) with r6 « 0.28 1 nm and A ■ 1J748, we get w » 94. The small discrepancy between the experimentally
determined value of n and the one calculated from equation (3.16} is due to a very small contribution from
van <fcr Waals forces io the total energy.
Physical properties of some selected ionic crystals are given in Table TC
XL THE BORN-HABER CYCLE

The formation of NaCl molecule may be visualized as occurring in different steps* each of which results in
energy absorption ar evolution. An experimental check on the calculated values of the lattice energies may
be obtained from Born-Haber cycle,
• NolGoU
n«ci .< .1 < . i । cr
Fig h 37 Ekjm-Hahcr Cycle.

The Born-Haber cycle for NaCl crystal can be represented as follows:
Those quantities that require the expenditure of energy are represented as positive and those that take
place with the release of energy are represented as negative. The cycle can be as follows:
(i) Initially we start with solid scdium and chlorine molecule Solid sodium is vaporized by sub-
jetting the sublimation energy (S) while chlorine molecule is dissociated into its constituent
atoms by supplying dissociation energy (DK Dll is the dissociation energy per chlorine atom.
(ii) The outer electron of Na gaseous atom is removed by applying the ionisation energy (i) and
this electron is added to Cl atom. As the chlorine has the electron affinity E, an energy E is
given out
(iii) The two ions (Na+ +■ CT) are arranged in the lattice and hence the lattice energy (U$ is
released.
(iv) We again reach to the starting point by supplying an energy (AH) known as heat ofdissoci-
aiiott.
T a t i* X C P hysical properties o f som e io n ic crysials
lnteratomie Forres and Utmdings tn Solids
63
All quantities excepting t/() are experimentally determinable. Hence the lattice energy (/0 can
calculated. In the case of sodium chloride solid, the value oi the various quantities are found
experimentally as follows:
5= 108.8 x lO’kJ/kmol
D = 242.8 x JO3 kJ/kmol
/ = 494.0 x 103 kJ/kmol
E = 364.2 x 103 kJ/kmol
AH = 410.2 x 103 kJ/kmol
Substituting the above values in equation (3.25), the lattice energy UQ works out to be 770.4 x 103
,, kJ/kmol. Knowing the value of in equation (3.16) from X-ray diffraction data and the value of the
repulsive exponent n from the compressibility data, the lattice energy Uq can be calculated. The
experimental value obtained from Born-Haber cycle data agrees well with the calculated value. This
. . indicates that the electrostatic theory is quite satisfactory for ionic crystals.
All ionic or electrovalent compounds are rigid and crystalline in nature. It has been confirmed by X-ray
diffraction that the constituents of the crystals are ions and not atoms. The ionic bond is fairly strong.
All ionic solids have high melting points and boiling points. This is because more energy is
needed to make the ions mobile, there being a necessity to overcome the strong electrostatic force of
attraction created due to the ionic bond in addition to the already existing interatomic force of gravitational
attraction. This explains why ionic compound possesses high melting point and boiling point.
Pure and dry ionic compounds are insulators, because of the non-availability of free electrons.
However, in solution they conduct electricity because of the movement of the charged ions instead of
free electrons. In a solution the ionic bond is weakened by the solvent molecules. Thus the ions become
free to move about and thereby become conductors of electricity and the solutions are good electrolytes.
Ionic solids are easily soluble in polar solvent like water. This is because the molecules of the
polar solvent interact strongly with the ions so as to reduce the attraction between the ions. Also, the
polar solvents possess high dielectric constants, for example, water has a high dielectric constant of 81,
i.e., it will reduce the electrostatic force of attraction between the ions to 1/81 of the original value.
Ionic compounds are insoluble in non-polar solvents like benzene (CL HA carbon tetrachloride
(CC14), because their dielectric constants are very low.
Interatomic Forces and Bondings m Solids 65
Reaction between ionic compounds in bolution state is always fast Thts is because in a solution, ionic
substances exist as ions and chemical reactions take place between the 10ns. The ionic crystals are transpar*
ent for all frequencies up to the value called ihe fit/ulamental absorption frequency At frequencies higher
than this, ihej are opaque.
High hardness and low conductivity are typical properties of these solids. When subjected to stresses,
ionic crystals rend 10 cleave (break) along certain planes of atoms rather than to deform in a ductile fashion
as metals do.
XIII. EXAMPLES OF IONIC SOU DS

Sodium chloride, magnesium oxide, caesium chloride and potassium iodide. Lithium hydride and potassium
oxide are other examples of ionic crystals
XIV. COVALENT BOND

(a)
Ihe covalent bond is formed by sharing of pairs of
valence electrons between like atoms raihcr than by
elec in in minster .A simple example uf ci a al ent be Hiding
is found in the chlorine molecule. Here the outer shell of
each atom possesses seven electrons. Each chksnnc atom
would like to gain an electron, and thus form a stable
(t>)
(Kiel This can he dune by sharing Iwo electrons between
patni of chlorine Atoms., thereby producing stable
diatomic molecules In other words, each atom contrib*
utes one electron for the sharing process.
\ ThemTriples! case of a single euvjletil bund occurs
Fig. 3,fi
C ♦ • J
_X
Molecular orbital formation froms orbitals

in the hydrogen molecule. The nature of (he covalent
bonding in this molecule
follows:
can be demonstrated u
(a i two isolated atomic orbitals (b) overlap u) rhe Consider the hydrogen molecule, H}. When two isolated
molcctlar orbital. H atoms, each with its Electron in the ground state Ij
orbttal approach each other, the Ij clouds begin to overlap, Each electron is attracted to the other nucleus
and I he overlap increases (provided ihe ekermns have opposite spin). The two atomic orbitals merge into a
molecular orbital. Within the molecular orbital^ the two electrons are attracted to both nuclei. When the
repulsive forces have been ba landed the attractive forces a molecule results, having stability greater than that
of the two isolated atoms. The co valent bonding is also known as homopolar or electron-pair bonding. It is
the common type of bonding in organic molecules and in many inorganic molecules.
In the molecular orbital of H:. the two electrons are equally shared between the nuclei and cannot be
specifically identified with either nucleus. The two shared electrons are more likely to be found between the
two nuclei and thus the electron density is relatively targe.
The balance between the attractive and repulsive forces in hydrogen molecule occurs at a separation
of 0.074 nm, Hence some energy must be spent to break the covalent bond in a hydrogen molecule into
hydrogen atoms, About 4,5 eV is required to break one H—H bond. T hus
K+4.5 eV~->H + H
Copy ri g hl ed fn aleri $ I
In the molecular orbital of //,, the two electrons arc equally shared between the nuclei an(j
cannot be specifically identified with cither nucleus. The two shared electrons arc more likely t0 l
found between the two nuclei and thus the electron density is relatively large.
The balance between the attractive and repulsive forces in hydrogen molecule occurs at a
separation of 0.074 nm. Hence some energy must be spent to break the covalent bond in a hydrogen
molecule into hydrogen atoms. About 4.5 eV is required to break one H—I I bond. Thus
Hi 4- 4.5 eV-----------> H + H
*r
If N represents the number of electrons present in the valence shell ol an electrically neutral
atom, then (8 - N) is the number of electrons which arc required to obtain a stable octet. This is also the
maximum number of covalent bonds which an atom can form with the adjacent atoms. Thus (8 - M j.
the coordination number in normal covalent bonding.
A covalent bond is usually indicated by showing two electrons between the symbols for the
atoms
H : H
It is desired to make clear that one electron has come from each atom, they may be indicated as
H * H
Say the dot electron has come from the atom on to the left and x electron has come from the atom
on to the right. The actual bond is generally represented as H—H. Thus
H + H ----- > H:H ----- > H*H ----- > H—H, or H2
:cr + :CP —> :C1: Cl: —> :C1 x Cl:.—> Cl—Cl or Cl2
In the element chlorine, each atom has seven electrons in the outer shell. When two atoms of
chlorine tend to form a chlorine molecule, one electron from each atoms is shared with the other.
Table 3.4 gives bond lengths and binding energies of some covalently bonded substances.
Interatomic and Handings /« SaHds 67
Table X D Cuvatent bond lengths and associated binding energies
fkmd tSond length Binding energy Btmd Bond Imgik Binding

fW in kJrtjn&t energy in
(in 1(f) kJ/bnol
(in 1(f)
H H 0.074 436 0=0 0.121 498

OH 0108 414 CkO 0.199 242
C-C 0.154 N-N 0.100 390
r 0J34 615 H-a 0.128 431
oc 0.120 840 C-F 0,136 486
C-0 0.143 358 C~Si 0.193 301
co 0.122 745 Si~H 0.145 293
c-a 0.177 327 Si Si 0.234 176
N*N 0 KB W5 Si Cl 0.216 360
O-H 0,097 463 Si-O 0.183 368
Other examples are:
N + N ------- - N; ------- * !N } —* N S N, (or) N,
H
H |
C+2H2—• CH<—♦ H !£t H —• H — C—H.lorJC
H I
H
It is interesting to note that a hydrogen molecule can be stable with only two atoms. If a third hydrogen
atom is brought near the hydrogen molecule H2, it is repelled. This means that the covalent bond exhibits
saturation. We can show that it is not possible for a molecule H3 to be formed by covalent bonds. When
H2 molecule is in the ground state, electron spins are anti-aligned (? ?). When a hydrogen atom with a
spin (1/2) approaches the H2 molecule and if there is to be chemical bonding by covalent forces, it can
be formed by exchange of spins between H and H2. There are only two ways in which the single
electron spin (?) of the hydrogen atom can interact with the H2 molecule. One is by exchanging the spin
with one electron having the spin (?) or with the other electron having the spin (?). If the hydrogen
atoms electron having spin (?) exchanges with the hydrogen molecules electron having spin (?), the
two spins are aligned in the same direction and the exchange force between the hydrogen atom and the
molecule is repulsive. Suppose the hydrogen atoms electron having spin (?) exchanges with the hydrogen
molecules electron having spin (?) the electron spins of the hydrogen molecule will be aligned which is
disallowed by Pauli’s exclusion principle. So, the only possible exchange between the H2 molecule and
the H atom is repulsive and so the molecule H3 cannot be formed.
The covalent bond is formed as a result of pairing of two electrons in the atomic orbitals of two atoms.
The bond then should lie along the direction of the overlapping atomic orbitals. Hence covalent bonds
will have strong directional preferences unlike ionic bonds. According to quantum mechanics, the electron
is associated with a wave and it can be described in terms of the wave function y (x, y, z). The physical
significance of y is that the square of y, (I y I2) represents the probability of finding the electron at any
instant in unit volume.
The solution of Schrodinger wave equation gives rise to three constants, called quantum numbers.
One is called principal quantum number ln' which can take integral values from 1 to «>. The other is
called the angular momentum quantum number 7’ which can take values from 0 to (n - 1). The third
one is called magnetic quantum number 'm,' which can take only integral values from mt = -1 to m, = +1
including zero in steps of one. The wave functions ; are called orbitals. According to different I
values, the orbitals are classified as:
I = 0 is called ‘s’ orbital
/ = 1 is called ‘p’ orbital
/ = 2 is called 'd orbital
I = 3 is called *f' orbital
CHAPTER 3
Fig. 3.9 Different orbitals
Covalent bonds are not only formed by pure s orbitals or pure p orbitals but can also be formed
by the overlapping of s and p orbitals called hybrid bonding. For example, we consider the case of water
molecule. In the bond formation, the two hydrogen atoms use Is
orbitals. The electronic configuration of oxygen is Is2 2s2 2p\ 2p\
2 n2, which shows that p and p orbitals should be used.

rZ a j
Figure 3.10 shows the xy plane of water molecule. It is observed
that p and p orbitals lie mutually perpendicular to each other in .vy
planemo obtain a maximum possible overlap between Is orbitals of
hydrogen atoms and px and py orbitals ot oxygen atom, it is necessary

for hydrogen atoms to approach along the x and y axes. This leads to
the overlap as shown in Fig. 3.10, and the H O H bond angle should
Fig. 3.10 Overlapping of orbitals
in water molecule
amount to 90°. It is experimentally observed that the value ol (he bond angle is 104.5° which is due to
the repulsion between the two hydrogen atoms and also due to the effect of some contribution to the
bond of Is electrons of oxygen atoms.
The simple approach based on the overlap of 5 and p orbitals tails in the case of organic compounds of
carbon. The occupancy of the orbitals of the carbon atom is
Is 2s 2px 2py 2pz
This shows that Is, 2s spins are paired, while 2p electron spins are not paired and they are
available for bonding. But when the carbon atoms approach each other, one s electron is excited to the
p level and the electronic configuration becomes as follows:
Is 2s 2px 2py 2pz
This shows that there are foup unpaired electron spins. The
bonding directions of these orbitals are disposed towards four comers
of a regular tetrahedron with bond angles 109.5°. This arrangement of
orbitals is called hybridization and the four orbitals are called sp3 hybrids
as shown in Fig. 3.11. The four bonds are of equal strength. Covalent
bonds in diamond, CC14, CH4 exhibit this tetrahedral symmetry.
Hybridization is the mixing of the orbitals of the valence shell
of the same atom to form new orbitals with the same energy and similar
shape. The resulting orbitals are called hybrid orbitals. Hybridization
involves the following steps: Promotion of one of the paired electrons
in an orbital to an orbital of higher energy. The atom is now in the
excited state and, pure orbitals in the excited atom are hybridized or
Fig. 3.11 Sp3 hybrid wave
mixed to form hybrid orbitals having definite orientation in shape. The
functions
hybridization of carbon [sp3 hybridization is shown in Fig. 3.11 (A)].
The three-dimensional arrangement of carbon atoms is called the diamond structure. The strength
of the covalent bond is aptly illustrated by the strength and hardness of diamonds.
Carbon is usually found as graphite rather than as diamond. The graphite structure results from
I *
the sp2 hybrid orbitals in which 3 bonds are formed in a plane with interbond angles of 120°, with the
fourth p orbital metallic and is therefore non-directional.
Sheets of atoms can bond to each other by weak secondary bonds. These weak bonds have no
valence requirements. The structure which results from bonding the sheets together is shown in Fig. 3.12,
and is the flaky structure of graphite. Because the bonds holding the sheets together are weak, the sheets
can readily slide past each other. The ease of sliding accounts for the lubricating properties of graphite.
Both diamond and graphite have the same chemical composition, but the manner in which the atoms are
Interatomic forces and Ifanditiff in Solids 11
Sheets of atoms can bond to each other by weak secondary bonds. These weak bonds have no valence
requirements. The structure which results from bonding the sheets together is shown in Fig. 3.12, and is the
flaky sirueture of graphite. Because the bonds holding the sheets together are weak, the sheers can readily
2*
(b) (c)
Fig* 3.11 (A) (i) Cjrbod m the ground ante (h) in the excited stale (c) tn the hybridited ttate.
slide past each other. The ease of sliding accounts for the lubricating properties of graph at. Both diamond
and graphite have the same chemical composition, bin the manner in which rhe atoms are arranged has a vast
effect on physical ties. The metallic orbital accounts from the fact that graphite is an electrical con
ductor while diamond is not. Graphite is used as 'lead* in ipencils for Its softness and as lubricant, for weak
van der Waals forces between the sheets, in important applications. The following important points may also
be noted in addition:
(i) Attainment of octet configuration or noble gas configuration is not essential in covalent bond forma*
lion. For example, in the case of borontnfluoride, each fluorine atom has a noble gas configuration,
buf the boron atoms has only six electrons in its ouiermost orbit
(it) The paired electrons shared by two atoms should be of opposite spin. This rule is called the rule of
tys Q. Thus the two electrons forming the pair which is shared between the two atoms can occupy the
available stable orbital in either atom without violating Pauli's exclusion principle.
(iii) Depending on whether the electron pairs are shared equally or unequally between the atoms, covalent
bonds can be subdivided into non -polar and polar bonds respectively.
For example, hydrogen co hydrogen bond during the formation of H; molecule is a non polar covalent
bond. since the electron pair is shared equally between the hydrogen atoms.
Similarly chlorine to chlorine bond is also a non-polar covalent bond. But in the case of hydrogen
chloride, hydrogen to chlorine bond is a polar covalent bond since the electron pair is more shifted
towards chlorine because of its high affinity (electronegativity) for electrons. This results in a slightly
negatively charged (- 6) chlorine end and an equal positively charged (+ 8} hydrogen end, in the HC1
molecule.
XVIII. PROPERTIES OF COVALENT COMPOUNDS

(i) Covalent compounds are mostly gases and liquids.
Fig. 3.12 Structure of graphite, illustrating sheet molecules connected by metallic bonds
(Hi) The melting point and boiling point are usually low as compared to those of ionic crystals.
This is because the covalent bond is not so strong as the ionic bond and also because the
atoms are less powerfully attracted towards each other, the forces that attract them towards
each other being van der Waals forces, dipole etc. which are quite weaker.
(iv) Most of the covalent substances do not conduct electricity because of the non-availability of
free electrons or charged ions to carry the current. However, certain substances like HC1
which exhibit polarity in aqueous solutions behave like ionic substances and allow the passage
of electricity through them accompanied by their own decomposition thereby acting as
electrolytes.
(v) Covalent substances are insoluble in polar solvents like water. However, they are soluble in
non-polar solvents like benzene, carbon disulphide, etc. This is because of the covalent nature
of the solvent. However, the giant molecules are not soluble in any solvent because of the
large size of the molecules.
(vi) A very interesting property of covalent crystals is the apparent lack of sensitivity of their
physical properties to their bonding type. For example, carbon in the diamond structure is the
hardest substance and has a very high melting point of 3280 K. The hardness and melting
point then decrease as we proceed to other elements in column IV of the periodic table from
silicon to lead. Tin, for example, is very soft and has a low melting point. The variation in the
electrical properties is also pronounced. Diamond is very good insulator. Silicon and
germanium are well known semiconductors while tin is a good conductor. Depending on the
number of electrons shared, the bond length and bond energy vary. When the number of
electrons shared is more, the bond length between the atoms is decreased and bond energy is
increased. Diamond, silicon, germamum, silicon carbide, tin and rutile are some examples of
covalent crystals.
In some respects, the metallic bond is similar to the covalent bond, yet it is quite different in others. In
the covalent bond, two atoms are linked together by pairs of electrons shared between them. In metallic
_ _ _ -_ Interatomic Forces and Bondings in Solids BL 7 3 I
bonding, thi? valenceÛions, which hold the atoms together are not bound to individual atoms or
pairs o a ( >___________ rec y t uoug out the whole metal. The similarity to the covalent bond lies in
thesianng o ions. e i cicncc is that these electrons belong to the metal as a whole rather than
to any particular atom. b
Metallic elements have low ionisation

11 on energies and ,hence, in
'(i) this bonding, atoms ofe the
....................... . same
element 01 dilfeient elements give their valence electrons to form an electron cloud or say "electron gas"
throughout the space occupied by the atoms. Having given up their valence electrons, the atoms are in
reality positive ions. 1 hese ions are held together by forces that are similar to those of ionic bond in that
they are primarily electrostatic, but arc between the ions and the electrons.
Most ol the atoms in metals have one or two valence electrons. These electrons are loosely held
by theii atoms and therefore, can be easily released to the common pool to form an electron cloud. The
electrostatic interaction between the positive ions and the electron gas hold the metal together. The high
electrical and thermal conductivities of metals follow from the ability of the free electrons to migrate
through theii ciystal structures while all the electrons in ionic and covalent crystals are bound to particular
atoms.
CHAPTER 3
Unlike other crystals, metals may be deformed without fracture, because the electron gas permits
atoms to slide past one another by acting as a lubricant. As we have seen carbon can exist in the covalent
form and so it is an extremely poor conductor. However, it may also exist in an alternate form as
graphite. In this case, bonds are formed in which covalency is not fully achieved and these bonds can
break and reform fairly easily as in metallic bond. For this reason graphite is an electrical conductor. If
a potential difference is applied between any two points in a metal piece, the electron gas will flow from
the negatively charged part to the positively charged part, constituting an electric current.
___>■
(i) Bonding energies and melting temperatures for some metals are listed in Table 3.7. Bonding
may be weaker or stronger, energies range from 64 x 103 kJ/kmol (0.7 eV/atom) for mercury
to 850 x 103 kJ/kmol (8.8 eV/atom) for tungsten. Their respective melting points are -39°C
and 3410°C.
(ii) Due to the symmetrical arrangements of the positive ions in a space lattice, metals are
crystalline.
(Ui) Metallic bonds being weak, metals have a melting point moderate to high, i.e., the melting
points of metallic crystals are lower than those of the electrovalent crystals.
(iv) Since a large number of free electrons are available, metallic crystals have high electrical
conductivity.
(v) Metallic crystals have higher thermal conductivity because of the availability of large number
of free electrons which act as carriers of heat.
(vi) Metals are opaque to light since the light energy is absorbed by free electrons. Copper, sodium,
silver and aluminium are some examples of metallic crystals.
74 W State Physic s
result tom either a transfer ot electrons or from a sharing of electrons, secondary bonds do not generally
involve the valence electrons at ail. Secondary bonds are those comparatively weak intennolccular bonds
formed as a result of dipole attractions, the dipoles being formed as a result of the unbalanced distribution of
electrons in asymmetrical molecules* Dipoles may be permanent as in (he case of hydrogen fluoride ttnd
water molecules, or they may be temporary, as in the case of noble gases. The three types of intermolecular
bonds are dispersion bonds; dipole bonds; and hydrogen bonds.
Fig. X13
XXIL DISPERSION BONDS
Bonds of first type are made possible largely
because the electrons of adjacent atoms in a mol
ecule tend to repel each other As the electrons
revolve around their nuclei, they tend to keep in
phase as illustrated in Fig. 3 J 4. for a hydrogen
molecule The result is that the molecule has a
small fluctuating net charge on each end and acts
an oscillating dipole, The hydrogen molecule,
illustrated in Fig. 3 J4( is instantaneously charged
negatively on the right cod and positively on the Fig. 3.14Dispersion effect in a hydrogen molecule (H"),
left. This fluctuating charge on one molecule showing momentary polarization* negative on the right,
lend* 1,1 interact with the fluctuating charge un a positive on the toft
neighbouring molecule, resulting in a net attraction. The strength of (he bond depends on the ease with
which one atom can influence the other. Molecules of the inert gases, which consist of single atoms, are held
together by dispersion farce* when the gases are solidified.
C opy ri g hi ed m a ter i a I
Interatomic I'area and Bondings Solids 15
Aloni* of noble gases, h is found, have little attraction for one another and with rare exceptions they
remain monoatonuc at ordinary tempera lures Only at extremely tow temperatures, when thermal vibrations
have been greatly reduced, do these gases condense. It is this condensation uhich makes it evident that there
are weak interatomic attractions which puil ihe atoms together This is what knuuri as -.r^j tier
forces.
Fig, 345 thsperKkm foctei bdw^tnhti ahwns d vfxia
Consider the case of two aioms of the noble gas, argon, in close proximity to each other - If the elec
tron clouds are evenly distributed as in Fig. 3-15 (i.b then there will be no resultant displacement in cither
atom and they Will neither attract dot repel each other. If, however, an uneven distribution of the electron
clouds is present as in (ii), the atoms will repel each other, but if the electron clouds are distributed as in (iii),
the electron cloud of atom A will be attracted by the 'unprotected' nucleus of the atom
The displacement of the electrical charges necessary so produce a dipole is temporary and random so
that a molecule, as a whole, over a period of time has nu resultant dipole However, if ft has a displacement
at any one instant it will induce another in a near by neighbour .iitd a force of attraction will be set up
between the two, It is thought that such interactions must be largely responsible for win der WWj kw?Jjny
between non-pt'rlur atoms and molecules.
XXM DIPOLE BONDS

A molecule of the hydrogen chloride gas contains one atom of hydrogen and one atom of chtoi ine, cova
lently bonded (H—Cl). In this covalent-bonded hydrogen chloride (HCl) molecule, the net effect of the
electron-sharing process is to give the chlorine atom a slightly negative charge while the hydrogen utom has
a corresponding positive charge. The magnitude of the charges are actually quite small, being 0,272 x tfr *
Copyrighted snaierial
The attraction is small compared with that
between ions because the charge on an ion is at least
equal to that of an electron. Dipole bonds are
consequently much weaker than ionic bonds, but at the
same time they are considerably stronger than dispersion
bonds. The other examples are hydrogen bromide,
sulphur dioxide and hydrogen cyanide.
The hydrogen bond desenes a special mention. This

bond must be considered as a special type of dipole bond,
but one that is considerably stronger. It occurs between
molecules in which one end is a hydrogen atom. hen
a hydrogen atom is covalently bonded to a relatively
large atom such as nitrogen, oxygen or fluorine, a Fig. 3.16 Dipole bonds
powerful permanent dipole is set up. (a) Electrical imbalance in a HCI molelcule
(b) The imbalance produces an electnc dipole
This is because the electron cloud tends to
(c) The resulting dipole produces a mechanism for
become concentrated around that part of the molecule
secondary forces of attraction
containing the nitrogen, oxygen and fluorine nucleus.
thus leaving the positively charged hydrogen nucleus relatively 'unprotected'. Consequently, a strong
permanent dipole is created that can bond to other similar dipoles with a force near that involved in the
ionic bond. A good example of hydrogen bond is water molecule. In water, the hydrogen and oxygen
atoms are held together by covalent bonds in a configuration as shown in Fig. 3.17. The four types of
chemical bonding in solids are shown in Fig. 3.18.
Table 33 Comparison between ionic bonds and metallic bonds
Properties,: Ionic bonds — *: Metallic bonds
Bonding force The bonds exist due to electrostatic force of The bonds exist due to electrostatic force
attraction between positive and negative ions of attraction between the electron cloud of
of different elements. valence electrons and positive ions of the
same or different metallic elements.
Bond formation Ionic bond is most easily formed when one of This type of bond is characteristic of the
the atoms has smaller number of valence elements having small numbers of valence
electrons, such as the alkali metals and alkali electrons, which are loosely held, so that
earths. they can be released to the common pool.
Conductivity Low conductivity is the property of the solids Good thermal and electrical conductivity is
formed by ionic bonding. the property of most of the solids formed
by metallic bonding.
Mechanical properties Solids formed have high hardness. Ionic Solids formed mostly have good ductility.
crystals tend to cleave (break) along certain
planes of atoms rather than to deform in a
ductile fashion when subjected to stresses.
Bond strength These bonds are generally stronger than These bonds are generally less stronger than
metallic bonds. ionic bonds.
interatomic Forces and Bondings in Solids 77
Fla- 3.17 Hydrogen bond between two water molecules.
Positive metal ion
Wteak attractive forces
(c) 2
Positive Shored valence

ion electrons
Centers of positive and of
negative charges seperated
in each atom
Flp. 3.18 The four types of chemical bonding in solidcs (a) Metallic bonding (b) Ionic bonding (c) Covalent bonding
(d) van der Waals bonding
Copy righted material

V.
Table 3. F c:u'r-:ri;*s properties of vat cws bontis

■W/d State
/V. L (. rf Bmdf Woofo Bondi

Bonding fotcc Elet irx u.iik attraction oi oppcrMtdy Minuai sharing of valence Attrition between the ion Electrostatic force due to
P fy jK J
charged ions deerr-ons between atom* cores and conduct? on vtec- < wci Ihtmg dipolrs, i ii pct -
tron Lus manent dipoles between
molecules or dipoles
bet w mi sim 11 ar tuolc -
cutes.
Energy of boitf kJ/kmol (500- 1000) I01 (6G 700) 10' <100 - 35OHO’ (21 - 50) 103
Char acier of bond N^n- JirtMbiâl Directional Non directional Directional for dipole and
hydrogen bonds, non*
directional for dispersion
ones.
Bond formation u iTidiln-n) When ime n! the jhuns h;^ smaller When aiunnc ortmaJs of two For cieftieirts having stnali For molecules fomting
number of valence electrons. atoms overlap. number of valence dec- dipoles
uons.
E 1Cctrical conduct! v । ty Low conduct) viiy Low electrical conduct] vity C'khkI conductivity Low conductivity
Lustre Transparent or coloured bin not Transparent to highly reflective Highly reflective. Trstis parent <u coloured
highly reflective
Colour Wide v«neiy erf good colours While io grey Colour derives from tnolcr
Usually grey with a few
exceptions cuie, not from cry sial..
Density Intermediate Intermediate High Low
Cleavage Very good Fairly good Difficult except lowtetn- Easy
peraturvs because of high
ductility
Milling pGun Intermediate High Intermediate Low
Vapour State Diatomic molecules or Moms Atoms or occasionally siTiall mole Atoms or occasionally Molecules
cular aggregates small molecular aggregates
H ampler NaCI, CsCt etc. Diamond, Uermanrum etc AL CX Nx etc. Argon, Calomel, ice, solid
COête. ]
i
C opy right e q rn a ter a
Initmttomic flam and Bonding* in Solid} 79
Table 3. E, Bonding energies and melting temperatures nt some selected substances
Bcrndmif type Substance Bonding energy Meifbtg

lemperature T‘
or molfcuU
Ionic NaCl 640 33 SOI
MgO 1000 54 2800
Covalent Si 450 4J 14)0
C (diamond) 713 74 3600
Metallic Hg t& 0.7 -39
Al 324 3.4 660
Fc 406 42 1538
W 849 O 3410
render Waals Ar 35 0.08 *189
Cl, 51 0.32 -101
Hydrogen NH} 35 036 -72
H.O 5i 0.52 0
OBJECTIVE QUESTIONS
1, Which is the electronic structure of sodium ion if the atomic number of sodium is 11?
(*) limp's*1 (b) L?2»*2p‘
(*) W> ij’ij’ap5

2. The nature of binding for a crystal with alternate and evenly spaced positive and negative ions is
(a) ionic (b) covalent
(c) metallic (d) dipole
3. Which of the following elements is a covalently bonded crystal?
(a) aluminium (b) sodium chloride

(c) germanium (d) lead
4. 44 electron volt of energy is required to break one H—Cl bond This is equal to
W 42 x IO*W/kmol (*» 420x 10’kj/kmol

(c) 42 J/kmol (d) 420 kJ/kmol
5- What is the nature of binding in CH4?
(a) covalent (b) ionic
(e) metallic <d) dispersion

6 The bond energy of NaCl molecule is given by the relation
(a) V-r/(4«e4r^ <b>
(c) V = e/{4«G0r01) W) V = -*/(4jteB
Copyrigiiled- material
7. The length of H—11 bond is
(a) 0.074 nm (*0 0 01 nm
(c) 0.037 tun 2 nm
8. The sublimation energy of sodium is

(a) 1.08 x 103 kJ/kmol (&) 10.8 x 103 kJ/kmol
(c) 108 x 103 kJ/kmol (d) none of these
9, Which of the following relation gives the potential energy of a diatomic molecule?
(d)-aJrm + b/rm (b) a/rm - b/.rn
(c) arm + br” (d) ar'n-brn
10. If 0.28 nm is the spacing between the nearest neighbouring ions in NaCl lattice, the unit cell parameter i$
(a) 1.4 A (h) 5.6 A
(c) 0.7 A (d) 1 nm
11. In NaCl, the Na ions are positively charged and chlorine ions are negatively charged. Inspite of the coulomb
attraction between them, why do the two ions not collapse?
(a) because of the presence of free electrons (b) because of its low melting point
(c) because of its high specific heat (d) because of short range repulsive forces
12. Which of the following gives the lattice energy per kmol of NaCl crystal?
. ANAr0 n n-1
a' 4rt£o e n-1 (b)-
4n e0 r02
ANAr0 n AN. e2 rn-l
(J)-—--------------
4n Eq e n-1 4 K Eo r0 L n
13. Why are lithium and sodium look similar chemically?
(a) both have the same number of electrons
(h) both are adjacent elements in the atomic table
(c) both have one electron in the outermost incomplete shell
(d) both are alkali metals
14. The radii of Cs and Cl are r1 and respectively. Which of the following gives the lattice constant of CsCl
if it crystallizes in bcc structure?
(a) 2(r( +r2) 141 (Z>) 2(r, +r2) / ^3
(c) (q +r2)/ 43 (J) 2(ri +r2)/ 45
15. Which of the following relation gives the compressibility of an ionic crystal?
(a) 72jc£0 /q
Ae2(n -1)
w— ?.e°
Ae~(n -1)
Ae2(n-1)
(c)----- ------ r
72n e0 72 n e0 r02
Interatomic Forces and Bandings in Solids 81
15. Which of the following relation gives the compressibility of an ionic crystal?
72fte4rf 72n?^
(a) (b)
Ae\n-J) 1)
4 eXn - 1} - 1)
?2hG0^ 72tee0^
SHORT QUESTIONS
L How is a covalent bond formed in a hydrogen molecule?
1 What are directional bonds?
3. What is a covalent bond? Give the structure of a crystal having this bond.
4. Distinguish between covalent and ionic bondings: include examples.
5. What is Madelung constant? Give its value for NaCI structure.
6. Distinguish between tonic and metallic crystals,
7. Distinguish between ionic and van der Waals crystals.
8, Describe the salient features of covalent and metallic bonded crystals.
9, What is exchange interaction?
10. Give two examples for (i) ionic solid (ii) covalent solid.
IL Account for the difference in the physical properties of materials diamond and graphite in terms of
the structural arrangements and bonds.
1Z Classify the various types of interatomic bonds.
11 Explain the physical properties of solids on the basis of their bonding.
14. What are the distinguishing characteristics of metallic bonding?
15. Why U the binding energy high in transition metals iron and tungsten?
16. Describe the covalent bond with examples,

It Give two examples each for (a) ionic solid (b) covalent solid.
18. Discuss Born-Heisenberg theory of ionic lattice
19. Explain the tenor ionisation energy and lattice energy.
20. Discuss ‘cohesive energy* and electron affinity.
21. Explain saturation in covalent bonds. Explain why the molecule H, cannot be formed.
REVIEW QUESTIONS
L Assume that the interatomic force between two atoms is given by (he following function of the dis
tance r between the centres of the panicles:
with N > Af
Phys.cs, ;,
2. The potential energy of a diatomic molecule is given in terms of the interatomic distance r by the expr,^.
a b
Derive an expression for the equilibrium spacing of the atoms and hence obtain the dissociation energi
3. The net potential energy U{} between adjacent atoms may sometimes be represented as a function of tj.
interatomic distance r according to the relation
a b
in which a, b, tn and n are all constants whose values depend on the specific material. Calculate u-
bonding energy U(j in terms of the parameters a, b, m and n using the following procedure:
(a) Differentiate U(r) with respect to r, then set the resulting expression equal to zero, since the curve of
U (r) versus r is minimum at UQ.
(b) Solve for r in terms of a, b, m and n which yields r0, the equilibrium interatomic spacing.
(c) Get the expression for U() by substituting
in the equation for U(r).
r()
4. Write down the general equation of a bond. Derive an expression for the interaction energy of a diatnmL.
molecule and hence obtain the equilibrium spacing r().
5. The potential energy of a diatomic molecule is given in terms of the interatomic distance r by the expression
... . a b
u(r) = ~ +
(a) Derive an expression for the equilibrium spacing of the atoms and hence obtain the dissociation ener»
(b) Explain the importance of equilibrium spacing as the configuration of lowest potential energy and
hence obtain an expression for the dissociation energy of the atoms.
(c) Prove n > m for U(r) to be minimum at r = r0.
6. Discuss Born-Heisenberg theory of ionic lattice and hence obtain the repulsive exponent of NaCl crystal
7. What is Madelung constant?
Show that the Madelung constant for a one-dimensional array of ions of alternating sign with a distance
between two successive ions is equal to 2 log 2.
8. What are ionic crystals? Explain the formation of an ionic crystal and obtain an expression for its cohesive
energy.
9. Explain the term binding energy. How is it calculated for an ionic crystal having sodium chloride structure?
10. What are the forces contributing to the binding of an ionic crystal? What do you understand by Madelung
constant? Obtain an expression for the lattice energy of an ionic crystal.
11. Draw a schematic figure showing the structure of sodium chloride. Obtain an expression for the total
cohesive energy of an ionic crystal in terms of the Madelung constant and other parameters.
12. Consider a line of 2N ions of alternating charge ± e with a repulsive potential energy Alt” between nearest
neighbours. Show that the minimum energy at the equilibrium separation is
✓
. (Ne2)2log2 (
l/(ro) = t/o = -i—J--- — 1-1)
, 47160 r0 V n)
Iru^rtitGmiC Farces and Bandings in Salids 65
Explain the term binding energy. Haw is it calculated for an ionic crystal having sodium chloride
structure?
ia Wh^t are the forces contributing to the binding of an ionic crystal?* What do you uixlersund by
Madelung constant? Obtain an expression for the lattice energy of an ionic crystal.
IL Draw a schematic figure showing the structure of sodium chloride. Obtain an expression for the total
cohesive energy of an ionic crystal in terms of the Madelung constant and other parameters.
11 Consider a Jine of 2/V ions of alternating charge ±e with a repulsive potential energy A/r’ between
nearest neighbours* Show that the minimum energy at the equilibrium separation is
(to3) 2jog2/
4n e0 r0 v nJ
13. Explain with Mutable examples the iume. vuvulenL metallic and mulecuhr type nf bonding in solids.
14. What are ionic crystals? Explain the formation of an ionic crystal and obtain an expression for its
cohesive energy.
IS. Explain The origin of van der Waals forces in molecular crystals. How does the binding due to \an tier
Waals forces differ from the binding in valence crystals?
16, Distinguish between ionic and covalent bonds, Explain metallic bonds. What is the nature of bonds in
Nad and diamond?
17. Obtain an expression for the total cohesive energy of an ionic crystal in terms of Madelung constant
and other parameters*
18. Explain the difference between ionic and covalent types of bunding* What du you understand by
Madelung constant?
19. Explain the terms:
(a) Ionisation energy

(b) Lattice energy
(c) Cohesive energy
(d) Electron affinity
20. Write down the electron configuration of Mif * ion, (Atomic weight of Mn is 25). Comment on (be
method of fillings of electron shells in atoms. Distinguish between different types of binding in sol
ids. Sketch the variation of the potential energy as a function of the atomic spacing.
21. Explain the different types of bandings in solids. Find an expression for the equilibrium potential
energy of an ionic solid.
22. Describe the theory of ionic solids. Show the method of calculating the Madelung constant for NaCl
lattice* Relate the value of the 'repulsive exponent* in rhe interactions to compressibility of sodium
chloride*
23. What is meant by lattice energy of an ionic solid? Is it released or absorbed when the solid is foroed
from its constituent ions. Explain Bom and Heisenberg theory of ionic lattices and show how the lat
tice energy is calculated from this theory* How is the experimental confirmation obtained ?
Interatomic Forces
13. Explain with suitable examples the ionic, covalent, metallic and molecular type of bonding in solids.
14. What are ionic crystals ? Explain the formation of an ionic crystal and obtain an expression for its cohesive
energy.
15. Explain the origin ol van der Waals forces in molecular crystals. How does the binding due to van der
Waals forces differ from the binding in valence crystals?
16. Distinguish between ionic and covalent bonds. Explain metallic bonds. What is the nature of bonds in
NaCI and diamond?
17. Obtain an expression for the total cohesive energy of an ionic crystal in terms of Madelung constant and
other parameters.
18. Explain the difference between ionic and covalent types of bonding. What do you understand by Madelung
constant?
19. Explain the terms:
(a) Ionisation energy (b) Lattice energy
(c) Cohesive energy (d) Electron affinity
20. Write down the electron configuration of Mn++ ion. (Atomic weight of Mn is 25). Comment on the method
of fillings of electron shells in atoms. Distinguish between different types of binding in solids. Sketch the
CHAPTER 3
variation of the potential energy as a function of the atomic spacing.
21. Explain the different types of bondings in solids. Find an expression for the equilibrium potential energy
of an ionic solid.
22. Describe the theory of ionic solids. Show the method of calculating the Madelung constant for NaCI
lattice. Relate the value of the “repulsive exponent” in the interactions to compressibility of sodium chloride.
23. What is meant by lattice energy of an ionic solid? Is it released or absorbed when the solid is formed from
its constituent ions. Explain Bom and Heisenberg theory of ionic lattices and show how the lattice energy
is calculated from this theory. How is the experimental confirmation obtained?
Show that the potential energy of two particles in the stable configuration is equal to - — form = 2
Lro J
and n = 10.
a b
The interaction energy of two particles in the field of each other is given by U(r) =----- + -^ where a and
• • t I •
~ f r r
I
b are constants.
(u) Show that the particles form a stable compound for r = r0 =
(b) Show that in the stable configuration the energy of attraction is 9 limes the energy of repulsion.
(c) Show that the potential energy of the two particles in the stable configuration is -
MW
Assume that the energy of two particles in the field of each other is given by the following function.
... . a b
=------ + ~8
r r
where a and b are constants and r is the distance between the centres of the particles.
(a) Show that if the particles are pulled apart, the molecule will break as soon as r=
’ 36b 1l/7
(b) Prove that in the stable configuration, the energy of attraction is 8 times the energy of repulsion
(c) Also show that the minimum force required to break the molecule is equal to (36b)2/7 I? 36
Assuming an overlap interaction between nearest neighbours of the type <|> (r) = B exp(- r/p), where B
and p are constants, calculate the equilibrium spacing r0 in terms of B and p.
5. Develop a new form of equation for the force between two atoms or molecules from the equation
A B
F (r) = —----- . Determine from this equation, expressions for the following properties of the energy
curve : (a) the potential energy at r = rQ; (b) the spacing for which the force is maximum and (c) the
value of F„.max
6. Evaluate the expressions described in the previous problem for M = 2, N = 6, r0 = 0.4 nm and A =1 unit.
Develop a new form of the equation for the potential energy of a pair of atoms or molecules from the
equation.
a b
U(r)
rm rn
Determine from this equation, expressions for the following properties of the energy curve: (a) potential
energy at r = r0, (U^); (b) the spacing at the point of inflection.
8. Evaluate the expressions described in the above problem for the following case:
* «
m = 1, n = 10, r0 = 0.1 nm and a = 1 unit

9. The potential energy of a diatomic molecule is given in terms of the interatomic distance r by the expression
T J/ \
TO = - — + io
r r
Calculate the equilibrium spacing of the two atoms and the dissociation energy (a = 1.44 x 1(T 39 joule m2
and b = 2.19 x 10“115 joule m10).
10. Suppose the interaction energy between two atoms is given by the expression
m \ a b
U{r) =
r r
and the two atoms form a stable molecule with an intemuclear distance of 0.3 nm and a dissociation
energy of 4 eV, calculate a and b. Also calculate the force required to break the molecule and the critical
distance between the nuclei for which this occurs.
11. Assume that the energy of two particles in the field of eaeh other is given by the following function of the
distance ‘r’ between the centres of the particles:
a b
TO = -- + -g-
r r
Interatomic Forces ano
IT* i<i
(a) Show that the two particles form a stable compound for r = r0 =
(b} Show that the potential energy of the two particles in the stable configuration is equal to - I — I
\8/ 'o
1/7
(c) Show that it the particles are pulled apart, the molecule will break as soon as r = | and that the
\ a
9/7 r o -
minimum force required to break the molecule is------ 1 - —
(36£)z L 36-I
12. Assume that the eneigy of two particles in the field of each other is given by U(r) = - — + -£■ where a, 0
r r
are constants and r is the distance between the centres of the particles. Show that the two particles form a
stable compound for r = r0 = I —

iW7 and that in the stable configuration, the energy attraction
. is. o .
8 times
\ J
energy of repulsion.
13. Calculate the binding (lattice energy) of the Nai for which the nearest neighbour distance is 0.324 nm.
Express the energy in eV/molecule and also in kJ per kmol. Madelung constant for Nai = 1.748 and
n = 9.5.
14. Calculate the compressibility of sodium chloride assuming a repulsive potential of the form B/r3 to act
between nearest neighbours. The nearest neighbour distance r = 0.281 nm. The corresponding Madelung
constant is 1.7476.
15. The Coulomb electrostatic energy is given by —-—— in eV per molecule where A is the Madelung
ro
constant, taking into account all nearest neighbours in the lattice. Show that this is reasonable. The value
of A for NaCl structure is 1.7476.
Calculate the binding energy of Nai for which the nearest neighbour distance is 0.324 nm. Express the energy
in eV per molecule and also in kJ/kmol. The experimental value of binding energy is 670 x 103 kJ/kmol.
Calculate the repulsive energy.
16. If the ionic radius of Na decreases by 0.88 and that of Cl increases by 0.89, calculate the binding energy of
NaCl. Madelung constant for NaCl is 1.75 and n = 9 for ionic crystals. Express your result in kJ/kmol
[ra = 0.0905 nm and rNa = 0.186 nm].
17. Calculate the compressibility of CsCl, using 1.76 for the Madelung constant, 0.411 nm for the lattice
constant. The repulsive exponent n for this structure is 10.5.
18. How many kg-atoms of potassium iodide will be required to treat with 709.1 kg of chlorine to form KC1?
19. Suppose an atom A has an ionisation energy of 5 eV, and an atom B has an electron affinity of 4 eV.
Suppose the atoms A and B are 0.5 nm apart. What is the energy required to transfer an electron from
A to B?
*<1
Physics
SM®---------- ------ - of Na. and Cl- ions when thcy are 02 "m apan
20.
Calculate the potential energy ol the system a aK)nB,
How much energy is required ‘o fonn a K* and Cl glve„ mat the rmusata rattg)
21.
separation between a K an 1 ,g 3 $ ey?
„t K - 4 1 eV and the electron altmny equilibrium separation betw«,
\ b,riye energy of NaCI from the following da«= of Q . , 6( *
22. Calculate e co j,748, n=9, ionisation energy is 0.314 nm. calculate the cohesive
:eZ m is“77. Madeiung constant is 1.75 and nearest separano
(“X muchenergy required to formand Br ton par horn
25. The ionic radii 01 v_z$ anu

-xs S Calculate the density of CsCl. ,im;ne a repulsive potential of the form B/r to act
tt.;X the compress,bih,^^^
between nearest neighbours

constant is 1.7476.
CHAPTER 4
CRYSTAL PHYSICS
I. INTRODUCTION
A CQMal ts a solid cortijxêd uf akims or other mien iscupic particles ar ranged in an orderly repetitive array.
Thai is about the shortest definition rf a crystal. It may not be a complete definition, yet it is a true descrip-
tiOtL
The three general [ypes of solids — fima/phtfuw frfrt\xryâ!!iiif and wmlc crx.î!—are distinguished
by the size of ordered regions within the materials. Order in Amorphous solids is limited to a few molecular
distances In poly crystal tine materials, the solid is made-up of grams which are highly ordered cyMalime
regions of irregular size and orientation. Single crystals have long-range order Many important properties of
materials arc found to depend on the structure of crystals and on the electron states within the crystals. At the
beginning id the study of crystals il uas their external form which was related to the physical properties. In
this way only a limited success was achieved. Towards the middle of last century u deeper understanding
developed regarding the correlation of the structure of crystals and mechanical, thermal, electrical and mag
netic properties of solids. This is primarily due to the advances in ?he hand theory of electron states and in
the theory of bonding in solids This knowledge has led to the development of newer and better materials for
electrical, electronic and structural engineering, t he study of crystal physics aims to interpret the macro-
scopic properties in terms of properties of die microscopic particles of which the solid is composed. The
study of the geometric form and other physical properties of crystalline solids by using x-uys. electron
bcirm.s and neutron beams constitutes the science of cry stallography or crystal physics.
IL LATTICE POINTS AND SPACE LATTICE

The atomic arrangement m a crystal is called crystalstructures In perfect crystal, there is a regular arrange
ment of atoms. This periodicity in the arrangement generally varies in different directions. It is very conve
nient to imagine points in space about which Ihcsc atoms are located. Such points in space are called lattice
points and the totality ol such points forms a cryrta/ lattice or space lattice. If all the atoms at the lattice
points are identical. the lattice is called a Bravias lattice. Thus the three-dimensioisal space lattice may be
defined as a finite array of points m three-dimensions in which every point has identical environment as any
other point m the array.
Let us now consider the case of a two-dimensional array of points as shown in big 4 1 It is obvious
from the figure that environment about any two points is rhe same and hence it represents a jpace lattice.
This is explained as follows:
Let us now consider the case of a two-dimensional array of points as shown in Fig. 4.1.
obvious from the figure that environment about any two points is the same and hence it represents a
space lattice. This is explained as follows:
We choose any arbitrary point as origin and consider the position vectors rt and r2 of any tw0
lattice points by joining them to O as shown in Fig. 4.1. If the difference T of the two vectors rt and
satisfies the following relation:
T = a + n2 b
where, n. and n, are integers and a and b are fundamental translation vectors characteristic of the
array, then the array of points is a two-dimensional lattice.
fig- Two-dimensional array of points
For three-dimensional lattice:
T =. nâ + + n^c
Hence it should be remembered that a crystal lattice refers to the geometry of a set of points in
space whereas the structure of crystal refers to the actual ordering of its constituent ions, atoms, molecules
in the space.
For a lattice to represent a crystal structure^ we associate every lattice point with one or more atoms
(i.e., a unit assembly of atoms or molecules identical in composition) called the basis or the pattern.
When the basis is repeated with correct periodicity in all directions, it gives the actual crystal structure.
The crystal structure is real, while the lattice is imaginary. Thus,
Lattice + Basis = Crystal structure
Figure 4.2 shows the basis or pattern representing each lattice point. It is observed from the
figure that a basis consists of three different atoms. It can also be observed that the basis is identical in
Crystal Physics 89
O+ O
■
o« o
o■ o• o op o
O
o* o
Fig. 4 Ji Basts or pattern
IV. UNIT CELLS AND LATTICE PARAMETERS

The atomic order in crystalline solids indicates that the small groups of atoms form a repetitive pattern.
Thus, in describing crystal structures, it is often convenient to subdivide the structure into small repeat enti
ties called unit cells, i.c., in every crystal some fundamental grouping of particles is repeated. Such funda-
menial grouping of particles is called a un/f cell. Unit cells for most crystals are pa ral Ie topi ped or cubes
having three sets of parallel faces, A unit cell is chosen lo represent the symmetry of the crystal structure,
wherein all the atom positions in the crystal may be generated by translations of the unit cell through integral
distances along each of its edges. Thus, the unit cell is the basic structural unit or building block of the crys-
tai structure by virtue of its geometry and atomic positions within. Furthermore. mure than a single unit cell
may be chosen for a particular crystal structure; however. we generally use the unit cell having the highest
geometrical symmetry. Unit cells may also be regarded as the "building blocks' that make up the crystal,
each one indistinguishable from the next Fig. 43, shows a unit cell of a three-dimensional crystal lattice. A
space laities is a regular distribution of points m space, in such a manner that every point has identical
surroundings, The lattice is made-up of a repetition

of unit cells, and a unit cel) can be completely
described by the three vectors a,bX when the
length of the vectors and the angles between them
(ct, fl, y) arc specified. Taking any lattice point as
the origin, alt other points on the lattice can be
obtained by a repeated operation of the lattice vec
tors a, btc. These lattice vectors and the above said
mierfacial angles constitute the lattice parameters
of the unit cell, ft is thus obvious that if the values
of these intercepts and in ter facial angles are
known, we can easily determine the farm and
actual size of the unit Cell
Fig. 4 3 Lattice parameters of a unit cell.
The vectors a, b and c may or may not be equal. Also, the angles a, P and y may or may n
right-angles. Based on these conditions, there are seven different crystal systems. Thus in a cubic syst
a = b = c and a = p = y = 90°. If atoms are existing only at the comers of the unit cells, the seven cry
systems will yield seven types of lattices. More space lattices can be constructed by placing ato
(or particles) at the body centres of unit cells or at the centres of the faces. Bravais showed that the total
number of different space lattice types (obeying the condition that every point has identical surroundin
is only fourteen. Hence the term "Bravais Lattice."
In the literature, reference to unit cells and primitive cells are often made. Primitive cell may be defined
as a geometrical shape which when repeated indefinitely in three dimensions will fill all space and is the
equivalent of one lattice point, i.e., the unit cell that contains one lattice point only at the comers is
known as primitive cell. The unit cell differs from the primitive cell is that it is not restricted to being the
equivalent of one lattice point. In some cases, the two coincide. Thus, unit cells may be primitive cells
but all the primitive cells need not be unit cells. ^
There are thirty-two classes of crystal systems based on the geometrical considerations (i.e., symmetry
and internal structure). But, it is a common practice to divide all the crystal systems into seven groups
or basic systems These seven basic crystal systems are distinguished from one another by the angles
between the three axes and the intercepts of the faces along them. The basic crystal systems ate:
• Cubic (isometric) . ”
• Tetragonal . •
• Orthorhombic
• Monoclinic
• Triclinic
• Trigonal (rhombohedral) ’ . • .
• Hexagonal.
We shall now discuss all the above-mentioned seven types of the basic crystals systems one by
one.
(i) Cubic Crystal System
a = b = c, a = p = y = 90°
The crystal axes are perpendicular to one another, and the repetitive interval is the same
along all the three axes. Cubic lattices may be simple, body-centred or face-centred.
crystal system
CHAPTER 4
(w) Trigonal crystal system
(yii) Hexagonal crystal system
(ii) Tetragonal Crystal System
a = b * c, a = p = y = 90°
The crystal axes are perpendicular to one another. The repetitive intervals along two axes are the
same, but the interval along the third axis is different. Tetragonal lattices may be simple or body-
centred.
(iii) Orthorhombic Crystal System
a* h * c, a = fJ = y = 90°
The crystal axes are perpendicular to one another, but the repetitive intervals are different
all the three axes. Orthorhombic lattices may be simple, base-centred, body-centred or
centred.
(tv) Monoclinic Crystal System

a*b*c, a = p = 90° # y
Two of the crystal axes are perpendicular to each other, but the third is obliquely inclined Th?
repetitive intervals are different along all the three axes. Monoclinic lattices may be simple <■<
base-centred.
(v) THefiiuc Crystal System
a* b * c, a p y 90°
None of the crystal axes is perpendicular to any of the others, and the repetitive intends ae
different along all the three axes.
(n) Trigonal (Sometimes Called Rhombohedral) Crystal System
a = b = c, a = p = y * 90°
The three axes are equal in length and are equally inclined to each other at an angle otter tfai
90°.
(m) Hexagonal Crystal System
a = b*c, a= p = 90°,y = 120°
Two of the crystal axes are 60° apart while the third is perpendicular to both of item The
repetitive intervals are the same along the axes that are 60° apart, but the interval along the dmd
axis is different The seven systems and their properties are given in Table 4.1.
The definite ordered arrangement of the faces and edges of a crystal is known as crystal symmetry. A
sense of symmetry is a powerful tool for the study of the internal structure of crystals. It is a simplifying
key to the endless various arrays of atoms which make-up crystalline solids, enabling us to thmk of
them in terms of a familiar pattern.
Crystals possess different symmetries or symmetry elements. They are described by certain
operations. A symmetry operation is one that leaves the crystal and its environment invariant
Symmetry operations performed about a point or a line are called point group symmetry operatitms
and symmetry operation performed by translations as well as rotation are called space group symmetry
operations. Crystals exhibit both types of symmetries independently and in compatible combinations.
A symmetry operation is a transformation performed on the body which leaves it unchanged or invariant
Table 4.1 Seven basis crystal systems with their characteristics
SLNo. Crystal, system Axial lengths of unit cell (a, b and c) ' Interaxial angles (a, fiandf) Examples
1. Cubic a=b=c a=p = y=90o Au, Cu, NaCl

, »
2. Tetragonal ' »
a=b c 1
a=p = Y=90° ■nO2, SnO2, NiSO4
3. Orthorhombic a b c a=p = Y=90° KNO3, BaSO4, PbCO3
4. Monoclinic atbtc a=P = 90°*Y CaSO4 - 2HjO (Gypsum), FeSO4,
r l Na^
5. Triclinic at b # c a*p*Y*90° K2Cr2O7, CuSO4 5H2O
1
6. Trigonal a=b=c a= p = y* 90° As, Sb, Bi, Calcite

7. Hexagonal a = b*c a= P = 90° and y= 120° SiO2, Zn, Mg, Cd
CHAPTER 4
VfMMbiwtiMBKt
C ...■j.*...,___________________
That is. after performing an operation o„.»«. twlv' if element becomes indistinguishable
the bodycorresponding from
to that particular iu
o^ .
configuration, the body is wd to possess tftrv elements exhibited by crystals:

The following are the different point group symmetry elemen
• Cmfrr of symmetry or inversion centre.
• Reflection symmetry.
• Rotation symmetry.
One of the most noticeable features of many crystals, as we have already seen, is a certain regularity in
the arrangement of faces. The next regular feature we must notice is the frequent occurrence
of similar
faces (of the same size and shape) in parallel pairs on opposite sides of the crystal.
A cube possesses three such pairs of parallel and opposite faces
(all of them of the same size and shape). Hence a cube is said to show
a centre of symmetry, i.e., the body centre of the cube is a centre of

symmetry. This centre lies at equal distances from various symmetrical
positions. Centre of symmetry is also known as inversion centre.
A crystal will possess an inversion centre if for every lattice
point given by the position vector 7, there will be a corresponding
lattice point at the position - r. Fig. 4.4 Centre of inversion

in a cubic crystal
Thus, inversion is a symmetry operation in a crystal equivalent
to reflection through a point This is shown in Fig. 4.4.
The second kind of symmetry element in a crystal is a plane of symmetry or reflection symmetry.
A crystal is said to possess reflection symmetry about a plane if it is left unchanged in every way after
being reflected by the plane. Highly regular crystals may be bilaterally symmetrical about several planes
cutting them in different directions. They may have several planes of symmetry. There is one important
characteristic, however, about a crystallographic plane of sy Hill etry which differentiates it from our
ordinary conception of a plane of geometrical symmetry; that not only must the plane be such that it
divides the crystal into two equal portions, but these two portions must be so situated that they arc
minor images of each other with respect to the plane. The two sy ni l I etry elements, namely, centre of
inversion and plane of reflection, may easily be understood by saying that inversion is a symmetry
operation similar to reflection, with the only difference that reflection occurs in a plane through the
lattice point, while inversion is equivalent to reflection through a point. The three straight planes of
symmetry in a cube are shown in Fig. 4.5 and the six diagonal planes of symmetry in a cube are shown
in Fig. 4.6.
The next kind of symmetry element is the symmetry about a line, known as axis of symmetry or
rotation axis.
Fig. 4.S The three planes of symmetry parallel to the faces of the cube
A body is said to possess rotational symmetry about an axis if after rotation of the body about
this axis by some angle 0n, the body appears as it did prior to rotation, i.e., the body is left invariant as
a result of rotation.
The axis of symmetry may thus be defined as a line such that the crystal assumes a congruent
360 . The value of n decides the fold of the axis. Only one-, two-,
position for every rotation of
n
three-, four- and six-fold rotation axes of symmetry alone are possible in a single crystal lattice.
Rg. 4.6 The six diagonal planes of symmetry in a cube

If a cube is rotated about a line perpendicular to one of its faces at its midpoint, it will turn into
a congruent position every 90° (indistinguishable from the position it occupied originally), four times
during a complete revolution; the normal is thus an axis of four-fold symmetry, a tetrad axis, and a cube
clearly possesses three such axes, one normal to each of the three pairs of parallel faces. The three tetrad
axes of a cube are shown in Fig. 4.7.

Let the cube be now rotated about a solid diagonal (body diagonal) through 120° to get congruence,
and such a line, of which there are four, is therefore a triad axis. One of the triad axes in a cube is shown
Rg. 4.8 One of the triad axes of the cube Fig. 4.9 One of the diad axes of the cube
Finally, a line joining the mid points of a pair of opposite parallel edges proves to be a diad axis,
and there are six such axes present in a cube. One is shown in Fig. 4.9.
The total number of crystallographic symmetry elements of the cubic system are thus given by
- centre of symmetry
- straight planes
- diagonal planes
9 planes
6
- tetrad axes 3
- triad axes 13 axes
- diad axes 6
IX. TO SHOW THAT FIVEFOLD*ROTATION AXIS IS NC

COMPATIBLE WITH A LATTICE
Consider a lattice row XPQY as shown in Fig. 4.10. Let the lattice translation be ‘a’ and the lattice have
n-foid rotation axis of symmetry. Let us rotate the vectors PX and QY through an angle 0 = (360/n)° in
the clockwise and anti-clockwise directions respectively. The tips of the vectors P, and & in the new
positions must e attice points if the lattice were to possess n-fold rotation axis of symmetry.
II III As per the
definition, rotation operation must leave the lattice invariant. Clearly, PlQl must be parallel to PQ and
must be equal to an integral multiple of the lattice
translation ‘a’ ; P1Ql = ma where m is an integer.
PR
Thus, cos 6 = -r—
n PPX
CHAPTER 4
PjP = PPjCos 0* = a cos <|)n
Similarly, SQ1 = a cos <j)n
Therefore = P{R + SQ1 + RS

Fig. 4.10 The possible rotation axes in a single
Now
Thus, 1+2 cos 4>n= m
2 cos <J>n = [m- 1] = N; where, N is an integer
COS 6 = — ~ —
2' JI = 2 (4.1)
Table 4.2 Absence of five-fold rotation axis

r %
r • i a ' -
f 360Y
■ • i'
N
N Possible fold of axis, n = Un J
2
-2 -1 -1 180° 2
-1 -1/2 —1/2 120° 3
0 0 0 90° 4 .
+1 +1/2 +1/2 60° 6
+2 "Fl +1 360° 1
M Saud'Swi Physic
The possible values of A can be obtained such that cos lies between +1 and -1. This gives t.
values of <J>h which decides the permitted values of n, the fold of the rotation axis. e
The different symmetry elements (centre of inversion, reflection and rotation) can also be combined if
they are compatible. The different combinations give rise to different symmetry points in the crystal ft
must be noted that all the crystals do not possess all the symmetries enumerated above. The different
crystal systems exhibit different symmetries. It is found that there are 32 compatible combinations of
the above three point group-symmetry elements, called simply point groups. Crystals belonging to different
crystal systems can be classified on the basis of point groups.
A crystal structure is said to possess a rotation-inversion axis if it is brought into self-coincidence by

rotation followed by an inversion about a lattice point through which the rotation axis possess. See
Let us now consider an axis normal to the circle passing

through the centre, operating on a pole 1 to rotate it through
90° to the position 4, followed by inversion to the position 2;
• this compound operation is then repeated until the original
position is again reached. Thus from position 2 the pole is
rotated a further 90° and inverted to position 3; rotated a further.
90° and inverted to position 4; rotated a further 90° and inverted
to resume position 1. Crystals can possess 1-, 2-, 3-, 4- and 6-
_ _ _ _ ~ . Fig. 4.11 Stereogram to show the operation
fold rotation-inversion axes, represented by 1,2, 3, 4 and 6. of 4,foid roto-inversion axis
^?ÎMNSI>TlOrr^YMWTR^TrrrM|.|M|i. i.1.1 ................................................... .
The translation symmetry elements exhibited by crystals are Glide Plane and Screw Axis.
(i) Glide Plane
When a mirror plane is combined with a simultaneous translation operation in a crystal, one gets
a glide plane. The glide plane in crystal is always parallel to the mirror plane. The different glide planes,
their symbols and their translations parallel to the different axes and planes are listed in Table 4.3..
Cryjtof Physics 99
axes possible in crystal lattices are shown in perspective in

Fig, 4.13.
XIII. SPACE GROUPS
In a cryslat point group symmetry operations can also be

combined with translation symmetry elements. provided J hey
are compatible. Such combinations are called space groups.
There are 230 space groups exhibited by crystals, The study of
symmetry elements of the different crystals enables one to
classify the crystals and their properties bused on different
symmetries-
XIV. THE BRAVAIS SPACE LATTICES
There are number of ways in which an actual crystal may be

built up and atoms piled together resulting in a great many
crystal structures. But each of the structures consists of some
fundamental pattern repeated al each point of a space lattice.
Fig, 4x12 Screw axis. The scheme of repetitions of a space lattice are very limited
in number; while the possible crystal structures are almost unlimited. But it was shown by Bravais in 1848
that there are only 14 different arrays or networks of lattice in which points can be arranged tn space so that
each point has identical surroundings. These are known as Bravais space lattices.
To specify a given arrangement of points in a space lattice of atoms in a structure, a set of coordinate
axes with an origin at one of the lattice points is chosen. Cubic crystals, for example, arc referred to a cubic
set of axes; he . three axes of equal length that stand perpendicular to one another and form the three edges
of the cube. The seven different systems used in crystallography possess certain characteristics like equality
of angles and equality of lengths. These seven crystallographic axes generate the 14 space lattices Most of
the common metals and some important alkali hahdes have cubic structures. In cubic crystals, atoms arc
packed in a cubic pattern with three different types of repetition; simple cubic (sc), body centred cubic (bcc)
and face centred cubic (fee)* The 14 space lattices are shown in Fig. 4.15. Table 4.D gives the seven crystal
systems and the fourteen lattices
XV. METALLIC CRYSTAL STRUCTURES

Since atomic bonding in this group of materials is metallic, within the hard sphere model for the representa
tion of a crystal structure* each sphere represents art ion core. Three relatively simple crystal structures are
found for most nF the common metals; body centred cubic face centred cubic and Aewg<ww/ dose packed.
An important characteristic of roost of the metals is that they are crystalline, i.c„ the atoms are arranged in
some regular repeatable pattern indefinitely in space
(if Simple cubic structure (sc)
The simplest and easiest structure to describe is the simple cubic crystal structure. Fig, 4J6 shows the
unit cell of a simple cubic structure* In a simple cubic lattice, there is one lattice point at each of the eight
corners of the unit cell . If we take an atom at one comer as the centre, it is observed that this atom is sur
rounded by six equidistant nearest neighbours and hence ihe t ‘uwdi nation number of a simple cubic lattice is
six. In this structure, each corner atom is shared by eight unit cells. Hence the share of each corner atom to a
Inble 4.3 Possible glide planes
Types of glide Symbol

Translation component (T)
Axial glide a a/2
Axial glide b b/2
Axial glide c c/2
*
Diagonal glide n (a b\ (b c\ nr (c a\
U 2) U 2J U 2)
Diamond glide d - + b\ (b —c} orf—c + —a A

(a
\4 4/ 14 4> V4
(ii) Screw Axis

Just as it is possible to combine a proper rotation with an
inversion to produce a hybrid roto-inversion axis, it is possible to
combine a proper rotation with a translation parallel to the rotation
axis, i.e., rotation axis coupled with a translation parallel to the
rotation axis will give rise to a new symmetry element called the
screw axis. This operation is shown in Fig. 4.12.
A screw axis is usually represented by the symbol ‘n *. This •
• ~2n‘ f/l
is performed by a rotation of — and translation of — times the
n n
translation vector parallel to the rotation axis. For example, the screw
axis 42 is performed as follows:
Rotate the point through 90° about the symmetry axis and
2 1
translate the point by — = — times the translation vector parallel to
the rotation axis. Apply the operation successively until the cycle is ■
complete. The eleven screw axes possible in crystal lattices are shown Fig. 4.12 Screw axis
in perspective in Fig. 4.12.
In a crystal, point group symmetry operations can also be combined with translation symmetry elements,
provided they are compatible. Such combinations are called space groups. There are 230 space groups
exhibited by crystals. The study of symmetry elements of the different crystals enables one to classify
the crystals and their properties based on different symmetries.
CHAPTER 4
Fig. 4.13 Picture of the eleven possible screw axes
cell is one. Thus sc is a primitive cell. In this structure the atoms touch each other along the edges.
Hence the nearest neighbour distance is 2r = a. We note the following features in an sc structure:
Coordination number, N = 6
Nearest neighbour distance, 2r = a
Lattice constant, a = 2r
Number of atoms per unit cell, n = — x 8 = 1

Table 4.4 The seven crystal systems and the fourteen Bravais lattices
System Space lattices or Lattice Nature of unit cell [Axial

Number of lattices
Sl.No. . in the system Bravais lattices symbol length and interaxial angles]
1. Cubic 3 1. Simple p a=b=c

- 2. Body centred a = p = y=90°
■
3. Face centred F
1
2. Tetragonal 2 1. Simple p a=b#c

- 2. Body centred I a = p = y = 90°
3. Orthorhombic 4 1. Simple p atbtc
t
2. Base centred c a = p = y=90°
•
3. Body centred I
4. Face centred F
4. Monoclinic 2 1. Simple P a b*c
2. Base centred C a= P = 90°*y
5. Triclinic 1 1. Simple P a b£c
a* P*y* 90°
6. Trigonal 1 1. Simple P a-b=c
a = p = Y*90°
7. Hexagonal 1 1. Simple P a=b*c
a = P = 90° and y = 120°
Fig. 4.14 Network of space lattice
CHAPTER 4
Fig. 4.15 (Contd.)

Soufrtrxrc Pwwa
Monoclinic
a#b#c
a = P = 90°*y
Base-centred
Simple
120°
Triclinic Trigonal
a=b=c Hexagonal
a*b*c a = b*c
a*P*y a = p = y*90°
a=P = 90°
y = 120°
Base-centred
Orthorhombic
.a#b&c
a = p = y = 90°
Body-centred Face-centred
Fig. 4.15 The fourteen space lattices and the seven crystal systems
Number of lattice points = 1
Volume of all the atoms in a unit cell, v = 1 x —nr3

3
Volume of unit cell, V = a3 = Qfj3
Fig. 4.16 Simple cubic structure
Hence the packing factor or density ofpacking of this structure is:
4 nr3 '
3 a3
•T41 (nr3)?it .
. i PF = - = - = 0.52 or 52%
.l3J 8r3 6 ■
CHAPTER 4
Only one element polonium at a certain temperature region exhibits this structure; sc structure is
a loosely packed structure.
Some important crystal structure terms are defined below:
Coordination number (N): The coordination number is defined as the number of equidistant
nearest neighbours that an atom has in the given structure. Greater is the coordination number, the more
closely packed up will be the structure.
Nearest neighbour distance (2r): The distance between the centres of two nearest neighbouring
atoms is called nearest neighbour distance. It will be 2r if r is the radius of the atom.
Atomic radius (r): Atomic radius is defined as half the distance between nearest neighbours in a
crystalline solid without impurity.
Atomic packing factor. The fraction of the space occupied by atoms in a unit cell is known as
atomic packing factor (APFf, or simply packing factor; i.e„ it is the ratio of the volume of the atoms
occupying the unit cell to the volume of the unit cell relating to that structure.
(ii) Body Centred Cubic (bcc) Structure
Elements that exhibit this structure are Li, Na, K and Cr. In this structure, in a unit cell, there are
8 atoms at the eight comers and another atom at the body centre. As the body centre is contained
pHVS,cs _—-------------~ Ut the number of atoms per
K-———. rt hv any surrounding uni
entirety .tthm -ceil - is not share eaeh but each
. 1 *0x1=: 2. The corner a e coordination number of this

ceil in a bcc suture ,s V ♦ Hence. the
tenches the hod, centre atom aiong the
structure is 8.
■r ■£»-
The calculation of the lattice constant can be made with the help of Fig. 4.17.
(AC)2 = a2 + a2 = 2a2
(FC)2 = (AC)2 + (AF)2
(FC)2 = 2a2 + a2 = 3a2 .
(4r)2 = 3a2
<4r>2
4r _ avj
: a = —;= or 2r = -—
............................. ' V3 2 .
We shall now calculate the packing factor from the following data:
a
/
Nearest neighbour distance, 2r =
. 4r
Lattice constant, a = —f=
y/3 J ■ • •
Number of atoms per unit cell, n = -^x8 + l= 2

o
of all the atoms in a unit cell, v 2x

Volume
64r3
3 -—
Volume of unit cell, v - a - $ x
V
Therefore, atomic packing factor,
v 8 7tr3373
APF = — =------------ 5—
V 3 64r3
— ='0.68 or 68%
o
bcc structure is a closely packed structure.
Closest packing: In metallic crystals in which all the atoms are identical, there are two forms of
closest packing: face centred cubic (fee) and hexagonal close packed (hep).
fig. 4.18 Closest packing of spheres in two dimensions and in three dimensions
CHAPTER 4
A closest packing is a way of arranging equi-dimensional objects in space so that the available
space is filled more efficiently. Such an arrangement is achieved when each object is in contact with the
maximum number of like' objects.
*
(iii) Face Centred Cubic (fee) Structure
In the case of fee lattice, there are eight atoms at the eight comers of the unit cell and six atoms
at the centres of six faces. Considering the atom at the face centre as origin, it can be observed that this
fare is common to two unit cells and there are twelve points surrounding it situated at a distance equal
to half the face diagonal of the unit cell. Thus, the coordination number of fee lattice is twelve. The
atoms touch each other along the face diagonal. Each comer atom is shared by 8 surrounding unit cells
and each of the face centred atom is shared by 2 surrounding unit cells. Thus the total number of atoms
in fee structure is 4. We thus note in fee structure that:
4r
Lattice constant, a = —<==
V2
Nearest neighbour distance, 2r = ——
Number of atoms per unit cell, n — 4

Fig. 4.19 Face centred cubic structure
Volume of all the atoms in a unit cell, v = 4 x ~nri
64r3
Volume of unit cell, V = a3 =
2V2
Atomic packing factor of fee structure is thus calculated:
APF = v/V
Copper, aluminium, lead and silver have this structure.
(iv) Hexagonal Close Packed (hep) Structure
The specific hexagonal structure formed by magnesium is

shown in Fig. 4.20. The unit cell contains one atom at each comer,:
one atom each at the centre of the hexagonal faces and three more
atoms within the body of the cell. Each atom touches three atoms in
the layer below its plane, six atoms in its own plane, and three atoms
in the layer above. Hence the coordination number of this structure
is 12.. Further the atoms touch each other along the edge of the Fig. 4.20 Ideal hexagonal close
packed structure
hexagon. Thus, a = 2r.
The top layer contains seven atoms. Each comer atom is shared by 6 surrounding hexagon cells
and the centre atom is shared by 2 surrounding cells. The three atoms within the body of the cell are
fully contributing to the cell.
3 3
Thus the total number of atoms in a unit cell is - + - + 3 « 6.
2 2
Calculation of ratio for an ideal hexagonal clone packed structure: Let ‘c* be the height of
the unit cell and ‘a’ be its edge. The three body atoms lie in a horizontal plane at c/2 from the orthocentres
of alternate equilateral triangles at the top or base of the hexagonal cell. These three atoms just rest on
the three atoms at the corners of the triangles.
In the triangle ABY,
AY
cos 30° = —
AB
AY = a cos 30° = ~ and

2
(AZ)2 = (AY)2 + (ZY)2 (4.2)
In triangle AXZ,
Fig. 4.20 (A) Pottom layer of hep structure
But, AX = —AY = — = —f=

3 3 2 y/3
Substituting this in equation (4.2):
CHAPTER 4
Volume of the unit cell:
Area of the base = Six times the area of the triangle AOB
Area of the triangle, AOB = ^(BO) (AY)

£
Thus, area of the base = 6 x
3 -
Volume of the cell, V = ~ V3 “ c
Calculation ofpacking factor of hep:
Lattice constant, a = 2r
Nearest neighbour distance, 2r - a
Number of atoms per unit cell, n = 6

4
Volume of all the atoms in a unit cell, v = 6 x $ nr
Volume of unit cell, V = — 73 a(i)

2c with da -
Packing factor, (APF) = v/V
Magnesium, zinc, and cadmium crystallise in this structure. The packing factor of fee and hep
are 74% and hence they are known as closest packing structures.
*3Rri. RELATION BETWEEN THE DENSITY OF CRYSTAL MATERIAL AN tT

LATTICE CONSTANT IN A CUBIC LATTICE___ ....___ _
Consider a cubic crystal of lattice constant a. Let the number of atoms per unit cell be n and p be the
density of the crystal material. The atomic weight of the material is MA. Let NA be the Avogadro’s
number. Thus —3 of the material will contain NA atoms. Hence n atoms in a unit cell will occupy
m
â”
a volume
Pâ
Thus, (4.3)
(i) Diamond Cubic Structure

The diamond lattice can be considered to be formed by interpenetrating two fee lattices along the body
diagonal by (l/4)th cube edge. One sublattice has its origin at the point (0,0,0) and the other at a point
quarter of the way along the body diagonal (at the point a/4, a/4, a/4). The basic diamond lattice and the
atomic positions in the cubic cell of diamond projected on a cube face are shown in Fig. 4.21. The
fractions denote height about the base in units of cube edge. The point at 0 and 1/2 dre on the fee lattice,
those at 1/4 and 3/4 are on a similar lattice displaced among the body diagonals by 1/4 of the cube edge-
The packing factor of this structure is thus calculated as follows:
2 1
(AT)2 = - a
8
2 < = 3n2
(XZ)2 = (XT)2 + (KZ)2 =
o 16 " 16
CHAPTER 4
Fig. 4.21 Diamond structure
But, - - XZ = 2r . ...
Therefore,
. >/3a
(or) the nearest neighbour distance, 2r = ——-
8r ••
Lattice constant, a = —/= .
■ 32 nr33>/3 nj3 „
j. Packing factor = v/.V> ; “T - •# — — =-—r- “ 0.34 or 34%
3 (8r)3 16
Thus it is a loosely packed structure. Carbon, silicon and germanium crystallise in this structure.
(ii) Cubic Zinc Sulphide or Zinc Blende Structure
Zinc blende structure is almost identical to the diamond structure except that the two
interpenetrating fee sublattices are of different atoms and displaced from each other by one-quarter of
the body diagonal.
Crystal Physics 111
The cubic zinc sulphide structure results when

zinc atoms arc placed on one fee lattice and S atoms on
the other foe lattice as shown tn Fig. 4 22. The conven*
uoiui cell of this structure is a cube There are four
molecules per conventional cell. For each atom, there
are four equally distant atoms of opposite kind
arranged at a regular tetrahedron The compounds
which have cubic xinc sulphide structure are CuCl,
ZhS, faSb and Cd$,
(Hi) Sodium chloride structure
In sodium chloride, sodium loses its outer electron and

acquires an excess of positive charge while the chlorine Fig 4.22 Zinc blende structure.
atom accepts one electron from sodium and becomes a negative ion. Now, due to the electrostatic farces
between the excess charges, the two ions attract each . Further, due to the strong forces of repulsion as
their outer electron shells come into close proximity, the two ions cannot approach each other to within less
than certain distance- When attraction and repulsion balance, equilibrium is obtained. The Bravais lattice is
a face centred cube, with a basis of one Na ion and one Cl ton separated by one-half the body diagonal of the
unit cell There are four molecules of NaCI in a unit cell* with ions in the positions:
„Na: «0 0J ; 0*0; lrt „0

rtlrt ^0
W iM **■ 4B? HW
Cl: 0“«^2»r<>22
fa this stnjcture. each ion is surrounded by six nearest neighbours of the opposite kind. The coordination
number is therefore six. There are twelve next nearest neighbours of the same kind as the reference ion.
Representative crystals having NaCI structure are KC1. KBr. MgO, AgBn etc. See Fig, 4,23.
(tv) Caesium chloride structure

CsCl structure is shown in Fig. 4.24.
The space lattice is simple cubic. The basis has one Cs* ion at 0 0 0 and one CT ion at Hath ion is
at the centre of a cube of ions of the opposite kind, the coordination number is thus eight. Obviously, the
lattice points of CsCl are two interpenetrating simple cubic lattices, the comer of one sub-lattice is the body
centre of the other. One subdattice is occupied by Cs* tons and rhe other by CT ions. CsClt RbCI and LiHg
are name materials crystallizing m this structure. Table 4.E gives the properties of de, sc, bee. fee and hep
structures.
XVHL DIRECTIONS, PLANES ANO MILLER INDICES

In a crystal there exists directions and planes which contain a large concentration of atoms. It IS necessary to
locate these directions and planes far crystal analysis. In Fig, 4.25, two directions are shown by arrows in
two-dimensions. These directions pass through the origin 0 and end at A and B respectively. The directions
CHAPTER 4
Table 4.5 Comparison of cell properties of some crystal structures
■ \
Face centred Hexagonal close
Diamond cube Simple cube Body centred
cube cube (fee) packed structure
Sl.No. Properties ' (de) (sc)
(bcc) (hep)
n
uSl
a
a3 a3 a3 a3
1. Volume of unit cell
N) I
2. Number of atoms per unit cell 8 ' 1 2 4 6
8 1 2 4 4
3. Number of atoms per unit volume 73 a2c
r a3
4. Number of nearest neighbours 4 ' 6 , . 8 12 12

(coordination number)
aj3_
to]
a73
5. Nearest neighbour distance (2r) a a
to
4 2
a
|cn
a ajl a
6. Atomic radius
? 00
2 4 4 2
•
/ 7. Atomic packing factor — = 0.34 % = 0.52 —. = 0.68
16 6 — = 0.74 — = 0.74
8 6 6
8. Examples Germanium, Polonium
• 1 Sodium, Lithium Aluminium, Magnesium,
Silicon and Chromium Copper, Silver Zinc and
and Carbon and Lead Cadmium
-phe directions are described by giving the coordinates of the first whole numbered point (x, y) through
which each of the directions passes. For direction OA, it is (1, 1) and for OB it is (3, 1). In three-
dimensions, the directions are described by the coordinates of the first whole numbered point (x, y, z).
Generally, square brackets are used to indicate a direction. A few directions are shown below:
Fig. 4.2S Crystal directions
OA [1 1 0]
OB [0 1 0]
OC [1 1 1]
CHAPTER 4
OD [1 0 2]
OE[112]
The crystal lattice may be regarded as made-up of an

aggregate of a set of parallel equidistant planes, passing
through the lattice points, which are known as lattice planes.
For a given lattice, the lattice planes can be chosen in different
ways as shown in Fig. 4.26. The problem is that how to
designate these planes in a crystal. Miller evolved a method
to designate a set of parallel planes in a crystal by three
numbers (hk I) known as Miller indices.
The steps in the determination of Miller indices of a 426 DifFerent ^stal Pla"«
set of parallel planes are illustrated with the aid of Fig. 4.27.
(0 Determine the coordinates of the intercepts made by the plane along the three crystallographic
axes (x, y, z).
x y z
2a 3b - c
pa qb rc (p-2,q-3 andr = 1)
Table 4. F Crystal structures and selected properties of representative dements
Lattice constant Melting point

Eiemrnr SymM Atomic wcigAl Cryrta/ 2/rur/k/-^ (20’C)(nm) (nrt) V
Aluminium Al 26,97 2.70 fee 0.40*9 0,1428 660 2
Cadmium Cd i 12.41 8.65 hep a =0.2979 0.1489 320.9

c = 0.5617
Carbon (2 12.01 2.22 de 0.3564 0.0770 3700
Chromium Cr 52 01 1A9 bcc 07885 0.1249 1890
Copper Cu 63.54 896 fee 0.3615 04278 1083
Germanium Ge 72,59 536 de 0,5658 01224 937

Iron (a) Fc 55,85 7 87 bee 0.2866 01238 1539
Lead Pb 207.21 11,34 fee 04949 01750 327
Magnesium Mg 2432 1 74 hep a - 0.3209 01594 650

c« 0.5210
Potassium K 39,10 086 bee 0 5339 0 2312 63.7
Silicon SI 28.09 2 34 de 0 5428 0.1 !76 1430
Silver Ag 107.88 10-49 fee 04086 04444 9605
Sodium Na 22.99 0,97 bee 0.4281 OJ857 97.8

Zinc Zn 65.38 7,13 hep a » 0.2664 0J332 419,5
c = 0,4945
C rystal Physics
115
Table 4.7 Crystal structures of representative compounds
■'"u 1 ..........
Density (kg/nr) Lattice constant
; ' Compound Symbol Molecular weight Crystal structure
1 A
(2D°C) (nm)
A/'* ’• V-'..
1 v . i. :
Zinc sulphide ZnS 97.43 4.1 Zinc blende 0.541
Cadmium sulphide CdS 144.416 4.6 Zinc blende 0.582
Silver iodide Agl 334.79 5.7 Zinc blende 0.647
Sodium chloride NaCl 58.44 2.18 Sodium chloride 0.563
Lithium hydride LiH 7.947 2.5 Sodium chloride 0.408
Potassium bromide KBr 119.011 2.7 J Sodium chloride 0.659
Silver bromide AgBr 187.779 6.5 Sodium chloride

« 0.577
168.362 4.0 Caesium chloride 0.411 PX

Caesium chloride CsCl •
Ammonium chloride nh4ci 53.497 1.5 Caesium chloride 0.387
CHAPTER 4
i
b 26\3b 4b
X
Rg. 4.27 Miller indices of planes
(o) the intercepts as multiples of the unit cell dimensions, or lattice parameters along the ■
2a 3b
a b
2
!Kv*-
(iii) Otemme die reciprocals of these numbers:
2 3 1 !
(tv) Reduce these reciprocals to the smallest set of integral numbers and enclose them in brackets: !
r r ~ 3
<>x- 6x- 6x
s- (3 2..... 6)
In general it is denoted by (h k I). We also notice that:
h:k:l
Thus, Milter indices may be defined as the reciprocals of the intercepts made by the plane on the
crystallographic axes when reduced to smallest numbers.
(i) All the parallel equidistant planes have the same Miller indices. Thus the Miller indices
define a set of parallel planes.
(iz) A plane parallel to one of the coordinate axes has an intercept of infinity.
(zzz) If the Miller indices of two planes have the same ratio, i.e., (8 4 4) and (4 2 2) or (21 1), then
the planes are parallel to each other.
(iv) If (A k I) are the Miller indices of a plane, then the plane cuts the axes into h, k and I equal
segments respectively.
In Fig. 4.28 (a), the plane cuts the T-axis at a, X-axis at <» and Z-axis at Therefore, the coordinates of
the intercepts of the plane are <», a and That is, <», 1 andare the intercepts as the multiples of the
unit cell dimensions. Take the reciprocals; They are —, 1 and —, (or) 0,1 and 0. Hence (0 1 0) are the
OO OO
Miller indices of the plane and, (0 1 0) plane is perpendicular to [0 1 0] direction, (1 1 0) and (1 1 1)
planes are shown in Fig. 4.28 (b) and in Fig. 4.28 (c). We see also [110] and [111] directions
respectively. ■
CHAPTER 4
Fit 4.28 Planes and directions in a cubic crystal

Crystal Physics 119
XXL DISTRIBUTION OF ATOMS IN THE ATOMIC PLANES OF A

SIMPLE CUBIC CRYSTAL
fi) (0 10) Plane
Let n be ihe hitice constant in millimetre and r be the radius of the atom in millimetre.
a7 sq.mm contains 1 atom
, 1 1
1 sq.mm contains —: =—; atoms
a1 4rz
(ii) (I I 0) Plane
Atoms per sq mm is
fW) (1 1 1) Plane
Are? of the plane is —2 and number of atoms - - x 3 » ~
Atoms per sq mm is U2
XXII. SEPARATION BETWEEN LATTICE PLANES IN A CUBIC CRYSTAL

The cube edge is Let (A k 0 be the Miller indices of the plane ABC. This plane belongs 10 a family of
planes whose Miller indices are (/t k 0 because Miller indices represent a set of planes. Lei ON = be the
perpendicular distance of the plane ABC from the origin* Let a\ 0' and y ' (different from the interfacial
angles a, 0 and y) be the angles between coordinates axes Xt ¥, Z respectively and ON.
The intercepts of the plane on the three axe are:
CM - 7, OB = 7 and OC - 7 (4,4)
h k I
From Fig. 430 (aL we haver
cOSa' = ™;,C<«P' = -±andcoSV' = ^ (4.5)
From Fig* 4.30 (b):
{ON? = x* + y* + zl
d;»(rf,J(cosJ a') + cocos’ P') + rf*(cos: y' )|
C opy ri g hi ed r n ateri a I
(a) (0 1 0) plane (b) (1 1 0) plane
CHAPTER 4
(ON)2 = d2 - [ J2 (cos2 a') + J2 (cos2 p') + J2 (cos2 y ')]1/2
Jj = df [cos2 a' + cos2 p' + cos2 y]iy2
Thus,
cos2 a' + cos2 0' + cos2 y' = 1 (z
Substituting the value of cos a', cos 0', cos y' from equation (4.5) to equation (4.6) we get:
r j q2
“i
OB I*.
OC ■■
^(/i2+#+12) = i
(4.7)
1 Jh2+k2+i2
Let OM = d2 be the perpendicular distance of the next plane PQR parallel to the first plane ABC.
The intercepts of this plane on the three crystallographic axes are:
OA' = —, OB' = — and OC = —

h . k I
and
cos a'=cos 0'=cos y'=(4.8)

OA' OB' 1 OC' 7
(OM)2 = [dfcos2 a' + d?cos2 0' + J2cos2 y"]
= d% [cos2 ct' + cos2 0' + cos2 y']
i.e., cos2 a' + cos2 0' + cos2 y' = 1
Substituting this in equation (4.8), we get:
-i2
i
d2h I2 d2k r î2
. 2a _ 2a 2a
—^(h2 +k? + Z2) = 1

4a
4g2
4 = A2 +fc2 + Z2
(4-9)
Thus the interplanar spacing between two adjacent parallel planes of Miller indices (hk I) in a
cubic lattice is given by:
(4.10)
Many metals have different structures without any change in chemical composition when the temperature
or pressure is varied, or when they are subjected to unusual thermal or mechanical treatments. This
phenomenon is known as polymorphism. The melting point of pure iron is 1535°C. Iron may exist in
several allotropic forms, e.g., a, 0, y and 8 in the solid state. The existence of one form to the other
depends upon the temperature to which the iron is heated. Figure 4.31 illustrates the cooling curve for
molten iron plotted in time vs temperature coordinates.
The first horizontal step appears on this curve at a temperature of 1535°C. It indicates that the
transformation from the liquid state takes place at a constant temperature. Upon freezing the melt, delta
iron is formed. This has a body centred cubic lattice with lattice constant a = 0.293 nm. The second
CHAPTER 4
temperature effect occurs at 1400°C on the iron cooling curve and corresponds to the transformation of
delta iron into a new allotropic form (gamma
fill! iron). It has a face centred cubic lattice with a constant
fig. 4.31 Cooling curve for pure molten iron

CrjjiflWifj l23
iron is very weakly magnetic (paramagnetic), and it can dissolve carbon upto 2 per cent at IL3TC. The thiid
temperature effect occurs at 910°C, Here, gamma iron is transformed into alpha it m with a body centred
cubic lattice having a lattice constant a - 029 mn, k is non-magnetic.
The last and the fourth retardation is observed at 768°C. It corresponds to alpha iron. The alpha firm
of iron is highly magnetic and is one that exists at room temperature. It can dissolve only a very small
amount of carbon, the maximum being about 0.025 per cent at 723'C and 0.0025 per cent at room tempera’
ture. Thus it is evident from the illustration, that there arc actually two allotropic forms of jton-the low
temperature modification, alpha iron: and the high temperature form, gamma iron. These changes are
reversible; i.e,, same allotropic forms are observed during heating.
Manganese ex i six in four forms. «p.y and 8. Tin has a metallic form at ordinary temperature (white
or p) but a non-melallic form (gray or ct) with the structure of diamond, below about 13°C* Several metals
that are hep at lower temperatures transform to bee at hi^h temperatures; these include zirconium titanium,
thallium, lithium and beryllium. Metals that are hep at low temperature, sometimes transform to foe at high
temperatures, e.g., calcium, lanthanum, and scandium. Similarly, cobalt which is stable in the hep form at
low temperatures is fee at high temperatures.
Generally, the ductility, malleability, and w/hiejj of pure metals depend to a large extent on the ease
with which planes of atoms can glide over one another. Gliding takes place along the most closely packed
planes and the directions of the gliding in these planes follow the lines of most closely packed atoms. In foe
and m hep structures gliding is nearly always parallel to the close packed atomic planes. The forces of
interactions between positive tons and "electron ?os' determine such properties । >f mcuh as thermal expan
sion and melting point. The 'e/ecr/wi gas' theory of metals also accounts for their high electrical and ther*
mal conductivity as compared with other solids.
XXIV. IMPERFECTIONS IN CRYSTALS

The mathematically perfect crystal is an exceedingly useful concept. In actual crystals, however imperfec
tions or defects are always present and their nature and effects are nlten ven important in Linders landing the
properties of cryslats. This is because some properties nf materials is sfotn^v dei’-Miy and electrical
conductivity which are termed are not a fleeted by the presence of defects in crystals
while many of the properties of greatest technical importance such as mechanical strength, ductility, crystal
growth, magnetic hysteresis, dielectric strength, conduction in semiconductorb. which are termed structure-
sensitive arc greatly affected by the relatively minor changes in cry skd structure caused by defects Ordmaj j
materials, however, contain imperfections of various kinds that produce both useful properties and also such
undesirable effects as causing the strength to decrease below ihat of a perfect crystal. Some of the common
defects found in crystals are discussed below;
The structural imperfections can be classified on the basis of their geometry as paint. jwi/nce,
and volume tmperfrenons The common types nf point defects in M>hd materials can he divided into three
classes: fl) lattice-site defects, such as wconcfei and Afferdtfrtafcfei; (2) compositional defects, that is,
impurity atoms; and (3) electronic defects. Line defet ti may be classified as H) edgt dislocation end (2)
jerew dislocation, Lastly surface defects may be the defects on (11 external surface represented by the dis
continuity at the surface and (2) internal vwr/cjci, e.g grton boundaries, tilt boundaries twin boundaries,
stacking fault, etc. To summarise, crystallographic detects arc:
1. Thermal vibrations
2. Point defects:
(to Vacancies
Schottky defect
124 5'fdid State Phv5:cs
{b i Inttrstitialctes
Frenkel defect
(c i Compositional defects
(i) Substitutional impurity
(ii) Interstitial impurity
(d) Electronic defects

3. Lint defects;
<a) Edge dislocation
(b) Screw dislocation
4i Surface defects;
(a) Grain boundaries

(b) Twin boundaries
(ci Tilt boundaries
(d) Stacking fault
5. Volume detects
Thermal vibrations
Atoms on a mathematically perfect lattice shouM occupy exactly the sites to which they are attached. Il has
been observed that no crystal is perfectly rigid, since it can be deformed by finite forces. Hence, h is possible
to displace atoms from their ideal rites with a finite expenditure of energy due to thermal vibrations. The
rrcqtiej^y of % ibrnckm ]> almost independent of temperature, but the amplitude increases with increasing
temperature* When the vibration becomes strong enough ihe atoms my break the bonds between them and
this corresponds to the solid actually melting and becoming liquid, the conruponding temperature b melting
temperature. Since the atoms interact with one another* they tend id vibrate in synchronism; that is, groups
of atoms tend to move in the same direction, somewhat as waves on the ocean. Because the energy of a pap
ticular type of wave can be measured in units known as phonom, the thermal energy of the entire solid
specimen is represented quite simply by a certain collection of phonons, each one of which is pictured as a
special kind of ‘particle’. The thermal vibration of atoms of a solid. as it is, does not seriously disturb the
perfection of the crystal Every atom on the average is* in its proper position* Each atom* therefore* has req-
uiMte number of nearest neighbours at proper spacing.
Point defects
Point imperfections are lattice errors at isolated lattice points. As ihe name implies, they are imperfect
poini-Hke regions in (he crystal and, therefore, they may be referred to as zero-dimensional imperfec
point defect extends its influence only a feu atom diameters beyond its lattice position. A point imperfec
tion comes about, as a rule. because of the absence of a matrix atom (an atom that would be present in a
perfect -.n o.iln the presence of an impurity jtom or a matrix atom in the wrong place. The most common
point defects in a crystal of a pure clement are described below:
Vacancies
\ \ancy ■> the samples: point defect in a crystal This refers to a missing atom or vacant atomic site. Such
J/Iccis fj\i; horn imperfect packing during the original crystallisation or from ihennal vibrations
j the atoms at high temperatures. In the latter case, when the thermal energy due to vibration is increased
opyrldnled iTimeiial
Crystal Physics 125
there is an increased probability that individual atoms will jump om of their positions of lowest energy. For
most crystals, this thermal energy is of the order of I eV per vacancy. Vacancies may be single or (wo or
more of them may condense into a dn vacancy or tri-vacancy [Fig. 4.32(a)].
<01
(c)
Rg. 4 32 Point defects in crystals-
Interstitialcies
In a close-packed arrangement of atoms if the atomic packing factor is low, an extra atom may be lodged
within the crystal structure. This is known as interstitials An atom can enter the interstitial void or space
between the regularly positioned atoms only when it is substantially smaller than the parent atoms [Pig. 4.32
(a)], otherwise it will produce atomic distortion. Interstitialcies may also be single interstitial, di-interstitiah,
and tri-in terstitials. The vacancy and interstitiatey arc* therefore, inverse phenomena.
Schottky defects and Frenkel detects

In non-metal he crystals, the formation of a vacancy involves a local readjustment of charge in the sur
rounding crystal such that charge neutrality is maintained in the crystal as a whole. Thus, if in an ionic crys*
Lal (here is a vacancy in a positive-ion site* charge neutrality may be achieved by creating vacancy in a
neighbouring negative-ion site. Such a pair of vacant sites is called Schottky defect (Fig. 432 (b)]. This is
closely related to vacancies.
On the other hand, if ihe charge neutrality is maintained by having a positive ion in an interstitial
position, the pair constitutes a Frenkel defect [Fig. 432(c)] closely related to interstitialcies.
Cluse-packed structures have fewer interstitialcies and Frenkel defects than vacancies and
defects. as additional energy is required to force ihe atoms in their new positions.
In spite of the care taken in the preparation of crystals* vacancies arc always present in all crystals. In
fact, as a result of thermal fluctuations, vacancies are prexiuced and destroyed constantly in the crystal* For
mally Such a defect might be produced by plucking an interior atom out of its regular lattice site and placing
it on the surface, This act requires energy. Moreover* the disorder increases resulting in an increase in the
entropy In thermal equilibrium, a certain number of lattice vacancies are always present which can be esti
mated as follows:
If £r is the energy required to take an atom from a lattice site inside the crystal to a lattice she on Hie
surface (called the enthalpy offormation of the point imperfection nEt is the increase in energy associated
with the generation of n isolated vacant sites. The total number of ways in which we can pick up n-atoms
from the crystal consisting of A atoms is given by:
Cnnvr inlilr-id irmtptir-il

_______
Since disorder increases due to the creation of n vacancies the corresponding increase in entropy is
given by:
S=*,logP
Nl
S = kg lo8(W^njii!
This in turn produces a change in free energy F,
F = tf*TS
nE’ *» 108 (/V-»)!„!
TFht second term on the right hand side can be simplified by using Stirling approximation:
tagjd a jr lag ;r -jr
<■■. n .i-quenilyb
F-n E. * iit log N - (N * ») log(V - n n log nJ
Free energy m thermal equilibrium at constant volume must be minimum with respect to changes in n\ LtU
-0-E^^TIog
Thus.
£. (N-n)
^ = log^T“
?t a (N
If n « N, we ciin neglect n in n h so that:
n « Af exp(-£h/^T) (4.11)
Ii = I eV and T KEI Kt then
?;*9JX10■^=10•,
The equilibrium concentration of vancancies decreases as ihe lemperalurc decreases.
Copy rig hied malerial

Table 4.8 Enthalpy of formation of vacancies in some crystals
1 Crystal Ev [kJ/kmol] in 103 Ev in eV/vacancy
1 0.08
7.7
1 Cd
38.0 0.39
Pb 48.0 0.50
Zn 49.0 0.51
Mg 56.0 0.58
Al 68.0 . 0.70
Ag 106.0 1.10
Cu 120.0 1.24
| Ni___________ 168.0 1.74
In ionic crystals, the formation of paired vacancies is most favoured i.e., an equal number of
positive and negative ion vacancies are produced. The formation of pairs makes it possible to keep the
surface of the crystal electrostatically neutral. The number of pairs can be related to the total number of
atoms present in the crystal on following the same procedure as adopted in pure atomic crystals.
The different ways in which n separated pairs can be formed are:
_(N-n)!n!
Increase in entropy is given by,
S = kB\ogP
= kfllog
(N-.n)!n!
with corresponding change in free energy:
F=U-TS
= nEp-kBTlOg
where, E is the energy of formation of a pair.
As before we now apply Stirling’s approximation to simplify the factorial term.
log = 2[log/VI - log(JV - n)| - log nl]

(N-n)lnl
“ 2[N log N-N-(N-ri) log(jV- n) + (N-n) - n log n + n]

= 2[Mog N - (jV - n) logflV - n) - n log n]
12 8 Sal id Stuie Physi cjt
Differentialmg rh*above equation with respect ton, we get:
8F
- Efi-2Asr{0 + log(Af-n) + 1 -logn -i|
,8n.
(*-«/
Al equilibrium, the free energy is constant, so that;
E?-2iBTfog[^W^]=0
(■V-n)'
n J
^=exp(£^r)
« = N^-EJ2kgT) (4.12)
provided n « N. In NaCl crystal, Ef = 2 02 eV and al room temperature:
~ KksT)
~ exp(- 2.02/2 x 0.025)
-404
i.c„ £ = 2.8xHr'‘
N
Proceeding in the same way as in the case of Schottky defect, we can calculate the number of Frenkel defects
in equilibrium at a temperature T, Let m a perfect crystal,
£j be the energy required to displace an atom from a regular lattice site to an interstitial position
.V be the number of interstitial atoms
N be the number of atoms
Now [be total number of ways m which n Frenkel defects can be formed will be given by:
r m i [
= L(V-n)’n IJ *[w - n)!n!.
The corresponding increase in entropy due to the creation of Frenkel defect is given by:
S = log
(N^n)fel
which in turn produces a change in free energy:
/
Copy rig hied innalerial
The corresponding increase in entropy due to the creation of Frenkel defect is given by-
X! Nj\
S» kg log (N-n)lnl (Nt-n)lnl
which in turn produces a change in free energy:

F-U-TS
/v!
- nEi - kBT log
(N-n)lnl (Nt-n)ln\_
Using Stirling‘s approximation for logarithmic term, we get:
Nl_________ Njl Nl Njl

log 108 (N-n)lnl +log (Nt-n)lnl
(N-ri)lnl ' (Ni~n)lnl
*
= N log N + N( log N( -(N-ri) \og(N - n)
- (N. - ri) iog(Ni -ri) -2n log n
Substituting this value of a logarithmic term in the expression for free energy and thei
differentiating with respect to n, we get:
At equilibrium, the free energy is constant, so that:

•«
rsFi
ctm arp
=0
5n
F ,T. (.N-nKN.-ri)
or Et = kBT log-------------------------
NN
= ^gTiog ^2 »
taking N » n and Nt» n.
Thus,
logîlogCW,)-^;
or
....
n s, cxp( E/2kgT)
showing that n should be proportional to [MV,]1/2

^Qinpositiorial Defects
C0nipositional defects arise from impurity atoms during original crystallisation. Impurity atoms
considered . as detects in a perfect lattice arc responsible for the functioning of most semiconductor
devices. They occur on a lattice point as a substitutional impurity or as an interstitial impurity.
\ substitutional impurity is created when a foreign atom substitutes for or replaces a parent atom
in the lattice (Fig. 4.33 (fl)]. In brass, zinc is a substitutional atom in the copper lattice.
(«) (b)
Fig. 4.33 Compositional defects; (<?) Substitutional impurity, (b) Interstitial impurity
An interstitial impurity is a small-sized foreign atom occupying an interstice or space between

the regularly positioned atoms [Fig. 4.33 (&)].
Electronic Defects
Errors in charge distribution in solids are termed electronic defects. This does not imply that deviations
from smooth uniformity of charge within the volume of a unit cell are defects. Far from it, the charge
distribution is actually non-uniform. However, departures from the normal regularity of charge distribution
or energy are electronic defects. Deviations of spatial distribution or charge commonly accompany the
CHAPTER 4
geometrical or structural crystal defects just discussed. For example, an impurity atom may have a
charge quite different from that of the host atoms and hence may produce a local electronic disturbance.
Similarly, a vacancy or interstitial is sure to produce electrical-charge deviations. In addition to these,
the electron in a geometrically perfect lattice may themselves move in such a way as to produce local
fluctuations in charge. Furthermore, the electrons may absorb varying amounts of thermal energy so
that their motion through the lattices is altered. These so-called electronic imperfections are primarily
necessary to explain electrical conductivity and related phenomenon in solids. Perhaps the most prominent
example of this is the creation of positive and negative charge carriers. This effect is responsible for the
operation of p-n junction and transistors.
Production of Point Defects
In addition to point defects formed by thermal fluctuations, point defects may be created by other
means also. Table 4.9 illustrates how the fraction of vacant lattice sites in a metal increases rapidly with
temperature. One method of producing an excess number of point defects at a given temperature is by
quenching (quick cooling) from a higher temperature. Another method of creating excess defects is by
severe deformation of the crystal lattice, for example, by hammering or rolling. While the lattice still
retains its general crystalline nature, numerous defects are introduced.
A third method of creating excess point defects is by external bombardment by atoms or high-
energy particles, for example, from the beam of the cyclotron or the neutrons in a nuclear reactor. The
first particle collides with the lattice atoms and displaces them, thereby forming a point defect. The
number produced in this manner is not dependent on temperature but depends only on the nature of the
crystal and on the bombarding particles.
Approximate fraction of vacant
lattice sites
500 1 x IO"10
1000 1 x IQ-5
1500 1 x IO4
2000 1 x 10~3
Une Imperfections
If a plane of atoms lies only partway through a crystal, the edge of such a plane is a defect in the fOrrn
of a line, and is. known as dislocations; There are in general, two types of dislocations: (a) Edge of
dislocation and (b) Screw dislocation. Both these types are formed in the process of their solidification
or crystallization of the metal mainly in the process of their deformation. These dislocations are the
most striking defects and are responsible for the useful property of ductility in metals, ceramics and
crystalline polymers.
Discussing the edge dislocation first, Fig. 4.34 (a) shows a perfect crystal, the top sketch depicting
a three-dimensional view and the bottom one showing the atoms on the front face. The perfect crystal is
considered to be made up of vertical planes parallel to one another and to the side faces. If one of these
vertical planes does not extend from the top to the bottom of the crystal but ends partway within the
crystal, as the Rg. 4.34 (b), a dislocation is present. In the perfect crystal, the atoms are in equilibrium
positions and all the bond lengths are of the equilibrium value. In the imperfect crystal on the right, just
above the edge of the incomplete plane, the atoms are squeezed and are in a state of compression. The
bond lengths have been compressed to smaller than the equilibrium value. Just below the edge, the
atoms are pulled apart and are in a state of tension. The bond lengths have been stretched to above the
normal values. The distorted configuration extends all along the edge into the crystal. Thus as the
region of maximum distortion is centred around the edge of the incomplete plane, this distortion represents
a line imperfection and is called an edge dislocation.
(a) (b)
Fig. 4.34 An incomplete plane in a crystal results in an edge dislocation

It should be noted that the dislocation of Fig. 4.35 (a) represents a defect that runs completely
through the crystal from front to back. This extra plane indicated in Fig. 4.35 (a) may be either above of
132 So lid State Phys ics
(ai
Fig, 4,34 An incomplete plane m a crystal revuki in an edge dislocation.
(4) (bi
Fig, 435 Fosnive and negauve edge dislocations.
Burgers vector
The Burners vector of a dislocation is an important property of a dislocation because, if rhe Burgers vector
and the <jrientation of the dislocation line arc known. the dislocation is completely described. This indicates
how much and in what direction the lattice above the slip plane appears to have been shifted with respect to
the lattice below the slip plane. Fig, 437 shows a method of determining the Burgers vector applied to an
edge dislocadon, It is first necessary to choose arbitrarily a positive direction for the dislocation and then to
find out the vector which closes a circuit (line of arrows). In the present case, a clock-wise circuit of atom-
to atom steps is considered round a dislocation. It is seen that A fails to close the circuit when repealed in a
perfect lattice B unless completed by a closure vector equal to the Burgers vector b, which is found normal
to the dislocation.
In Fig, 438 for a screw dislocation, the Burgers circuit fails to close by the amount indicated by rhe
Burgers vector 6, which is parallel to the dislocation line.
Crystal Physics 133
Fig . 4.36 Foimauon of screw dislocation-
Fig+ 4.35 Burgers vector far screw dislocation

134 Srafe Physics
Surface imperfections
SirjL\.c iiTip-rk'C'b uu ;j| .i structural nature arise frum ;i change m rhe slue king of atomic planes on or across
u Isujiula:}. Thu cii,lulu' may he one of the oriental iunx or of 1 he stacking sequence of rhe planes. In geo
metric concept, surface imperfcx ri oris are two-dimensional. They are two types; external and internal.
External surface imperfections

The external type is just what its name implies, the imperfections represented by a boundary. The most
obvious boundary is the external surface, Although we may visualise a surface as simply a terminus of the
crystal structure. we should appreciate the fact that the atoms on the surface cannot be compared with the
atoms within a crystal. The surface atoms have neighbours on one side only, while Moms inside the crystal
have neighbours on either side of them This is shown in Fig, 4.39. Since these surface atoms are not entirely
H iiner^. mey possess higher energy thii.n duit of internal jtoms This energy of the surface
atom, for must metals, is Of the order 1 J/m2,
Internal surface imperfections

Internal surface imperfections are manifested by such defects as grain boundaries, tilt boundaries, twin
boundaries, and stacking faults
Fig. 439 Ex tem& surf ace defects
Grain boundaries
Guin bsmiiilj] ics ;.ru th use sutlê i in pert cut kins uhich sepaiitfe crystals or gums of differed orientation in
a polycrystaUine aggregation during nucleation or crystallisation. The shape of a grain is usually influenced
by ihe presence ot surrounding grains. The boundary atoms in two randomly oriented grains, therefore,
tannul have a pcrfcu eumplernunt of .sumuinidi’ig dtnius. As a result. a region of transition exists in which
the atomic packing is imperfect In the boundary where the crystals or grains change abruptly orientation
difference between neighbouring grains is more than 10-15°. and the boundaries are known as high-angle
gium boundaries. These ii;ipuifuutiun> in the giain boundary enable the rnicio.scopist to see them, for in a
transparent crystalline material they may scatter light and in opaque material they can be etched chemically.
Although a grain boundary is two-dimensional it has a definite thickness of 2 to 10 or more atomic dis
tances. The mismatch of the orientation of adjacent grain produces a less efficient packing of the atoms at
the boundary. Thus, the atoms along the boundary have a higher energy than those within the grains. The
bmirjilary between iwo crystals wrnuh have different crystalline arrangements or different compositions, is
called an mrerphuse boundary or commonly an interface,
Crystal Physics ! 35
Hit boundaries
Tilt boundary is another surface imperfection This is called bourtdirry as the orient jIk n differ
ence between two neighbouring crystals is less than IO0. This is why the disruption in the boundary is not so
drastic as in the high angle boundary. In genera!, low-angle boundaries can be described by suitable arrays
of dislocation. A low-angle tilt boundary is composed of edge dislocation lying one above the other in
boundary. The angle or tilt will be 0 = where b is the magnitude of the Burgers vector and D the average
vertical distance between dislocations. See Fig 4 40,
Boundary
Fig, 440 Tdt boundar).
Twin boundaries
Another planar surface imperfection is a fwi boundary. The atomic arrangement on one side of a twin
boundary is a minor reflection of the arrangement on the other side Twin boundaries occur in pairs, such
that the orientation change introduced by one boundary is restored by the other The region between the pair
of boundaries is called the twinned region. Twin bound aries are easily identified under an optica! micro
scope. Twins which form during the process of recrystallization are called annealing twins and which
from during plastic deformation of the material are called deformation twins See Fig 4.41
Stacking defect
A stacking fault is a surface imperfection tfut arise from the stacking of one atomic plane out oi sequence on
another while the lattice on either side of the fault is perfect. For example, the stacking sequence in an ideal
fee crystal may be described as ABC ABC ABC„ But the stacking fault might change the sequence to ABC
AC ABC.... Faults in the stacking sequences of fee crystals are shown in Fig. 4,42.
t*e.' ■ .> *4
Twin boundaries
Fig. 4.41 Twin boundary
Ftg. 4.42 Faults in stacking sequences (a) Intrinsic fault (b) Extrinsic fault (c) Twin fault
Volume Defects
CHAPTER 4
Volume defects such as cracks may arise when there is only small electrostatic dissimilarity between the
stacking sequences of close packed planes in metals. Further when clusters of atoms are missing, a large
vacancy or void is got which is also a volume imperfection. Foreign particle inclusions, large voids or non-
crystalline regions which have the dimensions of the order of 0.20 nm are also called volume imperfections.
Physical properties of crystalline solids are different in different directions in them. i.e.» Crystalline
solids are anisotropic with respect to many of the physical properties. Hence a method of representation
of planes and directions has become inevitable in the studies of crystal structure. W.H. Miller introduced
the usage of a set of three integers, Miller indices, to represent a set of parallel planes and these indices
when put inside square brackets are also used to indicate the directions. Miller indices of different sets
of parallel planes have already been discussed. Let us consider one such plane of Miller indices (h k I)
nearest to the origin within the unit cell of a cubic crystal. Here hk laie related to the orientation of the
plane with reference to the crystal axes. The fractional coordinates of intercept of the plane (h k /) on the
o, b, c axes are 1/A, 1A, 1/7 respectively.
The equation of this plane may be written as
hx + ky + lz=\ (4.IJ
where, (x, y, z) are the coordinates of a point lying on the plane. Referring to equation (4,13) one Car)
have two possible interpretations. In the first case h, k, I may be considered fixed and x, y, z are variabu
In the second case x, y, z may be considered fixed and h, k, I arc variable. In the first case, equation
(4.13) represents a set of points lying on the plane and in the second case the same equation represents
a set of planes passing through a fixed point. Thus a plane and the set of points on it or a point and the
set of planes through it are said to be dual to each other.
After X-rays were discovered by Roentgen many physicists tried to characterize them. One of
the problems they were facing was their inability to correlate the measured X-ray intensities to their
energies. It was Bragg who established a relationship between the angle at which X-rays are reflected
and their wave length, X, considering a crystal as made up of parallel planes of atoms periodically
repeated by lattice translations and spaced by a distance d from each other. It is now familiar as Bragg’s
law and for practicising crystallographers, it is represented by
X=2ÂJfc/sin0 (4.14)
or X = 2d sin Qh k t (4.15)
or X=2JAHsin0AH (4.16)
This equation indicates that the diffraction is bythe planes specified (A k I) or at the particular
angle Qh k z, often called the Bragg angle of the plane (h k I). When the wavelength, of X, of X-rays is
known, equation (4.14) will be helpful in relating the measured angle 0 to the interplanar spacing dhkl
as in the case of diffraction experiments. The form of Bragg’s law as given by equation (4.15) is useful
in determining the unknown wavelength of X-ray by using measured angle 0 as in spectroscopic experiments.
But in real practice there are many a set of planes, with a variety of orientations and spacings that can
diffract a beam of X-rays. Hence one has to deal with planes of several slopes and it is very difficult to
bring into visualization several slopes of the planes. Also the Miller indices of a plane do not define a plane
uniquely since all parallel planes have a common normal and hence identical Miller indices. Hence it is
clear that a simplified representation of the planes in a crystal would be helpful in the understanding of X-
f ray diffraction phenomenon. It is here the geometrical concept of reciprocal lattice is handy.
Concept of Reciprocal Lattice

Whenever it is necessary to consider sets of planes in a crystal we can think in terms of their normals
since geometrically we have an advantage. The planes are of two dimensions while normals are lines of
one dimensional nature. Simply normals to a set of planes may be viewed as a set of planes rather than
the planes themselves. But it is not enough we consider the orientations of planes alone to study the
diffraction of X-rays by crystals but it is also required to be known the interplanar spacings d as only
they determine the reflection angles 0. These interplanar spacings may also be represented in the normals
to the planes by appropriately limiting their lengths.

From the discussion in the preceding paragraph it is clear that one can indicate the orientation of
t of parallel planes by their common normal and the interplanar spacing by restricting the length of
Jje normals proportionately.
Now, if the normals are drawn, to each set of parallel planes, from a common origin and their
lengths are made proportional to reciprocal of the respective interplanar spacings, the points at the end
of these normals form a lattice array. Since the distances in this array are reciprocal to distances in the
crystal, the array is called the “reciprocal lattice” of the crystal.
The points in the reciprocal lattice are called reciprocal lattice points. These points in three
dimensional space form the reciprocal lattice space. This reciprocal lattice space is also called the
k-space. From the concept of reciprocal lattice it may be understood that the “coordinates ofpoints in
the reciprocal lattice space are defined by (A k I), the Miller indices.
Geometrical Construction
With what we have discussed until now, the general rules for constructing the reciprocal lattice may be
formulated by the following steps:
1. Fix up some point in the direct lattice as a common origin.
2. From this common origin draw normals to each and every set of parallel planes in the direct
lattice.
3. Fix the length of each normal equal to the reciprocal of the interplanar spacing (l/dAi/) of the
set of parallel planes (h k Z) it represents.
4. Put a point at the end of each normal.
CHAPTER 4
The collection of all these points in space is the reciprocal lattice space. It should be noted here
that the direction of each of the points from the origin preserves the orientation of the set of parallel
planes it represents and the distance of each of the points from the origin preserves the interplanar
spacing of that stack of parallel planes. It is well known that the d-spacing of parallel planes in crystals
usually is of the order of few Angstroms (A). Hence the distance of the reciprocal lattice point on any
normal from the origin (l/dh k will be too large to be accommodated within the frame work of the
figure representing the reciprocal lattice. It is because of this reason one may have to introduce a suitable
scale factor while picturising a reciprocal lattice. Thus for convenience, let us define the length of each
normal (o/; k J explained in step 3 of the procedure to be
ohki = K (4.17)
dhkl
where, K is the scale factor chosen for the construction of the reciprocal lattice. With all the rules
specified above and equation (4.17) one can make an attempt to construct a reciprocal lattice in two-
dimensional space as detailed below:
Let us consider, as an example for construction of reciprocal lattice, the unit cell of a monoclinic
crystal (a A c; a = P = 90°?t y) looking along its unique axis, namely, c-axis. To make the construction
further simplified, one may consider planes belonging to a single zone. This makes the normal to all
Parallel planes belonging to the zone all to lie in the same plane, normal to the zone axis, *>., normal to
c-axis. In Fig. 4.43 the zone axis lies perpendicular to the plane of the diagram and hence all normals
Crystal Physics i 39
planes of the family of the zone will Jie in the plane of the diagram. The Fig. 4.43 showi rhe edge views of
four (At/) planes* viz.* (100), CHO), (120) and (010) al! belonging to the [001] zone. Ii must be dear that the
normals lq the family of planes (100), (200), (300) etc., are parallel, It is also known that dlti! -
- etc, Hence while ottt>= = 20^ (!>[»" 3a,and so on. Therefore the distance of the
Fifl. 4,43 Graph j CflJ ronamic lieut <rf ret ip rdcah lattice
reciprocal lattice point representing the set of parallel planes (A 0 0) from the origin will be n times greater
than the distance of the reciprocal lattice point representing the set of parallel planes (A0 0) or simply, as an
example, the distance of the reciprocal lattice point from the origin representing the sei of parallel planes
(3 0 0) will be at a distance from the origin equal to three dines the distance of the reciprocal lattice paint
representing the set of parallel planes (I 0 0). In reciprocal lattice, hh is the convention to represent the reci
procal lattice point representing the sei of parallel planes with Miller indices (A A ft by the same Miller
indices without the parenthesis* Thus in the Fig. 4.43 it may be seen that the reciprocal lattice points
representing the set of parallel planes (100), (200), (300) etc,, are indicated by 100,200, 300 etc,., Since all
the set of parallel planes (100), (200), (300) etc., have common normal all the reciprocal lattice points 100*
200, 300 etc. He along the same straight hrte. As we have taken the planes belonging to [001] zone, soon
after the reciprocal lattice points of alt the (A 4 o) planes are plotted we get a two-dimensional lattice as in
Fig* 4.43. Buerger has proved that all these reciprocal lattice points must lie on a two dimensional lattice. A
vector-algebraic proof establishing that a three-dimensional reciprocal lattice is similarly formed in a real
crystal was given by Ewald,
Vector-algebraic Discussion
(i) Relation between chit and crystallographic axes

Relation between (he normal to a plane (as represented by 4.17) and the crystallographic axes a* b and c may
be obtained by considering the primitive unit cell shown in Fig. 4.44.
140 Suite Stare Physics
The volume of this unit cell V is given by
area
so that (418)
IW
Since the normal to a plane can be represented by the unit vector n equation (4J8) cun be written as
(4,19)
Also, we know ihai any area can be represented by

the vector product of its sides, Hence
(4.20)
R&4.44 Primitive unit cell

If the scale factor K in equation (4J7) is taken as I (for the convenience of simplifying the calculations)
then from equations, (4.19) and (4.20) we write
where a h x c represents the volume of the primitive unit celL Similar expressions for c^m and may be
easily obtained. These three vectors are (he three reciprocal axes defining the three - dimensional reciprocal
lattice. It is the convention to indicate a reciprocal lattice axis by putting an "asterisk" as a superscript to the
usual symbol {a is pronounced a-star). Thus the three reciprocal axes are defined as below:
(4.21)
Thus the relation between die normal io a plane and the crystallographic axes is estate! ished.
From the vector notation of equations (471) it follows that (he reciprocal axes have a simple ret abort
with the crystal axes as follows:
a is normal iu£ and c
b is normal toe undo
c* is normal to a andd
Copyrighted inaterial
CryMtd Physics 14 I
Also
a*’b^0 a*-cÔ (4.22)

b* c - o *a -0
C* - a = 0 c* - b “• 0
As a coroiiary we also have
S 1; b*>b = 1; c'*c = J (4.23)
(ii) Reciprocal lattice vector

One may construct a lattice using the reciprocal-lattice vectors of equations (4*21). It may be noted that
successive points in the *u’' direction represent successive submultiples h of ibe spacing of (1 0 0); in theft’
direction. successive submuhiples t of the spacing of (0 I 0); and in the c' direction, successive submuliiples
/of the spacing of (0 0 I).
(4.24)
Therefore to reach any reciprocal lattice point ft k I one may have to go ft units along a\ k units along b* and
I units along c\ Hence the reciprocal lattice can be written in vector notation as
^w*fta’ + ibP + /£* = G M.25j
Any vector G of this form is called a reciprocal lattice vector. a\ b and c" become the primitive translation
vectors of the reciprocal lattice, as long as they obey the equations (4*21)
(ill) Verification ofo^

h may aho be shown that the collection of points at the ends of the vectors ofltJ. conform to the conditions I
to 4 indicated under t he article geometrical construction* It is enough to show that the scalar products of
and vectors lying In the (ft k 0 plane vanish to prove that is normal to the crystal plane (ft k I), tn Fig.
4,45 shown below ihe plane (ft k I) intercepts n-axis at a/h, b-axis at b/k and c*axis at c/L
Let us consider the vector C
(4,26)
A
This vector lies in the plane (h k I). From equations (4.25) and (4.26),
^*chki = + &b*+/c*)
\h kJ
= (ha? + £b*+ /c’) - -(ha* + kb*+ be*)

h k
= 1-1=0 (427)
It can be proved, on the same line as equation (4.27).
A-aM,=0 (4.28)
.be
where, A- ~ ~
k I
From equations (4.27) and (4.28), aAitzis normal to C and A hence to the plane formed by them,
namely to the plane (h k 1). In view of this, n, the unit vector normal to (h k I) is parallel to (5h k t so that
equation (4.25) can be written as ,......

I ah k 1111 ~ ha* + ^b*+ ^c* (4-29)
Hence ...
5 ; _ +^b +Zc > (4.30)

lO'hkJ . -
CHAPTER 4
In Fig. 4.45, the length of the interplanar spacing of the plane (h k I) is given by
(4.31)
This verifies equation (4.17).

Thus from equations (4.27), (4.28), (4.29) and (4.31) it is clear that the normal to the plane (hkl)
® Fig. 4.45 is nothing but the reciprocal lattice vector and the foot of this normal lying on the plane
formed by C and A is at a distance equal to \/dhkl from the origin. Thus it is a reciprocal lattice point
satisfying the conditions 1 to 4 mentioned earlier.
Crystal Physics 143
Rg.445 ikk I) plane
f/irj Reciprocal lattice parameters to direct lattice parameters

In Eq, (4,21) we have represented the reciprocal lattice parameters in terms of the direct lattice parameters.
The convene may also be tried.
Let us now consider the reciprocal of the reciprocal lattice vector a {fl’)’
(4.32)
Multiplying the right side of equation (4.32) by a a ’ (~1), we get
(4.33)
=&
From equations (432) and (433)
c* x a*
a*b*xc*
a* x b*
(4.34)
a*»b*xc*
Equation (4.34) give the relationship between the elements of the crystal lattice and the elements
of their counterparts in the reciprocal lattice. Similar relationships between the other lattice parameters
may also be obtained. These relations are shown in Table 4.10.
Table 4.10 Relations between the dimensions of the direct and reciprocal cells
- . • - - ’ A ’ ? - - -
(v) Reciprocal Lattice Vector and Interplanar Spacings
Knowing the relation between interplanar spacings and the cell edges of a crystal lattice is helpful. By
combining equations (4.17) and (4.25) this relation is easily determined in the reciprocal lattice.
o..,. a. k, = (ha* + kb* + be*) • (ha* + kb*+ lc*)
nkl nKi
<y2 «. = —9-— = h2a*2 + fc2b*2 + Pc*2 + 2hk a*b*cos y *

hkl d2hki ' 1 '
+ 2klb*c* cosa * + 2lhc*a* cosp* (4.35)
which is the general expression applicable to the triclinic system.

Similar relation for cubic system may be obtained from equation (4.35) by applying the condition
**= b* = c* and a * = 0* = Y * = 90*. Hence
O2*t/=5T-=(',2 + A2+Z2)“' <436>

hkl d2hki
for cubic system.
Cryrm/ PAyrics 145
for cubic system.
Very often we need similar relationships indirect lattice also, i.e., relationship between d^ and unit
cell parameters of the direct lattice. These may be also obtained from equation (435) by substituting the
proper transformation equations from Table 4. J.
For cubic system, wc get.
fW> Properties of reciprocal lattice

From dw discussions above, it may be clear that every crystal structure may be imagined to be made up of
two lattices, direct lattice (or) crystal lattice and the reciprocal lattice. It is worth mentioning some of the
important points concerning the direct lattice and reciprocal lattice ai this stage.
L Any diffraction pattern of a crystal is a map of the reciprocal lattice of the crystal whereas the
microscopic image is a snap of the direct lattice.
2, When a crysu) is made to rotate both the direct lattice and reciprocal lattice rotate.
White the primitive vectors of a direct lattice have rhe dimensions of length those of the reci-
I lattice have rhe dimensions of (length J
Direct lattice or crystal lattice is a lattice in ordinary space ar real space Reciprocal lattice is in
reciprocal space or fc-space or fourier space.
The reciprocal lattice vectors are defined in equation (4.25). These lattice vectors and the corre
sponding reciprocal lattice points generate a unit cell in reciprocal space with edges a\ b* and c. As men
tioned earlier the reciprocal lattice is a geometrical concept and it has the following geometrical properties,
1 . Every reciprocal lattice vector is normal to a set of parallel planes of the crystal lattice
2. When no common factor exists among the components of G (reciprocal lattice vector), then
I G| U inversely proportional to the spacing of the lattice planes normal toG.
3. The volume of a unit cell of the reciprocal lattice is inversely proportional to the volume of the
unit cell of crystal lattice.
4. The direct lattice is the reciprocal of its own reciprocal lattice.
5. The unit cell of the reciprocal lattice need not be a parallelepiped.
Based on the above properties it will be interesting to prove that

(i) the reciprocal [mice of a simple cubic lattice is also a simple cubic lattice.
(ii) the reciprocal lattice of a face centred cubic lattice is a body centred cubic lattice.
(m) the reciprocal lattice of a body centred cubic lattice is a face centred cubic lattice, and
(tv) the reciprocal lattice of a hexagonal close-packed lattice is a hexagonal close-picked lattice.
The concept of reciprocal lattice is useful in understanding the X-ray diffraction phenomena in a
simple way and the wave mechanical behaviour of the electrons in a periodic crystal lattice.
14<j Solid Stare Physics
X-RAY DIFFRACTION
Bragg’s law
The concept of reciprocal lattice may now be applied to understand the actual situation under which X-rays
are diffracted by crystal planes and thereby the Bragg's law. Bragg’s law given by equation (4.16) may now
be represented, to suit our convenience, by
■In&w = (4.37)
Now let us consider a circle of radius kA and construct a

right argted triangle with its diameter as hypotenuse and one
of the sides of length equal to 1/d^ This is shown in
Fig. 4,46. The angle opposite to the side of length equal to

will be equal co & as evidenced by equation (437).
Now Fig. 4.46 explains Bragg's law graphically.
We will try to understand the Bragg's law from Fig. 446 by

making the latter resemble to a real practical situation. Let us
suppose the direction of incident x-ray beam to coincide with
the diameter AO in the figure* Since PAO is equal to the
Fig. 4.46 X-riy diflfriitztujp Bragg angle, the side AP of the triangle APO should have the
same slope as those of the set of parallel planes
which diffract x-rays. Let us try to go more closer
to the real situation by modifying Fig. 4.46 to Fig
447 where one may imagine one of the set of par*
allel planes of Milter indices {h k 1} diffracting
x-rays being put at the centre making an angle O
with AO and AO is the direction of the incident
x-ray beam. In Fig. 4,47> OP is normal both to the
crystal plane (when extended) and AP. Hmce
ZOCP1$ equal to 20^ making CP the direction of
the diffracted x*ray beam. Hence Fig. 4.47 is a
graphical representation of Bragg's law in terms of
Figt4*47+ X-ray diffraction* rhe reciprocal lattice vector (since OP is equal tn
it represents the reciprocal lattice vector). Thus the following conditions may be emphasised to explain
Bragg’s tew with the aid of Fig 4.47,
1- The crystal has to be thought of being placed al the centre of a circle of radius l/X. In real cases
it should be imagined to be at (he centre of a sphere of radius
2. Ongrn of the reciprocal lattice vector is the point O» where (he x-ray beam leaves the circle
(sphere in three dimensions).
Copy rig hied malerial

Crystal Physics 147
3. The point P has to be the position of the reciprocal lattice point (at the end of the reciprocal fat’
tice vector or G of length I or in other words it is sufficient to understand that whenever
a reciprocal lattice point lies on the circle (sphere in three dimensions) Bragg's taw will be
satisfied and the diffracted vray beam passes along CR In three dimensions this sphere of
radius IA is also called Ewald's sphere of reflection or simply sphere of reflection or simply
Ewald's sphere. Thus reciprocal lattice may be used m coryunctioa with the sphere of reflection
to explain x-ray diffraction experiment. As it is easy to imagine the reciprocal lattice point
centred it the point of emergence of the x-ray beam from the sphere of reflection, a construction
like Fig, 447 can be used to analyse the different ways in which a crystal can be made to satisfy
Bragg's condition for its various planes. It is important to note that the x-ray diffraction takes
place only when a reciprocal lattice point intersects or lies on the sphere of reflection. Hence a
photographic record of the diffracted x-ray beams is nothing but a photographic record of the
reciprocal lattice. It is precisely because one normally records the reciprocal lattice of crystals in
x-ray diffraction experiments that die concept of reciprocal lattice is so essential to their straight
forward interpretation.
OBJECTIVE QUESTIONS
L If r is the radius of the atom in a crystal, crystallizing in the simple cubic structure, then the nearest
neighbour distance is
(a) rft (b) 4r
(c) 2r (d) none of these
2 Classify the following unit celt into proper crystal system: a - 1.08 nm,
b - 0.947 nm, c = 0.52 nm and a « 41\ £= 82\ y = 95 *.
(a) triclinc (b) monoclink:

(c) orthorhombic (d) hexagonal
3. Is rotation of 2kA5 or 2n/7 possible; through an axis passing through a lattice point for symmetry
operation in a single crystal
(a) Yes (b) No
4. The number of diad axes of symmetry elements that are present in a cubic crystal are
(a) 1 (b) 3
(c) 2 (d> 6
5, The number of lattice points in a primitive cell are
(a) I (b) 1/2
(c) 2 (d) 3/2
6 The nearest neighbour distance in the case of &cc structure is
W (oVT>2 (*»> (a^2V2

(«) 2af^3 <d> 2fl/i/2
7, The co-ordination number in the case of simple cubic crystal strut-fare is
(a) 12 (b) 6
(c) 2 <d> 1
. The coordination number in the case of simple cubic crystal structure is
(o) 12 0)6
(c)2
(d)l
8. The number of atoms present in the unit cell of hep structure is
(o)2 0)4
(c)6 0)7
9. The packing factor of diamond cubic crystal structure is
(a) 60% 0) 56%

(c) 90% (d) none of these
10. Magnesium crystallises in hep structure. If the lattice constant is 0.32 nm, the nearest neighbour distance
in magnesium is
(a) 0.32 nm (Z>) 0.64 nm
(c) 0.16 nm (d) none of these
11. Which of the following metals crystallises in fee structure?
(a) aluminium (Z>) zinc
(c) sodium (d) caesium chloride
12. If n is the number of atoms in the unit cell of the cubic system, NA and MA are the Avogadro’s number and
atomic weight respectively and p is the density of the element, then the lattice constant a is given by
XT 11/3
CHAPTER 4
r .z i1/3 nNA
(a) ^dP 0)
.njVA. LâpJ
.. 1V3 r i1/3
nM A (d) 2^-
(c)
LâpJ Afxn
The number of molecules present in the unit cell of sodium chloride is

(o)5 0)2 .
(c)4 (d) none of these
14. The maximum radius of the intestitial sphere that can just fit into the void between the body centred atom
of bcc structure is
(a) r [(2/V3) -1] 0) r [(75/2) -1]
(c)r[V3-l] (d)r[V2^1]
where r is the radius of the atom.

MH ^quhSixmPhysics
15. The packing factor of the fee structure is
(a) 52% (W 68%

(c) 92% none of these
I*. If 0.28 nm is the interionic distance in NaCl crystal, the lattice parameter is
(a) 0.14 nm <»> 0 56 nm
(c) 0.08 nm « ”°"e °f
17. The number of ions in the unit cell of CsCl crystal is
(«) 1 <» 2
(c) 3 W4
IS. Metallic iron changes from bee structure to fee structure at 910°C with an increase in the atomic radii.
density of iron in this structural:
(a) remains constant (b) increases ,
(c) decreases
19. Zinc crystallises in hep structure. If r is the radius of zinc atom, the height of the unit cell is
(a) 2r(8/3)1/2 (b) r(8/3)1/2
(c) 2r(3/8)lz2 (d) r(3/8)1/2
20. The number of sulphide atoms in the unit cell of zinc sulphide crystal is
(a)2 (b)4
(c) 3 (d) 6
21. The Miller indices of the plane parallel to the x and y-axes are
(a) (100) W(010)
(c)(001) - (<D(111)
22. If (3 2 6) are the Miller indices of a plane, the intercepts made by the plane on the three crystallographic
axes are
(a)(2a,3b,c) (b)(a,b,c)
(c) (a, 2b, 3c) (d) none of these
23. A plane parallel to one of the coordinate axes has an intercept of infinity.
(a) Yes (h) No
24. The Miller indices of the plane parallel to y and z-axes are
(n) (100) • (b) (0 1 0)
(c)(001) (4) (Hl)
25. A plane intercepts at a, b/2, 3c in a simple cubic unit cell. The Miller indices of the plane are
(fl) (1 3 2) (b) (2 6 1)
(c)(3 61) (<f)(l 2 3)
(o) 6 : 3 : 2 (Z>) 6 : 3 : 41
(C) 4f> • 45 - 41 (</) 4e : 4i- 4*
j7 If (h k I) are the Miller indices of a plane, then the plane cuts the axes into h, k and I equal segments.
(o) Yes (b) No
The number of atoms per unit area of the plane (0 1 0) of a simple cubic crystal is
(fl) iMr2 (b) Ir2
(c) l/4r (d) noneof these
where, r is the radius of the atom.
1. Define the following terms in crystal structure study: (i) Lattice, (ii) Primitive cell and unit cell.
2, Define crystal lattice, basis and crystal structure.
3. Explain the terms: Symmetry elements and Bravais lattices.
4. What are symmetry operations? Explain the meaning of a “n-fold rotation axis” and “n-fold screw axis”.
5. Enumerate the characteristics of various crystal systems.
6. Calculate the axial ratio for an ideal hexagonal close packed structure.
CHAPTER 4
7. What is meant by the atomic radii in a crystal?
8. What are the important space lattices in the cubic system? Give their characteristics.
9. Specify the nature of the unit cell, axes and angles.
16. How many atoms are there in the unit cell of diamond?
11. Mention the four lattice types of the orthorhombic system. Describe their characteristics.
12. Explain the terms primitive cell and unit cell.
13. Explain with examples, the characteristics exhibited by bcc and fee lattices.
14. Work out the coordination number and nearest neighbour distance for bcc and hep structures.
15. What is coordination number? What factors control the coordination number? '
16. What are Miller indices? How are they determined?
17. Lead is fee. If r and a are the radius of the lead atom and lattice parameter respectively, find the relation
between a and r. ♦
18. What are the various symmetry operations that are present in a crystal?
19. Explain what is meant by atomic packing factor in cubic lattices?
Explain “axis of four fold symmetry” in a cubic crystal.
21. Name the type of structure and sketch the unit cells of metals, iron and silver.
i
150 Soln/ S/arr Physics
SHORT QUESTIONS
L Define the Mowing terms tn crystal structure study. (i) lattice (ii) primitive cell and unit ceU
2. Define crystal lattice* basis and crystal structure.

X Explain the terms: symmetry elements and Bravais lattices.
4. What are symmetry operations? Explain the meaning of a 'infold rotation axis’ and (fl-fold screw
axis*.
5. Enumerate the characteristics of various crystal systems.
6. Calculate the axial ratio for an ideal hexagonal close packed structure.
7. What is meant by the atomic radii in a crystal?
3. What are the important space lattices in the cubic system? Give their characteristics.
i
9. Specify the nature of the unit cell, axes and angles.
10. How many ams are there in the unit cell of diamond0
11. Mention the four lattice types of the orthorhombic system, Describe their characteristics.
11 Explain the terms primitive ceil and unit celt
13. Explain with examples, the characteristics exhibited by bcc and fee lattices.
I
I
14. Work out the co-ordrTmion number and nearest neighbour distance for bee and hep structures.
13. What is coordi nation number? What factors control the co-ordination number?
16. What are Miller indices? How are they determined?
17. Lead is fee. If r and a are the radius of the lead atom and lattice parameter respectively, find the
relation between a and r.
18. W hat are the various symmetry operations that are present in a crystal,
19. Explain what is meant by atomic packing factor in cubic lattices.
20. Explain ‘axis of four fold symmetry* in a cubic crystal.
21, Name the type of structure and sketch the unit cells of metals, iron and silver.
22. Sodium crystallizes in bcc structure. If the radius of the sodium atom is 1.732 nm, compute the
spacing between rhe (1 U) planes.
23. Describe the ways in which crysub may have closes! packing of atoms.
24. What are Miller indices? Ihusinue with examples.
35. Describe the crystalline structure of silicon.
26. Explain the following terms with respect to a crystal (i) unit cell (ii) co-ordination number
(hi) packing factor.
Crystal Physics 151
27. Show that the packing factor for fee lattice is n\2?6.
M. Draw neat diagrams to indicate Miller indices of important planes systems in a cubic crystal.
29. What is meant by crystal imperfections?
30. Explain the difference between edge and screw dislocations.
31. What i> meant by point defecu in crystal lattice?
REVIEW QUESTIONS
1. Define crystal lattice, basis and crystal structure. Describe briefly the seven systems of crystals.
2. What do you understand by space lattice? Mention and explain with examples the types of lattices in
cubic system.
3. Define the following terms used in crystalography:
(i) Lattice
(ii) Primitive Cell
(iii) Unit cell
(iv) Packing factor
Describe various types of lattices and mention their distinguishing features.
4, Explain the following terms as applied to crystals:
(I) Crystal lattice

(ii) Unit cell
(iti) Lattice parameters of a unit cell
(iv) Primitive cell
5. Explain the following terms used in crystallography:
(t) Primitive cell

(ii) Unit cell
(iii) taking factor
6. Define the terms: lattice, basis, crystal structure and unit cell.
Explain the terms: symmetry elements and Bravais lattices.
7. What is a Bravais lattice? What are the different space lattices in the cubic system? How many lattice
points per unit cell are there in each of these lattices?
ft, With reference tt> crystals, state wbat do you underhand by the terms:
(i) Crystal lattice

(ii) Unit cell
(iii) Single crystal
(iv) Coordination number
(vj Packing factor
<vi) Atomic radius
Calculate the atomic radii in the case ol fax ami fee lattices.
Copy ri g hl ed rn aleri $ I
152 So/ id S/ate Ph vs ics
9* Describe rhe seven systems of crystals with suitable diagrams.
10. Define space lattice. Name the seven types of crystal systems and give the relation of lengths of axes
and the relation of angles between the axes of a unit cell in each type.
IL Explain the physical basis for classifying crystals into: (a) 14 Bravais lattice (b) 7 systems and (c) 32
point groups.
12, Whai is meant by ’Symmetry elements1 in crystals? Discuss the various types of symmetry elements
and symmetry operarions present in a cubic crystal.
13. Explain what is meant by symmruy dements in a crystal. Illustrate the various symmetry elements
present m a cube,
14. What are symmetry operations? Explain the meaning of a ’n-fbld rotation axis* and a 'a-foid screw
axis*.
15. Discuss the number of lattices in the orthorhombic system. Discuss the crystal structures of sodium
chloride and zinc sulphide,
lb. Explain the terms: Primitive cell and umt cell.

Discuss the various symmetry elements present in crystals.
Prove that five-fold axis of rotation is not compatible with a lattice.
17. Whai is coordination number? Obtain the coordination number for icr bee and fee lattices.
18, Define atomic radius in crystals. Calculate the atomic radii in the case of bee and fee lattices.
19. What do you understand by packing density or packing factor in crystals? Show that the packing fac
tor for her and fee structures are \:3tv8 and respectively.
20. Explain the dimensions <rf a unit cell Derive an expression for the edge element of a cubic crystal in
terms of the density of the crystal material,
21. Describe various types of lattices and mention their distinguishing features.
22. Show that for a cubic lattice, the lattice constant *a* is given by:
r *M-r
where fi is the number of atoms per unit cell, MA is the atomic weight. is Avogadro’s number and p
is the density of crystal material.
23. Is rotation of 2n/5 or 2n/7 possible, through an axis passing through a lattice point for symmetry
operation. Discuss your answer with a suitable theory.
24. Show analytically that a five-fold rotation axis does not exist in a crystal lattice.
25. Name the types of structure and sketch the unit cells of the following metals: copper, chromium mi
magnesium,
26. Describe the face centred cubic and hexagonal close packed structures, Prove that the close packing
of atoms in the hep structure demands an axial ratio. <7<r ~ M83-
27, Describe the two ways in which crystals may have closest packing of atoms. Work out the coordina
tion number and packing factor for her and fee structures.
27. Describe the two ways in which crystals may have closest packing of atoms. Work out the coordi
number and packing factor for bcc and fee structures.
28. Define the terms: Unit cell and Symmetry elements.
Describe the crystalline structure of silicon. Calculate c/a value for an ideal h p
». Distinguish between primitive cell and unit cell. Describe the diamond d^'s a’Wu< its
coordination number, atomic radius and number of atoms owned by the cell. What type bond ,s
in diamond ?
30. Show that the atomic packing factor for fee and hep metals are the sam
31. Establish the relation between the lattice constant of a cubic crystal and the density of the crystal material
Determine the size of the largest spherical impurity that will fit into the voids of the fee structure.
32. What is meant by symmetry operations in crystals ? Explain the different point group symmetry elements
in a crystal lattice.
33. Establish the relation between the edge of the unit cell and the atomic radius for the bcc and fee lattices.
Derive the relation between the lattice constant of a cubic crystal and the density of the crystal material.
34. Discuss the similarities and differences of primitive cells and unit cells.
What are Miller indices? What are their significances? How are they deter til 11 ed? What form of notation
is used?
35. What do you understand by Miller indices of a crystal plane? Show that in a cubic crystal the spacing
between consecutive parallel planes of Miller indices (h k 1) is given by:
36. What are Miller indices? Draw neat diagrams to indicate Miller indices of the important plane systems in
a simple cubic crystal. Obtain a relation between the interplanar spacings and cube edge.
37. Derive an expression for the interplanar spacing for planes of the (h k I) type in the case of a cubic
structure.
38. What is meant by crystal imperfections? Classify them in the order of their geometry.
39. Explain the difference between edge and screw dislocations. What is a Burgers vector?
40. State the difference between high-ahgle and low-angle boundary and their relative effects on materials.
4L What are the point, line and surface imperfections found in solid materials ? Illustrate these imperfections
with suitable sketches.
42. Explain with neat sketches the different imperfections in a crystal.
43. What is meant by point defects in crystal lattice? What are the different types of point defects? How are
they caused?
44. Describe with suitable diagrams edge dislocations and screw dislocations in crystal lattice.
Obtain an expression for the equilibrium concentration of vacancies at a given temperature in a metallic
crystal.
Show that the number of Frenkel defects in equilibrium at a given temperature is proportional to (A4V.)I/2,
where N be the number of atoms and A/(. be the interstitial atoms.
Find the maximum radius of the interstitial sphere that can just fit into the void between the body centred
atoms of bcc structure.
Show that the maximum radius of the sphere that can just fit into the body centre void of the fee structure
coordinated by the facial atoms is 0.414 r, where r is the radius of the atom.
Calculate the number of atoms per unit cell of a metal having a lattice parameter 0.29 nm and density of
7870 kg/m3. Atomic weight of the metal is 55.85.
Assuming that the lattice points of lattice parameter ‘a’ in a bcc structure are occupied by spherical atoms
of radius ‘r’. Calculate: (i) the free volume per unit cell, (ii) determine the radius-of the largest sphere that
will fit into the voids produced by the lattice point atoms not occupying in the full volume of the cell.
Explain that the diamond structure may be considered as made up of two interpenetrating fee lattices.
Given that the cubic edge of diamond is 0.356 nm, show that there are 1.77 x 1029 atoms/m3. From this
calculate the density of diamond and compare the result with the observed density. Atomic weight of
diamond is 12.01.
The crystal structure for NaCI is a cubic lattice, the successive lattice sites being occupied by Na and Cl
ions respectively. If the molecular weight of NaCI is 58.5, calculate the spacing between the nearest
neighbouring ions. Take the density of NaCI as 2.18 x 103 kg/m3.
Calculate the lattice constant for a-iron belonging to bcc structure. Take the density of a-iron as
7.86 x 103 kg/m3 and the atomic weight of iron as 55.85.
Copper has fee structure and its atomic radius is 0.1278 nm. Calculate its density. Take the atomic weight
of copper as 63.5.
The ionic radii of Cs and Cl are 0.165 nm and 0.181 nm and their atomic weights are 133 and 35.5
respectively. Calculate the density of CsCl.
Copper has fee structure and the atomic radius is 0.1278 nm. Calculate the interplanar spacing for (1 1 1)
and (3 2 1) planes.
Lead is fee and its atomic radius is 0.175 nm. What is its volume, its face diagonal and its body diagonal
in the unit cell?
The unit cell of aluminium is face centred cubic with lattice constant, a = 0.4049 nm.
(0 How many unit cells are in an aluminium foil with 0.005 cm thick and side 25 cm square?
(ii) It weighs 8.44 x Ifr"3 kg. How many atoms are present?
(Hi) How many atoms are there in each unit cell?
B. Zinc has hep structure The height of the unit cell is 0.494 nm. The nearest neighbour distance h o.fl
The atomic weight of line is 65.37. Calculate the volume of the unit cell and density of zinc. hn».
14. Lead crystallises in the fee structure. The lattice constant is 0.495 nm. Calculate the radius of the
'arjest
sphere that can just fit into the void at the body centre of the fee structure coordinated by the facial
atoms
15. Chromium has bee structure and its atomic radius is 0.1249 nm. Calculate (i) the free volume per u '
GO the radius of the sphere that will just fit in the largest void at the position (1/2,1/4, 0). **
14. The lattice constant of the unit cell of a-iron is 0.287 nm. Find the number of atoms/mm2 of the p]^
(1 0 0), (1 1 0) and (1 1 0). a-iron has bcc structure.
17. How many atoms per sq. mm are there in the (1 0 0) plane, (110) plane and (1 1 1) plane, for lead which
has fee structure and a lattice constant, a = 0.493 nm.
18. Obtain the Miller indices of a plane which intercepts at a, b/2, 3c in a simple cubic unit cell. Draw a n™
diagram showing the plane.
19. The Miller indices of a plane in a simple cubic crystal are (1 2 3). Get the coordinates of the plane and
sketch it
20. Draw the following planes in an fee structures : (1 1 2) and (1 2 0) planes.
21. Show that for a simple cubic lattice
• •■b
oo • io• 11= V6 : a/3 • -Jl

22. Find the Miller indices of a crystal plane that makes from some origin an intercept of 'a' on the a-axis, 'lb'
on the b-axis and '3c' on the c-axis.
23. Metallic iron changes from bcc to fee form at 910°C. At this temperature, the atomic radii of the iron atom
in the two structures are 0.1258 nm, 0.1292 nm respectively. Calculate the volume change in percentage
during this structural change.
24. Show that the spacing } ] is approximately 1.2 times the spacing d2 00in lead which has fee structure.
The radius of lead atom is 0.1743 nm.
25. Find the Miller indices of a set of parallel planes which make intercepts in the ratio 3a : 4b on the x and
y-axes and are parallel to z-axis, a, b, c being primitive vectors of the lattice.
26. Find the equilibrium concentration of vacancies in aluminium at 0 K, 300 K and 900 K.
27- Calculate the ratio of the number of vacancies in equilibrium at 300 K in aluminium to that produced by
rapid quenching from 800 K. Enthalpy of formation of vacancies in aluminium is 68 kJ mol.
28. In a tetragonal lattice a = b = 0.25 nm, c = 0.18 nm, deduce the spacing between (1 1 1) planes.
29. Jn a simple cubic crystal:
(i) Find the ratio of intercepts on the three axes by (1 2 3) plane.
(n) Find the ratio of the nearest neighbour distance to the next nearest neighbour distance.
(iii) Find the ratio of the spacings of (1 1 0) and (111) planes.
cubic lattice, compare the denaitv of lam ~~----------------
31. In a triclinic crystal, a lattice plane makes in, “I™** “> (I1 1) and (I I 0) planes.
P13 »f 'cngta u, 2b and - (3c/2). Rnd ,M1Us,
32. The fraction of vacancy sites in a metal k 1 v in-id

a’5°°°C Wta«" I*-he fraction of vacancy .ite. at
,3. The Chlorine ion (Cl) has a radius of 0.181 mm c,,t ,
coortnated with eight neighbouring chloride iona ““ ’maU«[ “Hch can be
Wave Nature of Matter and
X-RayJDiffraction_
The physical concept of a particle characterised by mass and velocity is more familiar to us; and naturally
so, because the results of most of the experiments dealing with particles lend themselves to ready
interpretation in terms of mass and velocity by Newton’s laws of motion. But this classical approach
was evidently not adequate for some experiments, the results of which appeared to contravene Newton’s
laws; and it was to explain this situation that the concept of wave mechanics was introduced. Its
application, first to atomic and then to molecular structure, revolutionised the different branches of
physical sciences.
The marvellous success of the quantum hypothesis in providing both qualitative and quantitative
explanation of photoelectric effect (1905), “blackbody” radiation (1901), emission of line spectra (1913),
and Compton effect (1924), coupled with adequate explanation of the phenomena of interference,
diffraction and polarisation on electromagnetic theory, established beyond doubt the dual aspect of
radiation (wave aspect and particle aspect). But despite the immense success of wave particle duality of
radiation, the two fundamental postulates underlying Bohr’s theory of atomic structure remained arbitrary
and unexplained for a long time and agitated the initiate minds. In the mean time Einstein’s mass
energy relationship, E = me2, had been verified in a number of cases in accordance with which radiation
and mass were mutually convertible. It was in this background, that the French Scientist Louis de
Broglie in 1924 extended the idea of dual nature of radiation to matter itself, when he proposed that
matter possesses wave as well as particle characteristics and that motion of electrons within the atom is
guided by a peculiar kind of wave which were called “pilot waves”, in the same manner as the radiation
field governed by electromagnetic theory served to guide the photons.
The dual nature of light possessing both wave and particle properties is clearly illustrated by combining
Planck’s expression for the energy of a photon E = hx) with Einstein’s mass-energy relation E = me2
(where, c is the velocity of light) to give
hX) = me2
Introducing v = —, we get
158
158 So/irf State Physics
h h
me p
where X is (he wavelength of photon
R was by analogy with this equation associating momentum with a photon that de Broglie proposed
(he cuncqn <ii mutter wjvexT iKxordinj.' <o which a material particle of mass m moving with a velocity v
should have an associated wavelength Xt called the de Broglie wavelength* given by:
h h
(5J)
momentuni aiv p
where h is Planck s constant. Equation (5.1) is known as the de Broglie wave equation. The mass m accord
ing to Theory of Relativity is not an invariable entity as in Newtonian physics but is given by:
where is the rest mass of the panicle and c is the velocity of light.
From equation (5.1), we find that if the panicles,

say, electrons are accelerated to various velocities, rx
we can produce waves of various lengths. The / \
higher the electron velocity, the smaller the ‘de / \ f\
Broghe wavelength-. Also the wavelength asso ------' X / ■\ j 1 /---- XZ'1---- -
ciated with a moving panicle is independent of any —JV
charge associated with it If the velocity v is given
to an electron by accelerating it through a Fig. 5 J Schematic diagram of a de Broglie wave,
potential difference V, then the work done on the electron is Ve. This work done is convened into the kinetic
energy of the electron, thus;
~mvJ = e V
2eVTa
L J
w = yfymeV
Substituting this value in the de Broglie equation, we have:
(52)
eF
Ignoring relativistic considerations, m = the rest mass of the electron
6.62 x 10*
X-
\'2^,e F \2x9.11 xlO’^ x 1.6x 11TIQV
Wflve Nature of Matter and Xây Diffracfu m L 59
1227 (5.3)
= 1 j-l' nm
VV
Note that 150 volt is enough to produce electrons of wavelength 0* 1 nm. in contrast with x-rays which
require about 12; •:o voir for 0.1 nm< Electron vote (eV i is another unit of energy. 1 eV is the energy gained
by an electron in being accelerated through a p.d of I vrdt. It is equal to L6 x 10” joule. Modem diffraction
equipments employ voltages usually of the order of 50 kvolt. corresponding to a wavelength of about 0.005
nm. In such □ case, a relativistic correction on account of variation of mass with velocity must be applied to
equation (5J)< It can be easily shown that for 50 kvoh electron this correction lowers the wavelength by
approximately 9.7^. Electron generated de Broglie waves are of short wavelengths and ure quite useful for
certain types of diffraction experiments.
111. RELATIVISTIC CORRECTION

If the electron is accelerated through very high potential difference, it is necessary ro Like mro acciumt i4 (he
relativistic increase in mass of the electron.
(5.4)
(55)
hW
From equations (5.4) and (5,5}
2E E2
2,
miZ
Thus
Now
1.227
nm (5.6)
CopyriglTled material
160 Sidiil Shite Physics
(b) Relativistic formula for total energy is (mJcSpV)1*
h c
We know, — - - ; h u» pr
p u
KJL of the election is + '
+h V)ta *- ntac2
Ratio of K E> of electron lo the energy of the photon (5 7)
IV. EXPERIMENTAL STUDY OF MATTER WAVES

One of the most direct pieces of evidence of wive aspect of particles was provided in 1927 independently by
the experiments of Davisson and Germer in the United States, and G.P Thomson in England and, subsc*
quemiy by experiment* ofO Stein and others with molecular and atomic beams The conclusion was that if
one asss elites a w^vre with a particle such as electron given by equation (5.1), then, the diffraction pattern
can be interpreted in exactly the same way as the x-ray diffrection patterns. However, it was found that
there was considerable difference between x-rays and short waves produced by electrons in that the scatter
ing coefficient of the electrons by atoms of the target substance is much higher than that of x-rays In fact,
atoms scatter electrons much more efficiently for the energies involved, and hence are preferred for structure
investigations to x-rays Electrons do not penetrate matter 10 well as x-rays. So that electron diffraction
effects result from penetration only to small depths in the material. Evidently, surface layers would nut be
n vesiigated by x-ray diffraction, because the patterns obtained are characteristic of the bulk material Note
also that diffraction of electrons by gases requires much shorter exposures than docs x-ray diffraction. This
is because of the relatively higher scattering coefficient of electrons by atoms
V. THE DAVISSON-GERMER EXPERIMENT

The first experimental evidence of the wave nature of atomic particles was provided in 1927 by C J. De vi
sion and I..H. Germer. They were studying scattering of electrons by a metal target and measuring the
intensity of electrons scattered in different directions.
The experimental arrangement used by Davisson and Germer is shown schematically in Fig. 5.2. An
electron gun. whiiih (tomprises of a tungsten filament F heated by a low tension battery £r. produces elec
trons, These electrons are accelerated to a desired velocity by applying suitable potential from a htgh tension
source The accelerated electrons are collimated into a fine beam by allowing them to pass through a
system of pin holes provided in the cylintter C. This entire arrangement u> produce a fine beam of electrons
accelerated to a desired velocity is called electron gun.
The fast moving beam of electrons is made to strike the target (nickel crystal) capable of rotating
about an axis perpendicular to the plane of th* diagnim* The electrons are now scattered in all directions by
the atomic planes of the crystalj
The intensity of rhe electron beam scattered tn a direction can be measured by the electron collector
which can be rotated about the same axis as the target* The collector is connected to a sensitive galvanome
ter whose deflection is proportional to the intensity of the electron beam entering the collector * The whole
instrument is kept in an evacuated chamber.
Copy rig hied material

Wove Nai irre < A ta Her and A- Ray Diffraction 161
—Z M’T t
(Bp
Fig, 5 h2 Davisson-Gc r w r c I ectrun di ff rac 1ion apparatus
In an investigation, the electron beam accelerated by 54 volt was directed to strike the given nickel
crystal and a sharp maximum (Fig, 53) in the electron distribution occurred at an angle of 50" with the inci
dent beam The incident beam and Ihe diffracted beam in this experiment make an angle of 65* with cite
family of Bragg's plants. The spacing of planes in this family as determined by a ray diffraction is 0 091
nm.
Fig. 53 El ecnun di (fraction.

Now according tn Bragg's equation for maxima in ttat diffraction pattern.
2d sinB •= nA.
2x0.9) x UT’(‘xsin65o= ixk
X-0,165 nm
For a 54 volt electron the de Broglie wavelength associated with the electron is given by:
^54 A*ftl66nm
This is tn excellent agreement wish the experimental value. The Davisson-Germer experiment provides a
direct verification of de Broglie hypothesis of the wave nature of moving particles*
VI. HEISENBERG’S UNCERTAINTY PRINCIPLE

The fact that a moving particle must be regarded as a de Broglie wave group rather than as a localized entity
suggests that there is a fundame rial limit to the accuracy with which we can measure its particle properties.
According la classical mechanics, a moving particle at any instant has a fixed position in space and a defi
nite momentum which can be determined simultaneously with any desired accuracy. In recent years it has
become apparent that the classical point of view represents an approximation which is adequate for the
objects of appreciable size; but does not describe satisfactorily the behaviour of particles of atomic dimen
sions.
Since a moving atomic particle has to be regarded as a de Broglie wave group, there is a limit to the
accuracy with which we can measure its particle properties. According to Born i probability interpretation,
the particle may be found anywhere within the wave group, moving with the group velocity.; If the group is
considered to be narrow»it is easier to locate its position but the uncertainty in calculating its velocity or
momentum increases. On the other hand, if the group is considered to be wide, its momentum can be esti
mated satisfactorily, but there is a great uncertainty about the exact location of the particle. Heisenberg, a
German Scientist, enunciated in 1927 the incfaerniirtacy or uncertainty principle, which states that the
simultaneous determination of the exact position and momemum of a moving particle is impossible. Jn gen
eral if Ax denotes the error in the measurement of the position of the particle along x-axis and tip represents
the error m the measurement of momentum, then
Ax * Ap = h (5*8)
where h is Planck's tamtam. 'I’he above relation represents the extern of the uncertainly involved in the
measurement of both the position and momentum of the particle.
When one defines (Ax) and (Ap) as r.ms, deviations and assumes the optimum measurement proce
dure, it turns out that the lower limit in equation (5,8) is
h h t A h
— or - where n -
4n 2 2rt
Thus (Ax l (&p) i | (5.9)
Equation (5.9} is one form of the uncertainly principle first obtained by Werner Heisenberg in 1927*
It states that the product of uncertainty Ax in the position of a body at some instant, and the uncertainty A/? in
its momentum at the same instant, is ai best equal to Planck’s constant. We cannot measure simultaneously
both position and momentum with perfect accuracy* In fact, equation {5.9} tells us that we could locate a
partide exactly (Ax -+ 0) only at the expense of imparting to it an infinite momentum (Ap —> «); i.e,T an
exact position measurement requires the expenditure of an infinite amount of energy.
The uncertainty relation discussed above applies specifically to position and momentum, There is not
an uncertainty relation between any pair of variables, but only between certain pairs. There are uncertainly
164 Souo State Physics
uncertainty relations, for instance, between position and momentum, energy and time, and angular
momentum and angle. All these relations have the form as equation (5.9). Thus, if the time during
which a system occupies a certain state is not greater than A/, then the energy of the state cannot be
known to within AE, where:
(AE)(Ar)>| (5.10)
Thus, for example, if an electron remains in an excited state for 10"$ s, the uncertainty in the
energy of that state must be:
1 h
(AE)>-— =------------
2 Ar 4tix10^
_ (6.62 x IO"34 xlO8)
4k
= 0.527 x IO"26 J
_ 0527 x 1026
1.6 x 10~19
= 3.29 x 10~$ eV
The uncertainty is best understood and illustrated

by the example of diffraction through a slit If we propose
to regard the passage of an electron through a slit and
the observation of the diffraction pattern as a
simultaneous measurement of position and momentum
from the stand point of the corpuscle concept then the
breadth of the slit gives the ‘uncertainty’ Ax in the
specified position perpendicular to the direction of the
flight. For the fact is that a diffraction pattern merely
allows us to conclude that the electrons have passed
through the slit; at what place in the slit the passage took
place remains quite indefinite.
Again, from the standpoint of the corpuscular theory the occurrence of the diffraction pattern on
the screen must be understood in the sense that the individual electron suffers deflection at the silt,
upwards or downwards. It acquires component momentum perpendicular to its original direction of the
flight, of amount Ap. The mean value of Ap in Fig. 5.4 is given by Ap =p sin a, if a is the mean angle
of deflection. We know that, the experimental results can be explained satisfactorily on the basis of the
wave representation according to which a is connected with the slit width Ax and the wavelength
h
X = —, by the equations:.
Ax sin a= X =
Wwe. Nature or MxrrtR ah6 Xfotf PfFtRAcno*,
Thus, A/>spsina= — = ——a —

Ax Ar p fa.
(Ar) (A/>) = h
or
which is Heisenberg’s uncertainty principle.
One interesting question is whether electrons are present in atomic nuclei or not. As is known,
typical nuclei are less than 10“14 m in radius. For an electron to be confined within such a nucleus, the
uncertainty in its position may not exceed 10~14 m. The corresponding uncertainty in the electron s
momentum is.
h
4tt(Ax)
. . 6.62 xl0~34 ....

Ap - --- ---------- 23— = 0.526 x IO-20 kg-m/s
4rc x IO-4
If this is the uncertainty in the electron’s momentum, the momentum itself must be atleast
comparable in magnitude. An electron whose momentum is 0.5 x IO-20 kg-m/s has a kinetic energy E
many times greater than its rest mass energy m0c2.
0.526 x IO"20 x 3 x 108 ..

•:. < E = pc — ———■----- ——rj——eV-.;
. 1.6 xlO’19 :,.-
feV 25 *=, lO MeV.$■„

The rest mass energy of the electron mQc2 is 0.5 MeV, which is negligible compared to the
kinetic energy. Experiments indicate that the electrons associated even with unstable atoms never have
more than a fraction of this energy, and we thus conclude that electrons cannot be present within nuclei.
X-rays are electromagnetic waves like ordinary light, therefore, they should exhibit interference and
diffraction. The wavelength of X-rays is of the order of 0.1 nm, so that ordinary devices such as ruled
diffraction grating do not produce observable effects with X-rays. In 1912, German physicist Laue
suggested that a crystal which consisted of a three-dimensional array of regularly spaced atoms could
serve the purpose of a grating. The crystal differs from the ordinary grating in the sense that the
diffracting centres in the crystal are not in one plane. Hence the crystal acts as a space grating rather
than a plane grating.
On the suggestion of Laue, his associates, Friedrich and Knipping succeeded in diffracting X-rays
by passing them through a thin crystal of zinc blende. The diffraction pattern obtained consists of a
central spot and a series of spots arranged in a definite pattern around the central spot. This symmetrical
pattern of spots is known as Laue pattern and it proves that X-rays are electromagnetic radiation. A
simple interpretation of the diffraction pattern was given by W.L. Bragg. According to him, the spots
are produced due to the reflection of some of the incident X-rays from the various sets of parallel crystal
Planes (called Bragg’s planes) which contain a large number of atoms.
- 9ou» SlWTt PHVSKS
"VWl. BRAGG’S LAW

*■*»>I *. *. W-- ' -w~«w <^.4 .- .w » »X «
Consider a ray PA reflected at atom A in the

direction AR from plane 1 and another ray QB
reflected at another atom B in the direction BS.
Now from the atom A, draw two perpendiculars
AC and AD on QB and BS respectively. The two
reflected rays will be in phase or out of phase Plane 1
depending on the path difference. When the path
difference (CB + BD) is a whole wavelength (A)
Plane II
or multiple of whole wavelength (nA), then the
two rays will reinforce each other and produce an
Plane III
intense spot Thus condition of reinforcement is:
Fig. 5.5 Reflection of X-rays from lattice planes
CB + BD = nA,
in a crystal
From Fig. (5.5), we have
CB = BD = dsin0
where, 0 is the angle between the incident ray and the planes of reflection (glancing angle). Therefore,
2d sin 0 = nA . • (5.11)
where, d is the interplanar spacing of planes and n = 1,2, 3,... stands for first order, second order, third
order,... maxima respectively. Equation (5.11) is known as Bragg’s law. Different directions in which
intense reflections will be produced can be obtained by giving different values to 0, i.e.,
for first maximum, sin 0, = —

1 2d
. , . • « 2A
for second maximum, sin 0, = —
2d
3A,
for third maximum, sin 0, = — and so on.
3 2d
It should be remembered that the intensity goes on decreasing as the order of spectrum increases.
Thus we see that when a beam of monochromatic X-rays falls on a crystal, each atom becomes
a source of scattering radiations. It has already been mentioned that in a crystal there are certain planes
which are particularly rich in atoms. The combined scattering of X-rays from these planes can be looked
upon as reflections from these planes. Generally, the Bragg scattering is regarded as Bragg reflection,
and hence are known as Bragg planes. At certain glancing angles, reflections from these set of parallel
planes are in phase with each other, and hence they reinforce each other to produce maximum intensity.
For other angles, the reflections from different planes are out of phase, and hence they reinforce to
produce either zero intensity or extremely feeble intensity.
Ways Narine of Mahw and JHImQwwcdD* *
1V bracG’S X-RAY SPECTROMETER

, - devised an apparatus known as X-ray crystal spectrometer where the crystal was used not as a
B^ntssion grating. but as a reflection grating. X-rays from an X-ray tube were allowed to pass through
°S' < and 5- so as to obtain a narrow beam which is then allowed to strike a single crystal D mounted
^<tS (um-tabie. The crystal is rotated by means of the turn-table so as to increase the glancing angle at
x-rays are incident at the exposed face of the crystal. The photographic plate or an ionisation
Juinber is used for measuring the intensities of the reflected rays. The angles, for which reflection
’ntensities are maximum, give the values of 0 of equation nk = 2d sin 0. The process is carried out for
h plane of the crystal, n = 1. creates the condition for the lowest angle at which the lowest reflection
'.mis. n = 2 creates the condition for the next higher angle at which maximum reflection occurs and
soon.
Thus, for n = 1, A. = 2d sin 0,,
n = 2,2X = 2d sin 0,,
n = 3,3X = 2d sin 03, etc.
where. 0., 0-> and 03are glancing angles for n = 1,2 and 3 respectively.
CHAPTER 5
Kg. 5.6 Bragg’s X-ray spectrometer
Now,
sin 0.: sin 0,: sin 0, = 1:2:3 (5.12)
Hence, by measuring glancing angles at which reflections occur, we can determine the interplanar
spacings by knowing the wavelength of X-rays. If the above proportionality is verified the assumption
of Bragg’s theory is that X-rays are reflected like ordinary light, gets proved.
The structure of rocksalt (NaCl) crystal was studied by using Bragg’s ionisation spectrometer
and intensity or ionisation current was determined for different glancing angles. If a graph is plotted
between intensity or ionisation current and glancing angle, the following intensity order of reflection
diagram is obtained.
Ufa IV Nature of Matter and J!-Roy BlffracfloM 1 /J
The experimental results from Bragg's method have shown that if x-rays from a palladium antica
thode are used, the first order reflection maxima occurred at 5.9*, 8.4* and 52* for (100). (110) and (111)
planes respectively. Now from Bragg’s equation.
sinO
Fbr first order reflection, n - 1
and hence
2 sin 0
or
sin9
Therefore.
îdo• : din . uj
sin ■ At/j, : sin
- ’ sin ■ Ui
Fig. 5.7 Variation of ionisation current with glancing angle.
rf‘“: J"»: sin 5.9’: sin 8.4’: sin5.2’
= 9.73 : 6.84 : J i .04
= I : 0.703,: 1.14
(5.13)
This procedure may also be followed for other crystal systems such as tetragonal, hexagonal, etc. Table 5.A
gives the values of ratios between interplanar distance of the planes (100)t (HO) and (111) for the cubic
structures.
Thus we see that sodium chloride crystal has a face centred cubic structure.
qwMKumwi nwijRiJuiRWB
The Laue’s and Bragg’s techniques for the investigation of crystal structures can be applied only if single
crystals of reasonable size are available. But in general, large crystals, without fault are difficult to obtain.
Therefore, Debye-Scherrer adopted a different technique. The specimen was taken in the form of a well
powdered sample of the crystal in a thin glass capsule. The experimental arrangement is shown in Fig. 5.7(a).
CHAPTERS
A narrow beam of these monochromatic X-rays
suitably collimated by two lead slits Sj and S2, falls on the
powdered specimen 5. The specimen is suspended vertically
on the axis of a cylindrical camera. The photographic film is
Fig. 5.7(6) Developed Film
mounted round the inner surface of the camera, covering
nearly the whole circumference in order to receive the beams diffracted up to 180°.
The powder specimen of the crystal can be imaginated to be a collection of random oriented tiny
crystals, presenting all values of glancing angles to the incident beam. For a given wavelength and a
given value of d, there can be only one value of 0 (glancing angle) which satisfies the equation 2J sin 0
s where, n = 1. Such reflected beams emerge out from the specimen in all directions inclined at an
angle 20 with the direction of the incident beam, because millions of tiny crystals in the specimen are
random oriented. The reflected rays will be on the surface of a cone, vertex at the specimen, base on the
photographic film and having a semi-vertical angle 20. The traces obtained on the photographic film
wil1 be as in Fig. 5.7(b).
170 Spun STATEPH^____________ - ^directbeam strikes the film at 0. Suppose
Let L be the radius of the cy * a distance R from 0. Then 0 = -. Using fc
—- '“-rX-—-x *
metals, alloys, carbon. —■
•'Xf.~RUTATiNG CRYSTAL METHOD' '
In this method a small and well-formed single crystal is mounted perpendicular to the beam. The fihn is
generally held in a cylindrical camera. Now when the crystal is rotated slowly, and during the time of
exposure, successive planes pass through orientation, which are necessary for Bragg’s reflection, each
producing a spot on the film. The position on the film when developed indicates orientation of the
crystal at which the spot was formed. The data obtained from these spots give information about the
structures of ordinary and complex molecules.
Let us consider the surface layer of a crystal on which an X-ray of wavelength A. (in air) is incident
Suppose 9 is the glancing angle, and we take the layer immediately below the surface, the glancing
angle at that layer will not 0 but O'.
The Bragg’s law for the reflection at that layer is:

nA' = 2d sin 9' (5.14)
where, X' is the wavelength in the crystal.
The refractive index Ji can be written as:
U “• ~
. sini
sinr
cos9
O' ~
cos 9
X
A
’
(5.15)
or
Substituting this in the above equation (5.14), we get:
Fig. 5.8 Refraction of X-rays on layers of a crystal

X
n —
nX = 2d p [1 - cos2 0']1'2
= 2d [p2 - p2cos2 0'],/2
a 2d [p2 - cos2 0]1/2
= 2d [p2 - (1 - sin2 0)]1/2 i
= 2d [p2 - 1 + sin2 0]1/2
1V2
sin2 6
The value of (1 + p) is approximately 2 as is p nearly 1.
. (1-H)
Thus nX = 2d sin 0 1
2 sin20
sin2 0
6= (1 -11)
5 (5.16)
sin20_
We know,
nX = 2d sin 0
■
sm0 = 7?"
CHAPTER 5
Substituting this in equation (5.16), we get.
4&T
nX = 2d sin 0 1- (5.17)
n2X2
_ • .
Hence, equation (5.17) is modified Bragg’s equation. The correction term 4rf25 decrease as n
increases for a given value of X. Thus, Bragg’s ordinary equation t)X = 2d sin 0 holds good for higher
values of n.
wtto Wre Physics
OBJECTIVE QUESTIONS
The wave property of large, massive objects is not observed because

(a) their accelerations are too small (b) their momenta are too large
(c) their speeds are too small (d) none of these
The de Broglie wavelength associated with an electron of mass m and accelerated by a potential V is
72m eV
(*)
h
z~ h
(d)-------
meV 2meV
The wavelength associated with a moving particle
(a) depends upon the charge associated with it
(b) does not depend upon the charge associated with it
(c) depends upon the medium in which the particle travels
(d) none of these.
A proton and an a-particle has the same kinetic energy. If the mass of the a-particle is four times that of a
proton, how do their de Broglie wavelength compare?
(c) Aj, = 21a (d) Xp = 4Xa

The de Broglie wavelength 1 associated with an electron taking into account the relativistic correction.
eV
(a) ———
IrriQeV m^c2
2m$eV eV
Th mQC2
Davisson and Germer were the first to demonstrate
(a) the straight line propagation of light (b) the diffraction of photons
(c) the effective mass of electrons (d) none of these
Can the X-rays of wavelength greater than 2d be diffracted from the crystal
(a) Yes (b) No
Because of which property of the crystals, X-rays can be diffracted from the crystals
(a) random arrangements of atoms (b) colour of the crystals
(c) periodic array of atoms (d) none of these
An electron, neutron and a proton have the same de Broglie wavelengths; which particle has greater
velocity ?
(a) electron (b) proton
(c) neutron
Wave Nature of Matter ano X-Ray 0W**c**g^
IO In Thomson’s experiment of diffraction, he used

(a) slow neutrons (ft) fast neutrons
(c) slow electrons (d) fast electrons
11 Electron behaves as wave because they can be
(a) deflected by an electric field (ft) diffracted by a crystal
(c) deflected by a magnetic field (J) they ionise a gas
12 In a Davisson-Germer experiment the hump is most prominent when the electron is accelerated by
(a) 34 volt (ft) 54 volt
(<?) 60 volt (d) none of these
13. The G.P. Thomson experiment confirmed
(a) the particle nature of electrons (ft) the negative charge of the electrons
(c) wave nature of electrons. (d) very light mass of the electrons
14. The de Brogile wavelength of the thermal neutrons at T kelvin is
3mkBT
<C) 3mk,T
~h
15. Which one of the following statements is correct?
(a) X-rays are electromagnetic radiation of long wavelength
(b) X-rays produced in a gas tube are different from those in Coolidge tube
(c) The wavelength of the scattered of X-rays by a material is longer than that of the incident beam
(d) X-ray spectral lines are produced when fast moving electrons are retarded by a material
16. If 50 kV is the applied potential in an X-ray tube, then the maximum wavelength of X-rays produced is
(a) 0.2 nm " (b) 2 nm
(c)0.2A (J) 2 A CHAPTER 5
17. X-rays consist of ' > ,
(a) negatively charged particles (b) electromagnetic radiation
(c) positively charged particles . (d) a stream of neutrons
18. X-rays are produced when an element of high atomic weight is bombarded by high energy.
(a) protons ’ (b) photons
(c) neutrons ' . (J) electrons
19. When the potential difference between the electrons of X-ray tube is increased, there take place an increase
in the
(a) intensity (b) frequency
(c) wavelength (d) speed of X-rays
20. X-rays can be deflected by
(a) magnetic field (b) electric field
(c) none of these
21. As the wavelength of X-rays is smaller than that of visible light, the speed of X-rays in vacuum is
(a) same as that of visible light (b) larger than that of visible light
(c) smaller titan that of visible light
22. According to Moseley’s law, the frequency of the characteristic X-radiation is proportional to the square of
(a) atomic weight of the element (b) atomic number of the element
(c) none of these
23. The wave number of the characteristic radiation
(a) decreases with increasing atomic number of the anode

(b) increases with increasing atomic number of the anode
(c) none of the above
24. Is the energy of Ka and La lines equal
(a) Yes (*) No

25. The constant a in Moseley’s law is
(a) screening constant (b) Rydberg constant

(c) atomic number (d) none of these
26. The constant a in Moseley’s law related with Rydberg constant as
4a
(a)R (b)R
4a
a T2cl
(c)R = — (d)R = —
L2cJ _a_
where, c is velocity of light.
27. If the angle between the direction of the incident X-ray and the diffracted is 16°, the angle of incidence
will be
(a) 32 o (b) 24'o
(c) 90 |O
(d) 82'o
28. The short wavelength limit of X-rays depend upon
(a) nature of the target (h) p.d. across the X-ray tube
(c) nature of the filament used (d) none of these
29. The variation of the intensity of X-rays with the thickness of the absorbing material is given by
(a) I -IQ exp(- px) (£>) I = IQ exp(px)
(c) I = IQ exp(- p /x) (c) I = Zo exp(p lx)
where p is the absorption coefficient.
Wavi Natum Of Mahm ANO X4UV DWWJfltW *
-SHOKI.QUESTIONS A
I. What arc matter waves? How are they experimentally verified?

*• Deduce an expression for the wavelength of matter waves.
3. Explain the considerations that led de Broglie to postulate matter waves.
What are de Broglie s matter waves? Derive an expression for the wavelength of such waves.
5. What are de Broglie’s matter waves? Describe their properties?
Explain matter waves ’. Give the principles of the experiment to establish the wave nature of electrons.
7. State the Moseley’s equation relating to X-ray wavelength and atomic number of the element.
8. Describe characteristic X-rays and explain how their study leads to Moseley’s law.
Give the significance of Moseley’s law.
10. Explain how X-rays are used for determining the crystal structure.
U- Enumerate the scientific uses of X-rays.
12. State and explain Moseley’s law.
13< Show that the circumference of an electron orbit in a hydrogen atom in an integral multiple of the de Broglie
wavelength of the electron in the orbit.
14- Explain Bragg’s law for X-ray diffraction in crystals.
15. Give the important applications of X-rays in industries.
10. Distinguish between soft X-rays and hard X-rays.
17. If the angle between the direction of the incident X-rays and the diffracted one is 16°, what is the angle of
incident?
- WIIRI Ulf
- 11”'1 ........... ..11 ftpV]£^ 00^10157""
frri winner aumnii
Explain de Broglie’s conception of matter waves. Prove the relation

X= h/mv.
CHAPTER 5
Discuss the de Broglie’s hypothesis of duality for material particles. Give in detail the experiment of
Davisson and Germer in support of the hypothesis.
Show that the wavelength of an electron moving with a small velocity compared to that of light accelerated
by a p.d. of V volt can be written as,
, 1.227
X = —- nm.
Show that the wavelength of an electron beam accelerated by a potential V volts is
h
J2mêv[
R eV
applying relativistic correction.
Ri' Souo Swre Physks
5. What is de Broglie’s hypothesis? Show that the wavelength X associated with an electron of mass m and
kinetic energy E is given by
6. Give the statement of Heisenberg’s uncertainty principle. Discuss its significance and importance.
7. State Heisenberg's uncertainty principle. Give an example of this principle. How does it help us to decide
whether electrons exist in the nucleus or not?
8. Deduce Bragg's law in X-ray diffraction. Describe Bragg’s spectrometer and explain how it is used to
determine the wavelength of X-rays.
9. Discuss a method of investigating the structure of a single crystal using X-rays.
10. Derive Bragg’s law of X-ray diffraction in crystals. Give an account of powder method of crystal structure
analysis.
11. Derive Bragg’s law for X-ray diffraction in crystals. How is it verified? Describe and explain X-ray
spectrometer method of determining X of X-rays.
12. Obtain Bragg’s equation for X-rays. Apply the necessary correction for this equation.
13. Discuss a method of investigating the structure of a single crystal using X-rays. .
1. 10 kV electrons are passed through a thin film of a metal for which the atomic spacing is 5.5 x 10-11 m
What is the angle of deviation of the first order diffraction maximum? ■
2. Determine the wavelength associated with an electron having kinetic energy equal to 1 MeV.
3. X-rays of wavelength 0.082 nm fall on a metal plate. Find the wavelength associated with photoelectrons
emitted. Neglect the work function of the metal.
4. An electron has a speed of 4 x 105 m/s, accurate to 0.01%. With what fundamental accuracy can we locate
the position of die electron? - .
5. Calculate the angle of incidence at which electrons of energy 100 eV must be incident on the lattice planes
of a metal crystal in order to give a strong Bragg reflection in the first order, given that the lattice spacing
is 0.252 nm.
6. A neutron beam of K.E. 0.04 eV is diffracted at the plane (1 0 0) of sylvine crystal (d. 0 0 = 0.314 nm).
Calculate the glancing angle at which first order Bragg spectrum is observed (neutron mass = 1.6 x IO-27 kg)
7. Compare the uncertainties in the velocities of an electron and a proton confined in a 1 nm box.
8. Calculate the time required for the atomic system to retain the excitation energy for a line of wavelength
600 nm and width 10-5 nm.
9. If the uncertainty in the location of a particle is equal to its de Broglie wavelength, what is the uncertainty
in its velocity?
| Wave Nature of Matter
10 The position and momentum of a I keV electrons are simultaneously determined. If its position is located
to within 0.1 nm, what is the percentage of uncertainty in momentum?
II An electron is accelerated by 50000 V. Calculate the wavelength associated with the electron, applying
relativistic correction. Find the percentage of error in the measurement.
12 In an experiment to study the wave nature of moving helium atoms, the gas was heated in an enclosure to
400 K, from which a beam of atoms emerged through a slit. Calculate X associated with helium atoms.
13. Calculate on the basis of wave mechanical theory the wavelength associated with (7) an electron moving
with the speed of the electron in the K orbit of hydrogen atom and (ii) a molecule of hydrogen at 0°C.
14. If E is the kinetic energy of a particle with rest mass /n0, prove that its de Broglie wavelength is given by:
. ch
A, = —j
^2E(E + m^c2)
15, An electron is confirmed to a box of length 10~9m, calculate the minimum uncertainty in its velocity.
16 Find the smallest possible uncertainty in the position of an electron moving with a velocity 3 x 107 m/s.
17. Determine the velocity of a particle at which its mass becomes double its rest mass.
18 An electron has a speed of 6.6 x 104 m/s within the accuracy of 0.01%. Calculate the uncertainty in the
position of the electron.
19 A nucleon is confined to a nucleus of radius 5 x 10~15 m. Calculate the minimum uncertainty in the
momentum of nucleon. Also calculate the minimum kinetic energy of the nucleon.
i 20. Calculate the glancing angle on the cube (1 1 0) of a rock salt crystal (a = 0.2814 nm) corresponding to
! second order diffraction maximum for the X-rays of wavelength 0.071 nm.
21. A beam of X-rays incident on a sodium chloride crystal (lattice spacing 0.282 nm). The first order Bragg
reflection is observed at a glancing angle of 8°35'. What is the wavelength of X-rays? At what angles
; would the second and third order Bragg’s reflections occur?
i- 22. Electrons are accelerated by 344 volt and are reflected from a crystal. The first reflection maximum occurs
when the glancing angle is 60°. Determine the spacing of the crystal.
23. Sylvine (KC1) crystallises in the form of a simple cubic structure. The density of sylvine is 1990 kg/m3
and molecular weight 74.6. Determine the principal grating spacing of sylvine. Also determine the glancing
r angle at which an X-ray spectral line of wavelength 0.1787 nm is reflected in the third order. CHAPTERS
! ' '
24. A crystal plate is mounted on an X-ray spectrometer. The glancing angles of incidence for three reflections
are 5°58', 12°01' and 18°12'. Show that these are successive orders of reflections from the same crystal
plane. Also find the spacing, given A, of X-rays used in 0.0586 nm.
I- 25. if the p.d. across the X-ray tube is 5,000 volt and the current through it is 2 mA, calculate the number of
electrons striking the target per second, and the speed at which they strike it. Also calculate the shortest
wavelength of X-rays produced.
26. Given a square piece of X-ray film 10 cm x 10 cm, radiation of A = 0.152 nm and powdered NaCI with a
lattice parameter 0.563 nm, devise a diffraction experiment in such a fashion that the rays from (111)
planes will produce a circle of diameter 0.1 m. If NaCI is replaced by AgCl, how would the intensity of the
i diffracted beam be affected, assuming that the structure and parameter remain the same?
F
pI
t
F
r
t-
r
1^8 Somd State Physics
27. An X-ray tube passes 10 mA current at a p.d. of 150 kV. Calculate (0 the rate at which the target is being
heated if only 1 % of the incident energy is converted into X-axis (ii) the average rise of temperature of the
target if it weights 0.3 kg and has a specific heat 146.5 J kg^K'l
2& A crystal piece of a cubic mineral is mounted in an X-ray spectrometer and the intercepts of the well-defined
crystal edges, in terms of unit cell edges, are found as follows;
1*
* t
Axes
Crystal faces
a b c
1 0.287 1.0 0.251

2 ' -0.287 1.0 oo
3 OO 3.0 0.125
4 0.287 oo oo
5 0.860 2 • .. 0.125
6 0.574 oo 0.125
Find the Miller indices pf these planes.

29. A certain orthorhombic crystal has a ratio a : b: c = 0.429 : 1 : 0.377. Find the Miller indices of the faces
whose intercepts are:
0.214 : 1: 0.188
0.858: 1 :0.754
0.4290.126.
30. What is the de Broglie wavelength of an electron moving with the velocity of — ?
[Take the value of the rest mass of the electron as 9.11 x 10r31 kg.]
31. A beam of silver atoms for an experiment is produced by collimating atoms that vapourise from silver
held in a furnace at 1200°C. If the beam travels 1 metre, use the uncertainty principle to find the order of
magnitude of the smallest spot that can be obtained at the detector.
32. A small 10 W source of ultraviolet light of wavelength 100 nm is held at a distance of 0.1 m from a metal
surface. If the radius of an atom is approximately 0.05 nm, how many photons strike an atom per minute?
If the efficiency, i.c., the fraction of the photons that succeed in knocking out the electrons is 1%, how
many electrons are ejected from unit area per second? ’ ' ' •
33. A beam of 0.25 eV neutrons incident on a nickel surface is found to produce a maximum at an angle of 70°
with the initial beam direction, but no other maxima are produced for angles greater than 70°. Determine
the interplanar distance for the crystal. . /
Wave Nature
What is the de Broglie wavelength of neutrons at room temperature? Can they be used to study crystal
structure?
An electron has a de Broglie wavelength equal to that of a photon. Show that the ratio of the kinetic energy
of the electron to the energy of the photon is
[(m^c4 + h2v>2)V2 - wipe2]

fro •
What is the limiting value of this ratio for low energy photons ? If the photon has an energy of 100 keV,
what is the kinetic energy of the electron?
An electron initially at rest is accelerated through a p.d. of 5000 V. Calculate (i) the momentum (ii) de
Broglie wavelength and (in) wave number. Also calculate the Bragg angle for first order reflection from
(1 1 1) planes which are 0.2 nm apart
ft CHAPTER 6
ELECTRICAL PROPERTIES OF METALS
t. INTRODUCTION
Moiion of charged elementary partk-k^ in solids is responsible for the manifestation of electrical resistivity
m much the same way as the motion of uncharged particles in fluids is responsible for the manifestation of
viscosity. Here, as m viscosity, the statistical nature of the motion calls for a study which in all rigour should
utilize methods of thermodynamics and statistical mechanics.
It is known from elementary physics that a metallic filament connected to the poles of a battery or any
other source of electric current becomes hot and incandescent and ends up by melting if the current is high
enough. This is one of the simplest and the more obvious mamfesiatiotis of the resistance materials offer to
the passage of an electric current. It is being exploited for heating and illuminating purposes in a variety of
domestic and industrial applications. In a broad sense, resistance to an electric current appears whenever the
motion of a charged particle in an electric held is being impeded by the motions of or collisions with other
charged or neutral part kies. Its manifestations then can vary from the glow of neon lamps to the controlling
action of photo cells, vacuum lubes, and transistors. The more recent manifestations have to do wiih prob
lems such as direct energy conversion (in solar batteries), stimulation and amplification of one kind of
energy by another (in masers and lasers) and control of thermonuclear reactions*
In solids the carriers of electric current are electrons alone, and their interaction with the relatively sta
ble rigid iomc lattice can be approximated to some extent by viewing the interaction as a collision between
small electrons and individual large ions. We begin by applying this concept to metallic conductors and then
extend it to semiconductors. Following are some of the outstanding physical properties of metals:
1 • Metallic conductors obey Oh/n r /an; which states that the current in the steady state is proportional to
the electric field strength.
2. Metals have high electric and thermal conductivities.

3. At low temperatures, the resistivity is proportional io the Fifth power of absolute temperature; teM
p « r3
4. The resistivity of metals at room temperature is of the order of 10 7 ohm metre and above Debye's
temperature varies linearly with temperature;
p« T
5. For most metals, resistivity is inversely proportional to the pressure; i.e., p^^
6, The resistivity of an impure specimen is given by Mathiessea rate
Blictnicai PnoFiimtt er Mv*m» 1*1
6. The resistivity of an impure specimen is given by Mathieson's rule.

P = Po + P(D
xvhere p0 is a constant for the impure speci men and p(7) is the temperature dependent resistivity
of the pure specimen.
7. Near absolute zero, the resistivity of certain metals tends towards zero; l.e., exhibit the
phenomena ot superconductivity.
: 8. The conductivity varies in the presence of magnetic field. This effect is known as magneto
resistance.
9. The ratio of thermal to electrical conductivities is directly proportional to the absolute
| temperature. This is known as Wiedemann-Franz Law.
Metals achieve structural stability by letting their valance electrons roam freely through the crystal
lattice. These valance electrons are the equivalents of the molecules of an ordinary gas. Since electrons
are negatively charged particles, their motion corresponds to a flow of electricity, or electric current. It
is assumed that the electrons are moving about at random and colliding frequently with the residual
ions. Hence, the laws of classical kinetic theory of gases can be applied to a free electron gas also. Thus
I
r the electrons can be assigned a mean free path X, a mean collision time X and an average speed c.
I
In the absence of an externally applied potential difference, there are on an average as many
electrons wandering through a given cross-section of the conductor in one direction as there are in the
opposite direction. Hence the net current is zero. In between two collisions, the electron may move with
the uniform velocity. During every collision both the direction and magnitude of the velocity get changed
in general. The zigzag motion is the thermal motion of the electron.
In 1990, P. Drude made use of the electron gas model to explain theoretically electrical conduction
in metals. According to his theory the kinetic velocities of the electrons are assumed to have a root
mean square velocity c given by kinetic theory of gases in conjunction with the law of equipartition of
energy, c is obtained as follows:
J For unit volume of the metal
„ 1 _2 1 _2
P = -pc = -mnc
3r 3
where, m is the mass of the electron and n is the number of free electrons in unit volume and p is density
of the electron gas.
For molar volume of the metal
„ 1 -2 1 mNAc2
p=-;pc 2 =
m
where, Vm is molar volume and N. is Avogadro’s number,
CHAPTERS
r\
Now PV = 7mNA c2 = RUT

m *2 *» *
"3V
Thus, = 3kflT
where, Ru and kB are universal gas constant and Boltzmann's constant respectively.
The kinetic energy of the electron is
(6.1)
and
(6.2)
At 20°C
__ [3x1.38 x!0~23 x293

C~[ 9.11 xlO-31
c = 1.154 x 105 m/s

Equation (6.2) indicates that the root mean square velocity of the electron is directly proportional
to the square root of the absolute temperature of the metal. At room temperature, the drift velocity
imparted to the electrons by an applied electric field is very much smaller than the average thermal
velocity. The time T taken by the electrons in traversing the distance X, will thus be decided not by the
drift velocity due to the field but by much greater velocity c due to the kinetic thermal motion. Now
(6.2a)
A vital test of the validity of any theory of electrical conductivity is whether or not it can account
for Ohm’s law. This law is usually expressed as V = RI, where I is the current flowing through a
conductor as the result of applying a potential difference V across its ends; at a given temperature, R the
resistance, is a constant for a given conductor. In order to simplify the analysis let us rewrite the law in
I dV
terms of the current density, J=— and field strength along the conductor, E =-------- .
A dx
Thus, we have
F'-
1 _ AR _ Api _ p
7 = V" ~AEl = ~E
.. ' J= — =gE (6.2b)

P • • *
where, the resistivity p and conductivity o of a conductor of length I and area of cross-section A are
related by
ELECTRICAL Pitoncm ,OF- Mem*» >1
Let us now assume that there are n free electrons per cubic metre, and that in the absence of any
lied field, these are darting about in all directions with no net velocity just like gas molecules in a
^taincr. When a field Ex is applied in the x-direction, all electrons are accelerated in the x-direction,
. the acceleration of the ith electron, a^, is given by
Alternatively, this equation may be written as
(6.3)
5
may write equation (6.3) in another form: 10D *S same for electrons> we
d eEx
—<v > = - —- (6.4)
_dt x j£ I m
where, < vx > is the average velocity of all n free electrons as given by
We have used < vx > to denote the average value of v. The current density J is the charge flowing
through unit area in unit time, so that x-component, Jx must be the number of electrons times the charge
on each in a volume of unit area and length vx; that is,
Jx = n<vx>(-e) = -nevx .. (6.5)
The minus sign, which is coupled to the charge on an electron, underlines the fact that the
conventional direction of current of Jx) is in the opposite direction to < vx >.
On differentiating equation (6.5), we have
d , , 1 f dJx
[<v >] = -------- -i (6.6)
dt ne L dt
Comparing this with equation (6.4), we see that

CHAPTER 6
Fd/rl = Constant x Ex
X
(6.7)
dt
i,
so that for a constant Ex, this free electron model leads to a current which increases linearly with time.
Nothing could be farther from Ohm’s law\
Electrical Properties of Metals 1S3
>M
Fig. 6 J Calculation of current denitiy

dZ
ft is dew* from equation (6.6) that the law cun only be satisfied that is, ~ = 0 < Vx >=E 0.
Since nothing that we have just written is actually wrong* the difficulty must arise because we have omitted
to include a decelerating term which* when added to
gives a net — < vA > = 0.
Once again we conclude that the electrons cannot be completely free. From the observation that a
conductor always warms up when a current it flowing, we deduce that the conduction elecwms must collide
and exchange energy with the ions-a process normally referred to as electron-lattice scattering. The equa
tion governing the sum of the accelerations should* therefore* contain two terms:
(6.8)
We can* m principle, feed details of applied electric and magnetic fields as well as temperature gra
dients into this type of equation, and solve it in order to obtain the resultant electric and thermal current.
Unfortunately, in practice; this is an exceedingly difficult operation. The main problem is in obtaining the
scattering term, which can only be obtained by quantum-mechanical technique. Furthermore* this method
normally ends up with an integnxfiffereiuial; equation which is extremely difficult to solve We shall
therefore, obum an expression for by a method which by-passes these difficulties
Suppose at an insiant* / - 0, the average velocity of the electron is < Just at that instant we
switch the field off, so that < vT > subxequemiy tends to aero*
In other words, the velocity will be randomized by electron-lattice collision*. Now let ns assume that
this process follows the simplest law of decay*
<», >*<•', >9*^* (6.9)
| T 'S 8 cons*ant °f system known as the relaxation tune, because it gives a measure
' It is, infect, the time taken for the drift velocity to decay to 1 of its initial value. Since E = 0 during this
relaxation process, we see that equation (6.9) can be used to obtain electron-lattice term in equation
(6.8), and that this is done in such a way as to avoid having to consider any details of the collision
process. The result is
d
(6.10)
[ ' ff we assume that this expression is unchanged by the presence of a field, we have, from equations
[ (6.4), (6.8) and (6.10)
=0
(6.11)
Fig. 6.1 (a) Relaxation of a system of electrons to equilibrium

after removing the electric field
This steady average velocity imposed by the field and proportional to it, is called the drift velocity
of the electrons. The constant of proportionality, _, is known as their mobility, p and the drift velocity
CHAPTER 6
m
for unit electric field is given by
■ Swre tanas
The units of p are metre per second per volt per metre or m2 V *s l.
Finally, we see that by combining equations (6.2Zj), (6.5) and (6.11), we have
ne2X m
a =------ or p = —q— (6.12)
m ne x
1
and G - nett or p =----- (6.13)
nep
This last equation is of great importance in the theory of conductivity, and embodies the difference
between the electrical properties of metals and semiconductors. In metals, where all the valence electrons
are free at all temperatures, n is a constant and the temperature variation of o is essentially the temperature
variation of p. In semiconductors, however, n may also vary with temperature and it is usually the most
important factor.
Alternate Method
Materials in solid form exhibit quite a lot of interesting properties very useful for devices in science and
engineering practice. In ionic materials, the movement of ions is mainly responsible for electric
conduction. Experiments show that charge can be carried both by positive or negative ions, which
become more mobile as the temperature increases and thus more free to wander through the lattice
when an external electric field is applied across the crystal. Such a charge transfer process is termed
ionic conduction. However, in metals the atoms no longer hold their outer electrons because of their
low ionisation energy (or loosely bound to the nucleus), held within the metal, but otherwise essentially
free. The metal is supposed to be held together by the electrostatic forces between the positively charged
ions and the free electrons.
The two types of internal energy in metals are (i) the vibrational energy of the metallic, atoms
(ions) about their mean lattice positions and (ii) the free energy (kinetic energy) of the free electrons. If
thermal energy is supplied from any external source to the metal under consideration, its temperature
rises and hence the internal energy increases. The well known thermal properties of solids such as
thermal expansion, thermal conductivity and heat
capacity depend totally upon the changes in the energy /\
of the lattices and free electrons. Once an electric field / \
is established across the metallic solid the free electrons \ \
are accelerated. Their kinetic energy increases; a part \ \
of the kinetic energy is of course lost by collisions ^'"'x s'
with atoms attached to the lattices. The resulting flow “0 • —\
of charge or current is directly proportional to the \
velocity of the electrons. This velocity is determined V
by the applied electric field and also the collision 6-1(^) zigzag motion of the electron due to
frequency. frequent collisions with the atoms at the lattices
It is not unreasonable to suppose, as did Drude and Lorentz, that the electron gas in metals could
be considered as a classical gas obeying the classical laws including laws of kinetic theory of gases.
Thus in the absence of an electric field, the electrons can move from place to place randomly in crystal,
without any change in their energy and collide occasionally with the atoms. In between two collisions
the electron may move with a uniform velocity; but during every collision both the direction and
______________________ gtfcnucAi PiwHjmei
magnitude of the velocity gets altered in general. This zigzag motion of the electron due to thermal
energv *s shown *n Fig- 6.1(fe). The average speed of this thermal motion say c depends on absolute
mmperature and is calculated using equation (6.2).
The thermal velocities calculated using equation (6.2) may not bring any net transport of electric
charges. since on the average, for every electron moving in one direction there will be another moving
in the opposite directions.
Rg. 6.1(c) Drift of electrons under.an electric field
Classical Theory of Electric Conduction

Because of the random motion of electrons in a free field, the resultant motion is zero; hence no current
flows. When an electric field E is applied to a conductor an electric current begins to flow and the
current density by Ohm’s law is
The constant o is the electrical conductivity of the specimen and its reciprocal is electrical
resistivity p. This indicates that the electrons move in a specific direction under the influence of the
field. Naturally the distribution function of the electrons in the conductor undergoes a change. The
directional motion of the free electron is called a drift. The average velocity gained during this drift
motion is termed as drift velocity.
As electron is being a negatively charged particle, the force acting on it under the electric intensity
E is, F = - eE. The electron drift is in a direction opposite to that of the applied field. During the
accelerated motion, the electron collides with the defects in the lattice. As a result of the consequent
scattering, the electron loses the velocity it gained from the field. The effect of the lattice may be
reduced considerably due to a retarding force (may be due to damping). This force is proportional to the
velocity v and mass m of the electron. Thus the retarding force is represented as - a mv, where a is a
constant. Now the equation of motion of the electron is
'-eE-amv t (6.13a)
fi dt 4
Ik--------- - —;--------- - ---- —J
On the application of the electric field, the velocity rises till the retarding force which is
proportional to the velocity equals the force due to the applied field.
When these forces become equal the acceleration ceases. Thereafter the electron moves with the
drift v,a .
Etef ric a/ Properties of Metals 187
Now
=0
e£ (6.J3W
ar a pi
The drift velocity pnxluced for urn! electric field is called earner mobility, p
e
lcM
Suppose that as soon as the velocity of the directional motion of the electrons attains its steady value,
the field is cut off. On account of the collision of the electrons with the lattice defects the velocity starts
decreasing. After tome time the electron gas resumes its equilibrium condition. Such a process which leads
to the establishment of equilibrium in a system for which it was previously disturbed is called the relaxation
process When the applied ftdd is cut off, the equation of motion of the electron becomes
dv
dt
On integration
logv =*-’0/ + C (6J3r)
When r * 0, v = and C = log

Thus Eqn, (6,13c) becomes
bgv + Iogvd
i.e.t y vêxpfâr) (6 I3tf)
If we define the time taken by the electron to attain a directional velocity which is - of the drift velocity
as the relaxation lime symbolcd as Tt then
—= expt*
This yields a - - ♦ Substituting this value of a in Eqn, (6J3bX one gets
(6.13e)
vd et
and — » —is called the mobility of the electron, p -
c m
It m assumed in Fig (6Jc) that the distance between (he layers A and B is n ij with n as the number of
free electrons in unit volume (one metre*), Thus the charge flowmg through unit area for unit time at die
layer S is ne vd. This is nothing but the current density.
i.eM J = - ne Vj with vtf -
Elbctwcal Pnoptnmttf or MtrMt tl
ne2Et
Of m
J_ ~ ne2x
of E m
The electrical resistivity, (6.13/)

► ne X
*
r
This is the microscopic expression for the resistivity of the metal. Here the measurable resistivity
|1 of metals is related to the density of electrons, the charge of the electron, the mass of the electron and
the relaxation time as expressed by equation (6.12). Mobility of the electron in the metal is defined as
I.
the steady state drift velocity per unit electric field,

r
b
j
(6.14)
f'
i
ie.,
ii
I
r
(6.15)
and hence
The unit of mobility is mW1. Mobility is an important term in the study of semiconductors.
The macroscopic definition for resistivity is given by
/ AR (6.15a)
R = P —; or p = t—
r A l-
(6.156)
F
Also a= — and E = —
!
i
■ P 1
r
t
r
Again
I
I
J = E<s
I
Substituting for p and E = y from equations (6.15a) and (6.156), we get

i
*
Substituting for p, we get,

CHAPTER 6
U, V = IR. This is Ohm’s law in the customary guise.
Temperature Dependence of Electrical Resistivity

In the absence of an electric field, the free electrons in a metal will be moving about at random in all
directions and will be in temperature equilibrium with it. ITte kinetic energy associated with the electron is
------------------------------------- ----------- ------ ----------------------- Bucnuci P,owim>
magnitude of th ity gets altered in general. This zigzag motion of the electron due to thermal
cnCI^' ? ~ onzt ic calculated ii 1 ° avera8c speed of this thermal motion say c depends on absolute
temperature and is calculated using equation (6.2). 7 1
The thermal velocities calculated using equation (6.2) may not bring any net transport of electric
charges, since on e average, or every electron moving In one direction there will be another moving
in the opposite directions.
fig. 6.1(c) Drift of electrons under an electric field
Classical Theory of Electric Conduction

Because of the random motion of electrons in a free field, the resultant motion is zero; hence no current
flows. When an electric field E is applied to a conductor an electric current begins to flow and the
current density by Ohm’s law is
The constant <5 is the electrical conductivity of the specimen and its reciprocal is electrical
resistivity p. This indicates that the electrons move in a specific direction under the influence of the
field. Naturally the distribution function of the electrons in the conductor undergoes a change. The
directional motion of the free electron is called a drift. The average velocity gained during this drift
motion is termed as drift velocity.
As electron is being a negatively charged particle, the force acting on it under the electric intensity
E is, F - - eE. The electron drift is in a direction opposite to that of the applied field. During the
accelerated motion, the electron collides with the defects in the lattice. As a result of the consequent
scattering, the electron loses the velocity it gained from the field. The effect of the lattice may be
reduced considerably due to a retarding force (may be due to damping). This force is proportional to the
velocity v and mass m of the electron. Thus the retarding force is represented as - a mv, where a is a
constant. Now the equation of motion of the electron is
. m — = -eE- a mv ‘ (6.13a)
dt i
On the application of the electric field, the velocity rises till the retarding force which is
proportional to the velocity equals the force due to the applied field.
When these forces become equal the acceleration ceases. Thereafter the electron moves with the
drift va .
Elbctmcal Pnoptwnu of MtrMf' “
ne2 Ex
J _ ne2x
ar E m
m (6A3f)
The electrical resistivity, P~ 2~
ne X
This is the microscopic expression for the resistivity of the metal. Here the measurable resistivity
of metals is related to the density of electrons, the charge of the electron, the mass of the electron and
the relaxation time as expressed by equation (6.12). Mobility of the electron in the metal is defined as
die steady state drift velocity per unit electric field,
(6.14)
ie.,
(6.15)
and hence
The unit of mobility is m^V ^s Mobility is an important term in the study of semiconductors.
The macroscopic definition for resistivity is given by
I AR (6.15a)
7? = p—;orp = —
A 1
I V (6.15b)
Also o = -and E = —
. P I
Again <y= —
E
■ J = Eo
•
V from
Substituting for p and E= — - ' and (6.15b), we get
equations (6.15a)
I
£ _V_
p " pZ
Substituting for p, we get,
V = IR. This is Ohm’s law in the customary guise.
Temperature Dependence of Electrical Resistivity

I" the absence of an electric field, the free electrons in a metal will be moving about at random in all
directions and will be in temperature equilibrium with it. The kinetic energy associated with the electron is
Sec rricat Properties of Metals 191
Referring equation (6 20)
X = -w = 2.47 x 10“ x 1.154 x 10’
X = 2.85 nm
The experimentally found value for X is about ten times above this value. Classical theory could not
explain the large variation in X values.
(iii) Relation between electrical conductivity and thermal conductivity

(Wiedemann-Franz law)
Meat conduction in solids may lake place either through (he mechanism of the atoms or through that of the
free electrons. In metals, electrons are the principal carriers of heat energy. Free electrons do this by being
excited by energetic scattering centre*. and carrying the extra energy to another scattering centre in a coo I er
part of the metal
Fig. 6.2 Row of heat through a conductor.

Consider a copper conductor in the form of a rod of uniform cross’Section (say i sq. m). Let us
assume that a thermal gradient be established. Consider three layers at A, B and C normal to the direction of
the heat flow. Let each of them be separated by a distance the mean free path of the electron gas in the
metal
X ,T and T - r X lire the steady temperaturd of lite layers, as shown in fig 6.2. Let ibe thermal
d£ dE
energy of an electrons in these layers be E v X ,E and E X respectively.
Thu^ the excess of energy carried by an electron from A tu B is Il is well known Ircun kinetic ihcury of
y;jsci, the numbei of electrons flowing in a given direction through turn atea for unit linu*■■ /»<, uherc n is du- num-
berof free electrons per cubic metre and Eis the average thermal velocity of the electron. Thus the excess of
energy transported by the process of conduction through umi mea in unit tune at the middle layer B is
Ijoetic energy -kBT [refer equation (6.1)]. Thus one kmol of a metal which has NA atoms will therefore
N free electrons, assuming that each atom contributes one valence electron to the electron gas.
OB’* 1 4 °
Now the energy associated with one kmol of such a metal is
V=^NAkBT (6.18)
If heat is supplied to the metal, these free electrons also absorb part of the heat, and the molar
êctmnic specific heat is obtained as follows:.
[dU
- k„NA = 1.5 (6.19)
where Ru is the universal gas constant

U [C1 , = 1.5 x 1.38 x KT23 x 6.02 x 1026 = 12.5 x 103 J/kmol/K
That is, molar electronic specific heat = 12.5 kJ/kmol/K. The above value of 1.5 Ru due to free
elections is about hundred times greater than the experimentally predicted value. Since the heat capacity
of a solid due to atomic vibrations in 3 Ru, free electrons should make a significant contribution to the
total specific heat of a metal. It is, however, that at least at high temperatures, Dulong and Petit law
(lattice specific heat) holds good and the total specific heat of a solid is 3 Ru, this means that the free
elections do not contribute significantly to the heat capacity of a metal. It is, therefore, concluded that
the law of equipartition and hence classical Maxwell-Boltzmann statistics must not be applied to evaluate
the electronic specific heat in metals.
(/7) Computation of Mean Free Path

The microscopic expression for the resistivity of a metal is given by the equation (6.12),
m
P = —2“
ne t
The resistivity of the most useful metal copper at 2Q°C is 1.69 x 10-® ohm-m and the concentration
of free electrons in copper, n — 8.5 x lO^/m3. Thus -
m
T— J
ne p
9.11X10"3'
" 8.5 x 1028 x (1.6 x IO’”)2 x 1.69 x 10~8
CHAPTERS
T = 2.47 x 10’14 sec
T= 4 (6.20)
c
1
dE\
-nek
6
Similarly deficit of energy transported through B in the opposite direction is
fdE
rtC’X
6
Hence net heat energy transported through unit area in unit time from A to B is
1 -JdE nek ( dE
-ncA, —
t —A
■nek —
<<*
(6.21)
6 V dx
This must be equal to the product of the thermal conductivity and the temperature gradient.
'dT'
(6.22)
T
.dx.
Brom die general definition Q = cTAt —
' dE 1 [ dT' r</ri

Now n = n .dT. |_dx. = n[Cv]
r
_ Substituting the value of n — in equation (6.22), we get,
^C.1 Fdrl.. dT~\ -
Thus, (6.23)
The electronic specific heat associated with each electron is
3k bT
= — ko and c =
2 B m
•M i'*— T”
: 7 ’
3kBT nkkB 3kBT

Now
m 2,
The expression for electric conductivity is

: 1
’ y[3mkBT (6.24)
L.e 1
a
Thus,
T”
This linear dependence of — on absolute temperature is known as the law of Wiedemann and
cr
Franz (classical one). The multiplying constant is called Lorentz number L, that is
L= = 1.12 x KT8 WOK-2 (6.26)
The validity of equation (6.25) can be checked using experimentally determined values of o and
<Jr Equation (6.25) is
Or
<XT)
For copper at 20°C, the electrical resistivity and thermal conductivity are 1.72 x IO-8 ft-m and
386 Wm-'K'1 respectively.
°r 386
Now L = oxT = 5.81 xl07x 293
or L= 2.26 x 108 WftK"2 —
The value of Lorentz number does not agree with the value calculated from the classical formula
given in equation (6.25). Thus the classical assumption that all the free electrons of a metal participate
in thermal conduction is not correct Quantum theory with Fermi-Dirac statistics reveals that only the
electrons near the fermi level take part in thermal and electrical conductions.
(/) Relaxation Time

Suppose at a given time t = 0, the average velocity of the electron is < vx >0. Just at that instant we switch
the field off, so that < vx> will subsequently tend to zero. In other words, the velocity will be randomised
by electron-lattice collisions. Now let us assume that this process follows the simplest law of decay.
<v,> = < . (6.27)
The factor t is a constant called relaxation time, because it gives a measure of the time that the
system takes to relax when a constraint (the electric field) is removed. When t = T, the equation (6.27)
becomes
< >0
Thus relaxation time may be stated as the time taken for the, drift velocity to decay to — of its
initial value.
Electrical Properttm of Metau
---------------------------------- -------------------c '
Differentiating equation (6.27), we get
0 e
L<* elec-latt
'd_
.dt (6.28)
-lelec-latt
r
i. n‘ij Collision Time
In the last section we introduced the concept of relaxation time in a highly mathematical way. However,
we shall now show that it also has a very simple physical meaning. Suppose that the probability of an
electron making a collision in time dt is —, so that on an average there are —-, collisions per second.
It is now our intention in what follows is to show that T = T.

Let us assume that all electron collisions are elastic; that is, energy is conserved, so that the
speed of the electron is the same before and after collision. This assumption is not strictly correct,
because a conductor warms up when current is passing; it implies that energy is transferred to the lattice
during electron-lattice collisions. However, the actual energy change at each collision is minute, and the
fractional change in velocity in a metal is typically 1 in 106, so that the assumption is entirely reasonable.
If we assume that after collision the velocities are completely random, we have
- <Vx>after = 0-SinCe<Vx>before = <Vx>’
it follows that the change of < vx > on collision = - < vx >. j
There are — collisions per second, so that
t
CHAPTER 6
Fig. 6.3 Relaxation of a system of electrons to equilibrium after

removing the electric field as given by equation (6.27)
the rate of change of (6.29) .

However, we could equally write the left-hand side of this equation as
R* 6.4(a) Scattering equally probable Rg. 6.4(b) Scattering predominantly in the forward
in all directions, so that the average direction at average angle 0. Change in any y is
angle is 90° therefore, on an average, vx (1 - cos 0)
d< vx >
dt elect - latt
so that on comparing equations (6.29) and (6.28) we see that T = xc and the relaxation time, therefore,
equals the mean time between collisions.
In deriving this result, we assumed that the velocities took up random directions after each
collision [Fig. 6.4 (a)]; this is equivalent to stating that after each collision the electron had no memory
of what went before. However, it is possible that the scattering is very weak, in which case such an
assumption is unrealistic. If, on an average, the velocity direction changes by 0 on collision [see Fig.
6.4. (h)], then the change of < vx > is on an average, - < v* > (1 - cos 0). Consequently
(6.30)
where, x is the relaxation time and r, is the mean time between collisions.
In other words, the relaxation time islhen much longer than the mean time between collisions;
these electrons have a memory. -• 1
(iii) Mean Free Path

The mean free path X of an electron is defined as below:
In case, the obstacles are hard spheres, the mean free path X is determined by the concentration
of these obstacles. Then for a given concentration of obstacles, the collision time t becomes inversely
proportional to the velocity c of the electrons. Then, with < cos 0 > independent of the velocity of the
electrons, in accordance with equation (6.30), the relaxation time t becomes proportional to xc and
hence, inversely proportional to the velocity c. But in the preceding article, we have taken relaxation
time to have a single value, having no relevance to the distribution of electron velocities. It may, however,
be shown that for metals the relaxation time T, which eventually determines the conductivity of metals,
always pertains to a single velocity; i.e., the one corresponding to the Fermi level EF. The proof of this
statement involves Fermi statistics which is treated in the next section.
KucflucAi humutnt* <* MttM
•pjc class’*-'3’ mode) of a metal is eminently successful in explaining many properties of metals. The
^standing properties of metals are their high electrical and thermal conductivities. In metals, the
a|encc electrons are not merely dissociated from their parent atoms, but are assumed to be as free to
move about inside the metal as the atoms or molecules of a perfect gas. In general, their motion is
random, but in an electric field, the negatively charged electrons stream in the positive-field direction
and produce an electric current within the metal. In order to prevent the electron from accelerating
indefinitely, it is assumed in this model that they collide elastically with the metal ions. This leads to a
steady-state current, which is proportional to the applied voltage, obeying Ohm’s law. Although, the
details of this classical model require modification, it should not be overlooked that it was proposed
almost fifteen years before the periodic nature of atomic arrays in metals was firmly established by
X-ray diffraction. Although it correctly predicted the magnitude of electrical resistivity, dependence on
temperature was proportional to Tm instead of the observed linear dependence.
Another success of the free electron model is the semi-quantitative agreement of the Wiedemann-
Franz law. One more characteristic property of metals is their high luster and complete opacity. Suppose
an electromagnetic radiation, such as a light beam, falls on a metal crystal, the free electrons are set into
forced oscillations having the same frequency as the incident light. Thus all the incident energy is
absorbed by the free electrons, and the metal appears to be opaque. When an electron, thus excited,
returns to its initial state, it does so by emitting a photon of the same energy as it absorbed initially. The
light given off by the electron goes off equally in all directions, but only the light rays directed towards
the metal’s surface can get through. Thus the metal appears to reflect virtually all the light that is
incident on it giving it the characteristic metallic luster.
The two most notable failures of classical free electron theory are: (i) Its inability to explain the
discrepancy between the observed and predicted electronic specific heats of metals discussed earlier
(equation 6.19) and (ii) each electron has a magnetic moment associated with its spin, and classically,
should therefore give rise to a paramagnetic susceptibility inversely proportional to the temperature.
Experimental results, on the other hand, show that the paramagnetism of metals is nearly independent
of temperature.
These quantitative errors were removed by Sommerfeld in 1928, who substituted the quantum
statistics of Fermi-Dirac in place of the classical statistics used by Lorentz. Finally, it should be noted
that even this quantum free-electron theory fails to explain two important aspects of materials. It is
incapable of explaining why some crystals have metallic properties and others do not and why the
atomic arrays in crystals, including metals, should prefer certain structures and not others. These properties
of crystals can be explained by the more general zone theory discussed in the next section.
The difficulty in the classical theory arises because the Maxwell-Boltzmann statistics permits all
the free electrons to gain energy, leading to the prediction of much larger physical quantities than are
actually observed. When quantum statistics are used, however, it turns out that only about one per cent of
the free electrons can thus absorb energy. The resulting specific heat and paramagnetic susceptibility
values are in much better agreement with experimental values. The introduction of Fermi-Dirac statistics
into these calculations, therefore, is the principal accomplishment of the Sommerfeld theory. He retained
that concept of free electrons moving in a uniform potential within the metal as in the classical theroy, but
treated the electrons as obeying the laws of quantum mechanics instead of those of classical mechanics. A
further modification was later introduced by postulating that the potential field inside the metal is not
uniform but, instead, the field experienced by a moving free electron varies periodically with the
periodicity of the crystal.
Soud Stm Phhks
Before discussing the detailed modifications of the

classical free electron theory proposed by Sommerfeld, it is
necessary to determine the restrictions imposed by quantum
mechanics on the energies that a free electron can have inside
the metal crystal. We know that, the allowed energy levels of
an electron bound to a single atom are quantised. In this section,
the permissible energy levels are determined for an electron
that is free to roam within the crystal but is prevented from
F>g. 6.5 f lectron in a potential bOz
escaping it by very high potential barriers at its surfaces; i.e., it
is assumed that the valence electrons travel in constant potential inside the metal and they are prevented
from leaving the crystal by very high energy barriers at the boundaries of the crystal. In other words the
electrons are trapped in a constant potential well as shown in Fig. 6.5.
The two main problems now to be treated are:
1. What are die possible and permissible energy states for an electron to occupy in the potential
box?
2. How are the very large number of free electrons distributed in the various permissible energy
states?
The first problem is solved by giving suitable solutions to Schrodinger’s wave equation. The
second one is answered by applying Fermi-Dirac distribution formula to free electrons.
The genera] form of the classical wave equation can be most conveniently obtained by considering the
wave equation for transverse waves in stretched strings. Let PQ be the undisplaced string and AB = 6/,
be a small portion of it in the displaced condition. The amplitude of displacement is supposed to be
small. As the string is perfectly flexible, the tension T will be the same throughout and act tangentially
at every point on AB. Let the tangent at A make an angle 0 with PQ. As 0 is small, the transverse
component of the tension along AA} will be
Over the element AB the rate at which the tangent of the angle 0 changes is approximately
Electrical Properties of Metals 199
Only the real part of equation (6,33) has significance in the case of waves m stretched string, where y
represents the displacement of the string from its normal position; in this case the imaginary part is dis
carded as intfevant This, however, cannot be directly followed in the case of material panicles, because the
wave function V of de Broglie* unlike y, is not itself a measurable quantity and may, therefore, be complex.
We now proceed to get the wave equation for de Broglie waves associated with material particles such as
electrons.
VH. SCHRODINGER'S WAVE EQUATION

77if wave function ¥ for a particle moving freely in the positive x-direetkm has the same form as the solu
tion for undamped, harmonic waves in the positive x-direction.
exp (6,34)
where T is a function ot x and r.

We now use to - 2ti v and v - VA, the well known relations for waves. Thus,
¥=Mexp
=4 exp
«A exp (635)
Xpp/wijr Planck J quantum theory and Einstein x rnojj energy relation * we get
E » ftv and E
Momentum of the photon is
Av h
p - me - —
Thus for electron
or
where v is the velocity of the electron.

Substituting these values in equation (6.35), we get
Copyrighted maierial
&KTIUCAL htOMMltt 00 MfTM* 19S
~ (tan 6) = — T ~ sf d^
dx rfxL drj dx2
The total change is dx2 5x since 6/ and &x are practically the same.
Therefore, the component at B along BB} will be
dx dx2 J
Now the net force tending to displace AB is, therefore
J2y Jy
-2 dx2
This force must be equal to the product of mass and acceleration.
%•, where m is the mass per unit length of the wire

Ar
dt
d^y d y
Hence, dt2 _f~2
d2y
2
dt2 m
Here v is the velocity of the transverse wave. Since y is a function of both t and x, the total
derivatives must be replaced by partial derivatives.
(6.31)
This wave equation is also valid for several other types of waves. In practice, sound waves in air
and light waves in vacuum are two of the important types of waves that obey equation (6.31).
Equation (6.31) admits many solutions depending on the initial displacement and the imposed
boundary conditions. Of the numerous possible solutions, the solution corresponding to the case of
undamped, monochromatic harmonic waves in the positive x-direction, is of particular interest. The
general solution in this case has the form
(6.32)
This can also be written as
(6.33)
¥(•*♦ 0 = 4 exp - 2ni
'F A exp - ~L (g( _ pxy

(6.36)
L h
Let fl = h
Thus, ¥ = A exp ~h(Et~ Px> (6.37)
The general expression for the wave taction *P given by equation (6.37) is correct only for
finely moving particles and hence may not work well in a situation where the motion of a particie is
subject to certain restrictions. Therefore, we are advised to obtain the fundamental differential equation
fa' W.IC en e s0'vcc' *n a specific situation. We thus begin by differentiating, equation
(6.37) twice with respect to x and once with respect to r
dT
i.e. — = A exp I - ~ (El - px)
dx
= A exp i P
h2
d2T _ p2 T
dx2
(6.38)
and
h dT
=-£T
i at (6.39)
The total energy of a particle is sum of its K.E. and P.E.
E= “»iv2 + V(x)
CHAPTER 6
+ V
Yoi Souo State Physics
Multiplying by 'P on both sides, we get

p2vP
= -+VVP
2m (6.40)
Substituting the values of E¥ and p2vP from equations (6.38) and (6.39) in equation (6.40) We
’ get
ft ft 2 ra2vp“
i dt 2m dx2
(6.41)
Equation (6.41) is known as one-dimensional Schrodinger’s time-dependent wave equation. The

use of this equation, rather than Newton’s second law, to solve a dynamical problem is similar to the
wave optics rather than geometrical optics in solving a problem in light. One point about equation
(6.41) needs special mention. This equation is a complex equation because of the presence of the factor i.
This means that T is a complex function, but of real variable x and t. *P cannot, therefore, be observed
like the displacement of a string.
In three dimensions the time-dependent form of Schrodinger’s equation is
(6.42)
where, the wave function T* is function of x, y, z and t. The quantity

d2T d2T d2¥
. dx2 • dy2 3z2
is often abbreviated as V2vP, where V2, the laplacian operator is given by
The one-dimensional Schrodinger’s time-dependent wave equation is
fft2>t
i dt K 2m ?
This equation can be simplified for a great variety of problems for which the potential energy of
a particle does not depend upon time explicitly, the forces that act upon it, and hence V, varies with the
position of the particle only.
You
^nden, It is always possible

of time. to find
If a particle solutions
can of equation
be described by such h «n ,th.f .
(6a4wave Pr°bab"‘t)' *• “
^ry sure. Slationary-srare wave firncuon can be obtained b^Zl ViX''f'7 “
jitfefling to equation (6.37)]. wr,t,n% T ,n following way
TO./) = AexP -^(Et-px)

. n
T = A exp (- i Etlh) [exp (i pxlh)]

T=Ay(x)0(O
»f* is a function of x and t, and y is a function of x alone and 0 is a function of t alone.

*P = A y exp (- i Etlh) (6.42a)
---- v exp (- i Etlh)

h
= A exp (- i Etlti)—
a2q> d2y
A exp (-i Etlti)
A exp (- i Etlfl) - exP 1

t
- Vw
(6.43)
-V-
-V)y = 0
CHAPTER 6
(6.44)
(£-V)y= 0
You Smvc Pmvkb
Here v is a function of (x, y, z), independent of time.

The difference between Y and y is well appreciated with the following simple analogy. c0 .
a string of length a. If one end of the string is free, waves of any wavelength X can be made to pass i *
the string. However, if the free end is fixed (that is, if boundary conditions are imposed), a continu
range of X values is no longer possible and stationary waves are set up with specific wavelengths
such
that n— = a, where n is an integer. Such a standing wave may be represented by
. 2kx 2nt
Y = A sin----- cos------
Substituting X = — in the above equation, we have

n
(6.45)
Fig. 6.7 Standing waves along a stretched string
where Y represents the transverse displacement of the string. Here Y is the product of the functions
Y (*) — A -------and 4(0 ~ c®5----- • Each point on die string vibrates in simple harmonic motion, and
a T
the amplitude y of this motion, although varying from point to point along the string, remains constant
with respect to time. Thus equation (6.45) indicates that only certain values of the wave function Y
(and therefore the energy of the motion) are possible.
The Schrddinger equation, like Newton’s laws of motion, is a fundamental relationship, showing logical
coherence to a vast amount of experimental observations. However, Newton’s laws agree with
experimental observations only so long as they are restricted to macroscopic systems and events, for
experiments have proved that they are not completely valid when applied to phenomena on the
microscopic scale. In comparison, the Schrodinger equation has been found to hold true in both the
Otses.been
f have
equation
context,Thus.
has the
Newton deductions
continued
been
’s found
laws to which
experimentnllv
seem|ead have
m l,t0? h. en madc
furth
Same aboutappli^,^'
when atom,
^"elusion«
co ? ”3 from
° macros «'Pic«* th, e eouat
Schrodinger
bodies d l,on
tttttdt easier to apply and ^4^
comparison to atoms, eauaJlv f than the schrddinrt H Wever< Newton’s laws ‘

then,. But, when Newto ’ aw 7^ “ <»ter Noh ^°n' a"d ** obZ Z COn"y
The wave function T enables all possible information about the particle to be derived, and being in
general a complex function, does not have a direct physical meaning. In all experiments we can detect
only that an electron is present or is not present; we can never detect a part of it. Born suggested that the
value of the wave function associated with a moving particle at the particular point x, y, z in space at the
rime instant t, is related to the likelihood of finding the particle there at the time. But T itself cannot
actually equal this probability because of the following reasons: If P represents the probability of finding
some particle somewhere at a given time, then it can have any value between the two limits; zero,
corresponding-to the certainty of its absence, and one, corresponding to the certainty of its presence.
But the amplitude of any wave may be negative as well as positive, and a negative probability is
meaningless. Hence the wave function 'P, which is complex number of the form (a + ib), cannot be an
observable quantity and it has no direct physical meaning.
While T itself has no physical interpretation, we notice that the square of its absolute magnitude,
[*P]2 can be given a definite meaning by looking upon the corresponding case of an electromagnetic
wave. The intensity due to monochromatic radiation at a given point is proportional to the square of the
amplitude. By analogy, we may interpret that |'P|2 as the probability density of the particle associated
with the de Broglie wave described by the wave function T at the point x, y, z at the time instant t is
proportional to the value of |'P|2 there at that instant.
Since the wave function is a complex quantity, it may be expressed m the form
^(x, y, z, t) = (a + ib)
where, a and b are real functions of the variables (x, y, z, t) and i = 4-i. The complex conjugate of T
which is denoted by T* is obtained by changing i to - i. Therefore, we have
T*(x,y, z, t) = (a- ib)
Multiplying the above two equations, we have
'P'P* = (a + ib) (a - ib) = a2 + b2
The product on the left hand side of this equation is denoted by P. Thus
CHAPTER 6
P = I 'P(x, y, z, t) I2 = a2 + b2 (6.46)
Thus the product of T and T* is real and positive if T * 0. Its positive square root is denoted by
y, z, t) I and it is called the modulus of V. The quantity I HPfx, y, z, t) I2 is called the probability
The mathematical expression for a complex wave is obtained by combining a real wave with an
““aginary one.
e* Soud Stati Pwywci
If Y' = A cos 2n
and H'" = iA sin 2rc W - ;
' X 1 ( X
then ¥ = H" + T* = A cos 2k vt - — + IA sin 2n w —
I V I X
*F = A exp
The fact expressed by equation (6.46) has been used by Maxbom to give the interpretation of
T(x, y, z, t), which is as follows:
For the motion of a particle, the quantity
P dv = *P(x, y, z, t) Y‘(x, y, z, f) dv = I T(x, y, z, t) I2 dv
is the probability that the particle will be found in a volume element dv surrounding the point at position
(x, y, z), at the instant t.
For the motion of a particle in one-dimension the quantity,
P dx = T(x, 0 *F*(x, t) dx = I ¥(x, r) I2 dx
is the probability that the particle will be found over a small distance dx at position x, at the instant t. In
this case 1 T(x, r) I2 is called the probability per unit distance.
Since *P(x, y, z,t) = u (x, y, z)e~im‘
and T* (x, y, z, t) = u (x, y, z)^ . .
for particular value of die constant energy E, we now get

Pdv = u(x, y, z) u*(x, y, z)dv = \ u(x, y, z) I2 dv
Thus for the wave function satisfying the time-independent Schrodinger equation, the probability-
is always independent of time.
(7) Limitations of q/
Because of the above interpretation of h|rt2 as a probability density, the solutions that can be allowed for
y from die Schrddinger equation are Subjected to certain limitations. The most important limitations
are:
(i) V must be finite for all values of x, y, z.
(ii) y must be single-valued, i.e., for each set of values of x, y, z, V must have one value only.
(iii) y must be continuous in all regions, except in those where the potential energy V (x, y, z)=°°-
(iv) The first derivative of y must be continuous.
) I
...................... ....................... .. —...................
illation of Wave Functions

ôrrna*'
** Motion of the three-dimensional, time-independent Schrtklinger wave equation for a particle gives
fl* S°ression for the wave function for the particle. The expression is a function of (x, y, z) and contains
definite constant. The value of the constant with its sign is determined by the following
^derations.
Since I y* z) '2<^v *s Probability that the particle will be found in a volume element dv
-uflvunding the point at position (x, y, z), the total probability that the particle will be somewhere in
SUn\nUst be equal to 1. Thus we have
space
y is a function of the space coordinates (x, y, z).

From this "normalisation condition” we can find the value of the constant and its sign. A wave
fimrnon which satisfies the above condition is said to be normalised (to unity).
The normalising condition for the wave function for the motion of a particle in one-dimension is
From these equations we see that for one-dimensional case, the dimension of y (x) is £ 1/2 and
for the three-dimensional case the dimension of (x, y, z) is Lr3f2.
The main task in applying the Schrodinger wave equation to a particular problem is to obtain a
suitable expression for xg showing how the wave amplitude varies with distances along x, y, z-axes, and
then to derive solutions of the differential equations. There will be, in every case, many expressions for
y satisfying the Schrodinger equation, all of which are, however, not acceptable. Only those functions
which satisfy certain conditions are acceptable and are called eigenjunctions of the system, while the
energies E, corresponding to these eigenfunctions, are called eigen values. In looking for solutions to
the Schrodinger equation, the following conditions are operative:
1. The solution must be everywhere finite (not everywhere zero) and single valued, implying
that a solution for V exists which can only have a unique solution for a given position in
space.
2. The solutions must be continuous and its first derivative must also be continuous.
CHAPTER «
When a particle is not subjected to any extern al force soicthat

part the particle
|e. Such moves
a particle has in a region
definite in which
value its
of total
potential energy is constant, it is said to e a re’ of thg partic|e is completely unknown. In this
energy and definite value of momentum. “ equation to two simple cases: (1) One-dimensional
section we consider application of the c mensional motion of a stream of particles, and the
motion of a particle under no forces, an ( )
effect of a rectangular potential barrier on the m
Yoi'
(r) The Free Partide

Suppose a particle of mass m is in motion along the x-axis. Ixt no other force act on the particle so
the potential energy of the particle is constant. For convenience, the constant potential energy j*
to be zero. The one-dimensional, time-independent wave equation under this condition is gjVen
d2
f + -r
, L “ .
n2
Here E = ——, where px is the momentum of the particle.
i.e*f
(64g)
or
The solution of equation (6.47), we get

V(x) = Ae^ + Be~lkx (649)
where, A and B are constants.
Equation (649) gives the time-independent part of the wave function. The complete wave function
for the particle is given by
*P(x, r) = (Refer equation 642a)
Substituting the value of y(x) from equation (6.49), we get
¥(x, t) = (Aeto + Be-^ye-1*
*P(x, r) = Ae-*™ ~^ + Be-**+ (6.50)
Equation (6.50) represents a continuous plane, simple harmonic wave. The first term on the right
side of the equation (6.50) represents the wave travelling in the positive x-direction, and the second
term represents the wave travelling in the negative x-direction. Therefore, for the motion of the particle
in the positive x-direction, we have
V(x)=Aeaat , .
and ^(x, r) = Ae-**'^
The momentum operator — — operating on the wave function (x, r) gives,

/ ox
OT h 4,f U(et ..
— — = - Alke~*to,~kx}
I OX I
= hW
But from equations (6.47) and (6.48), we have
Px = hk
ft ay
Therefore
7a7 = w'1'=^
7 a7 = («•»•)
This equation shows that the wave function T(x, t) for the particle is an eigenfunction of the
linear momentum operator, and the momentum px is the eigenvalue of the operator. Hence the momentum
regains sharp with the value px.
The probability of finding the particle between x and (x + dx) is given by
Pdx = T(x, 0 ^(x, t) dx = Constant = A1
Therefore, the probability density P for the position of the particle with the definite value of
momentum is constant over the x-axis; i.e., all positions of the particle are equally probable. This
conclusion is also obtained from the principle of uncertainty.
According to the interpretation of the wave function, the probability of finding the particle
somewhere in space must be equal to 1.
co
ie„ J *(x, /) 'P'Cx, r) dx = 1 (6.51)

— QO
But T(x, t) T*(x, t) = Constant = A2

Therefore, the integral on the left side of equation (6.51) is infinite. Hence the wave function for
the particle cannot be normalised and A must remain arbitrary. The difficulty arises because we are
dealing with an ideal case. In practice, we cannot have an absolutely free particle. The particle will
always be confined within an enclosure, and hence its position can be determined. This means that its
momentum cannot be determined with absolute accuracy.
("') The Rectangular Potential Barrier: The Tunnel Effect

If a particle isimpinging on a potential barrier with energy certainly less than the height of the potential
harrier, it will not necessarily be reflected by the barrier but there is always a probability that it may
cross the barrier and continue its forward motion. This surprising phenomenon is known as tunnelling
^d forms the basis of a number of electronic devices. One of the most familiar of these is the tunnel
diode, which is used as high-frequency oscillator.
CHAPTER 6
■t
vo
E
,„ . v ,,, । width a for a particle is shown in Fig. 6.8. u

A rectangular potential banter of heigh 0 potential energy (V) of the particle will be
extends over the region (II) fronts = 0 to x = « >• (I) and (UI). V = 0; this mean, that
constant and equal to V, On both sides of the tam .
when the particle is in these regions, no * (o righ( is incident
Suppose a beam of particles (revelling pare! * lc ... ,,nd in the ,egim
potential foamer. In the regions (I) and (111). y mechanics> prob bilitJ
îsp^yWnetic^pardyl"^^region (II) is zero. However, accordmg to
Of any pantcie reachmg <* » Xhifiry has a small but definite value. This hehav.our n
quantum mechanics
called tunnel effect. uvuv„. for the motions of the particle in regions (I), (II)
Let y{(x), V3CO be the wave functions
-independent Schrodinger wave equations are as follows:
and (TH) respectively. In these regions the
In region (I): -
d2V, |'2m£A
rfc2 ( »2 J ’
(6.52)
2mE
h2
If E< Vo then the equation can be written as
+ ^(E- V^2 =0
(6.53)
^-PV2 = 0
dx
_ /2«(V0-E)
where •P=^——
d2y3 2mEy3 _
dx2 + h2
Yoi’
-p- + ^V3 = o
or (6.54)
The general solutions of equations (6.52), (6.53) and (6.54) are of the forms
V] = Ae^ +
(6.55)
V2 = + De~&
(6.56)
V3 = Fe** + Geikx
(6.57)
As there is no reflection in the region (III), the term Ge~ i
is discarded.
Therefore, \|/3 = Feikx
In equation (6.55), the term Aeikx is a wav« . (6.58)
and the term Be-** is the wave of amplitude B reflected hi th & traVeU“g.in the Positive x-direction
barrier, when the incident wave falls on the barrier. In eauarinn X'dlrecti°n from potential
decreasing wave function representing a non-oscillatoX disturbance hT * *" exponentiaDy
in the positive x-direction, and the term Ce^ is the refl t j whlch m°Ves throu«h barrier
exponentially decreasing wave function Equation (6 sri & 1StUrbance within barrier; it is an
(III). This wave travels in the positive xêc "on WaVe “
The constants A, B, C, D and F can be determined by applying boundary conditions.

(a) At x = 0, we have ■
Vi(0) = V2(0)
Therefore from equations (6.55) and (6.56), we get
We also have (6.59)
rî~| _fdv2i
x=0 x=0
i.e.,
Aike** - Bike~ikx = CfyP* - Dê~^
When
x= 0
Aik- Bik = Cp - Dp
/.e., (4-5)=£(C-D)
t/v (6.60)
From equ
ations (6.59) and (6.60), we have
2A = C
(6.60a) •
P 0
(6.606)
8*9UD SlAtB PKYSK3
. (b) When x = a, we have

V2(a) = T3(a)
i.e., Ce^ + De^ = Feika
(6.6|j
‘^3
Also
Jx = a
Cpe^ - Dpe-0° = Fikeika
Ce^ - De-fc = — Feika
Adding equations (6.61) and (6.62), we get
2Ce^ =
(6.63)
Now subtracting equation (6.62) from (6.61), we get
ZDe-fc =
(6.64)
Substituting the values of C and D in equation (6.60a), we get
ik ik
.2A = Fe^
= F^1 (e^
A = F^
You h<
g the trigonometric relations.
- cos h pa
- e~â A
V'
= sin h Pa
af>d
ik 1 . .
cos A Ba— £ + — sin A pa
Thus, 2 Ui
(6.65)
Again, substituting the values of C and D from equations (6.63) and (6.64) in equation (6.606)
Xfl ik}
2 Ui P>
(sin h Pa) Fe^
£ + -i(sin/ipa)Fei*B
(6.66)
i PJ
Transmission Probability
The flux of particles in the incident beam is given by
CHAPTERS
f\ ~ Probability density of particles in the incident beam x Particle velocity

fx = (A A* e'^Vj
= Ae/htA*rtov1
. = AA*v,
Yoi State Physics
where, A* is the complex conjugate of A and v, is the particle velocity in the incident beam Sim
the flux of particles in the transmitted beam may be written as ,ni
/3 = {Fe^ (Fe'^)*^ = FF*v}
The transmission probability T is defined as

2
FF*v}
A4*v. UJ|_a A (6.67)
The quantity Tis also called the transmission coefficient. Now equation (6.65) can be written
i
cos h Pa + ~
and cos h Pa - “ _ q sin h Pa
Thus, = cos h2 pa + - -
A2 rta HP
Le., — = cos npa + “ T
But cos h2 Pa — sin h2 Pa = 1

1.2
Therefore. (sin A2 Pa)
2
+4 (sin h2 Pa)
2
or (sin /t2 pa)
(6.68)
Referring equations (6.52) and (6.53), we write

h1
2mE
(Vo-E)
or
k V E (Vo - E)
E(VO-E)
sinh2 pa
Vo£ - E2
o (sin h2 Pa) (6.68a)
Thus in the case when E < Vo, the transmission probability is given by
(6.69)
V2
vo
4£(V0-£)
This is the expression for the transmission probability, or the transmission coefficient in the case
whenE<V0’ t .
The expression leads to the following conclusions: 1 .
When E<Vq " .

(a) There is a finite probability for the particle to tunnel through a potential barrier of height VQ
even when the initial kinetic energy of the particle is less than Vo.
(£>) When pa » 1, then e^ is large, but e_pa will be small compared with 1.
T
g2Pa
Hence sin h2 Pa =
2
V2
vo -e2(a
4E(Vo-E)J\4
16E(V0 - E)
T=^(V0-E)e-2^
CHAPTER 6
W 11
16E
(6.70)
v0 L 0
Equation (6.70) is true only when E < Vo.
EMhm/ Pawi'h of Mmls 213
Thus when JJa » lt T becomes very small
and it decreases exponentially with increase in
the thickness of the barrier. Equation (6.70) also
shows that if a is constant, and E/VQ decreases,
then Tdecreases exponentially. This variation is
shown by the part AO of the curve for T (Fig.
6.9).
(c) When the particle energy E approaches the

potential energy Vo of the top of the barrier, then
2zn(V0-f)
will bc<
Hg. 6.9 Variation of transmissivity with the energy of
incident particles.
Thus Stnh0a =0a
2m(V0-E)at
and smh20o =
ti-
1 Vq ]~2ffl(V0-£)g2
Hence T" + 4£(V0-£)[ # (6.70a)
2m
4£tf
Since E -> we get
1 _ mVtfl1
r3l+ 2#~
(6.71)
Thus when £ approaches T increases and when £ = Vq, the transmission probability is getting the form of
equation (6.71) which shows that T< L
Case 2: When E > Vfl
In this case> we write
/2/n(V0-E) 2m(E - Vo)

-------- 1------- = 10t
V A2
where
Thus. sin h pa = = i sin aa
Squaring both sides the above equation, we get

sin h2 Pa = -sin2 aa
Substituting this value in equation (6.68a), we get
1 V2
— = 1---------- ------- sin2 aa
T 4£(V0-E)
V2
------- ------- sin;„2
2 aa
4E(E-V0)
Hence, (6.72)
V2 . 2
Ko
sin aa
4E(E-V0)
This is the expression for the transmission probability or the transmission coefficient for E > VQ.
The above equation leads to the following conclusions:
(a) When E approaches Vo, then
2m(E-V0)
aa = a ------ 73------ will be « 1
n
2m(E-V0)
Hence sin aa = aa = a fl2
2m(E-V0)a2
sin2aa =
h2 -
Referring equation (6.72),

1= i Vo2 2m(£-V0)a2 2mV^
T 4£(E-V0) h2 4Eh2
E->VQ, we get
1 _ mVoa2
T~ + 2h2
CHAPTER 6
mV~a2 (6.73)
2 ft2
This expression is the same as that obtained in the previous case (for E < VQ.
(b) Equation (6.72) shows that for E > Vo, T- 1, when aa = nn where n = 1, 2, 3.
nil nn
a l2m(E-V0)
nith
Substituting
nh_____
a 2j2m(E-V0) (6.73a)
But = — is the de Broglie wavelength X of the particle in the region of the kinetic
72m(E-V0)
energy (E — Vo). Hence T= 1, when a = n — .
x. ✓
This means that if the width of the potential barrier is an integral multiple of half wavelengths,
there is perfect transmission of the incident beam of particles. Equation (6.72) also shows that as E
increases, T oscillates between the maximum value 1 and a value less than one (Fig. 6.9).
Reflection Probability
The reflection probability is given by
2
B
R-
where, is called the complex conjugate of — . The quantity R is called the reflection coefficient.
Dividing equation (6.66) by equation (6.65), we get
sin A pa
B
i! I P k ) .
cos h Pa + —
+ — sin A pa
Now
cos A Pa — - — sin h Pa
Hence, R
(6.74)
for reflection coefficient. Adding equations (6.74) and (6.68), we get

This is the expression
n . T 1 (6.75)
The tunnel effect provides explanations for the following phenomena;

1. The field emission of electrons from a cold metallic surface.
2. The reverse breakdown of semiconductor diodes.
3. The electrical breakdown of insulators.
4. The switching action of a tunnel diode.
5. The emission of ot-particles from a radioactive element. I
I
}
I
There are only a few situations in which an exact solution of the Schrodinger equation may be obtained.
Some of these are hypothetical, but they are approximate to real situations and also serve the purpose of
illustrating the application of the Schrodinger equation. In this section we propose to treat by the methods
of quantum mechanics certain of the simple systems for which the Schrodinger equation can be solved
exactly. These systems are an idealisation of naturally occurring systems, but the consideration of them
is not without value, as they furnish an insight into the methods of quantum mechanics and give results
which are useful in the discussion of many problems of physical sciences.
£?« i nral Prop*rites of M eia /r 216
particle can only be inside the box, and hence must be zero when 0 £ x £ a.
Inside the box, V = 0 and the oftt-diwensrDnaJ form of Schrodinger equation for stationary state,
equal ion (6.43) becomes
V(x:
*
K*O
Fig. 6.to A onedimenskmal potential box ûh âJKuiinfinite height mx = OatxIx“ii
2/n
*0
+ A\f™0 (6.76)
where
For a particular value of ihc energy E, k is a constant. The general solution of equation (6.76) is of the form
y(x) = A sin Ax + B cos Ar (6.77)
where A and B are arbitrary constants. The values of these constants can be obtained by applying the
boundary conditions of the problem.
(0 at x ® 0. v (x) = 0
From this we get B - 0 and hence tg (x) A sin Ax
(ii) all* c, y(x)« 0
Now using the second condition, we have
) - A sin ka « 0 (6,78)
We cannot take A - 0, because there will then be no solution. Hence equation (6,78) is satisfied only when
ka - /tit
w k =— (6.79)
a
where n« 1.2.3.
This is the necessary condition for the solution of the wave equation to exist; ix.» io be an eigen function
of the system.
We cannot take n = 0, because for « = 0* fc = 0. E - 0 and hence ip (x) - 0 everywhere in the box. This
means that a panicle with zero energy cannot be present in the box. Thai is, a panicle in the box cannot have
zero energy.
Hence the wave functions for the motion of the particle in the region 0 < x < a are given by
V¥(x)-Asm—
(6.80)
Eigen values of energy

Substituting the value of k from equation (6.79) in equation (676), we get
(6.81)
Equation (6.81) reveals that
L The lowest energy of the particle is obtained by putting nm I in equation (6.81) and ii is
A3*
Et =------ ; and E = nÊ,
&TW2
This is known as zero point energy of the system.
2, The possible values of energy of the particle in the potential box are discrete, corresponding to n = I,
3, The spacing between the n“* energy levd and the next higher level increases as (m if E> - ns E\ -
(2fl+l)£r
The wave-functions tp„ corresponding to E, are called eigen functions of the particle. The integer n corre
sponding to th? energy E, is called the quantum number of the energy level Hg. 6d I show? the energy
level diagram for (he particle.
Normalisation of the wave function

It may be noted that the solutions of the wave equation are independent of the magnitude of A (Refer aqua-
tion 6v80) and this pennies us to choose a value for A tn order to satisfy any condition we want to impose
Customarily, the value of A is adjusted so that |iyj" becomes actually equal to the probability (Fj of finding
the particle at a point x, instead of being simply proportional to this probability, as is the case otherwise. This
is done by process called normalization. The wave functions for the motion of the panicle are:
You ha
2. The possible values of energy of the particle in the potential box are discrete
to n = 1, 2, 3,...
COTresPonding
o
3, The spacing between the nth energy level and the next higher level increase
-n2E, = (2n+1)E,. as(n +
The wave functions corresponding to En are called eigenfunctions of the particle Th

n corresponding to the energy En is called the quantum number of the energy level E p- 1
shows the energy level diagram for the particle. . n' ®Uri
Normalisation of the Wave Function

It may be noted that the solutions of the wave equation are independent of the magnitude of A (d
equation 6.80) and this permits us to choose a value for A in order to satisfy any condition we warn *
impose. Customarily, the value of A is adjusted so that lyl2 becomes actually equal to the probability (p\
of finding the particle at a point x, instead of being simply proportional to this probability, as is the case
otherwise. This is done by process called normalisation. The wave functions for the motion of the
particle are:
E4=16E1
Fig. 6.11 Schematic representation of energy levels of a particle in a one-dimensional box
mix
= A sin-in the region 0 < x < a
= 0, in the region 0>x> a.

The total probability that the particle is somewhere in the box must be unity. Therefore, we have
a a
0 0
2 mix (6.81a)
a
o
a _ r-
2nnxl
1- cos
a
o
(6.82 J
The wave functions for ths first three values of n are shown in
Fig. 6.12.
It is evident that the wave function Vp two tt at
X - 0 and x ~ <x
ll is now dear that the wave function has three nodes at

a
x -0tx m- and*
2
a 2a
The wave function ty5 has four nodes atx = *,x “ — and at
x -a. Thus the wave function will have (n *1) nodes.
Probability of the location of the particle
The probability of finding a panicle over a small distance dx

aix is given by X«0
P[x}dx Fig. 6.12 The wave functions for n = 1,2
and 3
/>(r)dx =—
a a
Thus the probability density for the one dimensional mon cm is
. 2 _ jrtTUf
P(x) = -sm3----- (6.83)
a a
The probability density is maximum when
ntu n 3rt 5n
.---------- — ■— -—
a T 2* 2
a 3a So
W Xa2n'2n’U
a
Thus for the state far which n = ir the most probable position of the particle is at x ~ -.
Fur n = 2. the most probable positions are at
For n - 3t the most probable positions arc at
C opy ri g hl ed r ri a ten a I
This is shown in Fig. 6.13. This wave mechanical result

is quite contradictory to the classical one. According to
classical mechanics, a particle in such a potential box
would travel with a uniform velocity from one wall to
the other, and at the wall it would be perfectly reflected.
Therefore, the probability of finding the particle within a
small distance rfr anywhere in the box is the same and is
equal to 4x/n.
The probability density is represented by a straight line
at height i above the e-axis.

Ir.l’ /A,
Thus the wave functions and the probability den
sity functions for the partide in a one-dimensional box <■0
can be written as follows:
Fig. BA3 The probabiIrty density tn a one-
dimensional case.
The respective energy values are:
Therefore, only certain values of ET namely E^ are possible, and these are the only ones allowed. The energy
values E* are usually called eigen values and eigen functions; the integer n is termed a quantum number,
and it arises here merdy as a consequence of the boundary conditions imposed. This quantum number can
be L 2. 3 ... but not zero because w and if? then would be zero everywhere within the box.
This example has many instructive features. For example? for the same value of the quantum number
the energy is inversely proportional to the mass of the particle and to the square of the length of the box.
The energy is quantized and so, H cannot vary continuously. This wave-mechanical result is in sharp con
trast Io the prediction of classical mechanics that there is a continuous range of possible energies. It is only
when the quantity ma1 is of the same order of h* that quantum energy levels are discrete. As the particle
becomes heavier and the box larger, the energy levels become more closely spaced,
Fur example, the permitted energies of an electron, confined in a box OJ nm wide, are:
224 So/ id Suite Physics
r - nft
£ «3<663 x IQ-34)3
" ~8x9 1 x lO^'flO-10)2
= 6* 10''*«J joule
»38fl2eV
The minimum energy that the said electron can have is 38 eV. corresponding to it- L The other per*
mitted energy values are E: - 152 eV, J-,\ = 342 eV, and so on. For a box of macroscopic dimensions, say I
cm wide, the permitted electron energies arc E\ = 38 x KF1*/? eV, In such cases the energy levels become so
closely spaced that they seem to us to be continuous. The quantum mechanical formula, therefore, gives the
classical result for systems with dimensions such that mo2» h\ This is an illustration of Bohr's correspon
dence principle which states that quantum mechanics must yield identical results with those of classical
physics in the limit of large quantum numbers.
(ii) Funicle m a rectangular ihree-dsmenstu/tul box
Wc now consider a particle of mass at constrained to move in a fixed region of space, which for sim^
plkity, we assume to be a rectangular box with edges of length a, b and c and volume v - abc. The potential
energy V may be put equal to zero within the box; at the boundaries of the box and in the remainder of space
we put V - We take our coordinate system to be the cartesian coordinate system with the origin at one
corner of the box and the y and z axes along the edges of length a, b and c respectively* The potential
energy is then
Vf - 0.0 < x < a; Vt = otherwise

Vy = 0, 0 < y < u; Vk =« otherwise
V, = 0,0 < z < ti; V, = otherwise
LfiJ+ inside the box ihc potential function V (xt y, z) is equal to zero but it rises suddenly to a very large value
at the boundaries of this region, remaining infinitely large everywhere outside the boundaries. Therefore, the
particle will rebound when it strikes either of the boundaries.
The three-dimensional Schrodinger equation for such a system is
VSr + Ê-VMr-O
For this particular problem where V - 0, inside the box, the equation takes the form
any dV try
a?+a7+d?+-^-=0 (6.84)
C opyri g til ed riia feri a I

In this equation i$ a function of three variables, x, y and z. One way of attempting to solve the equation is
to see if it is possible to write u the product of three functions, each of which depends only on one of the
variables, h is assumed, therefore, at first instance, that
Y(j.y,j)«Xfx)ny)ZU) (OS)
which means that v {a function of xT y and i> is equal to

the product of three functions, X. F and Z where X is a
function of x only, Y is a function of y only and Z is a
function of x only. Equation (6.R5) may be written as
W^XYZ (6.86)
in which the variables are not indicated. Since the

functions Y and Z are independent of x, (he differenti
ation of equation (6.86) with respect to x gives
Fig S, 14 A-three-dijiitna ional potential box.
and further differentiaeton with respect to x yields
Similarly
and
Substituting these values in equation (6.84). we get
Dividing throughout by XYZ
1^? lrf:z f2”^ (6.87)
Now the first term in this equation is a function of x only, the second a function of y only, and the third s
function of z only, while the sum of the three is a conMsnt. This can only be so. in fact, if each term is equal .
to a constant. We must therefore have
226 tore PAy.tiri
where (6.88)
Now the differential equations in x* y and z coordinates may be written as
(6.89)
(6.90}
(6.91)
The general solution of equation (6.89) will be of the form
X(.r) - A 4 sin ktx + 8r cos £rr (6.92)
When x = (X X - 0. hence B* = 0
When x = X - 0 = Aa sin kt a
Therefore
* fltn
njz
kx *~f where - 1(2>3-
Equation (6 92) becomes
^!U
sin------ (6.93)
a
Applying the normalization condition between x = 0 and x = a, we have
J0 |X|1d<»A;Jsi0 n1^dx = l
or yfa)^! (Refer equation 6 81a)
Substituting this value in equation (6.93)» we have
(6.94)
Similarly, the solution of the equation (6.90) will be of the form
F(y) « A, sin cosily (6.94a)
Wheny ~ 0, T - 0, hence B, ~ 0
When v ® Z>T K - 0 AT sin
This will be true only when kyb - fl,it. Le.t =—
Substituting flt - 0 and A -

■ jh
fl.H t t
in equation (6.94a), we get
K « A, sin (6.946)
Applying the normalisation condition between y - 0 and y = b. we have
Thus equation (6.94b) becomes
(6,95)
Copy rig hi eci material

The complete wave function y, z) = XYZ
i.e-
(6.97)
(6.98)
where, n , n and n denote any set of three positive integers. Equation (6.97) gives the total normalised
wave functions inside the rectangular box for the stationary states. Similarly equation (6.98) gives the
eigenvalues of the energy of the particle. These values are called the energy-levels of the particle.
If the particle is confined in a cubical box in which a = b = c, the eigenvalues of energy are given by
= (6.99)
. . 8/na / .
,2 2
n n
8ma2 ’
where n2 = n2 + + n2
and the normalised wave functions are
(6.100)
CHAPTER 6
From equations (6.99) and (6.100), we derive the following conclusions:

1. The three integers nx, ny and nz which are called quantum numbers, are required to specify
completely each energy state. No quantum number can be zero, because if any one of them is
taken as zero, then ig(x, y, z) = 0, which would mean that the particle does not exist in
the box.
SliWl PHYSIO ’
“■ <■”* ' ,i i, ■ i| 1
2. It should be noted, however, that the energy E depends only upon the sum of the squares of
the quantum numbers nx, n and nz and not on their individual values.
3. Several combinations of the three integers may give different stationary states or different
wave functions, but of the same energy value. Such states and energy levels are said to be
degenerate.
Example:
1. n = l,n=l,n=2
J <■
2. nx=2, ny- 1, n,= 1

3. n = 1, nJr =2, n = 1
. The corresponding wave functions are then
kx ny . 2nz 8
V(ii2) = A sin — siny sin —, where ! -
. . 2itx . • 712
Vrsin =4 sin------ sm—sin—
( J a a a
. . 7tx . 2ny . nz
and V(i 2 n — A sm — sm----- sm
a a a
but in each case the energy value is exactly the same; that is
■ j? 67,2 •
We know that, if several states have the same energy, they are said to be degenerate. Thus for the
level for which the energy is----- r, there are three independent states having quantum numbers (112),
8ma
(2 1 1) and (1 2 1). The level is, therefore, said to be three fold degenerate of triply degenerate. It will be
noted that the groundstate (1 1 1), as also several other states like (2 2 2), are non-degenerate.
It can be shown with an example that the degeneracy breaks on introducing a small modification
t ., - • 6h2 ..
to the system. Consider, for example, the triply degenerate level, having E = -—j-. For this energy
is/nn
value, there are three independent energy states having quantum numbers (2 1 1), (1 2 1) and (112) for
n? ny’ nt fhe cubical box be increased by a small amount, da along the x-axis keeping
breadth and thickness unaltered. The corresponding change in energy of the first state (21 1), which has
4A2
an energy - , 2 associated with the x-direction, will be different from that the other two states (1 21)
8ma
A2
and (112), which have an energy -—t associated with the x-direction. The decreases in energy of the
8ma
first state (2 1 1) is
1
4ft2 4ft2 4ft2 1 1

8ma2 8m (a + da)2 8m a2 (a + da)2
4ft2 a2 + 2da (a) + (da)2 - a2

F. - 1■
i'
r- 8m
i
V
I-
F
ft2 f 8daA (6.101)
8ma2k a )
But for the other two states (1 2 1) and (1 1 2), the energy will decrease only by
which is shown below:

ft2 p l 1
8m a2 (a + da)2
. ft2 [az + (da)2 + 2a (da)- a2
8m ■ a4
p ft 2 V2dh>
-^8mI a3 )
(6.102)
^8/na2
This breakdown of degeneracy is shown

inFig. 6.15 by comparing equation (6.102) with
(6.101).
Breakdown of degeneracy, which thus
occurs due to some modification applied to
the system, has relevance to what is often
observed in practice, such as the splitting of
spectral lines in a magnetic field or electric
field. As a result of the application of a magnetic
or electric field the degenerate level breaks up
into separate levels, and consequently, spectral
CHAPTER 6
lines which were single become multiples. Fig, 6.15 Breakdown of degeneracy
of the level (21 1)
i
The most important assumption of classical statistics is that any number of particles may have identical
energies. Though the classical approach gives an understanding of the conductivity of metals, it faj^ b
give a proper explanation for the contribution by electrons to the specific heat and magnetic susceptibility
As the electrons are free, the total molar specific heat of a metal at room temperature and above shouu
L 3/f 1 3RU (
3RU being the contribution from the lattices and — from the electrons. But
L 2 J
experimentally the specific heat of a metal near room temperature is only 3RU. Thus the specific heat
3Ru
associated with the electron must be very small and not
2
In order to account for the unexpectedly low specific heat of metals, we must look more closely
into the statistical behaviour of the electron gas. Such an electron gas behaves like a system of Fermi
particles and hence obeys Fermi-Dirac statistics. Fermi-Dirac statistics is applied to indistinguishable
particles (called Fermions) which are governed by Pauli’s exclusion principle. Sommerfeld investigated
the behaviour of a free electron gas taking into account the quantum theory and the Pauli’s exclusion
principle. He considered the distribution of a large number of electrons of the order of ItP/m3 in
thermal equilibrium among the various states in a three-dimensional box.
inti ediately the wave
8 nznz
th, n, a3
sin------ sin —-— sin
a b
within the metal and zero outside, and the energy levels are
h2
[n2+n2+n2]
8ma2
where, n,n and n are integers.

h2n2 . 2 2 2
E =------=- with n2 = n, + nZ +n?
n Sma2 \ z'
According to the Pauli’s principle, not more than two electrons may occupy any orbital state, so
that, at the absolute zero of temperature, two electrons will go into the ground state, two into each state
of next higher energy, and so on, until all the electrons are allocated to states of lowest possible energy-
Since the number of electrons is very large, it is thus understandable that, even at the absolute zero o
temperature, some electrons have kinetic energies of several electron volt. For a piece of metal
macroscopic dimensions, say centimetre cube, the energy of the ground state (nx = n =nz=l)i$
order of IO-15 eV and hence may be taken to be zero for all practical purposes. Also the maxima®
spacing between consecutive energy level is less than KT6 eV, so that the distribution of energy nmy **
regarded as almost continuous or sometimes “quasi-continuous".
Now we shall consider how the many electrons of a real material distribute among these available
energy states. Since we are talking about an almost continuous range of energies, we can represent the
probability of occupying a given state by a continuous distribution function. The probability F(E)of 80
electron occupying a given energy level is given by
(6.103)
Here F(E) is called the Fermi function, E is the energy of the level whose occupancy is being
nsidered. EF is the Fermi level and is a constant for the particular system. At absolute zero F(E) = 0
. g > g and F(E) = 1 for E < EF. Thus at absolute zero, the Fermi level divides the occupied states
. m unoccupied states; i.e., it is the highest energy state for the electrons to occupy at absolute zero.
Energy Quantum numbers Degree of

levels (n,, n,, nJ degeneracy
1
(42 1) (1 42) (2 1 4) (421) (142) (2 1 4) - Six-fold degenerate

(3 3 1) (1 3 3) (3 1 3) ' Three-fold degenerate
--------- >E
1 1 1 1 1 1 1 1
(41 1) (1 41) (11 4) Three-fold degenerate

(3 2 2) (2 3 2) (2 2 3) Three-fold degenerate
(1 2 3) (3 1 2) (2 3 1) (132) (21 3) (3 2 1) Six-fold degenerate
.
8ma2
-h L .
(2 2 2) - ‘ ' Non-degenerate
(3 1 1) (13 1) (113) Three-fold degenerate
(2 2 1) (12 2) (2 12) Three-fold degenerate
(2 1 1) (1 2 1) (1 1 2) Three-fold degenerate
w
Non-degenerate
O
§to
(HD
O
Fig. 6.16 Energy levels of a particle in a cubical box
of electrons
The Fermi function does not, by itself, give us thp numberstate which
by a sing have a Since
ie electron. energy,
certaineven it
at the
gives us only the probability of occupation of an e gy eV we caQ say
highest energy, the difference between _ stU1 many discrete energy levels. So we can
that in a macroscopically small energy in which will simplify our calculation considerab y. o
introduce the concept of density of energy s enereY One must know the number of states in the
know the actual number of electrons wi a 8 ■phen by multiplying the number of states by the
system which have the energy under consi eiaj N(& is nUmber of electrons in a
CHAPTER 6
probability occupation we get the actualI nume energy, then

system that have energy E, and Z(E) is
ME) & • ZWME F(Ey~i
(6.104)
We know that, the number of energy states, with a particular value of E, depends on how
*nany combinations of the quantum numbers result in the same value of n. Since we are dealing with
You Sous Sixth Physio
almost a continuum of energy levels, we may construct a space of points represented by the values
of
nx, ny and nz and let each point with integer values of the coordinates represent an energy state.
A radius vector n from the origin may be drawn to a point nx,n? nz in this space, and all points on
the surface of a sphere of radius n will have the same energy. Thus n represents a vector to a point nx>n ,
n (n2 - nx + nJ + nj) in three-dimensional space. In this space every integer specifies a state; that is a
unit cube contains exactly one state. Hence the number of states in any vo ume is just equal to th^
numerical value of the volume expressed in units of cubes of lattice parameters.
Fig. 6.17 Density of energy states calculation
Therefore, the number of available states within a sphere of radius n is given by
factor — accounts for the fact that only positive integers are allowable and thus only one octant of the
o
sphere alone be considered. Again the number of states within a sphere of radius (n + dn) is, therefore,
(n + dn)3. Thiis the number of energy states having energy values lying between E and E + dE
in the energy interval dE) is given by
HE) dE = —[(n + dn)3 -n3] = ~[n3 + dn3 + 3n2dn + 3dn2n -n3]

o o
= — (3n2dn) = ^n2dn (6.105)

6 2
Yok

h2n2
8ma2
2 8ma2E 2 -|V2
8ma
« = —-J— and n = - Em
h ~h2
8nta2
2ndn = dE
and h2
( 1 A 8mn2
d"=
Z(E) dE= ~ n(n dn)
To 21’/2 1 I 8ma2
n 8ma
Z(E) dE = rl/2 n---- dE
h2 2n h2
n 8ma
2 I3/2
Z(E)dE ,2 EmdE
/r
It should be now remembered that the Pauli’s exclusion principle permits two electrons in each
state, so that the number of energy levels actually available are
(6.106)
The simple parabolic function is illustrated in Fig. 6.18.

Hence the number of energy states present in unit volume having energy values lying between E
a°d E + dE (called density of energy states) is given by
CHAPTER e
fig. 6.18 Density of energy states for d free electron gas

Electrical Properties ofMetals 235
&
Z'tE'jdE = ”
L a1 . E^dE
(6 J 07)
The actual number of electrons N (E) dE in a given energy internal dE will now be obtained by
multiplying the number of energy states in the interval by the Fermi distribution function.
N(E)dE- Z(E)dE F(E)
f — \f -7
N(E)dE J -
Rm
VEW dE
t)L h j + eW[(E-Er¥ktT[
This distribution is shown in Fig. 6,19.
Fig, 6.19 The population density of a free electron gas.
At absolute zero, the distribution problem is simple, all states upto Fermi level are filled and those
above Er are empty, At higher temperature the typical tailing appears, the extent of this tailing being, of
course, very small compared with the wale of the distribution until very high temperatures are reached. The
relation for the Fermi level in a metal is possible at any temperature, but is simple at zero degree absolute.
The general expression for N(E) dE is
8ma3 EmdEF(E)
When 0 K, f (£) * I since E< Ef

Thus
/V
(6.108)
Yo
______ ____________________ __________ J&jktwcm PRoramw or MtrM JU
Therefore, the number of electrons per unit volume (called density of electrons) is
(6.109)
r
E?
Km
r3^2/3 = 0.58 x 10"37 n273 joule (6.110)
Ef = 3.65 x 10“19 n213 (in electron volt)

This expression for Fermi energy is a very useful quantity, because whenever we use the free
electron model, which is quite often, the value of EF gives the top most energy level at absolute zero.
The Fermi energy values of some selected metals are given in Table 6.1.
The figures given below show the shape of the Fermi function at different temperatures. The probability
F(E) for the occupation of a particular energy level E by an electron is given by
1
F(£) = . e-ef
l+e v
At T = 0 K and for E < Ep the function attains the value 1. When E>Ep F(E) will be zero. This
means that at absolute zero, all the quantum states below EF are occupied while all the quantum states
having energies greater than EF are unoccupied. So, EF is the maximum energy of the filled state. The
Fermi function plot at a temperature greater than zero shows very little change from the Fermi plot at
f’= 0 K. Only very near Ep F(E) begins to fall and at E = Ep F(E) = —. So, Fermi level is that level at
'¥
which the probability occupation is X*.

£
CHAPTER 6
Sometimes in the literature, a temperature, TF called Fermi temperature, and a velocity, vF known
Fermi velocity are used. They are calculated as follows: For sodium EF = 3.2 eV.
Now Ef « 3.2 x 1.6 x 10~19 J

Scms^mtb Fumes'«
2x3.2xl,6xl0~19 _ 3.22 x IO12

9.1 lx IO’31 " 9.11
vF = 1.1 x 106 m/s

and yy=ep
Ep 3.2 x 1,60 x 10~19
” 1-38 x IO-23
7-=
r
37100 K
Figure 6.20 (a) shows the Fermi function
at a finite temperature, say, T = 300 K. The Fermi
curve at this temperature differs from the Fermi
plot at 0 K in the smearing of the drop from 1 to
0. In the actual case, the extent of the smearing
is very small except at very high temperatures.
This can be seen by considering an example,
say F(E) = 0.2 at 300 K.
-9 -
F(E) = 0.2 =------ \-p-

* ' XI — Xjjp Fig. 6.20 (a) Fermi function at 300 K
1+e B
i .e., —^ = 0.2.
l+e
0.2 + 0.2c1 = 1
0.2r* = 0.8
e* = 4
x=1.39
E-EP
i.e.. = 1.39
kBT
E-Ef= 1.39 x 0.025 = 0.035 eV
L
Thus the extent of the smearing (about 0.035 eV) is very small compared with the energy
dlStnbutionof5eV.
Table 6.1 Parameters connected with Fermi energy for metals
Electron concen Fermi energy at Fermi velocity at Fermi tempera

Mdency Metal tration (n) 0 K (Ef) in eV 0 K (vF) in 106 m/s ture
in 1028/m3 (Tf) in 10*K
1 Li 4.71 4.72 1.29 5.48
Na 2.65 3.23 1.07 3.75
K 1.40 2.12 0.86 2.46
Cs 0.91 1.58 0.75 1.83
Cu 8.50 7.05 1.57 8.12
Ag 5.85 5.49 1.39 6.36
Au 5.89 . 5.52 1.39 6.39
2 Mg • 8.60 7.13 1.58 - 8.27
• Ca 4.60 4.68 . 1.28 5.43
Ba 3.16 3.65 1.13 4.24
Al 18.06 y 11.63 2.02 13.49

3
In ,11.49 ■ ■ / 8.60 < 1.74 9.98
1. At absolute zero, F(E) = 1 for E < EF

and . - F(E) = 0 for E >EF
At 0 K, Ef is the maximum energy of the occupied state.
2. As temperature increases, an electron may get energy of the order of kBT and go to higher
vacant state, and so Fermi function falls. But for energies below Ep such that (EF - E) »
kBT,the value of F(E) will be unity; i.e;, only in the region of Er F(E) begins to fall. When
1 . '
E = Ep F(E) will be
*
Classical statistical mechanics predicts that all particles in an assembly would be able to absorb energy,
and so contribute to the heat capacity. Hence, the electronic contribution to the heat capacity of a
3EU
CHAPTERS
monovalent metal will be = . But the observed electronic contribution at room temperature
2
is usually less than 0.01 of this value. This discrepancy is explained as follows:
When we heat the specimen from absolute zero not every electron gains energy of the order of
iaTas expected classical, but only those electrons in orbitals within an energy range k^F of the Fermi
level alone are excited thermally; these electrons gain an energy which itself is of the order of k^F and
Souo State Physics
go to higher unoccupied energy states. This gives an immediate qualitative solution to the problem of
the heat capacity of the conduction electron gas. Thus the minimum energy required for exciting all the
free electrons will be Er Hence the fraction of electrons that will be excited at T- 300 K is given by
_ 0025 _ 0 0()5 _ Q 5%
Ef 5
i.e., at ordinary temperatures, less than 1 % of the valence electrons contribute to the heat capacity. This
result contrasts with the classical view in which all the electrons in a system would absorb energy, and
so contribute to the heat capacity.
3
Each of the electron may absorb a kinetic energy of the order kBT. Hence the energy associated
with a kmol of the metal will be
(dU\ „„ , kBT]
Thus, [C 1 , = — = 3NA k„ -s—
[Cv]e/ = 3RU [0.005] with kBT = 0.025 eV and EF = 5 eV

[CX = O.O157?M (6.110a)
while the lattice contribution is 3RU. This value of 0.015 Ru agrees with the experimental value. However,
at very low temperature, the lattice contribution is small and falls as 73 and the electronic contribution
is significant.
The Fermi energy at absolute zero is given by equation (6.110), i.e.,
It is now possible to estimate the average electron energy at 0 K. To do this, first obtain the total
energy UQ at 0 K, which is given by the following equation:
Uq = f Z(E) dE F(E)E with F(£) = 1 (6.11 Oh)

o
q>- [Er]“
Thus, the mean energy of the electron at 0 K is
E =
0 N
Substituting the value of N from equation (6.108), we get
(6.111)
NJBj Since the Fermi temperature of the electron oyer a wide range of temperatures did not vary
much, equations (6.122) and (6.125) may be assumed for further discussion of die subject
. matter. The following details are not required up to equation (6.125) for indents
In the above treatment of free electron theory of metals, we assumed that the electron gas is at
zero degree absolute and, in accordance with the Pauli’s principle, we fill the levels Hilt
up all electrons at the Fermi level of energy Ep But the kinetic energy of the electron gas increases as
the temperature is increased and some energy levels are occupied which were vacant at absolute zero,
and some levels are vacant which were previously occupied at absolute zero.
The number of electrons dN having energy values lying between E and E+dE is given by
dN = Z(E) dEfiE)
co
N= J Z(E) dEflE) (6.112)

\ ' 0
00
E = \z(E)EfiE)dE (6113)
N J0 — ' -
£ = 1JZ(E> (6.114)
0 1+e V
For solving this integral, we shall first evaluate the integral given by equation (6112)
/= J/(£) g<E)& (6115)
0 . "
where, flE) is the Fermi distribution function and g(E) any other function, such that g(£) -» 0 as E —> 0.
Integrating equation (6.115) by parts
Souo.^njre Pxw»......
BO
1= (/(£") g(E)K - j g<E) f'(E) dE (6.116)

0
The first term on the right side of the above equation vanishes at the upper limit because the
probability of finding an electron with infinite energy is zero. The same term vanishes at the lower limit
because we suppose g(0) = 0. Now expanding g(£) by Taylor's theorem about Eâs
8(E) = g(Ef) + (E - Ef) g'(Ef) +
Substituting this in equation (6.116)
I = - J/7(E) g(Ef) + (E- Ef) g\Ef) + |(£ - Ef)2 g"(Ef) + ...

dE
o
I . Ltfty + + I^g’XEj) + ... (6.117)
oo
-\(E-Ef)f(E)dE
and L2 = -fjjf(E-E/)2f'(E)dE -
■ o .
However, at low temperatures such that kBT « E<, the derivativef'(E) is large only at energies
near Zy as shown in Fig. 6.21; it is negligible for other values of E, particularly for negative values of E.
The lower limit on the integrals may thus be replaced by -*>; we shall now solve the integrals as
follows:
fig, 6.21 The functions /(E) and -
00
A> = J/'(E)dE=-
Yo
»[/(£)];“ = 3 [1-0]= 1
L(= - j(E-Ef)f'(E)dE
where, J[E) - = [ l+exp(E-£p/^7r‘
Thus /'(£) = -
E-£z
E-Ef e k»T dE
Thus
This integral vanishes because f ’(E) is an even function of (E — E^, and the integral is thus an
odd function, which when integrated from -<*> to °° will yield zero.
Now
E-E
with f'(E) = - E-Et-\i

k.T
E-E
Put
CHAPTERS
*b*
(kBT) dx = dE
Substituting these values in relation,
1 f (kBT)2x2ex(kBT)dx
(k„T)2 7
La= 2 J (l+ex)2
—M
The solution of this standard integral is
Thus z.2 =
Thus equation (6.117) becomes (referring equation 6.115)

°° 2
I = J g(E) flE) dE = g(Ef) + y (kBT)2g"(Ef) + ... (6 J 18)
o
Equation (6.118) is a convenient form for working out the Fermi integrals given by equations
(6.112) and (6.114). But it is restricted by the condition g(E) = 0 when E = 0 and by the condition that
V«E,.
Thus, to evaluate the integral given by equation (6.112), we choose
o
with g' = Z(E) and g” = T{E)
Referring equations (6.112) and (6.118), we write
~ 2
N= jf(E)Z(E)dE= J Z(E)dE+~(kBT)2Z'(E) (6.119)
o o . . .. 9
At 0 K, F(E) = 1 for 0 < E < EF and thus
* N= J HE) dE F(E) with F(E) = 1
ef
N~.\ Z(E)dE i ’ (6.120)
o
Equating equations (6.119) and (6.120), we get
El
I JC^
J Z(E) dE + — (kBT)2 [Z(E)]fi = 0 . (6.120a)
E £, 6 '
* We assume here that Z(E) does not vary much in the interval from EF to Ef, which for kBT« Ef
", will be only a small fraction of EF. Thus the above equation can be written as
i -
Zty (Er Ef) + y (kBT)2 [Z(E)] = 0

You
Since Z(E) is of the form CE1/2 [refer equation (6.106)], we write the above equation as
=0
n2 (kBT)2
(EF-Ef) =0
12 Ef
(6.121)
where, Ef is the Fermi level at absolute zero and E? that at higher temperature such that kBT « E^.
However, the second term of equation (6.121) is a very small correction term that should be
subtracted from a relatively large term EF. For example, the Fermi energy of copper is about 7 eV. Thus
n2 (fcBT)2 < 0.0232

= 1(T4 eV
12 7 ” U2) 7
Under these circumstances no much error will be introduced if 2^. in equation (6.121) is replaced
by EF on the right hand side. Thus equation (6.121) can be written as
n2 (kBT)2
it2 (kBT)2 Ef
12 Ef 12 E2
f
(6.122)
Equation (6.122) indicates that Fermi energy is not constant, but decreases slowly as the
temperature rises. The result given by equation (6.122) is quite satisfactory, but while using it, we must
remember that it is applicable only at temperatures such that kBT « Ef , which happily includes the
whole range of temperatures for which the metals are solids.
For determining the mean energy of an electron at other temperatures, we have to evaluate the
mtegral given by equation (6.114) choosing
E
g(£)= jEZ(E)J£
o
with g'= EZ(E) and g" = A [£?(£)]
Referring equation (6.119), the total energy of the electronic system may be written as
o& Ef
it2 d
u= J Z(E)E dE f(E) = j £Z(E) dE + 2^(EZ(£))£,
o o
V = f EZ(E) dE +
EZ(E) dE + —(kBT)2\ — [EZ(E)]
6 dE
0
Replacing the first term of the above equation by Uo from equation (6.110&)
[ EZ(E) dE + ~—(kBT)2
-^{EZ(E)}
J o aE
The procedure used in equation (6.120a) is carried out here also to solve the second term of the
above equation. In the last term Z(E) is evaluated at Ep rather than at Ef. Thus,
Er
U=UQ + Z(Ep)EF$dE
71^
U= Uts + Z(EF>EF(Ef-EF)+~(kBTii
CExrl is nothing but Z(£)
U= U0 + Z(EF)EF(ErEF)+ ^(kJfZl.EJ
Now substituting the value of (E\—E^) from equation (6.122)
u = u« ~ n + a£f)
■ t,= (7„ + ytt1(r)2z(£f) (6.123)
From equation (6.106) at E = EF
fn V 8m I372
^)=l2j|jq ^l/2 (6.124)
and from equation (6.108)
uAsjvJLa2] v"uJep
3An i
or
2 Je*2
Substituting this in equation (6.124)
3NA 3 N_
Z(Ef) =
2 J(EF)*2 = 2Ef
Substituting this value of Z(Ef) in equation (6.123)
2 Ef
v *2 (W2 '
N N 4 Erf
; n2 (fcflT)2
0 4 Er
From equation (6.111),
£f~3£°
Substituting this value of EF in the above equation, we get
5 _
E
3 E°
+ ■ 12 I Er . (6.125)
o
In equations (6.122) and (6.125) EF and Eo refer to quantities at T= 0 K. It is thus observed that
is only 2 x 10~5 for EF = 5 eV and so for

E
practical purposes, the Fermi level may be considered a constant.
The significance of the above equations may be studied by considering the specific heat problem.
dE
rp
It2 Eo g2 [from equation (6.125)]
dT
Using Eo « tEp we get
E
fIf f frifflf fr^ffflff tfMmli ?7
Thus for a monovalent metal, the heat capacity per kmol of the metal due to free electrons is
(6.12M
(6.126)
where
For Ef. = 5 eV and 300 k
(6,126 a)
This value is higher than that predicted by equation (6.110a) and this result fairly agrees with experimental
values. Expression (6.126) differs from the classical result of -R* by a factor — which amounts to 0,025
for Ep = 5 eV at 30*C. Thus the quantum mechanical theory predicts a specific heat much smaller than the
classical value of *
Ratio of electronic specific heat calculated quantum mechanically and classically is
[CJ/Q.AfedQ )
(6.126 b)
(CJ^fCloisica/)-
= 0.57x)0^r
The electronic specific heat together with the lattice specific heat gives the total specific heat of a
solid. Equation (6.126) tells that the electronic contribution varies linearly with temperature whereas the
lattice specific beat vanes as the cube of the absolute temperature at low temperature range. Thus the total
specific heat at low temperature is given by
C, (Tola!) -IC.^+lCJj,
iz.. [CJÂT+fiT3 (6.127)
where A and B are constants. But the lattice specific heat contribution at high temperature region is 3 R* and
is independent of temperature. Equation (6.127) is thus written as
-jwA + 87*
(6.127o)
7
Figure 6.22 (a) indicates the lattice, electronic and total specific heats for the metal cobalt at low
lenipcratutv range. It is clear from the graph that the electronic contribution to the total specific heat in
this range is significant.
r
Figure 6.22 (h) shows that a plot of as a function of T2 gives a straight line.
From this graph the values of the constants A and B can be determined, which are useful in
checking the theoretically predicted specific heat values of metals. The plot for copper in Fig. 6.22 (b)
yields a value 0.695 for 4. Using 7.1 eV, one gets 4 = 0.508 using the equation (6.126). Thus the
calculated value is much smaller than the observed value. This is resolved if we remember that the free
electrons in the system are not actually completely free, and that they rather move in a periodic potential.
Hence if we use the effective mass m* instead of m (for copper tn* = 1.5 m) for calculating EP the
expected agreement with the experimental results immediately appear.
Fig. 6.22 (a) Different contribution to the total specific heat of cobalt
(b) Kok and Keesom plot for copper
In equilibrium the valence electrons obeying classical free electron theory do random motion with no
preferential velocity in any direction. It is now conveniently plotted the velocities of these free electrons
in velocity space such that the points inside a sphere correspond to the end points of velocity vectors.
Fermi velocity (vj is the maximum velocity that an electron can assume i.e., vF is the actual velocity
value of the electron at the Fermi level. The shape having vF as a radius represents, therefore, the Fermi
surface. The velocity vectors cancel each other pair wise at equilibrium and not net velocity of the
electron exists.
It is very interesting to note that although all the electrons participate in the conduction mechanism,
the relaxation time of only those electrons which are at the Fermi level occurs in the conductivity. The
conductivity is proportional to the Fermi surface area. Thus, metals with large Fermi surface areas will
You
have high electric conductivity; whereas insulators with zero Fermi surface areas will hav
e zero
conductivity.
Since, for a free electron
’/ik
v= —
. ni J
the equation of motion of each electron in the Fermi surface under the influence of a static electric field
of intensity, E is
x dk
h — = Ee
dt
This means that in the absence of collisions, the Fermi

sphere will be at a constant rate in k-space.
The following approach yields the quantum mechanical
expression for electrical conductivity. Integrating the above
equation of motion, one gets
k(r) - k(0) =
Thus if the electric field is applied at time t = 0 to a filled

Fermi sphere centred at the origin of k-space, then in a
characteristic time Fig. 6.22 (a) Displacement of Fermi
surface with an electric field
The sphere will have moved to a new centre at

eEk
Ak = —-
n v,
Collisions create an opposing effect tending to restore the displaced surface back to its (t = 0) i
equilibrium position: A steady current is ultimately reached with
ne/iAk
(6.127a)
neh EekF
or m* hvF
ne2kF
(6.127b)
m*vF
ne2tF
or —/-
m
The above treatment is based on the free electron approximation. A similar treatment may be
given for the band approximation. The result of such a calculation is
(6.128)
The real picture of electrical conduction in metals is quite different from the classical one, in
which it was assumed that the current is carried equally by all electrons, each moving with an average
drift velocity vd. But quantum mechanical treatment tells us that the current is in fact, carried out by
very few electrons only, all moving at high velocity (vF). Both approaches lead to the same result, but
the latter is more accurate.
The only quantity on the right side of equation (6.128) which depends on temperature is the
mean free path Since this mean free path is inversely proportional to temperature at high temperatures,
it follows that o« or p Tt in agreement with experimental conclusions. Thus the Fermi surface is
very important in transport phenomenon. Since the flow of current is by electrons close to the Fermi
surface, these phenomena are very sensitive to properties, shape etc. of this surface. Thus the inner
elections are irrelevant so far as conduction processes are concerned.
The mean free path on the electron in a metal may now be computed from the above said quantum
mechanical treatment of conductivity. The resistivity of copper is 1.7 x IO-8 Q-m. Thus
with m* = 1.01 m (6.129)
Table 6.2 Electrical conductivities and other transport parameter for some selected metals
■BT ’ TF" ► A
Li 1.07 x 107 4.6 x 1028 0.9 x IO*14 1.2 x 106 10.8 1.2
Na 2.09 x 107 2.65 x 1028 3.1 x IO-14 1.1 x 106 34.0 1.2
K 1.39 x 107 1.3 x 1028 4.3 x IO-14 0.85 x 106 37.0 1.1 1
Cu 5.76 x 107 8.5 x 1028 2.7 x IO-*4 1.6 x 10* 53.0 1.01
Ag 6.15 X 107 5.85 x 1028 4.1 x IO-*4 1.4 x 10* 57.0 0.99
Au 4.47 x 107 5.9 x IO28 2.9 x l(T‘4 1.4 x 106 41.0 1.0
Al 3.65 x 107 18.06 x 1O28 0.7 x 1G-14 2.02 x 106 14.1 0.97
1.69 x 107 13.10 x 1028 0.4 x 10-‘4 1.97 x 10* 7.9 0.85
Elecmeal Properties of Metals 251
x m* . 1.01 xKT^x9,11
f ~ ne!p ~ 8.5 X lO:*x I 62x 10 ” x 1.7 x 10“*
1.01x9.11x10 3
« 0 24 x 10”
8.5x 1 62x 1.7
= 2.4 x W14 s
E, s lfvr ~ 2.4 x IO’1"1 x vr
- 2x701 * 1.6* IO'"

-2.4X1012
l.OmO'M.ll
v^ = 1.55 x
X? = 2.4 x 155 x I O’* - 3.78 x KF1 - 378 x 1O'K) m
Ay«37ffinm
This value agrees with the experimental value fairly welt
XXI- ELECTRON SCATTERING AND SOURCES OF RESISTANCE

IN METALS
At room temperature the conductivity of metals is largely independent of impurities or lattice defects; the
electron concentration is dote rm med only by the nature of the metal being comparable with the total number
of atoms in the meuh and the mobility is limited primarily by crystal lattice vibrations, which scatter the
electrons and determine their mean free path in an electric, Held. At very low temperatures, however, the
lattice vibrations are not limiting; in fact one would expect them to die cut at 0 K and the conductivity to
become infinite, m a pure, perfect crystal. As shown in Fig. 6.23(a), the resistivity in such a crystal should
go as T6 near 0 Kas thia is the temperature dependence of the scattering due to lattice vibrations, and the
electron concentration is independent of T. No real crystal is completely pure or perfect, however, and
imperfections of any kirxl-chenHcai impurities, lattice defects, even the crystal surface act as scattering
centres for the electrons even in the absence of lattice vibrations. Thus the resistivity does not fail tu zero at
0 K. and the resistivity curve is displaced upward by an amount which reflects the extent to which these
imperfection# are present and effective as scattered. At high temperatures, this displacement is insignificant
compared to the much larger effect of the lattice vibrations. For this reason the resistance ratio, the ratio of
the resistivities at room temperature to liquid hchum temperature is used as a simple measure of the purity
and perfection of a metal crystal. Actually the sensitivity of the resistivity to different imperfections varies
widely, as seen in Fig. 6.23(b), where the effect of certain impurities in copper is shown. It can be seen that
__ _____—- ■ ■~"' ■— ■*■ । -i ' _-ZZZZ_Z3OZ£Z39EaSH
iPstOP^RTlES <BivlETAiKj 253
ffect of certain impurities in copper is shown. It can be seen that as little as one part per million of
• creases the resistivity at 4.2 K by more than an order of magnitude. The resistivity of metals at
’^ygly high temperatures varies slowly with temperature, increasing with the first power of T.
& The general characteristics of electrical conduction in metals are summarised as follows:
1 The electric current density in the steady state is proportional to the electric field strength
(Ohm’s law).
2. For pure specimens, the electrical conductivity (<j) and the thermal conductivity (<jy) vary
with temperature as follows:
rt * T~{ and gt = Constant (for T > 0D)
(J y
so that —— is independent of temperature (Wiedemann-Franz law);
cT
G T 5 and t~2 (for T< Qn)

where is the characteristic Debye temperature. The relation p <*= T5 is known as the Bloch-
Gruneisen T 5 law.
3. For metals that exhibit the phenomenon of superconductivity, their resistivity disappears at
temperature above 0 K and below the critical temperature (Tc) for the superconducting phase
transition (T. = 4.15 K) for mercury.
4. For metals containing small amounts of impurities, the electrical resistivity (p) may be written
as
where p0 is a constant that increases with increasing impurity content and p (T) is the
temperature dependent part of the resistivity discussed in item 2 above. This is known as
Matthiessen’s rule.
5. For most metals the electrical resistivity decreases with increasing pressure.
CHAPTER «
Rfr 6.23 Resistivity of metal (a) its temperatures dependence at very low temperature
its dependence upon small concentration* of selected impurities (in Cu), at low temperatures
6. The resistivity of alloys that exhibit order-disorder transitions shows pronounced minima
corresponding to ordered phases.
The relation for electrical conductivity given by the general equation (6.12) helps one to calculate
the relaxation time t from the experimentally determined values of the resistivity of different metals
For monovalent metals, the number of free electrons in a given volume is equal to the number of atoms
present in that volume. The values of t at 0°C for some selected metals are given in Table 6.2. We infer
from the table that the relaxation times are of the order of IO-14 second. Since this value of relaxation
time does not give any significant clue except that it is small, it is suggested to consider the results in
terms of the mean free path of the electron. Equation (6.128) tells that T in metals refers to electrons
with the Fermi velocity vF. Thus, if the scattering in metals is isotropic, one can use t = t_= and
hence X = Xrr = vrr Trr. X values for eight familiar metals are _
given in Table 6.2. The point of special interest is the fact that / \ / x
the mean free path of the electron is of the order of several . V—/
hundred Angstroms. This value is much larger than one would
expect if the electron really did collide with the ions as x——Z"
illustrated in Fig. 6.24 and such a model inevitably leads to ( ) ( ) ( J
mean free path of a few Angstroms. Especially in close-packed
structures, in which the atoms are densely packed, it is difficult Classical picture of scattering
to see how the electrons could travel so far between collisions. an e'ectron by positive ion cores
The other difficulties of this model are the explanation of the temperature dependence, pressure
dependence, influence of impurities on the conductivity, etc. This paradox can be explained only by the
use of quantum concepts.
Now a model must be developed, and it is necessary to take account of the fact that the electrons
are moving through a region containing a regularly arranged lattice of positive ions. These ions produce
a pattern of periodically varying electric fields (or potentials), and as the electrons travel within the
metal, they experience the influence of this periodic potential. The problem is analogous to that X-ray
faction.
Drude-Lorentz assumes that the mean free path is of the same order of magnitude as the inter
atomic spacing, thus a constant; and the temperature variation of conductivity is due to the variation of
the average velocity of the electrons. According to quantum statistics, however, the average energy,
hence the average velocity, of the conduction electrons changes very little with temperature, and it is
necessary to assume, therefore, that the observed variation of conductivity is caused by a change in the
mean free path. To calculate this mean free path (XF), a knowledge of the source of resistance in metals
is essential.
The wavelength of the electron in a crystal lattice is given by the de Broglie relation.
m*v
It is well known from the theory of wave propagation in discrete structures that when a wave
passes through a periodic lattice, it continues propagating indefinitely without scattering. The effect of
the atoms or ions in the given lattice is to absorb energy from the wave and radiate it back, so that the net
result is that the wave continues without modification in either direction or intensity. The velocity of
propagation, however, is modified. This is what happens in the case of an electron wave in a regular
lattice, except that in this case we are dealing with a matter wave. In other words, the electron wave in
a perfect crystal resembles the electromagnetic wave corresponding to visible light which passes
___ _______________________________ Prophtto op Metals 2$ft
jgviated through a crystal such as NaCl. The only effect the crystal has is to introduce the refractive
c
g so that the velocity in the medium is —. Therefore we see that, if the ions form a perfect lattice,
is no collision at all, i.e., A = <» and hence t =<», which in turn leads to infinite conductivity. But
observed value of the mean free path is about 10 nm. The finiteness of the conductivity must thus be
. e to the deviation of the lattice from perfect periodicity. Thus, in order to discuss the electrical resistance
must study the ways in which the periodicity of the lattice may be upset.
The two main types of lattice imperfections which can contribute to the electrical resistivity are:
1. The thermal vibration of the lattice, which will prevent the atoms from ever all being on their
correct sites at the same time.
2. The presence of impurity atoms and other point defects that will upset the lattice periodicity.
It is possible to explain the temperature dependence of resistivity using the following model: We assume
that the crystal is free from the deviations of the type (2) mentioned above, and estimate or AF as
determined only by lattice vibrations. We, thus, proceed by assuming that the scattering of the electron
wave is due to the finite size of the vibration amplitude of the atoms, that is, the vibration amplitude
produces a scattering cross-section; and that the mean free path is obtained directly by using kinetic
theory formula. It is also assumed that at high temperatures, the lattice vibrations are essentially classical.
If M is the mass of the atom, and (- fic) is the restoring force on the displaced atom, the equation
of the atomic oscillator is
+fx = G
dt2 J
x is the amplitude of vibration.
The potential energy of the oscillator will be
(6.130)
per degree of freedom. At high temperatures, as the Einstein and the Debye frequencies are essentially
the same, and most of the modes are the high frequency modes, we write
0J2 = ©£ ~ ©fl (6.131)
with ZroU
D = jtD0 U
Thus
MoT
2«*A
From equation (6,130).
4m$
Substituting Dr from equation (6J31)
' *ir.v_.C'|2
' &T V 1^1
; a3r
(6.132)
1 “a#*X
Since the scattering cross-sections are proportional io the squares of the amplitudes, we write scattering
cross-sect ion, (£?/) Constant X (j?)
rfT
Constant x
Mk^D
From kinetic theory that the mean free path is given by
H (Constant)
ie., X w —-, where n is the number of atoms in one cubic metre.

nx
We know that r = -
Thus t = (Constant) x —
/JVJT
Yoik
From equation (6.132), we get
(Constant) MkB$2D
nv. h2T
(Constant) MkBtfD
(6.133)
ft2!
. _ (Constant) Mkô 1
h2T , (T»eD)
(6.134)
Substituting this value of tFin equation (6.128), we get
(6.135)
assuming there is one conduction electron per atom.

Le., p oc T
The temperature dependence of resistivity given by equation (6.135) is in agreement with the experimental
value. It is emphasised once again that the theory applies only to temperatures T » 0D.
At low temperatures, we use the model suggested by Bloch and Debye. At temperatures much
lower than the Debye temperature (T « QD ), a relaxation time cannot be defined consistently. The
above theory, therefore, cannot be extended to low temperatures. It can however be said that at low
temperatures, since the lattice vibrations begin to die out, the scattering cross-section would fall and we
would therefore expect that their contribution to the resistivity, usually denoted by p will decrease at
low temperatures, eventually becoming zero at 0 K. A detailed calculation shows that at low temperatures,
Pp varies as T5 and this changes over to a linear dependence on T at higher temperatures.
The larger the amplitude of vibration at any temperature, the greater will be p . Since this amplitude
depends on the inverse of the Debye temperature (0p), it is to be expected that p will be less for metals
with a high 0D, and vice-versa, and this is confirmed by experiment. The arrangement of point defects
in a crystal resistivity p0, which they produce, would be expected to be constant. Their contribution to
•he resistivity is temperature independent, but it does, of course, increase with the impurity concentration.
The total resistivity p is therefore
P»Po + P/^ (6.135a)

This is shown in Fig. 6.25, in which it can be seen that p at first decreases linearly with T, and at
temperatures, it flattens off to a constant value, equal to p0, which is called the residual resistivity.
18 clear that, for a very pure sample, p0 will be very small, whereas for an impure specimen, it will
a high value.
**** Probabilities of electrons being scattered by phonons and by impurities are additive, since
tWo Mechanisms are assumed to act independently. Therefore we may write
F»g 6.25 The electrical resistivity, p, is the sum of two contributions. A constant p0 due to
scattering by impurities and pp which is caused by electrons being scattered by phonons
(6.135b)
where, the first term on the right is due to phonons and the second is due to impurities. The former is
expected to depend on T and the latter on impurities, but not on T. Thus
The simple addition of p0 and p (T) in equation (6.136) is often referred to as Matthiesseri’s rule.
The thermally induced part of the resistivity, p , is sometimes known as the ideal resistivity, whereas
the resistivity which has its origin in impurities and defects is summed up is the residual resistivity, (pJ.
Since, the resistivity in equation (6.128) is inversely proportional to associated with the
electrons at the Fermi level, the impurity scattering leads to a constant term in Matthiessen’s rule. For
not too high impurity concentrations, — is proportional to impurity concentration and so is p in equation
T0 z’
(6.135a). Figure 6.26 shows the resistivity of pure copper together with that of copper containing small
amounts of nickel, as a function of temperature.
Ai room temperature pp(7) dominates and so the resistivity at room temperature, p^, is almost
Prt
the same for all the samples. This means the ratio which is called the residual resistance ratio,
can be used as a measure of the purity of a sample. p0 can be measured by immersing the specimen in a
bath of liquid helium, because the resistivity of nearly all metals is in the residual range by that
P/w
temperature. The values of , which can be easily obtained will, of course, depend on the particular
metal which is being studied, but for high-purity samples of metals such as aluminium and copper, the
ratio can be 200, although for very carefully prepared materials it is possible for the ratio to be as high
Electrical Properties of Metals 259^
—.... — I ■ — —- --- ■ —_. . ■— -
as 104 - 105- The measurement of this resistance ratio is a very straightforward method of determining
the quality of a particular sample although it gives no indication of the nature of the impurities or
defects.
Rg. 6.26 The resistivity of alloys of nickel in copper as a function of temperature
The number of vacancies or grain boundaries present in a sample can also be changed by various
heat treatments. For example, if a metal is annealed at temperatures close to its melting point and then
rapidly quenched into water of room temperature, its room temperature resistivity increases noticeably
due to quenched-in vacancies. Frequently, this resistance increase diminishes during room temperature
ageing. Likewise, recrystallisation, grain growth and many other metallurgical processes change the
istivity of metals. Asa consequence of this, and due to its simple measurement, the resistivity is one
l£W.I
of the most widely studied properties in materials research.

Sommerfeld gave a different interpretation for the values of vd and X. Drude-Lorentz incorrectly
predicted that the temperature dependence was due to the variation of average energy or the velocity of
the electrons and that X was the same order of the magnitude as the interatomic distance. According to
die quantum mechanical theory due to Sommerfeld, the average energy of conduction electrons vary
very little with temperature. It is therefore necessary to assume that the observed variation of resistivity
is caused by a change in the mean free path. To understand the variation property, it is necessary to
consider the wave nature of the electron and to treat the collision time between the detectors and the
atom by a scattering process similar to the diffraction of X-rays. When the atoms in a metallic crystal
are essentially at rest, the electron waves are coherently scattered by the perfectly periodic array and
proceed in a forward direction without disturbance. It is similar to the passing of the light wave through
a perfect crystal So it follows that electrons can pass through a perfect crystal without any resistance
whatsoever for its passage. If all the atoms were to be at rest, the mean free path for the electron
scattering would be infinite. What then is the mechanism which give rise to resistance to the passage of
CHAPTER 6
electrons through a metallic crystal? Deviations from the periodicity of the lattice are the essential
cause for the phenomenon of electrical resistivity. Only at absolute zero of temperature the atomic array
may tend to periodic Quantum mechanics tells us, that even at absolute zero of temperature the atoms
make zero point vibrations which may not be perfectly harmonic. As temperature increases the periodicity
the atomic array is considerably disturbed by the unharmonic oscillations executed by the atomic
oscillators. These atomic displacements cause an incoherent scattering of the electron waves, since they
are not is phase with each other The periodicity of the lattice is not only disturbed by the lattice vibrations
El ettrical Propen ies of Metals 2 59
not only disturbed by the lattice vibrations but also by the lattice defects such as vacancies, interstitials, and
dislocations, presence of foreign impurity atoms and boundaries. The mean free path is inversely propor
tional to the square of the atomic displacements which however are directly proportional to the temperature.
Thus or p «I • Actually thia is correct only above a critical temperature called the Debye temperature,
and below this critical temperature, the temperature dependence is non-linear,

The reactivity of metals arises due to scattering of the conduction electrons by the lattice vibrations
(or phonon scattering as it is called), by the impurities and by structural imperfections. At low temperatures,
the impurity scattering is dominant and the resistivity due to it is found to be practically temperature inde
pendent The total resistivity (p) of the metal can be given as the sum of the three components, namely, pf
the resistivity due to lattice scattering which is temperature dependent. p; the resistivity due to scattering b v
impurities and pj the resistivity due to defects or dislocations in the structure. That is,
This is Mattheissen’s rule in the stick sense. The reasons for the above behaviour of resistivity less in the
mechanisms of the scattering process. The probability of scattering (p.) of the electron per unit time is given
by the reciprocal of the relaxation time (r). That is.
This means that larger the relaxation time, smaller is the probability of scat ten ng and greater is the electrical
conductivity as given by the expression^
(j = —
at
We will define another quantity called the scattering probability per unit length (X»X K lhe electrons are
assumed to move with a mean velocity (corresponding Fermi energy) we can write
p,“2;v«
i
ar t= =—
The calculation of X, « some what difficult and so we will make an approximation by assuming char X, is
proportional to (he number of scattering centres per unit volume (nJ and so we can write.
where the constant is called the scattering cross-section per centre, So
Any variation in the value of T is only due to variation in cr, since v* and a, are constants for a given metal. It
can be shown by rigorous theoretical calculations that for lattice vibrations o, is proport ionat to the square of
the amplitude of the lattice vibrations. That is,
Since, the energy of the atomic oscillator is proportional to the square of the amplitude and again
since the vibrational energy of the oscillator is proportional to the absolute temperature we can say,
O foc T
So, T«l/T
Hence the conductivity G « l/T and this relation is in accordance with experimental results.
When we make the reasonable assumption that the scattering probability per unit length (Xt) as
** T = v° ^‘si + +
. 1 " 1 • 1 WB
? P=— 2x -—
ner- ne2 1 31 n +Z J
4 p = p/+pi+p</
The resistivity of alloys increases with increasing amount of solute content as shown in Fig. 6.27. The
slopes of the individual p versus T lines remain, however, constant. Increasing solute concentrations
merely cause a linear shift of the p versus T curves to higher resistivity values is in accordance with
Matthiessen's rule. The dependence of p0 on a single impurity is
(6.137)
where, x is the concentration and A is a constant which depends on the base metal and the impurity- The
value of A increases with valency, atomic size, or other difference between the two materials. Equation
(6.137) is called Nordheim's rule. For dilute solutions x «1, hence
(6.137a)
The additive nature of the resistivity is illustrated in Fig. 6.27 in the case of Cu-Ni alloy. The
residual resistivity or the extrapolated resistivity at 0 K gives the value of the resistivity due to impurities
and defects.
Matthiessen’s rule tells us that the resistivity of metals increases with impurities. Hence alloying
also must increase the resistivity of metals. This increase is found to be dependent on the amount of
ordering the alloy. When the alloying atoms take up preferred position in the lattice, the scattering is •
decreased as compared to the random placement of the alloying atoms. This is illustrated in Fig. 6.28 in
CHAPTER «
•he case of Cu-Au alloy. Curve (a) represents the resistivity variation of the alloy quenched from 650°C
leading to a disordered system. Curve (b) represents the resistivity of the alloy annealed at 200°C which
gives rise to ordered arrangement. There is a pronounced minimum of resistivity when the atoms arrange
•hemselves in a periodic array.
Ml Souq State Prana
Fig. 6.27 Specific resistivity (Q-m) as a Fig. 6.28 Resistivity of Cu-Au alloys
function of temperature for copper and (a) unannealed (b) annealed at 200°C.
. cop per-nickel alloys; the numbers refer

to atomic percentage
5B0V. RESlSriviTVWlfH'PREsSliRE
At room temperature the general behaviour of p of metal is to decrease initially with increasing pressure
and it may pass through a minimum. The initial decrease is due to the effect of pressure in reducing the
amplitude* of lattice vibrations. The subsequent increase is probably due to modification of the electron
band structure which leads to increased phonon scattering.
Heat conduction is the transfer of thermal energy from a hot body to a cold body when both the bodies
are brought into contact. For best visualisation we consider a bar of a material of length x whose ends
are held at different temperatures. The amount of thermal energy Q which crosses unit area of this bar
dT
per unit time (<>., the heat flux JQ) is proportional to the temperature gradient —. The proportionality
constant is called the thermal conductivity ar. We thus write
(6.138)
The negative sign indicates that the heat flows from the hot to the cold end. The unit of he*
conductivity is Wm1 K"‘. The thermal conductivity decreases slightly with increasing temperature.
example, arfor copper decreases by 20% within a temperature range of 1 C. In the same temper80"’
region 0rfor iron decreases by 10%.
In insulators, heat is carried entirely by phonons, but in metals heat may be transported by both
electrons and phonons. The conductivity oris equal to the sum of the two contributions. .
roraoe*q/, ~|
In most metals. the contribution of the electrons greatly exceeds that of the phonons, because of
typically n
the great concentration of electrons-’ tvnicallv o p—
- in-2 r* u
|(tz g, Hence oîs• usually ■ - j
*• neglected.
Ûe^t’°n ar’^’.as.to w^*at velocity do the electrons have, and do all the electrons participate
in the heat conduction. This is answered with following model:
Electrons at the hot end travel in all directions, but
.certain fraction travel to the right and carry energy to the
cold end. Similarly, a certain fraction of the electrons at
the cold end travel to the left, and cany energy to the hot
end. These oppositely travelling electron currents are equal,
but because those at the hot end are more energetic on the
average than those on the right, a net energy is transported
to the right, resulting in a current of heat Note that heat is
fig. 6.29 Energeoc tv
transported almost entirely by those electrons near the
carry ret to the rgnt
Fermi levels, because those well below this level cancel
each other’s contributions. Once more it is seen that the electrons at the Fermi surface play primary role
in transport phenomena. The velocity of such electrons is calculated using the formula
1 2
^mvF=EF
To evaluate the thermal conductivity Op we use die expression <JT= [CJe/ c nX, used in
equation (6.23). In this expression, is die electronic specific heat per unit volume In the present
case [CJrf should be substituted from equation (6.125a); also Ru should be replaced by R= nkg, since we
are dealing here with unit volume rather than a kmol Tn addition; r and X should be replaced by vF and
Xy, since only electrons at the Fermi levels are effective. Thus
CHAPTER 6
(6.139)
This equation expresses thermal conductivity in terms of the electronic properties of the metal.
Substituting the usual values of the microscopic quantities in equation (6.139), one gets Oj. = 350 Wmr1 K’1.
ne2X?
Recalling that a « , wc get
fTl
<6 J 40)
(Refer classical Eqm (6.25) and compare the restdt$|

Ulia quantum mechanical equation gives a comparison of thermal conductivity with electrical conductivity.
The relation is the Wiedemann-Franz law obtained using quantum theory. Thus Lorentz number L is given
(6.141)
= 2.45 x 1(T* watt ohm kelvin-2

This remarkable result involves neither m nor n. It does not involve the relaxation time t. This Lorentz
number Lt because it depends only on the universal constants Aj and e, should be the same for all metals.
This conclusion suggests that the electrical and thermal conductivities are closely reUied, which is to be
expected since bod electrical and thermal current are carried by the same agent electrons. Experimental
values of L al 0*C and IO0*C given in Table 6.C are in good agreement with the theoretically predicted value
given by equation (6441).
Table B. C Electrical and thermal conducbvrties of some metals a: 300 K
<»
Metal Lorentz Number fL)

*
w
sI
(Wm'lC’) re IQO’C
e
fwxur3) (WQ1C1)
Ag 6.22 x itf 423 2.31 x I0-1 2.37 x Iff*
Cu M2 x 107 387 2.23 x I0'1 2.33 x Iff*
A! 3 .65 x iff 230 2.01 x Iff* 2.06 x Iff4
Zn 1.69 x 107 130 2.31 x 10* 2.33 x Iff4
Pb 0.48 x 10’ 35 2.47 x 10'* 2.56 x Iff*
Cd 1.30 x 10’ 102 2.42 x 10'* 244 x Iff*
Au 4.4? x 10’ 295 2.35 X Iff4 2.40 x Iff*
Al low temperatures (T« 0^). the Lorentz number tends to decrease; for pure copper near 15 K, the
value is an order of magnitude smaller than the values tabulated in Table 6<C This is due to a difference in
the collision averages involved in the electrical and thermal conductivities; the thermal and electrical relax
ation times are noi identical
We can draw several conclusions from equation (6,139), For T 300 K, n = 10^ t = IO"14 second, ;h
« 9.11 x 10 Xlkg and kp » 13? x 10"u J we get OT » 100 WraT1 K \ which is of the corneci order of
We can draw several conclusions from equation (6.139). For T ~ 300 K, n = IO28, t = IO14
second, m = 9.11 x 10’31 kg and kB = 1.38 x IO*23 J K ', we get or = 100 Wm1 K', which is of the
correct order of magnitude. How does the thermal conductivity depend on temperature? All quantities
in equation (6.139) are independent of temperature, except t . t varies as P4 for temperature above the
Debye temperature. Hence in this region is independent of temperature.
The theory for low temperature region is very complicated; but it can be said that at very low
temperatures t becomes constant and ar, thus, has to go to zero as T-> 0. However, ^continues to rise
as T goes down, because scattering is less likely even among the phonons that do exist. There is less
anharmonicity in small amplitude vibrations. The thermal conductivity keeps rising as T goes down
until the mean free path is limited by geometrical scattering; that is, the sample dimensions themselves
finally set an upper limit to X. Further reduction of temperature now causes to drop since Cv 0. It
may also be mentioned that if the metal contains impurities, then besides the electron-phonon scattering,
there will also be an electron-impurity scattering. In such a' case, if the two types of scattering are
independent, we may write for the total conductivity cT as
(6.141a)
where Gj is the contribution arising from electron-lattice scattering and a. is the contribution from
electron-impurity scattering. It is found that the addition of impurities decreases the thermal conductivity.
The thermal expansion of solids is the most common effect of heat: According to this property, all solids
increase their size when they are heated. Different solids expand to different extents for the same rise of
temperature. In order to specify this expansion of solids, we often determine the quantity called the
coefficient of linear expansion a, defined as the ratio of the increase in length of the solid per degree
rise of temperature to its original length. If Zj and Z2 are the lengths of a rod at two temperatures
T. kelvin and T, kelvin, a of the rod is defined by
(6.142)
or, if Zq is the length of the rod at 0 K and lT at a temperature T kelvin, then
Most of the solids expand on heating and from the atomistic point of view it means that the
average interatomic distance increases as the temperature increases. As temperature increases the
amplitude of lattice vibrations increases becoming as high as 12% of the interatomic spacing, at the
melting point, If the lattice vibrations are exactly harmonic, thermal expansion cannot be accounted for.
In Hg. 6.30 (a) we have a potential energy diagram exactly parabolic in shape. As temperature goes up
the vibrational energy levels go up, but the mean position of oscillations remain the same so that the
interatomic spacing (r0) remains the same. But consider the potential energy diagram shown in
Rg. 6.30 (b) given by the equation (6.142a).
l/(r) = -4 + 4 (6.142a)
r r
1 atomic distance
(Kg)
(a) (*)
Fig. 6.30 (<j) Symmetrical potential energy curve
[b) Asymmetrical potential energy curve
where, n and m are the attractive and repulsive exponents of the interatomic distance. For ionic crystals
n = 1 and m is the order of 6. So the potential energy curve is asymmetrical about the apex and because
of this the mean interatomic spacing increases as the temperature increases. So the atomic oscillators
are actually unharmonic oscillates. If n is high as is the case with covalently bounded materials, the
curve, on the right side becomes steeper restoring some of the symmetry. This gives rise to smaller
thermal expansion. If n is small as is the case in weak metallic bonds, the curve on the right side
becomes shallow resulting m larger expansion coefficients. Thus we see that the bond strength plays an
important part in the thermal expansion of a solid. The alloy invar (Fe 64% and Ni 36%) has a low
temperature coefficient of expansion due to a magnetic transition. When the temperature is increased
die tendency to expand is nullified by magnetostriction until the material approaches the Curie point of
473 K. Above the Curie point it expands normally. Polymers have strong covalent cross linkage bonds
and so their thermal expansion coefficients are small.
Anomalous Expansion of Water

in majority of liquids, the increase in temperature produces an increase in volume of the liquids but
water is a notable exception. The expansion of water is so markedly irregular that even ordinary laboratory
methods can detect the anomaly. In the case of water, from 0°C to 4°C, instead of expanding, actually
contracts, from 4°C upwards it expands, but far from uniformly. In the range 5° to 10°C, the coefficient
of expansion is only 0.53 x ltT4, whereas in the range of 20° to 40°C, it is 3.02 x KT4 and between 60°C
and 80°C, 5.87 x KF4. Hence for a given mass of water, the volume is minimum or density is maximum
i r dvi' dV
at 4°C. In other words, in the relation for volume coefficient is negative for temperature
LVLdr Jr dt
less than 4°C and positive for temperature greater than 4°C. At 4°C, ~ = 0. This means that the
at
specific volume decreases first, reaching a minimum value at 4°C and then increases; it is evident that
the density curve will follow an inverse path, increasing from 0°C to 4°C, where it reaches a maximum
and then decreases. It may be noted that the curve is not linear and hence the expansion is not uniform
even beyond 4°C. This anomalous behaviour of water has been explained on the assumption that three
types of water molecules, (H2O), (H2O)2 and (H2O)3 which have different specific volumes and are
mixed an different proponions al differcn,
so that the max,mum density at 4"C is probab7y d
greater proportions of the higher types
r . The
i result
i . .is, . water at 4°C sink® l
slnKs t0 the bottom
of a lank or lake during winter, while ice floats on the
top. This prevents the freezing of a ,ank ,hc
and thus enables aquatic life t„ survive d||ri
winter. See the beauty of Nature for a Mfe and
living of beings.
-
ME?AW^^FrtCf^ft mdFl^LTgreiCAL RESIStANCE------
e
l ..wW J MIUI ■
The changes in the volume of a conducting wire on the application of hydrostatic pressure, tensile
stress, or other forms of mechanical loading may produce changes in resistance that are of particular
interest in connection with electromechanical transducers. Dimensional changes and resistivity changes
are the two sources for resistance to change. The resistance of a given wire is given by the following
equation:
Table 6.4 Linear expansion coefficients of some selected solids at 300 K
- Substance a (iT-1) in 1(H ;; ; 7 Substance ; a (K~A) in IO-6
Diamond 1.2 Aluminium 23

Glass (Ordinary) 9 Brass 19
Glass (Pyrex) 3.2 Copper 17
Steel 11 Tin 29
Platinum 9 Zinc 16
Nickel 13.1 Cast iron 8

Ice 51 , Silver 19.4
Lead 29 Palladium 12.4
Magnesium ;• ri 26 Graphite 0.6
Hard rubber 80 Gold 14.2
s=pi
JR _ dp dl _ dA
R = p + I A (6.143)
This equation shows that the relative change in resistance is related to the relative changes in
resistivity and dimensions. However, the resistivity itself is also affected by changes in dimensions.
Electrical Properties of Mewls 267
where N is the total number of electrons present in the specimen wire of length I and area of cross-sect ion A.
Thus
dn 4V M
‘------- 3^ —-—_ ««.
<ff
n N A I
Equation 6,144 becomes
d pdeAdNdA di
p 1 jV * A + f
Tliis tout relative change in resistivity is partly due to a change in intrinsic resistivity, p,+ associated with
changes in the average electron velocity, ci the mean free path, X, and the total number of conducting
electrons V, and partly due to the change in dimensions of A and I Thus
dl
P " ft A i
dp
Substituting this value of — in equation (6.143), we get
d» dp, <#
*= p, I
(6,145)
Thus an increase in length of the conductor, not only increases the distance to be travelled by the electrons
but also decreases the number of electrons per unit length. This is the double effect of a change in
dl
length. — is the tensde straw in the direction of the flow of current and it is usually represented by f, -
dR dpr
ix*. * ’ ft
dR . .
It has been found experimentally that —- varies linearly with over a considerable range of strains, an indica*
A
tian that if it varies at alL p, vanes linearly with tr
Thus
(6.145a)
Gt is a constant called gfactor,
ie. (6.1455)
dR
Thus, = ce + 2eX
R
= ex (c + 2)
(6.145a)
where, Gs is a constant called gauge factor.
i.e., (6.145^)
Electrical Strainometer
The bonded electrical resistance wire strain gauge is commonly used for measuring strains. The working
of this instrument is based on the change in resistance of a material under strain. A very small wire is
connected to the specimen, parallel to the axis of loading. As the specimen is strained under load, the
wire is strained by exactly the same amount. Thus the wire becomes a true strain gauge, measuring
strain directly. For many metals, the resistance increases directly with strain, according to the equation
R = Rq + ex Rq Gs. Here 7?0 and R are the resistances with and without load, Gs is the gauge factor.
Thus, (6.146)
The gauge factor is defined as the ratio of the unit resistance change per unit resistance to the
corresponding strain. For a given material the value of Gs may be found experimentally by making a
series of observations of resistance at known strains Gs may be computed from the slope of the straight
line graph connecting ——against Ex. Once Gs is known, the wire can be used for measuring
Ro ...
strain.
Alternating electric fields differ from static electric fields in that they do not penetrate uniformly through
a conductor, but decay in magnitude exponentially from the surface inward. Let an alternating field of
strength EQ cos (Ot be applied in the x-direction, (0 beiiig the angular frequency. The force on the electron
cloud resulting from the field is -eE0 cos tot and the equation of motion in the a.c. field is almost the
same as equation (6.8).
(6.147)
CHAPTER $
To solve this equation for v , it is conveniently to use the complex notation. We shall now write
Eo cos tot = Eo Real [eZor|
and we shall assume the solution to be of the form
v (t) = Re [A* ete j; = Re [i(M* e/ay]

x at
Fwwc*
—a.i ■ । h,
where, A* is in general a complex amplitude. Substituting this in equation (6.147),
Re [mA*zco e10*] + Re A* —e,al + eEQRe [<?'“'] = 0
Re A'mito e'^+A'—e io#

0
Re A* Tico e,Mf + A* ei(Ot + pitot =0

m
Since ei<S3t * 0
eE^t
A*rtco + A* + —— =0
m
eEQx ~
A*(l + nco)
. m
(eE^m) e™
Hence, vx(t) = Re
1-ztco ((
1 + t2©2 e
1 - ztco
< m J 1 + t2co2 1 + t2co2 (cos coz + i sin cot)
(eEpt) cos cot Tcosincot

m 1 + t2co2 I+.t2©2.
jx = nevx(t)
ne2xE0 1 Tt0
------------ ;—cos a*+------ T-7 sin coz (6.148)
L m J l + r2CO2 . l + T2©2
In equation (6.148), the term represents the static conductivity, a,
i.e., jx = °A cos cot + sin cot (6.149)

EtaCHKM PUDMRftarW'MMI
Thus the current density, according to equation (6.149), depends upon af, the relaxation time of
the electron distribution, and the angular frequency of the applied field (co). Equation (6.149) further
indicates that the current density consists of two parts, one in phase with the applied field and the other
it
shifted by 2 from the applied field. Also we notice that as long as on « 1
A= Eo cos
Jx
or Eo cos at
Le, the metal behaves as a pure resistance with conductivity given by the static value, 6S = The
variation of with the angular frequency of the applied field is shown in Fig. 6.32. In the region of
ojt = 1, the conductivity drops sharply and reaches zero.
fig. 6.32 Variation of conductivity with the angular frequency of the applied electric field
For on = 1, equation (6.149) becomes

<5sEq cos tot
»j.' ■ .> ,■ ..<■ ... _______ :
17" Jx -• • =
(6.149a)
.. ® £0 cosot . 2
This occurs at approximately a frequency of 1014 Hz remembering T for electrons in metals is

approximately 10~14 sec. For the conductivity to decrease sharply, the frequency of the applied field
must be in the region of ultraviolet light. The loss of conductivity under such conditions is reasoned by
the fact that the electrons cannot move fast enough with the field and hence lag behind.
CHAPTER 0
iHMt .gftO
The heat developed in a currrent carrying conductor is given by

Electrical Properties of Metals 2 71
Hence heat developed per unit volume per second U

W-uE1
Current density, j = □£
■h
Thus (6.1 50)

£
W will be found to be watt/m\

In an isouopic r unt consider a particular electron which at the instant t ■=> 0, has carried out a Col
lision with the lattice, and let the velocity components of the electron be v> and vr Now at the instant
(r > 0)f the electron has yet to collide with the lattice again, and assuming an electric field of intensity E is
applied along the negative x-directiun, the velocity components of the electron are:
The increment I Ie velocity is due tn the acceleration due to the field on the electron. Thus the increase
I in
in energy of the electron over the field is
The above expression may be averaged over a large number of electrons which have aJI lived through the
period without having suffered a collision, but which presumably have a random distribution of their velo
cities, Thus one finds
(6.151)
If represents the probability that an electron moves for a time! without suffering a collision, then P(t>«
exp (- For isotropic scattering the average lime between collisions, is equal to the relaxation time T-
Also, the probability that an electron will suffer a collision during a time 4r is given by
dt dt
So, the probability that the electron makes a collision between t and t + di is given by
[e*p(-r^ ( *J
Thus, the average energy increase of the electrons during the period between two collisions is equal to
(AW)’ J (AW),*"***
f-fl
Thus, the average energy increase of the electrons during the period between two collisions is
equal to
(AW) = j(AW),^/T dt
f=0
e~,fxdt
Ilmx);
n!
e2E2 2
Thus (AW) =
2mx (1/t)3
(AW) =
•2bV
(6.151a)
m
If n is the number of electrons present in unit volume, the total energy dissipated per unit volume
per second is
W = —(AW)
T
(6.152)
This agrees with the experimental relation.
• when
Many interesting effects arise me i is subiected
u aomPtsl J to a magnetic field. Amongst them are the Hall
effect and magneto resistance.
Hall Effect „ ffect sometimes also seem to contradict completely

The result of the well known experiment -Hurtino material is placed in a uniform magnetic
the classical picture of conduction. If a s^Pfe^conducfor shown in Fig. 6.33, a voltage is found
field and a current is passed along the length current flow and that of the magnetic field. This
to develop at right angles to both the direc on depend on the magnetic field strength and
voltage is known as the Hall voltage, andi simple dynamics of charges
CHAPTER 6
on the current passed. The mathematics of Hall effect

moving in electromagnetic fields. cross.section as shown in Fig. 6.33 carrying a
Consider a specimen m the tonn is appUed m
current lx in the x-direction. If a uniform magnetic le -axis,
Jocular to / and B . This it is found
voltage is called an
thatHall
e.m.f. develops along the y-axis i.e., in a direction pe
voltage.
Let us first consider the situation before the magnetic field is introduced. There is an electric
current flowing in the positive x-direction, which means that the conduction electrons are drifting with
a velocity vx in the negative x-direction. When the magnetic field is introduced, the Lorentz force FL
causes the electrons to bend downward as shown in Fig. 6.33. As a result, electrons accumulate on the
lower surface, producing a net negative charge there. Simultaneously a net positive charge appears on
the upper surface, because of the deficiency of electrons there. This combination of positive and negative
surface charges creates a downward electric field, which is called the Hall field.
The Lorentz force FL which produces the charge accumulation in the negative y-direction, has
the value,
fl = evA
y
Fig. 6.33 Origin of Hall effect and Hall field
Now the field created by the surface charges produces a force which opposes this Lorentz force. The
accumulation process continues until the Hall force completely cancels the Lorentz force. Thus, in the
steady state, FH = FL.
eEH = evJBzy :
n x z
(6.153)
The current density, is given by the equation
(6.154)
Dividing equation (6.153) by equation (6.154), we get
=_«.
Jx
The Hall field is thus proportional, both to the current, and to the magnetic field. The
eh
proportionality constant, that is is known as the Hall constant and is usually denoted by RH i.e.t
J XE1
EH/jx g 1
(6.155)
---------------------------------- _ _ _ _
Electrical
...- -• ---------------------- ----- —- •*—Tir^ —
Now the Hall constant or Hall coefficient, RH is defined as the ratio of the electric field strength
produced per unit current density to the transverse magnetic field. It will be noted that RH depends on
the sign of e and the reader should verily that if EH is in a certain direction for a flow of negative
charges, then it will be in the opposite sense for the same current when it is produced by a flow of
positive charges in a reverse direction. In the monovalent metals, RH is negative, which is consistent
with our belief that the current is produced by a flow of negatively charged particles; the magnitude of
Rff is then such that there is of the order of one moving charge per atom. In more complicated metals,
particularly those in which there is band overlap, RH can be positive (e.g., in zinc and cadmium), and
here it is assumed that most of the conduction occurs by the motion of positive holes. From
equation (6.155)
(6.155a)
TT . n Volt-m , ,
Unit of R„ = —---------—-—- = Vm3A-1 wb-
Amp-weber/m
Table 6.5 Hall coefficient and mobilities for some metals at 300 K
Metal ; ’ Rh (Vm^ 'A^wtr1) in 1CH° '

Silver -0.84 0.0056
Copper ’ -0.55 0.0032
Gold -0.71 0.0030
Sodium -2.50 0.0052
Aluminium -0.31 0.0012
Lithium -1.70 0.0018
Zinc +0.30 0.0060
Cadmium +0.60 0.0080
The general expression for current density is

/ = nevr
i.e., electrical conductivity

■ I
_ A O)v* -
&x &x
The drift velocity produced for unit electric field is called the mobility of charge carriers.
i.e..
CHAPTER 6
(6.156)
Electrical Properties of Metals 27 5
The sijjri of current-carrying cli&rges can b determined.

L
2. The number of charge carriers present in unit volume can be calculated from the magnitude of R„.
The mobility of the charge carriers may be obtained directly from the measurement of Hail voltage.
The Hall coefficients and mobilities of some selected metals are given in Table 6E,
Magnetoresistance
The magneto-resistance of a crystal refers to the change of electrical resistance of a crystal when a
magnetic field is imposed. This effect is due to the fact that, when the magnetic field is imposed, the paths of
the electrons become curved and do not go exactly in the direction of the superimposed electk field. In the
case of metals the resistance generally increases. The mag to resistivity, —T where is zero field
ft? .
resistivity and &p - p(B) - pQ is found to increase with magnetic field and varies as f? in small fields. But in
large fields this may vary as B or even tend to saturation or vary as either B1 or as B
For a magnetic field applied perpendicular to the electric field, the magneto resistivity is given by
Ap _ atg/Po)-
Po ' l+y(B/p)2 (6.157)
where a and y are constants. For small fields, the

magneto resistivity varies as B*. If y “ 0* this is
directly proportional to B*t but if y#0t it tends id a
finite limit We also notice an isotropy of
magneto-resistance. For example, in lead the mag
neto resistivity attains a saturation value in one
direction, white it increases without limit as B1 in
another direction as shown in Fig. 6.34, It can be
shown theoretically that magneto-resistance is
absent if t is independent of velocity. However,
under certain conditions like dominant lattice scat
tering, and presence of targe B< Ap/p& can also be
shown to saturate* In the case of polycrystallioe
specimens. Ap/p0 vanishes linearly with B* This is Fig. 6.34 Field dependence of magneto resistivity of lead
due to averaging for several crystallites. for direction (a) magneto resistivity saturates. but for (b) it
increases without limit as tf.
XXXL THERMIONIC EMISSION

When a metal is heated, electrons are emitted from its surface, a phenomenon called thermionic emission.
This property is widely used in vacuum tubes, m which the metallic cathode is usually heated in order Io
supply die electrons required for the operation of the tube.
The above figure shows the energy level scheme for electrons in metals, according to free electron
tel. At 0 K, all the levels up lo the Fermi level EF are filled up, above which all levels are empty. Note
also that an electron at Ez cannot escape from the metal because of the presence of an energy barrier at the
surface. The height of this barrier, denoted by 0, is known as the work function. This function varies from
Eucttccm
The above figure shows the energy level scheme for electrons in metals, according to free electron
model. At 0 K. all the levels up to the Fermi level EF are filled up, above which all levels are empty.
Note also that an electron at EF cannot escape from the metal because of the presence of an energy
barrier at the surface. The height of this barrier, denoted by 0, is known as the work function. This
function varies from one metal to another, but generally falls in the range 1.5—5 eV.
At 0 K, no electrons can escape from the metal. But as the temperature of the metal is increased,
the levels above EF being to be occupied because of the transfer of electrons from below EF. Even the
levels above the barrier, i.e., at energies higher than (EF + d>) become populated to some extent. The
electrons in these latter level now have enough to overcome the barrier, and they are the ones responsible
for the observed emission from the surface to the metals.
Consider the x-direction perpendicular to the surface of the electron emitting solid. The critical
value of the electron’s momentum in the x-direction, so that it just escapes from the surface, is given by
■^-1
(6.158)
K2m
Inside Outside
n(e) AAAA
Fig. 6.35 Thermionic emission Fig. 6.36 Idealised potential energy of an electron along
a row of atoms near the surface, and the potential energy
barrier at the surface which constrains the electrons to
remain inside, the shaded area represents electron energy
as given by the Fermi distribution shown on the left
The height of the potential energy barrier at the surface (Vfl) is greater than that of the Fermi
energy (EF) by an amount 4>, called the work function.
The product of electronic charge and the number of electrons having a momentum in the x-direction
greater than this critical value, which strikes unit area of the surface in unit time, gives the thermionic
current at a certain temperature. Let N(PX) represent the number of electrons per unit volume having
momentum values p andp +dp in the x-direction. When the electron having momentum px arrives at
X x x
the surface, its velocity will be . Thus the number arriving at unit area of the surface in unit time is
N(p) dpx
Thus, the emission current density is

no
e J Px N(px) dpx (6.158a)
m
p^>
I
Here N(px) is the product of the number of possible states of momentum px and the probability
that an electron is in each state. The number of states having momentum values lying between p and
P «p
p + dp may be written, referring to equation (6.107) and substituting E= -— and dE=p\ as under:
2m J
2-il/2
7tV8ml3/2F P PjP
Z(p) dp = I—
h2 2m m
Z(p) dp = -y p2 dp (6.159)
This result gives the momentum values of p in any direction, but we are concerned with momenta
in the x-direction specifically. We have to now calculate the number of electrons that have a momentum
lying in the range dp at p when p and p values are unrestricted. To do this, we construct a plot in
“momentum space” such that each point represents a particular combination of the momentum
components p, pv and p_ with p2 = p2 + p2 + p2.
" Jr *■ /
* • / 2 2 2
A spherical shell with p = ^px + py + pz as radius and dp as thickness is drawn. Each quantum
state with momentum between p and p + dp lies in this shell. Thus the fraction of states at momentum p
which have momentum values lying in the interval p_ to pr + dp. pv to pv + dp. p • to p + dp , is given
by the ratio of the volume dpx dpy dpz to the volume of the spherical shell of radius p and thickness dp.
dpx dpy dpz
i.e., fraction of states in dp, dpx, dp, =------ —=---------.
x y z 4itp2dp
Hence, the number of states in the momentum interval dpxdp dpzis obtained by multiplying the
above fraction by the total number states in the momentum interval dp at momentum p. Thus
( , dpx dpy dpz
Z(pxPy pj dpx dp, dP = J p2 dp -4-2^
= \rf)dPxdPydPz (6.160)
, Equation (6.160) gives the number of states per cubic metre with momentum component in the
x-direction lying between the values px and px + dpx and, similarly, for py and p?.
Now number of electrons per unit volume having momentum values px and p + dp in the
x-direction is given by
N (px) dx = p- dpx J
1 + e k'T .
C dPy dpz
J (6.161)
1 + e k>T
i°C (300 K), E-Ef» KbT, hence 1 is neglected. We also know that,
AtZ »
2m

E Ej,
VekBT dpydpz
Nip,) dpX
p^-*
kBT lmkiT dPydPl

e B e
R.H.S. =
EflkBT -p}i2mkBT ’B dpy Jexp[- p2l2mkBT]dpz

C-
The integrals have the standard form
N(p ) dx = ,eEFlkaT e~p^2lHkBT dpx y]2itmkBT y/2nmkBT

Thus,
4itmkBT
c e ’
A3 .
Substituting the above value in equation (6.158a)
y f.4itmfcBr cEr/ktT c-Pll2mktT dp

m J h3-
Substituting for - — from the general equation (equation 6.158), we get

2tn
e AiunksT^ -EFlkaT -^/kaT mdfy

c
m h3
CHAPTER 6
eV 4imkBT> d<|>
m
h3
. AnemklT2 -*/k,T
(6.162)
This eqiiaii is commonly known as Richardson-Dushman equation with A the emission cocffctenL Thus
Equation (6.162) indicates that the emission current is exponentially dependent upon the work function
(which is charactensoc of the material because H is determined by the interatomic spacing)* and inversely
dependent upon the absolute temperature, which means that the variation ofcmission with these quantities is
very rapid.
Now
or (6463)
log^îogX --
A plot of log yj against IfT is a straight line having a negative slope (^f) and an intercept equal to kigA.
Table 6.F shows representative values of thermionic emission constants for some metals,
Tabk 6* F Thermionic consume
A (amp m /0* fiuwifon 4 (in eV)

Caldum 60 3.20
Chromium 4S 460
Cesium 162 1.93
Iron 26 4,48
Tamalum 55 4J3
Tungsten 60 4.52
Pi an num 32 536
Sodium 41 230
Comparing these values of A with the value obtained theoretically from equation (6362)t one finds
greater discrepancy. This discrepancy is related to the difficulties associated with experimental measure*
merits. The theory docs not assume the use of any external field to remove the electrons from the emitter.
ftlCTMCM P«FWFW * HMM*
- r
the emitter. Hut II we do not uno It* it space cluirge will be existing hi the vicinity the emitter, which
intends to decrease the eiirrciit. Thus, hi older Io prevent the dccrc/ise (ri'current, the mte of an electric
Held in a muNt. This Held muni be strong 01 tough to remove nil the electron* us soon it* they an emitted,
However, the application of electric Held changes the apparent work function; It decreases with
increasing external Held strength. Therefore, it is suggested Io measure J(T) for different electric Held*
and then extrapolated to get the correct value. Because of thermal expansion, the work function (0)
itself is a function of temperature. For metals is of the order of IO4 eV/K. Therefore, 0 should not
be regarded as a constant, independent of temperature. The actual emission current is strongly dependent
upon the surface conditions. Contamination of the surface may have a large effect on the value of 0 and
because of this, the exponential function may greatly modify the thermionic effect. In the choice of the
materials suitable for the practical applications of the thermionic emission, the following points may be
kept in mind.
The materials must be stable at relatively high temperatures. They should have a small work
function, 0 i.e,, to increase the thermionic emission from metals, it is necessary to lower the work
function. Depositing a layer of thorium on tungsten will lower 0 and enhance the thermionic current.
The ionisation potential of a thorium atom (4 eV) is less than the work function of tungsten (4.5 eV), so
that when the atom approaches very close to the surface, it loses an electron to the metal. The positively
charged thorium ion is tightly bound to the surface by electrostatic forces, and the positive charge
effectively lowers the work function because it aids electrons to escape. Such a thoriated tungsten
cathode has an effective work function of about 2.6 eV as compared to 4.5 eV for pure tungsten.
We are now going to refine our model for thermionic emission further by including (a) image force and
(b) electric field. n
An accelerating electric field is usually applied to the emitter, in order to remove the emitted
electrons from the vicinity of the surface, and to accelerate them to the collector, where they constitute
the thermionic current. This electric field, besides doing this, also lowers the height of the potential
energy barrier at the surface and hence increases the emission. This increase of emission and its
dependence on the external electric field is culled the Schottky effect.
We now consider the following model of the potential energy hairier near the surface of the
metal. The refinement is to add to the potential barrier the force on an electron outside the metal surface.
Any charge when placed near the surface of a conductor experiences a force arising from the polarisation
of the conducting material. For distances that are large compared with the interatomic distances, the
surface of the metal can be considered to be a plane perfect conductor for the present problem. The
force on the electron can thus be calculated by “method of images” principle used in electrostatics
problems. Now the force on the electron is equivalent to that of an equal positive charge placed at an
equal distance behind the plane surface as the electron is in front The force acting on the electron can
be expressed as
f. =_±_fxY=_i_f4)
ima"e 4rtE0 V 2x) 4tce0 4x2 >
_ Ixe2
“ 16jre0x2
The potential function for this force is
The potential junction is shown in Fig. 6.38.
Fig, 6.38 Actual form of the potential barrier near rhe surface ofthe merat
Under the influence of an external electric field Ex, the potential experienced by the charge is the
sum of the image potential and the applied potential. The total potential is shown in Fig. 6.39.
The most important significance of this result is that the work function in the field is less than
that without the field. If the applied electric field is strong enough, it is clearly possible for <J>eff to vanish
completely. When this happens, the top of the electrons distribution is free to leave the metal without
the necessity for tunnelling. This reduction in work function is known as the Schottky effect. The
magnitude of the reduction in the work function for a given system is obtained by the following method:
The effective potential energy in the presence of the field is given by
Fig. 6.39 The total potential at the surface of a metal including both image forces and an
external electric field. (Reduction in the surface barrier due to the external field)
(6.164)
Since the work function is the difference between the barrier height and the position of the Fermi
level, equation (6.164) represents the effective reduction in the work function due to the applied field.
The maximum value of V may be obtained by differentiating the above equation with respect to x and
putting x = x^.
dV n e2
i.e., —- = 0 = — =—
dx - loTCEo^max
e2
or eE
l^ttEo-^max
,2
e
max
16tce0£
“11/2
e
o max (6.165)
0 L£J
Thus equation (6.164) become
<?
CHAPTERS
max
e2
V
max
Substituting the value of from equation (6.165), we get

Elect rival Properties of Metals 283
16ne0£
V
I6rt€0£|_
i6ne0E[t’£ *ffl
-- -2^’ V ' >

i.e.
y foile
(6,166)
that it, the energy needed to escape from the metal is reduced by an amount Vlfm, The effective work
function is thus reduced from $ io
Substituting this value in equation (6J62), we get the new formula for thermionic emission as
(6.166a)
L *»r J
Fig. 6.40 Schotiky plots of the thermionic emtsston from a uranium,

carbide cathode st three icmperaiure.^
Plotting logy against Ê we get the so called Schottky line.
A comparison with experimental results in Fig, 6 40 shows that above a certain value of the electric
field the relationship is quite accurate. The effect is (A* * 0.012 eV for a field of itf Vm Jh but the effect on
the emitted current may be appreciable.
tacnucM. PnpMKMt «* Mratft
- ~ -i- -«- , - -t * i" I.-.-j - -— ■ ,t a ■ a
'XXXIII. MAGNETISM IN METALS ' --------

*" * “ iav< I*. «u ,. .. ».■ <* . h»«i •' .•*# • •
Most metals are paramagnetic. There are also a few well known metals which exhibit ferromagnetism.
In this section, we discuss paramagnetic metals. The free electrons in metals make two contributions.
A paramagnetic one due to their spins, and a diamagnetic one due to their orbital motions, induced by
the magnetic field. Therefore the net electronic susceptibility is the difference between these contributions.
Spin Paramagnetism
Spin paramagnetism arises from the fact that each conduction electron carries a spin magnetic moment
which tends to align with the field. The expression for paramagnetic susceptibility associated with the
conduction electrons from classical statistics is of the form
(6.167)
But experimentally this spin susceptibility in metals is independent of temperature, and the
magnitude is also small compared to the value calculated using equation (6.167).
The source of the difficulty lies in the fact that equation (6.167) is derived on the basis of localised
electrons obeying the Boltzmann distribution. The free electrons, on the other hand, are delocalised,
and satisfy the Fermi-Dirac distribution.
0) (c)
Rg. 6.41 Division of electrons into spin-up and spin-down distributions, {a) B - 0;
(b) instantaneous shift of states when the external field is present;
(c) equilibrium occupation of states when the external field is present
In the absence of an external field, half of the number of electrons have their spins pointing in
the positive z-direction, and the other half in the negative z-direction, resulting in a vanishing net
magnetisation. When a magnetic field is applied along the z-direction, the energy of the spins parallel to
CHAPTER 6
the field B, is lowered by the amount while the energy of spins opposite to B is raised by the same
amount [ Fig. 6.41 (b) ]. The situation which ensues is energetically unstable, and hence some electrons
near the Fermi level begin to transfer from the opposite-spin half to the parallel-spin one, leading to a
net magnetisation, keeping in mind that only relatively few electrons near the Fermi level are able to
flip their spins and align with the field. The other electrons, lying deep within the Fermi distribution, are
prevented from doing so by the exclusion principle.
let h and n he the concentrations of eleettons with their spins, and hence magnetic momenta,
parallel and anti parallel to the magnetic Held respectively.
Thun, fW Z(K + pMn)dK
whore, ~Z(.h' + paB) is the density of states of parallel spin orientation with allowance for the downward
shift of energy by - p^B, The factor - indicates that in the present circumstances only one spin direction
«ta
is involved in the /lipping. Since f*\&) ■ I throughout the interval of the integration al T = 0 K, we write
from equation (b.107),
Mil" T .a’ (£ + M)1/2

X “ / L ’* M
Thus,
Similarly,
aa®
Thus, the magnetisation, M is given by
M = P-B («P “ ««)
We can set the lower limits in these integrals equal to zero, because (i) pfiB « kBT and
(ii) there are very few states near E = 0, Thus
p.flrcr8m*|y2 J(E+pBB)^dE- J(E-mB)V2dE

M-
.0 o
But
(E ♦ m )•« - (E - m >“ ■ X1+¥) - J41 -“r)

Ve
Thus,
icp-gB^ [ 8m T/2 EJ®

f
-,3/2
iqx2BB [ 8m
Exl2
=2
4 JL/t2j
The paramagnetic susceptibility, xp = M/H ~
F'2
^2B)[8m-\3/2E3
Now, ; Xp-w .2 Lfc2J ef
Substituting for E3J2 from equation (6.110), one gets;
(6.168)
(6.169)
y Xp = X,
- is the Fermi temperature. Equation (6.168) is known as

CHAPTER 6
where, x is the classical susceptibility, and TF is

-------’ Ar ----------------- - - .. _____ th ft/ is independent of temperature. Such a temperature
.Lnt, y
Pauli paramagnestism formula. It sh metals like lithium, sodium, potassium and aluminium,
independent susceptibilityis J"®. satisfactory so long as , which condition is
Formula (6.168) is true for T = OK, but it is ? verylarge for metals, often 30,000 K, or higher, we
always true for metals since TF s 10* K.si f, t ,n2 apajn in good agreement with experimental
can see that is smaller than X^y a factor 0
result.
Electrical Properties of 287
Biamagnetism
Free electrons also exhibit diamagnetism on account of the cyclotron motion they execute in the presence of
the magnetic field. Each electron loop is equivalent <0 a dipole moment whose direction wilt be opposite to
that of the electric field. Classical approach indicates that the total diamagnetic contribution is neutralized by
the effect of the electron moving in (he opposite direction along the boundaries. But quantum treatment
predicts that there is a non-vanishing diamagnetic contribution which is equal to one-third of the spin para-
magnette susceptibility given by equation (6.169).
In this comparison <rf theoretical values with experimentally observed values. one must also include
the diamagnetic effect of the ion cores.
Temperature)
XXXIV. A NOTE ON SELECTION OF ELECTRICAL ENGINEERING

MATERIALS
The choice of conducting materials depends on the following factors;
1. Resistivity of the material
2. Temperature coefficient of resistance
3. Resistance against corrosion
4. Oxidation characteristics
5, Easy in soldering and welding
6. Drawability/RdUbility
7- Mechanical strength
8. Flexibility and abundance
9. Durability and low cost
10. Resistivity to chemicals and weathers
Conducting materials are broadly classified into two categories:
L Low resistivity materials— copper. alumtmum. steel, etc.
2. High resistivity materials—tungsten, nichrome^ platinum, etc*
(i) Properties of Low Resistivity Materials
A low resistivity material, such as copper, besides possessing a low value of resistivity, should also
possess the following additional properties:
(a) Low Temperature Coefficient of Resistance: This means that the change of resistance with
change in temperature should be low. This is necessary to avoid variation in voltage drop and
power loss with changes in temperature. With the rise in temperature, due to the flow of
electrical current in the transmission lines and windings of electric machines etc., the resistance
increases, and hence the power loss and voltage drop increases. To keep these losses low, the
conducting material should have low resistance temperature coefficient.
(b) Mechanical Strength: Mechanical stresses are often produced in overhead line conductors
used for transmission and distribution of electrical power due to the wind and their own
weight. Mechanical stresses are also produced in conducting materials used for the windings
of motors, generators and transformers when loaded. Therefore, to withstand the mechanical
stresses in such applications, the conducting material should possess sufficient mechanical
strength.
(c) Ductility: Different sizes and shapes of conductors are required for different applications. To
fulfil this requirement the conducting material should be ductile enough to enable it to be
drawn into different sizes and shapes.
(d) Solder ability: Conductors are required to be jointed very often. The joint should offer
minimum contact resistance.
(e) Resistance to Corrosion: Conducting materials should be such that they are not easily
corroded or rusted when used without insulation in outdoor atmosphere.
(ii) Low Resistivity Materials and their Applications

(a) Copper: It is mostly widely used metal because of its high conductivity (i.e., low resistivity).
Silver has the lowest resistivity but due to its high cost it is not used as conducting material.
Copper is available in two forms, viz., annealed copper and hard drawn copper, for use as
but
conducting material. The annealed and hard drawn copper are both chemically the same,
■ have different mechanical strength due to the different heat treatment processes used for
making them. Hard drawn copper is about 4% less conducting than annealed copper, but has
more tensile strength and is used in transmission and distribution lines where conductors
have to be stretched. Annealed copper is used at places where flexibility is required e.g.,
wiring of buildings, winding wires and electrical machines and transformers. Hard drawn
copper is obtained by drawing copper bars or rods in cold condition. Annealed copper is
obtained by heating at a specific temperature and then cooling.
Generally, copper and copper-base alloys are unique in their physical and mechanical properties.
They have moderate to high strength and hardness; excellent corrosion resistance; ease of workability,
CHAPTER 6
both in primary and secondary fabrication operations; high electrical and thermal conductivities; non
magnetic properties; superior properties at subnormal temperature, ease of finishing by polishing; plating;
good to excellent machinability; excellent resistance to fatigue; relative ease of joining by soldering and
available in wide variety of forms. Chief elements alloyed with copper are zinc, lead, nickel, silicon,
aluminium, and to lesser extent, cobalt, iron, cadmium and chromium.
For windings of electrical machines and transformers, copper is preferred to aluminium. This •
because aluminium wires have a tensile strength much lower than that of copper. This results in
tendency in the breaking of the aluminium wire under tension as well as developing kinks. Moreover
the resistivity of aluminium is higher as compared to copper and, therefore, aluminium wire has to have
a thicker cross-section to keep i2R losses low. The winding thus occupies more space and the machines
size increases. However, aluminium wound machines have less weight because of low density of
aluminium as compared to copper. Hence for winding in electrical machines, copper is preferred as
compared to aluminium due to higher tensile strength and lower resistivity of copper in comparison
with aluminium.
Copper and aluminium are low resistivity materials and if they are used for making the elements
for electric heaters, the length of the wire would be too large which would increase, to a large extent, the
overall size of the equipment. Hence copper and aluminium are not suitable for this purpose. For the ■
element of electrical heaters, a wire of high resistance is required, e.g., nichrome, which is an alloy of
nickel 80%, chromium 20%.
(b) Aluminium: Its electrical conductivity is next to copper. Aluminium occurs in abundance on
earth’s surface. It is available in various forms such as oxides, sulphates, silicates, phosphates,
etc.
Aluminium is a white metal with bluish tinge and is very light in weight, which is its chief asset
It is 3 J times lighter than copper. Pure aluminium is softer than copper, so can be rolled into thin sheets
or foils. Due to low mechanical strength, it cannot be drawn into very thin wire. The resistivity, is about
1.65 times greater than copper. Keeping in view the resistivity, mechanical strength and density, for the
same resistance and length of a wire, an aluminium conductor should have a cross-section are 1.6 times
that of the copper conductor; the weight of the aluminium will be equal to 0.48 times the weight of
copper.
Use of aluminium as an electrical material, particularly in the aircraft industry, has considerable
advantages because of the saving in weight involved. Again electrochemical plants are enormous users
of aluminium busbars. This is because electrolytic cell operate with heavy currents at low voltages and
to carry these currents, massive bars are required. Aluminium, because of its lightness, is being used
more and more for such busbars. The current carrying capacity of aluminium being 75% that of copper,
and its density being approximately one-third that of copper, an aluminium busbar is only about half the
weight of copper busbar of equal current carrying capacity. Since aluminium costs much less than
copper, an aluminium busbar will cost only about half as much as its copper counterpart
. 3
Aluminium wires have greater resistance to corrosion. In open air, aluminium apparatus becomes
coated with thin film of aluminium oxide, which protects the metal from further oxidation. Oxide film
insulation is extensively used in electrolytic capacitors. The steel reinforced aluminium conductor (SRAC)
is extensively being used for long span transmission lines. Aluminium is not easily solderable, but
fluxes have been devised to make soldering easy. Mechanical clamping and screwing methods have
also been developed.
Since pure aluminium does not have good machining properties, and has poor strength and is
mechanically weak, it is alloyed to improve these properties, while keeping its corrosion resistance
unharmed. The addition of other elements to aluminium makes it strong and machinable. The alloys of
aluminium are very useful for making pistons and connecting rods of internal combustion engines
where strength, along with lightness, is the main requirement.
(c) Steel: Steel is not very often used as a conducting material because of its low electrical
conductivity, in spite of the fact that it has higher mechanical properties and low cost. When
alternating current flows in steel wire, its resistivity increases and power losses are much
higher then when d.c. current flow$, due to the magnetic properties of steel. Steel is easily
corroded by moisture and heat. Overhead steel conductors are galvanised to prevent corrosion.
In this method, steel is thoroughly cleaned and then it is dipped in a path of molten zinc. The
layer of zinc protects steel from rusting. Steel overhead conductors, due to less electrical
conductivity, are used only to transfer small amounts of power. Aluminium conductors used
for high voltage systems, long spans, are usually reinforced with steel, which gives high
tensile strength to overhead lines.
(Hi) High Resistivity Materials and their Applications

Alloys of copper, nickel, chromium, iron and manganese are extensively used aS resistance
materials. A resistor is a device which is used to introduce resistance in an electric circuit for the . ■
various purposes such as
1. as heater elements to produce heat energy from electrical energy,
2. as meter elements such as ammeter shunts and voltmeter multipliers, and
3. for controlling of current such as rheostats.
(a) Tbngsten: The resistivity of tungsten is about twice that of aluminium. The melting point of
tungsten is very high (3300°C). Therefore, its refractory qualities are very much favourable.
It is very hard and does not become brittle at high temperatures. It can easily be drawn into
fine wires for making filaments. It has very high tensile strength even in its thinnest form. It
oxidises very quickly in the presence of oxygen, even at lower temperatures. Tungsten does
notexhibit magnetic properties in the purest form, but can easily alloy with steel called
“Tungsten steel” which is a magnetic material of top quality. Tungsten is used as an emitter
of electrons thermionically in tubes. Tungsten steel is used for making permanent magnets.
The resistivity of tungsten is 5.5 x 10*8 ohm-m. . '
(b) Nichrome: It is an alloy of manganese 1.5%, nickel 75% to 78%, chromium 23% to 20%
and a little percentage of iron. Nichrome has good mechanical, strength and desirable thermal
properties. It is ductile and can be drawn into thin wires. It has a high resistivity (100 x KT8
ohm-m) at 20°C. The temperature coefficient of resistance of nichrome is0.0001. This alloy
is widely used in making heating elements for electric heaters, electric ovens, electric iron,
room heaters, etc, /
(c) Manganin- 86% copper, 12% manganese, 2% nickel gives manganin. Its melting point is
• 102°C. It can easily be drawn into thin wires. It has high electrical resistance but possesses a
low value of temperature, coefficient of resistance. The resistivity is 42 .x 10-8 ohm-m.
Manganin is usually used for making wire-wound precision resistances for measuring
CHAPTERS
instruments, shunts for electrical measuring instruments, resistance boxes, standard resistance
coils and coils for precision electrical measuring instruments.
(<0 Constantan or Eureka: It is an alloy of 60% copper and 40% nickel. It can be drawn into
wires as manganin. Its melting point is 1300°C. The temperature coefficient of resistance is
0.00002. Its electrical resistivity is 48 x 10*8 ohm-m. It is rust proof and does not corrode in
the presence of air and moisture.
»-------------
Constantan is used in making resistance elements for loading rheostats and starts for electric
motors. It is used in making resistance elements in resistance boxes and thermocouples. It is also used
as resistance elements in field regulators used for regulating the generated voltage of a generator.
With the Sommerfeld's quantum modification of the free electron theory so as to account for the electrical ।
and thermal conductivities, a new value of L was obtained [refer equation (6.141)]. However, the
expressions for individual conductivities are not very satisfactory. This is due to the fact that this theory
does not include mean free path. In order to obtain the correct values of conductivities, it is necessary to
assume that the mean free path varies inversely as T, and its value at ordinary temperatures is of the
order of 100 interatomic distances. The existence of such a long mean free path cannot be explained on
the bias of classical theory.
This model also suggests that the electrical conductivity is proportional to electron concentration
[equation (6.128)). But it is surprising that the divalent metals (Be, Cd and Zn), and even trivalent
metals (Al, In) are consistently low conductive than the monovalent metals. (Cu, Ag and Au), despite
the fact that former have higher concentration of electrons.
A far more damaging testimony against the model is the fact that some metals exhibit positive
Hall constants, for example, Be, Zn, Cd. The free electron model always predicts a negative Hall constant.
Again the Weidemann-Franz law given by equation (6.141) is well obeyed for most metals at
room temperature, the numerical value of the constant as given by it is quite satisfactory with the
experimental value. The fact that the agreement is not perfect [observed values are somewhat higher
than that given by equation (6.141)] should not be surprising, because our derivation assumes that the
relaxation times for both the conductivities are the same. This is perhaps a reasonable approximation
when the electrons only are the main carriers for both heat and electricity. As a matter of fact the
phonons also carry an appreciable portion of the thermal energy, specially at low temperatures, so that
T . and Te are not equal. The ratio rather decreases at low temperatures, although the ratio may be
of the order of unity at room temperature. The difference in xph values for different materials gives rise
to a difference in the value of L for different metals.
■
Measurements of the Fermi surface indicate that it is often non-spherical in shape. This contradicts
the model, which predicts a spherical Fermi surface. This theory is incapable of explaining why some
crystals have metallic properties while others are semiconductors and insulators.
The most important feature of this theory is that it destroys the notion of classical theory that all
free electrons are conduction electrons. According to Sommerfeld’s theory only few free electrons,
whose energies lie in the vicinity of Fermi level, contribute to the mechanism of conduction and only
those free electrons are called conduction electrons.
The quantum free electron theory of metals assumes that a conduction electron in a metal experiences a
constant (zero) potential and so is completely free to move about in equal in the crystal, restrained only
by the surface of the crystal. This theory explains successfully the phenomena of specific heat, electrical
rhe mc*n free path varies inversely u T, and tta value at ordinary temperatures la of ike orJef of 166 inter
atomic distances. The existence of such a long mean free path cannot be explained on the bias of classical
luctivity is proportional to electron concentration

XfrJOJ
(Equation {6.128)], But it is surprising that the divalent meals {Be, Cd and Zb), and even trivalent metals
{Alt In) ire consistently low conductive than the monovalent metals, (Cu, Ag and Au), despite the fact that
former have higher concentration of electrons.
A far more damaging testimony against the model is the fact that some metals exhibit positive Hall
constants, for example. Be, Zn, Cd. The free electron model always predicts a negative Hall constant.
Again the Weidemann-Franz law given by equation (6J41) is well obeyed for most metals at room
temperature, the numerical value of the constant as given by it is quite satisfactory with the experimental
value. The fact that the agreement is not perfect (observed values are somewhat higher than that given by
equation (6J41)} should not be surprising, because our derivation assumes that the relaxation times for both
the conductivities are the same. This is perhaps a reasonable approximation when the electrons only arc the
main carriers for both heat and electricity. As a matter of fact the phonons also carry an appreciable portion
-7- rather decreases at low temperatures, although (he ratio may be of the order of unity at room temperature. The
difference in values for different materials gives rise to a difference in the value of L for different metals.
Measurements of the Fermi surface indicate that it is often nonspherical in shape. This contradicts the
model, which predicts a spherical Fermi surface. This theory is incapable of explaining why some crystals
have metallic properties while others are semiconductors and insulators,
The mos t important feature of this theory is that it destroys the notion of classical theory that all free
electrons are conduction electrons. According to Sommerfeld's theory only few free electrons, whose ener-
trons are called conduction electrons.
XXXVL BAND THEORY OF SOLIDS

The quantum free electron theory of metals assumes that a conduction electron in a metal experiences a
constant (zero) potential and so is complete!y free to move about in the crystal, restrained only by the sur
face of the crystal. This theory explains successfully the phenomena of specific heat, electrical conduct! vity,
thermionic emission, thermal conductivity and paramagnetism, Yet, there are many other physical
properties which could not be explained by the free electron model* The model also fails to explain why
some solids are good conductors of electricity, some are semiconductors and others are insulators.
When we considered the solid as a collection of free electrons in a box, we imposed the condition that
the wave function vanishes at tee walls of the box-that is, on tec surface of the sample, allowing tee con
duction electrons to move in a region of constant potential* Obviously this appcoxi of the potential
inside the crystal is too drastic
k is now suggested to disregard the surface and to treat tee crystal a$ an infinite array of lattice points
To do this. sightly different forms of boundary conditions, called cyclic or periodic boundary conditions,
have been developed. Inside a real crystal, there is a periodic arrangement of positively charged sons through
which tee electrons move. The motion of a representative electron is shown in Fig, 6.42(a). The potential of
the electron at the positive ion site i> zero and is maximum in between. So along any line passing through tee
j__________; - ■ •<
conductivity, thermionic emission, thermal conductive anH
physical properties which could not be explained bv the fn»P amagnetlsny Yet’there are many other
explain why some solids are good conductors of electricitvôme™ ‘ T?6 m°del *lso/a,ls tO
c f . ,,,rt electricity, some are semiconductors and others are
insulators.
When we considered the solid as a collection «r r ।

that the wave function vanishes at the walls of the box-tVI” & ™ imp°Sed the condition
the conduction electrons to move in a region of con,tn t h ’S’ SUrfaCe °f the Samp,e’ aJ,owing
potential inside the crystal is too drastic6 ‘ Potential. Obviously this approximation of the
It is now suggested to disregard the surface anri......

ntc To do this sliahtlv different r r, Ce and 10 treat cryatal as an infinite array of lattice
points, io do tnis, sngntty different forms of boundarv conditio., „ n . . ,. .
conditions, have been developed. Inside a real crys7 theê k a'„ f r 7
charged ions through which the electrons move The mî r ' arrangement of pos.tively
Fig. 6.42 (a). The potential of the electron at the nos,t™,™,°",' “ represe,nlatlve eleclron is shown
along any line passing through the centres of the positive ions the ™t° T I” maX'ml”n ^‘ween. So
in Fig. 6.42 (b). We find that the potential varies neriodiX ,h7" ''“"‘““’I m"S'
as shown
have now to study the motion of the electron in such a htf W' a ' Si™e penod as the latt,ce- We
appropnate Schrodinger equatton for the motion of the electron is given by
occupy. The
dx2 ft*
EE - V(x)]y - 0
3
87T2m
h2 7. - *-•• —
& (6.170)
where, the potential function V(x) has the periodicity of the lattice given by
V(x) = V(x + d)
with a as the periodicity of the lattice.
(6.171)
Bloch has shown that an equation of the type (6.170)-has a solution of the form
y(x) = uK (x)eiKx
where, uK(x) has the periodicity of the lattice given by
(6.172)
K represent* the Mate of the motion of the electron and Kth Mate corresponds to an electron
hK 2n
having a momentum, p « and a de Broglie wavelength X is given by X - In the simple one-
In
dimensional model we are considering, lIC is directed along the x-axis and, in the general case, Khas to
be treated as a vector, and so it is also called the propagation vector. The solution of equation (6.172»
consists of a plane wave eIK' modulated by the periodic function u^x). With a sinusoidal type of potential
inside as shown in Fig. 6.42 (b), the Schrodinger equation is not easily tractable. So Kronig and Penney
introduced a simpler model for the shape of the potential variation. The potential inside the crystal U
approximated to the shape of rectangular steps as shown in Fig. 6.43.
Fig. 6.43 Ideal periodic square well potential used by Kronig and Penney
For the treatment of our problem, a periodic repetition of the potential well of Fig, 6.10, i.e., a periodic
arrangement of potential wells and potential barriers, is most probably very close to reality and is also
best suited for the calculation. Such a periodic potential is shown in Fig. 6.43 for the one-dimensional
case.
Although this model is highly artificial, yet it illustrates many of the characteristic features of
the behaviour of electrons in a periodic lattice. The wave functions associated with this model can be
calculated by solving Schrddinger Equations for the two regions I and II. The time-independent
Schrddinger equation takes the following forms for the two regions
^ + Ê^£V = 0;forO<x<a (6.173a)

dx h2 . •
and ^ + ^^(E-V0)y = 0;for-b<x<0 (6.174)

uX h
Making use of Bloch's theorem, the solution can be written in the form
y(x) = uK (x)elKx (6.175)
Assuming that the total energy E of the electron is less than the potential energy Vo, we define
real quantities a and P such that
8rc2m£
(X ~v~ (6.176)
8n2m „
P2= -^-(Vo-£) (6.177)
and
Thus, y. + a2y = 0; for 0 < x < a (6.178)
- P2V = 0; for-/? <x<0 , (6.179)

and
The solution that will be appropriate for both the regions suggested by Bloch is of the form
y(x) = uK (x)eiKx
On differentiating this equation, one gets
^=e^^L + uiKeucx
^ = eiKx + iKeiKx ^+iKeiKx^-^2eiKxu

and K
-r d2U.
- K 2 eiKx uK +.2iKeiKx + ,/Ax------ *
ie dx2 K dx >2
Substituting these values in equations (6.178) and (6.179), we get

d2u. duy .
+ 2iK + (a2- ityu. = 0; for 0 < x < t (6.180)
rtir ■ 1
2ih dU2
and ^ + 2iK^- (6.181)
/iy 2“
where,«! represents the value of uK (x) in the interval 0 < x < a and u2 the value of uK (x) in the interval
The solution of the differential equation (6.180) is of the form
u, = e™
dui d Mi , __
__L _ and
dx dx2
m2 + 2/ Kme™ + (a2 - K =0
-2/K±7-4/C2 -4 (a2 -K2)
tn = - iK ± ia
i.e., mt = - iK + ia = i(a - K)
and m2 - - iK -ia = - z(oc + K)
Thus, the general solution is
Uj = A em'x + B e™2
ux= A ei(a ~ *>x + B e"/(a + (6.182)
where, A and B are constants.
Similarly equation (6.181) can be written as .
m=
m = - iK ±p
= - iK + P = (P - iK)
m2= - iK - p = (p + iK
Thus,'
w2 = C+ D +lK)x (6.183)
where, C and D are constants. The values of the constants A, B, C and D can be obtained by applying the
boundary conditions.
Jwj(x) . ^(x)'
[u1(x)]x=0 = [m2(x)]x=0,
J;c = O
Ml, . „ = [«2(x)Jz.; [ ^1 =[
L dx Jz=fl L dx jx=_b
■ Applying these conditions, we get

(0 (A+fi) = (C + D) (6.184)
00 . . [A i(a-K) e,(“-K’x-Bi(a + r)e-i(ot + K>]x = o
= [C(p-iK)e<P-^-D(p4j#r<P+fl^X550
i (a - K)A - i(a + K)B = (P - iK)C - (p + iK)D (6.185)
,4 gila - K)a + g e~i(a + K)a iK)b + £) €(P + UQb
(Hi) (6.186)
(iv) [Aieâ-i^x(a-K)-Bi(a + K)â+l(^]isa
= [C(^-iK)e^-ll^>-D^ + iK) «*]x = b
A i(a - K) e'(a-20° - B i(a + K)e~(a +11)0

' = C(P~zK)e-<P-'*>-D(p + iT)e(P + ^ (6.187)
You *
—I
f.
Eauations (6.184), (6.185), (6.186) and (6.187) will have non-vanishing solutions if and only if
determinant of the coefficients A, B, C and D vanishes. This requires that
i(a-k') - i(a + K) (P ~ /*)

e~i(a+K)a =0
gi(a-Kya e-W-iK)b e<3 + iK)b
i(a~K)ei(a-^ -i(a + K)e -t(a + K)a J- Sir\ „b(fl + iK)
solution of ftedeterminan. iS a separate mateSTafiork, equations (6.189) cante'
assumed, and the last part of band, theory pay be discussed accordingly- . 5
Solution of the Determinant

(The details of the solution of the above is beyond of the scope of the students and hence the solution
can be assumed.)
The above determinant can be written as
a d
s =0 I
P <1
ap bq cr
C d b d a b c
b 'c - d \. a
s P r s p <1 s P « T 0
<1 r
bq cr ap cr ds] ap bq ds ap bq cr
b (rds - crs) - c (qds - bqs) + d (qcr - rbq) - a (rds - crs) + c (pds - sap) - d (per - apr)
ie.,
+ a (qds - bqs) - b (pds - aps) + d (pbq - apq) - a (qcr - bqr)
+ b (per - apr) - c (pbq - apq) -Q r
Expanding
brds - bers - cqds + cbqs + dqcr - drbq- ards + aers + cpds - csap - dper + dapr
+ aqds - abqs - bpds + baps + dpbq -dapq - aqcr + abqr + bper - bapr
- cpbq + capq = 0
In other words
ab (ps + qr-qs -pr) + ac (sr+pq-qr + ps) + ad(pr + qs- rs-pq) + be (qs + pr - sr -pq)
+ bd (rs +pq-rq-ps) + cd (qr + ps-qs -pr) - 0
Le. ai>[q(r-s)-p(r-s)] + ac [q(p- r) -s (p - r)] + ad[r (p-s)-q(p-s)] + bc[p (r- q) — s

CHAPTERS
(r- q)] + bd[p (q - s) - r (q -s)] + cd [q(r-s)-p(r- s)] = 0
Thus ab [(r - s) (q - p)] + ac [(p - r) (q - $)] + ad [(p - s) (r - ?)] + be [(r - q) (p - s)]
+ bd [(q ~s)(p~r)] + cd [(r-s) (q-p)] = 0

or «r - s) (q - p)] [cd + ab] + (p-r)(q- s) [ac + bd] + (r-q)(p-s)[bc + ad\ = 0
i.e. <P~r)(q-s) [bd + ac] + (r - q) (p-s) [be+ ad\ = (s-r)(q- p) [«b + cd]
Now substituting for a, bt c, d, p, q, r and st we get
[i (a + K) (p + iK) + i (a - K) (0 - iK)] [ e'(a - ** - c (P -] [ el (a+*>a - & + j
+ [- i (a + K) (0 - iK) - i (a - K) (P + iK)] [ «<<«-*>_ e(P + /o>i
[ e~ (P - iK)i> _ e-ta(a + K) j
= (a2 - K2 - K2 - P2) [ e_/fl(a + *> - e~ k,(a~ *>] [ e(P + lK)b - e*®-«)i
i.e., (2i ap - 2K2) [ e*a ~ V* - e~ M “ llC)b ] [ e~l «* + *)<»- e(fi + iK>b] + (~2iap - 2K2)
[ e»(a - K)a _ e(p + iK)b ] [ g4P - iK)b _ e-ia(a + X)j
= (a2 - p2- 2K2) [ e(P+ilc>b - er ^P~,A)]

R.H.S. is expanded as follows:
— (a2— P2— 2K2) [ e-Wa + K) e$b giKb + g-ia{K-a) g-b$ g-ibK _ ^-ia (a+ K) g-ty
giKb _ îaa giK(b - a)l
L.H.S. is now expanded as follows:

(2i ap -2K2) [e‘° (a ~ - ia (a + *) - e~b (P " iK) -«’<“ + *) + (P -»«) + /> <p + zx)
_ eia (a-X) + h(P + iK)] + (_ 2/ a0 - 2K2) [ g-(P-*^ + ia(a-X) + g-ia(a + K) +
b(P + iX)_ e-w(a + X) + ia(a-X) _ eb(p + iK)-b(P + iK)j
RU.S. is further simplified as

(a2 - P2 - 2K2) [ ex e^1 + eiK(~b ~ a) eiafl a) ^-*P -a)
e^b eiaa j
R.H.S. = (a2 -P2 - 2A2 ) (b ~ fl)) [«Pfc (e-,aa - e,afl) + )]

Simplifying L.H.S. further
(2i ap - 2K2) [e~ '2iaK + e2ibK -e*®- «) e~iaa - eiK (b - a> eItM e^P] '
+ (2i ap - 2X2) [e'r (b ~ e~^ eiaa + eX(b~a) e~iaa e* ~ P - e~‘2iaK - e2** ]
LJLS. can be further simplified as
(2l a0 — 2K2) ^b ~ a) [ e~ -iK(b-a) Û>K -iK(b-a)_ g-bfi - iaa _ gioui + bpi
+ (2i ap - 2K2) eiK (b - a) ^g-fU> + iaa + gbfl - iaa _ g-2iaK- iK (b-d) _ ^LibK - iK (b -aft
Sinte is a common factor both for the L.H.S. and R.H.S., the equation is simplified and
written as under R.H.S.
(a2 - p2) [eP* (e_f<M - eicur) + e-^ (e^ + e~iaa)] - 2A? [ (e~i(u - e™) + e~^
L.H.S. is
(21 ap)[ + g2ibK-iK(b-a)_ e~b^-iaa_eiaa + b^ _ [ e-2iaK-iK(b-a)
«iK (b - a) _ giaa + bpj
(-2i ap) [e~^b + laa + ebP ~ iaa - e~2iaK ~ iK - «) - e2ibK(b - ah _ 2K2 [e~Pfc + to
+ ebP-taa_e-2iaK-/K(b-a) _ £ibK-iK(b-a)]
~ _ _ - - --------------------------------------------------------------------------------------------- —...... .._ - „.. , ,f.
On expanding K2 terms of both L.H.S. and R.H.S. and equating them, we find the result yields
value. Thus R.H.S. is equal Io
(a2 - p2)(- (e'“ - «" + e* (e'“ - e’'“)] = (a2 - fj2) [(a"” _ «-«“) «*■ -<*“)]
= (P2 - a2) [(e,Ofl - e~laa) (e^° - )]
L.H.S. is
2ia0 [2e-2/<1/f ~IK (* " fl) + 2e2M “iK <b “ a) - e - bp - iaa - elaa+- e - b$ + iaa - ' **)
= 2<ap [ 2e~IK (-a + b'> + 2eiK (fl + *) ] _ 2/ap [eb$ (?<“ - e~iaa) + <r*P
= 2iaP [ 2e~iK W + 2eiK <a + *> ] - 2/ap [ («*" + e-iaa) + trty]
Now equating L.H.S. and R.H.S. and simplyfying
12!__ 5L1 [(e>cw _ e- iaa ) (ep<2 _ g-fc )] _ |- 2e- IK (a + b) + (fl + b) j
2iap
- [ (eiaa + g-laa) (eph + e-^b )j
Dividing throughout by 2
y>~iaa
(P2 - a2) {e —e
2aP 2i
^X(a + h) + e-.iK(a + b)]
(p2 - a2)
2 ap 2 sin aa sin h pb = 2 cos K (a + b) - 2 cos aa cos h pb (6.188}
Thus the solution of the determinant (equation 6.187) is
—---- —- sin oca sin b pb + cos h Pb cos aa = cos K(a + b) (6.189)

2aP
Equation (6.189) is complicated but a simplification is possible. Kronig and Penney considered
the possibility that V^b remains finite. Such a function is called delta function. Under these circumstances,
sin h pb pb and cos b pb —> 1 as b —> 0. Hence equation (6.189) becomes
' (p2 -a2)

—2ap—ot+cos Ota = cos Ka i
CHAPTERS
Now,
Since VQ » E,
P2-a2-^(V0)
Since Vo > > E.
Substituting this in the above equation, we get

f 8rfm
pfrsinow + cosout - cos Ka
< 200ft1 j
where
sin a#
- - - - + cos On = cos K a
aa
sinaa
— + CUSCUZ =COSAtf
(6.190)
m Voab
The term is called the barrier strength. The term P =---- j— in equation (6.190) is sometimes referred as the
scattering power of the potential barrier. It is a measure of the strength with which electrons in a crystal are
attracted to the ions on the crystal Lattice sites. Also
&VmE _ a2/]2
- -------=—, or E - ——
hl
and (6.19te)
Equation (6.190) is a condition of the existence of a solution for the electron wave function.
There are only two variables in equation (6.190), namely a and K. The right hand side of equation
(6.190) is bounded since it can only assume values between + 1 and - L If we plot the left-hand side of this
equation against aa, it will be possible to determine those value of a (and hence energy) which are peimis-
sinouj
sible; that is, permit P--------- +ccs ao to take values between + 1 and - 1 *
When each of these values is set equal to cos Ka, K is determined. Then a can be found from equation
(6. ISO).
Fig. 6.44 shows this plot for a value of P assumed arbitrarily as 3rt/2. Indicated in the figure are the
permitted values of this function, shown as a solid line bqtweeen white portions. This, then, gives rise to the
a1/!3
concept of ranges of permitted values of a for a given ion lattice spacing u, and since E - ——, permitted bands
8rrm
of energy are predicted. The following interesting conclusions may be drawn:
1. The allowed ranges of (Xa which permit a wave-mechanical solution to exist are shown by the shadow
portions. Thus the motion of electrons in a periodic lattice is characterised by the bands of allowed
energy separated by forbidden regions.
2. As the value of aa increases, the width of allowed energy bands also increases and the width
of the forbidden bands decreases; this is a consequence of the fact that the first term of
equation (6.190) decreases on the average with increasing aa.
3. Let us now consider the effect of varying P. It is known that P is a measure of the potential
barrier strength. If Vo b is a large, i.e., if P is large, the function described by the left hand side
of the equation (6.190) crosses +1 and -1 region at a steeper angle as shown in Fig. 6.45 (a).
Thus the allowed bands are narrower and the forbidden bands are wider.
«7t
Also in equation (6.190), when aa = ± n tc, cos aa = cos Ka with Ka = ± me; or K=± ~. These
value of AS are points of discontinuity in the (E- K) curve for electrons in the crystal.
In the limit P -> oo the allowed band reduces to one single energy level; that is, we are back to the
case of discrete energy spectrum existing in isolated atoms.
P -> °° it follows from equation (6.190) that sin aa = 0; or aa - ± mt
2_2
n it
a2
or
(6.191)
tc0>aa
aa
Rg. 6.45 (a) The left-hand side of equation (6.190) for P - 3n/2 as a function of aa; (6) P -» «; (c) P o
Here E is independent of K. The energy level in this case are discrete and the result is similar to
the energy levels of a particle in a constant potential box of atomic dimensions. This is expected because
for large P tunnelling through the barrier becomes almost improbable.
4. The other extreme case, when P -> 0, leads to
cos aa = cos Ka .
Thus, a=K
t/> * 2m E
K1 * (X2 « ~
hJ
(6J9la)
Referring equation (6,190a)
(6,192)
Free Intermediate light

electron case binding
Fig, 6.46 Energy level structure for differentiating degrees of binding
Equation (6.192) is appropriate to completely free particles. Hence no energy levels exist; all
energies are allowed to the electrons.
Thus by varying P from zero to infinity we cover the whole range, from the completely free
electron to the completely bound electron.
C H A P TE R *
The electron moving in a periodic potential lattice can have energy values only between allowed regions
or zones. With the help of equation (6.109), it is possible to plot the total energy E of the electron versus
the wave number, or the propagation vector ‘AT, and the plot is shown in Fig. 6.47.
The right hand side of the equation (6.190) becomes ± 1 for values of K = ntt/a, and hence the
discontinuities in the E versus K graph occur at K = nn/a, where n takes the values of ± 1, ± 2, ± 3,... etc.
XXXVIII. BRILLOUIN Z9NE$

The electron moving in a periodic potential lattice can have energy values only between allowed regions or
zones. With the help of equation (6.190), it is possible to plot the total energy E of the electron versus the
wave number, or the propagation vector 'K\ and the plot is shown in Fig* 647*
The right hand side of the equation (6.190) becomes ± 1 for values of - mda* and hence the dis
continuities in the £ versus K graph occur at K = nn/a^ where n takes the values of ± 1,1 2« ± 3 .. . de.
h^K1
The dotted curve shows the free electron parabola = ——. From the graph we see that the electron has allowed
8?t m
energy values in the region or zone extending from K - — to K = + . The zone is called the first Brillouin zone *
d a
After a break in the energy values called the forbidden region or band or zone we get another allowed zone
7T
of energy values in the region extending from K = - - to------ and +- to +—. This zone is called the second
a a a a
Brillouin zone. Similarly the other higher order Brillouin zones can be defined.
Allowed
bands
Allowed
bands
-3TT -2TT -IT 0 IT 2TT 3TT K

a □ a a a a
Fig. 6.47 The relation between energy and wave number for a one-dimensional lattice.
Thus we see that the various Brillouin zones arc demarcated by the values of the propagation vector
'K\ Since is a vector* and has different values along different directions, it is pertinent to ask the ques
tion as co how the limiting values of K in different directions can be determined and on what factors Che
value of K depends. In as much as the zone picture of the crystal is found to be fruitful in the understanding
of the electron propagation in periodic structures, it is necessary to study about the demarcation of the Bril
louin zone boundaries and Che part played by the propagation vector "IC.
The main point we have to note is that in a constant potential lattice, the electron energy values are
q ms (Continuous, whereas, in a periodic potential lattice the electron energy values art discontinuous, sepa
rated into allowed and forbidden zones or bands occurring alternately as in Fig. 6.47. We also notice that the
width of the forbidden band increases. Again we find that as P decreases the discontinuous E-K graph will
1st zone
I_______ I i j |_______ ।________ ।
-3n -2n -_n 0 it 2n 3n

a a a K a a a
_7
2nd zone
Fig. 6.48 The first two Brillouin zones for one-dimensional case
Brillouin Zones in Two Dimensions

Let us now consider the motion of an electron in the field of two-dimensional square lattice. The motion
of the electron in two dimensions can now be discussed using a wave number ‘A?, which, as before, is
measured in the direction of propagation of the wave. The wave number K can be analysed into
components along the x and y axes, which are respectively, K and AT *. .
. 7t
To sketch the first Brillouin zone, we note that along the Kx axis in Fig. 6.49, the values of ± —
represent the limits of the zone. Similarly, along the K axis the values of + — also represent the limits
of the zone. In general, the condition for any energy discontinuity is
So in two dimensions the condition reads
where, and n2 are integers corresponding to the single integer n and referring to each of the axes. To
sketch the first zone, n{ and n2 are made equal in turn to ± 1, or 0. The equations of the lines bordering
the first zone are therefore ........
n, ± 1, iL = 0, giving K - ± - . . ‘
. ' J' 71 i■
and . nt = 0, n2 - ± 1, giving Ky = ± —
O’?:‘.k U ‘.V* ‘\ *' * - -:81X’C * <4 I .
Thus a square passing through the points A, B, C and D gives the first Brillouin zone.
The second Brillouin zone should obviously pass through the points E, F, G and H. The complete
CHAPTER 6
picture of the second zone is obtained by taking «j and n2 as the next integers in the series above those
used for the first zone. These are nx = ± 1 and = ± 1. The equations giving the boundaries of the
second zone are
306 Soud State Physics
Fig. 6.49 The first three Brillouin zones for a two-dimensional square lattice
nj = +1, n2 = +1, giving Kx + Ky = —
. 2tc
ni = -1’ n2 = +1’ glvillg ~KX + Ky - —
n.= +1, n2 = -1, giving K -K - — .

- - - - . - y a
•. • nl ~ T1 ’ n2-1* giving: : - K*-Ky - —
The above four equations describe a set of four lines at 45° to the Kx and K axes passing through
E, F, G and H. The second Brillouin zone is thus the region between the squares ABCD and EFGH. The
third Brillouin zone is obtained giving and n2 values of 0, ± 1 and ± 2.
Brillouin Zones in Three Dimensions

The equation used to describe the zones in three dimensions is given by
X/i + Kn2 + Kji3 = I I (w2 + n2 + ni)

* \ z
The first zone for a simple cubic lattice is clearly a cube intersecting the K, K and K axes at the
points itia. Just as in the triangular form of the second zone in two dimensions, the second zone in three
dimensions is obtained by adding a pyramid to each face to the first zone cube.
Let us consider a one-dimensional crystal of N lattices. The length L of the lattice is N (a + b). Imposing
the periodic boundary conditions for obtaining the running wave picture of the de Broglie wave, we
find that the wave function must be periodic in ‘L\ That is
W) = V(x + L)
The wave function in a one-dimensional periodic potential lattice is given by
Y(x) = uK(x)eillx and + L) = uK(x + L)elKfx +
Imposing the periodic boundary conditions, we get
uK (x)eiKx = uK(x + L) eiK(-x+L) (6.193)
We have already seen that the modulating function u^x) has the periodicity of the lattice.
i.e., u^x) = u^x + a) = u^x+ 2d) = ... = u^X + Na)
where Na is the length ‘£* of the crystal. Substituting this in equation (6.193), we get
giKx — giKx gifCL
... e‘K£ = 1 .
. .. „ 2lUt
(6.194)
with n = ±l,±2, + 3... :
Now n=
2k
Thus, the number of possible wave functions in the interval dK is
Hence total number of possible states in a band is.

- 1 - •x/a -
n= (dn= — (dK
J 2k. J,
- n/a
n= [K&a = i.e.,na = L (6.195)
with b -> 0, a + b = a. Also length of the crystal L = N (a + b) - Na. Comparing this with equation
CHAPTERS
(6.195), we get n-N, where N is the number of unit cells. Thus the total number of possible states in a
6and is the number of unit cells. Taking into account the spin of the electron and Pauli’s exclusion
P^ciple, each state can be occupied at most by two electrons, and hence the total number of electrons
10 a band is 2 N.
Electrical Properties o/Metals 307
uith + b b a. Also length of the crystal L = A'fw + Comparing this with equation (6.195), we
get rt ~ fV, where /V is the number of unit cells Thus the total number of possible states in a band is the
number of unit cells. Taking into account the spin of the electron and Pauli's exclusion principle, each stale
can be occupied at most by two electrons, and hence the total number of electrons in a band is 2 V
XXXX. MOTION OF ELECTRONS IN A ONE-DIMENSIONAL

PERIODIC POTENTIAL
Cntfa/ For a free electron, (he quantity represents the true momentum of the electron. This
can be seen from
(6.196)
We can, therefore understand the dynamical behaviour of the free electrons with respect to the true
momentum. However, few an electron moving in a periodic potential, does not represent the true
momentum. This is because, there the energy does not vary with £ in the fashion as it does for free elections
Hence a reference to 'crystal momentum' is made, h is the quantity with respect to which we study the
dynamical behaviour of the elections m a periodic potential. When wc deal with the interactions of the
electrons with lattice* we use the conservation of crystal momentum and not of the true momentum.
The true instantaneous momentum of an electron in the presence of ihe lattice potential is nut a con-
slant of the motion and cannot be calculated directly bj quantum mechanical methods; we can calculate only
its average value. The crystal momentum, on the other hand, is a perfectly welLdefined constant for a state
of given energy, just in the same way as is the true momentum of a particle of given energy.
Velocity U has been known for a very long time that an electron has a well-defined mass, and when
accelerated by an electric field it obeys Newtonian mechanics. What happens when the electron » acceler
ated inside a crystal? How will it react to an electric field? The mass of an electron in a crystal appears, in
general, different from the free electron mass, and is usually referred to as the effective m\ We will
now get the answer using a semi-classical model.
The quantum mechanical part describes that the velocity of the electron in a one-dimensional lattice
equals the group velocity of the waves representing the electron:
(6.197)
dK
which depends on the actual (E-K curve) Here u> is the angular frequency of the de Broglie's waves and can
be expressed us £ = fau
dE dto
Now dA' = " dK
Substituting this m equation (6 197), we gel
1 dE
(6.J98)
hLdKJ
For free electrons
_ h2K2
fc = —----- -
2m
dE
i.e.,
dK
Thus equation (6.198) can be written as
1h hZR
m
(6.199)
giving a linear variation of v with K. In band theory of solids,

however, E is, in general, not proportional to K2; there the
variation of E with AT is as shown in Fig. 6.50 (a). Using this type
of variation of E and K and using equation (6.198), one can
calculate the velocity v; this gives a curve of the type illustrated
as in Fig. 6.50 (b). We observe that at the bottom (K = 0) of the
energy band, the velocity is zero and as the value of K increases
(i.e., the energy E increases), the velocity increases reaching its
maximum, at K = KQ, where Ko corresponds to the point of
inflection on the E-K curve. Beyond this point the velocity begins
to decrease, and finally assumes the zero value at K = ida, which
is the top of the band. Thus one notes that the decrease of the
velocity beyond the point of inflection (with increase in energy)
and its zero value at the top of the band are entirely new features,
which do not appear at all in the behaviour of free electrons. The
negative values of the wave vector exhibit a similar behaviour.
It has been known for a very
Effective mass of electron:
long time that an electron has a well defined mass, and when
accelerated by an electric field, it obeys Newtonian mechanics.
What happens when the electron is to be accelerated inside a
crystal? How will it react to an electric field? The mass of an
electron in a crystal appears, in general, different from the free
electron mass, and is usually referred to as the effective mass.
CHAPTER 6
Sg. 6.5D Energy, effective mass

The velocity of the electron in a one-dimensional lattice is
*od fK a$ a function of K
described by its group velocity given by equation (6.198).
(6.200)
The acceleration is simply
271^1 d ( dE)
a=
h MUK;
2tc> d2E dK
a= h JdK2 dt (6.201)
E
Since, we have the quantity —- from the E and K relation, all we have to do now is to find the
dK2
dK
value of under the influence of an applied field E.
Let an electron be subjected to the influence of an external field of strength E for a time dt. If the
velocity of the electron is v, the distance travelled in a time dt is v dt so that
dE—eEv dt
Thus substituting the value of v from equation (6.200) in the above relation, we get
dE=eE dt (6.202)
dK 2ite E
Thus, (6.203)
dt h
Combining equations (6.201) and (6.203), we have
d2E
dK2 (6.204)
Comparing this formula with that for a free, classical particle,
or (6.205)
It is obvious that equations (6.204) and (6.205) are identical in form if we define a new quantity
(6.206)
So as to write in all cases
eE
« (6.207)
m
Euctmcal Pnonofttei or Mera* 31*1
Equation (6.206) indicates that the effective mass is determined by ; this result indicates
JX2
once more the importance of the (E-K) curves for the motion of the electrons. It can be easily shown that
for a free electron m* — m, because
. d2E h1
2m dK2 m
One expects this result. But for an electron moving in a periodic potential, E does not vary with
K in the above manner and so m *m. One may thus conclude that all the results of the free electron
theory are correct provided m in each case is replaced by suitable m*
Thus, E=
2m
This is known as the “effective mass approximation.”
The effective mass m can be determined experimentally. In the discussion of electronic specific
heat in Section 6.19, it was seen that at very low temperatures, the electronic contribution becomes
substantial and its value can be determined experimentally. The theoretical value of electronic specific
heat is given by equation (6.126), namely,
n2 ^Bn
[C ]L =
L ve^the for unit mass
Substituting the value of EF from equation (6.110), we have
■2mir87t 12/3
_h2__3n_
2/3 4ir2
[m fc2n1/3]
(6.208)
rrn. c .Hl
The ratio of ——— gives —. (6.208a)
LCvJrte m
When a core electron of an atom in a metal is knocked out, as in any X-ray tube, an electron from
the conduction band can fall and occupy this stage, giving rise to an emission line. As the energy of the
CHAPTER 6
electrons is almost continuous, this results in a continuous X-ray emission spectrum. There will be a
short wavelength cut off corresponding to the maximum in the conduction band. Equating this energy
to the Fermi energy with m replaced by the effective mass can be determined. Effective mass can
also determined using cyclotron resonance experiments. An estimation of m in alkali metals is done
from the measurement of the reflection edge.
Electrical Properties of Metals 3 JI
fee region ii now close to ihc top of the band, and a ttcptivE mass is to ft rapcM thc negative mass can
be seen dynamically by noting that the velocity decreases for K > Thus acceleration is negative, i.c.»
opposite to the applied force, implying a negative mass. This means that in this region of K-space the lattice
exerts such a large retarding force on the electron that it overcomes the applied force and produces a
negative acceleration. This means in the upper half of the band the electron behaves as a positively charged
particle referred to as a hole.
The degree of freedom of an electron is generally defined by a factor
fl-j m d2E
(6.208a)
Here/* is a measure of the extent to which an electron in slate K is free. If m is large* fK is small, i.e., the
particle behaves as a ‘heavy’ particle. When fK = 1, the electron behaves as a fret electron. Note that fK is
positive in the tower half of the band and negative in the upper half, as shown in Fig. 6.50(d).
XXXXI. DISTINCTION BETWEEN METALS, INSULATORS AND

INTRINSIC SEMICONDUCTORS
We shall now see the distinction between metals,
insulators and semiconductors on the basis of band
theory. Let us consider a particular energy band which
is filled with electrons upto a certain value (Fig
6.51), which is less than itia. As far as the influence of
an external electric field is concerned, one is interested
to know as to how many of free electrons are effective.
The number of free electrons in a band is equal to
Nrf- X/jr
Fig. 6.51 Energy band filled upto stales Kt at T= 0
where the summation extends over all occupied states in the baud. For a one-dimensional lattice of lengh L,
the number of states in the interval dK is
drt = T~dK (Refer equation 6.194)
Since two electrons can occupy each state, the term on the R.H.S. of the above relation must be multiplied
by 2. Thus
^=Jrfit4 = 2 £ rii*1jfx<iK
Substituting the value offK from equation (6.208a), we get

Yoi
Since two electrons can py each state, the term on the R.H.S. of the above relation must be
multiplied by 2. Thus
r
fadK
Substituting the value of fK from equation (6.208a),

we get
(6.209)
Eg = 0
(c) Lead
Fig. 6.52 Energy band model of insulator, semiconductor and metal

K a band is completely filled,
nit
K » ± — with n = 1,2, 3,4,...
a
CHAPTER 6
dE nit
«Oattf=± —
dK a
In such a case
N* = °
dE
i.e., the effective number of free electrons in a completely filled band is zero. Further, because
.dK
reaches a maximum al the point of inflection, the effective number of free electrons is a maximum if the
band is filled to the point of inflection.
In the case of insulators where there are no effective free electrons, all the bands up to the
valence band are completely filled and the top most band called the conduction band is completely
empty.
Between the completely filled valence band and empty conduction band is a forbidden energy
region so wide that it is impossible to excite a significant number of free electrons across this region.
The forbidden energy gap of diamond is about 6 eV. If the energy gap between the valence band and
conduction band is quite small, then there is some statistical probability that the electrons will be excited
from the states near the top of the filled valence band across the energy gap to states near the bottom of
the empty conduction band, i.e., if the forbidden gap is small then few electrons will be available for
conduction of electric currents. A material of this type is called semiconductor. The forbidden energy
gap of the semiconductor, silicon is about 1 eV. The electrical conductivity of semiconductors is much
smaller in comparison to metal and it is also a function of the forbidden energy gap.
Metals are generally good conductors. Electric current flows easily through them. Obviously
there will be a large number of conduction electrons even at low temperatures. In terms of energy
bands, there will be a overlapping of valence and conduction bands as shown in Fig. 6.52 (c). Due to
this overlapping, a larger number of free electrons are available in metals, almost independent of
temperature.
F The classical expression for die electrical conductivity of a metal in terms of mass of the electron, charge
of the electron, concentration of electrons and collision time is given by
(a) mner (b) (rnedn)
(c) (d) (ruPlPlm)
2- The collision time and the root mean square velocity of the electron at room temperature are 2.5 x 1014 s
and 1 x 105 m/s respectively. The classical value of mean free path of the electron is
(a) 25 nm (b) 25 x IO-19 nm
(c) 25 A (d) 100 run
3' If the mobility of electrons in a metal increases, the resistivity
(a) decreases (b) increases
(c) remains constant
4. Most widely used conducting materials are
(a) germanium and silicon (b) copper and aluminium
(c) gold and silver (d) tungsten and platinum
5. The temperature dependence of the classical expression for electrical resistivity of a metal is
(a) p oc T4 (b) p oc I//2
(c) p 06 (d) p oc l/T
-*
AA Am
6. Mobility of the electron is

(o) flow of electron per unit electric field
(&) reciprocal of conductivity
(c) average electron drift velocity per unit electric field
(d) none of these
The classical value of molar electronic specific heat is
(a) 1-5 Ru (b) 0.5 Ru
(c) 3 Ru (d) 4.5 Ru
where Ru is universal gas constant.
8. Ohm’s law relates to the electric field E, conductivity o and current density j
(a) J = E/o (b) J = oE2
(c) J = <J/E
Order of resistivity of silver is
(a) nano ohm m (£>) milli ohm m
(c) ohm m (d) micro ohm m
10. The average drift velocity vx of electrons in a metal is related to the electric field E and collision time, T as
eEx m
(*) J—
m V eEx
eEx m
(c)----- (d)~
m eEi
If e, p and n respectively represent the charge, mobility and concentration of electrons respectively, then
the electrical conductivity of the metal is given by
(a) n/ge (b) lle/n
(c) ne (d) nep
12. Which of the following relation gives Wiedemann-Franz law?
(a) ar/a = LT (b) (S/(JT = LT
(c) or/o = LIT (d) g/<jt=T/L
where <jt and a are the thermal conductivity and the electrical conductivity of the metal respectively. L is
Lorentz number and T is temperature in Kelvin.
The experimentally determined value of Lorentz number for copper is approximately
(a) 2.45 x 1(H WQK’2 (ft) 1.1 x 10~8 WQK-2
(c) 2.45 x 108 WOK’2 (d) 1.1 x 108WQK-2
14. The classical expression for molar electronic specific heat is 1.5 Ru. Express its value, giving the units
(a) 12.5 JkmoHK-1 (b) 1250 kJkmol-'K’1
(c) 125 kJkmol-'K^1 (d) 12.5 kJkmol-'K-1
15.
The wave function for the motion of the particle in a one-dimensional potential box of lengths is given by
CHAPTER 6
= A sin(/ircr/a) where A is the normalisation constant. The value of A is
(a) 1/a
(<0a
9
where a is the length of the box.

16- The energy of the lowest state in a one-dimensional potential box of length a is
(a) zero (b) 2b2/8ma2
(c) h2/8ma2 (d) h/8ma2
17. The spacing between the nth energy level and the next higher level in a one-dimensional potential box
increases by
(a)(2n-l) (b)(2n+l)
(c)(n-l) (d)(n+l)
IS. The normalised wave function for a particle in a rectangular box of dimensions a, b, c is .
nziiz
sm sm—— sin
a b c .
nr7DC
sin-----sin—— sin-----
a b c
. njtx . nvity . n,nz

(c)Wn = sm—— sm—— sin ——
a b c
(d) none of these
19. If^ is the energy of the lowest state of a one-dimensional potential box of length a and E2 is the energy
of the lowest state when the length of the box is halved, then
(a) Ej = Et (b) E2 = 2EX
(c)E2 = 3E1 (d)E2=4E1
20. The energy of a particle constrained to move in a cube of side a is given by
E=-^-z(n^ + ny + n2)
8mzz JC r z
If n* ny and nz may have either values out of 1,2, 3; the degree of degeneracy of this energy level is
(fl) 2 (b)3
(c) 6 (d) 8
21. The general expression for the Fermi energy of a metal at 0 K is
(a) 3.65 x ICT19 x n273 eV (b) 3.65 x 1019 x n2 eV
(c) 3.65 x 1019x n1/3 eV (d) 3.65 x 1019 x n372 eV
where n is the number of free electrons/m3
If the Fermi energy of silver at 0 K is 5 electron volt, the mean energy of electron in silver at 0 K is
(a) 6 eV (b) 12 eV
(c) 1-5 eV (d) 3 eV
[f the Fermi energy of a metal is 1.4 electron volt, the Fermi temperature of the metal is approximately
(fl) 1.6 x IO3 K (b)1.6xlO4K
(c)1.6x!05K (d)L6xlO6K
The quantum mechanical expression for electrical conductivity is
24.
ne2Xf
(h)a = —
KFne
ne kf
25, If E\ is the energy of the electron in the lowest energy state in a cubical potential box of side a and £2 is the
energy of the electron in the state with nx = n? = nz = 2 when the side of the box is a/2, then
(a)^=16£t • (b)E2 = 4El
(c)^ = E,/2 (d)E2 = SEi
2$. £] is the lowest energy value of the electron in a one-dimensional potential box of side a and E2 is the
lowest energy value of the electron in a cubical box of side a/2, then EÊl is
(a) 12 (b) 3
(c)4 ' (d) 2
27, If Ef is the Fenni energy of a metal at 0 K and Ef is the Fermi energy at T K, then
(a) Ef = Ef [1 + (7t2/12) (kBT/EF)2]
(b)EF = Ef[l- (rt2/12) (kgT/EF)2]
(c) Ef = Ef [1 + (rt2/12) (kBT/Ep)2]
(d) Ef= Ef [1 - (n?/12) (kBTIEF)2}
28. The energy of free electtons in the state (1 2 1) in a rectangular box of sides a = b # c is
8m T 1 1
8m L# ,2 (h)TT
n LaT+ —
c
(c) 8m La2 (d) none of these

c2
29. £Fand E, are the Fermi levels of sodium at 0 K and 1 K. Ef for sodium is 3 eV. Then — is
(a) 0.93 ■(h) 1.93

(c) 0.02 (d)21
30. The quantum mechanical expression for Lorentz number is
(a) (JC/3)(ye)2 .
CHAPTER 0
(c) (Jt/3)(e/y2 (d) (^73) (e/y2

If Pq and p(7) are the temperature independent and dependent parts of the resistivity of a metal, then the
total resistivity is
(a)p = p0+p(7) (h) p = p0 - p(D
WP=P(/P(7) (d) p^/po
32. The static conductivity and the conductivity in an alternating field of a metal are equal, when
(a) on « 1 (b) an = 1
(c) an » 1 (d) none of these
where co is the angular frequency of the applied field and t is the relaxation time of the electron distribution.
33. If a and E are the electric conductivity and applied field respectively on a current carrying conductor, the
heat developed per unit volume per second is
(a) aE2 (b) <s2E
(c) (J/E (d)
34, If E", jx and Bt are the Hall field, current density and magnetic field strength, then the Hall constant is
given by
«■)
<0 = (d) none of these

^hHx
35. The unit of Hall coefficient is
(a) Vm3A“l wb-1 (b) Vm2 A wb-1
(c) Vm3A+l wb-’ (d) Vm2A~2wb
36. The quantum numbers of an energy state for the electrons in a cubical box is (1 2 3).
This is
(a) a three fold degenerate energy state
(b) a six-fold degenerate energy state
(c) a non-degenerate energy state
(d) none of these
37. The eigenvalue of the energy of a particle in a cubical box is 11 (h2/ 8 ma2). The quantum numbers of the
state are
(a) 0 1 1) (b) (3 0 1)
(c) (2 2 2) (dHlU)
3g. Manganin is an alloy of
(a) m Cu, 13% Mn (b) 60% Cu, 15% Mn, 25% Ni
(c) 80% Cu, 10% Mn, 10% Ni (d) none of these
39, Which of the following metals has the lowest temperature coefficient of resistance?
(a) copper (b) aluminium
(c) silver (d) gold
40. Temperature coefficient of resistance is given by
J_dE
(a) RdT
1 dT
(c) R dR (d)
41, An insulation is a material having resistivity approximately in the range

(a) 103 to 10” £l-m (b) 107 to IO9 £2-m
(c) 10~3 to 103 Q-m (d) none of these
p
In thermionic emission a plot of

42.
. „ -4 against 1/Tis
log 7-2 J
. a straigllt line with positive slope
(W a straight line with negative ’lope
(c) none of these
At iOw temperatures the mean free path and collision time of an electron in a metal are proportional to
43. (b) 1/T 2
(a) yr
(d) independent of T
(0 1/T3
a ry high temperature, the mean free path and collision time of an electron in a metal is
(«) 7= <» 1/r2
j 1^7 (d) independent of temperature
Depositing a layer of thorium on tungsten will
45.
(a) lower the work function
(b) raise the work function
(c) no effect on the work function
If £ is the energy of the electron in the lowest energy state of a one-dimensional potential box of side a
and £,£ is the energy of the electron in the energy state just above the lowest state of a three-dimensional
cubical box of side 2a, find .
(a) 1/2 (b) 2/3
(c) 1/4 (4)2
47. If £j is the energy of the electron in the six-fold degenerative energy state (1 2 3) in a cubical potential box
of side a and E2 is the energy of a particle of mass twice that of electron in the second non-degenerative
energy state of side all, find (E2 - E-).
(a) (4A2/8/na2) (b) (lOhfama2)
(e) (6A2/8ma2j (d) (7h2/8ma2)
Near absolute zero the temperature independent part of the resistivity of a metal
(fl) decreases with increase of impurity substance added
(b) increases with increase of impurity substance added
(c) remains constant '
49. faho of electronic specific heat calculated quantum mechanically and classically for silver of EF = 5 eV
at.TKis
(fl)0 57 x tesla (/,) 0.27 x IO-4 tesla
® 1.2 x 10* tesia 2.4 x 104 tesla
SO.
(i i i) and j 2) are the wave functions of the electrons in the two energy states (1 1 1) and (I I 2)
CHAPTERS
pectively in a cubical box of side a, then y(], 12) is

fe) sin—/gin £2. ... . 2nz .. nz
a a (b) sm /sm—
a a
ste^/sin^ • W, . 2rz
a a (J) sm-----/sm—
a a
1. What are the main drawbacks of classical free electron theory?
2. Explain “molar electronic specific heat” in metals. Give its value with units.
3. Discuss relaxation time, collision time and mean free path of free electrons in metals.
4. Explain free electron theory of electrical conductivity in metals.
5. Write a note on relaxation time.
6. Briefly describe Drude’s free-electron theory of metals.
7. Explain the term “mobility of charge carriers.”
8. Give the classical expression for calculating Lorentz number. -
9. What are the assumptions made by Drude and Lorentz in explaining the behaviour of free electrons in
metals?
10. Explain Wiedemann-Franz law.
11. How do you explain the electrical conductivity of metals on the free electron gas model?
12. Explain drift velocity and relaxation time of free electrons in metals.
13. What is “electron gas” approximation as applied to electrical conduction in metals?
14. Explain the terms relaxation time, collision time and mean free path as applied to electric conduction.
15. Outline Sommerfeld’s quantum theory of electrical conductivity of metals.
16. Explain how Pauli and Sommerfeld modified the free electron to remove its shortcomings.
17. Write down the Schrodinger wave equation for a particle in a three-dimensional box.
18. Explain an infinite potential well.
19. Discuss the physical significance of the wave function t|/.
20. The energy expression for the electron in a one-dimensional potential box is given-by E = (n2h2/8ma2).
Derive the important conclusions from this equation.
21. Give Fermi-Dirac distribution function. Plot it as a function of energy.
22. Discuss “Quantum free electron theory” of metals.
23. The energy of an electron in a metal is quantised. Explain.
24. What is Fermi energy? Write down its relation with the concentration of electrons in metals.
25. Give the significance of the normalised wave function for the free electrons in a cubical box given by the
expression:
. nyfty . n-Ttz
sin——sin——
a a
26. What is Fermi energy? Write down its relation with the concentration of electrons in metals.
27. What is Fermi momentum? What is its value in the Sommerfeld’s free electron theory of metals?
28. Discuss the drawbacks of Sommerfeld’s free electron theory of metals.
29. Get the quantum mechanical value of Lorentz number. Give its units,
30. Formulate the problem of electrons in a “box.”
31. What is meant by density of energy states in metals?
i
i
- -- -
nurces of electrical resistivity in metals?

32. What are the so ribution function. Plot this function for various temperatures including 0 K.
33. Explain Fermi- “Fermi level”? Explain its significance in metals and semiconductors.
34. What do you change with the frequency of an applied alternating electric field?
35 How does the conductivity or
the strain resistivity relaxation.
36. Derive
u nf freouency of the applied electrical field on electrical conductivity.
37 Discuss the eneci vi *
‘ ‘ does (he electrical conductivity of a metal vary with (a) impurity content (h) temperature?
38.
What are the factors that affect the resistivity of electrical materials?
39.
40. Discuss electrical conductivity in metals and alloys.
41. Schematically show how F(£) varies with energy for a metal at T = 0 K, 300 K and T = «>.
42. How the conductivity of a metal is affected by temperature and alloying?
43. Discuss the motion of an electron in a periodic potential.
44. Explain quantum mechanical tunnelling in solids and its significance.
45. Explain what is meant by thermionic work function in metals.
46. Give the expression for density of energy states in metals.
47. How does Fermi energy change with temperature? . - .
48- Explain the zone theory of solids.
How does zone explain the electrical behaviour of metals, semiconductors and insulators?
5®. Show that the average energy of the electron at 0 K is (3/5) th of Fermi energy.
51* What are Brillouin zones?
Illustrate the three Brillouin zones for a two-dimensional square lattice.
$4 n band theory of solids, explain the nature of conductors, semiconductors and insulators.
88 P Brillouin zones with particular reference to any cubic lattice.
rillouin zones? How are they related to the energy of an electron in a metal?
fine electron theo*5 e'eclficat conductivity and (ii) thermal conductivity on the basis of classical
Hence obtain Wiedemann-Frana law.
Assume the electr
Exnh;n j .... °nS m a meta^ to behave like a classical gas, deduce Wiedemann-Franz relation.
pialD drift VPlrmiw j
c*assical free 1 relaxation time of free electrons in metals. Discuss the various drawbacks of
•he drawbacks ®eOr^ meta^s and explain the assumptions made in quantum theory to overcome
CHAPTER 6
^rive the expre ’

“drying? SSlOn f°r electrical conductivity of a metal. How is it affected by temperature and
a®®’coUision time and mean free path as applied to free electrons.

^ribethe
this model 9 u" e'ectron” model of a metal, introduced by Sommerfeld. What are the achievements of
' Where did it fail?
6. Discuss the breakdown of classical theory with special reference to mean free path of electrons and molar
specific heat of metals.
Give the main assumptions of Sommerfeld’s quantum theory of free electrons.
7. Calculate the contribution made by free electrons to the specific heat of metals on the basis of the classical
free electron of Drude and Lorentz, Does the result agree with experiments?
Explain how Pauli and Sommerfeld modified the free electron theory to remove its shortcomings.
8. Explain as to what are matter waves. Derive the Schrodinger’s wave equation for the motion of an electron.
9. What are the postulates of wave mechanics? Derive Schrodinger’s equation. What is the significance of
the wave function V?
19. The potential function for a certain particle moving along positive direction of x-axis is given by
V(x)=0forx<0
and V(x)= V0forx>0
Calculate the transmittance and reflectance at the potential discontinuity and show that (/? + T) = 1, where
R is reflectance and T is the transmittance.
11. A particle moving in a more dimensional potential, is given by
V = 0 for x < 0
V= V0forx>0
- (a) Write down the Schrodinger wave equation for the particle and solve it.
(£>) Find the reflection and transmission coefficients for the case (0 E > Vo and (ii) 0 < E < Vo, where E is
the total energy of the particle.
12. A beam of electrons, each of energy E, is incident on a rectangular potential barrier of width a and height
Vq, where Vo > E. Obtain an expression for the transmission coefficient through the barrier.
13. A beam of particles each of mass m and energy E, moving in a region of zero potential energy, approaches
a rectangular potential barrier of width a and height VQ, where Vo > E.
If Pa »1, where P = _^21 prove that the transmission coefficient is given by

V A '
14. Write down the Schrodinger equation for the wave function y(x, t) of a particle of mass m in an infinitely
deep potential well, given by V(x) = 0 for 0 < x S a, V (x) = «»otherwise. Hence obtain the time-indepen
dent equation for y(x) involving the energy E.
What are the boundary conditions to be imposed on y(x) in the above case? What is the solution of the
Schrodinger equation consistent with these boundary conditions?
15. What is an infinite potential well? Obtain Schrodinger’s time independent wave equation. Solve it for
particles in a cubical box of side ‘a’, and hence obtain expressions for the allowed wave functions and
discrete energy values of the particles.
16. Write down the Schrodinger’s wave equation for formulating the problem of electrons in a ‘box’. Indicate
the nature of the solutions for the wave function and hence obtain expressions for the discrete energies of
the electrons. Represent the wave functions and probability functions graphically.
17. Solve Schrodinger wave equation for a particle of mass m bounces back and forth in a cubical box with
perfectly elastic sides of length ‘a’ and obtain the expression for the discrete energies of the particle.
0
Yoi
|H> Obtain the eigenvalues and noi'inullsod wave functions for a particle in a one-dimensional infinite potential
box of side
19. Solve the Schrikilnger wave equation for a particle in a rectangular potential box and obtain its energy
levels. Show that the eigenvalues of energy arc discrete. Discuss the importance of Schrodinger equation.
20. A particle ol mass mi Is confined in a field Ircc region between impenetrable walls at x — 0 and x = a. Show
that the stationary energy levels of the particle are given by
n2h2
£ =------ T-
8ma2
Discuss the physical significance of the wave function y.
21. Explain what you understand by the terms potential well and potential barrier. How does a particle with
energy lower than the barrier height, tunnel through it? Give an example.
22. Define Fermi energy. Write down the expression for Fermi-Dirac distribution law. Derive an expression
for Fermi energy of a system of free electrons.
23. Indicate the main steps in the derivation of Fermi level and calculate its value for sodium taking data from
tables.
24. Based on Fermi-Dirac statistics, state of the nature of the Fermi distribution function. How does it vary
with temperature?
25. What are density of energy states in metals? Derive an expression for density of energy states and hence
obtain Fermi energy of a metal.
26. What is meant by Fermi level in a metal? How does it vary with temperature in a metal? Show
diagrammatically where the Fermi level exists in (i) a metal (ii) intrinsic semiconductor.
27. (i) Show that the wavelength associated with an electron having an energy equal to Fermi energy is given
by
A r tr -|l/2
XF=2 — .
'-3nJ
(ii) Calculate the molar specific heat of metals on the basis of Fermi statistics and compare its value with
the classically predicted value.
28. Define Fermi energy. Obtain a general expression for the Fermi energy of electrons in solids at zero
degree kelvin. Show that at the same temperature, the average energy of . the electron is (3/5)th of the
Fermi energy.
• Explain Fermi-Dirac distribution for electrons in a metal. Obtain the expression for Fermi energy £ at
temperature T = 0, and relate it to Fermi energy Eat non-zero temperature T, where T is such that knT « E-
30 Th ° ■* *
The Fermi energy expression at room temperature is given by
CHAPTERS
"'here EF is Fermi energy at 0 K.

Using the above equation, obtain the expression for the mean energy of the electron at room temperature.
A|so get the expression for the molar specific heat of metals on the basis of this distribution.
Calculate the specific heat of a free electron gas by using classical statistics and Fermi-Dirac distribution.
“xplain why experimental results agree with the latter.
324 ,5ouo Stati Phyiici
32. Discuss the variation of Itarmbdlslrlbulloii fuiicllon grnplilcidly. licwicr ilrliiic Fermi energy ol 11 inrbil,
Show thin the Fermi curve nl room temperature shows only n very Huh' I'hangc from llutt nl (I K.
33. The density of stiktcs |»cr eV at the Fermi level (Ii/, ■ 7 eV) win* calculated lor ii certain tiictal to lie about
IO17 energy states per eV. Some one was linked Io calculate the number <if electrons lot this nirlnl using ihc
Fermi energy us the maximum kinetic energy which the electrons have. lie argued tlial bcciimm of tfir
Pauli principle, each energy state in occupied by two electrons. Consequently, there arc 2 x |<);/ clednaM
in that bund.
(i) What in wrong with thin statement'.’
(ii) Why is the answer, after all, not loo fur off from the correct numerical value?
34. Explain Fermi temperature of u metal. Show that the Fermi distribution curve ut ordinary temperature
shows only u little change from the distribution curve at 0 K,
35. Discuss electrical conductivity of metals on the basis of quantum mechanical considerations, Compare
this expression for electrical conductivity with the classical expression. Calculate (he mean free path of
electrons from quantum mechanical expression for a standard metal and discuss its agreement with ex*
perimenial value.
36. Workoui ihe energy levels of free electrons confined to a cubical box of side ‘a'.
What is Fermi level? Derive an expression for the Fermi energy in terms of the number of electrons per
unit volume.
37. What do you understand by ‘non-degenerate’ and ‘degenerate’ states? Taking the example of a particle in
a cubical box of side ‘a', obtain first few states and represent them graphicully.
38. How are the free electrons distributed among the allowed energy states ut a finite temperature? Obtain die
change in Fermi level with respect to its position at 0 K.
39. What are the main sources of electrical resistance in a metal?
Discuss the effect of impurity, temperature and alloying on the electrical conductivity of metal.
44) . Explain the variation of electrical resistivity with temperalure both al low and high temperature regions.
Hence explain Matthiessen’s rule.
41. Discuss electron-scattering mechanisms in metals and show that the mean free path is inversely proportional
to absolute temperature for T » 0D. Discuss also the temperature dependence of resistivity.
42. State the sources of resistance in metals. Explain why and how the conductivity varies with temperature
and composition. How do the conductors become superconductors at very low temperatures?
43. Why do alloys have higher resistance than the materials of which they are composed?
State and explain the strain-resistivity relation. Describe a strain gauge and explain its working.
44. Give the schematic representation of the temperature dependence of the resistivity of copper and various
copper-nickel alloys. Discuss the physical significance of residual resistance ratio.
45. Explain how the electrical resistivity of alloys increases with increasing amount of solute content. Write a
note on variation of resistivity with pressure.
46. Outline the Sommerfeld theory of electrical conductivity.
1 Relating the relaxation time of electrons to their interaction with lattice vibrations, bring out the temperature
♦j dependence of conductivity for temperatures above the Debye temperature of the solid.
■g 47. How does the conductivity of a melal vary with rise of temperature and added impurity content? Explain
v how the band theory of solids accounts for the above behaviour.
0 48. Arrive at the strain resistivity relation. Describe the construction and working of a strain gauge.
Electrical Property Of Mstti# • 30
49. Derive an expression for the change in the electrical resistance of a wire as a function of the longitudinal
strain in it. Define gauge factor. Describe the construction and working of an electrical resistance strain
gauge.
5G» What is Wiedemann-Franz law? Apply Fermi distribution function to the electron gas in metals and show
that the general expression for thermal conductivity is
51. Show that the Lorentz number obtained on the basis of quantum theory is equal to , where the
symbols have their usual meaning. Compare this value with the one predicted by classical theory.
52. Suppose the conduction electrons in a metal are subjected to an alternating electric field E = Eq cos (ot
applied along the x-direction. Let vx represent the average x-component of the velocity of the electrons,
and T be their relaxation time. Set up the equation of motion for an electron and show that
rerE0 V cos cor cot sin cot
k m J|_1 + co2t2 l + coV
where m is the electronic mass.
53. Discuss high frequency conduction in metals and show that the frequency dependence of the conductivity
is given by '
_ G static
“"l+wV.
54. Consider the standard geometry for Hall effect where a rod shaped specimen is placed in a magnetic field
along z-direction. An electric field is applied along the length of the rod which is taken as x-direction.
Describe the Hall effect and explain its relation to the mechanical force exerted by the magnetic field on
the conductor. Show that the Hall coefficient is equal to 1/ne.
55. Describe the Hall effect. Explain how the measurement of Hall coefficient helps one to determine the
mobility of electrons in metals.
S6. What is Hall effect? Give an elementary theory of Hall effect. Mention the important uses of Hall effect.
57. Show that the Hall coefficient is independent of the applied magnetic field and is inversely proportional to
the current density and electronic charge. Mention some of the applications of this effect.
58- Explain the terms “mobility of charge carriers” and “Hall effect”. Obtain an expression for the Hall
coefficient in terms of the density of conduction electrons and explain how it is used to determine the
mobility of charge carriers.
Discuss the phenomenon of thermionic emission in metals. Obtain Richardson-Dushman equation for the
emission of current density.
CHAPTER 6
Show that the Pauli spin paramagnetism of a free electron metal is given by
WF
where the symbols have their usual meaning.
M. Write an essay on the selection of electrical engineering materials.
•X Discuss the Kronlg-Penncy model for the motion of an electron in a periodic potential.
What is meant by the density of energy .states?
Solve the wave equation for an electron moving in the following potential field.
m(a) = 0 for 0 < x < a ; u(x) = Vo for a < x < b
and periodically repeated outside that interval. Show that for E < Vo it leads to the following equation
P2 - a2
2a[3 sin h p& sin aa + cos h ph cos eta = cos K (a + b)
where a2 - 2m£//P; p2 = 2m (Vo - E)/#.

Discuss the motion of an electron in a periodic potential and show from (E-K) graph, that materials can be
classified into conductors, insulators and semiconductors.
<4> Discuss the motion of electrons in a region of periodic potentials. Indicate, how the discussion helps one
to understand the electrical conductivity in a solid.
€5, Discuss the Kronig-Pcnney model for the motion of an electron in a periodic potential.
Show from (E-K) graph that materials can be classified into conductors, insulators and semiconductors.
<6. What are Brillouin zones? How are they related to the energy levels of an electron in a metal?
How does zone theory explain the conducting or insulating character of a material? -
Draw the Brillouin zone for a two-dimensional square lattice of side ‘a’.
€7» Discuss the problem of an electron moving in a periodic potential. Explain the occurrence of energy gap in
a semiconductor.
4X How does the band theory of solid lead to the classification of solids into conductors, semiconductors and
insulators?
0. . What are Brillouin zones? Illustrate your answer by constructing two Brillouin zones for a square lattice.
1. The density of silver is 10.5 x 103 kg/m3. The atomic weight of silver is 107.9. Assuming that each silver
atoms provides one conduction electron, calculate the density of electrons. The conductivity of silver at
20°C is 6.8 x 107 fl-1 m. Calculate also the mobility of electrons in silver.
X Using the data in the previous problem, estimate the collision time for free electrons applying classical
. free electron theory. What is the corresponding mean free path? Compare this value with the experimental
one.
X The following data are known for copper:
(/) Density » 8.92 x 103 kg/m3
(//) Resistivity of copper ■ 1.73 x IO"8 ohm m.
(i//) Atomic weight = 6.35.
Calculate the mobility and the average time of collision of the electrons in copper obeying classical laws.
4. The resistivity of aluminium at room temperature is 2.62 x IO"8 ohm m. Calculate (i) the drift velocity
(//) their mobility and (Ui) their relaxation times and mean free path on the basis of classical free electron
theory.
You
5. A copper wire whose diameter is 0,16 cm carries a steady current of 10 amp. What is the current density in
the wire? Also calculate the drift velocity of the electrons in copper.
6. A copper wire of length 0.5 m and diameter 0.3 mm has a resistance 0.12 ohm at 20°C. If the thermal
conductivity of copper at 20 C is 390 W m ' K-', calculate Lorentz number. Compare this value with
value predicted by classical free electron theory.
7. Compute the electrical resistivity of sodium at 0°C, if the mean free time at this temperature is 3.1 x IO"44 s.
Further more, sodium builds a b.c.c. lattice with two atoms per unit cell, and the side of the unit cell is
0.429 nm.
g. A stream of electrons, each of energy E = 3 eV is incident on a potential barrier of height, Vo = 4 eV. The
width of the barrier is 0.2 nm. Calculate the percentage transmission of the beam through this barrier.
9. An a-particle having energy 10 MeV approaches a potential barrier if height 30 MeV. Determine the
width of the potential barrier of the transmission coefficient is 2 x 10-3. Given: Mass of the ct-particle =
4 x 1.67 x IO-27 kg; h = 1.054 x 10-34 J sec.
10. Find the least energy of an electron moving in one dimension in an infinitely high potential box of width
0.05 nm.
11. An electron is bound by a potential which closely approaches an infinite square well of width 0.2 nm.
Calculate the lowest three permissible quantum energies the electron can have.
12. A particle is confined to an one-dimensional infinite potential well of width 0.2 x 10-9 m. It is found that
when the energy of the particle is 230 eV, its eigenfunction has 5.antinodes. Find the mass of the particle
and show that it can never have energy equal to 1 keV.
13. Find the lowest energy of a neutron confined to a nucleus of size 10-14 m. Given: Mass of the neutron =
1.67 x 10 27 kg.
14. Calculate the energy of the electron in the energy level immediately after the lowest energy level confined
in a cubical box of side 0.1 nm. Also find the temperature at which the average energy of the molecules of
a perfect gas would be equal to the energy of the electron in the above said level
IS. Find the energies of the six lowest energy levels of a particle in a cubical box. Which of the levels are
degenerate? :
r 38/t2
16. What is the degree of degeneracy of the energy level <8/na2> of the particle in a cubical potential box of
side ‘a’.
Write the complex conjugate of:
(a) i sin x + cos ix
(b)
(c) ie toin ‘x ■
Determine when y equals
(0 i sin x + cos ix
CHAPTER 6
(ii) e^ -
(Hi) Ne ~ ““
Evaluate the normalisation constant, N, for
(i) = N r g~ ar for 0 < r < oo
(«) v =: W sin 0 cos (|>, for- - £ 0 £ o £ 0 £ 2rc

bx1
(Hi) y = 2 for - <x> < x < oo
20. A particle is moving in a one-dimensional potential box of infinite height of width 2.5 nm. Calculate the
probability of finding the particle within an interval 0.5 nm of at the centre of the box when it is in its state
of least energy.
21. The wave function Y of a particle is given by
Y= for 0 < x <«»
Y = 0 for - oo < x < 0
2 x
Find A in terms of k and evaluate the probability of the particle lying in the region — < x < —.
k k
22. A particle is moving in a one-dimensional potential box of infinite height. What is the probability of
finding the particle in a small interval Ax at the centre of the box when it is in the energy state next to the
least energy state?
23. Show that the functions
exp(-hx2/2)
4b
(x) exp (- bx2!!)
( b Y/4 ,
. = (2&X2 -1) exp (-fer2/2)
are ortho normal over the interval — 00 < x < «.

24. The wave function y of a particle is given by y = N exp (- xVp) for- < x < « Find the value of N.
25. The electrons in a cubical box for a metal are subjected to the influence of a magnetic field, such that the
length increases by da, while the width and thickness remain the same. Show that the energy different
between the states
r A2 r16dg-
(3 11) and (1 3 1) is k 8ma2 J _ a in the new positions.
26. Calculate the number of energy states available for the electrons in a cubical box of side 1 cm lying below
an energy of 1 eV.
27. The Fermi energy of sodium is 3 eV. Calculate the difference in energy between the neighbouring levels at
the highest energy state in a cubical box of side 1 cm.
28. The electrons in a cubical box of side a are subjected to a magnetic field. The length of the box increases
by a small amount x, while the other dimensions remain constant. Show that the shift of the energy level
[2 1 1] is approximately k8ma2 a.
29. Evaluate the Fermi function for an energy kgT above the Fermi energy.
"nd the icinperniure al which there In I per cent probability that a state, with an energy 0.5 eV above the
Pcrnii energy, will be occupied by an electron.
The atomic radius of silver which cryHtulliHCH in f.e,c. structure In 1.4. Calculate the Fermi energy of silver
31.
nt 0 K.
□now *t,u the wavelength associated with on electron having an energy equal to the Fermi energy is given
chnw ihnl
32.
n Copper has a mass density of 8.95 x IO3 kg/m1 and an electrical conductivity 6.4 x 107 fi-1 nr1 at room
tcinperalure. Calculate (/) the mean free time (//) Fermi energy (Hi) the Fermi velocity and (v/) the mean
free path at the Fermi level. Atomic weight of copper is 63.54.
u Calculate the number of states lying in an energy interval of 0.02 eV above the Fermi energy for sodium
crystal of unit volume and of E/(. = 3.24 eV.
15 Use the Fermi distribution function to obtain the value of F(E) for E-EF- 0.01 eV at 200 K.
34. Show that the probability that a state A£ above the Fermi level EF is filled equals the probability that a
state AE below is empty.
37. Calculate the probabilities for an electronic state to be occupied at 20°C, if the energy of the states lie
0.11 eV above and 0.1 i eV below the Fermi level.
38. Calculate the extent of the energy range between F(E) = 0.9 and F(E) = 0.1 at a temperature of 200 K.
39. Assuming the electrons to be free, calculate the total number of states below E = 5 eV in a volume 10-5 m3.
40. Consider a chamber containing monoatomic potential free molecules of a gas. Determine the root mean
square velocity of the molecules if the gas is at room temperature (27°C). The mass of the molecule may
be taken as the rest mass of a proton. Determine the pressure exerted on the walls of the container if the
mass number of molecules per cubic metre is 1023.
41. Obtain the expression, connecting the pressure and volume of an electron gas at 0 K. Show that the bulk
9P ’5F1 1OEO
modulus B a - V— of an electron gas is . 3 J’Or 9V ‘
42. If the Fermi energy of a metal is 10 eV, calculate (/) the average energy of free electrons in a metal at 0 K
(»’) corresponding classical temperature and (Hi) the speed of the electron with average energy calculated
above.
43. what is the occupation number at room temperature of an electron state lying
(«) 0.1 eV above the Fermi level, and (b) 0.1 eV below the Fermi level? Answer the same question for a
temperature of 1000 K. Also sketch the Fermi function in the neighbourhood of the Fermi level for
the two temperatures,
44. ^cêrrn* energy of silver is 5.51 eV. (a) What is the average energy of the free electrons in silver at 0 K?
(c)un,al.tCmPeratur®18 necessary f°r the average molecular energy of an ideal gas to have this value?
at is the speed of an electron with this energy?
45.
that thp n
unit rCrmi ener8y of copper is 7 eV at room temperature, what is the number of electrons per
44.
The d° Um° Wlth enCr8y grCatCr than 8 eV?
is 0 85 Z*n^ “ 7130 and its atomic weight is 65.4. The effective mass of an electron in zinc
47. ^*nd C^calate the Fermi energy of zinc.
hes o 2:rbHi,y 3n e,cclron’c Hlatc being occupied at room temperature, if the energy of the state
the ab°vc 1,16 Pcrmi level. Do the same for a state that lies 0.2 eV below the Fermi level. Repeat
^PutationsatiooKandlOOOK.
48. At what temperature can we expect a 10% probability that electrons in silver have an energy which is 1%
above the Fermi level (EF = 5.5 eV)?
49. Calculate the density of states I m3 of copper at the Fermi level [m‘ = m, T= 0, EF = 7 eV], Take 1 eV as
interval.
50. Calculate the heat capacity of the electron gas at room temperature in copper assuming one free electron
per atom. Compare this with the lattice specific heat value of 2.4 x 10* J/k mol/K. Fermi energy of copper
is 7 eV.
51. The resistivity of a piece of silver at room temperature is 1.6 x 10^ 8 Q-m. The effective number of conduc
tion electrons is 0.9 per atom and the Fermi energy is 5.5 eV. Estimate the mean free path of the conduc
tion electrons. Calculate the electronic relaxation time and the electronic drift velocity in a field of 100 V
nr1. The density of silver is 1.05 x 10* kg/m3.
52. Estimate the electronic specific heat of aluminium and copper at 300 K. Assume EF = 11.7 eV for Al and
7 eV for copper.
53. Compute the Fermi level in copper at absolute zero and at 500°C. There are four atoms per unit cell
Radius of copper atom is 0.128 nm.
54. Estimate the relative contribution of electrons and lattice to the specific heat of sodium (at constant volume)
at 20 K. The Fermi temperature of sodium is 3.8 x 10* K and its Debye temperature is 150 K_
55. The electrical conductivity and thermal conductivity of silver at 20°C are 6.22 x 107 Q-1 m ' and 423 W
m-1 K-1 respectively. Calculate Lorentz number on the basis of quantum free electron theory.
56. A conducting rod contains 8.5 x 1028 electrons per m3. Calculate its resistivity at room temperature and
also the mobility of electrons, if the collision time for electron scattering is 2 x 10-14 sec.
57. An electron is confined in a one-dimensional potential wall of width 0.3 nm. Find the kinetic energy of the
electron when it is in the ground state. Also determine the special frequency resulting from a transitinn
from the highest state to the ground level.
58. Calculate the energy difference between the nx — n — nz— 1 level and next higher energy level for free
electrons in a solid cube of 10 mm x 10 mm x 10 mm
59. Estimate the electronic contribution to specific heat for copper at (i) 4 K and (u) 300 K given that EF far
copper is 7.05 eV. Assume that EF is independent of temperature.
60. If the Fermi energy of silver is 5.5 eV, what is the maximum value of the random velocity of the conduc
tion electrons? If the mean free path of these electrons at room temperatmy. is 55 nm, how great an electric
field would have to be placed across a silver specimen before the drift velocity of the electrons became
comparable to their maximum random velocity?
61. Estimate the fraction of electrons excited about the Fermi level at room temperature for Na and Cu.
62. An electron is moving freely in a one-dimensional box of width a, having impenetrable walls
(a) Write an expression for the force on the walls of the box due to the trapped electron, when in its lowest
state.
A nucleonic particle (1.66 x IO-27 kg) is trapped in an infinitely deep one-dimensional well. The width
of the well is the diameter of a small nucleus (10~ls m).
(b) Calculate the force that this particle must be exerting on the wall when the particle is in its lowest
state, in order to achieve an appreciation of the magnitude of a typical nuclear force.
63. The Fermi energy for tungsten at 300 K is 4.5 eV. The electrons in tungsten follow Fermi energy distribu
tion function:
Find the probability of an energy level with energy value 10 per cent below the Fermi energy being
occupied.
(/>) Repeat the same at 3000 K, assuming Fermi energy is relatively temperature independent.
(C) What is the occupation probability at 2kBT units of energy above the Fermi energy?
At what temperature we can expect a 10% probability that the electrons in silver have an energy which is
' 1% above the Fermi energy [EF = 5.5 eV]?
; A copper wire has resistivity of 1.7 x 10” 8 Q-m at room temperature of 300 K. If the copper is highly pure,
find the resistivity at 700°C.
56 An alloy of metals is found to have resistivity of 1.2 x IO-6 Q-m at 300 K. When it is heated to a tempera
ture at 700°C, the resistivity is found to increase by 11%. Assuming Matthiessen’s rule to hold good for
the alloy, find its resistivity due to impurity scattering alone.
67. A sample of pure copper has resistivity of 1.5 x 10~8 Q-m at 0°C. If nickel is added to copper, the resistiv
ity increases by 1.2 x 10-8 Q-m per added atomic per cent nickel. If silver is added to copper, the resistiv
ity increases by 1.2 x 10-8 £2-m per added atomic per cent silver. If the copper alloy consists of 0.3 atomic
per cent nickel and 0.5 atomic per cent silver, what is the theoretical resistivity of the alloy at 0°C and 4 K.
68. The relaxation time of a conduction electron in copper is 3.5 x 10-14 s. An electric field of 2.5 V/cm is
applied along negative x-axis. Calculate the increase in the x-component of velocity between two collisions.
What is the average increase in energy of the electron between two collisions?
69. Hie relaxation time of conduction electron is 10-14 s. Compare the thermal conductivity of the material at
0°C and 100°C. Assume density of electrons to be 6 x 1028/m3.
T
70. Electrical resistivities of copper and nickel at room temperature are 1.65 x IO-8 Q-m and 14 x 10"8 Q-m
respectively. If Wiedemann-Franz law applies to these materials, find the electronic contribution to the
thermal conductivities of these materials.
71. The distribution function of velocity v of a gas molecules of mass m at a temperature T may be written as
9 1
1 mv
=/(v) Av = c exp 2~k^T v1 (Av)
where v can assume all values from zero to infinity.

(fl) Normalise the distribution function.
(^) Calculate the average value of v •
(^) Find the value of v0 for which/(v) is maximum.
A copper wire has a resistivity of 1.8 x 10"8 Q-m at room temperature (300 K). Assuming copper is very
estimate the resistivity at 700°C and the percentage change in the resistivity from room temperature
to 700°C.
71 The resistivity of pure copper is 1.56 micro-ohm-cm. An alloy of copper containing 1 atomic per cent of
CHAPTERS
“kkel has a resistivity of 2.81 micro-ohm-cm. An alloy of copper containing 3 atomic per cent silver has
8 resistivity 1.98 micro-ohm-cm. What is the resistivity of an alloy containing 2 atomic per cent nickel and
atomic per cent silver?
At what frequency will there be a 0.01% change in the conductivity of a material from the static value, if
7g e taxation time is of the order of 10-14 sec?
' ne Strode specific heal of zinc is a 1.5 x IlH T cal mol’' K’1. Find Ihe Fermi energy of zinc.
Proves . ;
76. An alloy of a metal is found to have a resistivity of 10"6 fl-m at 0°C. When it is heated to a temperature
700°C, the resistivity increase by 8%. Using Matthiessen’s rule, find the resistivity of the alloy.
77. A sample of pure nickel has resistivity of 1.6 x IO-8 m at 300 K. If copper is added to nickel, the resistivity
increases by 1.3 x 10*8 £l-m per added atomic per cent copper. Similarly silver increases the resistivity of
nickel by 0.1 x 10* 8 Q-m per added atomic per cent silver. If the alloy consists of 0.25 atomic per cent
copper and 0.2 atomic per cent silver, calculate the theoretical resistivity of the alloy at 300 K and at 4 K.
78. By how many orders of magnitude is the mean free path reduced in a certain metal when temperature
increases from 0°C and 340°C. Take the temperature coefficient of resistivity as 5 x IO*3 Q-m.
79. The Hall voltage for the metal sodium is 0.001 m V, measured at / = 100 mA, B = 2.0 weber/m2, and the
width of the specimen = 0.05 mm.
(a) Calculate the number of carriers per cubic metre in sodium, and
(b) Calculate the mobility of the electrons in sodium, using its known value of electrical conductivity.
80. Calculate the Hall coefficient of sodium on a free electron model given that sodium has a (b.c.c) structure
of cell side 0.428 nm. Calculate also the Hall coefficient of pure Insb at 300 K, given that E = 0.15 eV?
tn= 0.014 m, mh - 0.18 m, and that electrons are the only effective carriers.
Estimate the e.m.fs generated in each case when a current of 100 mA passes along a sample 5 mm wide
and 1 mm thick in a perpendicular field of 0.1 Tesla.
81. The work function of tungsten is 4.5 eV. Calculate the thermionic emission of a filament 0.05 m long and
10*4 m diameter that is at a temperature of 2400 K. How much would the current increase if a field of
107 V/tn is applied to the surface?
82. An impregnated thermionic emitter consisting of a monochromatic layer of barium on oxygen has a current
density of 100 A/cm2 at 1320°C. The emitter has an area of 0.2 cm2. If the work function of the emitter is
1.6 eV, compute the extra heat power needed to maintain the temperature of the emitter, if a continuous
current is drawn from the emitter.
83. In Schottky effect, find x^ for a field of 105 V/m.
84. What is the field strength required to make the barrier thickness 10 nm for a tungsten filament?
85. Evaluate spin paramagnetic susceptibility for a standard metal with 1\ = 64700 K.
86, Estimate the paramagnetic contribution to the magnetic susceptibility per m3 of potassium, for which the
Fermi energy is 2.1 eV.
87, A paramagnetic system of spins is subjected to a homogeneous field of 10$ amp/m at a temperature of
300 K. Find the average magnetic moment along the field direction per spin in Bohr magneton.
88. Find the ratio between the kinetic energies of an electron in a two-dimensional square lattice which has
K K
kY = kv = — and an electron has k = — and k - 0.
y a a y
89, Consider a two-dimensional square lattice of side 03 nm. At what electronic momentum values do the
sides of the first Brillouin zone come? What is the energy of the free electron with this momentum?
90, The Fenni temperature of potassium is 24600 K. Calculate the Fermi velocity of electrons in potassium.
91. If electrons are treated as distinguishable particles* at what temperature would they have an average energy
of 5.5 eV the Fermi energy of silver],
92, What is Fermi Momentum? The Fermi energy of sodium is 3.2 eV. Calculate the Fermi momentum of the
electron in sodium.
93* Consider a grain dust {tn —Ip gm) confined to move between two rigid walls separated by 0.1 mm. It
requires 100 sec to cross the gap. What quantum number describes this motion?
Thermal Properties of Solids
Heat capacity per unit mass of a substance is known as its specific heat. Specific heat is really a measure
of the number of degrees of freedom of a system. Since degrees of freedom imply freedom to absorb
potential or kinetic energy, the question to be answered is how many ways can energy be given to a
system. The system we would like to be concerned with, is the oscillating lattice, but its analysis is quite
difficult, particularly in three dimensions. Instead, we will carry out the development of the theory in a
series of warming-up exercises, each of which bears a little more to reality. Atoms vibrate about their
mean equilibrium lattice sites in a solid. These vibrations occur at any temperature, even near absolute
zero. They are almost entirely responsible for the thermal properties—heat capacity, thermal conductivity,
thermal expansion, etc. of insulators and contribute the greater part of the heat capacity of metals. (The
conduction electrons contribute only a small part of the heat capacity of metals but are almost entirely
responsible for the thermal conductivity).
Different substances need different amounts of heat energy to raise their temperature by a given
temperature interval. For example, it takes 4184 joule to raise 1 kg of water by 1 K. But the same heat
energy raises the temperature of 1 kg of copper by about 11 K. In other words, water has a large heat
capacity compared to copper. The heat capacity at constant volume Cv is the most useful quantity than
the heat capacity at constant pressure C because the former can be obtained immediately from the
energy of the system.
All of the analyses will be based on the following considerations. The first law of thermodynamics
states that
dQ = dU - dW-dU - P dV
Then the specific heat at constant volume is
(7.1)
333
Thermal Properties of Solids 335
On the other hand. h is much easier to measure the heat capacity of a solid at constant pressure than at corp
Siam volume. Fortunately, the difference between Cp and Ct for solids vanishes at low temperatures and is
only about 5% at room temperature. cart be calculated from C, if the volume expansion coefficient a and
the compressibility ft of a material are known by applying the relation,
(7.2)
where V is the volume of the solid. Thermal properties of some substances are given in Table 7. Ax
Tabto Z A Experimental thermal properties of some substances at room temperature and at atmoRphcric pressure
Substance Specific Heat Molecular, ar Molar heat capacity (JArnol K) (in IO*)
Atomic weight
c, c.
CM 0385 e.5 24.4 214
Al am 27.0 243 23,0
Fe 0.460 559 25.7 24.7
Ni 0.456 58.9 26.8 24,6
Pb 0130 207.O 269 24.7
A« 0.236 108.0 2J.5 243
C (graphic) 0.904 12.0 10,9 92
Water 4.184 18.0 75.3
The heat capacity per kmot of a substance » called malar heat capacity, and it is obtained by multiplying the
specific heal C, (or by the molecular weight.
Fig. 7,1 shows the experimental variation of molar specific heat of some typical solids as a function
of temperature. This behaviour is characteristic of all observed solids, the only difference being the temper
ature at which C* starts to drop off.
We thus note the following facts:
L Al elevated temperalures Cv is fiat (independent of temperature) and equal to 3ft* per kmol for all sol
ids. This is the so catted Dulong*Petit law, It holds good just below the melting point, at which C, starts
tense.
2. Al tow temperatures C, begins to fall off and approaches zero as T *+ 0.
The approach to zero near T® 0 is by a T1 law; i.e., Cr« (constant) T\
Let us now evaluate G theoretically, and compare the value so obtained with experimental results.
We shall consider a crystal composed of N-atoms, which arc held together in a periodic array. These atoms
are assumed to be free to vibrate about their equilibrium sites subject to constraining forces which to a first
approximalion obey Hooke's taw.
HL CLASSICAL THEORY (DULONG ANO PETIT LAW)

The classical theory is based on the fol tow t ng assumptions:
L. Each solid consists of a large number of atomic panicles executing simple harmonic morion
about their equilibrium sites. They are called atomic oscillators.
2. The atomic oscillators vibrate with the same frequency, but their energies are different because
they vibrate with different amplitudes.
Fig. 7.1 (a) General dependence of specific heat of solids
(b) Experimental curve of specific heat for silver, germanium and silicon
3. The internal energy is largely contributed due to vibrational energy of all atomic oscillators.
4. There is no restriction on the energy values of the atomic oscillator and it can take up continuum
of energy values right from zero to infinity.
5. The total energy of the crystal at a given temperatures is N times the average energy E of the
oscillator.
The classical calculation assumes that each atom is a classical three-dimensional harmonic
oscillator, which executes simple harmonic motion independently about the mean position. Under these
Clrcumstances, one may calculate the total internal thermal energy of the crystal by finding the average
ê^rgy of a single oscillator and multiplying it by N. The frequency of such oscillator may be determined
din. • 6 restor*n8 force of a harmonic oscillator is proportional to the elongation but opposite in .
““ection, i.e.t
.. F x x, or F = -fx
where, f;s.
elastic constant. If m is the mass of the oscillator, then
d2x
m
(7.3)
(7.4)
If one of the atoms is displaced over a small distance, much smaller than the interatomic distance
and set free, the displaced atom would carry out harmonic vibrations about its equilibrium and its
energy of vibration would be as that of a harmonic oscillator. For a single one-dimensional isotropic
harmonic oscillator, the total energy is given by
2 2
marx
2
■■ ■■ ■■
f P P2 mto2x2- .
Now, ‘ E= -±- +------ ----- ■ ’ ! (7.5)
> 2m. ,. 2 ■
Hie first term of equation (7.5) represents kinetic energy and the second term, potential energy-
Px is the linear momentum along the x-axis, and x is the displacement at that instant. Even if all the
atomic oscillators vibrate with the same frequency, their energies may be different, because they vibrate
with different amplitudes [this means that when x is constant, the second term is constant, but may
2m
vary, because the energy changes from one atom to the other. The converse is also true].
An expression for the total energy of the crystal at a given temperature can easily be obtained by
adding up the energy of the various atomic oscillators in the system due to lattice vibrations. Let £ be
Thermal F T 4r
Sou«» If
— ■ ■ ——4k ■ ■■, । X ii ■
the mean
of me substance). the oscillator
energy of The classical and N bethftî
model does . of osc,llatOTS in a «iven mass (say a kgmole
“ "™ber
CHAPTER 7
oscillator no nP0Se anY restriction on the energy values of the
Thus the mean energy of the oscillator is given by

OO
ZEdN
o
oo
XdN
o
From statistical mechanics, dN is the number of atomic oscillators having their energies lying
between £ and (£ + dE) at a given temperature T is proportional to the Boltzmann, factor exp (- E!kBT).
Now
Substituting the value of £ from equation (7.5),

2 2 2
px mGTx px men x
X exp ■b
o I 2m 2 Jim 2
2 2\ /
(7-6)
Px mco x ] L ~
Zexp - B
o 2m 2
OO — 2
y Px
exp (~px /2mkBT) £exp (-mto2x2/2kBT)
o 2m o
2 ‘ 2
+ X m<° X exp (-m<o2x2/2A;sT) Zexp {-p2x/2mkBT)
o 2______________________o
co
Lexp {-p2/2mkBT)exp (-m(a2x2/2kBT)

o
2 2
E exp (-p2 /2mkBT) I —-—exp (~m&2x2/2kBT)
or o 2m . o
<30
I exp (-p2xl2mkBT)Lexp {-m(a2x2/2kBT)

0 o
Now one can replace summation by the integral sign and we will get
OO n . DO
exp (-p2 /2mkBT) dpx f WC° X-exp (~m(a2x2/2kBT) dx

2m J 2
(7.7)
exp(-p2/2mkBT)dpx j exp (-/nCD2 x2j2kBT} dx
— oo - °o
1x2 f 2 . 2, .
-------- u exp (- a u ) du
2m J
o________________
oo
2 Jexp (- a u2) du
o
where, u=p and a = —!—
x 2mkBT
1 (u2 exp (- an2) du

—
___________________________
Thus, 90 (7.8)
2 J exp (- an2) du
o
Jwd[exp(-au2)]<Zi4
J u2 exp (- an2) du = o_________
-2a
o
-an2)];
2a
o
i f ,
= — I exp (-an ) du
2a J
Lo
1 • oo
2am J
:01
4am
2 Jexp(- au2)du
■ ■ o
(2mkBT) = -^—
4m
Similarly the solution of the integrals of the second term of equation (7.7) may be obtained as
follows: . ■
x2 exp (^ma2x2 /2kBT) dx
2m©2 J u2 exp (- pi?) du ■" ■

2
o ' ' .4 . JO man2
B =-------
with u = x and H 2kBT
(7.9)
2 jexp(-pi?)4« •_
0
Now.
CHAPTER?
du
=“ 1“ e*P (-Mio - Jexp(-(to2) du

o
= ™ J exP (- P«2) du
" o
mo)
mo2
r o___________ mo ’Vl k„T
2 fexp(- Pu2)du T 4 J[m(D2.
o
— k$T kBT
Thus, (7.9a)
2 2 B
The amplitude A of a harmonic oscillator is its maximum displacement on either side of the
equilibrium position. When x A, all the energy is potential, and hence
2J °
^k^y2
(7_-9b)
Evidently A depends only on/and T and not on the mass m of the particle. The Hooke's law
constant (/) for an aluminium atom in solid aluminium was found earlier to be -20 N/m. At 300 K, the
average amplitude of such an atom is '
. ■ 2x138x10 *300
A - 0.02 nm
which is about 7% of the 0.286 nm equilibrium bond length at that temperature. The actual value of A in
aluminium is somewhat less than 0.02 nm, because/is greater than our estimated value of 20 N/m.
Since each oscillator has three degrees of freedom, the classical value of the vibrational energy
of a crystal of N\ atoms is thus given by
U = 3N. knT
A P
C =^ = 3N.k = 3R
V AB «
Cv = 3RU = 3 x 6.02 X 1026 x 1.38 x IO"23 (7.10)
Cv = 25 kJ/kmol K____________________ _
This result Cv = 3RU for most solids (independent of temperature) is known as the Dulong-Petit
law in their honour. However, the Dulong-Petit law fails for such light elements as boron, beryllium,
and carbon (as diamond), for which Cv = 14, 16 and 6.1 kJ/kmol K respectively at room temperature.
(This is because the Debye temperature of these elements is much above 300 K). Even worse, the
specific heat of all solids drops sharply at low temperature and approaches 0 as T approaches 0 K.
Figure 7.1 (Z>) shows how Cv varies with T for various elements. Clearly something serious is wrong
with the analysis leading up to equation (7.10) and it must be something quite fundamental, because the
curves of Fig. 7.1 (b) share the same general character.
The observed fact that the specific heat of all solids drop sharply at low temperatures and approaches 0,
as T approaches 0 K, could not be explained satisfactorily on the basis of classical theory.
In order to account for the low temperature specific heat of solids, Einstein, in 1907, applied
quantum principles to the thermal vibrations of atoms in solids. Einstein considered a solid of TV. atoms
(per kg mole the substance) to behave as 3NA independent harmonic oscillators, each of frequency v. In
classical mechanics, a mode of oscillators can have any of a continuous range of energies, the only
restriction being that the energy is half kinetic and half potential; the meaning of quantisation is that
only certain discrete values of energy are allowed. In other words, quantum theory assumes that atoms
are again identical, independent harmonic oscillators, all of which vibrate independently with the same
natural frequency, but have discrete energy values. These discrete values are given by the Planck’s
formula
En = nhv = nft(O (7.11)
If dN oscillators have energies lying between E and E + dE, then the mean energy of the atomic
oscillators is given by
- YEdN
E = ——— (7.12)
ZdN
From statistical mechanics, one knows that the number of atomic oscillators dN, having energies
lying between E and (E + dE) at a temperature T, is proportional to exp (~E/kBT).
Thvrmm
Thus,
I exp [-nh\)/knT]
2ta*
V + 3e *"r + ...oo terms,
5/rv
V + e **r +... oo terms
Au
Put
V
g __ Êe + 2e2jf + 3e~Vt +...<*>terms]
[1 + ex + e2x + e3x + ... ©o terms]
E =hv
d,
E =h\) —log
(1 hx>(-ex)
= hx> — {log 1- log (1-e*)} =_
ax
(l-eJ)
ex
hve^
(l-ex)
fro _ hx>
e~x(l-ex) ~ (e~x -1)
(7.13)
The total internal energy of a kmol of a solid therefore becomes

_ 3NAh\)
U=3NaE = ---- —57——— and therefore the molar specific heat is
A [exp (JiV)/k s T -1)]
dU. _ (3Na hvi) exp [Zru/fcB T] [- hv!kBT2 ]

. dT J “ [exp(/iv/JtflT)-l]2
Let, Ad = kD
D
6,,
E £
where 6Us known as Einstein temperature.
(3NM exP [^MbT] [WkeT?
Thus,
v~ [exp (hv/kBT) -L I]2
jiff
2 j
Cv Au f ^xp[AWM1__
3/?m kBT [exp(hv/kBT)~ I]2
Im ■"
_ exp (Oc/T)
(7.14)
<rj [exp (0£/T) -1]
f\E) is called Einstein function.
Case 1
At high temperatures Au « kBT. Now equation (7.13) is written as
Au
with x =
kBT
and e*= l-+x+— + — + ... = 1+x

2! 3!
Hence at high temperatures,
- _ Au _ Au
(1 + x-l) x
E =----------- = k T
hv/kBT B
A Ad 3N. kRuT= 3RT

U=3N.E=
dU
C>=^=3R‘
i.e., for large values of T, the expression reduces to the classical expression.
Case 2
At low temperatures, Au » kBT and hence, exp (hx>/kBT)» 1; therefore

E =_____ to
exp (hvJkp'T)
Thus at low temperatures, the total energy of a kmol of a solid is given by
U = 3Na Au exp (- hxt/kBT)
f Au
= (32Va Au) [exp (- fa)/kBT)]
kB exp (- hv/kBT)
(7.15)
Yc TffljftW,
Equation (7.15) indicates that at low temperatures, the exponential term is more important than
hv
CHAPTER 7
term in determining the temperature variation of C.
kBT
Thus with decreasing temperature, Cv drops exponentially. Equation (7.15) is plotted in Fig. 7.2
for aluminium with v - 6.4 x 10 Hz. There is, evidently, good agreement with data except at very low
temperatures, where Cv is more nearly proportional to T3 than to equation (7.15).
Fig. 7.2 A comparison of specific heat data for aluminium (dots)

and the predicted curve from Einstein equation
Debye in 1913 improved Einstein’s theory by taking a more realistic model for the frequency spectrum
of the solid. The essential feature introduced by Einstein, the quantisation of oscillator energies, was
retained. Debye’s theory, with minor exceptions, fits low temperature data successfill and is still in use.
Debye regarded the solid as a system of coupled oscillators. The motion of such a coupled
system can described in terms of normal modes; these modes belong to the whole assembly, not single
atoms. The total number of modes is 3N, where N is the number of atoms in a monoatomic, homogeneous
solid. These 3N modes, in general, all have different frequencies and energies up to a maximum frequency
which is fixed by the knowledge that the total number of frequencies must equal 3N.
The Vibrational Modes of a Continuous Medium
Consider a one-dimensional, continuous string of length I. If one end of the string is fixed, wave of any
wavelength can be propagated. However, if the other end is also fixed, continuous range of A. is not
X •
possible and stationary waves are set up with specific wavelength such that n— — I.
Let Y(x, f) represent the displacement of the string at any point x at the instant t. By considering
the forces acting on a differential element of the string, and its resulting acceleration, we easily obtain
the partial differential equation
a2y _ i Ta2y>|
dx2 ' V2 ^x2?
Here v is the velocity of the waves in the string. This wave

equation is also valid for several other types of waves. In practice,
sound waves in air and light waves in vacuum are two of the
important types of actual waves that obey equation (7.16). The
solution of this equation is given by
2nx 2m
K=A sin ----- cos (7.17)
X
with
nltx
Le., cos 2?UV (7.18) -
n
where n is positive integer > 1. The wavelengths and frequencies of the possible vibrations represented
by equation (7.18) are given by
v V
V =— =n (7.19)
.21.
The frequency spectrum is discrete. Note that for the one-dimensional string the frequency
spectrum corresponds to an infinite number of equidistant lines, as illustrated in Fig. 7.4 (a).
The number of possible modes of vibration, having frequencies lying between v and v + do (i.e.,
in the frequency interval do) is, on the average, equal to
'2/'
dn = do (7.20)
In three-dimensional case, the wave equation reads
d2Y d2Y d2Y _ 1 32y

dx2 dy2 + dz2 v2 dt2 (7.21)
Assuming a continuous medium in the shape of a cube of edge I, and assuming the faces of the
cube to be fixed, the possible standing wave solutions are, in analogy with equation (7.18),
n^nx olnnylty . n.nz _

Y
lx, y, i.O
sin sin—— sin-5— cos 27vu„r (7.22) '
I / I "
where nr, n and n, are positive integers £ 1.

* Z i
CHAPTER 7
Ag. 7.4 (*) Frequency spectrum for a finite continuous string according to equation (7.20) (b) Frequency
spectrum for a three-dimensional continuum, according to equation (7.27)
d Y n7lt
-------- _ y-J,----
az2 i2
and 1?” = “ 7 47t21)2
Substituting these values in equation (7.21), one obtains the following expression for the possible
inodes of vibration:
Thus, (7.23)
ie., in a three-dimensional case, wavelengths and frequencies are determined by the three integers n
n, andnr
Density of Vibrational Modes

The number of possible modes of vibrations Z(u) dv in the frequency range u and (u + du) can be
calculated as follows: Refer also equation (6.104).
Consider a network of points, each point being determined by the three cartesian positive integer
coordinates n , n and n .
Thermal Properties of Solids 347
2
(7,24)
h is evident that the number of points tn a shell between n and n + tin is equal tci
4/vj'
k(« + dh)1
HF
”;f«**d»* + 3?) dn +3aJrt;-n^]
E - |3h'î[
^-nfdn (7.25)
Now* each point corresponds to y set of three integers nA, nr «. and each set of integers determines, accord
ing to equation (7.22)* a possible mode of vibration; hence equation (7.25) immediately gives the number of
possible modes of vibration in a given range. Substituting for n and dn from equation (7.24) in equation
(7.25). one gets
„ MF^vlrf2/V7
4ti/ Vd V
Z(v)rfu = (7-26)
Thus the number of vibrational modes per unit volume in the irequenev interval d\\ t known us. density of
vibrational modes) is given by
. 4jn?do
Z(vXv -——- (7.27)
Since longitudinal nicies have one state of polarization and transverse waves have two states of pokiriza-
tion+ we have
Z(V)du-4?tf Vdu (7.28)
where vT is the velocity propagation in the longitudinal nuxie and i r is that of trunsversu mode
Debye’s approximation
Tire Debye*s cut off procedure leads io a maximum frequency uc (the Debye frequency) common to
the transverse and longitudinal modes; it is defined by
Copyrighted inaterial
«D„
Z(v)dv =3AT
CHAPTER 7
Substituting the value of Z(v) dv from equation (7.28), we get
r1 2 r vi
4nV -r + —r
0
3 =9yv r_i 2
or D 4nV vf+v.
(7.29)
It should be noted that this procedure assumes that the velocities v and v, are independent of the
wavelength, ut s is not correct for the actual crystal. vt and vz for the transverse and longitudinal
modes respectively. Note that v,-< v,. The order of magnitude of „„ may be obtained by taking
y - IO28 per m3 and using for the velocity of sound s 1000 ms1
(7.29a)
Fig. 7.5 (a) The Debye cut-offtakes place at the debye frequency nD, common to the transverse and
longitudinal modes, (b) In Born’s procedure, the cut-offtakes place at a common minimum
wavelength, corresponding to the maximum frequencies.
3 _ 9 x 1028 r 3
Vd~ 4n L10003
vD = 1013 Hz .
The corrcnponding minimum wavelength is given by
v s» I) Xm
x JO-13 = 0.1 nm
VD
This indicates that the wavelengths are greater than interatomic distances and hence continuum
theory may not work, especially in the high frequency region.
Now the total energy of the oscillators in the frequency interval dv is given by
E(v)d\) = EZ%X))d\3
Total internal energy of the solid is

E= ÊZ(v)di)
o
Substituting the value from equations (7.13) and (7.28), we get
hv\Pdv
E = 4nV (7.30)
e\p(fr\)/kBT) -1
which in terms of equation (7.29) can be written as
"1
9N f /nn)2dv
v3o J | [exp <Jtv/kBr) -1] (7.31)
and kfijy- htop, where is called the Debye temperature, we write
xmax
m, -
kBT
i.e„ x
max kBT ' T
Thus one gets the energy expression as
E = 9Nk„T
For getting molar specific heat, we write
(7.32)
Thermal
Case 1
At high temperatures
CHAPTER
ex= I +x
P dx = 3N. kn T
l/=9N4kBT
J /i D
0
dU
= 3NAkn=3R
dT A U U
The result at high temperatures is in conformity with experiment and classical theory.
Case 2
At very low temperatures, T 0 and -> ~ one can thus use
NAkBT*n4
to get U = 9NAAkDRT
el
c = — = forT«0 (7.33)
v dT 5 ■ \eDJ D
The model thus predicts that the specific heat at very low temperatures is proportional to T3,
which is in agreement with the experimental observation. This is the famous T3 law, which holds good
for7£ . The general expression for the specific heat as a function of temperature may be obtained
by differentiating equation (7.32) with temperature. Thus one obtains
where FD is Debye’s function.
The general agreement between theory and experiments is quite good, Op being about 100 K for
lead, 160 K for sodium and about 1860 K for carbon (diamond).
„v is
The resulting curve for C • show g 7.6. The curve levels out at
hnwn in Fig d -1, when Cv
= 23.75 kl/mol K, which is 95% of its maximum v iue 0D = *»• Hence when T > Op, a
93 when —
solid behaves classically and has a specific heat f c* =, ?>Rdecreases with

, the Dulon vaiue’temperature.
decreasing
$'Petlt while when
T< Op, its behaviour is dominated by quantum ettect At Wgh lemperatures
The reason for the change from classical to quant so spectrum is effectively continuous,
spacing /m between possible energies is sm
while at low temperatures the spacing is large relative to kDT and inhibits possession of energies above
the zero-point energy. However, the Dulong-Petit law fails for elements such as boron, beryllium and
carbon (as diamond), for which Cv = 13.98, 16.11 and 6.11 kJ/kmol K respectively at room temperature.
At very low temperatures, referring equation (7.33)
Fig. 7.6 The Debye specific heat as a function of

T/0D, 0o being the Debye temperature
Table 7.2 Debye temperatures of some materials
Material Material . ; ^d(K) ’

Na 160 Mg 290
K 100 Zn 250
Cu 340 I- w ■ 310
Pb 88 ,C (diamond) 1850
Al 373 AgBr 150
Be 1200 NaCl 280-
Ge 290 KC1 230
Si 650 CaF,£ 474
Table 7. 3 Deviations from T3 law
NaCl
•
KCl ■ • *. !
T (K) cv T (K) eD(V Q

kJ/kmol K kJ/kmol K
1 4
20 288 0.649 14 213 0.551

15 297 0.249 8 I 222 0.091
10 308 0.066 3 227 0.005
Thus the famous Debye T* law [see equation (7.33)] must very well hold good for T £ $D /10.
_____ -----—— ■ -------------------- ■■ -
Thermal ProperTiesof SoMfif 35^
. _ _ - - - g.
Accurate measurements of specific heat at low temperature region show deviations from the
theoretical predictions. According to the Debye theory, the T3 law should hold in the region T < 0.1 QD.
^t this is not always the case, may be seen from some examples given in Table 7.3, taken from
Blackman’s work. The Debye s temperatures of the materials given in this table were obtained from
equation (7.33), and should be constant if T3 law is satisfied. Such deviations are found in other materials
also. These deviations are as a result of the deficiencies of the continuum approximation, a conclusion
which is supported by the work of Blackman and Kellerman. According to them one may expect the 7$
0
law to hold good for the temperature region T < ~ ie., at considerably lower temperatures than
predicted by Debye s approximation. The Debye temperature is one important factor in the discussion
of many physical properties such as elastic constants, electrical conductivity and X-ray diffraction.
The total molar specific heat of a metal at temperatures above Debye temperature 0p in the
usual form is thus given by ..
[cJr=[CX + tC,]d = 3R1,+ ('|V -
\Z/
Actually, [Cv]r = at high temperatures, from which we conclude that the free electrons do
not in fact contribute to the specific heat at high temperatures. This has been already discussed in
Chapter 6.
Highlights.
Thermal Behaviour: The two principal types of internal energy in most solids are the vibrational
energy of the atoms about their mean positions and the kinetic energy of the electrons. As a solid
absorbs heat, its temperature rises and its internal energy is increased. The important thermal properties,
such as heat capacity, thermal expansion and thermal conductivity, are dependent upon energy changes
of the atoms and free electrons. .
Heat Capacity: The amount of heat necessary to raise the temperature of a system by one
kelvin.
Specific Heat: The heat capacity per unit mass.
Electronic Specific Heat: The contribution to total specific heat due to transitions of electrons
to state of higher energy.
Lattice Specific Heat: The contribution to total specific heat due to transitions of vibrating
1 atoms in the crystal lattice to vibrational, states of higher energy. "
• I «
- Lattice Vibrations: Just as it was possible to construct a quantum picture from apparently
continuous electromagnetic waves, we can also describe the lattice vibrations by quanta of sound waves.
These are given the name phonons. In electromagnetic radiation each quantum of energy is given the
name phonon. The phonon is a quantum of elastic energy and travels with the velocity of sound in the
medium, •
kgmole: A kgmole (kmol) of any substance is that mass of the substance that contains a specified
number of molecules (6.02252 x 1026) called Avogadro’s number.
dt/
Internal Energy: If U is the internal energy of the solid,— is rate of change of internal energy
w,th temperature. Then — is the rate of change of internal energy at constant volume. Thus
\dT
dU
L</7
Because the electronic contribution to the internal energy, and hence to the specific heat of the
solid, is very small at room temperature for most of the solids, we take into account the lattice contribution
to the internal energy.
oBjECTivrquEsnowr w
The classical expression for the mean energy of a one-dimensional atomic oscillator is
(b)(kBT+kBT)
2
(c) (d) none of these
where kB is Boltzmann constant.

The classical value of molar lattice specific heat is
(a) ^5“
(b) 3RU
Ru
(c)Ru to~2
The discrete values of energy the atomic oscillators can have are
(a) nhm1 (h) n2ha>
(c)nflO) (d) 2nh(0
where n is an integer including zero.
The quantum mechanical expression for the mean energy of the atomic oscillator is
. . hv
(a)-------------------- (h) /ru[exp (JrolkBT) - 1]
[exp(/n)/^T)-l]
(c) /rt)[cxp (Wk0T) - I]2 (d) none of these
Einstein's theory concludes that at lower temperatures the specific heat
(a) drops linearly with increase of temperature
(b) drops linearly with decrease of temperature
(c) drops exponentially with decrease of temperature
(d) remains constant
6. If both ends of a string of length I are fixed, then the wavelengths of the wave that can be propagated
through it is
CHAPTER 7
where « is an integer.
7. The expression for the density of vibrational modes in a continuous elastic medium is given by
4jcv2<A) 2
(b) 4tcv d\)
(c) 4jtv2<A) (d) none of these
s if the Debye’s temperature of a metal is 450 K, the Debye’s frequency is

(a) 1013 Hz (6) jq2
(c) IO23 Hz (d) 10 Hz
9. At lower temperatures the lattice specific heat varies as
(«)'3 (» p
(» T W|
10. Dulong-Petit s law obeys at room temperature for many metals while it fails for light elements such as
boron, beryllium because
(a) the Debye temperature of these elements is very high
(b) the Debye temperature of them is about 300 K
(c) the Debye temperature of them is low
(d) none of these
1. Give the assumptions of classical theory of lattice specific heat

1 Give the expression for the frequency of a classical oscillator.
3. Give the salient features of Einstein’s model discussing the molar lattice specific beat
4. Explain Einstein’s equation for molar lattice specific heat both at lower temperatures and higher
temperatures. Discuss its agreement with the experimental results.
5. What are density of vibrational modes in a continuous medium? Write down the expression for density of
vibrational modes and explain the symbols.
6- Obtain the expression for Debye’s frequency.
7. Show that at lower temperatures Cv varies directly as 7^.
8- How did the Einstein’s theory explain the failure of Dulong and Pent s law?
S&* r loufi'iSun Phywgs
L « «i ■ -■■■■ > ■ ■— ■ ■■ ■■ *” '
9. What is Debye's F1 law? How far is it satisfied by solids?

10. Discuss die merits and demerits of Einstein’s quantum theory of specific heat of solids.
IL How far Debye’s theory is conformity with experimental results?
12. Discuss salient features of Debye’s theory of specific heat of solids.
13. Discuss the classical theory of specific heat of metals.
14. Give an account of Einstein’s theory of specific heat of solids.
15, Give the salient features of quantum theory of specific heat of solids.
X—ârwrf^'rtur.^ t ■ m n«n-••••■•>-ri-*- ---■ _
1.State Dulong-Petit’s law and show how the departure from this law at lower temperatures has been explained
by Einstein’s theory.
2. Discuss the variation of specific heat capacity of solids with temperature and give Einstein’s theory to
explain it.
3. Obtain an expression for the specific heat capacity of a solids on the basis of
(a) Einstein’s theory and
(b) Debye’s theory. How far do the results from these theories agree with experimental data?
4. Show that the Einstein’s relation for the heat capacity per. kmol of a solid reduces to the classical value
of 3RU when k„TD
> hv.
5. ■ What is the Einstein’s model for the phonon frequency distribution? Use this model to calculate the internal
energy per kmol for a solid. Show that the specific heat varies experimentally with in this model
How does the Debye’s model differ from the Einstein’s model? Mention essential differences in the model
and note the consequences of these differences.
7. Work out an expression for the specific heat of solids following Einstein’s model. How does specific heat
depend on temperature and to what extent does this model agree with experimental results ?
8. Discuss the reasons for the failure of Dulong and Petit’s law to predict the specific heat at low temperatures.
Why should the law be valid at high temperatures? Find an expression for the specific heat of a solid on
the Einstein’s model and show that it converges to 3R at high temperatures.
9. Show that for the Einstein’s model of a solid, the molar specific heat at constant volume C is given by
exp (hv/kBT)
[exp -1]2
10. Discuss the salient features of Debye s theory of specific heat and show how far it agrees with the
experimental values.
11. Derive an expression for the specific heat of a solid on the Einstein’s model and show that at low temperatures
it drops exponentially with decreasing temperature.
12. Dulong-Petit’s law fails at room temperature for elements such as boron, beryllium and carbon (diamond)
for which Cv is much less than 3RU. Why?
13. Give an account of the various theories of specific heat of a solid. Discuss any one of them in detail.
14. Show that the electronic specific heal of a conductor is very small compared to the lattice specific heat at
room temperature. Calculate both the values in the case of copper.
Yo Thermal pROMffns OF Scum aiH
~. VroBLEMS" ~
CHAPTER 7
The Debye temperature of carbon (diamond) is 1850 K. Calculate the specific heat per kmol for diamond
at 20 K. Also compute the highest lattice frequency involved in the Debye’s theory.
2 If the classical theory of specific heat is valid, what would be the thermal energy of one kmol of copper at
the Debye temperature? [ 0D for copper is 340 K].
j Calculate the Debye specific heat of copper at
(0 10 K and
(rt) 300 K, given that the Debye characteristic frequency is 6.55 x 1012 Hz.
4. In aluminium, v/ = 6.32 x 103 m/s and v, = 3.1 x 103 m/s. The density of aluminium is 2.7 x 103 kg/m3 and
its atomic weight is 26.97. »
(a) Calculate Debye cut-off frequency (y>D) for aluminium from these data.
(b) The Debye temperature for aluminium, as obtained from specific heat measurements, is 375 K. Find
Up from this figure and compare it with the result obtained in (a).
(c) Are the preceding values of vD consistent with the vibrational frequency of aluminium atoms in solid
aluminium?
5. Lead has an fee structure with a lattice constant of 0.494 nm. Young’s modulus of lead is 1.6 x 10'9 N/m2.
If lead melts when the average amplitude of its atomic vibrations is 15.8 per cent of the interatomic
spacing, compute the melting point of lead.
6. For copper, the lattice specific heat at low temperature has the behaviour of Cv = 4.6 x IO-2 T3 J/kmol K.
Estimate the Debye temperature for copper.
7. The electronic properties of copper may be deduced by assuming that each atom contributes one electron.
The atomic weight of copper is 63.54 and its density is 8.96 x 103 kg/m3
8. At what temperature does the electronic contribution to the specific heat of silver become identical with
the Dulong-Petit value? EF = 5 eV. ,
9. At very low temperatures, the specific heat of rock salt varies with temperature according to Debye’s T3
law: .
Qp for rock salt is 281 K. How much heat is required to raise the temperature of 2 kmol of rock salt from
10to50K?
* te » •
10. Estimate the relative contributions of electrons and lattice to the specific heat at constant volume of sodium
at 20 K. The Fermi temperature of sodium is 3.6 x 104 K and its Debye temperature is 150 K.
11. Diamond (atomic weight of carbon = 12) has Young’s modulus of 1012 Nm-2 and a density of 3500 kg/m3.
Compute Debye temperature for diamond.
12. Copper has an atomic weight 63.5, a density of 8.9 x 103 kg/m3, and v( = 2.32 x 103 m/s and vt = 4.76
x m/s. Estimate the specific heat at low temperature say at 30 K.
Yo
Superconductivity
t. HISTORICAL INTRODUCTION
The electrical resistivity of all metals and alloys decreases when they are cooled. When the temperature
is lowered. the Arrwa/ librations of the atoms decrease and the conduction electrons are less frequently
scattered. The decrease of resistance is linear down to a temperature equal to one-third of the characteristic
Debye temperature of the material, but below this the resistance decreases less rapidly as the te i ri ratine
falls (Fig. 8.11 For a perfectly pure metal, where the electron motion is impeded only by the thermal
I
vibrations of the lattice, the resistivity should approach zero as the temperature is reduced towards 0 K.
This zero resistance which a hypothetical perfect specimen would acquire if it could be cooled to absolute
zero. is not. however, the phenomenon of superconductivity. Any real specimen of metal cannot be
perfectly pure and will contain some impurities. Therefore the electrons, in addition to being scattered
by thermal vibrations of the lattice atoms, are scattered by the impurities and this impurity scattering is
more or less independent of temperature. As a result there will be a certain residual resistivity (p^)
which remains at the lowest temperatures. The more impure the metal, the larger will be its residual
resistivity.
Fig. 8-1 Variation of resistance of metals wh temperature

Certain metals, however, show a very remarkable behaviour: when they are cooled, their electrical
resistance decreases in the usual way, but on reaching a temperature a few degrees above absolute zero
they suddenly lose all trace of electrical resistance (Fig. 8.2). They are then said to have passed into the
superconducting slate. The transformation to the superconducting state may occur even if the metal is
356
Supe rcr mdiwtiviry 359
Certain mct&K however, show a very remarkable behavior, when they art coaled, their electrical
resistance decreases in the usual way, but on reaching a temperature a few degrees above absolute zero they
suddenly lose all trace of electrical resistance (Rg. 8.2). They are then said to have passed into the super-
conducting state. The transformation to the superconducting stale may occur even if the metal is so impure
that it would otherwise have had a large residual resistivity In a laboratory in Leiden in 1911, a Dutch
scientist observed the remarkable disappearance of all electrical resistance from a ihin capillary of mercury
meld sitting m a bath of liquid helium Seventy Six years later, in a laboratory in Huntsville, Alabama,
another scientist saw the same thing happens to a greenish ceramic pellet sitting in a wanner bath dtf liquid
nitrogen. The two events ihc original discovery of superconductivity and the recent discovery of high tem
perature superconductivity are linked by a rich history of scientific and technological accomplishments.
Over the years, superconductivity has flourished as a field of scientific endeavor, leading to the
awarding of many Nobel prizes in physics. In addition, it has emerged as a technology, contributing to
advances in medicine, electronics, astronomy, transportation and experimental science, But inspite of all
these things, superconductivity has remained a little-known phenomenon on the periphery of science.
IL A SURVEY OF SUPERCONDUCTIVITY
■■
To understand anything about superconductivity, we have to know something about ordinary conductivity.
All ordinary materials resist the flow of electricity to a lesser or greater extent Electricity or electrical cur
rent consists of the movement of electrons through a material. In order to make electrons flow, we need to
add energy. We need to push them. Electrons in a metal behave like water in a hose. The water would not
flow unless we supply some pressure. The amount of pressure it takes depends on the kind of hose w c use.
Similarly, the amount of energy needed to produce a certain electrical current in a material depends
oft the kind of material we are using. The energy we supply to electrons or the push we give them is called
voltage. We get it from a battery or from an outlet in the walk A 1,5 volt battery can supply a certain amount
of energy to each electron in a wire, A 6-volt battery supply four times that energy. The amount of voltage
we apply to a conductor determines hou much electrical current uill flow. The more we push on the elec
trons, the faster they move. We measure currents in units called ampere and one ampere current corresponds
to 10w electrons passing by every second.
The actual amount of current we get for a given voltage depends on the nature of the material we are
tising. The more the material resists the flow of electricity, the more we have to push to keep current flow
ing, We call the measure of this property the resistance of the material If we apply I volt across a material
and we gel 1 ampere of current to flow, then by definition the material has a resistance of 1 ohm. If only half
as much current flows, then the material has a resistance of 2 ohmT since it resists the flow of electricity
more strongly. Resistances of common materials vary widely, A chunk of cupper has a resistance of only a
few millionths of an ohm. A piece of glass, on the other hand, can easily have a resistance in millions of
millions of ohms. Almost nothing in nature has a much diversity as the resistance of materials. But all ordi
nary materials have one thing in common: they have some electrical resistance, it takes at least some amount
of energy to permit current to flow. Electrical resistance is n form of friction tike rhe heat generated by tires
skidding on pavement, A car slops moving when it loses its energy of motion to heal in its brakes and tires,
Similarly, electrons- lose their motion in a metal by heating up the metal. We call this loss of energy.
Joule Heating
Superconductors are extra ordinary because they alone are immune from the effects of Joy Ie heating. It takes
Niobium is the metallic element with the highest transition temperature (9.3 K). but some alloys
and metallic compounds remain superconducting up to even higher temperature (Table 8.2). For example:
j\jt»,Ge has a transition temperature of about 23 K. These alloys with relatively high transition temperatures
gie of great importance in the engineering applications of superconductivity.
On cooling, the transition to the superconducting state
niav be extremely sharp if the specimen is pure and physically
perfect. For example, Nb3Ge has a transition temperature of
about 23 K.
CHAPTER 8
Certain metals, particularly those that have low
melting points and are mechanically soft and easily obtained
in pure, strain free condition, display similarities in their
superconductive behaviour. They are distinguished as ‘ideal’,
Type I’ or ‘soft’ superconductors. The behaviour of many
alloys and some of the more refractory superconducting
metals is more complex and individual, particularly in respect
of the way in which the superconductivity is affected by a Kg. 8.3 Superconducting transition in on
magnetic field. These materials are distinguished as ‘Type
II’ superconductors; or, if the superconductivity can be retained in high magnetic fields, as ‘hard’ or
‘high field’ superconductors. Superconducting materials may be either Type I or Type II.
Table 82 Critical temperature T. and critical magnetic field
Hq (at 0 K) of some compounds and alloys
-• (Abi) A:
Nb - 44% Ti 10.5 9.5 x 106 n
NbN 16 8 x 106 n
Nb-25%Zr 10.8 5.6 x 106 n
} 17 1.3 xlO7 n
V3 Si
Nb3 Sn 18.5 1.6 x 107 n
V3 Ga 16.5 . 2.8 xlO7 ii
Nb3Al 18 3.2 x 107 r n
The theory of superconduction has been developed over many years, but Bardeen, Cooper and Schrieffer
CBCS) theory in 1957, published the first really satisfactory account of the mechanism. They showed
that superconductivity occurs when a special state of affairs exists between the conduction electrons.
Two electrons in free space will be mutually repelled by the Coulomb force between, but, in the
s°hd state, the force between the two electrons will be modified by the interaction of the electrons with
crystal lattice. In certain substances, the lattice interaction is so great that simple repulsive force
c°mes modified into an attractive force binding certain electrons together into what are called
0 Souna State Physics
Cooper pairs. For two electrons to become bound into a Cooper pair. They must be in the equilibrium
condition, i.e., with no current flowing, has equal and opposite momenta.
Those materials in which Cooper pairs can exist are the superconductors; but, it general, the
phenomena occur only at the lowest temperature when the thermal energy is not sufficient to disrupt the
binding. The Cooper pairs can drift through the crystal carrying current, and we shall see below that
there is no way in which the electrons in Cooper pair can be scattered. The current flow is thus resistance
less and the material is a superconductor.
There are two important principles which govern electron behaviour in an ordinary conductor:
Only certain energies are permitted, and no two electrons may be in the same state. Electrons may
nevertheless have the same energy if their momenta differ. If we consider a simplified, one-dimensional
solid, then two electrons with the same energy can have momenta of equal magnitude but of opposite
sign, i.e., one will be directed to the right and the other to the left. Under normal equilibrium conditions
with no current flowing, the energy levels will be filled from the bottom upwards, with the electrons of
opposite momentum in each level. There will be thus equal numbers of electrons moving to the left and
to the right, giving zero net electron drift.
When an electric field is applied to the solid, the motion of the electrons is modified. The electrons
have a net energy gain from the battery, and there will now be more electrons with momentum directed
to the right, say, than to the left, and a current is said to flow. Electrons with momentum to the right will
occupy energy levels up to a greater height than electrons with opposite momentum. Any of the electrons
may collide with a phonon, provided that the phonon energy, and the conditions of the collision are such
that the electron after collision, still has permitted values of energy and momentum. The phonons in the
material are, in general, moving at random, so that when a current is flowing, the effect of electron
collisions with phonons is to destroy the net momentum of the electrons in the direction of the current
flow. The effect of phonon collisions or resistance—when a current is flowing is thus to remove electrons
from high energy states with momentum directed to the right, to lower energy states with momentum to
the left. This process continues until the original equilibrium is restored with equal number of electrons
moving to right and left, i.e., until no current flows.
In the superconductor, the interaction of electrons and phonons is modified by the fact that the
electrons may no longer be independent, but may be bound together in Cooper pairs which can drift
through the material when current flows. If either of the electrons in a Cooper pair is to be scattered by
a collision, and its momentum in the direction of current flow changed, then, in addition to the ordinary
criteria concerning permitted energy and momentum before and after collision, the phonon must also
provide sufficient energy to break the bond holding the pair of electrons together. At sufficiently low
temperatures, the number of phonons in the material possessing sufficient energy to disrupt a Cooper
pair becomes very small, and such pairs may pass through the lattice without scattering, i.e., these
- electrons experience no resistance.
Some of the important properties of superconductors are the following:
1. The current in the superconductors persists for a very long time. This is demonstrated by placing
a loop of the superconductor in a magnetic field, lowering its temperature below T and then
removing the field. The current which is set up is found to persist for a long period without any
attenuation.
2. Superconductivity has normally been observed only for those metallic substances for which the
number of valence electrons Z lies between 2 and 8.
3. In all cases involving transition metals, the variation of T with the number of valence electrons
shows sharp maxima for Z = 3,5 and 7.
where. H is the maximum critical field strength at the temperature, T, Ho is the maximum critical field
strength occurring at absolute zero, and Tc is the critical temperature, the highest temperature fOr
superconductivity. Thus the above equation defines a curve which divides the normal region of the field
temperature diagram of the metal from the superconducting region.
The critical field curves for a number of pure metals are shown in Fig. 8.5. It is from these curves
that the surprising paradox of superconductivity arises. We shall consider it with reference to lead. At
absolute zero temperature, the critical field of lead is 650 A/cm. This means that in the absence of lattice
vibration, which has ceased at absolute zero, an increase in the energy content of the metal equivalent to
a field of 650 A cm-1 quenches superconductivity. The energy density is 240 Jm-3 or 10r7eV/atom.
Fig. 8.5 Variation of critical field as a function of temperature
By contrast, in zero magnetic field strength, the critical temperature of lead is 7.175 K, which
corresponds to a lattice energy about 8 x Ifr4 eV/atom. Thus we see that the magnetic energy required
to raise the electrons of lead from the superconducting to the normal state is only one-ten thousandth of
dial required to normalise the superconducting state by thermal energy. This is the paradox that any
successful theory of superconductivity must explain. To understand the origin of this phenomenon we
must briefly review the quantum electronic model of a metal.
The fact that a superconducting metal has no resistance means, of course, that there is no voltage drop
along the metal when a current is passed through it, and no power is generated by the passage of the
current This, however, is only strictly true for a direct current of constant value. If the current is changing
an electric field is developed and some power is dissipated. To understand the reason for this we must
first discuss briefly some aspects of conduction electrons in superconductors.
Superconditctiviiy 363
Fig. 8.4 (aj The critical magnetic fie id ai which superconductivity disappears
(b> Specific heal in superconducting and normal slated
5. Tie magnetic field does not penetrate into the body of the superconductor. The property known as the
Meissner effect, is the fundamental chaiacterization of superconductivity, However, when the mag*
netfc field B is greater than a critical value B (7). the superconductor becomes a normal conductor
(7) is zero at T= Te] and has the largest value at T ~ 0
6. Superconductivity occurs in materials having high normal resistivities. The condition > 10' is a
good criterion for the existence of superconductivity, where n-is the number of valance electrons per
cm1 and p is the resistivity in electrostatic units at 20*C.
7, When the current through the superconductor is increased beyond a critical value /£. (T)t the super
conductor again becomes a normal conductor,
8, The specific heat of the material shows an abrupt change at T - Tt jumping to a huge value for T< T
If one observes the total list of superconducting materials. the general features to be noted are:
(a) Mono v alent metaIs are gc nerally not su perconduciors.
(b) Ferromagnetic and antiferromagnetic materials are not superconductors.
(c) Good conductors at room temperature are not superconductors, and superconducting materials
are not very good conductors at room temperature as the normal metals
{di Amorphous thin films of Be, Bi and Fe show superconductivity.
(e) Bismuth, antimony and tellurium become superconducting under high pressure, However
exceptions are there,
IV. EFFECTS OF MAGNETIC FIELD

The superconducting state of a metal exists only in a particular range of temf>erature and field strength, Tiic
condition for the superconducting stale to exist in the metal is that some combinstfion of temperature and
field strength should be less than a critical value, Superconductivity will disappear if the temperature of the
specimen is raised above its Trt or if a sufficiently strong magnetic field is employed. The curves are nearly
parabolic and can be reasonably be represented by the relation.
Below the Inm*llhm Irdipcruture the conduction electron* di vlde into Iwo clewe*, Mirne behaving
ns superch'i inmx which can pax* through the metal without r«*i*lamc Mffrrinu no colli*i<m*/, the
remainder behaving as normal rlrclronit which can he scattered and no experience just like umdnction
electrons in a normal metal, The fraction of supc/eleclrons lipprnr* to decrease a* the temperature t*
raised toward* the transition temperature, At 0 K all conduction electron*, behave like supcrclecirmt*,
but, if ihe temperature is raised, a few begin to behave a* normal electron*, and on further hentinu the
proportion of normal electron* increases, Eventually, at the transition temperature, all the electron*
have become normal electron* and Ilie metal loses It* superconducting properties, Hence a superconductor
below its transition temperature appears to he permeated by two electron fluids, one of normal electron*
and one of superelcctrons, The relative electron density in the two fluid* depend* on the temperature,
This “two fluid model" is suggested by thermodynamic arguments based on the results of specific heat
and similar measurements on superconductors,
In a superconducting metal the current can in general be carried by both the normal and
superclectrons. However, in the special case of a constant direct current all the current is carried by the
superconducting electrons, We can sec that this will be so by noting that, if the current is to remain
constant, there must be no electric field in the metal, otherwise the superelectrons would be accelerated
continuously in this field and the current would increase indefinitely. If there is no field there is nothing
to drive the normal electrons and so there is no normal current. We sec, therefore, that for a constant
value of total current all the current is carried by the superelectrons, A superconducting metal is like two
conductors in parallel, one having a normal resistance and the other zero resistance. We can say that the
superconducting electrons .short circuit the normal electrons. To put this another way, if we suddenly
apply a voltage source, such as a battery, across a superconductor, the current tends to rise to infinity
but is in fact limited by the internal resistance of the source. While the current is changing, and electric
field must be present to accelerate the electrons. Electrons do, however, have a small inertial mass and
so the supercurrent does not rise instantaneously but only at the rate at which the electrons accelerate in
the electric field. If we apply an alternating field, the supercurrent will therefore lag behind the field
because of the inertia of the superelectrons. Hence the superclectrons present an inductive impedance
and, because there now is an electric field present, some of the current will be carried by the normal
electrons. The current is not, therefore, carried entirely by the superconducting electrons as in the d.c,
case. Of course, the normal electrons also have an inertial mass by their resulting inductive reactance is
completely swamped by the resistance resulting from their being scattered in the metal. We can, in fact,
represent the bulk properties of a superconducting metal by a perfect inductance in parallel with a
resistance.
The fraction of the current diverted through the normal electrons dissipates power in the usual
way. The mass of the electron is, however, extremely small, so the inductance due to their inertia is also
extremely small. The inductance in henry of a typical superconductor due to the inertia of its
superconducting electrons is only about 10"12 of its normal resistance in ohm, so at 1000 Hz, for example,
only about 1(T8 of the total current is carried by the normal electrons and there is only a minute dissipation
of power. Nevertheless, this contrasts with the absolutely zero resistance in the d.c. case.
If the frequency of an applied field is sufficiently high, however, a superconducting metal responds
in the same way as a normal metal. This is because, superconducting electrons are in a lower energy
state than normal electrons, but if the frequency of the applied field is high enough, the photons of the
electromagnetic field have enough energy to excite superconducting electrons into the higher states
i where they behave as normal electrons. This happens for frequencies greater than about 10" Hz. The
j behaviour of a superconductor at optical frequencies is therefore no different from that of a normal
metal and there is, for example, no change in the visual appearance of a superconductor as it is cooled
below its transition temperature.
VI. CRITICAL CURRENTS
The magnetic field which causes a superconductor to become normal from a superconducting «
need not necessarily by an external applied field, it may arise as a result of electric current flow jn tk
conductor. The minimum current that can be passed in a sample without destroying its superconductivih,
_____ ___ i________ _ t
is called critical tr - _____ c___ i:_______ r - -r.____ I---------------------------------------------------- „________ . ,
current /f. If a wire of radius r of a Type I superconductor carries a current /, there i
v
- is a
surface magnetic field. H, = 1/2 Jtr associated with the current. If Ht exceeds Hc, the material will g0
normal. If in addition, a transverse magnetic field H is applied to the wire, the condition for the transition
to the normal state at the surface is that the sum of the applied field and the field due to the current
should be equal to the critical field. Thus we have
H=H,+ 2H
H. =-±-=H -2H
= (82)
This is called Silsbee’s rule. The critical current Ic will decrease linearly with increase of applied
field until it reaches zero at H - HJ2. If the applied field is zero, Ic = 2nrHc.
It was assumed that the effect of a magnetic field on a superconductor would be as that in a metal.
However, in 1933 Meissner and Ochsenfeld measured the flux distribution outside tin and lead specimens
which had been cooled below their transition temperatures while in a magnetic field. They found that at
their transition temperatures the specimens spontaneously became perfectly diamagnetic, cancelling all
flux inside even though they have been cooled in a magnetic field.
This experiment was the first to demonstrate that superconductors are something more than
materials which are perfectly conducting; they have an additional property that a merely resistanceless
metal would not possess: A metal in the superconducting state never allows a magnetic flux density to
exist in its interior. That is to say, inside a superconducting metal we always have
B=0
whereas inside a merely resistanceless metal there may or may not be a flux density, depending on the
circumstances. When a superconductor is cooled in a weak magnetic field, at the transition temperature
persistent currents arise on the surface and circulate so as to cancel the flux density inside, in just the
way as a magnetic field is applied after the metal has been cooled. This effect, whereby a superconductor
never has a flux density even when in applied magnetic field, is called Meissner effect.
Suppose a magnetic field of flux density Bfl is applied to a superconductor. In order to neglect
demagnetising effects, we consider long superconducting rod with the field applied parallel to its length.
An applied magnetic field of flux density Bc produces in the material flux density equal to p,Ba, where
p. is the relative permeability of the material. Metals, other than ferromagnetic, have a relative
permeability which is very close to unity, i.e., pr = 1, so the flux density within them due to the applied
magnetic field is equal to Ba. However, as we have seen, the total flux density in a superconducting
body is zero. This perfect diamagnetism arises because surface screening currents circulate so as to
produce a flux density B/ which everywhere inside the metal exactly cancels the flux density due to the
B = g0 (Ha + M) (8.3)
where M is the magnetisation or intensity of magnetisation of the material. The magnetisation of a

superconductor, in which B = 0, must therefore be
M = -Ha
and the magnetic susceptibility
' z = M/Ha=-l (8.4)
This is the maximum value for the susceptibility of a diamagnet. In this sense a superconductor
is a perfect diamagnet. However, it must be noted that superconductivity is not only a strong diamagnetism,
but also a new type of diamagnetism.
Like the electromagnetic properties, the thermal properties—entropy, electronic specific heat, etc. of a
metal also change sharply as the temperature is lowered through the transition temperature of
superconductivity. We have shown that the Meissner effect shows that the transition in the presence of
magnetic field through the normal-superconducting (N-S) boundary Hc = Ho [1 - (77T.)2] is reversible,
and therefore, that the laws of thermodynamics also apply to (N-S) phase transition.
(/) Entropy
In all superconductors the entropy decreases markedly on cooling below the critical temperature.
We know that, entropy is a measure of the disorder

of a system and hence the observed decrease in entropy
between the normal state and the superconducting state tells
us that the superconducting state is more ordered than the
normal state.
For aluminium we observe that the change in entropy

is small and of the order of IO-14 kB per atom. The decrease
is entropy between the normal state and the superconducting
state means that some or all of the electrons thermally
excited in the normal state are ordered in the
superconducting state. It has been predicted that in simple
superconductors (Type I), there is a spatial order which fig. 8.7 Entropy of aluminium
extends over a distance of the order of IO-6 metre. This range is called coherence length. Entropy of
aluminium in the normal and superconducting states as a function of temperature is plotted in Fig. 8.7.
(//*) Specific Heat

The specific heat of the normal metal is seen to be of the form,
Su/v rcun du di v try 36"
density exactly equal in magnitude, but opposite in direction, to the flux density due to the applied magnetic
field To create a flux density of -U the magnitude of the cjreuht;ng >urface current per unit length must,
from ordinary solenoid formula. be j « -.
Fig .6,6 Magnc lic be’ ru tor ot a s upc. ri otiducto r.

(a)-(b) Specimen becomes resistance less in the absence of a magnetic field.
(c j Magnetic fiek I apf>1 ied to a superconduct i ng spec t me;i,
(d) Magnet i c Geld removed.
ip' i! ■ Specimen becomes superconducting in applied magnetic field.
(g} Applied magnetic field removed*
In ocher words j - where II. is the applied field strength,

We can, however, describe the /■( >feci diamagnetism in another way. Because we cannot actually
observe the surface screening currents which arise when a magnetic field is applied* we could suppose that
rhe perfect diamagnetism arises from some special bulk magnetic property of the superconducting metal,
and we can describe the perfect diamagnetism simply by raying that for a \u perconduct in:: metal, p, » 0, so
that the flux density inside, B = tu B r. is zero. Here we do not consider the mechanism by which the dia*
magnetism arises; the effect of the screening currents is included in the statement pr - 0. The strength H. of
ihc applied magnetic field is given by
K = b„h
and the flux density in a magnetic material is related to the strength of the applied field by
Cn(7) = Yr+p7* (8.5)
The first term is equation (8.5) is the specific heat of electrons in the metal and the second term
is the contribution of lattice vibrations at low temperatures. The specific heat of the superconductor
shows a jump at Te. Since the superconductivity affects electrons mainly, it is natural to assume that the
lattice vibration part remains unaffected, i.e., it has the same value 07$ in the normal and superconducting
states. On subtracting this, we notice that the electronic specific heat Cîs not linear with temperature.
It rather fits an exponential form
Ca(r)Âexp(-A/y)
CHAPTER 8
This exponential form is an indication of
the existence of a finite gap in the energy spectrum
of electrons separating the ground state from the
lowest state (Fig. 8.9).
The number of electrons thermally excited

across the gap varies exponentially with the
reciprocal of temperature. The energy gap is
believed to be a characteristic feature of the
superconducting state which determines the
thermal properties as well as high frequency
electromagnetic response of all superconductors. Fig. 8.8 Temperature dependence of the electronic
specific heat in the normal and superconducting states
(i/7) Thermal Conductivity
Prof. Hulm and others discussed the results of thermal conductivity in superconductors. The thermal
conductivity of superconductors undergoes a continuous change between the two phases and is usually
lower in the superconducting phase, suggesting that the electronic contribution drops, the superconducting
electrons possibly playing no part in heat transfer.
fig. 8.9 (<?) Conduction band in the normal state

• (b) Energy gap at the fermi level in the superconducting state E - 10‘4 eV
368 $OU0 State Physics
Mf - -................. - . - - - . . . . ■ - - - -■ ■ ■ ■■ ..................-........................................ .. . ____ _ _
The thermal conductivity of tin at 2 K is 34 W cm-1 K1 for the normal phase and 16 W cnr1 K~'
the superconducting phase. At 4 K, it is 55 W cm-1 K_| (At 4 K there is no superconducting phase for tjn
as T =3.73 K).
Fig. 8.10 Thermal conductivity of a specimen of tin in the normal and superconducting states
(iv) Acoustic Attenuation

When sound wave propagates through a metal, the microscopic electric fields due to the displacement
of the ions can impart energy to electrons near the Fermi level, thereby removing energy from the wave.
This is expressed by the attenuation coefficient, a, of acoustic waves. The ratio of a for superconducting
and normal state is given by
(8-7)
- 1 + exp (A/fcBT)
At low temperature
^-=2 [exp (~ A/kBT)]

(8.8)
MB
uAJ bi* a... i I Ilir tflWMMMi
MM
The heat capacity in the superconducting state varies with temperature in an exponential manner; that
is, it is of the form exp (- MkBT) with & = bkB Tc. where b is a constant. This indicates, in accordance
with the fact that the exponential form is compatible with the thermal excitation across a gap in eneigy,
that an energy gap may exist in the superconducting electron levels. The jump in the heat capacity at the
critical temperature Tc supports this idea of the existence of the energy gap further. See Fig. 8.9. The
energy gap in superconductors differs from the gap in semiconductors or insulators in a very fundamental
way. The energy gap in superconductors is often an entirely different nature than the energy gap in
ins„tatora because in (he Conner, the gap is
l0 (he Fenrn gas whereas in (he later (he san is ,iJ
t0 the lattice. In semiconductors, the Pan X
the flow of electrical current. Energy must u

(0 I,fl electrons Cron, the valence band into th,
conduction band before current can flow I„
superconductor, on (he other hand, current flows
despue (he presence of a gap. The energy gap h
effec. upon (he behaviour of the special electrons h °
CHAPTER 8
cany current
contam normal aelectrons as well.Superconductors
superconductor. and it is ,h‘ Fig. 8.11 A plot of the temperature dependence
electrons that are affected by the gap. * e of the energy gap parameter A(T). Note that A(T)
vanishes with infinite slope as T —> T leading to
the second-order phase transition
The existence of energy gap jn
superconductors has been confirmed by a number of experiments: Electron tunnelling observation across
the supercondueung junctions by Giaever being one of them. Some experiments have been employed
for the experimental determination of its value. From theory and ftom comparison with optical and
other methods of determination of gap, it is concluded that ' ' '
or (8.9)
2b is about 3.5 i.e., the gap decreases from a value of about 3.5 kRT at 0 K to zero at the transition
temperature. Values of energy gap of some selected superconductors are given in Table 8.3.
It has been observed that the critical temperature of superconductors vanes with raotoptc mass. Tire
observation was first made by Maxwell and others, who used mercury isotopes. To grve an rdea of .he
magnitude of the effect, for mercury Tc varies from 4.185 K to 4.416 K as the tsotoprcmass M vanes
from 199.5 to 203.4. The argument was that isotopic mass can enter in the process of the formation of
the superconducting phase of the electron states only through the electron-phonon mteractron.
In the early years of the developmentof the BCS theory the simple law
T ocM-P
c
with [J = + 0.5 was thought to be valid for most materials.
IWc 8.3 Energy gap al 0 K tor some superconductors
Element Eg (0) in 10"4 eV TJX) £J0)

[2d (0)] kBTc
Niobium 30.5 9.5 3.7
Aluminium 3.4 1.2 3.3
Tantalum 14.0 4.48 - 3.6
‘ Tin 11.6 3.72 3.6
Lead 27.3 7.18 4.4
Mercury 16.5 4.16 4.6
73 nc 2.4 0.9 3.1
Gallium 3.3 1.09 . 3.5
Thus T M+P = Constant 2

c
However, later significant departures from the value of p have been observed;
Both the transition and the critical magnetic field of a superconductor are found experimentally to be
slightly altered if the material is mechanically stressed. Many of the mechanical properties of the
superconducting and normal states are thermodynamically related to the free energies of these states,
and the critical magnetic field strength depends on the difference in the free energies of the two states,
there is an extremely small change in volume when a normal material becomes superconducting, and
the thermal expansion coefficient and bulk modulus of elasticity must also be slightly different in the
superconducting and normal states. It is possible to derive expressions for these effects by straightforward
thermodynamic manipulation, but the effects are extremely small and hence not considered here.
In 1935, F. London and H. London described the Meissner effect

and zero resistivity by adding the two conditions E = 0 (from the
absence of resistivity) and B = 0 (from Meissner effect) to
Maxwell’s electromagnetic equations. According to them, the
applied field does not suddenly drop to zero at the surface of the
superconductor, but decays exponentially according to the equation,
H= exp (- xft) (8.10)
where Ho is the value of magnetic field at the surface and k is a

characteristic length known as the penetration depth1, 1 is the
distance for H to fall from Ho to (HJe).
Ilie magnetic field and surface current are likely to penetrate a superconductor to a depth of
i(X) nm. If a superconducting film or filament is thinner than this, its properties are significantly
Afferent from those of the bulk material. In particular, the value of the critical magnetic field increases
ihe thickness decreases, and the special property of type II superconductors arise from this.
Titus the presence of surface currents and associated magnetic fields will obviously have a
)found effect on the properties of thin film superconductors, or indeed of any superconductors whose
^tncnsions are comparable to the penetration depth. The values of X for some superconductors are
mven in Table 8.4.
CHAPTER «
ruble 8.4 Penetration depth at 0 K
Superconductor X (in nm)

Mercury 70
Indium 64’
Lead 39
Tin 50
Aluminium 50
The penetration depth does not have a fixed value but varies with temperature, as shown in
Fig. 8-13. At low temperature it is nearly independent of temperature, however, the penetration depth
increases rapidly and approaches infinity as the temperature approaches the transition temperature. The
variation of penetration depth with temperature is found to fit very closely the relation,
(8.11)
where
XIII/TYPE Ta^^WIT^P^^ ~~
Superconductors are classified as soft (Type I) and hard
(Type II) superconductors. A superconductor which
. exhibits complete Meissner effect is called Type I. The
magnetisation curve for Type I material is shown in
Fig. 8.14 (a) and that for Type II material in Fig. 8.14 (b).
It is somewhat disappointing that the critical fields
of superconductors are so low, because one of the early
hopes was to use superconducting wires to produce high
magnetic fields needed in many applications. Since a
supercuirent once started continues to flow steadily
w<thout heat losses, it was thought that magnetic fields
Could be produced and maintained without any loss of
T(K)
energy. This is true, but if the magnetic field produced Fig. 8.13 Variation of penetration depth in tm
You
exceeds Hc the material goes normal, and the current cannot be sustained by itself. This was noted
1916 by Silsbee, and is known as the Silsbee effect. Since Hc is typically 0.1 T or less, high rnagnJn
fields cannot be produced this way. It turns out however that there is another class of superconductor0
which can exist in a mixed state, with superconducting and normal regions in a very interest!
arrangement. These type II superconductors partially admit magnetic flux, and have zero electri
ca]
resistance. Some of these are used for producing steady magnetic fields of the order of 10 T.
(fc) Magnetisation curve for Type II superconductors
Type II superconductivity was discovered and recognised as a distinct phenomenon by Schubnikov

and co-workers in the 1930’s. He studied the superconducting properties of alloys. The B-H curve for
a lead-indium alloy with 2% indium, at a temperature of 1.5 K (Tc = 7.1 K) has several striking features.
Up to about 0.065 T, there is a complete flux expulsion ( Meissner effect). This field is significantly ..
lower than the critical fields of lead, namely 0.08 T. For Ba = Ha > 0.065 tesla the magnetic field is
not completely excluded; there is an incomplete Meissner effect which disappears at about 0.16 T. The
magnetic field then penetrates fully and the normal resistance is restored. The region 0.065 T <
Mo Ha < 0-16 T in this case can be obviously thought of magnetically as a mixed phase, but electrically j
as a superconductor. On reducing Hc to zero, B does not go to zero, but a residual value. ;

Type n superconductors are indeed a new kind of magnetic phase. They are characterised by a J
lower critical HCi field at which magnetic flux begins to enter the superconductor and an upper critical
electrical field HC1 at which superconductivity disappears. The magnetic field penetrates in the form of •
quantised flux tubes. It is found that whether a superconductor is Type I or Type II depends on whether
the superconductor normal interface energy is positive or negative. The retention of magnetic flux is
▼
er a nonequilibrium phenomenon. The magnetic phase diagram of a Type II superconductor is
ôwn in Fig- 8.14- These predictions spurred the search for materials with high HCi. Many such materials
S -e synthesised, and after years of development effort, made into wires and tapes for stable high field
^conducting ma8nets' I*turns out ât new C0PPer oxide superconductors are extreme Type II
terials with an of order 150 T. A material can change from Type I to Type II on the substitution
o/some impurities. For example, lead is a Type I superconductor with Hc = 4.8 x 104 A/m at 4 K. When 2
indium is added to it, it becomes as Type n superconductor with HCt = 3.18 x 104 A/m and HCt = 7.96
x 104 A/m. On adding 20 wt% of indium in lead, HCi = 5.6 x 103 A/m and HC2 s 2.9 x 105 A/m. ’
CHAPTER 8
The London theory is based on rather the old ideas of the two fluid model, according to which a
superconductor can be thought to be composed of both normal and superfluid electrons. The Maxwell’s
electromagnetic equations are inadequate to explain the electrodynamics of superconductors, namely,
the zero resistance state coupled with perfect diamagnetism. The London brothers in 1935 derived two
field equations though successful in explaining the two important experimental facts about
superconductors, do not give any insight into the underlying electronic process in superconductors
anything more than what Ohm’s law does for normal conductors. In this respects London’s theory is
purely macroscopic.
According to London’s theory, it is assumed that there are two types of conduction electrons in
a superconductor, namely, the superelectrons and the normalelectrons. At 0 K a superconductor contains
only superconducting electrons, but as temperature increases the ratio of the normal electrons .to
superconducting electrons increases, until at the transition temperature all the electrons are normal. At
any temperature the sum of the superconducting electrons and the normal electrons is equal to the
conduction electron density in the material in the normal state. The superconducting electrons are not
subjected to any lattice scattering and therefore are merely accelerated in electric field.
Let nn Nn and ns v? be respectively the density, and velocity
of the normal and superfluid electrons. If n is the number of electrons
/n3 then on the average
n=n +n ' -
ns .
The current density is given by

. J = J_n + Js = en_v
ft n
+ env
s s
(8.12)
In a superconducting metal the superconducting electrons
encounter no resistance to their motion, so, if a constant electric
field E is maintained in the material, the electrons accelerate steadily
under the action of this field.
The equation of motion for the superconducting electron is
Fig. 8.15 Magnetic phase diagram
m(dvjdt) = eE of a type II superconductor
mN.a = <?E
You
The supercurrent density is

dvt
JT = ensvs and (djjdf) = (ens)
dt
ie., jr = nseV j = (ne2E)/m (8.13)

This is the first London equation which describes the absence of resistance. Since no electric
field is necessary unless the current changes, it becomes possible to have steady currents in the absence
of electric field. This is the superconducting phenomenon. The corresponding equation for the normal
current is
n n
= o E = —- -
—
m
(8.14)
This equation says that an electric field is necessary for establishing a steady current. If E = 0, J
becomes zero unlike the superconducting state.
A magnetic field is related to an electric field and current by Maxwell’s equation as
B = -curlE=-g0H (8.15)
Again from Maxwell’s equations, .
curlH = J+D - - ... (8.16)

■> * , _
Now, curl B = ^(Js + D) (8.17)

where JS is the current density within the metal. Furthermore, unless the fields are varying very rapidly
with time, the displacement current D is negligible in comparison with Jr Hence inside a superconductor
we can write Maxwell’s equations in the form
B = - curl E (8.18)
and curl B = pT)JJ (8.19)
Substituting from equation (8.13) into equation (8.18), one gets
B = - (m/nse2) curl (8.20)

and we can eliminate J, by means of equation (8.19), we get
B =- curl curl B (8.21)
Thus, B = - a curl curl B with a = —^—5- (8.22)

lt0M2
or curl curl B = grad div B - V2 B , (8.23)
but from Maxwell’s equations div B = 0, so equation (8.22) becomes
B = aV2 B
*
or V2B = — (8.24)
a
You
This is a differential equation which B must satisfy.

In order to study the implication of this, consider the plane
boundary of a superconductor with a uniform magnetic
field applied parallel to the boundary (Fig. 8.15a).
Suppose that the flux density outside the metal is Ba and
let the direction normal to the boundary be called the x-
direction. Because the applied field is uniform, B will
have the same direction everywhere, so may regard
CHAPTER 8
equation (8.24) as a scalar one; also there will be no
gradients of the field parallel to the boundary, so in this
fig. 8.15 (a) Magnetic field applied parallel
case equation (8.24) reduces to to the boundary of the superconductor
d2B _ B
dr2 a
The solution of this equation is of the form
• •
B(x)= Ba exp(~x/va) (8.24a)
where B (x) is the flux density at a distance x inside the metal and Ba is the value of B outside the metaL
This means that B dies away exponentially as we penetrate into the superconductor. In other words,
changes in flux density do not penetrate far below the surface, so at a sufficient distance inside the metal
the flux density has a constant value which does not change with time, irrespective of what is happening
to the applied field. ■ _ --
We have deduced the above behaviour by applying the usual laws of electrodynamics to a
conductor with zero resistance; however, though equation (8.24a) completely describes the magnetic
properties of perfect conductor, it does not adequately, describe the behaviour of a superconductor. Hie
Meissner effect shows that inside a superconductor the flux density is not only constant but the value of
this constant is always zero; so not only B but B itself must die away rapidly below the surface.
F. London and H. London suggested that the magnetic behaviour of a superconducting metal might be
correctly described if equation (8.24) applied not only to B but B itself,
(8.25)
The solution is of the form [Refer equation (8.24a)]

B(x) = Baexp (-x^/a) (8.26)
Examination of the argument by which we derived [equation (8.24)] shows that we could have
derived equation (8.25) if everywhere we had replaced B by B. If we retrace the argument, we arrive at
equation (8.20) which would now have the more restrictive form
curl J (8.27)
This equation and equation (8.13), namely
= —E (8.28)
m
which together describe the electrodynamics of the supcrcurrent are known as London equations. Equati^
(8.28) describes the resistancclcss property of a superconductor, there being no electric field in the
metal unless the current is changing; and equation (8.27) describes the diamagnetism. For a one-
dimensional case equation (8.25) lakes the form
d2B(x) B(x)
Ox2 ~ a
where, B(x) is the flux density at a distance x inside the metal. This equation has the solution
B(x) = Bfl exp (-x/a/cx ) (8.29)
where, Bfl is the flux density of the applied field at the surface. Equation (8.29) indicates that the flux
density decays exponentially in a superconductor, falling (lie) of its value at the surface at a distance
x = Va. This distance is called the London penetration depth, X.
Now a = m/\itfvse2, so the London penetration depth
X. will be of the order of 1 nm.

We can now write the London equations (8.27) and (8.28) as
(8.31)
(8.32)
p0X2
London equations do not replace Maxwell’s equations, but are additional conditions obeyed by
the supercurrents. The penetration depth is found to depend strongly on temperature and to become
much larger as T approaches Tc. At low temperatures, it is nearly independent of temperature and has a
■ value Xq characteristic of the particular metal. Above about 0.8 of the transition temperature, however,
the penetration depth increases rapidly and approaches infinity as the temperature approaches the
transition temperature (see Fig. 8.13). The observation can be fitted well by a simple expression of the
form.
This equation implies that

‘t
density of superconducting electrons increases from zero at

at absolute zero.
1( the most general case the total current J is the sum of a
^'"unent and a supercunent
The normal current need only obey Maxwell’s equations and
Ohn*laW
CHAPTER 8
Fig. 8.16 Variation of flux density at
is conductivity associated with the normal electrons. We the boundary of a
BK>w"bring together the special equations which apply to a superconducting metal.
(8.35)
(8.36)
(8.37)
(8.38)
In the steady state, when fields and currents are not changing with time, the only current is the
supercurrent, i.e., Jn = 0, and we need only employ the London equations (8.37) and (8.38).
These lead to
(8.39)
The behaviour of superconductors in d.c. fields is given by the equation (8.27)
curl J = - B =- go”jg2H
(8.40)
m m
Under high frequency fields even the superconducting electrons have to be accelerated, since
y ve to change directions on the reversal of the field. They therefore introduce a reactive impedance,
nowFeSence which ‘unmasks’ the normal conducting electrons in the superconductor, since there are
w electric fields in the material. We start with Maxwell’s equation:
You ,$|78 Sows Simi Fmwa
c/1)
curl H ■ Jn + Jf +
dt
and equation (8.38) gives
<4J, _ E
dt p0X2 («42)
Let us assume that fields and currents are sinusoidal. That is

Jr = J() exp (/cor) and H = Ho exp (Zcoz)
,. d}3 . dH , „
and hence = ico J,; —- = /CoH
dt ’ dt
u'coj|_ dt ,
Substituting for (djjdt) from equation (8.42), one gets
J (8.43)
' zcop0X2 cop0V
Further from D = Do exp (/’co?)

dD
one gets ~7~ ~ZcoD (8.44)
dD „
i.e., — = z'co e E (8.45)
dt
with D = eE
Also for normal current density we know that,
J„ = a,E
Substituting the values of Jn, J, and (dD/dt) in equation (8.41), we get
tE
curlH - Gn E + i(o e. E -
<0%2|i0
=E + i<oe-(i/<opol2)}
Taking curl on both sides,

curl curl fi » curl E [an + ko e - (i/copyX,2)]
- V2!! - curl E (a„ + /to e - (//topoX2)]

dH
Putting curl E = - g0— , one gets
at
curl E = - |1O (dH/dZ) = - (za)|i0) H

Thus the above equation can be written as
V2H = icop,o [nn + (cue - (z7co|i0X2)] H
or (8.46)
H/X2 represents the field penetration due to supercurrent and - (02|10e H represents the field
penetration due to the displacement current.
cogo<5n H represents the field penetration due to eddy currents.
(i) For d.c. fields (to = 0) the last two terms of equation (8.46) reduce to zero and we get
which is the same as predicted by London theory.

(m) At microwave frequencies, frequency w will be sufficiently high and the wavelength 1 will
be small so that
,co2 1
CD LL.E = —5- as C= r=
4k2u2 4it2
Thus 2
c2
will be negligible compared with the other two terms. Thus equation (8.46) becomes
r 1
V2H = + ^0O„ H (8.47)
A2
The penetration depth X and a.c. skin depth 8 are related by
giving
which predicts that when frequency is sufficiently high, 8 is small; and penetration depth X becomes
larger compared to skin depth 8. With X > 8, we infer that Jn > Js or normal current predominates. This
implies that at high frequencies, superconductors behave like normal conductors. i.e., above microwave
frequencies the London theory is found to be inadequate.
Yoi MMS
ÊTfiERMObYNAMiCS SFSU^gfeCdKbjJCTQBS? ....

*■■ i i..* —I .. ..^ . .... .... — . .... .m.
The Meissner effect suggests that the transition between the normal and superconducting states is
thermodynamically reversible, just in the same way the transition between liquid and vapour phases of
a substance is reversible under the conditions of slow evaporation. This is because the superconducting
currents do not die away with the production of Joule heat when superconductivity is destroyed by the
application of a magnetic field. Van Laer and Keesom confirmed this nature of the transition
experimentally. We may therefore apply thermodynamics to the transition, and thereby obtain an
expression for the difference of entropy between the normal and superconducting states in terms of the
critical field curve Hc vs T. We treat only Type I superconductors with a complete Meissner effect, so
that B = 0 inside the superconductor. We may thus apply the laws of thermodynamics to N-S phase
transition, and thereby obtain an expression for the entropy difference between normal and
superconducting states in terms of the H and T.
Though the free energy density gn of a metal in the normal state is independent of the strength of
the applied magnetic field say Ha, the application of a magnetic field raises the free energy density g of
ii
the metal in the superconducting state by an amount Fo-a-. The critical field Hc is that field strength
winch would be required to raise the free energy of the superconducting state above that of the normal
state. Hence the difference in free energy between the normal and superconducting state, in an applied
(8.48)
The Gibbs free energy, G is

G(T,p)=U-TS+pV ' (8.49)
The free energy of a magnetised body is given by the relation,

G=U-TS+pV-nâM (8.50)
where U — internal energy
S = entropy
p = pressure
V = volume
- applied field strength
M = magnetic moment
When the temperature is varied by an amount dT (keeping pressure and field constant), there
will be a change of free energy,
dG = dU-TdS+ SdT+pdV-\LQHa dM (8.51)
But, by first law of thermodynamics,
dU=TdS-pdV+y^Ha dM (8.51a)
So, dG~-SdT and hence S = -1 I

p>
Hence entropy for unit volume is given by
s=- ( (8.52)
Yol 381 Soup State Physics
- -- . . . . -. _ _ 1 - , _ . r _ _ ■_....- . _ - . - - - - ■ .... —-- -
change in entropy and therefore no latent heat. The second condition follows from the fact that the
specific heat of a material is given by
ar
arj
with v the volume per unit mass, so the different in the specific heats of the superconducting and normal
states can be obtained from equations (8.53)
d Hr (dHc V
C-C------ r-+v7U0 —“
j n c dT2 dT J
Since at the transition temperature, H - 0 and so we have for the transition in the absence of an
applied field,
(dHc\
C - C = vT ~dT )T (8.56)
s n c *^0
This is known as Rutger’s formula, and it predicts the value of the discontinuity in the specific
heat of a superconductor at the transition temperature. If v = 1, then
(8.57)
. Since the right-hand side of equation (8.56) should be a finite quantity, it is clear that if the metal
is cooled or warmed in the absence of magnetic field, there
must be a discontinuity in the specific heat at the transition
temperature. This has been experimentally found to be so. For
example, the specific heat of tin with 4% bismuth is found to
be discontinuous at T= Tc as shown in Fig. 8.18.
We note from equation (8.57) that when H = 0
but at lower temperatures when superconductivity is destroyed

in a magnetic field, the sign C-Cn must change corresponding
to the fact that Sn- Ss passes through maxima. It is found that
electronic specific heat increases exponentially with
temperature unlike that of normal metals for which the Fig. 8.18 Specific hear variation with
electronic specific heat varies linearly with temperature. temperature for bismuth in two phases
Just as medical researchers want to know how a virus attacks a body cells to cause a fever or inflammation,
physicists wanted to know what makes the electrons in a superconductor behave in such an unusual
fashion. The Bardeen, Cooper and Schrieffer (BCS) theory provides just this sort of explanation for the
symptoms of superconductivity.
3 S3
(8.33)
Since the critical magnetic field decreases with

JR
increase of temperature, - - will be negative and hence
the R.H5 of the above equation must be positive. Thus

we have been able to deduce rhat the entropy of the
superconducting state is less than that of the normal
state, i.e. the degree of order in a superconducting slate
is much higher than that tn the normal state. This con
clusion is in total agreement with BCS microscopic
theory of superconductivity where in a superconductor
'condense' into a highly correlated system of elec mm
pairs. The critical field //, falls io zem as the tempera
ture is raised towards Tf, The entropy difference 8.17 Free energy as a function of the magnetic
between the normal and superconducting steles field m tte normal and the superconducting state*
vanishes at this temperature. Furthermore, by the third law of thermodynamics, S', must be equal to 5. at 7‘-
0 K. From the observation that the entropies of the superconducting and normal states muit be ihc same at T
- 0 A', we can deduce from Eqn (8,53) that, since (be critical field.
Ht is not zero, - ■? must be zero at 0 K. This is in accordance with the experimental observation that for all
superconductors,, the slope of Ht versus Tcurve (Fig. 8.4J appears to be zero as the temperature approaches
OK.
Specific Heat
Many physical properties of supereunducUMs have been understood from a study and the measurement of
their specific heal The solid curve in Fig, 8.4 shows how the specific heat of a typical type 1 superconductor
varies with temperature in the absence of any applied magnetic field* The corresponding curve for the nor
mal can be obtained by making measurements in an applied field strong enough to derive the super
conductor into a normal state, lire general expression for entropy is
(8.54)
Hence for a mpercortducri ng-normal transition at Tt
(8.55)
A phase transition which satisfies the condition is known as second-order phase transmon. A second order
transition has two important characteristics: at the transition there is no latent heat, and there is a jump in the
Copy ri g hi ed fn aleri $ I
The BCS theory in fact proposes a microscope mechanism that takes place within a superconductor
that leads to all the diverse phenomena we have been talking about to this point. Although a complete
counting of the theory requires sophisticated mathematical formulation, its most profound physical
insights can be explored on a more accessible level. The superconductivity energy gap and the evidence
of long-range electronic order both pointed out that the electrons in a superconductor are somehow
bound together. They want to act in unison. The question is what brings them together. Getting electrons
together requires a special mechanism because they are negatively charged particles. By their very
nature they repel one another. We call this interaction, the coulomb force, which is repulsive between
like charges. Sophisticated theories of the electronic properties of metals showed that such forces are
CHAPTER 8
tempered in the confines of a crystalline lattice; the influence of the positively charged ions in the lattice
acts as a screen against the coulomb forces between electrons.
Thus the theory of superconductivity must furnish a mechanism by which electrons can cooperate
with each other when electrical forces drive them apart. The right mechanism was proposed by Herbert
Frohlich in 1950. He suggested that the ions in a superconductor—the crystalline lattice itself must
participate in the interaction of the electrons. In otherwords, superconductivity does not come about
from a strictly electron-electron interaction but rather from an electron-phonon interaction. Phonons are
a fancy quantum mechanical name for the natural vibrations of the crystal lattice in a solid. The disruption
of the crystal lattice caused by moving ions causes ordinary resistance in metals. Raise the temperature;
the ions increase their motion. This increased motion brings more obstacles for passing electrons and
the resistance goes up. If we describes the process in particle terms, we say that the electrons interact
with phonons, so that the electron-phonon interaction causes resistance.
But now we are saying that electron-phonon interaction causes superconductivity as well. There
seems to be something self-contradictory about the same effect causing resistance and loss of resistance
in metals. The fact that the superconductors are always poor ordinary conductors and the best ordinary
conductors do not become superconductors provides evidence for the role of the lattice in
superconductivity. However, only a very compelling experimental result in 1950 convinced skeptics
that the electron-phonon interaction was indeed the mechanism responsible for superconductivity.
Momentum measures mass in motion. A fundamental law of kinematics states that when two
objects collide, momentum is conserved. This means that if we add together the momenta for the two
objects to find the total momentum for the pair, it will be the same before and after collision. The
momentum of each individual object can change but the sum of the two always gives the same answer.
Thus when a large truck crashes into a small car, the car lurches violently while truck barely slows. The
truck has transferred some of its momentum to the car, which, being lighter, gains more velocity than
the heaviour truck loses.
It is found useful and convenient to analyse the interaction between an electron and the lattice as
a collision between two particle: An electron and a phonon. Such a description proves useful because
collisions between electrons and phonons obey the same momentum laws as collision between cars and
trucks. A strong electron-phonon interaction appears to be favourable both to superconductivity and to
”*gh resistance. The best ordinary conductors—silver, gold and copper do not become superconductors.
Their very low resistance results from a weak electron-phonon interaction; the electrons in silver, gold
and copper are less likely to interact with ions than the electrons in other metals. However, a weak
c cctron-phonon interaction means that superconductivity is unlikely to occur. The flip side of this
argument holds as well. The best superconductors tend to be rather poor ordinary conductors because
eY have strong electron-phonon interactions.
3 SotlD Si at tr PHYSICS
The kind of lattice vibrations that cause resistance that is, the phonons which are responsible are
called thermal phonons because they are stimulated by temperature. They occur at random and impart
random momentum to passing electrons. The phonons that take part in superconductivity, on the other
hand, do not owe their existence to thermal agitation of the lattice. The distortions of the lattice we are
talking about are short-lived phenomena that come into being specially to enable the attractive electron-
electron interaction to take place. Nevertheless, both thermal phonons and the so-called virtual phonons
that bring about superconductivity are just vibrations of the ions in the metal, differing in how and when
they occur. We have solved a key problem in the theory of superconductivity, namely how to attract
electrons to one another. The theorists needed additional insights to fill in the missing steps between
such attracted electrons and superconductivity. The two time recipient of the Nobel Prize in physics
John Bardeen invented the transistor in 1947, thus initiating the modem electronic revolution. In later
years he was responsible for key concepts in the development of the photocopy machine. In 1950,
however, he turned his attention to the theory of superconductivity. He constructed a theory relating
superconductivity to the electron-phonon interaction, duplicating Frohlich’s results using a different
theoretical picture of superconductivity.
Superconductivity occurs because the superconducting state has lower energy than the normal
state. The theory of superconductivity had to provide a mechanism for this energy lowering. Leon
Cooper took the next significant step in developing the theory of superconductivity in 1956 by calculating
what happens when two electrons are added to a metal in the presence of an attractive interaction of the
sort we have been discussing.
According to classical physics, any two particles, no matter how weakly attracted, can form a
bound state, lower in energy. In contrast, tightly bound quantum mechanical particles have large average
velocities and thus large energies of motion. Unless the attractive binding energy, is sufficient to overcome
this kinetic energy, no bound state will be formed. This was the puzzling aspect of superconductors. The
attractive interaction brought about by phonons was far too weak to produce a bound state.
What Leon Cooper was able to show was that in the presence of an attractive interaction, no
matter how weak, two electrons added to the Fermi sea will form a bound pair. Even though the kinetic
energy of the added pair is higher, the overall energy of the system is lowered by the formation of the
bound pair. This implies that the Fermi sea is unstable against the formation of bound pairs—it wants to
form them because the energy of the system could be lowered by taking two electrons of a given energy
from the top of the sea and putting into a bound state formed from energies above the sea. The presence
of the electrons of the Fermi sea allows this to happen; two isolated electrons in the presence of a weak
attractive interaction could not form a bound state. The interaction that attracts the electrons to one
another can be viewed as a scattering event involving two electrons and a phonon. The same sort of
scattering occurs when two billiard balls collide; they go off in new directions. Here is how we describe
the electron-phonon as a scattering event. The first electron collides with a phonon (it interacts with the
lattice), transfers some of its momentum to the phonon (it distorts the lattice), and gets scattered into a
new trajectory. The second electron then collides with the same phonon (it runs into the distorted part of
the lattice), picks up .the momentum originally given up the first elecfron, and also gets scattered into a
new trajectory. As long as the energy difference between the electrons is more than the binding energy
of the pair, such scattering events will lower the energy of the system. Within these restrictions, the trick
is to minimise the number of scattering events to maximise the energy lowering of the system.
Cooper showed that the energy lowering from the formation of a bound state will overcome the .
additional kinetic energy of the electrons when the electrons of a pair have equal and opposite momentum.
What does this mean? An example of two objects with equal and opposite momentum are a half-ton
of wave vector emits a virtual phonon q which is absorbed by an electron K2. is thus scattered
- q and K2 as K2 + t/.The process being a virtual one, energy need not be conserved (the phonoj
involved arc called virtual phonons because, as a consequence of uncertainty principle, their very shop,
life renders it unnecessary to conserve the energy in the process). In fact the nature of the resultin
electron-electron interaction depends on the relative magnitudes of the electronic energy and phonos
energy (M)). If this phonon energy exceeds electronic energy, the interaction is attractive.
The fundamental postulate of BCS theory is that the superconductivity occurs when such an
attractive interaction, mentioned above between two electrons, by means of a phonon exchange, dominate
the usual repulsive interaction. Two such electrons which interact attractively in the phonon field are
called a Cooper pair. The energy of the pair of electrons in the bound state is less than the energy of the
pair in the free state (electron separated). The difference of the energy of the two states is the binding
energy of the Cooper pair and should, therefore, be supplied this energy if the pair is to be broken. At
temperatures less than the critical temperature, electron-lattice-electron interaction is stronger than
electron-electron coulomb interaction, and so the electrons tend to pair up. Pairing is complete at
T ~ 0 K and is completely broken at a critical temperature.
The energy difference between the free state of the electron (i.e., energy of individual electron—
a case of normal state) and the paired state (the energy of paired electron—a case of superconducting
state) appears as the energy gap at the Fermi surface. The normal electron states are above the energy
gap and superconducting electron states are below the energy gap at the Fermi surface. Energy gap is a
function of temperature unlike to the case of constant energy gap in insulators and semiconductors.
Since pairing is complete at 0 K, the difference in energy of free and paired electron states (i.e., normal
and superconducting electrons states) is maximum or in other words energy gap is maximum at absolute
zero. At T = Tc, pairing is dissolved and energy gap reduces to zero. Across the energy gap there are
many excited states for the superconducting Cooper pairs. BCS theory thus predicts many electron
ground states as well as excited states for the superconductor in the range 0 to Tc and in these states
Cooper pairs are supposed to be in condensed state with a definite phase coherence. At the critical
temperature, this coherence disappears and the pairs are broken resulting in the transition of
superconducting state to normal state.
Coherence Length
The paired electrons (Cooper pairs) are not scattered because of their peculiar property of smoothly
riding over the lattice imperfections without ever exchanging energy with them. The concept of coherence
is the idea that superconductivity is due to the mutual interaction
and correlation of the behaviour of electrons which extend over
a considerable distance. The maximum distance up to which the
states of pair electrons are correlated to produce superconductivity
is called coherence length £0. The paired electrons can be many
thousands of atomic spacing (say 0.001 nm) apart. The properties
of a superconductor depend on the correlation of electrons within
a volume of called the coherence volume. It is because the
large number of electrons in such a volume act together in Rg. 8.19 Electron-electron inteaction
superconductivity that the transition is extremely sharp-other through lattice phonons
statistical fluctuation would cause broadening.
The ratio of London penetration depth to the coherence length is
the momenta ate equal and opposite, lite largest number of energy lowering scattering processes can occur
between electrons of equal and opposite momentum. Such bound electrons of equal and opposite momenta
behave been known as Cooper pairs. Cooper pairs are the second key element in the theory of supercon
ductivity. Io his paper Cooper considered the artificial case of two new electrons added to a metal. The task
awaiting BCS was to treat the case of 10?* etectroos/nr already present in a metal*
XVIIL BCS THEORY

The microscopic theory put forward by Bardeen, Cooper and Schrieffer (BCS), in 1957 provides the better
quantum explanation of superconductivity and accounts very well for all the properties exhibited by the
superconductors* This theory involves the electron interactions through phonons as mediators. The qualita
tive description of the theory is given below*
The basis of the formulation of BCS theory are the two experimental conclusions namely the isotope
effect and the variation of specific heat of superconductors* For isotope effect = constant, one can
infer that the transition resulting in superconducting state must involve the dynamics of ion motions, lattice
vibrations and phonons* Further we note that Tc attains a value zero when M approaches infinity. This all
suggests that non zero transition temperature is a consequence of rhe finite mass of the ions which can con
tribute phonons by their vibrations. Frohlich and Bardeen, in 1950, pointed out that an electron moving
through a crystal lattice has a self energy accompanied by virtual phonons. This means that an electron
moving through the lattice distorts the lattice and the lattice in turn acts on the electron by virtue of electro
static forces between them. The oscillatory distortion of the lattice is quantized in terms of phonons and so
one can interpret the interaction between the lattice and electron as the constant emission and ne-absorption
(rreotton and annihilation} of phonons by the latter* These are called virtual phonons because as a conse
quence of uncertainty principle their very short life time renders it unnecessary to conserve the energy in the
process. Thus one can think of the electron moving through the lattice, as being accompanied, even nt OK,
by a cloud of virtual phonons. In turn, this is inversely proportional to the lattice mass so that a condensation
energy equal ro this seif energy would have the correct mass dependence indicated by isotope effect.
BCS showed that the basic interaction responsible for superconductivity appears to be that of a pair of
electrons by means of interchange of virtual phonons. The accomplishments of the quantum theory of
superconductors due to BCS are now discussed.
Suppose an electron approaches a positive ion core* ft suffers attractive coulomb interaction* Due to
this attraction, ion core is set in motion and consequently distorts the lattice. Smaller the mass of the positive
ion core, the greater will be ihe distortion. Suppose towards that ride another electron comes and sees this
distorted lattice. Then the interaction between the two, the electron and the distorted lattice occurs which in
its effect lowers the energy of the second electron* Thus we interpret that the two electrons interact via the
lattice distortion or the phonon field resulting in the lowering of energy for the electrons* The lowering of
electron energy implies that the force between the two electrons is attractive* This type of interaction is
called electronTattJce-electron Interaction. This interaction is strongest when the two electrons have equal
and opposite momenta and spins.
Since the oscillatory distortion of lattice is quantized in terms of phonons, the above interaction can
be interpreted as the electron-electron interaction through phonons as toe mediator. Let an electron of wave
vector emits a virtual phonon q which is absorbed by an electron K'rX\ is thus scattered as JfL - ? and jf,
as Kj ♦ <?. The process being a virtual one, energy need not be conserved (the phonons involved are called
virtual phonons because, as a consequence of uncertainty principle, their very short life renders it unneces
sary to conserve the energy in the process). In fact the nature of the resulting electron-electron interaction
number For Type I superconductors k < 1/ V2 and Type II superconductors k > 1/^2. From BCS
a
theory
it is shown that intrinsic coherence length (£$) is related to the energy gap as
2A
where 2A is the energy gap and vF is the Fermi velocity.
A more refined form of this equation is
It has also been shown that the gap decreases from a value of about 3.5 kB T at 0 K to zero at Tc.
The accomplishments of the quantum theory of superconductors due to BCS are:
(i) An attractive interaction between the electrons through lattice phonons can lead to a ground,
state separated from excited states by an energy gap. The critical field, the thermal properties
and most of the electromagnetic properties of superconductors are consequence of the energy
gap. In special circumstances, superconductivity may occur without an actual energy gap,
called gapless superconductivity.
(ii) The electron-lattice-electron or electron-phonon-electron interaction leads to an energy gap
of observed magnitude. The indirect interaction proceeds when one electron interacts with
the lattice and deforms it, a second electron sees the deformed lattice and adjusts itself to
take advantage of the deformation to lower its energy. Thus the second electron interacts
with the first electron via the lattice deformation and forms a Cooper pair (Fig. 8.19).
'{Hi) The penetration depth (X) and the coherent length (e^ emerge as natural consequences of the
BCS theory. The London equations are obtained from the BCS theory for magnetic fields
that vary slowly in space. Thus the Meissner effect, the central phenomenon in
superconductivity is obtained from BCS theory in a natural way.
(iv) The superconducting transition temperature of an element or alloy is given by
kBTc= 1.14tn>Dexp [-1/^TV(0)]
smce /n)D = kfl0D . •
T.= 1.14 0D exp [-l/g JV(O)] ^ ■ / ’ (8.58)
where g is the electron-phonon interaction, N (0) is the electron density of orbitals dr density of states at
the Fermi level, and 0D is the Debye temperature. '
BCS Ground State

We know that, the filled Fermi sea is the ground state of a Fermi gas of non-interacting electrons. It is
just the filled Fermi sea bounded by the Fermi surface. This state allows arbitrarily small excitations;
one can form an excited state by taking an electron from the Fermi surface and raising it just above the
Fermi surface. In the BCS theory, on the other hand, there is an attractive interaction between the
electrons. Thus, in this case we cannot form an excited state unless we supply an energy which exceeds
e energy of attraction between the electrons. This implies that the BCS ground state is separated by a
IIUte energy gap Eg (= 2A) from its lowest energy state. Further, since the electrons having attraction
only those which are situated within about kB 0D of the Fermi energy. This energy gap is situated
ut the Fermi surface of the Fermi state. The position of energy gap about the Fermi surface is shown
ln Fig. 8.20.
You
Rg. 8.20 (a) Ground state of the Fermi gas of non interacting electrons
(b) The lowest excited state is separated from the ground state in this case by an energy gap E ,
The BCS Theory in a Capsule .

Starting from first principles and employing a completely quantum treatment, the BCS theory explains
the various observable effects, such as zero resistance, the Meissner effect, etc. In an ordinary metal, the
electrical resistance is the result of the collisions of the conduction electrons with the vibrating ions in
the crystal lattice. In the superconducting state, the forces of attraction between the conduction electrons
exceed the forces of electrostatic repulsion.
Normally two electrons repel each other, because of coulomb interaction. Suppose that, for some
reason, the two electrons attract each other. Cooper showed that the two electrons would then form a
bound state. This is very important, because in a bound state, electrons are paired to form a single
system, and their motions are correlated. The pairing can be broken only if an amount of energy equal
to the binding energy is applied to the system. This pair of electrons is called Cooperpair. Ai temperature
T< Tc, the lattice-electron interaction is stronger than the electron-electron coulomb force. At this state,
the Cooper pairs of electrons will have a peculiar property o*f smoothly sailing over the lattice point
without any energy exchange, i.e., the Cooper pairs are not scattered by the lattice points. Hence no
transfer of energy takes place from the electron pair to the lattice ions. If an electric field is established
inside the substance, the electrons gain additional kinetic energy and give rise to a current. But they do
' not transfer this energy to the lattice, so that they do not get slowed down. As a consequence of this, the
substance does not possess any electrical resistivity. So BCS theory explains the zero resistivity of a
superconductor. The Cooper pair of electrons can maintain the coupled motion up to a certain distance
among the lattice points in a superconductor called coherence length. This is found to be of the order of
lO^m.
In superconducting, the electron-electron attraction results from the electron-lattice interaction.

Suppose that the two electrons 1 and 2 pass each other. Because electron 1 is negatively charged, it
attracts positive ions toward itself (electron-lattice interaction). Thus electron 2 does not ‘see’ the bare
electron 1. Electron 1 is screened by ions. The screening may greatly reduce the effective charge of this
electron. In fact, the ions may over respond and produce a net positive charge. If this happens, then
electron 2 will be attracted toward electron 1. This leads to a net attractive interaction, as required for
the formation of Cooper pair.

You 390 Souo
*- ■
Statu Pmvski
____________________________ .
on the right side. There is no current in the circuit until a

certain critical voltage Vc is attained and the current begins
to increase afterwards somewhat as shown in Fig. 8.23. This N
is explained on the basis of quantum tunnelling as follows:
Quantum mechanically an electron on one side of a barrier
has a finite probability of tunnelling through it, if there is an Eg
allowed state of equal energy available on the other side of
E,
the barrier. Figure 8.22 shows the density of states function
in the energy space for a sandwich consisting of a
superconductor, an insulator and a normal metal, all at
absolute zero. In the normal conductor the electrons fill up
to the Fermi level.
Occupied energy states
In the superconductor the Fermi level is in the middle
of the band gap. When the sandwich is formed the Fermi
fig- 8.22 Superconductor-oxide-norrnal
levels are aligned as shown in Fig. 8.22. Suppose a voltage
is applied across the barrier so as to raise the Fermi level on
the right side of the junction. Until the Fermi level EFi on
the right side raised up to the level Ej electrons cannot go
1 # ri.Aa-14
from right to the left since there are no available energy '
levels on the left side; înce in that portion we have the band
- * «
gap. Once the Fermi level EF rises above the level of E'
the electrons can tunnel through the barrier from the right to
. the left since there are energy states available for the electrons
on the left-hand side. So the current increases. Obviously
there will be no current until the voltage becomes equal to
the band gap (E^- EFi ). Experimental measurements confirm
the theoretical prediction.
Giaever tunnelling
In Giaever tunnelling current is carried through the insulating barrier as single electrons, and quasi
particle excitations are left on the two sides of the junction. In 1962, B.D. Josephson predicted that a
supercurrent consisting of correlated pairs of electrons
can be made to flow across an insulating gap between
two superconductors provided the gap is small enough.
The nature pf Josephson’s effects can be
understood like this. A current is made to flow in a bar
of superconductor. A voltmeter is connected across the
ends of the bar as shown in Fig. 8.24 (a).
The voltmeter indicates a drop in voltage as zero
across the superconductor according to our expectation.
SupfraNufcrtfvfty 391
The energy gap in superconductors differs from the

gap in semiconductors in a very fundamemaJ way. In
semiconductors, the gap prevents the flow of electrical
current* Energy must be added to take electrons from the
valence bund into the conduction band before current can
flow. in a superconductor, on the other hand, current can
flow despite the presence of a gap. The energy gap has no
effect upon Che behavior of the special electrons that carry
current in a superconductor. But superconductors contain
normal electrons as well and h is these electrons that are
affected by the gap. Fig. fiF lechon - Electron mierac ticn thnnigh
lattice pltonons
An attractive interaction results in the Fermi sea of
electrons being unstable against the formation of bound
pairs of electrons formed from states above the Fermi level Therefore, it is necessary' to find a new ground
stale (lowest energy state) of the system in which many pairs of electrons of opposite momenta arc in higher
energy states than the maximum of the norms] sea, We thus focus our attention on a pair of electrons sitting
at the top of the Fermi sea, just below the Fermi energy level. These arc the most accessible electrons to use
for forming pairs. On we scatter two of them off of a phonon and form a Cooper pair to lower their energy
furtfier17 If the process results in a tower energy state, we can first promote two electrons from energy suites
below the Fermi level up to vacant stales above the Fermi level, and ihen let them interact to form a Cooper
pair.
The quantum mechanical calculation shows that the free energy is decreased, provided a Cooper pair
involves electrons with opposite velocities (or momentum) and the lattice serves as the medium for
exchange of momentum In reality/electrons are being continuously exchanged between the Cooper pairs
However, the transition to the superconducting stale requires only that a sufficient number of electrons
should condense into the pained state. At OK, all the conduction electrons arc paired, but with increasing
temperature, the number of pairs decreases. Anderson showed that non magnetic impurities do not usually
destroy superconductivity. Therefore, this phenomenum could he observed, even for not very pure samples.
However, the presence of magnetic impurities lowers the superconducting transition temperature nr sup
press superconductivity completely.
A Cooper pair may be considered as a new particle having twice the mass and charge of an electron.
In the superconducting stale, the electrical current is due to the motion of several Coe per pairs in the same
direction with the same velocity; only a single de Broglie wave can then be regarded as collectively repre
senting these Cooper pairs Since the momentum olThe Cooper pairs is a given current corresponds to
only a small velocity of the wave. Consequently, the wave length of the de Broglie wave becomes very
large. scattering from imperfections rarely occurs, and the conductivity tends to infinity.
XtX QUANTUM TUNNELING
Another interesting result which gives expenmental evidence ol the energy gup, is the quantum tunnelling
observation made by Giaever 1961 A thin film of superconductor, is deposited on a smooth glass surface by
evaporation. The surface of the layer is coated by an insulator layer of 10 nm thick. This can be done in the
case of aluminium h\ (>xid:sing the luyer lint deposited. Suppose a second rneud coining f normal metah is
made atop die instituting layer EkUrodes are connected to the ineiul states on either side of the insulating
layer and a gradually increasing potential is applied, so as to raise the Fermi level on the right side, There is
Suppose the bar is cut into two pieces and the two pieces are separated by say 1 cm as shown in
Fig. 8.24 (h). No current will flow and the voltmeter will indicate a voltage equal to the open circuit
voltage of the current source. If the distance between the pieces is reduced to 1 nm, the voltmeter
suddenly shows zero voltage showing thereby that a current flows across the gap in a superconducting
way. This is known as the d.c. Josephson's effect. Another effect which is observed if that the voltmeter
indicates a voltage, but at the same time a very high frequency electromagnetic radiation emanates from
the gap, indicating the presence of a very high frequency alternating current in the gap.
This phenomenon is known as a.c. Josephson’s effect. All these experimental observations show
that the BCS theory is gaining more grounds. The accomplishments of Josephson’s effects are:
CHAPTER 8
(i) A d.c. current flows across the junction in the absence of any magnetic or electric field.
(ii) When a d.c. voltage is applied across the junction, it causes r.f. current oscillations across the
junction. This effect has been utilised for the precise determination of the value of h/e.
Further, an r.f. voltage applied with d.c. voltage can then cause a flow of d.c. current across
the junction.
(iii) Whan a d.c. magnetic field applied through a superconducting circuit containing two junctions,
it causes the maximum supercurrent to show interference effects as a function of magnetic
field intensity. This effect can be utilised in sensitive magnetometers.
Let Tjbe the probability amplitude of electron pairs on one side of a junction and T2 be the amplitude
on the other side. For simplicity, let us suppose that both superconductors be identical. Let us also
suppose that they are both at zero potential. The time dependent Schrodinger equation is
[Refer equation (6.39)]
and applied to the amplitudes Tj and gives
and (8.59)
where hT represents the effect of the electron-pair coupling or transfer interaction across the insulator.
In fact, 7'is a measure of the leakage of into the region 2 and of *P2 into the region 1 (see Fig. 8.22).
If the insulator between the two superconductors is very thick, there is no pair tunnelling and Tis zero.
Let 4*! = n}/2 exp (Z©,) and V2 = n%2 exp (<02), then
CXP + 'n'/2 6XP = ” *T *2

ie■ ■ (IX1/2 exp <••> (10+exp
as - iTn%2 exp (i02) (8.60)
3% rae2
Similarly, -V2 exp (i02) exp (z’02)
n2 < dt
dr
= - iTnf2 exp (z’0t) (8.61)
Multiplying equation (8.60) by n['2 exp (- iOj) and using 5 = (02- 0j), one gets
i.e., - iT (n^)172 exp (z'S) (8.62)
Similarly multiplying equation (4.61) by n%2 exp (-z’02) and simplifying, one gets
2
- iT (n,nQ)lJ2
A - exp (—z’S) (8.63)
l^zziT^^sin8
i at
3»2 =_2T(n,n2)1/2sin8; (8.64)
| dt " .
30i_ .T^/n^cosbl
dt
302 - (8.65)
~dTz iT<nr/n2-)V2 cos8 -
Taking n2 for identical superconductors, we have from equation (8.65)

d0,00,d
= V <02- ®1) = 0 - (8.66)
dt dt dt 2 1
From equation (8.64),

dn2 dn}
(8.67)
dt dt
The current flow through the junction i.e., from 1 to 2 is proportional to (dn^/dt) or (- dnjdt).
Therefore, we ban conclude that the supercurrent J of superconducting pairs across the junction depends
on the phase difference 8.
(8.68)
Here Jq is proportional to T and represents the maximum zero voltage current that can be passed
by the junction. With zero applied voltage a d.c. current will flow across the junction with a value
between Jo and - JQdepending on the value of the phase difference (02- 0^. This effect is known as d.c.
Josephson’s effect.
Sqm> Simi Physic*
You
atoms of each metal element in the superconductor gives these compounds the name ‘1-2-3’, which has
the familiar way to refer to any of them.
The 1 -2-3 superconductors form as layers of copper and oxygen atoms sandwiched between
layers containing the other elements in the compound. Some of the copper-oxygen layers are made of
planes of atoms while others are made of chains of alternating copper and oxygen atoms. Some believe
that the copper-oxygen chains are crucial to superconductivity and others think that the planes are
important structures. In either case, only the layers containing oxygen and copper atoms appear to be
important for the electrical properties 1 -2-3. Nevertheless, there are three metal elements in the compound.
Although scientists believe that the metals themselves do not play a direct role in the electrical conductivity
of 1-2-3, they are not unimportant. The structure that atoms take to form a crystal comes about from a
delicate balance of electric forces between them. The spacing and placement of the attffns in the crystal
depends on atomic sizes and numbers of electrons.
In the 1-2-3 compound, the first element that scientists list in the chemical formula—the rare
earth metal turns out to be the least critical one. Since Chu’s discovery of 1-2-3 containing yttrium,
scientists have synthesised additional 1-2-3 compounds substituting for yttrium with other rare earth
elements such as gadolinium, holmium, europium, erbium and a host of others. The compounds have
the remarkable property that their superconducting behaviour does not depend on which rare earth
element it contains. Rare earth metals are not so rare at all, it turns out, but they are unfamiliar to most
of us. All are physically and chemically quite similar to one another and are therefore quite difficult to
separate. They tend to be soft silvery-white metals that oxidize readily in ordinary air. Most were
discovered during the nineteenth century and virtually all are found in monazite, the same mineral
Kamerlingh Onnes used for a source of helium gas.
The 1-2-3 compound is a complicated material. It contains four different elements that are arranged
in a very particular fashion. There was certainly no reason to except superconductivity from such a
substance. More pointedly, there was no reason to except conductivity at all from the 1-2-3 material. It
is an oxide like quartz or saphire, not a metallic compound, and most oxides are insulators. Yet, in the
normal state, 1-2-3 compounds are reasonable conductors of electricity. They don’t compare with really
good conductors like copper and silver, but they behave like metals nonetheless. Only experimental
evidence concerning the role of oxygen in the material has begun to explain the conductivity in 1-2-3.
Scientists currently explain the electrical conductivity of 1-2-3 in terms of hole conductivity of
the oxygen atoms. Holes are a name for missing electrons, or electron vacancies. Chemical compounds
form as a result of individual atoms giving up electrons to other atoms, borrowing electrons from other
atoms, or sharing electrons between one another. Such redistribution of electrons results in a lower
energy state, so that the compound becomes bound together. In 1 -2-3, the oxygen atoms pick-up electrons
from nearby copper atoms. Despite these additional electrons, the oxygen atoms still has room for more
in its outer shell, we say that the oxygen still has holes-electron vacancies. Evidence shows that electricity
flows through the material by allowing these holes to move from atom to atom in the crystal. In reality,
only electrons can actually move around, but there are no itinerant electrons in 1-2-3. The oxygen holes
have the freedom to move, so electrons rearrange themselves accordingly.
If we look again at the 1-2-3 unit cell, we notice something else. All the important copper
oxygen layers are not symmetrical located in the unit cell. In fact, the 1-2-3 material not only looks
asymmetric, it behaves asymmetrically. In other words, the compound’s properties are different in different
directions. In particular, current flows more easily across the copper-oxygen layers than it does along
the long dimension of the molecule. We call this kind of behaviour anisotropic (not the same in all
directions) conductivity. The new superconductors appear to be anisotropic in all their superconducting
properties. Critical currents, penetration depths, coherence lengths and other parameters all depend on
Supercom/m hviry ^95
AC Josephson Effects
Let a voltage Vbe applied across the Josephson junction. This is passible because the junction is an insula-
lor. An elcclrtHi poir cxpciiuiicvs a potential energy diikicncc </Vun passing acru.ss the junction, where 7 -
(-2r). One can say that a pair on one side is at a potential energy -eV and the pair on the other side at eV.
The equation of motion of a pair are:
= ftT%-eV%
P'F.’l ■w :
(«.69)
1 * ;
Let 4*| - rtj exp0'9() and % = exp (t03)
Nou
■F=br
Eq. (8.69) becomes
3/ij
/ft expert).,
< &r >
= tiT/i; •exp(/0;)-eV7i| 'e‘ '
Dividing throughout by ift exp uOi) rtf’ \ we get

1'tfa, dOj Ia
(8 70)
2) dT*’”1 aF = ’e,,|V^ -'H")'’:) expftS)
i.e.
21 dF; + fW) />«! V(ft) ’ - / 7jcos6 + i sinS] (n^j)1'2
Breaking this into real and imaginary pans, we obtain

1; dflj
= T(n ji7),csin&
2I dT
ur
y - = 2T(n1nJ)5 2 sin 3 (8.70u)
and
—= - T(nVn.)l7cos6
dr ft ‘ 1
This differs from Eq. (8.65) by the term —' Further, by extension of Eq.. (8.61). we obtain
2* + d7; Vn2/Tl-fT(/iln2),':e"lfi
SMHBMWNDURlvrrV
orientation of the crystal. The consequences of many of these anisotropic properties remain to be
j1 t
rmined, but they already present big stumbling blocks to technologists, because, as we shall discuss
6 the ability of the superconductor to carry current strongly depends on its orientation.
The anisotropy of 1-2-3 is not the only problem caused by its complex chemistry and structure.
The compound contains chemically reactive components particularly barium that strongly interact with
other substances. Furthermore, we cannot even produce superconducting samples of 1-2-3 without
°xposing the compound to very high temperatures (700 to 950°C). Without high temperature processing,
the compound does not incorporate enough oxygen into the copper-oxygen layers to produce the right
crystal structure. Such temperatures are a problem because they worsen chemical reaction problems
CHAPTER 8
with the materials upon which thin films are deposited and, in general, make it difficult to use the new
superconductors in conjunction with other materials. These and a host of other materials problems
make it difficult to produce high-quality samples of the new superconductors.
Superconductivity above 100 K

Several new oxide superconductors with above 90 K transition temperatures were discovered in the
year 1988. These materials do not even have the same crystal structure as 1-2-3. The newer compounds
are still layered copper oxide materials, but they do not contain rare earth elements. In place of yttrium
or other rare earths, the compounds contain metals like bismuth or thallium. And unlike either the
original Zurich superconductor or 1-2-3 they contain four metallic elements instead of three.
Thus, there exists a whole family of copper oxide superconductors. In fact, there are at least five
different crystal structures that result in high temperature superconductivity, all composed of layers of
copper-oxygen structures sandwiched around layers of other elements. For some reason, having more
copper-oxygen layers in the unit cell seems to be conducive to higher superconducting transition
temperatures. The superconductor discovered at the university of Arkansas—thallium-barium-calcium-
copper oxide contains three copper-oxygen layers and superconducts at a temperature thirty degree
higherthan 1-2-3, ; . ■ ■ : - ■. / ■ . ■ ;
These newer high temperature superconductors both the bismuth-strontium-calcium-copper oxide
discovered in Japan and the thallium compound from Arkansas create both problems and opportunities
for researches. On the positive side, transition temperature at 120 K and above mean that these
superconductors can actually be used at liquid nitrogen temperature. Furthermore, the new materials
seem to be more chemically stable and more apt to retain their oxygen than the 1-2-3 compound. On the
down side, the newest compounds are even more complicated than 1-2-3, containing five elements
instead of four, which increases the challenges faced in producing the material. Also, the thallium
compound presents the additional drawback that thallium itself is an exceeding toxic substance, which
greatly complicates its handling.
Most of us now believe that many more high temperature superconductors must exist and await
discovery. So far, the remarkable string of discoveries that started in Zurich has centred around layered
copper oxide compounds. It may take years to fully explore just these systems, and there may well be
other unrelated materials that also exhibit high temperature superconductivity. Now that the door has
een fully opened, there will be ceaseless efforts to find new materials that not only superconduct at
gher and higher temperatures, but also ones that can be made efficiently, effectively and economically,
remains to be seen whether all these new compounds provide new insights about the origins of high
temperature superconductivity and thallium superconductors, for example, do not have the copper oxygen
c a|ns that are present in 1-2-3. Therefore, at least in these newer compounds, the chains do not play a
m e in high temperature superconductivity. Clearly, high temperature superconductivity continues to be
mysterious phenomenon.
«M
"XXlrt, APPLICATIONS OF SUPERCONOUCfWffVTfc EARLY W/tSUffif
THEIR LIMITATIONS _
High Field Magnets

Magnetic fields greater than about 30 kOe are produced conventionally by passing a large electric
oirrent through a water-cooled copper or aluminium solenoid. This technique has been highly developed
over the last 30 years and is still capable of some improvement (Bitter, 1963). The difficulties in producing
magnetic fields using conventional conductors, however, seem to increase proportional to the square of
the maximum field required. An idea of the power P (in megawatt) needed to produce a field H Ckilo
Oersted) tn a water-cooled copper solenoid with a bore diameter D (inch) is given by the equation.
P- IO^DxH2
It is seen that power of the order of a megawatt is required to produce 100 kOe in a one inch
diameter bore. Most of this power input is released as joule heating in the coil and elaborate precautions
must made for its removal if the magnet is to be run continuously.
Neither the large power supply nor the means of removing the heat are needed when the resistance
of the coil is zero, i.e., if it is wound with superconducting wire. The only power required by a
superconducting magnet is to keep the magnet cool (so that the wire remains superconducting), to
overcome the small amount of dissipation in the normal leads and to set up the magnetic field. Once the
required field has been established the two ends of the wire in the coil can be joined with a superconducting
link (the magnet is then in the persistent mode) and the field will remain even when the power supply is
removed. In this case the only power required to maintain the field is that needed to cool the solenoid
and for high fields this is several orders of magnitude less than that required to maintain the same field
using a conventional resistive solenoid.
The electrical power requirements of a small superconducting magnet are modest (a supply
giving 30 amp into a 0.1 Q load is the one frequently used in the laboratory to produce up to 60 kOe in
a 0.5 inch working space) and the magnet current may be swept or modulated with relatively little
trouble. A suitable battery driven power supply, which includes a protective circuit to interrupt the
current if the magnet goes normal, is described by McAvoy (1963). A further advantage of a
superconducting magnet is that, in the persistent mode, the coil forms a superconducting ring so that
any spurious magnetic field changes outside the ring are compensated by changes in the current following
in the wire and the magnetic flux within the coil will remain constant Hence the effect of the external
field changes will be greatly reduced and the region inside will be almost free from noise. The absence
of large pumps which are required to circulate the cooling fluid in conventional high field also means
absence of acoustic noise a great advantage for the magnet operator.
The low power requirement and simple cooling lead to a large reduction in the cost of producing
high magnetic fields and a high magnetic field facility need no longer be restricted to a few laboratories.
To produce higher fields over large volumes, magnets are wound using standard cable containing
large amounts of copper (Laverick, 1965) since this makes the magnet more stable (less likely to go
normal). Then, since current is fed to a larger cross-sectional area cable, the power supply may be
required to produce up to 200 amp. This adds appreciably to the cost and also to the difficulty of taking
the current into the low temperature region of the magnetic coil.
The possibility of a superconducting magnet was first suggested by Kamerlingh Onnes but
superconductivity in the materials known at that time was quenched in a field of less than 1 kOe. De
Hass and Voogd (1931) found that some Pb-Bi alloys remain superconducting in fields greater than
20 kOe. Subsequent measurements showed the critical current densities to be low, however, and a
prohibitively large amount of wire would have been required to produce high fields. The element helium
was scarce and also difficult to liquify and, since this material would have produced only fields already
available using conventional magnets, it was not applied to magnet production. A further 24 years
passed before the possibility of high field production using superconductors was demonstrated by Yntema
(1955) who produced an electromagnet with niobium wire carrying a current density of almost
105 amp/cnr in a field of 5 kOe.
The major advance in the application of superconductivity for producing high fields came with
the discovery, by Kunzler (1961), that Nb3Sn will carry a current density of greater than 105 in a
field of 88 kOe.
CHAPTER 8
Since then, a large number of alloys, and particularly those having a |$-tungsten structure similar
to Nb3Sn, have been examined for high field superconductivity. Other materials which may be useful in
the future are V3Ga (HC1 « 350 kOc) and V3 Si ~ 150 kOe). In the absence of a completely detailed
theory of Type II superconductivity, the search for new materials has been largely empirical, based on
the rules put forward by Matthias (1957) that superconductivity is found only in metallic element with
between 2 and 8 valence electrons and that, of these materials, the ones with the highest critical
temperatures (and, therefore, probably the highest critical fields) are those with valence electron/atom
ratios of 3, 5 or 7.
Only Nb-Zr and Nb-Ti alloys with critical fields of the order of 100 kOe are normally ductile and
can easily be wound into coils. Attempts have been made to overcome the brittle nature of Nb3Sn by
pressing niobium and tin powders into niobium tubing and firing this to form the compound after the
coil has been wound, while a ductile form of Nb3Sn can be made in the form of a thin film by power
deposition (Heraeus). A number of other methods of producing Nb3Sn in a ductile form have also been
proposed. Thin films of pure materials separated by insulated layers may be grown by evaporation and
thin filaments can be produced using Bean’s method of pressing the material into a porous matrix
Finely divided superconducting/non-superconducting metal structures have also been suggested
(Berlincourt, 1963) as possible magnet materials.
The particular design problem of superconducting coil is to minimize the length of the wire
which will produce the maximum field with the required homogeneity, since the cost of the wire is a
major factor in the design. The method of designing rectangular cross-section superconducting solenoids
has been considered in detail by Boom and Livingston (1962) and a pair of design curves which allow
the optimum shape and minimum length of wire required to be found particularly easily are given by
Thomas and Bright (1966). Design considerations of Helmholtz pair arrangements of superconducting
coils have been considered by Day (1963).
Other Magnetic Field Applications .

(i) Flux Trapping and Shielding
When a Type II superconductor is cooled in a magnetic field or when a magnetic field is applied to
Type II superconducting cylinder and is then decreased again, if the field is large enough to penetrate
into the cylinder then, in each case, persistent currents are induced in the cylinder walls and a magnetic
field is trapped in the ring. In the bore of a small cylinder (with about 0.5 cm wall thickness) of suitably
treated Nb3Sn, fields of greater than 50 kOe have been trapped. The field inside the cylinder will remain
effectively constant as long as it is superconducting and it may, therefore, be used as a very high field
permanent magnet. The field in the bore of the cylinder at the moment that it becomes superconducting
will remain constant until a very high external magnetic «“Id value is reached. Hence, if a suitable high
field superconducting cylinder is cooled in zero field it can maintain a field free region in the bore until
the external field reaches at least 50 kOe.
loo
penetration depths, coherence lengths, and other parameters all depend on the orientation of the crystal. The
consequences of many of these anisotropic properties remain to be determined, but they already present big
stumbling blocks to technologists, because, as we shall discuss later, the ability of the superconductor to
carry current strongly depends on its orientation.
The anisotropy of 1-2-3 is not the only problem caused by its complex chemistry and structure. The
compound contains chemically reactive components particularly barium that strongly interact with other
substances. Furthermore, we cannot even produce superconducting samples of 1-2-3 without exposing the
compound to very high temperatures (700 to 950‘C). Without high-temperature processing, the compound
does not incorporate enough oxygen into the copper-oxygen layers to produce the right crystal structure.
Such temperatures are a problem because they worsen chemical reaction problems with the materials upon
which thin films are deposited and, in general, make it difficult to use the new superconductors in conjunc
tion with other materials. These and a host of other materials problems make ii difficult to produce high-
quality samples of the new superconductors.
Superconductivity above 100 K

Several new oxide superconductors with above 90 K transition temperatures were discovered in the year
1988. These materials do not even have the same crystal structure as 1-2-3. The newer compounds are still
layered copper oxide materials, but they do not contain rare earth elements. In place of yttrium or other rare
earths, the compounds contain metals like bismuth or thallium. And unlike either the original Zurich super
conductor or 1-2-3 they contain four metallic elements instead of three.
Thus, there exists a whole family of copper-oxide superconductors. In fact, there are atleast five
different crystal structures that result in high-temperature superconductivity, all composed of layers of
copper-oxygen structures sandwiched around layers of other elements. For some reason, having more
copper-oxygen layers in the unit cell seems to be conducive to higher superconducting transition tempera
tures. The superconductor discovered at the university of Ark anas-thallium-barium-calcium-copper oxide -
contains three copper-oxygen layers and supercon ducts al a temperature thirty degree higher than 1-2-3.
These newer high-temperature superconductors-both the bismuth-strontium-cakium-copper-oxide
discovered in Japan and the thallium compound from Arkansas-create both problems and opportunities for
researches. On the positive side, transition temperatures al 120 K and above mean that these superconduc
tors can actually be used at liquid nitrogen temperature, Furthermore, the new materials seem to be more
chemically stable and more apt to retain their oxygen than the 1-2-3 compound. On the down side, the
newest compounds are even more complicated than 1-2-3* containing five elements instead of four, which
increases the challenges faced in producing the material. Also, the thallium compound presents Che addi
tional drawback that thallium itself is an exceeding toxic substance, which greatly complicates its handling.
Most of us now believe that many more high-temperature superconductors must exist and await
discovery. So far, the remarkable string of discoveries that started in Zurich has centered around layered
copper-oxide compounds. It may take years to fully explore just these systems, and there may well be other
unrelated materials that also exhibit high temperature superconductivity. Now that the door has been fully
opened, there will be ceaseless efforts to find new materials that not only superconduct at higher and higher
temperatures, but also ones that con be made efficiently, effectively, and economically. It remains to be seen
whether all these new compounds provide new insights about the origins of high-tcmperaiure superconduc
tivity and thallium superconductors, for example, do not have the copper-oxygen chains that are present in
L2-3. Therefore, at least in these newer compounds, the chains do not play a role in high temperature
superconductivity. Clearly, high temperature superconductivity continues to be a mysterious phenomenon.
0Dv SoutrSTMi Physics
Ui) F/iw Concentration

The field which is trapped in a superconducting cylinder when the external field is increased around
and then reduced again depends upon the maximum value to which the external field can be taken a
particular cylinder may be capable of trapping a much higher field than this. Greater fields can be
produced in a cylinder which already contains trapped flux by inserting a superconducting plunger to
fill apart of the bore (Swarts and Rosner, 1962). The flux is then compressed into the volume of the bore
remaining unfilled and the field increases. As the internal field rises, more and more flux is lost into the
walls of the cylinder, however, so that the ratio of the final to the initial field is reduced (Goldsmid and
Corsan, 1964), and this sets a practical limit to the amount of compression which may be achieved by
this method. The field of an iron-cored magnet can also be concentrated by fitting superconducting
shields over the pole pieces.
(iii) Magnetic Bearings
The possibility of flux trapping and flux exclusion suggests that a superconducting cylinder and disc
may be used as magnetic bearing (Buchhold, 1960). The bearing is restricted in its lateral movement but
can spin on a cushion of flux. If the material of the moving part of the bearing is chosen so that no flux
will penetrate into it, the only friction in the bearing will come from the viscosity of the surrounding
medium and this may be made very small.
(iv) Energy Storage

Another possible use of superconducting coil is an energy store (Weiderhold and Ameen, 1963). A
trapped field of H Oersted stores and energy of (7/2/8jc) erg/cm3 so that a trapped field of 100 kOe
corresponds to a stored energy of 108 erg/cm3. A conventional capacitor bank stores about 106 ergs/cm3.
There is, however, difficulty in regaining the electrical energy quickly from the superconducting energy
quickly from the superconducting store since the inductance of the coil may be high and this will lead to
a long time constant in the withdrawal circuit. An analysis of the problem and a review of the factors
which may affect the time constant have been given by Ameen and Weiderhold (1964).
(v) D.C. Transformer
In the presence of a transport current, fines of magnetic flux are moved as if under the action of a
Lorentz force. If a magnetic field is established around the device and the input voltage applied to the
wider strip, then the flux lines in the primary circuit will move cutting the secondary and therefore,
inducing a voltage at the output (Giaever, 1965). The efficiency of the transformer is only about 10%
but the voltage output may be made larger by increasing the number of thin film units to which the
primary voltage is applied.
This device will work using not only Type II but also Type I superconductors in the same thin
film arrangement since the magnetic flux which penetrates into the latter when they are in the intermediate
state is acted upon by the current in the same way as the flux in a Type II superconductor in the mixed
state.
D.C. Power Transmission

Since there is no joule heat loss in a superconducting cable it would, at first sight, seem preferable to use
superconducting cables for d.c. power transmission. To use such cables, however, large amounts of
power would be lost in rectifying the alternating current coming from the generators and also in keeping
the cable cool. The power loss in conventional cables is fairly small (« 10%) so that with the present
materials and cost of rectification and cooling, d.c. power transmission using superconductors appear8
to be uneconomic. However, the cost of cooling is reducing and in applications where direct current is
in U i^Fgft nil
(ready used, e.g., in parts of the chemical industry, the time may soon come when the costs of using
Superconducting and conventional cables may break even.
A.C. Application5
m Current Carrying Characteristics
pjo power loss is expected in Type I superconductors until the frequency of the alternating current is
high enough to give the electrons energy to jump the superconducting energy gap. This frequency is of
(he order of 1013 Hz for most superconductors. Experiments on Type II superconductors show that -
losses appear at much lower frequencies and may be quite large. The calorimetric technique used to &
obtain the variation of power loss with frequency at constant field and with field at constant frequency
for a niobium block is very sensitive and losses can be observed even in well annealed high purity lead
with a current density below the critical value.
The variation of the critical alternating current with specimeh size for toroidal PB-Bi eutectic X
has been investigated by Kamper (1962) who found that the loss factor was independent of the frequency
up to 100 Hz. Similar measurements have been made with different sizes of Nb-25% Zr wires. These
results show that there is a logarithmic decrease in the r.m.s. critical current density with increasing
wire thickness at all frequencies and also that the critical current decreases logarithmically with frequency
when the wires are in coil form. The experiments indicate that the critical alternating current density
occurs at the same power level for different frequencies.
Two physical models have been put forward to account for the origin of the a.c. losses. Buchhold
(1963) suggested that the losses are due to imperfections on, or just beneath the surface. These trap flux
which has penetrated into the superconductor and therefore cause hysteresis when an alternating field
or current is applied. The model has been tested by calculating the voltage variation in a search coil
wrapped around a superconducting block. Smoothed out curves of the shapes predicted by the theory
have been found experimentally. An analysis of the power loss in a Type II superconductor has also
been made when a field is applied parallel to a flat slab (London, 1963).
Energy is dissipated in the form of heat when a flux line moves through a Type II superconductor.
Hence, in all Type II superconductors, once they are in the mixed state, heat is generated when an
alternating current is applied.
(«j Power Transmission

The high cost of rectification suggests that power might be transmitted by alternating current in a
superconducting cable. The results surveyed show that such cables have an appreciable power loss,
however, so there may be no advantage gained in transmitting alternating current. Once again the cost
of insulation and cooling determine the cost of using the cable. Although at the present time, the use of
superconducting cables for a.c. power transmission is not economic; the time may soon come when
êy will offer a substantial advantage in size and cost over conventional cables.
Power Transformers and Machines

he/eduction in the power loss which would result from the use of superconductors in heavy electrical
^gJneering machinery and transformers could lead to an appreciable decrease in operating cost as well
n Rowing the weight and size of the equipment to be reduced. The power of a current generator is
eJW by the dimensions of the machine. This must be transported by road from the factory to the
^tncal plant and the size must be limited. A design study of the use of superconducting windings in
lay er transformers (Wilkinson, 1963) indicates that, if a thin film superconductor capable of carrying
red. CUrrents in high fields were available, then the coil and core weight and therefore, size could be
Ced by almost 40%.
Yo ■te—.
Squd Smra
.
Physo
~ _
The advantages that superconductors have in heavy engineering applications have to be set agains
one great disadvantages: They must be maintained at a very low temperature. For power transmission
and for heavy machinery and transformers, the cost of continuous cooling more than outweighs the
advantages at present. However, the reduction in the cost of the producing high magnetic fields usin
superconducting solenoids indicates that other major benefits may result from using superconductors8
Benefits may also be expected from the use of the high fields produced by superconducting magnets in
other devices, e.g., in the production of power using magnetohydrodynamics and possibly by controlled
fusion. More efficient insulation, lower cooling cost and, possibly, the discovery of superconductors
with much higher critical temperatures will all add to the possibility of widening the applications of
Type II superconductors.
The potential applications of superconductors in vital areas are given in the following Table 8.5.
Table 8.5 Applications of superconducting materials in some important fields

Magnets • High-field magnet applications
• Nuclear magnetic resonance (medical diagnostics and spectroscopy)
• Ore refining (magnetic separators) f-
• Magnetic levitation
• Magnetic shielding
• Large physics machines (colliders, fusion confinement, r.f. cavities)
Energy related • Production by magnetic fusion and magnetohydrodynamics
• Energy storage (magnetic)
• Electric power transmission
Transportation • High speed trains
• Ship-drive system
Electronics and small devices • SQUIDS (superconducting quantum interference devices)
• Josephson devices (square-law detector, parametric amplifier, mixer)
• Bolometer
• Electromagnetic shielding
Computers and information • Semiconductor-superconductor hybrids (A-D converters)
processing • Active superconducting elements (FETs)
• Voltage standard
• Optoelectronics
• Malched filters
Of the many possible applications of superconducting materials reported since 1911, the high
field solenoid has become most useful. Commercial production of solenoids capable of exceeding 2.2 x
106 amp nr1 followed the development of non-ideal superconductors Nb3Sn and Nb-Zr wire at the Bell
Laboratories. The cost of ordinary conventional solenoid producing a magnetic field of 1 x 107 amp m h*
a volume of 50 cc, is more than ten times of a superconducting solenoid wound with Nb3Sn wire. Such
a conventional solenoid furthermore requires 200 kW of power and 1000 gals/minute of cooling water,
as well as considerable space for auxiliary equipment. A superconducting solenoid occupies little space,
Superconductivity 405
Electrical Switching Element

Because of the infinite ratio between the resistance of a meta! in the normal and superconducting state, a
superconductor can be used to switch electrical current between different possible paths. Either teni petal tire
or magnetic field can be used to control the change of state of such a switch. A temperature controlled
switch uses a film of lead as the switching element. The current carrying film is operated below the trans
ition temperature so as to be superconducting. The current can be htemipted by means of a healing coil
made of noivsuperconducting metal, As the lead film becomes resistive, the current flowing through it is
diverted through a parallel path of low resistance.
A magnetically operated current switch,
called is shown in Fig. 8.27. The fact that
superconductivity disappears for magnetic field
exceeding the critical value, has been utilized in a
cryotron. PQ is straight wire of superconducting
material 5, on which is wound a coil of supercon-
ducting material Sj. Temperature of the entire sys
tem is kept below the transition value of both the
superconducting materials S$ and Now if die
magnetic field produced by the coil B exceeds the
criiicj] field // tT the material jt the operating tem-
pemure. then die material S1 of core A operate*, in
the normal state, core A has non*zero resistance Fig. 8.27 ]*hc wire wound cryotron
and hence the cumini in the core reduces. Thus the current in core A may be controlled by the current in coil
B, This control current A in coil required to make the core A normal depends on the de. current ^flowing
through the core because /, also produces its own magnetic field.
If the operating temperature is (hat of liquid helium bath (4.2 K), metal such as tentalum having T( (-
4.38 K) only slightly greater (han 4.2 K may be used Tor the core A so that the critical magnetic field
required to cause the normal state is relatively small For a coil we must choose such a material which
remains superconducting even with the control cutrent flowing in the (oil. Niobium or lead may be used as
coil material. Single cryotron shown in Fig 8.27 may be used as an clement in, say a flip-flop. Elements
used being superconductors, the power consumption of the device is extremely small. A large digital com
puter using cryotrons may require extremdy small power of ihe order of only half a watt-excluding, of
course, the terminal equipment and the helium cryostat Further, the size of such a computer will be
extremely, small, occupying a very small space.
Superconductor Fuse and Breaker
Thin insulated superconductor film gets its normal states after the current of more than critical density has
passed through it Such films can be used instead of a fuse. Selecting ihe necessay material for a film it is
possible to regulate very precisely the admissible intensity of current. If a lung film is taken and at the
moment of its transition into normal state its resistance is rather high, then it can be used as a breaker. Lead
is used here.
Superconductor Transformers and Transmission Lines
If superconductors are used for winding of a transformer, the power losses will be very small By using
has no steady state power consumption. A superconducting solenoid occupies little space, has no steady
state power consumption. Superconducting solenoids are useful in magnetohydrodynamic power
conversion and in other engineering areas.
Superconductors are being used in many research and development fields, while superconducting
magnets are already taking precedence over conventional magnets in many equipments. Electrical
machines, transformers and cables are being developed using superconductors.
Electrical Switching Element

Because of the infinite ratio between the resistance of a metal in the normal and superconducting state,
Chapters
a superconductor can be used to switch electrical current between different possible paths. Either
temperature or magnetic field can be used to control the change of state of such a switch. A temperature
controlled switch uses a film of lead as the switching element. The current carrying film is operated
below the transition temperature so as to be superconducting. The current can be interrupted by means
of a heating coil made of non-superconducting metal. As. the lead film becomes resistive, the current
flowing through it is diverted through a parallel path of
low resistance.
A magnetically operated current switch, called
cryotron is shown in Fig. 8.27. The fact that super
conductivity disappears for magnetic field exceeding the
critical value, has been utilised in a cryotron. PQ is straight
wire of superconducting material S. on which is wound a
coil of superconducting material S2. Temperature of the
entire system is kept below the transition value of both the
superconducting materials Sj and S2. Now if the magnetic (lead)
field produced by the coil B exceeds the critical field Hc of
Fig. 8.27 The wire wound cryotron
the material at the operating temperature, then the material
S, of core A operates in the normal state, core A has non
zero resistance and hence the current in the core reduces. Thus the current in core A may be controlled
by the current in coil B. This control current I2 in coil required to make the core A normal depends on the
dx. current /j flowing through the core because also produces its own magnetic field.
If the operating temperature is that of liquid helium both (4.2 K), metal such as tentalum having
T. (= 4.38 K) only slightly greater than 4.2 K may be used for the core A so that tte critical magnetic
field required to cause the normal state is relatively small. For a coil we must choose such a material
which remains superconducting even with the control current flowing in the coil. Niobium or lead may
be used as coil material. Single cryotron shown in Fig. 8.27 may be used as an element in, say a. flip
flop- Elements used being superconductors, the power consumption of the device is extremely small
A large digital computer using cryotrons may require extremely small power of the order of only half a
watt excluding, of course, the terminal equipment and the helium cryostat. Further, t£e size of such a
computer will be extremely small, occupying a,yery small space.
Superconductor Fuse and Breaker
Thin insulated superconductor film gets its normal states after the current of more than critical density
has passed through it. Such films can be used instead of a fuse. Selecting the necessary material for a
it is possible to regulate very precisely the admissible intensity of current. If a long film is taken
at the moment of its transition into normal state its resistance is rather high, then it can be used as a
breaker. Lead is used here.
Yc
Superconductor Transformers and Transmission Lines

If superconductors are used for winding of a transformer, the power losses will be very small. By
superconductors, transformers of 2000 to 3(XX) MW can be manufacturer! and they will be of poq^
type.
Electrical transmission lines with the use of cables with superconductors are design
Theoretically such a line, if necessary cooling is provided, can transmit high power to any diu?n,
desirable without losses.
Magnetic Mirror and Superconducting Bearing

Zero resistivity is not the characteristic property of a superconductor. This is zero magnetic induction
which is responsible for the 'levitation' effects which are applied in frictionless bearings.
Perhaps the most famous levitation experiment was that in which a horizontal bar magnet w*
suspended from a flexible chain, and then lowered over a sheet of lead which had been cooled u> fl*
superconducting state. As the magnet approached the superconducting sheet, the supporting chain becane
limp, and eventually dropped down in a loop below the magnet, which remained floating horizontally
above the lead sheet. The field due to the approaching magnet induced a current in the surface of the
superconductor. Because the resistance was zero, the current persisted, and the field due to this current
repelled that due to the bar magnet. The superconducting surface can be regarded as a mirror below
which exists an image of the magnet.
With a different experimental arrangement, the superconducting sheet might have been supported
by the magnetic field from the permanent magnet. Also, instead of a permanent magnet, the supporting
field might have been provided by a superconducting solenoid carrying a current.
The repulsion between the magnetic field of superconducting solenoid and that due to the current
induced in the surface of a nearly superconductor is the basis of most designs for superconducting
mechanical support. Unlike simple magnetic repulsion systems, the superconducting support is usually
unconditionally stable, and thus needs no associated sevo system.
Various arrangements have been proposed to give the two-dimensional support needed for shaft
bearing, and the three-dimensional support needed for a floating sphere. This has been applied in a
superconducting gyroscope with a spherical rotor spinning for months under nearly frictionless conditions.
One more field of application of superconductors, which is very prospective, is the manufacture of
electrical machines, generators and motors with superconducting windings. It is possible to obtain high
efficiency and small sizes, less weight by using superconductors. The possibility of achieving extremely
strong magnetic fields, and using lossless coils to cut those fields, is of great interest to the power
engineer. The fact that, even in superconductors, there are losses with low frequency alternating current
is a disadvantage which may be overcome by using new materials. The most encouraging work that has
been done in producing rotating machinery, on the industrial side rather than on the laboratory scale,
has been concerned with d.c. machines. In particular, a superconductor homopolar motor has been
widely used for plant operation.
In this simple form, the homopolar machine uses, or generates, electrical power in the form of*
very high current at very low voltage, and this is rarely convenient. This difficulty has been overcome
by using a segmented structure for the rotating conductor, with a special brush arrangement which alto*5
the 2500 kW motor to accept its input power at the much higher potential difference of about 450 V.
*
I he superconducting homopolnr d.c. generator has, as yet, not been developed very far, but new
design studies arc proceeding in parallel with the more immediately rewarding work on motors.
Applications ol particular superconductors promise for the d.c. superconducting motor appear to lie in
fields like ship propulsion and large mills, where very high torques arc required at comparatively low
speeds, which can be controlled easily, In terms of capital and running costs, they are likely to be
competitive with conventional machines for large output powers, and will probably also be smaller,
lighter and more efficient. Similar savings In weight, cost, etc. are predicted for alternators.
Josephson Junction Devices

The e.m.l. ol standard cells using conventional materials is known to age or drift. These cells also have
a very large temperature coefficient and are sensitive to shock and vibrations. All these problems are
overcome in Josephson effect voltage standards which arc based on the Josephson a.c. effect.
The d.c. Josephson effect has been used to fabricate sensitive magnetometers with an accuracy
of IO~” gauss.
Superconductors have been used to generate and detect electromagnetic radiations from radio to
infrared frequencies using a.c. Josephson effects. Several millimetre and submillimetre detectors and
devices have been fabricated using this effect.
Besides solid state physics, there appear new promising applications of superconductors in
geophysics, medicine and radioastronomy.
Low Temperature Superconductors

The present applications involving low temperature liquid helium superconductors include high-field
magnets, electronic and radio frequency devices. Most nuclear magnetic resonance (NMR) spectrometers
today employ a superconducting magnet. Superconducting magnets are also used in NMR imaging.
This has appealed to the imagination of the common man since the NMR imaging technique is better
than the CT scan used in medical diagnostics. The advantages unique to high-field applications of
superconductors arise because conventional resistive conductors such as copper dissipate large amounts
of energy as heat when they cany large currents. Superconducting materials are also useful in high-Q
cavities because of their low alternating current losses at high frequencies compared to those in normal
metals. Electronic applications of superconductors require low electric currents and low magnetic fields.
The core element in these devices has been the Josephson junction. Superconductors would also eliminate
resistive current losses in electronic lines and device interconnections. Various kinds of superconducting
sensors have also been produced with the liquid helium superconductors. Except in magnets and in
sensitive instrumentation (e.g., SQUIDS), the utilisation of conventional liquid helium superconductors
has not been large till now. All the applications to-date based on liquid helium superconductors make
use of Nb alloys. These materials have been used to produce strong magnetic field required for NMR
imaging as well as in various applications in physics. The workhorse of the magnet technology has been
NbTi, a ductile alloy which can be made into wires. Nb3Sn is also a material of much promises since it
can carry larger, currents and remain superconducting in higher magnetic fields; unfortunately, it is
brittle. Pure Nb itself is used in radio frequency cavities and NbN in electronics. Nb3Ge films are being
tried in electronic devices.
A high speed levitating train (« 550 km per hour on an average) making use of a conventional
liquid helium superconductor has been tested in Japan. Japan expects to have more levitating passenger
trains between Osaka and Tokyo in another three or four years. Superconducting ship propulsion systems
with liquid helium superconductors have been successfully tested, mainly in Japan.
You Soud State Physics
High Temperature Superconductors I

The new high temperature superconductors (Tc > 77 K) eliminate the need to cool to 4.2 K with liquid !
helium. Liquid nitrogen is a better coolant than helium because of its larger heat capacity. The design of ;
the container is very much simplified while using liquid nitrogen. These coolant considerations become
important in many applications. Elimination of the needs to refrigerate below the ambient temperature
would have a great economic advantage, although in certain applications where thermal noise is a
disadvantage, high temperature operation by itself would not be of much value. The immediate need is
to get the high temperature oxide superconductors (Tc » 80-125 K) to be useful in high-field applications
This implies making them in the form of wires or tapes that can carry high currents (current density of
105—10fe amp cm'2) in moderate magnetic fields. This is not an easy task because of the low critical
current densities and the ceramic nature of the oxide materials. There is, however, some progress being
made in this direction.
For low current applications, films with high current densities («106amp cm-2) have been prepared
by many workers by employing a variety of techniques including laser ablation, rf sputtering, electron
beam evaporation, etc. A few applications of high Tc oxide superconductors in electronics and small
devices have already become possible. It is not as if there is no hope of using the high temperature oxide
superconductors for magnet and other large scale applications. While power transmission through high
Tc oxide wires seems remote, it is not entirely unlikely that magnets made of these materials will one >
day be available for medical applications. Prototype liquid nitrogen cooled motors or generators, operating
at modest currents and magnetic fields are being built. ;
With the new high Tc materials, military applications are likely to be first because of the relatively
small, but specific market. SQUIDS making use of Josephson junctions have been fabricated with high
T materials and they will have applications in medical diagnostics (e.g., checking the heart function
and the brain) besides under sea communications, submarine detection and geophysical prospecting.
There is little doubt that the new high temperature superconductors have extended the range of applications
of materials and there is every possibility that they and other high Tc materials yet to be discovered may
user in a new materials revolution.
Squids
Superconducting magnetic shielding which uses the superconductor’s ability to exclude magnetic fields
can be exploited in a number of applications. For example, engineers require the complete exclusion of
magnetic field that typifies Type I superconductors when ultrasensitive magnetic instruments are being
used. SQUID (Superconductive Quantum Interference Device) instruments used to study tiny magnetic
signals in the brain and elsewhere would be useless without superconducting magnetic shields. The
noisy signals emanating from the changing magnetic environment of the outside world would drown
out the minute signal that SQUIDs can detect. Another application of superconducting shields comes
from the need for security in computer installations. Functioning computers generate signals that can be
detected by sensitive enough equipment. Computers that handle confidential information could be
protected from such snooping by superconducting shields.
Whereas the techniques for constructing magnetometer and extracting information from them
have become sophisticated and complex, the basic concepts remain quite simple. Superconducting
magnetometers take advantage of flux quantisation with the use of SQUIDs. Remember that a
superconducting ring can only enclose magnetic fields from a specific set of values. Specially, the
magnetic flux in the ring—the product of the magnetic field and the area of the ring—can only take on
values that are multiples of a specific number: The flux quantum. Thus a ring may have one, two, or a
thousand flux quanta, but it can never have one and a half. As a result, when we place a superconducting
ring in a magnetic field, a current flows around the ring to keep the flux in the ring at a permitted value-
SQUlDs were named and first studied at the Ford Motor Company Scientific Laboratory in
Dearborn. Michigan, in mid-1960s. SQUlDs are fundamentally superconducting rings that act as storage
devices tor magnetic flux. We can turn this simple SQUID ring into a device for measuring magnetic
fields. A good balance can detect tiny differences in weight between two objects. Similarly, clever
electronic feedback circuits for SQUlDs enable engineers to detect magnetic field strengths that
correspond to less than a thousandth of a flux quantum in the SQUID ring.
Sensitivity to tiny magnetic fields is the key to the pre-eminence of superconductivity in
magnetometer applications. SQUlDs can detect small fractions of a flux quantum, and a flux quantum
can correspond to very small magnetic fields. Consider the example of the earth’s magnetic field.
CHAPTER 8
Detecting this fields by mechanical methods means is not a trivial task. One needs a well-balanced
compass needle to track the earth’s north pole. For a SQUID, on the other hand, the magnetic field of
the earth is enormous. A SQUID loop the size of your little finger would enclose about a million flux
quanta when threaded by the earth’s field. This unmatched sensitivity overcomes out lack of a biological
magnetic sense. It also opens the doors to a wealth of applications ranging from prospecting to submarine
hunting to medical diagnosis.
One of the most straightforward applications of SQUID magnetometry may turn out to be the
search for valuable ore deposits. Typically, miners know the kind of geological layers in which-minerals
are located but often these important strata are hidden from view by layers of surface-rOcETMagnetometry
can overcome this problem because different rock layers show different'diamagnetic or paramagnetic
responses to the earth’s magnetic field. Superconducting magnetic maps, and especially changes in the
maps over time may prove useful beyond just prospectmgTTiarthquake scientists study magnetic changes
caused by stresses and shearing motion in rock formation. Scientists hope some day it will be possible
to predict likely earthquake periodsbymagnetically monitoring strain build-up deep beneath the earth.
Of all the fields of prospecting, none offers greater rewards nor employs more people than the
hunt for oil. Geologists are able to emply SQUlDs in prospecting for minerals and oil where deposits
can cause local changes in the earth’s magnetic field. The magnetic response of materials has created
yet another application for superconductivity. Refiners can use powerful magnets to pull paramagnetic
impurities out of the ore. This magnetic separation technique has proven to be very valuable in the
processing of fine clay for the manufacture of pottery, paint and glaze coatings.
Finding a submerged submarine is no easy job. Visual searching does not do much better. Neither
radio waves nor light penetrates more than a few metres into sea water. Acoustical techniques like sonar
and passive listening work a little better, but are not ideal. Sound travels further than light or radio
waves underwater, but changes in water density reflect back sound waves, limiting the effectiveness of
acoustical searches. The problem boils down to one of transparency. When it comes to light, radio
waves, and sound, sea water just is not transparent enough for subhunters. Magnetic detection offers
searchers and advantageous alternative to sonar. To magnetism, sea water remains crystal clear. Today’s
submarines are big and have lots of iron-laden steel in them. As a result, the presence of tons of
ferromagnetic material strongly distorts the earth's magnetic field as a submarine passes by. To a magnetic
eye, a submarine shines like a beacon.
Magnetism and Medicines

When fighting diseases, doctors have always faced the challenge of diagnosing what’s wrong before
effective treatment can begin. Superconductive magnetometers are stepping in to create new diagnostic
procedures that are faster, more accurate and less painful. One of the earliest medical applications of
superconducting magnetometers relies on a simple application of what we know about passive
magnetisation. The target disease is hemochromatosis, a genetic disorder afflicting roughly a million
Americans to one degree or another. Despite its prevalence, the disease often escapes detection. It js
difficult to diagnose, often overlooked, and potentially life threatening.
Haemochromatosis involves an imbalance in the body of one vital element, i.e., iron. Iron is
essential for building blood cells and carrying oxygen throughout the body. A healthy body regulates
the amount of iron absorbed from foods and stores some of it in the liver. Any extra unneeded iron in
our diets ordinarily flushes away with other bodily wastes. Sufferers of haemochromatosis have lost
the ability to regulate iron in their bodies. Levels of iron 20 times normal can accumulate in the liver of
a haemochromatosis victim. Eventually the liver becomes saturated, releasing large amounts of iron
into the blood stream. In the blood, excess of iron eventually interferes with the action of the heart,
causing an unexplained heart attack in the undiagnosed haemochromatosis victim.
The control of haemochromatosis becomes relatively simple once accurate diagnosis has been
made. Doctors control mild cases by placing the patient on a restricted diet; in other cases
haemochromatosis sufferers get rid themselves of excess of iron by donating blood with greater frequency.
Neither course of treatment is very complicated; the tough part of the job is making the correct diagnosis.
Testing for iron ions in the blood is unreliable and often only shows signs when the disease has reached
its final, most dangerous stage. Liver biopsies, involving removing and chemically analysing a plug
out of the liver are more accurate, but subject the patient to an extremely painful procedure.
Superconducting magnetometers give doctors the sensitive, non-surgical diagnostic equipment
they need. The iron held in the liver is weakly paramagnetic; while the level of magnetism is far too
small to detect by a crude method like holding a permanent magnet in front of the patients’ torso,
doctors can detect iron concentrations quickly and easily with an instrument called superconducting
susceptometer. A susceptometer combines a superconducting magnet with a superconducting SQUID
magnetometer. The superconducting magnet applies moderately large magnetic fields to the area of the
patient’s torso. SQUID magnetometers then readily detect the paramagnetic response in the liver, giving
doctors an accurate read out of iron in the body. Unlike high-energy X-rays, magnetic fields do not
damage cells. Unlike biopsies, magnetisation testing does not require penetrating the skin and opening
the body to risks of infection, an especially dangerous factor in hospital environments.
So far we have seen the medical applications of SQUID magnetometers and susceptometers
resulting from passive magnetisation. A large superconducting magnet sets up a field, and we read the
response. For some diseases, and active magnetic signal already awaits us, without the need for an
external field. Epilepsy is just such an ailment. Epilepsy is a debilitating disorder. Sufferers of epilepsy
face a life of drug dependency and inevitable side effects from their medication. Recently researchers
have isolated the cause of epileptic seizures. Either through a head injury or a congenital condition, a
portion of the epileptic’s brain malfunctions. During an epileptic attack, the damaged portion of the
brain essentially short-circuits. In mild forms epileptic attacks produce a loss of concentration. More
violent attacks generate seizures as nerve pathways become jammed with meaningless signals from the
damaged site. The only known permanent cure for epilepsy is to remove the damaged portion of the
brain responsible for the disorder. Here doctors face difficult decisions. All brain surgery endangers the
patient. Since mental and physical impairment result from cutting key brain pathways, neurosurgeons
need to pin point the epileptic centre precisely if they are to successfully effect a cure.
Superconducting sensors provide doctors with a much needed to localise epileptic centres deep
within the brain. The short-circuiting action of an epileptic centre produces electrical currents that
generate a distinctive magnetic signature. Doctors place an array of a dozen or so SQUID magnetometers
around the patient’s head. Computers analysing the data from the different sensors can piece together a
three-dimensional picture of activity within the brain. The technique, known as magnetoencephalography
(MEG), has started to appear in leading medical centres.
MEG sensors outperform the electrical sensor grids that doctors relied upon. While an epileptic
centre generates both electric and magnetic fields, doctors can more readily locate it precisely with
magnetic techniques. The skull represents a major difficulty for electric voltage measurements on the
brain. The solid bone masks and smears the electrical signals from inner regions of the brain. Doctors
must actually drill a large number of holes in the patient’s skull to implant electrical probes within
detection range. Such surgery requires extended patient hospital care, and may introduce additional
risks of inflection otherwise.
Magnetic probing on the other hand, turns out to be conceptually must simpler. Magnetic field
pass through the skull as if it were not there. The three-dimensional nature of magnetic fields provides
CHAPTER 8
more information than the simpler voltage measurements. Doctors can nonintrusively search for epileptic
centres using an array of SQUID sensors surrounding the patient’s skull. Using such techniques,
researchers can localise the brain’s epileptic centres to within a few millimetre. MEG can also map
healthy brain tissue and describe its functions.
One final medical application of superconductivity has, within this decade, gone from laboratory
curiosity to widespread hospital diagnostic tool. Magnetic resonance imaging (MRI) has reached the
stage of both medical and commercial credibility. The principles of MRI differ a little from the other
magnetometry techniques so useful in iron susceptometry and magnetoencephalography. In fact MRI is
not really a form of magnetometry at all, although MRI does depend on superconductivity. Instead,
MRI relies on magnetism and a special kind of behaviour of atoms in a magnetic field.
The nuclei of many atoms, notably hydrogen atoms, act like tiny magnets. When an outside
magnetic field appears, these magnet like nuclei tend to line up with field like a compass needle. Some
atomic nuclei try to point out the otherway, but orienting against the magnetic field is not energetically
favourable. The signal used for MRI imaging comes about from the dynamic about of these nuclear
magnets. When an atomic nucleus switches from being aligned against the magnetic field to being
aligned with the magnetic field, a small amount of energy is released. The energy takes the form of an
electromagnetic (radio) wave. The frequency emitted depends on the strength of the magnetic field and
the particular kind of atom that emits the energy.
The MRI imaging process begins by placing the patient in the bore of a cylindrical magnet. The
magnet maintains a steady, precise magnetic field through a cross-section of the patient’s body. The
magnetic field aligns the nuclei of the body’s atoms and sets the frequency of the electromagnetic
energy they emit. Then we supply a sharp electromagnetic pulse—a brief burst of energy to kick these
atoms. This temporarily scrambles many of the atomic alignments with the magnetic field. After the
pulse has ended, the nuclei can realign with the magnetic field, and when they do they emit their
characteristic radio signal. Arrays of detectors pick up the emitted radio waves for computer analysis.
Sophisticated computer analysis then translates the data into a complete picture of a magnetic slice
through the body.
An MRI corresponds to taking an electronic census of the body’s hydrogen atoms. Hydrogen
turns out to be a very useful monitor of the body’s health. Since two-thirds of water consists of hydrogen
atoms, water rich tissues respond strongly to MRI probes. Most organic materials are also hydrogen
rich and also show up readily in MRI scans. In contrast, bones remain relatively dark. That is a big plus
point for doctors trying to examine brain tissue otherwise hidden by the skull.
MRI system designers must satisfy though demands and face some of their greatest challenges
in the magnetic system. For MRI to work, the magnetic fields must be strong, very uniform, cover an
area large enough to span the patient, and maintain stability to better than one part in a million even over
periods as long as an hour. Superconducting magnets, with their persistent currents’ ability to hold
StM© SwstJbwscs
fields absolutely constant, answer the demands made of MRI equipment, Because superconducting
magnets are more compact and lightweight than their normal metal counterparts, superconducting MR|
systems can fit into available hospital space without requiring big investments and special facilities,
In operation MRI complements X-rays, but offers some important advantages. Because bones
block X-rays, doctors still prefer X-ray images to study bone fractures and skeletal deformities. MR|f
on the other hand, resolves organs that are nearly transparent and featureless to X-rays. Tissue
abnormalities show up strikingly on MRI images. Furthermore, doctors using MRI do not have to cope
with the cell damaging ionising radiation of X-rays. All in all, in a very short period, MRI has emerged
as a key medical diagnostic tool and superconductivity has played an important enabling role in its
development
Within only a decade of being discovered, a new class of materials that conduct electricity with
virtually no resistance losses are inside working prototypes of some of the key elements of a
superconducting power grid. Several prototype devices are being tested or are nearing testing on
utflity systems in the U.S. Electric wires that become superconductivity when cooled to the affordable
operating temperature realm of liquid nitrogen as well as coils, magnets, conductors and machines
and power components made with these wires—appear a sure bet to enter commercial markets for
utility equipment over the next few years. Whether such high temperature superconductors capture a
significant share of these markets will depend on whether they can deliver a strategic competitive
advantage with offering reliability and costs comparable to those of conventional copper or aluminium
conductors.
As a scientific phenomenon, superconductivity has been recognised for about 85 years, but its
potential for electric power applications that could have a major technological and social impact has
broadly captured the interest of electric utilities only in the past 10 years. Worldwide scientific and
media excitement were ignited in 1986 when physicists of at an IBM laboratory in Switzerland working
with small samples of an obscure class of rare-earth, containing ceramic oxides of copper, reported
signs of resistance-free conduction of electric current at the unprecedented high absolute temperature of
35 K. Before that, the search for higher temperature superconducting materials had gone slowly; the
known transition temperature to a superconducting state had taken 75 years to increase the 4 K boiling
point of liquid helium (the transition temperature of the first metal Hg in which the phenomenon) was
observed to around 23 K.
Within a year of the 35 K achievement, other scientists reported superconductivity at a transition
temperature of 91 K in a similar ceramic copper oxide that contained yttrium and barium. Suddenly,
practical utility applications of superconductivity appeared to be within reach, because devices made of
materials having that transition temperature could operate with cooling by cheap unexotic liquid nitrogen,
which boils at 77 K.
Today materials that become superconducting at transition temperature as high as 135 K have
been verified, and over 100 compounds are considered high temperature superconductors (HTSs).
Successes by scientists around the world during the past decade have the commercial development of
HTS wires (in kilometre lengths) and devices having, at liquid nitrogen temperature, as much as
100 times the current carrying capacity or ordinary conductors. Such wires are already being employed
to fabricate prototype conductors for use in superconducting underground transmission cables and in
device prototypes for other applications.
But for key electric power applications such as motors, generators and magnetic energy storage
systems, superconductors must be able to maintain their super performance while saturated by very
strong, self-generated magnetic fields. The principal HTS material that has been successfully fabricated
into flexible wire for use in R&D and in prototype devices—a bismuth strontium calcium copper oxide
(BSCCO) compound—loses its superconductivity in the presence of moderate magnetic fields at 77 K,
although it performs quite well when cooled to 20-30 K. Recently, the original 91 K material, one of the
earliest HTSs known, has been shown to perform very well in high fields at liquid nitrogen temperature.
This has led to renewed hope for the material yttrium-barium-copper oxide (YBCO)—whose inherently
poor grain alignment had previously made it undesirable as practical wire material.
Research on next generation, high-field YBCO HTS wire technologies struct pay dirt last year
when scientists at the U.S. department of Energy’s Los Alamos National Laboratory obtained more
than 1 million ampere of current per square centimetre of superconductor cross-section (A/cm2) 77 K in
short lengths of flexible tape. To make the tape, a low-energy ion beam was used to texture a substance
for one micrometre thick film of YBCO.
The YBCO tape retained a critical current density up to 100000 A/cm2 (one-tenth of its zero
field current density) at 77 K under parallel magnetic fields as high as 8 tesla—several times the field
typically generated in medical magnetic resonance imaging (MRI) machines that use liquid-helium
cooled low-temperature superconductors (LTSs). The current density of the YBCO tape in a high magnetic
field is comparable to the highest density obtained today in zero magnetic field at 77 K with the more
readily manufacturable, commercial HTS wire fabricated by power-in-tube processing and mechanical
forming of BSCCO compound. And experts say that, in principle, YBCO conductors could be capable
of current densities as high as 5-7 million A/cm2.
Soon after the achievement at Los Alamos, which built on pioneering work in Japan five years
ago, researches at Oak Ridge National Laboratory said that they had successfully developed a fabrication
method for texturing wire substrate to achieve a high degree of YBCO grain alignment and, in turn high
current density. They have since reported obtaining up to 700000 A/cm2 with this approach—a rolling
and pressing method.
Although success in transferring the excellent performance properties of the YBCO tape from
the laboratory to useful lengths of wire produce in a commercial manufacturing environment is by no
means assured, the Los Alamos and Oak Ridge achievements with YBCO conductors have invigorated
the HTS R&D community, rekindling the excitement that originated with BSCCO wire technology.
Meanwhile, the handful of companies in the U.S. and abroad that are commercially producing
multi-filament BSCCO wire continue to increase critical current density, which is nearing 50000 A/cm2
at 77 K. Such a level is adequate for practical application because the fill factor (the fraction of
superconductor to metal) in such wire is significantly higher than in the thin-film processes used to
make YBCO conductors. The performance properties of long lengths of BSCCO wire are now comparable
to those obtained with short, research-grade wires, experts say.
Watershed Breakthrough
“It is worth considering the past decade’s progress in HTS in light of the experience with low temperature
superconductivity,” says Dr. Paul Grant, an executive scientist on EPRI’s Strategic R&D staff and a
former IBM research scientist. The basic practical LTS wire material used today in some large scale
applications, such as MRI magnets, is niobium-titanium (Nb-Ti). It took almost 25 years from its discovery
to fully understand and optimise that material.
He believed that two factors were critical in the rapid progress achieved with the ceramic
HTS materials—materials that are intrinsically more difficult to work with than LTSs, which are
Pwvstes
more like metals. “Unlike the case with low temperature superconductors, the discovery of high
temperature superconductors was one of those rare scientific breakthroughs that excited people
across a wide spectrum of science," says Grant. “Physicists were suddenly thrust into the lime
light, but it rapidly extended to engineering, materials science, and much in-between.” The
development of LTS materials was more evolutionary and incremental.
“Equally important in the case of HTS materials was the availability, beginning in the 1970s, of
really marvelous analytical instruments such as the transmission electron microscope and techniques
like Rutherford back scattering,” continues Mr. Grant. “The new instruments allowed scientists to peer
into materials at the atomic scale and to learn the role that each atom plays. That, in turn, led to the
development of new processing techniques, first used for semiconductors but now being successfully
applied in the equally challenging material area of HTSs.”
The Critical Role of Wire

Chip-sized HTS thin films and electronic devices such as signal filters and ultrasensitive magnetic
detectors are already at the threshold of commercial use. But virtually every significant electric power
application envisioned for HTS technology depends crucially on the development of high performance
multifilament wire. Such wire and stranded conductors fabricated from it must form the coils for motors,
the rotor windings for generators, and the conductors for power cables and superconducting magnetic
energy storage rings.
The EPRI has research that helped to identify a lead-stabilished BSCCO compound known as
Bi-2233 as one of the most promising compounds. This compound is now the material of choice for
wires and tapes produced by two leading U.S. companies persuing commercial HTS development
American Superconductor Corporation (ASC) and Intermagnetics general corporation.
Manufacturers continue to improve the performance of commercial BSCCO wire, which already
meets or exceeds the requirements for some power applications, such as connectivity for transmission
cables. “The key issue is BSCCO to identify those factors that control the conductivity of the
polycrystalline filaments of the wire” says Dr. David Larbalestier, professor of materials science and
engineering and also physics at the Applied Superconductivity Centre. “Continued progress in the critical
current densities of the wires has come from careful study of their current-limiting mechanisms”, he
notes.
Seemingly inherent limits on the ability of the two-dimensional, polycrystaline structure of
BSCCO to pin magnetic flux adequately at high temperatures may mean that it will remain as less than
ideal HTS wire material for high (1 tesla) magnetic field applications at liquid nitrogen temperature.
Scientists have identified many of the critical relationships that limit BSCCO’s performance in high
magnetic field at 77 K—relationships between poor flux pinning, low-angle grain alignment, cracks
and phase impurities, and the uneven distribution of supercurrent flowing in the material.
The current density and other performance characteristics of commercial BSCCO wire are good
enough to keep several application development efforts busy building prototypes, testing them, and
refining their designs. These programmers provide ongoing feedback to wire manufactures on how to
further improve performance properties. Such efforts provide a glimpse of how HTS materials promise
to transform today’s electric power grid and to shape the way electricity is managed and used in the future.
Generally, in every potential power applications of HTS materials, their much higher current
densities and reduced resistive losses will lead to components and systems that are smaller and lighter
as well as more powerful and efficient.
A superconducting power system will be able to meet growing demand for electricity with fewer
power plants and transmission lines than would otherwise be needed. Several branches of the defense
establishment are also pursuing HTS applications such as motors, generators and energy storage.
You Soda State Physics
Power System Control and Protection

Superconducting fault current limiters could afford utility equipment (for example, breakers, fuses and
switches) greater protection against large momentary power spikes caused by short-circuits or lightning.
• Moreover, such devices could provide utilities a way to interconnect parts of distribution systems more
tightly and to manage power Hows more effectively with less redundancy of protective equipment and
substation capacity. Such extra capacity is now maintained in order to limit the maximum potential fault
current on any particular circuit.
American researchers have* tested 2.4 kV, 2.2 kA single-phase fault current limiter. At the heart
of the device was a coil wound from BSCCO wires. In an energisted equipment test facility the prototype
met or exceeded all design targets.
Motors and Generators

Rotating electrical equipment depends on rotar windings or solenoid coils that can generate strong
magnetic fields as part of normal operation. Such fields can be achieved with BSCCO wire based rotar
coils operated at 20-40 K, and such coils are expected to provide cost-effective commercial motor
performance. If YBCO-coated conductor tape is successfully developed, it could offer the further benefit
of permitting operating temperatures around 77 K. In the mean time, although commercial BSCCO
based HTS wire shows relatively poor performance at 77 K in high magnetic fields, its properties are
sufficient to enable significant progress in the engineering development and scale-up of prototypes for
both HTS motors and generators.
Electric motors are used extensively by utilities and others. They are ubiquitous, consuming
! more than 55% of all the electricity generated. And large motors (greater than 1000 hp) accounts for
more than half of that consumption. HTS motors will provide such compelling benefits and operating
j advantages that they could eventually dominate the global market for large motors, which now exceeds
; £1 billion a year. HTS motors are expected to be half the weight and half to one-third the size of
conventional motors, to be much quieter, and to offer lower operating costs.
A 200 hp motor, built with BSCCO wire based rotor coils has been operated at 1800 r.p.m. at
27 K. The next goal is to demonstrate larger units, first a 1000 hp motor and then, by the year 2006, a
5000 hp pre-commercial prototype.
A conventional 10000 hp motor that uses the copper wire coils is about half the size of a bus. An
HTS motor of the same power will have half volume and weight and will save a lot in electricity costs.
In Japan, several large electric equipment manufactures are participating in a major
superconducting generator project, called Super GM. The effort is organised by the country’s Ministry
of International Trade and Industry. The LTS generator will have Nb-Ti coils and operate at liquid
helium temperature. The project reportedly has nearly completed a 70 MVA prototype at Kansai Electric
Power’s Osaka station and plans to begin testing of the machine this year. Commercial HTS generators
are expected to have ratings of 200 MVA or more.
Maglevs and More

High-field HTS magnets could open up an entirely new realm of applications both within and beyond the
utility industry, with potentially even broader social impact than those already glimpsed for the near future.
In Japan, railway research engineers are considering whether to make a major new push to
develop magnetic levitation (maglev) trains—prototype of which with LTS magnets have been
successfully tested—or to focus instead on developing a new generations of the country’s 30 year old
bullet train technology. Observers expect that high-field HTS magnets would be used in place of LTS
magnets if maglev is targeted for major development.
At the Texas Centre for Superconductivity at the university of Houston, researchers have made
(ic brings with melt-texturcd single-crystal YBCO. Such bearings could be used to reduce the
loss of rotational force in a large flywheels that, in turn, could be used both to store energy and to absorb
newer fluctuations in utility and customer applications. The bearings are expected to be simpler and
tess costly than the so-called active magnetic bearing used today in some rotating machines. Japanese
arealso working on developing and reducing the cost of producing single-crystal YBCO chips for
magnetic bearing. Other research groups in Japan have produced magnetic flux-trapping YBCO discs
that can levitate by several inches large permanent magnets with people standing on them.
Related applications of high-field HTS materials include large and medium capacity
CHAPTER 8
superconducting magnetic energy storage (SMES) systems. SMES designs based on the use of large
diameter, liquid helium-cooled Nb-Ti LTS conductor coils have been developed under government
R&D programmes in the U.S. Such designs could be adopted to use HTS conductors at 20-40 K.
Meanwhile, microcapacity SMES units—some with helium-cooled LTS coils and others with HTS
coils cooled with liquid nitrogen are already being commercialised by a number of firms for protecting
sensitive industrial and commercial loads from momentary power glitches or interruptions.
Towards Superconducting Future

It is ironic, although perhaps of little significance for the prospects for practical applications, that “we
still don’t know the mechanism of superconductivity at high temperature,” say Dr. Grant.
The many ongoing and approaching HTS prototype developments are solid evidence of the
rapid progress from discovery to demonstration that has been made in only a decade’s time. It appears
ever more likely that superconducting machines and power cables will be operating on utility systems
by early 21st century. These prototypes will provide the technical data and operating experience that
will determine whether the still-mysterious but marvelous scientific curiosity of high temperature
superconductivity can indeed be the basis for utility power system of the future.
— Electric Power Research Institute (U.S.) Journal (1988)
The happiest moment for us will be the moment of hearing a new theory with the details of
experimental procedures for converting aluminium into a superconductor in the temperature range
260 K to 320 K. One of the simplest theories in the case of many metals is that in the superconducting
state two electrons may form a bound state. This pair of electrons is called Cooper pair. For T < Tc, the
lattice-electron interaction is stronger than the electron-electron coulomb force. In the superconducting
state, the electrical current is due to the motion of several Cooper pairs in the same direction with the
same velocity; only a single de Broglie wave can then be regarded as collectively representing these
Cooper pairs. Since the momentum of the Cooper pairs is small, the wavelength of the de Broglie wave
becomes very large, scattering from imperfections rarely occurs, and the conductivity tends to infinity.
The energy gap in such cases is of the order of 10" 4 eV at 0 K and it disappears at T = Tc. Further
applications of higher mathematics and putting our heads together on these propositions may throw
some more light to achieve the said goal.
Important Events
Some important dates in the history of discoveries of different phenomena and new theories in
superconductivity are listed below:
1. 1908 H. Kamerlingh Onnes became the first person in history to liquefy helium.
2. 1911 Discovery of the phenomenon of superconductivity by H. Kamerlingh Onnes; persistent
currents and critical magnetic fields. He received the Nobet Prize in physics in 1913.
speculated the negative resistance characteristic seen in Giaever’s tunnelling junction* would
lead to important applications in amplifiers and switches.
1962 Brain Josephson, a brilliant graduate student at Cambridge University learned Giaever’*
work on electron tunnelling. Giaever had considered the possibility of superconductor-
pair tunnelling but, like others, decided that such behaviour was unlikely to be measurable
since the probability of two electrons tunnelling together would be vanishingly small. In
contrast to Giaever’s largely experimental approach, Josephson solved his problems by
reasoning and calculation. He considered the coherence of the electron pair. Eventually,
his expression for current flow through a superconductor-insulator-superconductor junction
predicted a current flow when the voltage across the function was zero (Josephson, 1962).
•
CHAPTER
Furthermore, if a small d.c. voltage (V) was applied across the junction, the current would
oscillate at a frequency equal to (2 eV/h). No one, of course, had expected such peculiar
behaviour in the simple junction structure. There was also the misunderstanding about the
probability of coincident tunnelling of two electrons. However, when the coherence of the
paired electrons is considered, the actual probability of pair tunnelling is much higher
(Tinkham, 1985).
Happily, Josephson’s predictions were confirmed in experiments by John Rowell and P.W.
Anderson (1988). The predictions of Josephson, which seemed so unlikely, are now the
very heart of a variety of practical superconducting devices used for ultrasensitive magnetic
field measurements and voltage standards, as well as for computer logic gates and memories.
Ivar Giaever and Brain Josephson each received Nobel Prize in Physics for their work.
13. 1975 A report by Sleight, Gillson and Bierstedt of superconductivity at 13 K in [Ba Pbj x Bi*
O3] was primarily of interest to theorists, since better practical superconductors at higher
temperatures were already in use. The report is now considered quite significant in the
history of superconductivity, since the material had ‘perovskite’ related structures. It-was a
hint of remarkable developments to come.
14. 1980 Juri Matiso had demonstrated a device that he called a tunnelling cryotron, in reference to
the relatively slow cryotron switch. This logic gate was the basis for a superconducting
Josephson computer.
15. 1986 Superconductivity in lanthanum-barium copper oxide at 30 K was reported. For the
development of scanning tunnelling microscope (STM), Binning and Rohrer won the 1986
Nobel Prize in Physics.
16. 1987 George Bednorz had a long-standing interest in the characteristics of perovskite crystals.
He had worked with Gerd Binning in a study of superconducting properties of SrTiO3.
Together they increased the Tc of this perovskitt from 0.3 K to 1.2 K by doping the crystal
with Niobium. Bednorz found this experimental efforts exciting. When he was asked by
AlexMuller to collaborate, he accepted. Muller-Bednoz discovery led to interest in a variety
of new compounds that like La-Ba-Cu-O, are structurally similar to a class of ceramics
known as pervoskites. In addition, the possible commercial application of materials with
Tc at 30—35 was a distinct improvement over the best to date for niobium-tin alloys at
about 23 K. The 1987 Nobel Prize in Physics was awarded to Muller and Bednorz.
17. 1988 A group including Robert Cava and Bertram-Batlogy reported superconductivity at about
30 K in a material (Ba06 K04 BiO3) that, as indicated has no copper.
18. 1991 It was pointed out by D. van der Marel that the cross-over from Bose-Einstein condensation
to BCS superconductivity is characterised by a change of character of the lowest excitations
of the system. Bosonic collective excitations in the former case and ferminoic pair-breaking
excitation in the later case. Depending on with type of excitation dominates, the phase
$18 StAio State Physics
transition to the normal state can be regarded as Bose*Einstein condensation or as BCS

superconductivity. An intermediate situation where both types of excitations contribute to
the superconductor to normal transition is also possible. In both extreme cases there is a
discontinuity at Tc of the chemical potential, although the detailed behaviour is quite different
19. 1996 D.M. Lee and others discovered superfluidity helium 3. Received Nobel Prize.
20. 2003 AJ. Legget and others proposed two areas of quantum physics—superconductivity and
superfluidity. They were awarded the 2003 Nobel Prize.
SUPERCONDUCTIVITY—TODAY AND TOMORROW

by
V.L. Ginzburg
(Russian Academy of Sciences, April 2000)

Undoubtedly, the study of HTSC in cuprates made us realise or rather recall that the phonon mechanism
and the BCS approach itself are not the only possible ones for the understanding of superconductivity.
Indeed, superfluidity in 3He and in neutron condensation (below BEC) leading generally to superfluidity
in the case of neutral particles and to superconductivity for charged particles does not depend on the
boson formation mechanism (we mean the formation of bosons as a result of pairing of two elections).
Such a mechanism may be called Schafroth according to V.L. Ginzburg.
‘Today’ should not be March 2000 when this paper being written, but it should be some events.
What event will be? It is desirable that this landmark be the insight in the mechanism of superconductivity
in HTSC cuprates. So many experimental results on cuprates have been obtained in the 13 years and the
experimental methods employed have so much advanced that a certain clarity may be expected in the
experiment in the near future. If this happens the theoretical comprehension will hardly keep us waiting
long.
If the phonon mechanism with strong coupling, though not the only one, it still determining, the
value of the critical temperature Tc is unlikely to exceed approximately 200 K. Undoubtedly, many
laboratories are engaged in the search for materials with increasingly high T values. The lack of advances
in this direction over a number of years (since 1994) testifies to the fact that the 7^ of cuprates and many
. other compounds can hardly be raised. But the number of possible components is huge, which of course
gives hope for finding a substance with a high Tc value.
It should be mentioned here that the current situation in solid state theory cannot yet be thought
of as satisfactory. The progress made over the past century is of course great if we look at the distance
passed from the idea of electron motion in conductors, suggested by Drude in 1900, up to today’s
condition of the physics of metals. But on the other hand, namely metallic hydrogen cannot be predicted
from “first principles”. There is no doubt that the theory of many particle systems faces unsolved problems
of great difficulty. Not until becomes possible to calculate the parameters and characteristics of compounds
of any prescribed composition and structure will be able to think of condensed-matter theory as
particularly accomplished. Certainly, this also refers to superconductors (true, it should be pointed out
that for simple metal like Al and Pb, advance have already been made. It is difficult to say how many
decades we shall wait for the achievement of this goal. We now have only one natural landmark in view
the year 2011, the centenary of the discovery of superconductivity. Unfortunately, we are unable to
make definite prognosis even for the decade left before this centenary. But I would not be very much
surprised if room temperature superconductors were created by 2011. This is, however, no more than a
dream. But high temperature superconductivity had also been only a dream before 1986.
Sharp Insight into Ceramics, Superconductors

Scientists at Research Centre Jiilich have made individual oxygen atoms directly visible with an electron
microscope in a certain class of materials, the perovskites.
They have developed a technique to correct the unavoidable aberrations in the microscope. In
commercial instruments, these aberrations inevitably lead to blurred images in which no individual
oxygen atoms can be recognised. The findings have been published in Science.
CHAPTER 8
Perovskites application is already widespread, for example as chips in phonecards or pay-cards.
Perovskites are also the base material for high temperature superconductors and will be increasingly
needed in future microelectronics where they will be used in ultra-thin films of just a few tens to several
hundreds of atomic layers.
One of the most important problems on the way to this goal is the correct adjustment of the
oxygen content of these oxides, which then has to be maintained throughout the large number of process
steps in device fabrication. “The oxygen content critically determines the electrical properties of the
perovskite oxides,” says Prof. Knut Urban from the Julich Institute of Solid State Research explaining
the problem.
“Since even the absence of a few oxygen atoms in the electricity active zones of the thin films
would seriously impair their function they must be fabricated with almost atomic precision.”
Transmission electron microscopy can be used in principle to check whether this atomic precision
has actually been achieved. The basic principle of electron microscopy is quite simple: An electron
beam penetrates a thin specimen. The outgoing electrons are guided by an electromagnetic lens system,
which combines them into a greatly magnified image.
However, for various reasons distorted images result in which no individual oxygen atoms can
be recognised.
The group headed by Knut Urban has now achieved a breakthrough. The scientists work with
the only so-called “aberration-correlated” transmission electron microscope in the world so far.
The problem of “spherical aberration” occurs in both optical and electron microscopes. Light or
electron beams that pass through the lenses of the microscope close to the edge are deflected too strongly—
the unage is blurred.
With specially shaped magnetic lenses, however, the researchers are able to correct this previously
Avoidable aberration.
They have metaphorically speaking, prescribed spectacles for the electron microscope thus
focusing its sight.
This step has now been proved to be extremely successful. It does not only permit oxygen to be
lmaged atomically for the first time, but also enables the content of the oxygen to be measured accurately
quantitatively in atomic dimensions.
A group of “high temperature” superconductors made with layers of copper oxides sandwiched
®^ween insulating filler material have been developed by materials scientists. This material reaches
cntical temperatures in the range of 130 K, the highest known critical temperatures to date. Previous
Judies on superconductors have established that while the critical temperature rises as the number of
ayers increase from one to three, it then drops off. The critical temperature has fallen below that of the
Slngle-layer superconductor by the time the number of layers rises to seven. It is previously suggested
^20 Soud 9mn Pmwo
by s< icntists that the critical temperature increases between one and three layered materials is due to the
ability of electron pairs to tunnel between layers of superconducting material.
The factors that combine with a mechanism—known as the competing order—that lowers a
superconductor's critical temperature in materials with more than three layers have been identified now
by Prof. Kee and her colleagues. That “competing order", in turn, is dependent on an uneven distribution
of electrons, resulting in a charge imbalance between the material multiple layers. Kee and her colleagucs
are the first group to put these three factors—the tunnelling, the competing order and the charge imbalance-
together.
“If we can find a way to affect the charge imbalance, we could supress the competing order and
develop superconducting materials with higher and higher critical temperatures,” says Kee. “And if
you can push the superconducting temperature higher, then it will become much cheaper to apply this
technology.”
Expressing concern over mounting transmission and distribution (T and D) losses in the power sector,
the former President A.P.J. Abdul Kalam asked the Union Power Ministry to bring down these losses
from 31000 MW to 12 MW in a couple of years comparing with that in developed countries.
Prof. Kalam said if the country were to set up fresh capacity to cover up the loss, it would cost cover
Rs. 76000 crores. This is the magnitude of the problem we are faced with; he added while addressing
a group of Engineers attached to Central Electricity Authority.
Prof. Kalani’s worry (24th August, 2004)
The phenomenon of superconductivity was observed by K. Onnes about hundred years ago in (1911)
mercury. The transition temperature of the widely used metal aluminium is 1.2 K. That is below this
temperature electron-phonon-electron interaction becomes stronger and Cooper pairs are formed.
AU of them have the same de Broglie wavelength with very small momentum and hence scattering
of Cooper pairs becomes absent, mobility becomes infinity. Thus, the conductivity of aluminium
tends to infinity and power loss may be reduced to even zero value.
Huge financial assistance is made available in U.S., U.K. and India too for research work in
this area. If any one in this planet develops a method to form such pairs or techniques to reduce
scattering of free electrons almost nil at 300 K in aluminium to prevent power loss, that day will
bring immense pleasure to our President and he will be the first person to jump with joy.
Dr. Pillai’s nightmare
QUES I lUNSi *....... ..............

1, Superconductors are generally
(a) ferromagnetic and antiferromagnetic metals (b) monovalent metals
(c) amorphous thin films of Be and Bi (d) thin films of barium titanate
2, Hard superconductors observe
(a) breakdown of Silsbee's rule (b) incomplete Meissner effect
(<■) high critical field and transition temperature (d) all of these
Soft superconductors observe
(a) Meissner effect (b) Silsbee’s rule
(c) both (u) and (b) (d) none of these
4. The temperature at which a conductor becomes a superconductor is called
(a) superconducting temperature (h) Curie temperature
(c) Onne s temperature transition temperature
5. The specific heat of a superconducting material shows an abrupt change at T - T jumping to a large value
■ for c
(a}T<Tc {b)T>Tc (c)T=Tc
6. In superconducting state
(a) entropy increases and thermal conductivity decreases
(b) entropy and thermal conductivity decrease
CHAPTER 8
(c) entropy and thermal conductivity increases
(d) entropy decreases and thermal conductivity increases
7. Superconductivity results due to
(a) crystal structure having infinite atomic vibrations at 0 K
(b) crystal structure having no atomic vibrations at G K
(c) all electrons interacting in the superconducting state
(d) all electrons having Fermi energy at 0 K
8. The transition temperature of most superconducting elements lie in the range
(a) zero to 10 K (b)10Kto20K ; '
(c)20Kto50K (d) above 50 K
9. The transition temperature of mercury is
(a) IK (b) 1.14 K (c)4.12K (d)9.22K
10. Wire wound crypton is a superconductor having -
(a) copper as control wire and tungsten as gate wire
(b) niobium as control wire and tantalum as gate wire
(c) nichrome as control wire and tungsten as gate wire
(d) tungsten as control wire and nichrome as gate wire
11- A superconducting material when placed in a magnetic field will
(a) attract the magnetic field toward its centre
(b) repel all the magnetic lines of forces passing through it
(c) attract the magnetic field but transfer it into a concentrated zone
(<f) not influence the magnetic field
12. A superconducting material on being subjected to the critical field changes to
(a) critical conductivity
(b) superconducting which is independent of temperature
(c) normal state
(cf) remains uninfluenced
I3- Value of critical current density (jc) in a superconductor depends upon
(a) temperature (*) magnetic field strength
(c) both (a) and (b) W Silsbee effect
1^* Transition temperature Tc and critical field Hc for a superconductor are related as
(b)//c = Ho (Tc + 1)
(c) Tc = To [ 1 - (<0 Hc = Hq [ I - MT,)2]
15. The width of the energy gap of a superconductor is maximum at
(a) 0 K (b) transition temperature
(c) room temperature (d) none of these
16. The width of the energy gap of a superconductor at 0 K is about
(a) 0 joule (b) 3.5 kB Tc
{c)kBTc (d) 300kBTe
where Tc is the critical temperature
17. As the isotopic mass of mercury decreases
(a) the critical temperature increases slightly
(b) the critical temperature decreases slightly
(c) remains constant
(d) none of these
18. Cooper pairs are formed
(a) at very low temperatures as the thermal energy is not sufficient to disrupt the binding
(b) at high temperatures as the thermal energy is sufficient to form the cooper pair
(c) none of these
19. The favourable condition both for superconductivity and high resistance is
(a) a weak electron-phonon interaction
(b) a strong electron-phonon interaction
(c) a weak phonon-phonon interaction ..
(d) none of these
20. The coherence length of the paired electrons is
(a) 0.25 nm (b) 250 nm ■ '(c) 0.01 nm (d) 0.001 mn
21. The London penetration depth is given by
(a) A. = [>n/zis|I0e2]i;2 (b) A. =
(c) A. = - (d) none of these
22. Superconducting state is more ordered than the normal state for type I superconductors
(a) true (b) false
1. What is superconductivity? Outline the experimental facts about this phenomenon.

2. Explain Meissner effect.
• . k. - ' - "
3. Mention the important property changes that occur in materials when they change, from normal to
superconducting state.
4. How does superconducting transition temperature vary with magnetic field?
5. What are the practical uses of superconductors?
6. Bring out the salient experimental features of superconductivity.
7. Mention three important applications of superconducting materials,
8. Explain the effect of isotopes on superconductors.
9. Define critical magnetic field.
10. How does the critical magnetic field vary with temperature in Type n superconductors?
II. Give the significance of London's equations.
12. How Cooper pairs are formed in superconductors?
13. Give a rough estimate of band gap in superconductors.
14. At what temperature the band gap disappears and why?
IS. Give the salient features of BCS theory of superconductors.
14. Explain 1-2-3 superconductors.
17. What is Josephson's effect?
HU Explain London's penetration depth.
CHAPTER 8
W. Give the principle of SQUID.
2ft. Explain coherence length for electrons in superconductors.
El ILIRPW
1. What are superconductors? Mention the important property changes that occur in materials when they
change from normal to superconducting state. Give some examples of practical uses that exploit the above
property changes.
2. Bring out the salient experimental features of superconductivity. Mention the important applications of
superconductivity.
X What is meant by superconductivity? Describe the effect of
(a) magnetic field
♦
(b) frequency and

(c) isotopes on superconductors.
Mention a few industrial applications of superconducting materials.
4. Nare two superconducting materials. Define the critical magnetic field and derive the thermodynamic
relation connecting the critical magnetic field and the transition temperature. What are the applications of
superconducting materials? /
X Explain the term critical magnetic field in a superconductor. How does the critical magnetic field vary
with temperature in T\pe I and Type n superconductors? What is Meissner effect?
6. Write an essay on superconductivity bringing out the importance of London’s equations in explaining
several expertmental facts related to this phenomenon.
%
7. Er plain the two components model of a superconductor. Arrive at London's equations and hence deduce
Meissner effect
Briefly outline BCS theory of superconductivity and describe one experimental evidence for the existence
of energy gap.
8. What is superconductivity? Give an account of the occurrence, properties and uses of superconductors. •
9. Give an elementary account of superconductivity and its applications.
1ft. Derive the London equations and explain the term coherence length. Explain 1-2-3 superconductors.
11. Arrive at London’s equations and explain how its solution explain Meissner effect.
12. Discuss fully the thermodynamics of the superconducting transition and derive Rutger's formula for specific
13. Write a short essay on superconductivity.

14. What is superconductivity? Explain Meissner effect What are the possible applications of superconductors?
15. Discuss the origin, development and important properties of superconductivity. What is BCS theory of
superconductivity? Discuss the various applications of superconductivity. What are superconducting
o
magnets?
16. Explain superconductivity. List out the properties that change below the transition temperature and those
that do not change. How is superconductivity affected by magnetic field?
Name three applications of superconductors and describe one of them in detail.
17. What are superconductors? Mention the important property changes that occur in materials when they
change from normal to superconducting state. Give some examples of practical uses that exploit the above
property changes.
18. Give an account of the phenomenon of superconductivity.
Explain Type I and Type II superconductors. Write a note on the application of superconductivity.
19. What does the equation (dB/dt) = 0 tell us? Is this equation adequate to explain superconductivity? If not,
why ?
20. Perfect diamagnetism of a material is due to a certain electron arrangement Do you think that this electron
arrangement is compatible with zero resistance of superconductors. Why are not all diamagnetic material
have zero resistance property?
21. Can you give an idea of the material parameters which you want to manipulate to raise the superconducting
transition temperature? Do you think that there is a theoretical limitation for raising the transition temperature
indefinitely?
22. It is said that the relaxation time of the conduction electrons in a superconductor is infinite. Do you think
that it is a correct concept?
It is said that the phenomenon of superconductivity is analogous to the phenomenon of superfluidity in
liquids. Comment.
23. Discuss d.c. and a.c. Josephson’s effects and explain their importance.
24. Describe the principle of a superconductive quantum interference device (SQUID). List out their uses and
their engineering applications.
25. Discuss high temperature superconductors with special reference to 1-2-3 superconductors.
26. Discuss briefly the potential applications of superconductors. Write a note on magnetism in medicine.
27. Derive the London equations and explain the term coherence length.
28. How are cooper pairs formed? Explain the BCS theory of superconductivity and discuss the energy gap
based on this theoiy.
29. Explain d.c. Josephson’s effect. Show that the supercurrent of superconducting pairs across the junction
depends on the phase difference.
30. Discuss a.c. Josephson’s effect. Show that the current oscillates with frequency,
1.Calculate the critical current which can flow through a long thin superconducting wire of aluminium of
diameter 10-3 m. The critical magnetic field for aluminium is 7.9 x 103 amp/metre.
2. The critical temperature, Te for mercury with isotopic mass 199.5 is 4.185 K. Calculate its critical temperature
when its isotopic mass changes to 203.4.
3. A superconducting Nb solenoid carries a current of 20 ampere in order to produce a magnetic field of
6 x IO4 ampcre/mctrc. If the solenoid is immersed in liquid helium (4.2 K) and Ho for Nb is 1.56 x 105
ampcre/mctrc, estimate the minimum diameter of the wire that may be used. Tc for Nb is 9.5 K.
4. Calculate the critical current density for 1 mm diameter wire of lead at
(a) 4.2 K
(b) 7 K. A parabolic dependence of Hc upon T may be assumed. Given: Tc for lead is 7.18 K and Ho for
lead is 6.5 x 104 ampere/metre.
5. A superconducting tin has a critical temperature of 3.7 K in zero magnetic field and a critical field of
0.0306 tesla at 0 K. Find the critical field at 2 K.
CHAPTER 8
6. For a specimen of V3Ga, the critical fields are respectively 1.4 x 105 and 4.2 x 103 ampere/metre for 14 K
and 13 K. Calculate the transition temperature and critical fields at 0 K and 4.2 K.
7. The penetration depth X of mercury at 3.5 K is about 75 nm. Estimate the values of
(a) X and
(b) ns (superconducting electron density) as T -> 0 and Tc = 4.12 K.
8. Estimate the London penetration depth for Sn from the following data:
Critical temperature = 3.7 K
Density = 7.3 x 103 kg/m3
Atomic weight = 118.7
Effective mass (m*) = 1.9 m
9. The resistivity of superconductor becomes zero. Consequently the flux density is zero due to this abrupt
change. Prove that the superconductors behave as perfect diamagnetic.
10. The lead material works as superconductor at a temperature of Tc = 7.26 K. If the constant characteristic
field of the lead material at 0 K is Ho = 8 x 105 ampere/metre. Calculate the magnetic field in the lead at
5 K. ' >
11. The magnetic field intensity in the tin material is zero at a temperature of 3.69 K and (3 x at zero
kelvin. Calculate the temperature of the superconductor state if the field intensity measured was
2X105
----amp/m.
4ti
12. Calculate the value of the London penetration depth Xo at 0 K for lead whose density is 11.3 x IO3 kg/m3
and the atomic weight is 207.19. Its Tc is 7.22 K. Calculate the increase in X at 3.61 K from its value at 0 K.
13. The London penetration depths for Pb at 3 K and 7.1 K are respectively 39.6 nm and 173 nm. Calculate its
transition temperature as well as penetration depth at 0 K.
14. Estimate the intrinsic coherence length of aluminium if the size of the energy gap is 3.4 x IO-4 eV,
vF = 2.02 x 106 m/s.
15. What is the frequency of the electromagnetic waves radiated by a Josephson junction having a voltage of
650 gV across its terminals?
16. In a Pb-oxide-Al junction, the maximum and the minimum currents in the I-V characteristics are obtained
at 11.8 x 10-4 V. Compute the values for the energy gaps of superconducting Pb and Al.
17. Using the parabolic temperature dependence of the critical magnetic field curve, show that
S„ - S} = 2Uo//2/Jc [(T/rp - (T/T )3]
for the entropy and heat capacity differences per unit volume; n and s respectively refer to the normal state
and superconducting state. .’
18. Calculate the stabilisation energy density of the superconducting state at absolute zero of aluminium if the
corresponding critical field is 0.0105 T.
I
•rt. - ,
Magnetic Properties of Materials
Magnetism has a very ancient history; it is perhaps that aspect of solid state physics which has been
familiar to man as early as 800 BC. In fact, almost every thing known about the magnetic properties of
materials has been derived from experimental discoveries and from a few inspired guesses.
The three important facts with respect to magnetic materials which require explanation are:
(/) Some materials are magnetic even without the application of any magnetic field and become
more magnetic when a weak magnetic field is applied to them.
(n) Many other materials lose their initially strong magnetism when heated above a certain critical
temperature and become comparatively weakly magnetised.
(m) Some materials show a magnetic response in a direction opposite to that of any externally
applied field.
Weak magnetic effects occur in all substances, gas and liquid as well as solid, but the greater
proximity of the atoms in a solid can lead to stronger cooperative effects. If the interaction is such that
the magnetism on the atom is aligned, this leads to the very strong magnetic effect known as
ferromagnetism below a certain temperature called Curie temperature (Tc). Iron, nickel, cobalt and
gadolinium are some ferromagnetic materials. There are other effects though that lead to a cancelling
(antiferromagnetism) or partial cancelling (ferrimagnetism) of the magnetism of different atoms. In
antiferromagnetic materials the resultant magnetisation vanishes in the absence of a field. The atomic
dipoles are arranged antiparallel to one another so that the net moment is zero. Above the Neel temperature
Tn, the dipoles are randomly oriented as in a paramagnet. NiO, MnS, MnO are some examples. The
atomic dipoles in ferromagnetic materials are antiparallel to one another but the moments in one direction
have a longer magnitude so that the net magnetisation is non-zero. Some examples of this category of
materials are Fe.O,, yttrium iron garnet (Y3Fe5O12) and nickel ferrite (NiFe2Op. Ferromagnetic materials
become paramagnetic above the curie temperature (Tc).
The magnetic effects in magnetic materials are due to atomic magnetic dipoles in the materials.
These dipoles result from the effective current loops of electrons in atomic orbits, from effects of electron
spin and from the magnetic moments of atomic nuclei i.e., to study the magnetic effects in an atom, we
should look for various sources of currents within the atom and their contribution to the overall magnetic
effects. The electric currents in an atom are caused by the orbital and spin motions of its electrons and
those of its nucleus. Since all these motions of charged particles form closed electric currents, they are
equivalent to magnetic dipoles. When such dipoles are subjected to an external electric field, they
experience a torque which tends to align their magnetic moment in the direction of the externally
427
applied field. The degree of alignment is characterised as the total magnetic moment per unit volume of
the material, also known as intensity of magnetisation or simply magnetisation, M. In the process of
orienting the dipoles, the energy spent by the magnetic field is stored as potential energy in the dipoles
Most experimental techniques used for the study of magnetic effects in matter are essentially based on
the measurement of this potential energy (also called the interaction energy between the magnetic field
and the dipole) which ultimately gives information about the magnetic moment of the dipole. The
magnetic moment per unit volume (Af) is related to the applied field strength (//) by the relation, M-
W where % is called the magnetic susceptibility of the material.
A knowledge of the magnetic behaviour of materials and its origin will be of great help in the
proper utilisation of such materials. We know that of all the different materials only a few like iron,
cobalt and nickel are strongly magnetic and others do not get magnetised. We can relate the magnetism
in materials to the magnetism exhibited by its constituents, the atoms. One may be interested to know
the contributing factors to the magnetism of atoms and why atoms of iron, cobalt and nickel alone
exhibit pronounced magnetic properties and that atoms of other elements do not exhibit the same amount
of magnetic behaviour. Magnetic properties of most materials can be explained and predicted from their
atomic structure, without a detailed analysis of the motion of each charged particle.
Consider an unmagnetised bar of a magnetic material in a uniform magnetic field as shown in Fig. 9.1.
It has been observed that the bar gets magnetised by induction and gets a polarity. After magnetisation,
the magnetic lines in the bar emanate from N-pole, pass through the outer region and then re-enter the
S-pole as in Fig. 9.1 (a). These lines form a closed loop within the magnet by passing from S-pole to
N-pole. It will be interesting to know, that the lines of the magnetised bar oppose the lines of the
original field outside the magnet and favour inside the magnet.
Fig. 9.1 A magnetic material in a magnetic field
The resultant field is shown m Fig. 9.1 (A). As a result of this, the magnetic field strength (H) is
increased inside the bar and decreased outside it. Similarly, the magnetic flux density (B) becomes high
inside the bar and low outside. Thus, we find that flux density (B) is directly proportional to the magnetic
field strength (H). Mathematically
B«H
i>.. B = pH (9.1)
1
where p. is a constant of proportionality and is known as absolute permeability of the medium. If the
flux density is established in air or vacuum or in a non-magnclic material, then the above equation may
be written as
Bo - Ho H (9.2)
where, Bo is the flux density in air or vacuum and p() is the absolute permeability of air or vacuum, 'rhe
ratio is known as the relative permeability of the medium. It is designated by the symbol
Mo
Mathematically
® B/B() (9,3)
It may be noted that the relative permeability of air or a non-magnetic material is unity. But for
certain nickel-iron alloys, its value is as high as 105.
CHAPTER 9
The term magnetisation may be defined as the process of converting a non-magnetic bar into a magnetic
bar. The term is almost analogous to the polarisation in dielectric materials. The flux density,
B=nH= H (9.4)
i.e.t B = p()prH + p0H - p0H
. = p0H + p0H (|ir-1) (9.5)
U, pB = p0(H + Mp| (9.6)
where the magnetisation, M = H (jx — 1). It is expressed in ampere/metre. From the above equation, we
find that if a magnetic field is applied to a material, the magnetic flux density is equal to the sum of the
effect on vacuum and that on the material. The magnetisation may thus be defined as the magnetic
dipole moment per unit volume of the bar.
The magnetic induction Bo inside a long solenoid which has a core of vacuum or air is p0 ni. If
the core is replaced by any other magnetic material and the value of B in the material is experimentally
measured, one of the following three results is obtained for any material:
B<B0
B>B0
B » Bo
On the basis of these observations, magnetic materials can be classified into three categories:
Diamagnetic, paramagnetic and ferromagnetic respectively. Other classes of materials which in structure
close to ferromagnetic materials but possess different magnetic effects are antiferromagnetic and
ferrimagnetic.
The properties of paramagnetic, ferromagnetic, antiferromagnetic and ferrimagnetic materials
are determined by the presence of permanent magnetic dipole moments. It is for this reason that it is
important to estimate the various contributions to the magnetic moment of an atom.
You ha\ t
According to Ampere's hypothesis a plane current

loop is equivalent to a magnetic dipole so far as the
magnetic effects both produced and experienced by them
are concerned. For example, a stationary loop carrying
\ /,M Paramagnetic
current in a plane produces a magnetic field which at large

distances may be described as resulting from a magnetic
dipole whose moment is given by Ferromagnetic
|im = /A (9.7)
where I is the current and A is the area of the loop. The
dipole direction is perpendicular to the plane of the loop.
Antiferromagnetic
Electrons in an atom move in certain prescribed fashions
about the nucleus of the atom. The electron motion can
be described by assigning a certain angular momentum
of each electron. Consequently the magnetic properties
of a substance are determined by the state of angular
* Ferrimagnetic
momentum which the electrons may possess. The state of
the angular momentum depends not only upon the orbital Fig. 9.2 Interaction of dipole moments in
motion of electrons but also depends upon the spin of the various types of matenals
electron and spin of the nucleus.
For simplicity, let us consider the simplest atom of hydrogen in which one electron revolves round the
proton, say, on a circular path of radius r. At any instant the electron at a point P and the proton at the
centre form an electric dipole, the direction of the dipole goes on changing as the electron moves
further. Obviously, the time average of the electric dipole moment is zero and there will be no electrostatic
field at a distance point due to this dipole.
i
» Again the moving electron is equivalent to a current ring. If v is the velocity of the electron, it
V CD
will make —— = — revolutions per second, and it is equivalent to a current given by
I = e(o/2n
The circular path is equivalent to a magnetic dipole and the magnetic moment due to this orbital
motion of the electron is
|le/ = IA = (eto/lnynr1 (9.W
etor2
(9.9)
2
You. ____ Magnetic
The angular momentum associated with the electronic motion is given by mr^to. Hence, we can
relate the magnetic dipole moment and angular momentum as
= - (e/2m) x Angular momentum
The minus sign indicates that the dipole moment points in a direction opposite to the vector
representing the angular momentum. A substance therefore possesses permanent magnetic dipoles if
the electrons of its constituents atom have a net non-vanishing angular momentum. The ratio of the
magnetic dipole moment of the electron due to its orbital motion and the angular momentum of the
orbital motion is called orbital gyromagnetic ratio, or orbital magneto mechanical ratio of an electron,
represented by T In our case, it is given by
_ Magnetic moment
= e/2m
Angular momentum
According to modem atomic theory the angular momentum of an electron in the orbit is determined
by the orbital quantum number I which is restricted to set of values:
/ = 0, 1,2....... , (n-1)
CHAPTER 9
where n is the principal quantum number which determines the energy of the orbit It can accept only
the integer values n = 1,2,3,4,.... The corresponding electronic shells are called K, L, M, N,.... shells.
Hie angular momentum of the electrons associated with a particular value of I is given by
Z(h/2n). The electrons associated with states I = 0, 1, 2, 3,.....are called s, p, d,f,........ electrons
respectively. The strength of the permanent magnetic dipole is given by
- Jld = -(e/2m) (Ih/2ic)

T t- (eW/4 ran) ==-.r I a (9.10)
The quantity = ehlAttm is an atomic unit called Bohr magneton and has a value 9.27 x 10-24
ampere metre2 and this represents the magnetic moment of an elementary permanent magnetic dipole.
From the above equation, it is clear that electron in an atom can take only certain specified values of
magnetic moment depending on the value of I. Hence for a s electron 1 = 0 and the magnetic moment is
zero. Bohr’s theory suggests that both magnitudes and directions of the I vector are quantised and this is
known as spatial quantisation. This introduces another set of quantum numbers known as magnetic
9*antum number m[t where m/ is restricted to set of values given by
mt = l, (Z-l),..... ,0,..... -(/-1),-Z
We find that mz can take (21 + 1) values in all. In any magnetic field the orientation of atomic
magnet tends to change. The atomic magnetic moment vector can take only those orientations for which
projections of angular momentum vector along the field direction are integers specified by magnetic
quantum numbers. For example, a d-electron has five possible components of angular momentum along
ftc direction of the magnetic field:
2h/2n,h/2n,0,-h/2n,-2h/2n
The corresponding possible magnetic moment along the directions of the field are:
(eh/4itm), 0, - (ehJ4nm), - 2(eM4nm)
Figure 9.3 shows the possible orientations of the angular B
m, * 2
momentum vector, specified by the orbital quantum number,
/«2.
We also see that the projection of these angular
m,=
momentum vectors OA, OB, OC and OE along the field
direction B are 2. 1, 0. -I, -2 respectively. In general the
m, = 0
component of the orbital magnetic moment along the external
applied field is equal to m, pfl. The total magnetic moment
contributed by the orbital motion of all the electrons in an atom
can be vectorially added. We can see that a completely filled
electronic shell does not contribute anything to the magnetic
mt = -2 ,,
moment of the atom. If we look at the electron configuration
E
of many elements in the periodic table we find that they have
incomplete electronic shells and so they do have resultant Fig. 9.3 Five possible orientations of the
angular momentum for I - 2
magnetic moments. But their contribution to the magnetic
properties of solids is negligible since it is found that the orbital magnetic moments of these elements
and their compounds are frozen in, i.e., they behave like immobile magnetic dipoles which cannot be
aligned by external applied magnetic fields.
»isai&iaaiiiuycis* ajhs
Besides rotating on a circular orbit around the positive nucleus, an electron also rotates around an axis
of its own. The magnetic moment associated with the spinning of the electron is called spin magnetic
moment po. Although, strictly speaking it has a quantum mechanical origin, we can think of this magnetic
moment as being due to the rotation of the electronic charge about one of the diameters of the electron
in a manner similar to that of the earth’s spinning motion around its north-south axis. If we consider the
simple case of an electronic charge being spread over a spherical volume, the electron spin would cause
different charge elements of this sphere to form closed currents, resulting thereby in a net spin magnetic
moment Clearly, this net magnetic moment would depend upon the detailed structure of the electron
and its charge distribution. It turns out that an equation, analogous to equation (9.10) connects |i with
spin angular momentum S by the relation.
lia = y(e/2m)S (9.11)

where the value of the coefficient y, called the spin gyromagnetic ratio, depends on the structure of the
spinning particle and its charge distribution. The experimental value of y for an electron is (-2.0024),
the negative sign indicating the in a direction opposite to that of S. Since 5 = h/4% for an electron,
equation (9.11) gives = 9.4 x JO"24 ampere-metre2.
Thus, the magnetic moments due to the spin and the orbital motions of an electron are of the
same order of magnitude. It may be mentioned that spin and are intrinsic properties of an electron
and exist even for a stationary electron (L = 0).
Since the magnitude of the spin magnetic moment is always same, the external field can only
influence its direction. If the electron spin moments are free to orient themselves, we except them to
You t Magnxdc Promrtmi ar
orient c ‘ samoie would m ° ° *pp,icd fie,d B- ln a varying field like that at the end of the
solenoi , . m(,mpnt„ f • P60®1106 a force in the direction of the increasing magnetic field due to
spin . 18 van°us electrons. Thus, paramagnetism is the result of spin magnetic
momen . ' a everyt ung is not paramagnetic? The reason is that in most of the atoms
and mo ecu es e e ec ns are grouped in pairs. What is left is the orbital magnetic moment which
produces lamagne c e ect. ome molecules contain odd number of electrons and obviously their spin
magnetic moments cannot cancel out and contribute to their paramagnetic nature.
3TWÊi^«5M®ITBUFTONucteAk^pi-KT" i Kido ‘ nr
So far we have considered the orbital motion and the spin of the electron only as possible contribution
to the magnetic moment of atoms. Another contribution may arise from the nuclear magnetic moment.
By analogy with Bohr magneton, the nuclear magneton arises due to spin the nucleus. It is given by
= eh/4itMp
rip, = 5.05 x IO"27 amp-metre2
CHAPTER 9
where Mp represents the mass of the proton. The nuclear magnetic moments are smaller than those
associated with electrons by a factor 103.
Thus we can summarise that permanent dipoles originate (i) the orbital motion of the electron,
(if) electron spin and (Ui) the nuclear spin.
SjOEABOliZHJ-OraGill^J^NE^
The magnetic behaviour of atoms, molecules, ions and solids is actually related to the orbital and spin
motion of the electrons which are negatively charged. In the atom of the lightest element hydrogen, the
motion of the electron is governed by the three well-known quantum numbers namely n with values
1,2, 3..... . I with values 0, 1,2, 3, ...., (n - 1) and mt with values I, (I -"1), ...., 0,...... - I. Here n
determines the energy of electron and I gives the magnitude of the angular momentum vector L; the
magnitude and orientation in space of the vector L are determined by I and mz. This indicates that for a
fixed value of n, different values of I and mt describe the energy state. If the system is subjected to an
external magnetic field, the degeneracy of the energy state is destroyed and each set of the quantum
numbers n, I and m.may give different energy states. The magnitude of the electron’s orbital angular
momentum L, is quantised and the value is given by
(9.12)
t
The electrons are designated by s, p, d,f, etc. for I = 0,1,2,3, etc. It is therefore not surprising
< to learn that the directions of L is also quantised with respect to an external field. This fact is often
। referred to as space quantisation. The magnetic quantum number m{ specifies the direction of L by '
; estimating the component of I. in the field direction. If we let the magnetic field direction be parallel to
die z-axis, the component of L in this direction is
(9.13)
J The possible values of mt for a given value I range from +1 through 0 to -1, so that the number
I of possible orientations of the angular momentum L in a magnetic field is (21 + 1). If 0 is the angle
L between L and the magnetic field direction, which may be conveniently taken as the z-axis, then
n mth ml
L JUl ♦ l)h Jlll + l) (9.14)
(.quaiions (9.1 J) and (9 |4> once again show that L can have (21 + 1) orientations in «n^,
corresponding u< the number of permissible values of mr See Fig. 94.
Fig. 9A 5paz< quantitation of orbital angular momentum
An electron also possesses spin angular momentum represented by vector S, whose magnitude
is quantised in terms of h such that
Sahfys + \) (9i5)
» /' ,
1 , . J3
with t" - is the spin quantum number. Thus S * —.
2 2
The tpace quantisation electron spin is described by the spin magnetic quantum number
Just like the orbital angular momentum vector can have the (21 + /) orientations in a magnetic field
from ♦ I to - I, the spin angular momentum vector can have (2s + 1) = 2 orientation specially by
1
i 2 (t^tt Pig, 9.5), The component Se of the spin angular momentum of an electron alonga magnetic
field In the ^direction is determined by the spin magnetic quantum number, so that
Maonchc
S; = msh=± £ & (9.16)
netic ratio characteristic of electron spin isalmost twice that characteristic of electron
Ther'^J’ this ralio as equa| t0 2, the spin magnetic moment of an electron is
01
rhitfll motion. ‘’
Fig. 9.5 The two possible orientations pf the spin angular momentum
The possible components of along any axis, say the z-axis are therefore limited to
„ (9.16a)
2m
The constant is again the Bohr magneton. The orientations in space of S, with respect to the
2m
1 axis (magnetic field direction) are determined by the relation,
St msh m,
cos 0 = — = .... --
Since nr = ± -, there are only two permissible values of 0.
If J is the total angular momentum vector, then

J=L+S
with J= + D ft
Here J is the total angular momentum quantum number. The z-component of J is also quantised
such that
and
Here nr is the total magnetic quantum number and a is the angle between J and the magnetic
field direction. Further, if 0 is the angle between L and S and the vectors couple to J, then
j(j-Hy-/(Z + l)-s(s + l)
2jj(F+ljJs(j + l)
Magnetic Moment of a Current Loop

When currents pass through two parallel wires in the same directions, the conductors attract each other;
a repulsive force develops if the currents are in opposite directions. The phenomenon js due to the
magnetic flux produced by the currents around the conductors. The vector B is the flux density or
magnetic induction; weber/metre2 is the unit of magnetic induction. The other important vector quantity
H is related to B by the equation;
B = p0H '
where pig the permeability offree space is 4k x IO-7 henry/metre. The unit of H is ampere/metre. If the
surrounding medium is other than vacuum or air, then
B = pH
where p is the magnetic permeability of the medium given by p = pr with pf a dimensionless quantity
called relative permeability which is 1 for air. The torque experienced by a coil carrying current placed
in a uniform magnetic field H is
T = MxH
The vector quantity M is called the magnetic moment and its direction is perpendicular to the
plane of the coil. Its magnitude depends on the strength of the current and the area of the coil. The
magnetic moment for unit volume of a magnetic substance is called the intensity of magnetisation and
is denoted by vector M. The unit of M is weber/metre2 or A m_|. The magnetic induction B is related to
M by the expression
Magnetic MxrERtfdt w!
B^M + H) (9.17)
Also M = %H
where X is ^8^^ susceptibility and
B = |1H
Then by equation (9.17),
HH = g0(M + H)
Le., = M-
M
or
.Bo
Le. (9.18)
Current.Loop
Magnetism on an atomic scale was first explained by
Ewing who argued that the molecules making up the (
material themselves behaved as tiny bar magnets. He

assumed that, in an unmagnetised specimen, these > (a) • (b)
molecular magnets were so arranged in small groups so Fig. 9.6 Arrangements of molecules: (a) In an
that the resultant magnetic field is zero. However, in a unmagnetised sample; (b) in a magnetised one
magnetised specimen, all the molecules would have their
magnetic moments pointing in the same direction, giving rise to a magnetic field [see Fig. 9.6 (a) and
Fig. 9.6(b)].
Though Ewing’s theory was fairly close to the
truth, his assumption that the molecules are the
elementary magnets has to be discarded. Instead the extra
nuclear electrons are to be regarded.
Since the magnetic moment of the orbital electron
a hydrogen atom depends upon its angular momentum
• both the magnitude of L and its orientation with
fig, 9.7 Angular momentum of an
IesPect to the field determine the extent of the magnetic
contribution to the total energy of the atom when it is in
gnetic field. The magnetic moment of current loop
Ml = i A - i It r2
®cre i is the current and A is the area it enclosest
jt r2ev evr
Now (K^) = (9.19)
2nr
The angular momentum,
mrv
L = Zq)=-------- = mrv
L
i.e.. rv = —
m
Substituting this value of rv in equation (9.19), the magnetic moment of the current loop is
(9.20)
Le., (9.21)
The negative sign in equation (9.20) indicates MLand L are in opposite directions.
The factor — consisting of universal constants on the right hand side of the above equation is
the Bohr magneton and its value is 9.27 x 10"M amp nt2 and it is represented by Thus from equations
(9.20) and (9.21).
g = Ub
2m h
and
or (9.22)
The term of equation (9.22) is the ratio of the magnetic moment vector in terms of Bohr
magneton to the orbital angular momentum vector in terms of the well known Planck’s constant. This
ratio is marked by the symbol gL (known as gyromagnetic ratio). gL is also called the Lande g factor and
it has a value-1.
The similar expressions for magnetic moments associated with spin and total angular momenta
of a valence of electron in an atom are:
Ms ~ SjU-b \ZS<S +1)

Mj = gj^By[j(j + 1) (L-S coupling)
Maqniuc PitoFWTtocF
where is given by
Further. IgJ = 2 for the electron spin motion.

When a coil of conductor carrying a current k ■
to a torque given by M x H. But what about the ehanie i„ . ™ * *’ ""l’jeC"d
The change tn energy, Ah is equal to - (M M t,uc 10 the interaction with the field?
The intention leads to p^ces i<,„ " M ™" a ‘ T 9„ 9“ b‘lw«" M' “"‘J "
obviously occurs only discrete Ch“"8C'
frequency of the precession in the presence of the n^■
2m
The electron will retain the new frequency as long as B does not change. The term ——- B is
,2m
CHAPTER 9
called the Larmor frequency
Now, co,L = 2k X), = —

L 2m (9.23)
eB
Thus, V). =--------
4jtm
where v£ is the Linear frequency.
/■
’ •’ ai i
Diamagnetism is a small and very weak effect in many

materials caused by the reaction of the orbiting electrons to
an applied magnetic field in accordance with Lenz s >
that the magnetisation and hence the susceptibility are both
negative. Antimony, bismuth, mercury, gold and copper .
some examples of diamagnetic substances. I a rnag
material is placed in a magnetic field, it can increa
decrease the flux density. Diamagnetic materia s re u
density of Unes of forces while paramagnetic
increase the flux density. Diarriagnetism is pro uce
circulation of electrons in atoms or m°’eculcS;J f
diamagnetic substances X < 0 and it is indePende";^
temperature. Unlike paramagnetic materials, w o
•Fig. F.8 Hua density in (tf) a diamagnetic
Or molecules have a net magnetic moment, the atoms or
molecules of a diamagnetic materials have zero magnetic
moment in the absence of an external field. With the application of an external magnetic field a net
dipole moment, opposing the field, is induced in (hc atoms or molecules. Paramagnetic mate I
have a diamagnetic effect but t| is much weaker compared with paramagnetic effect. I)jnrn *
materials reduce the density of the lines of forces in a field while paramagnetic materials incre?^*
flux density. The susceptibility of water is -9 x Iff* and that of graphite is -8 x 10 \
Classical Theory of Diamagnetism (Langevin Theory)

Consider a circular orbit of radius (r) in which an electron revolves with an angular velocity (Oosrotnul
tic ooefan of charge Ze Then
(9.24)
fig. 9.9 Variation of magnetic Misceptibility with temperature for («) paramagnetic subitance,
(b) a ferromagnetic substance and (<) an antiferromagnetic mbuancr
The magnetic moment of the electron is
g(oor
~2~ (9.25)
The Lorentz force FL acting on the electron is

FL = - Bev — — Beor
Now the equation for motion is
Ze2
m 0 ---------- 7 - eBor
47tcorz
^,2 2
mv
— = ---------- 7 - eBor
r 4tt£0r£
Ze2
mro2 = ---------- =- - eBor
47re0rz
0)2 = Zg2 _ eBo
4rcme0r3 m
2 eBo Ze
cd2 d-------- -------------- :
m 4rcm£or
o eBo Ze2
®2+---------~A----------r=0
eB a2 ,
2m V 4nmE0r3 4m2
(9.26)
(9.27)
■it •: *
The 1 Mgn on n\, indicnlc* that Ihow rlci iron* wh«»w orhllal moments were parallal it,fa -
are Mowed down and those whore momenta wore nnlipniallcl me speeded up. by an amount
m
direu&Mon, reMill* and nmchiMion* are culled fainnor ihromn. 'Iida frequency change give* b
pohih.uiliim or
magnerh pokinnuiim or simply
s inngnclixntlim The renatm for Ihh I* thill the frequency change *
equivalent to an additional vunvnl. and thh current component In every atom la in the anmc dire<iu*
whereas the original cireulnting current* were In random direction* and cancel each other. In the ahun^
of a field, the electron motion*, being apherlcully symmetrical, produce no net current* or flux, But m
r//
the field we can write a current for each electron due to i(* frequency change —. Now the charm
2m "
the frequency of the electron in
aha a cli
Ao)»2nAv«- orAv«-
2m 4nm
The related or corresponding change in the magnetic moment of the electron is
AM ■ IA ■ y 2tc r2« e (Av) (Ttr2)
4nm
^2 ~2 n
t r d
AM « - (9.28)
4m
On summing overall electrons in the atom, the induced moment per atom becomes
e2BZr2
AM«- (9.29)
4m
where the summation extends overall Z orbital electrons in the atom. Since the core electrons have
different radii, we may write
Ir2 = Z<r2> (9.30)
where l< r2 >lw is the average radius of the electron from the field axis (z-axis). If the orbit lies io the
sy-pUne. then
<f2>« <xa> + <y2>
If < r02 > represents the average distance of the electron from the nucleus,
You
<r02> = <.t2> + <y2> + <z2>
the atom has spherical symmetry

I
when
Then
I
o
2
2 2
or
Remembering equations (9.29) and (9.30), one gets
e2BZ
AAf = -
4m
CHAPTER 9
If N is the number of atoms/m3, then magnetisation (magnetic moment per m3) is,
M =--------------- -----------------
M yQZe2N < r02 > •

(9.31)
H - 6m ' ’
Equation (9.31) is Langevin's formula for the volume susceptibility of diamagnetism of core
electrons.
Conclusions
(i) Almost all materials exhibit diamagnetism though it is masked by the other magnetic effects.
(u) The susceptibility of diamagnetic substances is directly proportional to the atomic number.
(hi) The bigger would be the value of the susceptibility if the atom is bigger.
(iv) We are taught by equation (9.31) that the susceptibility depends on (the microscopic properties)
internal structure of the atom which is unchanged by variation of temperature. Hence in this
category of magnetic materials, x is independent of temperature.
(v) In the Langevin model, diamagnetism is attributed to the influence of the magnetic field on
the orbital momentum of the electrons. Although ^-electrons have a zero angular momentum
in the absence of a magnetic field, yet they acquire a small amount of orbital momentum
upon the application of field. This explains why all the electrons in an atom contribute to
diamagnetism.
X for most diamagnetic materials is of the order of 10"6 which is also found to be experimentally
hue. Assuming one electron and taking m = 9.1 x 10-31 kg, rQ = 0.1 nm, N = 5 x 1028/m3 and
c~l-6x IO-19 coulomb, one gets
5xlO’'*x4itxlO ’ x(Ux 10 w)x(O.I x 10 ”)'
ftxu.ixio "
X ■ -3 x 10’
The experimental value of x far copper is - 9 x 10 *.
XSUMMARY'--------------- --------- --
«*»!■. , - -V.. . ... _ *. W aiHRi ■ —I
(ri These are no permanent dipoles and hence the magnetic effects are small.
V'O Since the induced magnetic moments always oppose the applied field, the diamagnetic
susceptibility is negative.
(uO It is always temperature independent. A little variation observable Is due to orbital changing
slightly with temperature.
(iv) Although diamagnetic material usually refers to substances with no permanent dipoles,
magnetic moments induced by and applied field do exist in all substances and no docs
diamagnetism. However in substances having permanent dipoles the magnetic effects due to
them usually mask those due to induced dipoles.
Table V.l Diiections of electrons moments in a tilled Ip shelf
7rÂWjX5WFfij,M11 ’ ■ ■
Diamagnetism is an integral characteristic of all matter. But the presence of other types of magnetism is
a result of the fact that many atoms have a permanent magnetic dipole moment which outweighs the
diamagnetic effect In some materials, the permanent magnetic moments of the atoms or ions are acted
upon individually with no mutual interaction among them (randomly distributed), this effect is called
paramagnetism.
However, in the presence of the field, the
Field direction
magnetic moments have a tendency to turn
towards the direction of the field. If no opposing
force acts, complete alignment of the atomic
moments will be produced and the specimen as a Fig. 9.11 Alignment of elemental/
whole would acquire a very large magnetisation of a p.ir.iniAgiwiK nuicfiul m the umc
in the direction of the field. However thermal duciiion .n an applied filed
agitation of the atoms oppose the
o
£Z
Thblc 9.2 The spin slate* of three rcpwnUliK element*
LsMl M<swn N-stail Expected Mzgwfic 1

is 2s 3p 3s 3p 3d 4s Moment (Bohr magneton)
otMeil subsMl subsMl sdbsheU Tuhihril ________

K_-snfestett
_ _
o ' t T TTT 2
4- 1 1
Ne t T. TTT 0
1 4 XXX
Fe T t TTT T TTT T 4
1 4 XXX 1 XXX 1 4
Table 93 Spin distribution and magnetic moments in the first long period
Element K Ca n V Cr Mn Fe Co Ni
Number
of 3d 0 0 1 2 3 5 5 6 7 8 10 10
electrons
Spin w T TT TTT TTTTT TTTTT TTTTT TTTTT TTTTT TTTTT TTTTT

directions 44 U4U UU4
Magnetic moment
। in 0 0 i 2 3 5 5 4 3 2 0 0
Bohr magneton
t
CHAPTER 9
tendency and tries to keep the atomic dipole moments at random. The result is only a partial alignment
in the field direction. Therefore, a weak magnetisation and a small susceptibility. An increase of
temperature therefore will decrease the susceptibility. Effectively materials with atoms of unpaired
spins are paramagnetic.
Table 9.4 Diamagnetic susceptibility of some materials
Material Material %=(Vr-l) '
-0.95x10“-' Ge - 0.8 x 10“5
ai2o - 0.50 x 10“5 BaCl, - 2.0 x 10“5
Diamond -2.10x 10“5 Si - 0.3 x 105
NaCl - 1.20 x 10“5 Se - 1.7 x 10~5

1 A“
- 3.70 x 10“5 . He -0.5X10"5
In paramagnetic substances pr > 1, % is small, positive and varies inversely with absolute
temperature. Paramagnetic materials include manganese, platinum, tungsten, some members of rare
earth group and ions formed by removing and adding electrons to basic atoms thereby creating unpaired
spins.
Classical Theory of Paramagnetism

(Langevin’s Theory and Curie Law for Paramagnetism)
For the analysis of variation of the susceptibility of a paramagnetic spin system with temperature, the
following assumptions have been made:
(i) Only the effect of electron spin magnetic moments is

considered.
(ii) Individual spin moment can accept only two possible

components along the field direction, +1 or -1 Bohr
magneton, i.e., spin moments in the presence of field
are either parallel or antiparallel with the field.
(in) The interaction between individual spin system is

negligible, so that, the field at any point in the spin
system is the applied field.
The phenomenon of diamagnetism is a result of magnetic

dipole formation due to the presence of an external magnetic field.
However, paramagnetism is a result of the orientations of (already
existing) permanent magnetic dipoles due to the presence of an Fig. 9.12 Variation of paramagnetic
external magnetic field. This is explained, by the fact that susceptibility with temperature
paramagnetism is associated with the outermost electrons, which are less tightly bound to the atom than
the inner electrons causing diamagnetism. The permanent magnetic moments of the individual atoms
are therefore able to change their direction freely and, in the absence of an applied field, are randomly
• icd owing io the thermal agitation. When the field is applied, the magnetic moment* tend to beoê
d,tC .|el lo the field direction and overcome to some extent the disrupting influence of umpii *mr- As
pflr as the Geld is removed, they are restored again to random powtiom
s0on a* 1
In a nutshell diamagnetism is a result of magnetic dipole formation due to the presence no
dipoles due to the presence of an external magnetic field. Langevin theory here is purely damacai
ip nature. Statistical kinetic theory was applied to obtain the expression for the ia*cepuiN£ty cd a
moment g. When this paramagnetic gas is subjected to a magnetic field, the «ate of rmgnrfHitino wifl
be determined by the following two factors:
(i) The applied magnetic field which tends to produce alignment of die ■rgnrtir axes of molecules
(considered as permanent magnetic dipoles) in its own direction.
(ii) The thermal agitation which works to disorganise the orderly stale so produced.
For a quantitative understanding of the paramagnetic effect, we can calculate the induced
magnetisation in the sample in exactly the same way die induced electric polarisation in apolar tfielectric
under the influence of an external electric field. Using the classical laws of kinetic theory of gases and
classical statistics, Langevin derived an expression for the paramagnetic suscepcSiifity of a gas. At any
given temperature, a kind of statistical equilibrium is reached with majority of molecules basing their
axes parallel to the field and hence contribute to die intensity of magnetisation which can be calculated
as follows:
(i) The number of molecules which have an orientation indined at an ■m *i 0 wnh a fine of
reference is proportional to sin 0 d0.
(ii) On the basis of equipartition ofenergy, die number of molecules whose pcnential energy £, k
proportional to exp (- EJk^T), where kB is Boltzmann's constant and Tthe absotaue tompeoluae.
Let N be the number of molecules in unit

volume. If dN is the number of molecules having
inclinations 0 and (0 + d&) and energy value E,
then
dN oc exp (- ElkBT) sin 0 d0
dN = C exp (- E!kBT) sin 0 40 (932)
The torque on the dipole is
T=(mB) (QB) = mB(2Jan9)

Hgr 9.13 Torque acting, or? a
2/ J« the length of the dipole
T - (KJ B sin 0
*here
= 2bn is the moment of the dipole.
Now the potential energy stored on the dipole is
|rde
e
J|lmBsin0d0
E = - jx^B cos 0 (9.33)

Substituting this value of E in equation (9.32), one gets
dN = C exp [Qi^B cos 0)/fcfl7] sin 0 d0
dN= Cexp (a cos 0) [sin 0 d0] (9.34)
*«r
Ums an estimation of the number of molecules having inclination between 0 and n is done as
Htows:
JdV = C Jexp(acos0)sin0d0
Pwoos 0 = xso that sin 0d9 --dx
i
N=C Je^dbc
-t
-i
= f [(e° -e^)]
(9.35)
For a moUcidar magnet of moment pm inclined at an angle 0 to the field, the resolved component
of its moment in the direction of the field is cos 0. Therefore the resultant magnetic moment due to
all the N molecules in the direction of the applied
field is cos 0 dN, Hence the total magnetic
moment due to N molecules in one cubic metre
is
n
M= f cos 0 dN
o Fig. 9.14 Molecular magnet
M is nothing but magnetisation, Substituting the value of dN from equation (9.34)
M= cos 0 exp (a cos 0) sin 0 dQ
Let x= cos 0
dx = - sin 0 d0
-i
Now M = Cfim j (- dx")
CHAPTER 9
i
i i
= C|im jxe^dx- Qtm f (x/^dCe^)
-1 -1
a 11
ax
Cg e
a a
Substituting the value of the constant C from equation (9.35), one gets
a a
(9.36)
The term L(a) is known as Langevin function. In equation (9.36), the factor N is the magnetic
moment per unit volume (/m3) when all the dipoles are aligned or turned in the direction of the magneti»jn.
field; hence if gives the saturation value of M say Ms.
Hence M= M. cot ha —
\ a
(9.37)
The quantity M«cJI is a constant, characteristic of the gas and it always exceeds M. The function
L(a) may be graphically represented by a curve known as the Langevin curve. Taking different arbitrary
values of a, die Langevin function approaches unity and hence M approaches jVp.m. Physically thu
11 Q •
corresponds to the situation in winch is so large (at low temperature and large fields) that one
B
approaches complete alignment of the dipoles along the field direction. In practice, this approach to the
saturation of the intensity of magnetisation is never encountered in gases and so far practical purposes
we may consider the second characteristic of the
curve; the initial part of the curve (i.e.t for small
values of a) is sensibly linear and coincides with the
tangent to the curve at the origin.
Discussion
Li B
We kept a = —■ in the above discussion. Hence a
is small means p^B is small with kBT; i.e., at high

temperatures. We now discuss the Langevin function
under these conditions:
Ua) = cot An —
a.
magnetisation with a -
= (9.37a)
” 3 ", M, 3kBT
M I 1
Also —/ a = tan 0 = slope = -
Ms / 3
Now the paramagnetic volume susceptibility is
_M__ Mâ
H ~ 3H
U„B
•* and «=“
U Y_ '
Z 3H(isr>
= H>HqH
• 3Hk„T
(9.38)
This is written in a simplified way
(9.39)
where is called curie constant.

3^
This result namely the magnetic susceptibility of a paramagnetic arrangement of dipoles as —, is

^®ow
V Curie law. It is well obeyed in many materials such as Nd, CuSO4, KjSO4 .(SHÔ, O2. The
"^•“•cepiibility.x s X
m p
Yc
4S2 Solid.Mwi Pwwa . <
*“———.— - ■—— -■■—■■ .... ■ , ■■■ ■ ■ ■ I - . —■ "■ " -" —• ~_
* j* -
Let Nm be the number of molecules per kg and N be the number of molecules per mt '/hut
of one molecule is — and the volume of one molecule Is

/VrriM N
N
Hence the density of the substance* p = N,n '
Thus the mass susceptibility,
y
Xm - —; substituting for % from equation (9,38)
H>Ko
Xm 3k0T(N/Nm)
or y __ M'mMnM'O _ Cm
%m~ 3kBT ~ T
Similarly the molecular susceptibility is given by
3kgT
3^T
i.e.,
3R.T
Here NA is Avogadro’s number and Ru - NA kB is the universal gas constant. Thus
p *
► »
F’
(9.40)
where a0 = NA |im is the saturation value of the magnetic moment per kmol. It should be noted that the
same .expression holds good for atomic susceptibility also.
X« -
The important conclusion obtained from the study of paramagnetic materials which include not
only elements in the pure state but also salts and oxides, is that paramagnetic susceptibility is independent
of the magnetising field, but various inversely with absolute temperature. This is expressed by the
Curie's law already stated i.e., % = —. Now
(i) The volume susceptibility, % = — , where C =

3kB
9
(ii) The mass susceptibility, %m - -*■ ,7 where Cm =
3ks
(Ui) The molecular susceptibility, = ~=r, where CM

3^fi
The only condition imposed here is that a = should be small which can be obtained
B
easily using weak fields and having appreciable temperatures. That is, all the above expressions for x
are almost independent of flux density, but proportional to — which is nothing but Curie's law of
paramagnetism. This is experimentally verified in the case of oxygen, gadolinium sulphate (GdSO4)
and a few other gases and diluted solutions. The quantity known as Curie's molecular constant can
he used for getting u for paramagnetic substances.
Equation (9.40) is,
„ _ ^0q0
with ^0 ” NA
U,
M ~ 3/?„
or
P’OÂ .
(9.41)
Langevin theory failed to explain the complicated type of dependence of susceptibility upon temperature
exhibited by paramagnetic substances. Example: Compressed and cooled gases, solid salts, crystals,
etc. Furthermore, this theory does not throw light on the intimate relationship between para and
ferromagnetism.
Weiss introduced the concept of internal molecularfield in order to explain the complicated type
of dependence of susceptibility. In a real gas, the molecules are mutually influenced by their magnetic
moments and consequently, there should exist within the gas a molecular field. This field produced at
any point by all the neighbouring molecules, is proportional to and acting in the same sense as the
intensity of magnetisation. Let this internal molecular field be £L
Now =
where X is molecular field coefficient. Therefore net effective field should be
H = H + H.
c I
Equation (9.37a) is M = Af,(a/3)
itw|l0He'
3fcBT
Introducing the value of M from equation (9.37a) on the right-hand side of the above equation,
one gets
tOHo Ly J AWX
M-
3^T [ 3kaT
Yoi
Wo R t
3k BT L 3*ar
M=
L
Vj
ti^WSWW- 7^^'.^r-’*-,»;vy5»H»‘?<- f>-i^vrj
or
m_ m>ouY " _ (9.42)
H " 3i.tr-,Cn» JVX/3*»JJ< 3i„(T- ej •
v. ';_ . :J-Y inx.;.': '.: I
CHAPTER 9
where 0c = (jl2mjVX / 3kB ) is called paramagnetic curie point. Equation (9.42) is called Curie- Weiss law.
This strange conclusion of Weiss law finalises that below paramagnetic curie temperature (T < 0p,
susceptibility becomes negative.^However, it should be noted that for most of the paramagnetic substances,
curie temperature is quite low so that a situation for which T < 0c is rare.
To evaluate or compute the sc®Pnb11^ in solids one

. s“c/OTrfihiiirv M mustUefirst make a calculation
d magnetic of the number
field. The magnitude of
of the
magnetic dipole moments which line upjp PP moments which line up in
susceptibility will be determined by the ”Xh the magnetic dipole moments are
this way. Let us carry out the calculanon fo P y ° ^sumed
due to pure electron spin and assume that they do not interact wim one an
the spin quantum number, s so that them am just two possible orientations of the magnetic moment
with respect to the external field, one paraUe! to the magnetic field and the other antiparalleL
Let there be /V When the applied
N spins/m’ in the material. monetisation M isfield
zero.isWhen
zero, the up and down
an external spin
field H is
moments are equal in number so that the total g of t0 field.
Wlied, some of the dipoles have a ten ency assumed that the dipole moments do not
Hus gives rise to a certain amount of magneti . tic field< let N dipoles be aligned parallel
mteract with each other. In the presence of the apphed m kelCm. The total magnetisation
to the field and Na be aligned antiparaUel to the field at a temperature xeivm
« A.
Af = Aîfl-Njifl= ViB(Np~Na) (9.42a)
**tore BqJjj magneton and one Bohr magneton - 7^.

The susceptibility.
X = ^=^r-^
The values of and Na depend upon the temperature (7) and the strength of the applied field
(Ml and Boltzmann statistics is used to calculate their values. It is obvious that the dipoles antiparallei to
the field have greater energy as compared to the dipoles which have parallel orientation. This difference
is shown in Fig. 9.17.
The torque on die dipole is
If a dipole is inclined at an angle 0 to the applied field and assuming that the energy of the dipole
is aero when it is perpendicular to the field (0 = 90°), the energy of a dipole can be obtained as
9
Energy = J |1O |im H sin 0 dQ
90°
N.______________________ _
1------------------------ ----- :---- +
2^8
N_----------------
- ---------------- — EP = -^B
Hr 9.17 Energy difference between parallel and antiparallel spin dipoles
= ~^MqUotcosO
Hence energy of antiparallel dipoles is obtained by putting, 0 = 180°.
Similarly energy of parallel dipoles is obtained by having 0 = 0°.
Now the energy difference between <m,iparalM end parallel orientation of dipoles is.
O' e.-«, = 2|tol»aH

wtere g, - M. single spin-ntomenl is essured. n» nttio N, to N, st any temperature T is given by
Boltzmann suusucs as p
JVeip (-H p ________
exp (-go M* H/k,T) + exp (Po U . * /* « D
' 4 - . — _____ * ---------
exp (p0 - exp (-m
Thus N -N «N
p a exp (g0 \LBH/kBT) + exp (-Ho \LnH/kHT)
or Np - Na ■ N tan h (l^ ViyH/kyT) (9.46)

Taking this value of (Np - N(l) to equation (9.42a), one gets
M a |i/) (Np - Nu) a N}kB tan h (|i0 ^/HkBT) (9.47)
H *
Thus M = N|ifl tan ha, where a a —■ ■„ - (9.47a)
kgr >
Note that for a «1, tan ha=a and when a »1, tan ha - unity (strong field and low temperature),
Npa indicates that maximum value of magnetisation when all the spins are parallel to the field. For
normal temperatures and not too high fields, it can be seen that M-oM-/// « 1, and under this situation a
« 1, so that tan ha = a. Now equation (9.47) becomes
M = N\iBa
M _ NyB Uo PgH
kBT
■
M _—
(9.48) •
V' kBT 4
In practice, condition H « kBT is satisfied more often than the other. For example, for
relatively strong field of 1 weber/m2, we have p0 H = B |ifl = 9 x IO-24 joule, whereas at room
temperature kBT=4 x IO-21 joule. Now the relation for magnetic susceptibility as function of temperature,
is given by
M = UoM4 (9.49)
H kBT
Equations (9.49) and (9.38) show that paramagnetic susceptibility x in a two-level quantum
mechanical model differs by a factor 3 from the classical model. The susceptibility x may also be
expressed aS
(Ng2 \
which reduces to
Wo ^)
tan ha
I-*- Slope (unity)

I
I
I
M/Ms I
»
I
I
*
1.0 2.0
PoHbh
a= --------
kBT
Fig. 9.18 Variation of normalised magnetisation with (p0
with g = 2,J= —
Thus
where C- is called Curie constant. This expression is known as a Curie law.

. . •
• * J
Fe2O3, MnS04, FeCL, NiSO4, etc. are some examples of paramagnetic materials. It has been
observed that many paramagnetic materials do not obey the Curie law. They obey the modified law
called Curie-Weiss law,
(9.50)
where 0 is a constant with dimensions of temperature for any one substance, and equals zero for those
substances which obey Curie law. Many paramagnetic materials obey the Curie-Weiss law with small
values of 0, of the order of 10 K or less. The properties of paramagnetic are not much of practical
“uportant, but it helps to understand the theory offerromagnetism and ferrimagnetism.:
. Ute classical theory suggested by Langevin assumes respectto the magnetic

âr magnets capable of Nation of magnetic susceptibility of only some
i by (939)-
Quantum theory of paramagnetic materials assumes that the permanent magnetic moment of a
given atom or ion does not rotate freely, but limited, with respect to the applied field, to a finite set of
orientations. Let N be the number of atoms or ions per m3 of such a paramagnetic material. Let J be the
total angular momentum quantum number of each atom. This includes the total orbital angular momentum
L and the total spin 5 of the electronic system per atom.
The magnetic moment of each atom is now, |l7 = gJ where g is the Lande factor. In the
presence of a field H, the axes of the magnetic moment py will precess about the field direction such that
the resolved components of |iy in the direction of the field are of Here Mj is the magnetic quantum
number associated with J. It (Afy) can take values J, (J - 1), (J - 2),..., 0,... - (J - 1), - J. Therefore, an
atom with angular momentum quantum number J has (2J + 1) values. The magnetic dipole moment for
an atom for a given value of Mj is Mj g |tB. The potential energy associated with this dipole moment of
the dipole along H is - (My g pB H |1O). According to statistical mechanics, the magnetisation is given by
(9.51)
The term inside the bracket on the right-hand side of the above equation (i.e., coefficient of N) is
the statistical average of the magnetic moment component per atom in the direction of the applied field
H. Two main cases of interest are discussed below:
Case 1
Mj S ^8^ « I
Under this condition
exp (Mj g [l/jH Pp/kg/) — 1 + (Mj g [Lfk^T)
Now the R.H.S. of equation (9.51) leaving N is
f Mjg [1 + (Mjg p0
Ze*p(Mjg\iQpBHfkBT)
-J
+ H0H/fc8T)l
-J____________________________
i 1 + (Mj8 Jl0 pBHlkBT)
J
HMMme1
Heine £ M, = 0, toe numerator gets simplified as:

V/ y J
The denominator is simplified in a similar way:
£ l+(gpojLBH/^7)£Mz = (2J+l) + O
—J
Equation (9.51) becomes,
f g2no14#~| [J(J+1)(2J+1)1
(9.51a)
ie.,
Now
(9.52)
i.e.,
2
: g2j(j+ 1) Hb is found t0 quite identical with
where
• zo when compared with equation (9.3 J. to
The equation (9.52), wnen “F result tiz replaces pm- w J
classical result with a difference that in qu number of Bohr magneton. For groun s e
where ffJWTi) and is c*d relatio„ for p* when put io experimental
the atom 7 = S and L = 3. Hence gases but

verification was found to be quite true in ctism of transition group e
■een when it was applied to explain the state ts untrue.
that the assumption for every partic e
Thus, equation (9.52) becomes
(9.53)
Owe 2
ie.. at low temperatures and high fields. The conditions imposed in case 1 may not work here. Hence a
different approach is made to get the value of M—the magnetisation.
, one now gets
Z Mj exp (Mjx)
--------- ------
Z exp {Mjx)
= <Ng^— toZexp(M,x)
= + .~ +e^)]
= [In e* (1 +«"■+... + e’2*)]
Ms(Wb> I J. *« 1
Multiplying and dividing the logarithmatic term by exp (x/2), we get
Let fl 31 1J
M = Ng^B
(2J + l)q 1' cot ,.( a
Now -—cot A — n\ ——
2 2J 2 2J
M = NgV.BJ ------- cot h — cot A — (9.54)

2J 2Jj l2/ZI
JgBPs
*’’h a= kBT
The expression in the square bracket of equation (9.54) is called Brillouin function, Bj (a), and it
describes the variation of induced magnetisation with J, temperature and magnetic field.
Thus at low temperatures and strong magnetic fields, the calculation is done without approximating
the exponentials as in case 1. The relation now obtained is given by equation (9.54),
(9.55)
CHAPTER 9
where a =------------ and Bia) is the Brillouin Junction defined by
|tW» 2/*l W+l)a a

- ?
cot A — cot A (9.56)

2J A 2J . . 2J_ - 2J
' The physical significance of this result is the saturation of magnetisation at low temperatures.
ie., all dipoles are ultimately directed along H. In this respect equation (9.55) is the analogue of the
Langevin expression [equation (9.36)], the difference being that the latter holds for freely rotating
dipoles only. In fact, if J —* (infinite number of possible orientations, the Brillouin expression [equation
(9.55)] becomes identical with equation (9.36).
Brillouin function describes the
variation of induced magnetisation
* with J, temperature and field. Fig. 9.19
•hows the curve for J~
The curve at J = «> will be

corresponding to the Langevin
function L(a).
The maximum value of

^Snetic moment M, represented by
। will be iigNgj^ because Mj will then
*e the maximum magnitude J, the Fig. 9.19 Variation of Brillouin function fl (a) W(th a and J
gnctic axes of atoms being along
the field lines. Thus
M=M
s (9.57)
with Ma = Ng^
M
Now - W
(9.57fl)
TT r 1 >yi . O
ror J= — — = tan ha = a---------+ ...
2 Ms 3
It has been found that equation (9.57) is in good agreement with experimental result in comparison
to the results obtained from classical equation.
An estimate of the magnitude of x of paramagnetic substances at a given temperature may be
made by taking N= 5 x 1028 nr3, B = 1 tesla and T= 300 K. Substituting these value in equation (9.48),
one gets
. = M_ _ 7Vii05 xlO28 x 4% x 10~7 x (9.27 x 10~24)2

* H ~ kBT “ 1.38 x IO"23 x 300
' ' ■ - . **• ”2 • r -
_ 4k x 9.272 x 10~7 x IO-48 x 1028 x 5 _ 4kx9.272 x 10^x5

1.38 x 300 xlO-23 = 1.38x300
i.e., x=l-3xlfr'3
Table 93 Susceptibilities of some paramagnetic materials at 300 K and under a field of 1 tesla.
Substance -
MnSO4 ' 3.6 x 10-3 FeCl, 3.7 x IO"3

CrCLj 1.6 x IO"3 NiSO4 1.3 x IO"3
CoO 5.8 x KT3 FeSO4 2.8 x IO”3
CoSO4. h2o 2.0 x 10“3 Fc2O3 1.4 x 10"3
^r2®3 1.8 x IO"3 Fe2(SO4)3 2.2 x IO"3
Table 9.6 Values of 5 and for unpaired 3d electrons
Number of unpaired Spin quantum number, S

Magnetic moment U. in Bohr ' i
electrons magneton}Lt = g.JS(S +1) withg-2 '
...I .. .
1 1.73
2
2 1 _ ___________ 2.83_____________ _
3
3 3.87
2
4 2 4.90
5
• 5 5.92
.2
Spin Paramagnetism
The details of the band structure depend on the
type of bonding, interatomic distance and crystal
structure. As discussed in Chapter 6, the bands
formed by overlapping wave functions of the
valence electrons and the adjacent, empty
conduction band are relevant. The position of
the fermi level and the disposition of the valence
and conduction bands with respect to each other
determine whether the solid is a metal,
semiconductor or an insulator. An electron is
presumed to carry a magnetic moment of one
Bohr magneton. The detail of Pauli’s expression fig. 9.20 The effective moment in Bohr magneton as
for the spin paramagnetic susceptibility have function of the number of electrons for the trivalent
already been discussed in Chapter 6. positive rare earth ions. The full curve represents the
values calculated from Pt/f- g -jj(] +1)
Temperatures below 1 K can be ®Gainedthe thermodynamic

with the help of
paramagnetic salts. This is done yu entropy of t e
paramagnetic materials. Figure ■ erature (oAB^‘ n
working substance as function o minimum at T* •
entropy, which is the degree of disor , uch as possible, y
The first step is to cool the crys »^.CoolingtoAKwtnch
conventional low temperature techn q nroblem. ÎS st
®the temperature of liquid helium, is $ versus T curve
represented by a point B on the en of the external y
OAB. The next step is to increase the tntenstty
fig. 9.21 Entropy of paramagnetic salt
as a function of temperature
Yc
applied magnetic field from H = 0 to some value of H with temperature maintained at B. During this
process, which is isothermal, the applied magnetic field introduces an alignment of the atomic magnetic
dipoles and hence a decrease in entropy of the crystal. Let C be the new entropy of the crystal lying in
the S versus T curve for the applied field of H. The specimen is now adiabatically demagnetised by
taking away the field with change in entropy jdS = 0. The entropy now corresponds to the point A
Successive repetition of these processes result in a very very low temperature of the order of 10-3 K.
Qualitatively this may be explained as follows:
According to the second law of thermodynamics,
Le., dE = dQ-dW
dQ = dE + dW
But dQ = T dS, where dS is the change in entropy. Thus,

TdS = dE + dW
But dW = MdH (9.58)

where H is the intensity of the magnetic field and M is the magnetisation.
Again . dE = QEfcT)HdT+QEfoH)TdH
Equation (9.58) becomes
I dE 1 ( 3F Y
TdS = -r- dT+ dH + MdH =
\&T ) \Mi)T
Because dS is a total differential, it follows that
(1/T) = (dS/dH)T = (dM/dT)w
where the last equality follows from one of the Maxwell’s relations. For the isothermal process (B to O
one may write,
. dS dH
Integrating this equation

H
$ = $H=0+ J o'” 'h

dH (9.59)
From equation (9.51a)
M = [Ng2Pty/(/+ WBH]/3kBT
(9.60)
Le.,
(
Substituting this value of in equation (9.59), one gets
H
H 9
c_ c + f + DUflH dH
Ha0 i 3V5
-Afe2p0J(J + l)p,fif/2
mbt2
Thue ac — c_ c _ N& M-o + 1)/T

Inus ao ~ o - o#_n = ---------------------- ---------------
? ' ~ < 6kBT
where AS is the change in entropy at a given temperature TB for a given value of H. The distance BC in
Fig. 9.21 is AS.
The magnetocaloric effect described above has been used by many workers for the production of
very low temperatures. The first experimental test of the phenomenon was carried out at temperatures
down to 1.3 K. The results confirmed the theory in satisfactory manner. Temperatures as low as 0.0015 K
have already been obtained by the effect. Typical paramagnetic salts used in attaining low temperatures
CHAPTER 9
by magnetocaloric effect are FeNH4 (SO4)2 .12H2O and CeF3.
Usually the response of paramagnetic and diamagnetic substances even to high magnetising field is
quite feeble which causes a great difficulty in the measurement of their susceptibilities.
Theory
Let a body of permeability p- and volume v be placed in a magnetic field with permeability of the
medium as The broken line indicates the direction along which the body is free to move.
Let the region surrounding the medium is evacuated; i.e„ the permeability of the surrounding
medium is unity, then the potential energy of the body will be - H2 v/2. Since the body is situated in
a medium of permeability it displaces a volume of the medium whose potential energy will be
Therefore, the total change in potential energy due to the introduction of the body is,
Thus the force which tends to move the body along the x-direction will be
0*2 - H,) H® W2J

dx
r/ x„d(/f2)v
- KWa (9.61)
Putting jiri = 1 + x2
^=1+Xi
and = Ho Hri and m = Hrp one gets
(m> - m) = Mn (Pr2- U„) = Ho (Xi- X1)

Substituting this value of (p^ - p,) in equation (9.61),
>o(X2 -Xi)v] d(H2)

2
(9.62)
K.’-a 2>
(9.63)
$
Since H2 = H2 + H2 + H2 where Hx, Hy and Hz are the components of the fields along the
x-axis and any two mutually perpendicular axes y and z.
Guoy Method
It is one of the best methods of susceptibility determination particularly when a sufficient quantity
(about 10 cc) of the material is available and variation of susceptibility with temperature is desired.
The material whose susceptibility is required must be in the form of a rod of circular cross
section or as a solution or very finely ground powder liable to be placed in a glass tube of uniform cross
section.
The specimen or its container is suspended with its axis vertical from one arm of a sensitive
microbalance. The lower end of the specimen is kept near the mid-point of the field (H) between two
flat pole tips while the upper end is a field of negligible strength (HA This explains why 10 to 15 cm
specimen is required. HQ can, then be less than 1 % of H. Due to this field a vertical force, acting on an
element of solid specimen of length dx and volume dv, is equal to
dFx _ Uo(X^-Xi) I- d (h2} + d_(h2) + d_2 J(9.64)

2 L«x ax dx
where x2 and are the respective susceptibilities of the specimen and surrounding medium usually air-
Since in the gap flux lines will be direct from one pole piece to another, i.e., in y-direction,wC
can neglect Hx and Hz. Hence,
’ *H
CHAPTER 9
If a be the area of cross-section of the specimen, then
dv = a dx .
The total vertical force on the specimen due to the whole field along its length from region
where Hy = H to Hy = HQ will be
. _ Hq(X2-%i)Q
x O- —. J J,
"o
i.e.
H0a(X2-Xi)[H2-H£]
(9.66)
This pull will be downwards if the material is paramagnetic and upwards if diamagnetic. In
equation (9.66), Hq is small and can be neglected. Thus
(X2-Xi)Ho q//2
(9.67)
This pull can be calculated by the microbalance. The specimen is weighed when the electromagnet
w not excited i.e.. in the absence of field, and again when the current is switched on. The difference in
Weights in ni kg; represents the magnetic pull on the specimen.
Therefore, -------------- 7-------------- -
Xj-Zj =<WM0a#2) (9.68)

The value of susceptibility will be accurate, provided the field measurement is accurate. This
method can be used at low temperature.
Quincke’s Method
This method is suitable for the susceptibility measurements of aqueous solutions, many liquids and
liquefied gases.
Liquid under investigation is placed in a vertical U-tube as shown in Fig. 9.24 with one limb of
wide bore and the other narrow. The cross-section of these limbs must be necessarily uniform The
narrow limb is placed in between the pole pieces of the electromagnet such that the surface of the liquid
in the limb lies at the line of centres of the pole pieces when the field is off.
When the energising current is switched on, a strong uniform field is established as the upper
surface of the narrow column of the liquid, while lower portion of the column is in a region of
comparatively weak field.
Consequently a force will act upon the column and if the liquid is paramagnetic, it will rise.
Let x be the vertical direction and y be the direction perpendicular to the pole pieces, then vertical
force on a small volume dv of liquid of length dx will be
You
(9.69)
L 2 J dx 7
If a be the cross-section of the narrow limb then,

dv = a dx
dF = >o(X2-Xi)~l d
—(H?) a dx
zttt *
Thus the total vertical force acting on the liquid column is
Uo(X2 ~ XiX
Ro^(X2 ~Xl)^m
(9.69a)
CHAPTER 9
2 .
when Hm is the final field applied.

The rise in the surface of the liquid is noted with a travelling microscope. There will be no
appreciable change in the level of the liquid column of the wider limb because of the larger cross-
section.
If p be the density of the liquid and o, the density of air, then change in hydrostatic pressure
when the liquid rises to a height h will be
(p - <5)g h
Thus the corresponding change in force acting vertically will be
(p - G)g h a
and this must be equal to Fx discussed already
i.e., (X2 ~ Xi)P-o a^m =(p-(y)a g h
. fi- [2gMp-a)J ’
(9.70)
X( is the susceptibility of air whose value can be taken from tables and can be calculated.
The bore of the narrow limb must be strictly uniform if surface tension changes are to be avoided.
The bore should not be very much narrow. Otherwise on applying the field, the surface of the liquid will
be deformed and thercwill be no rise and fall of liquid column.
Thble 9.7 Magnetic susceptibilities of some paramagnetic materials at room temperature
i Material x-K-1) Material x=(ur-i)

Air 0.038 x IO’5 Ebonite 1.4 X 10"5 1!
Aluminium 2.3 x IO"5 MnSO4 360 x 10-5

Magnesium 1.2 x IO-5 Fe2O2 140 xlO-5
Tungsten 6.8 x IO"5 FeCl2 370 x 10“5
Platinum 30 x 10"5 NiSO4 120 x Iff-5
Oxygen 1.94 x IO-6 CoO 580 x 10“5
Nitrogen 0.0013 x IO"5 Titanium 7.06 x 1(T5
Paramagnetism in general is a relatively small effect that has found a few technical applications
e.g., paramagnetic salts have been used in obtaining very low temperature of the order of 10-3 K by
adiabatic demagnetisation- They are also essential materials used in the solid state MASER.
It is required to obtain the characteristics of the ground state of an atom or iron whose electronic
configuration is known through L-S coupling. The orbital angular momenta of the Z electrons in the
atom are vectorially added to obtain the total orbital angular momentum of the atom, _
L = Lj +1^2 + ...
The contribution from the electrons in the closed shell vanishes, and so the summation has to be
carried only over the electrons outside the closed shells. In a similar manner the total spin S of the atom
is obtained by summing over the spins of the electrons outside the closed shell. Finally, L and S are
coupled to give the total angular momentum J=L+S. For example, tungsten, 74W, has a d4 configuration. ■
Since the d subshell can hold 10 electrons of which 5 can have the same spin, the greatest S for the
ground state (4 x 1/2 = 2). Since all the four electrons have the same spin, they must have different mp
and the biggest possible ML is then
[2 + 1 + 0 + (-1) = 2], With L = 2 and S = 2, the smallest J is 0 and hence the ground state 74W
is SDO.
The ground state is obtained using the following three Hund rules*.
(I) Choose the maximum value of S consistent with the Pauli principle.
(ii) Choose the maximum value of L consistent with the Pauli principle and rule 1.
(iii) If the shell is less than half full J = L — S, if it is more than half full J = L + S.
Let us apply these rules to a free iron atom whose electronic configuration is Is2 2s2 2p6 3s2
■ 3d6 4J2. The only electrons outside the closed shell are 3d6. According to Hund rules these should be
distributed as in Table 9.8.
ite . 4.. « i
Tbble 9.8 Distribution of 3d electrons in iron atom
Now L=X w;=2, S = Z ms = 2. Since the shell is more than half full, J = (L + S) = 2 + 2 = 4. The
denoted as 5D4 where the letter D denotes L = 2, the subscript on left denotes the multiplicity,
state is
2S+1
_ 5, and the subscript on right denotes J = 4.
Oystal Field and Quenching of the Orbital Angular Momentum

The relation (9.52) fits well for many paramagnetic crystals including the materials containing ions of
rare earth group. Deviations do occur, however, these are due to the fact that energy level system and
states of an ion in a crystal are not necessarily the same as those for a free ion. The main reason for this
is that in a crystal, a paramagnetic ion is surrounded by other ions with which it will interact. In particular,
the neighbouring ions whether magnetic or not, will still be electrically charged and these create an
inhomogeneous electric field in the neighbourhood of the paramagnetic ions which we are considering.
CHAPTER 9
Hus is often called crystal field. The interaction of the paramagnetic ions with the crystal field has two
major consequences: The coupling L and S is largely broken up, so that the states are no longer specified
by their J values; further, the (2L + 1) sublevels belonging to a given L which are degenerate in the free
ion may now be spilt up by the crystal field. The splitting decreases the contribution of the orbital
motion of the magnetic moment.
For ions of the iron transition group, the comparison of equation (9.52) with experiments far
from satisfactory. The reason for this is that for the iron group, the ground state of the ions in a crystal
is very different from that of the free ion. This is because, the partly filled electron shell, which is
responsible for producing the magnetic moment, is the outer most (3d) shell of these ions. It is, therefore,
very strongly influenced by the crystal field. The interaction is so strong that the orbital angular momentum
of the electrons in the 3d shell is very often reduced to zero. This does not mean, that electrons no longer
encircle the nucleus, but rather that they will be travelling around it as often in one sense or in the other
sense. This effect when L averages to zero is termed quenching of the orbital angular momentum and it
means that when the ion is in the crystal, there is no orbital magnetic moment. In quenching, the crystal
hardly interacts with the spin and hence, the spin magnetic moment still exists. Therefore, while
calculating the susceptibility on the basis of equation (9.52), we must replace J by S.
Let us now consider Ni2+ ion. If we put S = 1, L = 3 and J = 4, g becomes
; J(J + 1) + S(S + 1)-L(L + 1)
g =1+ ■ -—--------------------------
5 2 J( J +1)
, 4x5+2-3x4
2x4x5
, 20 + 2-12
= 1 +------ 77--------
40
You
Now C = g2 J (J + Wp2/3kfi]
= (1.25)2 x 4 x 5
= 31.3 (in units of N^2Bt3kB)
If J is replaced by S,
then J = S = 1,L = O
Thus, C = g2 (J + lW2/3fcB] . f '
= 4(1 +1) = 8 (in units of ?/|i2/3fc^) y
This value well agrees with the experimental value of 9.1.
(i) A paramagnetic substance has a non-vanishing angular momentum and so they possess
permanent dipoles.
(ii) In the absence of an applied field, the dipoles are randomly oriented and so the net
magnetisation in any given direction is zero.
(iii) At a finite temperature each atom has a thermal energy on the average equal to kBT and the
resulting thermal agitation tends to make the dipole observation random. To align the dipoles
in a given direction, a field strong enough is needed to compete with the force due to thermal
agitation. The field ordinarily available in the laboratory is far too small to turn the dipoles in
the direction of the field. What the field does ? Is it to turn the dipoles slightly in the direction
of the field so that on the average there are slightly more dipoles pointing in the direction of
the applied field than in the opposite direction ? Since the applied field has to compete with
thermal motion, paramagnetic susceptibility decreases with increasing temperature.
Introduction
When the avenge person speaks of a magnet Ha ;
maZ T 10 »P oZ'
experimental ' th ' i”' magnellc Properties even in the abse *° *
/ raatenal is said to he a permanent
specimen M 6 magnetisation is increased when • nCC° an appIied field; however it is found
u°re0Ver’the re,atio"shiP between B and Zk * ma«nelic «Md »

the res ysJcresis c°mes from the Greek word (hvstem U ‘ ferromagnellc materials exhibit
the response of a materia! to a change in the appifed Zd T“ ‘“’d refos 10 “

n Pig. 9.25 (a) is plotted a typical (B-H)
MAGNEfi&pRO?
He for a fenwnagnet
r» polansacion
reverse as increasert
theB.appfej
of the material,
direction then then h
„/, u“
. incre ®ed Io , „ ... ‘ n'w large enoneh ,
“ "'Sacive
hysteresis
“““ to is zero
thus is
forme d. The
eaiied magnehe i2
the Kmmace °"“ a°"
'^ "n^ A „~-< closed loop
e whe
r,eld ^ccdeeed fraa
Fig. 9.2S Hysteresis loop
The size of the (negative) field required to reduce the induction to zero is known as the coercivity
or coercive force, H. Remanence and coercivity are the properties we shall try to explain above all as
they are of the highest practical significance. If the applied field is insufficient to saturate the material,
then the loop plotted has a smaller area than the hysteresis loop, and is called an inner loop. Transformers
and inductors should always below saturation around inner loops. In this case the working remanent
induction is less than Br and the coercivity is less than Hc. In a similar way, we can construct (M-H)
curve using equation (9.17). Here the magnetic polarisation (magnetisation), unlike the magnetic
induction, saturates in sufficiently large applied fields to a value known as saturation polarisation. The
(M-H) loop, often termed the intrinsic loop, is more convenient for a theoretical study of magnetisation
than the (B-H) loop.
The ferromagnetism in Fe, Co, Ni and Gd is mainly due to the self-alignment of groups of atoms
carrying permanent magnetic moments in the same direction. These elementary permanent moments
are those responsible for paramagnetism. The question now is why the atomic moments should be self
aligning without the> help of an outside field. A review of some of the physical characteristics of the
ferromagnetic elements is worth while before the study of the ferromagnetic interaction begins. Some
°f the required data for the elements mentioned above are listed in Table 9.9.
For a given ferromagnetic material, the spontaneous magnetisation can occur only below a certain
®perature ferromagnetic curie temperature. Well above the Curie temperature, such materials
ave like a paramagnetic material and have a well defined susceptibility given by Curie-Weiss law,
liable 9.9 Some physical properties of lerromagnctic element*
1^"
Element Electronic Crystal Magnetisation o/k; Meltbig

temperature
configuration structure at 0 K (amp/m)
K .
Fe 3d6 4s2 bcc 1.7 xlO6 1043 1810

Co 3d7 4s2 hep 1.4 x 106 1404 1750
Ni 3d8 4? fee 0.48 x 106 632 1728
Gd 4f 5d> 6? hep . 5.66 x 107 290 1586
C
o \
Above the transition temperature, a ferromagnetic material becomes a paramagnetic one, hecmw
then the parallel spin aligning energy is insufficient to overcome the randomising effect, which rotate
the spin direction. The data supplied in Table 9.9 indicates that ferromagnetism is not exclusively
characteristic of the crystal structure. Similarly they have a wide range of curie tei e and a
considerable range of magnetic moment. The one common thing is the electronic structure. Three of
them are found in the 3d transition group, the other in the 4/rare earth transition group. The existence of
partly filled d orf shells is essential in modem theories of ferromagnetism.
Origin of Ferromagnetic State

A ferromagnet has a spontaneous magnetic moment—a magnetic moment even in zoo applied field.
The atoms (or molecules) of ferromagnetic materials have a net intrinsic magnetic dipole moment
which is primarily due to the spin of the electrons. The interaction between the neighbouring atomic
magnetic dipoles is very strong. It is called spin exchange interaction and is present even in the absence
of an external magnetic field.
The three metals have closed shells for the Is, 2s, 2p, 3s and 3p levels. Since a closed shell has
do magnetic moment, clearly the 18 inner electrons do not participate in the magnetisation Attention
must, therefore, be given to the 3d and 4s levels, which are split into bands by the overlap of the wave
functions in the metal. Recall that the 4s splitting is considerable and the 3d somewhat less as shown in
Fig. 9.26. ,
Since all the states up to the Fermi level are full, the ten 3d+4d electrons of Ni for example, fiD
the states to the approximate position shown. In a ferromagnetic material below the curie temperature,
transfer of electrons must occur from one spin state to the other, so that half hand with the larger number
of electrons has a spin moment greater than that of the other, hence the metal has a net magnetic momcat-
Theory of Ferromagnetism
In the whole of the periodic table, only iron, cobalt, nickel and a few of the lanthanides (Gd, Tb) possess
this property. So what is so special about these elements that confers this uniqueness on them? It is t**
their crystal structure; each of them have different structures and the structures are similar to those <d
other non-ferromagnetic metals. Iron, cobalt and nickel, however, do all have nearly full narrow 3d
band.
•
CHAPTER
9Jt Schematic representation of the band structure of nickel. The 4s and 3d bands overlap completely. The
ten 3d + 4s electrons of Ni fill the 4s and 3d levels up to a level just below the top of the 3d band
Ferromagnetism arises from die alignment of electron spins through out the solid, and this occurs
far partially filled hands with a high density of stales near the Fermi level. 4d and 5d orbitals are diffuse
faun 3d and produce wider bands so that ferromagnetism is not observed in the second and third row
ttnsaion dements. The 3d orbitals themselves become less diffuse across the transition series and lower
■ aagy. In titanium the valence electrons are in the 4s/4p band with low density of states and, at the other
end of die row in copper, die 3d band has dropped in energy so that the Fermi level is in the 4s!4p band.
Th“* it b only at the middle of the series that the Fermi level is in a region of high density of states.
Let us now consider the electronic ^^^ânUciockwise directions

r the ferromagnetic in shells
metal K,this
iron. In L and N.
atom
equal number of electrons spin in the clockwise f atom has 14 electrons in the third partiaUy
Uwe shells are, therefore, magnetically neutral. ’ opposite direction. The net spin magne c
filled shell, 9 with spin in one direction and 5 wi P magnetic
moment of the atom is 4 Bohr magneton.11118 ot of 3 Bohr magneton and a nickel atom
paramagnetic atoms. On this basis cobalt has a magn^celectron spm
ha* a magnetic moment of 2 Bohr magneton.111,8 fP due t0 the proximity of other atoms
»the M-shell which is near the periphery of theThe average values for
and therefore the actual magnetic Respectively.
foo. cobalt and nickel are 2.22,1.77 and
Thu, the net spin magnetic ro^n“' “f^gnetiaauon

ferromagnetic<*atoms is ^^ribed
nf
• of w same
the asorder
ferromagnetic, a
magnetic
asnot
u due to
nomem of paramagnetic aroma. ^^ba(ip<.08 i6 -hat in “C^sappears and the malenal becomes
the moment of individual atoms. coupling sudde y
•pecial form of interaction called exc
You h
Table 9.10 Values of the magnetic moment for different numbers of/electrons
Number off Number of y L S p in Bohr magneton

electrons unpaired electrons £
1 1 5/2 3 1/2 ■ 2.54

2 2 4 5 1 3.58 7 '
3 3 9/2 6 ■ 3/2 3.62 '

4 4 4 6 2 2.68
5 5 5/2 5 5/2 0.85
-------- —1 -
6 6 0 3 3 0
7 7 7/2 0 7/2 7.94
8 6 6 3 3 9.72
9 5 15/2 5 5/2 10.65
10 . 4 8 6 2 10.61
11 3 15/2 6 3/2 9.58
12 2 6 5 1 7.56
13 1 7/2 3 1/2 4.54
simple paramagnetic. For iron the Curie temperature is 1043 K. Thus, we conclude that ferromagnetism
is a property, less of the individual atom but more of the interaction of each atom with its neighbours in
the crystal lattice.
Both in the classical and quantum
models, saturation magnetisation could be
achieved in paramagnetic material at very
low temperatures and high applied
magnetic field. In ferromagnetic materials
saturation magnetisation occurs at ordinary
temperatures and at ordinary Helds and
sometimes even at small values of applied
field. Ferromagnetic materials have a
characteristic temperature below which
they exhibit the ferromagnetic behaviour
of spontaneous magnetisation. This
temperature below which they exhibit the
ferromagnetic behaviour of spontaneous
magnetisation is called the ferromagnetic
curie temperature Q,. Above this
temperature the behaviour of ferromagnetic ^8* 9.27 Inverse susceptibility versus temperature
materials is that of paramagnetic. curve for a ferromagnetic material
In Fig. 9.27, the inverse susceptibility x is plotted against temperature; the plot be a straight line,
starting from the temperature, 0^ on the temperature axis as shown in Fig. 9.27
In the vicinity of 9^ the variation of — is non-linear. The paramagnetic curie temperature 0 of
X
gx material may be determined from the curve by extrapolating the straight line portion of the curve
ipgards the temperature axis as shown in Fig. 9.27. A ferromagnetic material differs from a paramagnetic
00eri*l m the sense that for the latter G = 0 as shown in Fig. 9.16. The plot of — and T shown in
Hg 9,27 indicates that 0 is higher than Gy.; however the difference (0 - Gy) is small, being 20 to 70 kelvin
for the iron group of elements. For iron G and 9, are 1093 K and 1043 K respectively.
Table 9.11 Electronic configuration and spinmoment of iron group of elements.

Calcium and copper have been added for comparison
-- • •* • r ' 0- ■r • i
•
Resultant spin
Element Electronic configuration 3d subshell
somber moment in Bohr
magneton jf
2'Sc Scandium Is2 2s2 2pb 3s2 3p6 3d1 4s2 1 1 Tj
CHAPTER 9
»n Titanium Is2 2s2 2p6 3s2 3p6 3d2 4s2 2 2 | TT]
»v Vanadium Is2 2s2 2p6 3s2 3p6 3d3 4s2 3 3 TTT |
Xq
Chromium Is2 2s2 2p6 3s2 3p6 3d4 4s2 4 4 Tttt |
25Mn Manganese 1jr2 2s2 2p6 3s2 3p6 3d5 4s2 - 5 5 TTTTT
Iron l^y2 2s2 2p6 3s2 3p6 3cF 4s2 6 4 |TTtTTT|
^Co Cobalt Is2 2s2 2p6 3s2 3p6 3d1 4s2 7 3 TtTTt44|
®Ni Nickel Is2 2r2 2p& 3J2 3p6 3d® 4s2 8 2
Calcium Is2 2s2 2ffi 3s2 3pb 3d14s2 0 0
^Cu Copper Is2 2s2 2p63s23p6 3d10 4s1 10 0 wtmui
Below the ferromagnetic curie temperature the material exhibits normal behaviour and follows
weU-koown hysteresis curve shown in Fig. 9.25. Assuming the materia) to be virgin, the flux starts
budding up from the origin as the value of H is increased from zero. In this range, B is nearly proportional
to Af giving rise to constant permeability of the material. This permeability is called the initial permeability
■toce there is no hysteresis in the region. As H is further increased, the rate of increase B falls and
u*t“naidy becomes zero and the flux density B reaches a maximum value or saturation value indicated
in Fig. 9.25.
Along the virgin curve, one can consider a differential relative permeability of the material
'totaitied from the following basic equation on differentiation:
B = g0 (H + M)
(9.71)
This differential relative permeability may become very large for ferromagnetic materials because
of large value of magnetisation M. Such is the case with high permeability materials. As the value of ft
is reduced from saturation value to zero, the reduction of flux does not follow the same path (but quite
slow) as //becomes zero; there remains a certain amount of flux in the material called the remanent flux
density Br as in Fig. 9.25. The material remains magnetised even in the absence of an external force and
is spontaneously magnetised. This magnetisation corresponds to Br is Mr = The spontaneous
magnetisation is the most important characteristics of ferromagnetic materials.
To reduce the remanent flux Br to zero, it is necessary to apply H in the reverse direction and the
amount — Hc required to make Brzero is called the coercive force. The value of coercive force H varies
over wide range and be in fact controlled by alloying the ferromagnetic materials by other materials.
The materials required in the manufacture of permanent magnets must have very large coercive
force so that the magnetisation once established in the material does not decay with time. At the same
time, Br should be as large as possible so as to reduce the size of the magnets. The Br and Hc values Of
some such materials are given in Table 9.12.
Table 9.12 Two important properties of a few permanent magnetic materials
s--£, ^5P 7
" ■ Materials and approximate
~ " -S'" “ * "
d
i?' .
•7 maximum
chemical analysis (% by. d A -j 7 magnetic energy; 'J
=. weight) remainder Fe -.■:
Carbon steel
0.95 ‘ 4000 1.4 1
। (0.9% C, 1% Mn)
Tungsten steel
105 5200 2.4
(0.7% C, 6% W, 0.3% Mn)
Cobalt steel
0.95 20000 7.6
(35% Co, 3.5% Cr, 3% W, 1% C)
Alnico V
1.26 - 52000 44
(13.5% Ni, 8% Al, 24% Co, 3% Cu)
Alni
0.62 38000 10
(13% Al, 24% Ni, 3.5% Cu)
High permeability materials are required in situations where high flux density is needed with
small force H such as in pulse transformer cores, diaphragm of telephone receivers, relay formers, etc.
These materials are, therefore, required to have large values of differential permeability and very small
coercive force. Small value of Hc makes the materials demagnetise quickly thereby avoiding wave
form distortion. At the same time, Bsal value should be as large as possible. Table 9.13 lists some
materials and their characteristics.
The remanent flux density Br of a typical ferromagnetic material used for permanent magnet is about
1 weber/m2. Since H=0 at this point on the hysteresis loop, one has from equation (9.6), Af = — = l^6
amp/metre, where Mr is the spontaneous magnetisation. If each atom in the material has a magnetic
You
Mammk
Table 9.13 Properties ot some high permeability materials
Materials and
approximate (u, )
' “r'mar Bt Hc (A/m) Resistivity Typical
suf
chemical analysis (Wb/m2) applications
(ohm-m)
. (% by weight)________
Iron Applications
7000 2.1 80 11 x KT8
are well known
1% silicon steel Small AC
6000 2.1 70 30 x IO"8
• motors
4.25 silicon steel Power
9000 1.95 30 60x 10~*
transformers
Supermalloy (79% Ni, Telephone
106. 0.8 0.16 60 x IO-8
16% Fe, 5% Mo) transformers
Hypemik (50% Ni, Radio
103 1.6 3.9 50 x IO"8
50% Fe) transformers
CHAPTER 9
Mumetal (70% Ni, Magnetic
14% Fe, 5% Cu, 4% 9x 104 0.65 4 62 x 10-8 screening
Mo)
moment of the order of one Bohr magneton, then the atomic density is N= —- = 1029 atom/m3. Since
the number of atoms in a solid is approximately lO^/m3, it is clear, that such a high remanent flux
density can be explained only by assuming a spontaneous magnetisation in which all the atoms of the
materials are so oriented that their magnetic moments are parallel. This example indicates that even
when H = 0, there exists some force or field in the ferromagnetic material which tends to orient the
magnetic dipole moments in parallel.
Weiss in 1907, postulated that in ferromagnetic materials the elementary moments interact with
one another. He suggested that the existence of an internal molecularfield, Hm which is proportional .tn
the magnetisation M.
Hm~yM:
where y is called the Weiss molecular field coefficient or referred as internal field constant, and it
actually determines the strength of the interaction between the magnetic dipole moments in a material
The effective magnetic field Heff on an atomic dipole is therefore,
(9.72)
,e” F H<ffsfi+yM~\ , (9^73)
The Weiss field yM has a tendency to align the dipoles and is opposed by the motion of the
~enn« agitation of the elementary moments. We may now replace the magnetic field strength H by
in the classical and quantum mechanical theories of paramagnetism and look at the possibility of
spontaneous magnetisation.
You hi
The following model has N spins per cubic metre, each giving rise to a magnetic moment of one
Bohr magneton, |ifl which may be either parallel or antiparallel to an external applied field. The
magnetisation of such a system is found to be given by equation (9.47), replacing H by H-.
i.e., M = Np.fitan/i rorB----- 1— (9.74)

B
Even in the case of ferromagnetic materials, at very high temperatures (T > 6y), the thermal
agitation is so great that the internal field is not sufficient to maintain alignment of magnetic dipole
moments. The behaviour becomes analogous to paramagnetism, except that the field acting on the
dipole is the internal field given by equation (9.72). At sufficiently high temperatures, the term in
square brackets in equation (9.74) will become small compared to unity. Thus tan ha = a for a « 1, we
may approximate equation (9.74) as
M=
kBT
(H + yM) (9.75)
or
kBT kBT
Thus, the expression for susceptibility, % is
Minld
where C = —;--------- and 9 = y C.
kB , -• . ' .
► • • I
Note that equation (9.76) is identical in form with the Curie-Weiss law in equation (9.50). Thus
we conclude that ferromagnetic materials behave in the same fashion as paramagnetic material for
T » 0. Figure (9.28) gives the details of the variation of versus temperature for paramagnetic materials
in the temperature range in which they behave.as paramagnetic materials. The slope of the curve
determines 77 x 0 can be computed. The experimentally obtained value of y is found to
be approximately equal to 1000. This value of y is much larger than that expected due to magnetic
Fig. 9.28 Reciprocal of magnetic susceptibility as a function of temperature for
CHAPTER 9
various types of magnetic materials
interactions. In fact, the forces acting between the dipoles in a ferromagnetic material cannot be explained
in terms of classical physics, they are due to the wave nature of the electrons and wave mechanics. They
are called exchange forces', G for iron is about 1100 K.
t -
Suppose we now go to temperatures which are too low. The Curie-Weiss law [equation (9.76)]
cannot hold good for T < 0, for then magnetic susceptibility would pass through a pole and become
negative; for T = 0, the susceptibility would become infinite. This fact suggests that when T = 0,
spontaneous magnetisation may occur i.e., when H = 0, M is non-vanishing. This can be explained by
the following analysis:
When H = 0, the magnetisation given by equation (9.74), can be written as,
M = WpBtanha . (9.77)
where q=
k*T
M - tan ha = (9.77a)
. Ms
where Ms
= 2vMb is the saturation value of magnetisation, because it gives the magnetisation when all
the dipole
moments of TV atoms in the material are aligned parallel to the external field and, therefore, is
maximum value of the magnetisation that can be obtained in a given specimen.
I .
• ' ■ *
Figure 9.29 shows a plot of —- versus a = . With the help of equations (9.75) and
’ . ■ Mt kBT
one can write
M ~ M _ ksTa _ Tot
~ TC
M _ kgTa
i.e (9.78)
M, ~ tywi
Hi
where Chas the value given by equation (9.76). Also yC is equal to 0, paramagnetic curie temperature.
Thus equation (9.78) can be written as
(9.79)
Thus far a given temperature T, equation
(9.79) is a plot of — versus a represents a
straight line with a slope equal to I. Since

V
must satisfy both equations (9.77a) and (9.79),
M
the value of far the temperature T is given
by the intersection of the straight line and the

tan ha curves as shown in Fig. 9.29. When the
procedure is repeated for different temperatures,
M T
one can finally plot — as function of —, as Fig. 9.29 Interaction of two curves AL =■ tan ha
Ar, 8 Mut
versus a. Graphical solution leading to the presence
shown in Kg. 930. At temperature T < 6, the
of spontaneous magnetisation in fertomagnets
. _______ . Af
two curves unmeet and — has some positive
value. indicating that spontaneous magnetisation is present, [Fig. 9.29]. At temperature T £ 0, the
■Maction of the two curves is only at the origion, clearly showing = 0 i.e., spontaneous magnetisation
Af,
vanishes. When T= 8, (he equation (9.79) gives — = a, but this line is a tangent to tan ha curve at the
' M
point a *0: so for 7 i G. there is no spontaneous magnetisation. The experimental curve showing
T
as a function of — for three materials Fe, Co and Ni is given in Fig. 930. Note that this is one curve
:±h ,‘UPPOfU ^°Ve * for the three metals, ^though curie temperatures and saturation
"Xared r “ “T Only differe"“ belw“" theoretical interpretation when
compared to experimental
Oirie a results is that the theorv dtw
d nn1t a;k
d,tferenl»ate .between the ferromagnetic
cune temperature, 8, and paramagnetic cune temperature 8, however, the difference is small.
You
Magmctk FMMntr
Metal Mt (amp/metre) Curie

temperature K
Fe 1.75 x 106 1043

Co 1.45 x 106 1393
Ni 0.51 x 106 631
VMTTBW i )» 'MW
The modem theory of ferromagnetism, due to Heisenberg and Weiss, is an extension of that put forward
by Ewing. These materials have their properties divided into two distinct and separate temperature
ranges in such a way that the properties above a
particular temperature are quite different from the
properties below that temperature. This
temperature is called the ferromagnetic curie
CHAPTER 9
temperature and is designated by 0y. Among the
materials, ferromagnetism occurs in Fe, Co, Ni,
Gd and Dy. The important common characteristic
of these elements is the existence of partly filled
inner electron shells. The thermal motion of the
lattices (atoms) affects ferromagnetic properties in
different ways. The effect is most pronounced in
Fig. 9.30 Relative spontaneous magnetisa
the vicinity of the curie temperature, but it is also
tion as a function of T/0 for iron, cobalt and
observable far below the curie temperature. nickel
I neighbouring
We have atoms which
already » m^netisSP>
atiortin
”15
I main cause for spon * effect is so s

I ferromagnetic substances. ^gnetisatio
I that all adjacent spins are ahg » long-rang
| the material has its maximum^neareSt neighbour
I alignment results from both e crystal. Therm
I interactions and the continuity misalign the s?in®’
l vibrations of atoms, however, magnetisation only
I hence we observe the maximum
l the lowest possible tempera u wer value, unti i
I temperature the magnetisation asHO K). magnetisation
very h‘rt
I becomes zero at the curie temperature^ 93V u
! as a function of temperature t curve drop
| decreases very slowly to start wit finaUy falls etic materials
more steeply at higher temperatures, . Fig. 9.31 Temperature dependence of
&ve like paramag
ww>pitou»hto»roatihecune« (enomag«hc m°‘’" spontaneous magnetisation
Well above the curie temper ’
have a well defined susceptibility gt
where C is the curie constant and Q is called the paramagnetic curie temperature. 0 is higher than the
temperature Oy (Fig. 9.27); but (0 - 0p is small. It is now clear that these elements have a large susceptibility
just above 0,, but they do not obey Curie-Weiss law. Metals like Fe, Co, etc. obey Curie-Weiss law best,
but just above its curie temperature (0,), its susceptibility deviates somewhat from exact agreement with
this law i.e., the behaviour of the metal just above 0, has an interesting interpretation. It shows that,
although thermal motion of the atoms has destroyed long-range order of the spin moments, some order
of a much weaker character still persists. It is a kind of short-range spin order in which a given atom is
surrounded by a small island in which the spins are more or less aligned. This phenomenon presumably
exists for all ferromagnetic solids just above 0,.
Spontaneous Magnetisation in Ferromagnetic Materials

Weiss, in 1907, postulated that in ferromagnetic materials, the internal field seen by a given dipole is
equal to the applied field plus a contribution from the neighbouring dipoles which tend to align it in the
same«direction as it neighbours. Mathematically it may be written as
H=H + H
m
with Hm oc Af
i.e., H^H+yM^ (9.80)

* ■ ‘ i
where is the internal field, Hm is the internal molecular field and y is the Weiss molecular field
constant.
Let us consider a ferromagnetic material with N atoms/nP each with an angular momentum J.
We have already shown in [equation 9.57 (a)] that the total magnetic moment of these'atoms in a field
H is given by .
M=NgViBJBJ(a-) = M3BJ(a) .’ (9.81)
where a =---------------
’ kDT
In the case of ferromagnetic solid materials,
• (ôltB(H + yAf)Jl '<•

a —-------- - ----- :-------------- (9.82)
kBT
- - -w /. .*>y
M
Thus '77=bj^
When we deal with spontaneous magnetisation H = 0 and thus
gpopayMJ
Yo ___________
MMwnc
knTa TP
Hence, (9.83)
SUoUb-7 I?;
M k„Ta
Thus,
Ng\iBJ
Af(T) _ |~ kfTa . 1 _ M(T)

(9.84)
. M, L^Wh'2J M(O)
Spontaneous magnetisation will

occur if there exists a solution of the
simultaneous equations (9.82) and (9.84).
M(T) . , .•
• Since must simultaneously
CHAPTER 9
satisfy both equations (9.82) and (9.84), its
magnitude at a given temperature can be
obtained graphically as the intersection of
, M(T) , n-
the two versus a plots (Fig. 9.32). yt ■ ;•
The straight line tangent to the

Brillouin function at the origin corresponds
to the plot at 8,. Below this temperature,
• the two plots intersect at two points, one at
the origin which is trivial, and the other at equation (9.84) will be followed
Tuf(rr\
some non-zero value of --------- . This
M(0)
.
justifies for T
spontaneous magnetisation. i.e., tor / < 0. spontaneous
< Op sp magnetisation results. [Although the
' origin is also a point of intersection it can be shown that the free energy of the state with non-vanishing
M is smaller than that for M = 0, i.e., thejatter is unstable]. For 7 - the slope of thetsttaigh ne curve
represented by equation (9.84) is equal to the tangent to the curve represented by equation (9.82) at the
origin. Thus for^-2 6, the two curves do not interact and there is no spontaneous magnetisation. It w.U
be evident that there must exist a relation between the curie temperature Sf and the molecular field
t
constants. t fact one z-tc
In fl m increase
expects with Y
8, to increase because
wwi t i■ for parallel alignment increases
the tendency
1
as a becomes ui:»u thic
larger. In order toJestablish this rpiationshin
reiaqonsmp we
we make « of the fact that tor a « L [near
nia^c use
the origin of Fig, 9.32], the Brillouin function is approximately given y
a(J 41)
Bj(a) =
3J
3
This slope must also be equal to------------ by putting T - 0, in the equation (9.83).
gM-oUaY7 f
Thus
WgiMJ+l) _ M/
3 ~ SM^bY^
3kBQf
or
or 3M/
(9.85)
is proportional to molecular field constant y.
Let us consider the susceptibility in the origin well above the curie temperature (0^ ). In this region
magnetisation occurs only when an external field H is applied because there is no spontaneous
magnetisation. Thus for fields low enough so that we are far saturation, we may use the approximation.
Bj (a) =
J 3J
w=^JM£+l)a
3
Substituting for a from equation (9.82),
M= fgPoP8J(H+yM)"l
_ ô^gVflÛ + lXH+yAf)
3kBTJ
MMwn£
replacing g2^ by Jlj.
+D(ff+YM)
34,77
(10^7(7 + 1)1 = MlfooW+D

i.e.. 34,77 J 34,77
A/p.og J +1)
Defining 0= , one gets
3kBJ
, e MtfcoW+i)
M 1--
3kBTJ
Mlfco '(74-1)1 H
CHAPTER 9
i.e.t . 3J J[^r_
[1-(O/D1
CH j
or M- -------
ni-(e/D]
J*;?.- '7;•
e
where C= —
Y
Thus, % “ (T- 0) J (9.86)
The value of 0 agrees with the value of Qf obtained from equation (9.85). In other words, the
Weiss theory does not distinguish between para and ferromagnetic curie temperature.
The maximum component of the magnetic moment of an atomic dipole associated with a quantum
number J js Zg|iB. Hence the maximum value of spontaneous magnetisation is given NgJ\LB. The value
spontaneous magnetisation also follows from the total magnetisation given by
M ^NgJUsBjia)
Because a A B. (a) = 1
J
From Fig, 9.33, we see that, the maximum spontaneous magnetisation occurs at T= 0. Therefore,
*C M (0) = NgtyB.
M(T)
Hence, = Bj (a) (9.87)
M(0)
But as long as we are interested in spontaneous magnetisation, H = 0 and we know that
akBT
Af(7) =
M(F) = akBT 1
Af(O) L^Wb] LWM'B
■_ akBT
~ NJ2g2wQVL2B
Substituting for y from equation (9.85), one gets
M(T). akBT ■ 1 MhP'j

M(0) NJ 8 M-oP-b _ _
QJV-J
1
with p2 = g2 J(J + !) 14
[refer equation (9.47)]
M(T) fl7g2J(J + l)
Thus,
M(0) 3J2g2ey
M(T) qT( J +1)

M(0) 85 376 y Jj (9.88)
The quantity must satisfy both equations (9.87) and (9.88). Hence it can be obtained by
the intersection method indicated already.

It is important to note that for a given value of J. this procedure leads to a universal curve when
is plotted as a function of i. In Fig. 9,33 such curves for J . [1] . J . 1 and J = - •«
represented; the latter case corresponds to classically freely rotating dipoles. It is observed that the curve
CHAPTER 9
Fig. 933 The spontaneous magnetisation as a function temperature
for J — fits the data best, indicating that the magnetisation is essentially with the electron spins
rather with the orbital momentum of the electrons.
Weiss’s theory was a great success in explaining spontaneous magnetisation and the behaviour of
ferroi IlF.TUi etic material at temperatures greater than the Curie temperature 0.
It may be mentioned that the actual transition from ferromagnetic behaviour to paramagnetic
behaviour occurs at a temperature slightly lower than 0. It is the ferromagnetic Curie temperature.
This relatively simple theory is not capable of describing the behaviour of ferromagnetic materials in
Ihe vicinity of the Curie temperature.
The M-H curve of a virgin specimen of a ferromagnetic material below the ferromagnetic Curie
temperature is shown in Fig. 9.34. For a virgin specimen M = 0 at H = 0. To explain this fact, Weiss
Postulated the existence of domains within the material. Within these domains the material is magnetised
saturation but the direction of magnetisation differs from domain to domain, resulting in a zero
^hltant magnetisation of the specimen. We shall take up the domain-wall theory of ferromagnetic
^tetials a little later,. With an increase in the value of H, the magnetisation of the specimen increases
&nm0 to Mw. Along the virgin c of the oriôf .. ^2.
H itwhich is a
is found
■ • curve one can st®*110'a f lrt>tol06tahigbVciroeab‘li^
f’MtctionotH.Thedifferentialpenneability riale alloys- Upon
nutenals such as iron, nickel, cob t
'hat there is a finite value of M - Mr a crnSsed by the Vfeiss
The presence of Mrbas already been t . ^nrv in terms of the internal field.
You r
Though the spontaneous magnetisation as envisaged by Weiss satisfactorily accounts for the
temperature dependance of ferromagnetism, difficulties were experienced in accounting for the origin
of the internal field. Ideas on the fundamental nature of the internal field were first formulated by
Heisenberg, Slater and Stoner using quantum mechanics.
Fig. 9.34 Hysteresis loop of a ferromagnetic material
First of all a rough estimate of the molecular field Hm

n may be made as follows. The energy of a
given atomic dipole in this field should be of the order of i.
_ 9 _ b6/ Le- “ kBQf For a Curie temperature
1000 K, this gives Hm
. - "• A/m or 10 gauss. From this one concludes immediately that the
LiTA/niT "h dUrt0za3’"T16 dipole'diP°le interaction between neighbours because such fields
ould be of the order ofpja3, where a is the lattice constant and this quantity is only « 106 A/m. So the
problem of explaining the origin of Weiss field becomes essential. *
The first theoretical explanation of the large Weiss field (internal field) in ferromagnetic materials
was proposed by Heisenberg in 1928. He explained that the large internal field may be described in
terms of quantum exchange interactions between the electrons. These interactions are essentially
electrostatic in nature. Considering exchange interactions between nearest neighbours, one could show
that there is a tendency for net spin alignment in transitions.
Magnetic interaction forces are generally much weaker than electrostatic forces. The electrostatic
coulomb repulsion between two electrons spaced 0.1 nm apart is many orders of magnitude greater than
the magnetic force between them that arises from the magnetic moment due to their spin. Though it is
difficult to account for the large internal Weiss field on the basis of magnetic interactions between
moments on individual atoms, one can find a spin dependant electrostatic interaction which accounts
for the large Weiss field. The newer quantum mechanics provides such a source of spin dependent
electrostatic forces. This is the basis on which Heisenberg worked out this problem. He developed his
theory on the analogy of Heitler-London model of the hydrogen molecule. In this treatment an exchange
interaction between electrons in different quantum states is shown to lead to a lower energy provided
that the spin quantum numbers of both the states are the same, i.e., the spins are parallel. According to
this theory for two atoms i and) the effective coupling between the spins is due to exchange interaction
which is given by -2 Jtj St S where is the exchange integral for the two atoms. 5. and are the spin
angular moments associateo with the ith and theyth state. In general this exchange integral is negative
and it * *
function of the interatomic
Fig. 9.35 shows the plot of the
dlShange integral value versus the
eXteratomic distance. It appears that in a few
111 ses it becomes positive. The positive value
^7 is found to be obtained when the ratio
° /r for the atom is greater than 3 but not
much larger, where rab is the interatomic
distance and ro is the orbital radius of
electrons. The following table gives the
values of the ratio rab/ro for the different
atoms. Rg. 9.35 Variation of exchange integral with
Fe Co Ni Cr Mn Gd
rJro 3.26 3.64 3.94 2.60 2.94 3.12
Table 9.14 Saturation magnetisation and paramagnetic (6) and
ferromagnetic (0.) temperatures for ferromagnetic materials
CHAPTER 9
Hi*- '■ 4 ”
at 300 K (A/m) % M~at0K

sat ?
'■& e Bohr magneton per
Substance
(X) atom
*• ......................
Iron 1.707 x 106 1.752 x 106 1043 1047 2.22

Cobalt 1.4 x 106 1.446 x 106 1400 1504 1.71
Nickel 0.485 x 106 0.510 x 106 631 645 0.606
Gadolinium 1.09 x 106 1.980 x 106 288 7.10
When the J., value is positive the exchange energy is negative and hence becomes a minimum
for parallel orientation and so the atom is found to exhibit ferromagnetic properties. From the above
criteria we find that Fe, Co, Ni and Gd are ferromagnetic. Cr and Mn are not ferromagnetic since the
ratio rjro is less than 3. Thus we get the criteria for ferromagnetism as, that the atom must have
unbalanced spins and the exchange integral J., should be positive. J is found to be positive when the
ratio rgilro is slightly > 3. The question arises whether an element with unpaired spins but with
unfavourable r(Jro ratio can be combined with another nonferromagnetic element to form a compound
for which the ratio r./r becomes greater than 3 will be suitable for ferromagnetism. In fact this is so
and is simply proved by the fact that Mn-As, Cu-Mn and Mn-Sb alloys become ferromagnetic because
°f the favourable r&lr ratio obtainable. This is the greatest triumph of the present solid state theory,
which enables us to find the criteria for a certain phenomenon from the microscopic point of view. Once
*** criteria are known, it is only a matter of proper cooking of the molecules to fabricate materials of
W desired characteristics.
Technical Magnetisation Curve
Fig. 9.31 shows, the drop off of M, as T -> Oy, is fairly precipitous, so that at temperatures well
Ow the saturation magnetisation M, is substantially equal to M/0). If 0 is of the order of 1000 K,
as for iron, we can safely assume that all the spins are still lined up at. room temperature, such that
M( (300 K) = M, (0 K).
In spite of this we know that most specimens of iron, or any other ferromagnetic material, which
have not lately been in magnetic fields, have no observable spontaneous magnetisation. Further, in the
presence of an external magnetic field they behave as if they have a finite (but not constant) susceptibility
(and permeability) as indicated by what is called the technical magnetisation curve shown in Fig, 9,36,
Fig. 9.36 Technical magnetisation curve of a ferromagnetic specimen
There are certain important facts about the technical magnetisation curve:
(0 Initially (at the point 0), M = 0 (for example in a specimen of iron fresh from the blast fumance).
(if) When a field is turned on, M gradually increases, eventually reaching M, its expected value as
H increases (M is called saturation magnetisation).
(«f) If the field is turned off, some residual magnetisation M, remains, shown in Fig. 9.36.
(iv) A finite reverse field is required to bring M back to its initial zero value at point A.
(v) A further increase in the reversal field will result in a complete reversal of M at B.
(vf) A second reversal of H now completes the hysteresis curve.
In most work with ferromagnetic materials we plot B-H curves instead of M-H curves for the
technical magnetisation curve, because B and H are directly measurable quantities. If B and H are
plotted on identical scales, the curve of Fig. 9.36 would appear as shown in Fig. 9.37 (a). However,
since it is often possible for weak fields (—0.1 oersted or less) to produce a saturation magm»ti sat ion of
1000 gauss, these curves are almost never plotted to the same scale, and the B-H curves are as drawn
usually appear qualitatively similar to M-H curves as shown in Fig. 9.37 (6). We also note that the
technical magnetisation curve has three distinct regions: Low field, intermediate field and high field.
The following definitions should prove helpful to the reader.
Initial Permeability or Reversible Permeability: This is the slope of the B-H curve in Ihe low
field region near the origin. In this low-field region there is no hysteresis. That is, if the field is turned
off, M and B go back to zero. This is why permeability in this region is called reversible.
B -Remanence: The residual induction when the field is turned off is pjjM, where, Mr is the
remanent magnetisation [since B = p0 (H + M)].
Magnetic
.. ... .......... - - -■
Fig. 9.37 Technical magnetisation curve plotted as a function of magnetic induction B instead of
magnetisation M. Br is called the remanence, and Hc is the coercive force • -
B-Saturation Induction: Defined as HqM,, this quantity is not representable on the B-H curve,
but the region beyond the hysteresis loop is equal to B = B v + pQ H. Strictly speaking, the induction
curve does not saturate in the sense that it approaches a limiting value.
Hc-Coercive Force: The coercive force is the value of reverse field necessary to make B = 0 in
the sample. It is thus die field that cancels the residual magnetisation - Hc = p0M; but it is of course less
than the field necessary to bring M to zero as in A of Fig. 9.36. The coercive force and the initial
permeability are the two most important quantities.
Since Weiss has shown that there exists an interaction field between the atomic moments within a
ferromagnetic material which causes alignment of the magnetic moments, we wish to understand the
meaning of the technical magnetisation curve and the fact that ferromagnetic materials have no observable
magnetisation unless they have been previously placed in an external magnetic field. These phenomena
are not understandable on the basis of the exchange field theory.
Though the origin of this Weiss field was not very clear at the time when Weiss proposed in 1907,
the modem quantum theory has clearly established that the so called exchange interaction is responsible
for this large internal molecular field in ferromagnetic materials. Again when he was confronted with
the problem of explaining the phenomenon of hysteresis, exhibited by the ferromagnetic materials he
made a bold and novel suggestion that a ferromagnetic solid is divided into a large number of small
regions called domains, each of which spontaneously magnetised to saturation. The domain size may
vary from KT6 to the entire volume of the crystal. The spin magnetic moments of all the atoms in each
domain are all aligned in a particular direction, but the direction of magnetisation of the different domains
are so oriented, as to make the net magnetisation of the specimen zero. The process of magnetisation
consists in rotating the different domains in the direction of the applied external field so that the specimen
exhibits a net magnetisation externally. The existence of domains was not very much clear until Bitter
successfully demonstrated the domain structure 25 years later.
These domains have nothing to do with the crystalline perfection of the sample but represent
only the direction of M? in each region of the crystal. They arise because the energy is not minimum
when a large specimen has a uniform magnetisation.
If the sample is a single crystal, the
orientation of MJ in each domain will be limited to
equivalent crystal axis directions. In a
polycrystalline material, the directions can, of
course, be random as the crystal axes are randomly
oriented. Figure 9.38 shows schematic domain
regions. For example, in iron, the normal directions .
of magnetisation are the [10 0] directions. In nickel
the [I 1 1] directions are normal. These are known
as the 'easy' directions of magnetisation. Other
directions are called 'hard' directions of
magnetisation because work is required to orient
the magnetisation in these directions. This is a manifestation of magnetic anisotropy, which is important
in determining domain wall thickness
If an external magnetic field is applied to a ferromagnetic specimen, two things can happen,
according to the domain model: (a) The domains parallel or nearly parallel to H can grow in size at the
expense of the antiparallel domains as shown Fig. 9.38, or (h) the magnetic moment of the domains can
rotate into the field direction. In either case the sample acquires a magnetisation, which increase as the
field increases, until all the domains are parallel to the applied field, at which point the material is said
On the basis of this domain model we may understand some aspects of the technical magnetisation
curve, in particular the initial (reversible) permeability and the coercive force. We have already seen
that the technical magnetisation curve has three distinct regions: (1) A low field region of low, reversible
permeability (no hysteresis); (2) an intermediate field region of high permeability and little hysteresis.
You h
Magnetic Propewhe»'<
w field Region - Reversible Permeability
the low field reôn die niaMnet'sation is thought to be reversible motion of domain wails. To understand
iâ of reversible domain wall motion, we consider a single crystal sample initially having no
anetisation. The domain walls all occupy equilibrium positions; that is, in arriving at the demagnetised
the domain walls are in positions representing energy minima, represented schematically as point
A in Fis- $(fl)- ”^he existence of potential maxima and minima for the domain wall position is due to
imperfections in the lattice.
Now if weak fields are applied, the

fomain walls will move short distances, within
their potential walls, those pointing parallel or
nearly parallel to the field growing at the
expense of the others. When the field goes off,
the domain walls will go back to their original
equilibrium positions, leaving the crystal in its
original unmagnetised state (the origin on Fig.
9.36 or 9.37); that is, there is no hysteresis.
CHAPTER 9
Hie magnitude of the initial permeability
(or initial susceptibility) is determined by the Fig. 9.40 (a) Imperfections in a crystal produce
slope of the potential well and is thus closely potential irregularities that determine the domain wall
connected to the density of imperfections. positions. Irreversible domain wall motion occurs when
. tt-■ i rr . ■ a potential hill is crossed
Intermediate Fields - High Hysteresis:
If the applied field is higher, some of the domain walls will cross the tops of their respective potential
wells and move into new equilibrium positions where they will remain when the fields is turned off,
resulting in hysteresis. This is represented by B in Fig. 9.40 (a). The permeability increases sharply in
this region because once the domain wall passes a hump, it moves down into its next potential well
without requiring much of the field to push it.
High Field Region: The final stage of saturation is represented by rotation of the magnetic moment
of the domains; that is, many domains are pointing in directions inconsistent with the requirements of
crystal symmetry. They are pointing in hard directions.
Coercive Force: The coercive force is a measure of the amount of hysteresis and of the height of
the potential hills that the magnetisation must traverse. These two contributions affect the slope of the
potential hills, and thus the coercive force should be inversely proportional to the initial permeability.
Two kinds of energy humps are associated with the coercive force. They are: .
(a) The irregularities that impede domain wall motion. These cause Hc in magnetically soft (low
H ) materials.
(b) The hump is due to the crystal symmetry, or magnetic anisotropy energy.
Let us consider a crystallite so small that a single domain represents the minimum energy. When
a field is turned on, the only permeability is due to the ability of the field to rotate the magnetisation of
die domain. Thus M is rotated away from its easy direction, represented by a potential well, into a hard
direction, representable as a position somewhere up the side of the potential well. If the field is laige
enough to rotate M over the potential hill into the next well, a magnetisation will remain when the field
is turned off (there will be hysteresis; B, = p0Mv) and a reverse field equal to Ht. (coercive force) will be
necessary to bring B5 to 0. This mechanism is thought to be responsible for H in certain magnetically
hard (high H ) materials.
If we consider a large single crystal with many domains, we can visualise the entire magnetisation
curve, when a field not in an easy direction goes on, as follows:
(a) Reversible wall motion in weak field region. The domains having large components in the
direction of H will grow.
(b) In the intermediate field region much domain wall motion will be irreversible. Finally, only
those domains having large components in field directions will remain.
(c) In the high field region the direction of the domains will be rotated into the field direction.
This region will then have little hysteresis and will contribute little to the coercive force.
When the field is reversed, the coercive force will be due mainly to the irreversible domain
motion in step (b), but because this kind of irreversible process requires little energy, this is a magnetically
soft material. The coercive force is relatively small.
The origin of domains is understandable from the thermodynamic principle. The first question we must
set ourselves is, why the entire crystal of iron does not organise itself as a single domain? In that case,
the specimen will be spontaneously magnetised even without any external magnetic field. But this does
not happen. We know from thermodynamics that every solid structure will take up that configuration
for which the free energy (E — TS) is a minimum. Due to the high degree of order in magnetic systems
we can neglect the entropy term and concentrate only on the internal energy term. The total internal
energy of the domain structure in a ferromagnetic material is made up from the following contributions:
(z) Magnetostatic energy or the magnetic field energy or the exchange energy.
(ii) Crystalline energy or the anisotropy energy.
(Hi) Domain wall energy or the Bloch wall energy.
(iv) Magnetostriction energy.
Anisotropy Energy
It is found that the ferromagnetic crystals have easy and
hard directions of magnetisation, i.e., higher fields are
required to magnetise a crystal in a particular direction
than others. For example, in bcc iron the easy direction
is [1 0 0], the medium direction is [1 1 0] and the hard
direction is [1 1 1]. In nickel easy direction is [1 1 1],
the medium direction is [1 10] and the hard direction is
[1 0 0].
The difference between the easy and hard
directions is, that for producing the same saturation
magnetisation, stronger fields are required in the hard
direction than in the easy direction. The excess of energy H in ampere m
required to magnetise a specimen in a particular direction
over that required to magnetise it along the easy direction Fig. 9,40 (b) Magnetisation curves for a
single crystal of iron
is called the crystalline anisotropy energy.
Magnetostatic Energy
magnetic field energy.

The interaction Let usmakes
energy which thein
suppose Fig 941 (J tJf
adjacent •• ” th. fmselvcs » exchange energy or the
domain in a specimen of ferromagnetic material BecauJ eStaMshed a

surface of the crystal, this configuration will have h- u - fKC maSaetK P°*<s formed on the
— reared in assembHng L ato ” Z^Z^

potential energy in the field outside. In Fig. 9 41 r/,1 th S doma111 and tins work done is stored as
as a result of dividing the crystal into two domains ™ & magn*MC has been reduced by one half
- be continued until theLuetio”

another domain and its boundary called Blnrh u,„n a 7 - mcrease m energy to form
has zero magnetic energy. Here the boundaries of trian d°mam.structure 35 ® 9.41 (c) and 9.41 (d)
ooundanes of tnangularpnsm domains as closure domains the
end faces of the crystal, make equal angles of 45° with the magnetisation dire
component of the magnetisation in crossing such a wall is continuous, Le., there are no free poles and
there is no field energy. The energy required to produce a closure domain is essentially derermTned by
the anisotropy of the crystal, i. e., by the fact that ferromagnetic materials have ‘easy’ and ‘hard’ directions
CHAPTER 8
of magnetisation. Summarising the ideas discussed above we may say that domain structure will depend
to a large extent on the shape and size of the crystal under consideration. The size of the domains for a
particular domain structure may also be obtained from the principle of minimum energy. The volume of
the domains may vary between say, IO-2 to 10-6 cm3.
(d) (*)
Fig. 9.41 The origin of domains
Bloch Wall or the Domain Wall Energy K adjacent magnetised in
The term Bloch wall denotes the trans*tj°° js that the spin direction in going from one
different directions. The essential idea o 00 b , gradually as indicated in Fig. ■ - over
to another does not change abruptly in oneb reason for the gradual nature of change ts
atomic planes. The domain walls are called Bloch .wallah
the fact that for a given total change of spin dtrectiondthe Bloch wall ts tiuck.
distributed over many spins than when the change
SOO Sou* Sucre fbnsict
But the anisotropy energy will be small if the spins Transition region
change abruptly i.e., the Bloch wall is thin. So the
thickness of the Bloch wall is a compromise be
tween the two. Usually the Bloch walls are about
200 to 300 lattice constant thickness.
Magnetostrictive Energy
When a specimen is magnetised it is found that it Fig. 9.42 schematic d.agram of the transition region
suffers a change of dimensions and this separating ferromagnetic domains in a 180’ Bloch wall
phenomenon is known as magnetostriction. This
deformation is different along different crystal directions. So if the domains are magnetised in different
directions they will either expand or shrink. This means that work must be done against the elastic
restoring forces. The work done by the magnetic field against these elastic restoring forces is the energy due
to magnetostriction or the magneto-elastic energy. If the lattice is not strained the magneto-elastic energy is
zero. But usually the lattice is strained along the different directions of magnetisation of the domains.
The most direct experimental evidence for the existence of the domains was furnished by
microphotographs of domain boundaries obtained by a technique called magnetic powder pattern. This
method originally applied by Bitter has in the hands of W.C. Elmore and H.J. Williams provided
convincing proof that domains exist and behave as expected theoretically. The powder pattern method
consists in placing a drop of colloidal suspension of finely divided ferromagnetic material such as
magnetite on the carefully prepared surface of ferromagnetic crystal under study. It is found on observation
through microscope that the colloidal particles in the suspension become strongly concentrated about
certain well defined lines which represent the boundaries between the domains magnetised in different
directions. The reason why the colloidal particles concentrate near these boundaries is that in their
vicinity there exists a very strong magnetic field which attracts the magnetic particles.
The domain concept is well suited to explain the phenomenon of hysteresis. The increase in the value of
the resultant magnetic moment of the specimen under the action of applied field may be imagined to
take place by two independent processes as suggested by Becker namely (1) by increase in volume of
domains which are favourably oriented with respect to the field at the expense of unfavourably oriented
domains or by rotation of the directions of magnetisation towards the direction of the field i-e., from
easy U> hard direction. These two methods are indicated below in Fig. 9.43.
When a weak magnetic field is applied, it is found that the domains which are oriented parallel
to the field and in the easy direction of magnetisation grow in size at the expense of less favourably
oriented ones. The domain growth requires Bloch wall movement which involves expenditure ol energy-
This movement of the walls are mostly reversible and is indicated by OA (Fig. 9.44u) of the magnetisation
curve. When the field becomes stronger the Bloch wall movement continues rather sharply and they are
mostly irreversible movement. This is indicated by the path AB of the graph. This irreversibility explains
the phenomenon of hysteresis.
Unmagnetised Magnetised by Magnetised by

domain growth domain rotation
Fig, 9.43 The domain structure
At the point B each domain magnetised along their easy directions. Application of still higher
fields rotates the domains into the field direction and this may be away from the easy direction thereby
storing anisotropy energy. In Fig. 9.44 (a) at C the positions of domains are such that the specimen is
saturated. On removing the field the specimen tends to attain the original configuration. This requires
CHAPTER «
the movement of Bloch walls. But this movement is hampered by impurities lattice effects etc., and so
more energy must be supplied to overcome the opposing forces. This means that a coercive field is
required to bring the specimen to zero magnetisation. The energy which is spent in overcoming the
forces opposing the Bloch wall motion is not recoverable and it is this loss of energy which is identified
as the hysteresis loss.
J>0 J<0
Ferromagnetism A nli ferromagnetism
fig, 9.44(b) Ferromagnetism and antiferromagnetism

A
The explanation for ferromagnetism is based on the fact that quantum mechanical exchange forces
(interaction) produce large internal fields and the neighbouring dipoles tend to align in the same direction.
It was also assumed in this theory that the exchange integral is positive. When the distance between
interacting atoms is very small, the exchange forces produce a tendency to antiparallel alignment of the
neighbouring spin dipole moments. Such systems were first investigated theoretically by Neel and
Bitter and later extended by Van Vleck.
I
Experimentally antiferromagnetism was first discovered as a property of MnO by Bizette, Squire
and others. The most characteristic property of a polycrystalline antiferromagnetic substance is that its
susceptibility shows a maximum as a function of temperature. An example of this behaviour is shown in
Fig. 9.45. This characteristic feature can be explained qualitatively on the basis of the following model
called two sublattice model.
Consider a crystal containing two types
of atoms A and B distributed over two interlocking
lattices. For example, let the B atoms occupy the
comer points of an elementary cube and A atoms
being located at the centres of these cubes. Further
let the interaction between the atoms be such that
the A spins tend to line up antiparallel to the B
spins. At low temperature this interaction is very
effective and in an external field the resulting
magnetisation will be small. As the temperature
is raised the efficiency of the interaction becomes
less pronounced and the susceptibility increases. Rg. 9.45 The molar susceptibility Xm of MnF2
Finally a critical temperature is reached (7Y called
Neel temperature) above which the spins are free. Hence above this temperature it shows paramagnetic
behaviour.
The most direct experimental evidence for the
basic picture of the above model has been obtained from
neutron diffraction experiments; when neutrons are
incident on a crystal, they are scattered by the atomic
nuclei but also by the interaction between the neutron
spin and paramagnetic ions that may be present.
Consequently, the ordered antiferromagnetic state gives
rise to extra diffraction lines. The intensity of these
extralines decreases as the temperature increases
because the antiferromagnetic order diminshes. Above
the Neel temperature the extralines disappear. The
example is MnO.
We shall follow a procedure similar to that used
to describe the internal field in ferromagnetic materials
with the difference that in antiferromagnetism we Fig. 9.46(a) Body centred unit cell with spins of A
consider a crystal containing two types of atom A and atom oppositely directed to that of b atoms
B distributed over interlocking lattices as in Fig. 9.46 (a). Atoms B occupy the lattice points and
MAGNtne
toms A occupy the centre of the body, 1-lence all nearest neighbours of an A atom are B atom and vice
versa Let there be antiferromagnetic A-B interaction as well as A-A interaction and B-B interaction. If
u and are the net molecular field at the A site and B site, we can write
Ha = H-aMa-fWb
Hb= H- aMb-(SMa
1
where H is the applied field, Ma and Mb are the magnetisation of the A and B lattices; a and fJ are the
Weiss constants (i.e., the interaction parameters for two atoms having like spins and two atoms having
unlike spins). We shall consider two temperature regions.
O>*(1)T>Tn
When the temperature is above Neel temperature, we aye far away from saturation, and magnetisation
of lattice A is given by ’
Ma = (NV2j/3kBT)Ha, where |1? = ^7(7+1) (9.89)

the number of atoms per unit volume. If we assume that dipoles on B sites are identical with
N is
CHAPTER 9
those on A sites and there are equal number of A and B sites, then we have
Mb = (9.90)
or M = M+Mh
a d
= (NVi2J/3kBT)[Ha^Hl)
= (Nyfy3kBT) [2H - (a + 0)M]
i.e., M [1 + (N\L2j/3kBT) (a + (3)] = (2Np}/3kB7)H
l= = (2NÎ3kBT)l(\ + (NpJ (a + py3^7)] (9.91)
i.e., X s= —, where C = (9.92)
and 0 = [Wj(a + [3)]/3kB is called the asymptotic Curie temperature.
We can compare the above expression with the expression, x — in the case of a ferromagnetic
substance above Curie temperature. Here we see that the antiferromagnetic case contains (T+ 0) rather
111311 (T- 0). Further the Curie constant C is twice the Curie constant for individual A or B lattice. In
to illustrate the difference between the paramagnetic, the ferromagnetic and the antiferromagnetic
baviour in the high temperature region, a graph is plotted between l/% versus T. For the three cases
01,6 obtains
Para Ferro Antiferro

1/X • TIC i/x=(T'-oyc i/x=(r+eyc
t
Case (2) T < TN
At the Neel temperature TN itself, we are still sufficiently far away from saturation effects to employ the
equations given below for Ma and Mb. Thus in the absence of an applied field we may write equation
(9.89) with T=Tn as
Ma = - (aMa + $Mb)
i .e., Ma [1 + (Nâ)/3kBTN] + [(W? $Mby3kBTN)] = 0 (9.93)

t
Similarly Mb [(1 + a)/3kBTN)] + [(ATJ12 $/3kBTN]Ma = 0 (9.94)
One solution of the simultaneous equations (9.93) and (9.94) is that
■ Ma =M;b = 0 .
Spontaneous magnetisation would take place if there existed a solution of the simultaneous
equations for a finite value of Ma and Mb. This is possible.if
- ■■ [1+ (Ca/2Tw)] ■ C^/2TN _a ? ' - ;'

-C£/2Tn [l + (Ca/27\)] ~U -- :• : J - -
I
Thus
. 2r*J
1+ —
1 + C®a2/47j + CoJT"-
- [C®P2/47$] = 0
=0
4T^ + &a2 + 4CaTN - C2P2 = 0
i.e., + CaTN + (C 2/4) (a2 - p2) = 0

- Cot ± Jc2g2 - c2(g2 - p2) Cg + Cp
N~~2 , (9.94a)
From this it is clear that Neel temperature increases as AB interaction (p) is stronger whereas it
decreases with AA or BB interaction (g) increasing.
In this model the Neel temperature is not identical with 0. According to equation (9.92).
8 = [(NjiJ)/3<:a](a + P) (9.94b)
C(a + P) -
,V = —--- ———
Hence (9.94c)
CHAPTER 9
It is to be noted that TN < 0 indicates that g must be positive.
Let us now consider the susceptibility of an antiferromagnetic material below Neel temperature.
For simplicity we can assume that there is only A-B
interaction i.e., g = 0. As a result of crystalline
anisotropy, there will be one or more of the natural
spin directions along which the spins will tend to
align. There are therefore two cases of special interest:
(a) An applied magnetic field perpendicular

to the natural spin direction (b) and applied
field parallel to the spin direction. It can
be shown that %± = 1/p and hence it is
independent of temperature. The
calculation of xN is complicated.
Fig. 9.47 The susceptibility of an antiferromagnetic
Calculations by Van Vleck give the curve
substance as function of temperature for spin
shown in Fig. 9.47 according to which the
values of 1/2, 3/2 and S/2
susceptibility rises smoothly from zero to
%(Tn) as temperature increases. So the susceptibility atT = 0 K is zero i.e., xM= 0.
The word ferrimagnetism was first coined by Neel to describe the properties of those substances which
below a certain temperature exhibit spontaneous magnetisation arising from a non-parallel alignment of
atomic magnetic moments. In his original paper Neel envisaged a partitioning of the moments into two
sublattices which because of their mutual interaction are aligned antiparallel to each other thus producing
a total magnetic moment equal to the difference between their individual magnitudes. The class of
materials having these properties namely a macroscopic moment that results from an antiferromagnetic
interaction but with an unbalance of the two spin systems has been given the name ferrimagnetism
Ferromagnetism materials which have wide applications in electrical engineering have a

disadvantage, that they have low electrical resistivity. The laminations used for electrical machines
have a resistivity of about 14 x 1CH Q-m and the highest value obtainable in ferromagnetic alloys is less
than IO-2 Q-m. This disadvantage of the ferromagnetic materials limit their application in the high
frequency alternating current applications, high eddy current losses and poor magnetic utilisation of
metals occur in sheets even at low frequencies. Ferrites or Ferrimagnetic materials are of great technical
importance because they exhibit a spontaneous magnetic moment below a Curie temperature such as
iron, cobalt, or nickel, but they are poor electrical conductors. A large resistivity is often desired for
high frequency applications (e.g., to prevent eddy currents in cores of coils).
Table 9.15 Some antiferromagnetic materials and their properties
. / ‘Material /.
MnO,£
SlOOs 83 316
. MnO ' 122 610
FeO 198 568
CoO 292 280
MnS 165 528
The external behaviour of a ferrimagnetic substance is similar to that of a ferromagnetic specimen,

but because of the difference in their internal structure the temperature dependence of their spontaneous
magnetisation may be quite different. For instance, the magnetisation of a ferromagnetic material does
not necessarily decrease monotonously with the rise in temperature but can pass through zero even
before the Neel point is reached.
Ferrimagnetic materials are the salts of some of the transition metals particularly which crystallise
in the spinel structure and contain in some measure one of the known ferromagnetic elements. They are
called ferrites. The chemical formula for the ferrites may be written as XY2Z4 in which X is a divalent
negative ion, Z is mostly the divalent oxygen ion O2^ and Y is Fe3*. The familiar example offerrimagnetite
is magnetite. The chemical formula is Fe3O4 or, more specially, to Fe2+Fe2+ OJ". Chemical composition
of ferrites may be written in the simple form as Me2+Fe|+ O4" where Me2* represents a variety of
divalent metallic ions such as Fe2+, Co2+, Mn2+, Zn2+, Cd2+, Mg2+, etc. For use at high frequencies,
Snoek and others developed a number of such ferrites which are known under the trade name Ferroxcube.
The most important of these are the Mn-Zn ferrites. The d.c. resistivity of ferrites is 104 to 1011 times as
large as that of iron. Thus in transformer cores, they can be used up to much higher frequencies than
iron.
aw*
Ferrites are said to have a spinel structure, the same as the structure exhibited by the natural mineral
MgAl2O4. In this spinel structure the oxygen atoms are closely packed in face centred lattices, into the
interstices of which the metal ions are distributed. A unit cell of magnetite, which is a natural ferrite
______ Magnetic
contains 8 molecules. There are 32 divalent oxygen ions, 16 trivalent iron ions and 8 divalent iron ions
unjt cell. When the oxygen atoms arrange themselves in fee structure there are 8 tetrahedral voids
^lled the A sites and 16 octahedral voids called the B sites. In the normal spinel structure as exhibited
by MgAl2O4, the divalent ions occupy the A sites and the trivalent ions occupy the B sites. Magnetite is
gaid to exhibit an inverse spinel structure. In this structure the 8 Fe*** ions occupy all the A sites and the
other 8 Fe*** ions occupy half the number of B sites. The remaining B sites are occupied by the Fe**
ions. In t*ie case n'c^c’ fcrr*te the divalent nickel ions occupy half of the B sites. The remaining B
sites and the A sites are occupied by the trivalent iron ions. There are infinitely many possible ferrites,
since there are several ion combinations possible in A and B sites. A wide range of ions may be used,
such as Ni, Co, Mg, Mn, Cu, etc. A combination of two or more can also be used in which case we get
mixed ferrites.
The magnetic moment of a ferrite material is found to be equal to the difference in the moments
of ions in A and B sites. For example, in the case of magnetite if we attribute 5 Bohr magneton to Fe***
and 4 Bohr magneton to Fe**, the net moment between A and B sites works out to be 4 Bohr magneton
(5 + 4 - 5 = 4). The experimental value is 4.1 Bohr magneton. If we assume 2 Bohr magneton per Ni**
ion we get 2 Bohr magneton per formula weight of nickel ferrite. The experimental value is 2.3 Bohr
magneton. The difference is attributed to the difference in the ‘g’ factors for the free electrons.
CHAPTER 9
Generally ferrites have very high d.c. resistivity (10l0times the resistivity of ferromagnetic iron).
High resistivity means low eddy current losses and hence the material shows very high promise for use
in high frequencies up to microwaves. Ferroxcube A is Mn-Zn ferrite. Ferroxcube B is Ni-Zn ferrite
and Ferroxcube D is Mg-Mn ferrite. Ferrites are widely used as core materials to increase flux linkage
and/or inductance in high frequency inductors and transformers. Due to low value of saturation
magnetisation per unit volume, in comparison to ferromagnetic materials, they are not used in high field
and high power applications, such as motors, generators and power transformers. Spinel ferrites, which
produce rectangular hysteresis loop are used as computer memory core elements. Ferrites find the
greatest use in high frequency applications and they have not found much use in power transformers
because of the relatively low permeability and flux density compared to iron. High resistivity (107 Q-m as
compared to KT8 Q-m for iron) combined with fairly high induction and permeability make ferrite,
ideally suited for high frequency applications.
Magnetic materials can be divided into soft magnetic materials and hard magnetic materials. We have
already seen that the process of magnetisation consists in the movement of domain walls so that favourably
oriented domains grow fast and the unfavourably oriented ones shrink. If the resistance to the movement
of the domain walls is small, the coercive force is small and it is easy to magnetise the material. Such
o^rerials.are called soft materials. If the resistance to the movement of the domain walls is large, the
coercive force is large and the material is called a hard material. In such materials the domain walls are
““mobilised from free movement by the lattice defects or imperfections or precipitates of a non-
magnetic material. It is these defects which lead to high hysteresis losses. The presence of defects has
me advantages of inerrasing mechanical hardness and electrical resistivity. Increased resistivity means
*°* eddy current losses.
Soft or permeable materials have high permeability and low coercive force and are magnetised
311(1 demagnetised easily. They are used for transformer cores, magnetic switching circuits and magnetic
amplifiers and in other applications under alternating magnetic fields. Hard or permanent magnetic
I
materials arc used entirely for their ability to retain magnetic fields. Hence both a large coercive fo^
and high residual induction are desirable to provide an adequate magnetic field from the magnet and to
retain this field under adverse conditions. The permeability is low and a large magnetising force k
necessary to attain saturation magnetisation of the material.
These differences in magnetic characteristics of the two groups of materials are best illustrated
by referring to their hysteresis loops as shown in Fig. 9.48. Soft magnetic materials are characterised by
steeply ascending magnetisation curve and high permeabilities. Since the coercivity is low the area of
the loop is small. This is an important consideration when the material is used for a.c. current applications
Hard magnetic materials are characterised by a relatively large area of hysteresis loop of more or less a
square shape.
(a) Soft (b) Hard (c) Hard
Fig. 9.48 Typical hysteresis loops; (a) Small coercive force and large B;
(b) Large coercive force and small B, and (c) Large coercive force and large B
Soft Magnetic Materials

The most widely used permeable materials are iron and iron alloys such as iron-silicon, nickel-iron and
lion-cobalt often with other alloying elements added. Relatively pure iron is frequently used as the
magnet core for direct current applications. Iron silicon alloys containing up to 5% silica are characterised
by high electrical resistivity and high permeability under high flux densities and are thus widely used as
core materials for a.c. current machinery. By a suitable combinations of heat treatment and cold rolling,
most of the crystals can be oriented along the rolling direction of the sheet. This increases the permeability
about 20 to 30% above that of non-oriented alloy. Nickel-iron alloys may range in composition from 35
to nearly 100% nickel. Generally higher the nickel content, higher will be the permeability at Io*
induction and lower the magnetic saturation of the alloy. The maximum permeability is obtained lota
composition of about 79% nickel and the balance is iron. Such an alloy shows zero magnetostriction
and zero anisotropy and that is why the permeability is high. The addition of molybdeneum or chromium
increases the electrical resistivity

Table 9.16 Distinction between magnetic materials
F ape 1 Magnitude pf susceptibility . Temperature dependence , Special remarks 1 Examples I
Diamagnetic Small, negative Independent There are no permanent dipoles, Organic materials 1
consequently magnetic effects are very and light elements.
small.
Intermediate, negative Varies with field and Alkali earths and

temperature below 20 K bismuth
Large, negative Exists only below critical Superconducting

temperature (Tc) or (9f) materials
Paramagnetic Small, positive Independent They possess permanent dipoles which Alkali and transition
in the absence of fields, are randomly metals
oriented so that net magnetisation in
Large, positive X = C/(T-9) any given direction is zero. Rare earths
“ 11
Ferromagnetic Very large, positive For?’ >7'c, Due to the large internal field, the Some transition and
X = C/(7’-9) permanent dipoles are strongly aligned rare earth metals
in the same direction and consequently
a large spontaneous magnetisation
results even in the absence of an applied
field.
The magnetic ions on lattice site A will Salts of transition

Antiferromagnetic Small, positive When T > TN,
be aligned antiparallel to those on lattice elements
site B because the molecular field is
negative. Also Afa =
It is a special case of antiferromagnetics Ferrites
Ferrimagnetic Very large, positive At ? > rv in which opposed moments are of
X = C/(/' ± 9) different magnitudes and a large
magnetisation thereby results.
CHAPTER 9
Table 9.17 Magnetic units
Name Symbol 'emu-cgs units1' ..‘r,, f mks rationalised (SI) units ., . . Conversions
_____ ________ ■■ ■
Magnetic induction B Gauss = g1/2/(cm1/2-s) weber/metre2 = kg/(s-C) = Tesla (T) 1 wb/m2 = 104 G
Magnetic field strength H Oersted = g^/fcm^-s) ampere/metre . 1 A/m = (4ti/103) Oe

t.
Magnetisation M Maxwell/cm2 = g1/2/(cmt/2-s) ampere/metre 1 A/m = (4rc/103) Maxwell/cm2
•' 1•
Magnetic flux <P ' Maxwell = (cm3/2~g1/2)/s weber = (kg-m2)/s-C = V-s 1 Wb = 108 Maxwell
»
Susceptibility X Unitless Unitless Xsi = 471 Xegs
Permeability (Relative) Unitless Unitless Same value
I gauss (line/cm2) = 1CH Tesla

I-
thereby reducing the eddy current losses. The alloy containing 79% Ni, 5% molybdenum, 15% Fe and
0.5% Mn known as supermalloy possesses very high permeability. Other important nickel alloys are
those exhibiting very high values of positive magnetostriction. When heated in a range of temperature
below Curie temperature the alloys lose their internal magnetism and contract. The contraction is opposed
by thermal expansion so that it is possible through suitable alloying to produce a material of any desired
value of coefficient of thermal expansion.
Iron-cobalt alloys have high magnetic saturation than either iron or cobalt alone. A maximum
magnetic saturation is obtained for a composition of about 35 or 50% cobalt. Small amounts of chromium
and vanadium are added to increase the electrical resistivity and to improve the cold working properties.
The characteristic property of these alloys is a very high positive magnetostriction (such alloys are
called permuvar alloys). The annealing consists of heating the specimen between 732°C and 1232°C.
Hard Magnetic Materials

The most widely used permanent magnetic materials are low alloy steels containing 0.6 to 1% carbon
which are hardened by quenching or precipitation hardening. Another important group are iron-nickel-
aluminium alloys with certain amount of cobalt known as Alinco alloys. The permanent magnetic materials
CHAPTER 9
are usually hard, brittle and difficult to shape so that they must be cast and finished by grinding. Recently
more ductile alloys such as copper-nickel-iron (cunife) and copper-nickel-cobalt (cunico) have been
developed. These can be cold washed and machined by ordinary methods. All these three types of
alloys are subjected to precipitation hardening which can be controlled in such a way as to produce
microscopically hetrogeneous structure composed of platy particles oriented in a required direction.
The size of these particles is very small (about 10-4 cm) and approaches the dimension of a simple
, saturated magnetic domain. The reversal of magnetisation can occur only by complete rotation of magnetic
domain within a particle. This requires a very high magnetising force because of crystal anisotropy.
Hence the boundary displacement of domains is suppressed resulting in a high coercive force.
The same principle has been observed in producing permanent magnets from powdered materials
having a particle size of collidal dimensions from 0.1 to 0.01 microns. A number of iron base permanent
magnet alloys made from such fine powders have very high coercive forces. The ceramic permanent
magnetic materials such as BaO-6Fe2O3, PbO-6Fe2O3 are considered to belong to the same class of fine
grained magnets. Recently a new permanent magnet which exhibits very high coercive force as well as
high flux density has been developed from powdered manganese bismuthide (MnBi).
1. The magnetic dipole moment is the product of current in the loop and
(a) flux enclosed by the current loop
(b) square of area enclosed by the current loop
(c) area enclosed by the current loop
(</) none of these
2. Relative permeability of a medium is the permeability relative to that of
(a) water 0) vacuum
(c) iron (</) none °* diese
k Magnetic susceptibility X >s
(a) dipole moment per unit volume
(b) torque per unit area
(c) magnetisation per unit magnetic field intensity
(d) none of these
4. Magnetic susceptibility has the dimensions of
(a) Wb/m2 (b) Wb/m
(b) amp/m (d) dimensionless
5. Magnetic induction B and the magnetic field intensity H are related by
(a) B=[i^ (b)B = ii02H
(c)B = poprH {d)B = ^0 + H
6. 1 Bohr magneton is
(a) 2.27 x IO-24 amp m2 (b) 6.67 x IO-34 amp m2
(c) 9.27 x IO'24 amp m2 (d) 9.27 x IO"9 amp m2
7. Bohr magneton is defined as
(a) magnetic moment of an electron spin
(b) magnetic moment of a nucleus
(c) magnetic moment of an electron orbital motion
8. eB/2 m is called the
(n) Debye angular frequency (b) Bohr magneton
(c) Larmor angular frequency (d) None of these
9. Magnetic susceptibility % of a magnetic material is given by
(<*)X = (gr-l) (b)% = M/H
(c) X - (P-- Po)/P0 ' . (d) all these are correct
10. The magnetisation of a solid is related to its magnetic induction B and the field strength H by the relation
(a) M = (B /p0) - H (b)B = y.QH + M
(c)B = H + [i0M (d) B = g0 (H - Af)
H* The magnetic material in which permanent magnetic dipoles (due to electron spin) are already aligned due
to bonding forces are known as
(a) paramagnetic materials
(b) ferromagnetic materials
(c) ferrimagnetic materials
(d) diamagnetic materials
12. In a ferromagnetic material, susceptibility is
(a) very small and positive
(b) very small and negative
(c) very large and positive
(d) very large and negative
You
U. The units of magnetic permeability are

(a) henry/metre (b) henry metre
(c) weber metre (d) henry/sec
14. Which of the following material does not have permanent magnetic dipoles?
(a) Paramagnetic (b) Diamagnetic
(c) Ferrimagnetic (d) Antiferromagnetic
15. Diamagnetic materials possess
(a) permanent magnetic dipoles
(b) no permanent magnetic dipoles
(c) induced dipole moment
(d) none of these
16. Interaction between the neighbouring dipoles is negligible in the case of a
(a) diamagnetic material
(b) paramagnetic material
(c) antiferromagnetic material
CHAPTER 9
(d) ferrimagnetic material
17. Induced dipole moment occurs in diamagnetic materials only
(a) true (b) false
18.The susceptibility of a diamagnetic material is alOlli
(a) 10s (b) 107
(c) 10-7 (d) -io-5
W. Permanent dipole moment consists of the following angular momentum
•*
(a) orbital angular momentum of electron
(b) electron spin angular momentum -
(c) nuclear spin angular momentum .
(d) all of the above
^8. The susceptibility of a diamagnetic material is essentially independent of temperature
(a) under all circumstances
(b) as long as the'electronic structure is independent of temperature
(c) at very low temperatures of the order of 10 K
(d) at very high temperatures
For copper the resultant spin in Bohr magneton is
(a) 0 (b) 1
(c)2 (d) 3
For a paramagnetic material, the energy difference between the spin magnetic dipole parallel and antiparaHei
to air external field H is
<«) It, H (b) it,// /4k
<514 ' SouqPhysics.:
23. Each ferromagnetic material has a characteristic temperature above which its properties are vitally different
from those below it. This temperature is called
(a) demagnetisation temperature
(b) Curie temperature
(c) Transition temperature
(d) Faraday’s temperature
24. Curie-Weiss law is
(u)Xm = C/T (fo)Xm = (C/0)
(c)Xm=C/(T-0) (d)xm = (T-WC
25. For paramagnetic materials, relative magnetic permeability pr at room temperature is nearly
(a) zero (b) 1/10
(c) 1 (d) 10
26. The ferromagnetic Curie temperature of iron is
(a) 631 K (b) 922 K
(c) 1428 K . (d) 1043 K
27. The relative permeability of iron is
(a) 7000 . (b) 100
(c) 700 (d) 5000 .
28. Which of the following material is used for making permanent magnet ?
(a) Platinum cobalt (b) Alnico V
(c) Carbon steel (d) All of the three
29. Below the ferromagnetic Curie temperature, the ferromagnetic material exhibits B-H curve in the form of
(a) B-H loop (b) straight line
(c) exponential curve .(d) none of these
30. At Curie temperature, the spontaneous magnetisation for ferromagnetic materials is
(a) infinity (b) 1
(c) zero . (d) none of these
31. At Neel temperature
(a) permeability is minimum (b) permeability is maximum
(c) susceptibility is minimum (d) susceptibility is maximum
32. Magnetic materials which can be readily magnetised in either direction are called
(a) soft magnetic materials (b) hard magnetic materials
(c) low hysteresis loss materials (d) high hysteresis loss materials
- ------------------------- - ■ v— xSZm
33. The temperature below which cer tain materia Is are antiferromagnetic and above which they are paramagnetic
is called
(fl) Curie temperature (*) Neel temperature
(c) transition temperature (d) Weiss temperature
34. Ferromagnetic materials or ferrites are obtained from
(a) copper (£) zinc
(c) aluminium (d) none of these
1. Give the dimensions of magnetic susceptibility.

2. What is the value of magnetic dipole moment associated with a loop carrying current?
3. Give the relation between magnetic susceptibility, magnetisation and magnetic field.
4. What is Bohr magneton?
5. Explain Larmor angular frequency and give its value for a field induction B.
CHAPTER 9
6. Materials having no permanent magnetic dipoles are called anti ferromagnetic. Is this statement true?
7. What is the order of the susceptibility of a diamagnetic material?
8. What is meant by hysteresis in magnetic materials?
9. Explain the origin of diamagnetism in a free atom.
10. Give the important applications of magnetostriction.
11. Give a few examples and the uses of high permeability materials.
12. What are the requirements of a high permeability material?
13. What are hard and soft magnetic materials? Mention their uses.
14. Discuss the various uses of ferrites.
15. Explain the terms susceptibility and permeability in magnetism.
16. Discuss adiabatic demagnetisation in paramagnetic salts.
1'. What is hysteresis? Discuss its importance in industries.
18. Discuss Curie-Weiss law and its applications.
19. Give Neel’s theory of antiferromagnetism.
30. What are ferrites and ferrites cubes?
31. What are ferrites? How are they superior to magnetic metals?
32. What is meant by anisotropy energy in ferromagnetic materials?
33. Explain Bloch wall and the domain wall energy.
!• A charge of e coulomb is uniformly distributed over the surface of a spherical shell of radius r. If the t
sphere rotates with an angular velocity m, find the magnetic dipole moment developed.
**
What are paramagnetic and diamagnetic materials? Give examples.

Discuss the temperature variation of paramagnetic and diamagnetic susceptibilities of materials.
3. Describe Langevin’s theory for a paramagnetic gas and its limitations. Obtain paramagnetic susceptibility
of a free electron gas employing quantum statistics.
4. How does paramagnetic susceptibility of a substance vary with temperature?
Derive an expression for the paramagnetic susceptibility of a substance on the free electron theory.
5. Describe with necessary theory Guoy method of measuring the susceptibility of a paramagnetic substance.
6. How do you classify a material as dia or para of ferrimagnetism? Explain ferrimagnetism and
antiferromagnetism.
7. Explain the physical basis of diamagnetism and paramagnetism of materials.
Describe the Weiss molecular field theory of ferromagnetism and derive the Curie-Weiss law.
8. What are paramagnetic and ferromagnetic materials? Give examples.
Discuss Langevin’s theory for a paramagnetic gas arrdzbbtain an expression for the paramagnetic
susceptibility of the gas. What are the main drawbacks of this theory?
9. How does the paramagnetic susceptibility of a substance vary with temperature?
What are ferromagnetic domains? Explain their existence.
How does diamagnetism arise in an atom? . ■. -
10. Describe the behaviour of magnetic substances with reference to their Curie points. ' • •
What are ferromagnetic domains? How is their existence explained?
11. Draw the B-H curve for a ferromagnetic material and identify the retentivity, and the coercive field on the
curve. What is the energy loss per cycle? " .
What are ferrites? How are they superior to ferromagnetic materials?
12. Give an account of Weiss theory of ferromagnetism and show from the plot- of Langevin function,
spontaneous magnetisation exists below the Curie temperature and vanishes above the Curie temperature.
13. Explain the different contributions for the formation of domains in a ferromagnetic material and show
how the hysteresis curve is explained on the basis of the domain theory.
14. Explain a simple method of measuring hysteresis loss in a sample of iron. Discuss the importance of
measuring hysteresis in electrical machinery. -
15. Discuss the domain structure, in ferromagnetic materials.
Explain the reasons for the strong ferromagnetic property found in iron, cobalt and nickel.
16. Distinguish between ferrimagnetic, ferromagnetic and antiferromagnetic materials Give an example for
each class of material. Discuss the various uses of ferrites.
17. Give an account of Heisenberg’s theory of the origin of the Weiss magnetic field. Establish the criteria for
ferromagnetism, and point out the experimental evidence in favour.
18. Give an account of the origin of atomic magnetism. Which source is important in thecase of ferromagnetics?
19. Give the theory of magnetic domains in a ferromagnetic material. How are the domains experimentally
studied?
20. What are the distinguishing features of ferromangetlsm?
Discuss Weiss theory of ferromagnetism bringing out its merits and demerits.
2J. Explain Heisenberg’s criteria for ferromagnetism.
Discuss ferromangetism as a cooperative phenomenon.
H. Distinguish between ferromagnetism and antiferromagnetism. Give examples.
State and explain the magnetic properties of ferrites an mention their industrial applications.
tj. Describe the experimental evidence to demonstrate the existence of ferromagnetic domains.
Explain the different factors which determine the structure in a ferromagnetic material-
14, Give an account of Neel’s theory of antiferromagnetism and show how the ferromagnetic behaviour of
A
ferrites can be explained from Neel’s theory.
_
25, Describe the structure of ferrites. How is the magnetic moment of ferrite molecule calculated?
24, What are ferrites and ferrox cubes? How are mixed ferrites prepared for industrial uses? Give an account
of the applications of ferrites pointing out their advantages over a ferrimagnetic material.
27. Explain clearly the difference between hard and soft magnetic materials.
What are mixed ferrites? Mention their uses.
2H Discuss the phenomenon of antiferromagnetism. How does an antiferromagnetic substance differ from a
diamagnetic substance? ’. .
29. Explain in detail the concept of ferromagnetic domains and explain how it was experimentally estabHsheri.
CHAPTER 9
Account for the strong ferromagnetism of iron, cobalt and nickel.
3t. Obtain an expression for paramagnetic susceptibility of free electrons on the basis of the classical laws.
. Discuss its inadequacy and show how Pauli modified it
31. Give an account of the quantum theory of paramagnetism. Discuss how the theory explains the behaviour
of rare earth ions. What do you understand by quenching of orbital angular momentum?
32. Draw temperature dependence of the susceptibility of all types of magnetic materials; comment on them.
Explain the Heisenberg’s exchange interaction in ferromagnetism-
33. Give an account of Weiss theory of ferromagnetism. On the basis of this theory, how will you explain
hysteresis and Curie point? Explain clearly the basic difference between paramagnetic and ferromagnetic
substances.
34. Explain Heisenberg’s exchange interaction. Show how it explains ferromagnetism? Discuss the difference
in the nature of the magnetic susceptibility for a ferromagnetic and antiferromagnetic substance.
!• A magnetic material has a magnetisation of3300 ampere/metre and flux density of0.0044Wb/m2. Calculate
the magnetising field and the relative permeability of the material.
2. A magnetic field strength in copper is 106 ampere/metre. If the magnetic susceptibility of copper is -O.8
x IO"5, calculate the flux density and magnetisation in copper.
3. The magnetic field intensity in a piece of ferric oxide is IO6 ampere/metre. If the susceptibility of the -
material at room temperature is 1.5 x IO-3, compute the flux density and magnetisation of the material
A typical magnetic field achievable with an electromagnet with iron core is about 1 tesla. Compare the
magnetic interaction energy p J? of an electron spin magnetic dipole moment with k^Tat roan icmperamre
and show that at ordinary temperatures the approximation » 1 is valid.
5. The magnetic susceptibility of copper b -03 x Uf'. Calculate the magnetic moment perunit -
copper when subjected U> a field whose magnitude imide copper b 104 ampere/metre.
6. A circular loop (4 conductor having a diameter <4 M cm came* a current of100 mA. The loop h pface^^
a magnetic field having a uniform flux density <4 OX/5 Wb/m2 with its axb indined at 6fP to the dirm^-
<4 the field. Calculate the values of magnetic dipole moment and torque experienced by the osrrent loop
7. The magnetic field strength in silicon b KXM) ampere/metre. If the magnetic field susceptibility m
- 0.3 x 10 *, calculate the magnetbation and flux density in silicon.
M, Approximately how large must the magnetic induction be for the orientation energy to be computable to
the thermal energy at room temperature? Assume, pw= 5 I
9, The saturation magnetic induction of nickel b 0^5 Wb/m2. If the density of nickel b 8906 kg/m* awl b
atomic weight b 58.7, calculate the magnetic moment of the nickel atom in Bob magneton.
19. Estimate the order of the diamagnetic susceptibility of copper. Use a value of 0.1 mn as the radbs md
assume that only one electron per atom contributes. Given: a ~ 03608 nm.
11. An iron rod 03 metre long and 2 mm2 cross section b placed in a long solenoid of25timK per centimetre
carrying a current of 2 ampere. Assuming the relative permeability of iron to be 400, find die magnetic
moment of the bar.
IX Calculate die frequency of die ratfiationnhsdi must be badent on a susbstanceptaeed ma magnetic fitid
strength (5 x Wfaf ampere/metre, so that the elections can absorb energy.
13. A paramagnetic substance has 1 (P atonn/m?, The magnetic moment of each atom b 1.8 x IO*22 amp b2.
Calculate the paramagnetic susceptibility at 300 K. What would be die dipole moment of a bar of this
material 0.1 m long and 1 sq cm cross section placed in a field of 8 x 10* ampere/metre?
14. A solenoid 03 metre lung containing 500 turns of wire carries a current of 10 ampere. When placed in a
atmosphere of oxygen at / = ~150r'C, it exhibits an increase of magnetic induction of AB = 1JM x IO4
Wb/m2 above that measured in vacuum. Compute die magnetic susceptibility of oxygen at - UO^C and
the magnetic dipole moment of die molecule.
15. The saturation value of magnetisation of iron b 1.74 x 10^ ampere/metre. Iron has body centred cubic
structure with an elementary cube edge of 0.286 nm. Calculate die average tutmhrr of Bob magneton
contributed to the magnetisation per atom.
16. An atom contains 10 electrons revolving in a circular path of radius IO'11 metre. Assuming boftogeaeous
charge distribution, calculate the orbital dipole moment of die molecule in Bob m^neton.
17. The magnetic momentof an electron in the ground state of bydtopm atom bone Bob magneton. Cafcubt
the induced magnetic moment in a field of 1 weber/metre2.
lg. Anhydrous nickel chloride, NiCl2 has a paramagnetic susceptibilily of 783 x IO4 kg"* at 20“C- Tb
atomic weights of nickel and chlorine are 58.7 and 353 respectively. Using the sunphfied Laagevb
formula, calculate the magnetic moment of die Ni2* ion in Bob magneton.
19, The atom of a paramagnetic material, each with a magnetic momem 1.2 x IO"23 ampere-metre2, are
placed in an external magnetic field of induction 13 Wh/m2. Calculate the tfifierence io magnetic potendal
energy for extreme orientaticns of the atomic dyoles and show dun dm fiwygy i«(t/ll5)tii«sthed>ennd
energy of translation of the atoms at a temperature of ZPC.
2g, A system (4 electron spins is placed in a magnetic field of 2 weber/metre2 at a temperature T. The number
of spins parallel to the magnetic field b twice as large as the number of antipole! spins. Determine T.
_______________________ Magnetic Pftumt nB IfJ*
21. Cakula» the average magnetic moment along the field direction per spin in Bohr magneton when a
paramagnetic spin system is subjected to a uniform field of 106 ampere/metre at 27°C.
j2 a magnetic field is applied to a salt containing Cu2* ions, which have nine electrons in 3d-shell. What
magnetic field must be applied to a salt containing Cu2+ when at 1 K, so that 99 per cent of the ions are in
(he lowest energy state?
yt, a paramagnetic system of electric spin magnetic dipole moment is placed in an external field of
105 ampere/metre. Calculate the average magnetic moment per dipole at 300 K. Also calculate the fractional
number of spins which are parallel to the field.
M The Curie temperature of iron is 1043 K. Assume that iron atoms, when in the metallic form, have moments
of two Bohr magneton per atom. Iron is body-centred cube with lattice parameter, a = 0.286 nm. Calculate
(a) the saturation magnetisation (b) the Curie constant (c) the Weiss field constant and
(d) magnitude of the internal field
2S. The ions in the molecule of magnetite are Fe2*, F^3* and O42", the subscripts giving the number of ions
per molecule In the conventional unit cell, which is cubic with a = 0.83 nm, there are eight molecules.
The Fe3* magnetic moments cancel and hence the magnetisation is produced by the Fe2+ ions alone. If the
saturation magnetisation of magnetite is 5.2 x 10s ampere/metre, calculate the moment per Fe2* ion in
CHAPTER 9
Bohr magneton.
A paramagnetic salt contains 1028 ions/m3 with magnetic moment of one Bohr magneton. Calculate the
paramagnetic susceptibility and the magnetisation produced in a uniform magnetic field of 106 ampere/
. metre when the temperature is 27°C.
27- A paramagnetic material is subjected to a homogeneous field of 106 ampere/metre at 37°C. Calculate the
average magnetic moment along the field direction per spin in Bohr magneton.
A paramagnetic material has body-centred cubic structure with an elementary edge of 0.25 nm. If the
saturation value of magnetisation is 1.8 x 106 ampere/metre, calculate the average magnetisation contributed
per atom in Bohr magneton
Consider a helium atom in its ground state (Is). The mean radius in the Langevin formula may be
approximated by the Bohr radius, 0.0528 nm. Density of helium is 0.178 kg/m3. Calculate the diamagnetic
susceptibility of a helium atom.
3®- Show that the ratio of the torque exerted on one magnetic dipole of magnetic moment 1 Bohr magneton by
a similar magnetic dipole oriented perpendicular to it, to the torque exerted on an electric dipole oriented
Perpendicular to the first electric dipole, is 3.7 x Itti4 when the distance between the dipoles in both
configurations is assumed to be 0.3 nm.
The rare earth elenrent gadolinium is ferromagnetic below 16°C with 7.1 Bohr magneton per atom. Calculate
the magnetic moment per gram. What is the value of saturation magnetisation? The atomic weight of
8*Winium is 157.26 and its density is 7.8 x 103 kg/m3.
Tie euth has a magnetic dipole moment of 6.4 x 1021 amp-metre2. What current would have to be set up
hi a single turn of wire going around the earth at its magnetic equator, if wo wished to set up such a dipole?
Given the mean radius of earth = 6.4 x 106 m.
An electron in an atom of hydrogen circulates in the orbit of radius 0.051 nm. Calculate the change in
““gnctic moment for this electron -if a magnetic field of induction 2 weber/m2 acts at right angles to the
P*** of the orbit.
34. For iron the Curie temperature 0 at which the mutual interaction of the dipoles is just strong enough to
overcome the thermal agitation, is about 1000 K. Assuming that each dipole has a strength of about
1 Bohr magneton, calculate the internal field at the Curie point.
35. The unit cube edge for Fe3O4 is about 0.8 nm and there are eight Fe^ atoms in a cell. Calculate the
magnetisation. For iron, the six outer electrons have five spins in one direction and the sixth in the other
giving a net moment of 4 Bohr magneton.
36. Calculate the theoretical saturation magnetisation in pure iron. Iron has bcc structure with lattice paramrty
a = 0.286 nm, = 9.27 x IO"24 A m2.
37. A typical magnetic field achievable with an electromagnet of iron core is 1 tesla. Compare the magnetic
interaction energy of an electron spin magnetic dipole moment with k^T at room temperature.
38. Consider the helium atom in the ground state (Is). The mean radius in the Langevin formula may be
approximated to the Bohr radius 0.053 nm. Get the value of the diamagnetic susceptibility of a helium
atom. The atomic weight and density of helium are 4 and 0.166 kg/m3 respectively.
TlNtRgDUCTIpN " ,.......... ' . ..
Semiconductors are materials whose electronic properties are intermediate between those of metals and
insulators. These intermediate properties are determined by the crystal structure, bonding characteristics,
and electronic energy bands and also by the fact, unlike metals, a semiconductor has both the positive
(hole) and negative (electron) carriers of electricity whose densities can be controlled by doping the
pure semiconductor with chemical impurities during crystal growth. The physical principles underlying
this intermediate behaviour were worked out by H.A. Wilson in 1931, shortly after the development of
the band theory of solids. The investigation of these principles was greatly increased between 1940 and
1950, particularly for the semiconducting elements, germanium and silicon, as an outgrowth of the
research and development programme on crystal rectifiers undertaken in connection with the radar
programme on crystal surfaces during World War II. The climax of this investigation was the invention
and development of the transistor by J. Bardeen, W. Brattain and W. Shockley in 1948 for which they
received the Nobel prize in 1956.
Considering first the classification of solids by their electrical properties, it is easy to see that
there are two types of materials.
(fl) Metals
These can be considered to have permanent electron gases permeating the whole of the solid but confined
to it. This ‘gas’ can be influenced and moved by magnetic and electric fields. This results in the familiar
properties of metallic conduction.
O’) Insulators
all these materials there are virtually no free electrons. Hence there is no electron gas and as a
consequence no electrical conductivity. Semiconductors are fundamentally similar to insulators and do
not form a separate basic class of their own. In fact, in their pure state they are perfect insulators at near
^solute zero of temperature.
A portion of the periodic table is shown in Fig. 10.1.
When one considers the two adjacent elements aluminium (Al) and silicon (Si), it is the eleven-
r r of magnitude difference in resistivity that stands out in contrast to the many similar features. See
•able 10.1.
The "le alom'c density N (atoms/m3) of aluminium is 6 x IO28, a value close to that of Si (5 x 1028).
mass densities are also of the same order. A review of the atomic physics of the electron configurations
521
Souo. Srxre Physics__________________ _______________________________________
and binding energies of electrons in individual atoms shows that these are also similar in both the
materials. As shown in Fig. 10.2, the 10 most tightly bound electrons form the closed-shell configuration
of neon (Z = 10). There are three outer shell electrons in Al and four in Si—all with about the same
binding energies. With the exception of electrical resistivity, the macroscopic and atomistic properties
of Al and Si appear to be similar.
Ill IV V
5 6
Boron B Carbon c Nitrogen N
13 14 15
Aluminium Al Silicon Si Phosphorus P
31 32 .... c-^31'. ■
Gallium Ga Germanium Ge Arsenic As
49 50 51
Indium In Tin Sn Antimony Sb
81 82 .. _. ■83
Thallium T1 • .-r v - Lead • . ; 1 Bisgg\,...
Pb
Rg. 10.1 Portion of the periodic table showing column III, IV and V
elements with their atomic number
Table 10.1 Comparison of the properties of Al and Si at 300 K
N Pm ... CP ' 1
Element P
(in 102W) .„(kgln?) (fl-m) .(•Mg1 K-’) j
Al —--------------
6.02 2700 2.5 x 10-8 908
Si 5.00 2300 2.3 x 103 700
The question then arises as to non-electrical method^ to distinguish between discs of Al and
as the materials are odourless, tasteless, and have about the same weight and colour. If one heats
materials, the difference is quickly evident, as Al melts at 660°C, whereas Si melts at 1414° C. An even
simpler method is to bend the two discs; Si is brittle and fractures and Al is ductile and bends easu
One difference, then between Al and Si is in the way the atoms are held together or bonded.
There are four essential quantum numbers associated with each election orbit.
(i) The Principal Quantum Number (n)

For a single atom the electrons are arranged in shells of definite energy level where the electrostatic
force of attraction is balanced by the centrifugal force on the electron. The principal quantum number •
which has integer values, gives the energy levels in these shells in arbitrary Units. The value of thesC
Physo
_______ <• - . --
units depends on the element since the heavier elements with a greater positive charge on the nucleus
give rise to a greater attractive force. Also n = 1 corresponds to the K-shell, n = 2 the L-shell, etc. Thus
a shell contains all the electrons with the same principal quantum number.
(//) The Subsidiary Quantum Number (/)

This is a measure of the eccentricity of the electron
orbits and has a slight effect on the electron energy.
It may have values of 0 < I < n -1 and corresponds
to the subshells. That is, n = 1 can only have one
value 0, i.e., one subshell: n = 2 can have values 0
or 1, i.e., two subshells. Thus a subshell contains
all the electrons with the same principal and
subsidiary quantum numbers.
(///) The Magnetic Quantum Number (mJ

This is associated with the rotation of the electrons
about the nucleus and has a slight effect on the
energy and may have values:
-Z <ml<l
Fig. 10.2 Electron distribution in aluminium and silicon
i.e., Z = 0; x 3 =0
I = 1; x 3 m[ = -1, 0 or 1
I = 2; x 3 ml = -2, -1, 0, 1 or 2
CHAPTER 10'
(/V) The Spin Quantum Number (mJ
This is associated with the rotation of the electron about its axis and may have two values ±1/2.
The application of Pauli’s exclusion principle, which states that no two electrons may have the
same four quantum numbers, will now give the number of possible electron orbits.
n = 1, AT-shell, I = 0, k subshell,
mz = 0
ms = ±1/2, 2 electrons
n = 2, Z>shell, I = 0, 2s subshell,
ml = 0
m = ±1/2, 2 electrons
Z = 1,2p subshell, ml = -1, 0, 1
m5 = ±1/2, 6 electrons
w = 3, Af-shell, I = 0, 3s subshell,
m{ = 0
m = ±1/2, 2 electrons
__________
I = 1, 3p subshell,
mt = -l, 0, 1
I = 2, 3d subshell,
m, = -2,-l,0, 1,2
n = 4, TV-shell, I = 0, 4s subshell,
mt = 0
I = 1, 4p subshell,
m[ = -1, 0, 1
m3 = ±1/2, 6 electrons
I = 2, 4d subshell,
ml = -2, -1, 0, 1, 2
Z = 3, 4/subshell,
ml = -3, -2, -1, 0, 1, 2, 3
This shows that the K-shell has two possible electron states, the £-shell 8, the Af-shell 18 and the
TV-shell 32. The number of electron states in any shell is twice the square of the principal quantum
number.
The significance of these quantum numbers lies in their application to the band theory of solids
and, in particular, to semiconductor theory. The electrons in any shell only have the same energy when
a single atom is considered. As soon as a collection of atoms is considered, the permissible energy
levels spread out into bands. Each of these bands correspond to a subshell. The interaction between
atoms and electrons is such that the electrons in certain subshells, e.g., in the fourth shell, may be more
tightly bound to the nucleus than electrons in lower shells, e.g., the third shell.
A typical band structure for a solid is illustrated in Fig. 10.3. This shows the outer conduction
band, the inner valence band, and dotted curves representing the binding energy of electrons to the
nuclei and the energy barrier constraining the electrons within the crystal.
The picture of the electronic energy levels in a crystal is known as the energy band model of the crystal
and it is very useful in determining the electrical properties of any crystalline solid, since it shows how
electrons can move in the crystal. In particular, the differences between insulators and semiconductors,
are reflected in their energy band model.
Let us first consider the band
structure of an insulator. Diamond is the
crystalline form of carbon, the sixth
element in the atomic table. This
element is of interest because it lies in
the same group of the periodic table and
has the same type of binding as silicon
and germanium. The shape of the
eneigy-band structure of diamond as a
function of interatomic spacing is
shown in Fig. 10.4.
*
CHAPTER 10
fig. 10.4 The bands arising from rhe k, 2i and 2p atomic states of carbon
(diamond) as a function of interatomic distance

526 Cfûo Swre PhymgPmt*-*
•<» ■ - -......................
In carbon, there are two electrons in the n = I shell and four in the n = 2 shell. However, there are
eight energy states in the complete n = 2 shell. In the isolated, free atom, six electron states have been
shown filled, and the remaining four states in the n = 2 shell are empty. As the interatomic distance is
decreased, the discrete levels broaden out into bands, and eventually the bands corresponding to the
subshells of n = 2 overlap. As the interatomic distance is further decreased, a spilt occurs between the
upper four states and the lower four states, and at the equilibrium spacing, the two bands are widely
separated. The upper and lower bands are called conduction band and valence band respectively. The
gap between the two band is known as forbidden energy gap (Eg). For diamond, * 6 eV Since
0.025 eV at 300 K, diamond with very few electrons in the conduction band, is therefore an extremely
good insulator at room temperature.
Semiconductors differ from insulators only in the width of the forbidden band. An insulator has
a forbidden gap which is so wide that very few electrons cross it at room temperature, whereas a
semiconductor possesses a narrow gap which allows a considerable amount of electrons to the conduction
band. The band structure of silicon is shown in Fig. 10.5.
Fig. 10.5 The bands arising from the 3 s and 3p states of silicon as a function of interatomic distance
In the case of semiconductors the stable atomic spacing is very close to the cross over point, and
hence the forbidden band is quite narrow (about 1 eV for silicon and 0.7 eV for germanium). These two
crystals are classified as semiconductors because at room temperature there are enough electrons excited
across the forbidden gap to make both electron and hole concentrations in the conduction and valence
bands, respectively, large enough to cause appreciable conductivity. These two materials have a resistivity
at room temperature (0.46 Q-m for germanium and 3000 Q-m for silicon) — intermediate between a
conductor and an insulator. In the case of silicon and germanium, both electrons and holes contribute to
the conductivity. The holes in each case contribute about half as much as the electrons because of their
different mobilities.
Physics of Semiconductors^ 527
In general there are two types of semiconductors. Those in which electrons and holes are produced by
thermal activation (in pure germanium and silicon) are called intrinsic semiconductors. In the other
type the current carriers, holes or free electrons, are produced by the addition of small quantities of
elements of Group III or V of the Periodic Table, and are known as extrinsic semiconductors. The
elements added are called the impurities or dopants.
Having looked at the energy band structure of semiconductors and the expressions which give
the energy distributions of electrons in materials, we are now in a position to calculate the densities of
electrons and holes in the conduction and valence bands of semiconductors, and to find the position of
the Fermi levels. The densities n and p, together with the mobilities, and \Lp of the electrons and holes
then enable us to determine the conductivity a of the semiconductor from the relation.
where e is the electronic charge. The electron and hole mobilities can be defined as the average drift
velocities of the carriers in an electric field of unit intensity.
The structure of silicon and germanium is diamond cubic which is characterised by bonds between
the atoms in which the neighbouring atoms share electrons [a = 8r/V3; number of atoms in a unit
cell = 8 and packing factor = (kV3 )/16]. In metals the free electrons carry current when influenced by
an electric field; the resistivity for any particular metal being caused by imperfections in the metal
lattice. In semiconductors the situation is quite different. Unlike that for metals, the number of conducting
electrons in semiconductors varies with temperature and field, giving rise to conductivities whose
dependence on temperature and field is quite characteristic. The number of current earners in useful
semiconductors at room temperatures are such that the conductivities have values between those of
metals and insulators.
Certain of the covalent bonds in the pure material must be broken before electrons are released
to carry current. The agency that breaks the bond is usually thermal agitation. At absolute zero, therefore,
a pure semiconductor will have no broken bonds and will have the electrical characteristics of an insulator.
When the conductivity in crystalline semiconductor is due solely to the breaking of covalent bonds, the
substance is said to be an intrinsic semiconductor. Certain atoms introduced into the crystal produce
localised energy states which are in the forbidden energy gap, and these may result in electric conduction.
A material where this latter mechanism is dominant is known as extrinsic semiconductor.
There are two groups of particles which must be considered in some detail in order to explain
adequately the properties of semiconductors. The first group is characterised by its comparative freedom
of motion and is composed of photons, phonons, electrons and holes. The second group is composed of
Ihe so called imperfections, consist of chemical impurities and defects.
■EEHsSSzSz
! iWhKUOtt band
Wtawe band \blcncc band
X^lcncc band
Vri Insulator (6) Semiconductor (c) Metal
Ffc 10.6 Typical enttgy bands
a vaiii^s^ww^w*wi»mw &i
These are semiconductor which have no impurity typo of imperfection but may have defects. Germanium
and silicon in the pure form are two examples of intrinsic
semiconductors. In these cases, there are four nearest
neighbours to each atom and there are two election bonds
between each of the neighbours and the atom. In an
intrinsic semiconductor a forbidden gap exists between
a tilled valence band and the conduction band, but the
width of the forbidden gap expressed in energy is much
smaller than that of an insulator.
Conduction occurs in an intrinsic semiconductor
by thermal excitation of electrons from the valence to
the conduction band. Electrons excited to the higher,
predominantly empty conduction band levels can move Fig. 10.7 thermal excitation of electrons
from atom to atom, thus contributing to conduction when in intrinsic semiconductors
a field is applied to the semiconductor.
The conductivity of u semiconductor depends strongly on temperature because of the need for thermal
energy to excite electrons into the conduction bund, The higher the temperature of the semiconductor,
the greater the number of electrons excited. Therefore, in a semiconductor the higher the temperature,
die lower the resistivity. Note that this is just the reverse in metals.
It might be thought a threshold temper Mwe aivi for mtrm.ur. artii'X^n 'j( derjrxM m
frequency for photoconductivity. Thu is not the case The pr/xtt of /
s is somewhat smnlar to that of heating a liquid to the hoslmg Zxnr «
grates electrons from the valence hand to the conduction b»d at
The rate of evaporation depends on temperature However. thermal acXr.atza zi ttr-z*
boding. in that there is no specific temperature at which the rate of rxûr^ scream
hence no real threshold exists. Temperatures much lower than that y, ie » zfr* -/ -Je
forbidden gap are sufficient to excite a substantial number of electrons from he vaieuce -usd i»e
conduction band, just as many water molecules can evaporate from a hr^wM txdf ltgter
the liquid is well below the boiling point.
U sTATisncsorELE^
SEMICONDUCTORS
. . .. u—~ - ------------------ ..r^ M „^..r- tr -- i
As previously stated, at any finite temperature some electrons will acqnce afficieM daeraai energy to
raise them from the valence band to the conduction band The actnal number depends oa the naaaber of
permissible electron energy levels and the prob^xlity of these levels being occupied
~~T.iSi > «,-Si > «,Si <» «,S » «.Si
OHAPTIR 10
(<•)
Vs <i—?7s 'i—
3, Sc* «& 5-----?St V

• \ • •
‘ Jh—?.s «—-r
(«
>• 10.8 iai Silicon at absolute it'o s. electro' ;o<*'u.t
Physics
In order to calculate the intrinsic carrier concentration, we first calculate the number of electrons
excited into the conductions band at any temperature T kelvin and which in turn are free to migrate in
the crystal. In carrying out these calculations it will be assumed that the electrons in the conduction
band behave as if they are free with effective mass m* and energy will be measured from the top of the
valence band.
Under the conditions of thermal equilibrium, the number of electrons per unit volume having
energy in a range dE about E in the conduction band of an intrinsic semiconductor is,
n(E) dE = Zc (E) dE Fn(E)
where Fn{E) represents the equilibrium Fermi distribution function and Zc (E) is the density of states
factor. The occupation number for electron is
w= E-Ee
(10.1)
1 + exp
and (E - 0)1/2 for metals (10.2)
For semiconductors, however, E starts at the bottom of the conduction band, hence
n r 8m*
Zc(E)dE = (E-E^dE (10.3)
2 h2
where, m* is the effective mass of the electron.
Since the Fermi level for an intrinsic semiconductor must lie well within the forbidden energy
region, and since kBT « Eg at all accessible temperatures, the condition (Ec - EF) > > kBT will always
be satisfied in practice and hence (E - Ef) will also » kBT, one can thus write equation (10.1) as
1 Ef-E
w= E-Ef
= exp by neglecting the term 1
1 + exp
. ksT .
Thus the total number of electrons per unit volume in the conduction band is
EF-E
exp dE (10.4)
kBT
Let E-Ec = x
Pwwa c» faxenw
, -p/2
n
' exp (ErJknT) J xV2 exp [- (Er + x)/k„T] dx
2 h2
0
-1/2
it Kni exp \(Ef- E,)lkBT\ Jx,/2 exp (- ax) dx (10.5)
2 h2
o
I
with «= knT
It can be shown with the help of gamma functions that
jx,/2e~axdx = ~~
= [(V)3/21
Substituting this in equation (10.5), one gets
exp [(Ep-Ec)/kBT]
n
CHAPTER 10
2nrnekBT (10.6)
or
ft2
The term 2(2nm'kBT/h2) is almost constant compared with the exponential term, and so it is
called pseudo constant and is given by the symbol Nc.
So finally, we have
n^Nc^p[-(Ec-EF)/kBT\ (10.7)
The number of holes p per unit volume in the valence band of a semiconductor can be found in
a similar manner. As the presence of a hole can be regarded as the absence of an electron, the Fei mi
function of holes in the valence band is the inverse function, equal to [1 — Fn(E)]. In this case we may
write p(E) dE as the number of holes in the valence band in a range of energy dE about E; then the
exPression for the density of holes in the valence band is
jp(E)dE = $Zv(E)Fp(E)dE (108)
The quantity F (E) is the probability that a hole will be associated with a quantum state of
en«gy E, in other word’s, that such a state will be unoccupied by an electron. This probability is just one
m|nus the probability of occupation F„(E). Since F„(E) is given by equation (10.1), it is easily seen that
FP(E) = U - Fn (£)] = 1 - 7------- t/J
p l + exp[(E- EF)/kBT]
_________ I__________
= \ + e*p[(EF - E)/kBT] (,0-9)
Again, if the Fermi energy is several kBT units above the edge of the valence band, that is, if
(^F - Ev)» kBT, the exponential factor in the denominator of equation (10.9) will be much larger than
unity for all values of E in the valence band, whereby one may set
(Ef-E)
Fp(E) = exp (10.10)
kBT
Referring equation (10.3), one can write
(Ev-E)l/2 (10.11)
where, m* is the effective mass of the hole.
Using relations (10.10) and (10.11) and integrating over the valence band, equation (10.8) becomes
3/2 E
n 8mp J ’ (Ev - E)1/2 exp E-E,
P=2 dE (10.12)
h2 J—CO kBT
Let E-E = x
3/2
K S'”P,
P=2 exp (— EjJk^T) jx1/2exp[(Ey-x)/As7]dx
h2
0
1
Let
kBT
OC
Now exp[(Ev-EF)/^T] jx1'2 exp (- ax) dx
o
This integral here is similar to the integral of equation (10.5). Hence the expression for the
density of holes becomes
.-1V2
2nmpkBT
p=2 exp [(Ey- EF)/kBTl = 7Vvexp [(Ey- EF)/kBT}
~~h2
3/2 A
2nnipkBT
with A„(or/Vp) = 2 (10.13)
~ A2
This is called pseudo-constant.
For intrinsic semiconductor, n - p
Therefore
> (m,*)** exp [- (Ec> EF)/Afl7] * (m;^ exp [- (EF- E^rf] (10 ‘4)
gf-g
exp .-|3/2
kBT WP
Lt gy-g,
exp
kBT
■ .13/2
r Ef+~ +^v) _ mp
«P kBT nr
2Ep £C+E, mp
+ll» ♦
kBT~ kBT
Ec+Ev
F = —------ - In (10.15)
F -2 4 m.
If it happens that mp equals me, then
•S,
CHAPTER 10
Kg. 1O-B(A) Generation of electron-hole pair in an intrinsic semiconductor
that is, the Fermi level is mid-way between the valence band and conduction band, but normally mp is
greater than m*, so EF is just above the middle, and rises slightly with increasing temperature. The
different results are shown graphically in Fig. 10.9.
Equation (10.15) can be re-written in terms of the pseudo-constants, as it can be seen that
Nc
Nv
Je»4 Solid State Physics
Ec + E, kjfT N,
Therefore £F = + 2 " (10.16)
2 Nc
From equation (10.15), it can be concluded that if mp me, the Fermi level is a function of
temperature.
For a given semiconducting substance, the effective masses and the energy gap Eg are fixed;
hence the product np in a given material must be a function of temperature only. This is essentially a
mass-action law governing the relative concentrations of holes and electrons in a given material. If the
semiconductor is in the pure or intrinsic state, then the concentrations of holes and electrons must be
equal, as we have already seen, because the holes and electrons which can be present are those which
are generated in pairs by direct thermal excitation of valence band electrons. In such a material we take
the product of the expressions for electrons and holes, equations (10.6) and (10.13) we get
2nkBT
np = 4 (m>;)3/2exp[-(£-Ev)/^r|
h2
Now, (E- Ev) equals Eg, the width of the forbidden gap. Therefore we can write
np = 4 (/n*»»*)3/2 exp [ (-£g/fcflT)] (10.17)

h2
or, alternatively, using the pseudo-constants,
«p = ^JVvexp(-Eg/^7) (10.18)
It is important to observe that neither
of these last two equations contains the Fermi
level, and therefore they are general results,
which, whilst they have been obtained by
considering an intrinsic material, apply
equally well to impurity doped, that is
extrinsic, semiconductors, provided that the
Fermi level is never within about 2 kBT of
either forbidden band edge. In fact, all that
happens is that if an intrinsic material has
impurities added so that the Fermi level rises,
then n becomes greater than p, and if the
Fermi level drops below the intrinsic level,
p exceeds n. All the time, however, the
product np is constant at constant
temperature.
Returning to the case of the intrinsic
semiconductor, the density of electrons Fig. 10.9 Electrons and holes in an intrinsic semiconductor
equals the density of holes, and they are both
called the intrinsic density, np where
Pwmcs or SemiCOma^. W
c = "p=<-W> cxp (- e/*bd

Rt = («piL- = (jV?V )^ exp (- E/lkJ) (10.18a)
for V.V and simplifying.
("»«"»,)’* exp (-E/2kBD (10.19)
If ■, = *"F - where. m is the rest mass of the electron, then equation (10.19) becomes.
r 2mtkBT 3/2
n = 2------ r5— exp (- EgnkBT) (10.20)
I *
n, = CT*2 exp [- E/2kJ] (10.21)
,-23^
2k x 9.1 x 10 31 x 138x10
(10.22)
(6.626)2 x 10" 68
la, C = 4.83 x 1021. Hence n. = 4.83 x 1021 x I372 exp (- E/2kBT) (10.23)
cr n, =1017/m3 forEg= 1 eV and T=300K
Since the number of atoms per cubic metre may be of the order 1028, only a very small fraction
of the valence electrons are excited into the conduction band.
yn. htctrical condoctivity^

If an electric field is applied to the intrinsic semiconductor in the x-direction, the electrons receive
energy and there is a drift velocity of electrons in the negative x-direction superimposed on their random
thermal motion. Tins means that a positive current flows in the positive x-direction. The field also
imposes a drift velocity in the positive x-direction on the random movement of the holes. Thus positive
charge is also carried by the holes in the positive x-direction. Based on the definition of drift velocity;
the mobility p can be defined as the drift velocity per unit electric field. In an ideal intrinsic semiconductor
the mobility is determined by scattering of the electrons by lattice vibrations. At low enough temperatures,
however, where the mean free path of the electrons becomes long, scattering by impurity atoms and
defects sets a limit to the mobility attained.
Since there are two types of carriers in the intrinsic semiconductor, electrons and holes, its
specific conductance is sum of the conductivities <Jn due to free electrons and Op due to holes. Thus the
electric conductivity of an intrinsic semiconductor is
ai=an + ap = ',e^ + êl1P
Since for an intrinsic semiconductor n = p = np one gets
(10.24)
1 Total current, 1 - fB *
Electron flow
Hole flow
Electron flow '
Conventional (flow)
Fig, 10.10 Conduce on of etectnc current in an intrinsic semiconductor
The mobilities depend on temperature as a modest power law. i.e., |t goes as
H,=aru and p)> = 07M-5

Thus, ^^ + ^^,= (0 +P)7",j=y7"'5
af= TCen.yr-*2
Substituting for n. from equation (10.21), one gets
<T.= yCe exp (-£^721^7)
O—Bexp^-EJlk^T) (10,25)
or * B
I Eg '
(10,26)
Taking logarithms on both sides,
E-
lnpf=^r~Z + lnX (10.27)
' 2kBT A.
Equation (10.27) suggests us a method of determining the energy gap of an intrinsic material.
A measurement of the intrinsic resistivity of the material at various temperatures helps us to plot
the results on a semi logarithmic paper. The slope of the curve is (EJ2k£t and hence the energy gap can
be determined. See Figs, 10.11 and 10.12.
Figure 10.11 shows the plot of In p( versus 1/Tfor
gg{oe important intrinsic semiconductors. For Ge and Si,
£ turns out to be 0.72 eV and 1.2 eV respectively. The
,io of the conductivity of copper to that of germanium is
3 x 107 while the corresponding ratio of conduction electron
density is 2 x 109 comes primarily from the fact that the
mobility of electrons in Ge (= 0.4 m2/V-s) is about 100
times that in copper. The mobility of holes in germanium
is roughly 0.2 m2/V-s, so that electrons carry about two-
thiids of the current while holes carry the remainder.
Further, we can find the incremental temperature
AT, necessary to double the conductivity, or more accurately
to double the number of carriers.
Using equation (10.18a), we have
n.= (NêxpC-E^T)
and at the higher temperature
Eg+ AT)J
2n/ = m)-exP^2Mr
Hence 2 = exp (EgAT/2kB7^)
CHAPTER 10
E.XT
i.e., -^j = h2
2kBT2
_ C2^7)^2 (10.28)
*7 kJ
For germanium with a gap of 0.75 eV the conductivity at room temperature doubles in 15°C, and
for silicon with a gap of 1.12 eV, the conductivity doubles in 10°C. This incidentally, shows how
sensitive these semiconductors are to temperature changes.
"vJuTYmPURITY SEMICONDUCTORS OR EXTRINSIC

jm. SEMICONPUnrO^^H,^^
In a lecture at the University of Pennsylvania in 1948, k. Lark-Horowitz characterised the study of
semiconductors as an investigation of the physics of drift. The reason for this statement lay in a fact that
had been known for years, namely, that the electrical properties of solids are extremely sensitive to the
presence and nature of even the tiniest amounts of impurity in the lattice.
538 Soud State Physics
Physicists struggled for decades to purify

semiconducting materials to a high degree. The problem
was difficult because the electrical properties of a solid
are sensitive to as little as one part in 10*', whereas chemical
methods detect impurities only to one part in 107 or 108 at
best. By 1958 many solids, including silicon and
germanium, could be refined to a degree such that unwanted
impurities were not troublesome in almost any application.
The ability to grow large, pure, single crystals was one of
die main aids in advancing semiconductor knowledge.
On the other hand, pure semiconductors are usually
of interest only from a theoretical point of view. Because
in pure semiconductors (intrinsic semiconductors) the
carrier concentration of both electrons and holes at normal
temperatures is very low, and hence for an appreciable Fig. 10.13 Plot of In p, versus (1/T) for some
semiconductors in the intrinsic range
current density through the semiconductor, the applied
electric field must be very large.
Table 10.2 Electrical characteristics of some selected semiconductors
Approximate
Band maximum device Dielectric Electron Hole mobility,
Semiconductor gap (eV) temperature (°C) constant mobility lip(m2 r’r’;
(theoretical) (air = 1) pe (m2^1^1)
Ge 0.67 100 16.0 0.39 0.19
Si 1.106 250 11.8 0.15 0.05
GaAs 1.4 450 11.1 1.0 0.045
SiC 2.8 > 1000 7.0 0.01 0.002
C (Diamond) 6.7 > 1000 5.7 0.18 0.12
InSb 0.18 - -196 15.9 8.0 0.1
InAs 0.33 --75 11.7 3.3 0.046
GaSb 0.68 100 14 0.4 0.14
InP 1.25 400 10.8 0.46 0.015
AlSb 1.6 500 10.1 0.04 0.04
GaP 2.4 1000 8.4 0.01 0.002
AlAs 2.2 900 - 0.12 0.02
Table 10.3 Electrical and mechanical characteristics of Ge. Si and (iaAs
SJVa
Property Ge Si GaAs Units
Melting point 937 1415 1240 "C

1.
Density at 25°C 5320 2330 5310 kg/m’
2.
Thermal expansion 6.1 x 1(T6 4.2 x 10 6 5.9 x KT6 /kelvin
3.
Thermal conductivity 630 840 520 Wm 'K 1
4.
Specific heat 310 760 361 Jkg 1 K’1
5.
Atomic weight 72.6 28.09 144.6 number
6.
7. Lattice constant 0.5657 0.5431 0.5654 nm
Atoms/m3 4.42 x IO28 4.99 x 1028 4.34 x 1028 number
8.
Dielectric constant 16 11.8 11.1 number
9.
10. Band gap energy 0.67 1.106 1.4 eV
11. Intrinsic resistivity 46 2300 3.7 x 106 Q-m
(300 K)
12. Electron mobility 0.39 0.15 1 m2V "'s'1
13. Hole mobility 0.19 0.05 0.045 m2V'Is"1
14. Intrinsic charge density 2.4 x 1019 1.5 x 1016 1.4 x 109 Zm3
15. Electron diffusion
constant at (300 K) 0.01 0.0038 0.031 m2 s~‘
16. Hole diffusion
constant at (300 K) 0.0049 0.0013 0.00115 m2s_|
CHAPTER 10
Table 10.4 Intrinsic carrier density in silicon and germanium calculated as a
function of temperature. Values are quoted/m1
’ ' 7 Silicon Germanium

Temperature (K) exp[(Ec- EF)t2kBT\
exp^-E^T] ni
200 8 x 1013 2.1 x 1011 4x 108 1.5 x 1016
240 3.5 x 1011 6.4 x 1013 1.5 x 107 5.6 x 1017
280 8 x 109 3.5 x 1015 1.5 x 106 7x 1018
320 5x 108 7.3 x 1016 2x 10s 6.1 x 1019
360 5x 107 8.8 x 10'7 6 x 104 2.9 x IO20
400 9x 106 5.1 x 1018 2 x 104 8.5 x IO20
440 2x 106 2.9 x 1019 8x 103 2.9 x IO2’
480 6x 105 1.1 x IO20 4x 103 6.7 x 1021
The electrical conductivity of a semiconductor is very much dependent on punty and unperfeettons
in the lattice. One way of increasing the conductivity of a senuconducung crystal ts to add a controlled
amount of certain impurities. For instance the conductivity of srbeon ts mcreased thousand wires by the
addition of 10 parts per million of boron. The conduction that occurs then rs cahed rmpunry conducnon
and is of paramount importance in the operation of semiconductor device. The rmpunt.es added are
called dopam. When these foreign or impurity atoms are added into the senuconducung structure, the
available quantum states are altered; one or more new energy levels may appear m rhe band structure.
This introduces significant changes in the properties of the semiconductor. Impunues frequendy employed
I* -.SouD State Physics
for Ge and Si are the elements of Group III and V of the periodic table. They are commonly boron,
gallium and indium from Group ID, and phosphorus, arsenic and antimony from Group V.
When small amounts (1 part in 107 approximately) of a pentavalent impurity such as phosphorus
are added during crystal formation, the impurity atoms lock into the crystal lattice since they are not
greatly different in size from a silicon atom, and the crystal is not unduly distorted.
Since at 0 K, the electronic system is in its lowest energy state, all valence electrons will be in
the valence band and all the phosphorus atoms will be unionised. The picture is similar to that for an
intrinsic semiconductor in that the valence band is filled and the conduction band is empty. However,
four of the valence electrons of the pentavalent impurity atom form valence bonds with adjacent silicon
atoms, but the fifth one occupies a state which lies 0.045 eV below the conduction band. Since the
ionisation energy for phosphorus is much smaller than the energy Eg, required to break one of the
valence bonds, the phosphorus atoms will donate these fifth electrons to the conduction band even at
much lower temperature than the valence band will. An impurity of this kind is called a donor, since it
donates conduction electrons without producing holes in the valence band. The donor level represents
the ground state of the fifth electron of the impurity atom. The small gap between the donor level and
the conduction band emphasises that many of the extra electrons are thermally excited into the conduction
band at comparatively low temperatures. Even at room temperature nearly all the donor atoms will have
lost their electrons to the conduction band in this way.
Table 10.5 Ionisation energy from donor and acceptor states in silicon
and germanium. Values are quoted in eV
Silicon (14) Germanium (32)
Doping element Donor '• Acceptor Donor Acceptor

(^-E^ (Ea~Ev) (Ec~Ed)
Phosphorus (15) 0.045 — 0.0120 —
Arsenic (33) 0.049 - 0.056 - 0.0127 —
Antimony (51) 0.039 — 0.0096 —
Boron (5) - 0.045 — 0.0104
Aluminium (13) - 0.057 - 0.067 — 0.0102
Gallium (31) - 0.065 - 0.071 — 0.0108
Indium (49) - 0.16 - 0.0112
The ionised donors remain fixed, positively charged centres incorporated in the lattice, but the
additional electrons are free to move in the conduction band and they substantially increase the
conductivity of the crystal. Thus, if pentavalent impurities exist in an otherwise intrinsic semiconductor,
electrons are added to the conduction band, outnumbering the holes in the valence band. The electrons
then become the majority carriers and the holes the minority carriers. This type of material is now called
an n-type semiconductor.
The electrons are majority carriers and thermally generated holes are the minority carriers in
n-type semiconductors. In an n-type semiconductor if n and p represent respectively the electron and
hole concentrations, it can be shown that np = n( pt= n’, where n. and are the intrinsic values with
n> n. and p < pr
i PMUCB OT SfMCONOOC rr^s 541
I Note that for each impurity atom there is a free electron in the conduction band but there is no
F corresponding positive hole in the valence band. As is a constant at a particular temperature, the
f product np is also a constant at a given temperature. This result can be understood in the following way
? The rate of recombination is proportional to the electron concentration n and also to the hole concentration
p, Le., to the product np. As the rate of recombination is fixed at a given temperature, the product np
must also be so. When the concentration of electrons is increased over the intrinsic value by the addition
of donors, the concentration of holes falls below its intrinsic value, making the product np constant,
equal to ft2.
(*)
Fig. 10.14 (a) Representation of n-type silicon, (b) Energy band diagram at 0 K
Conduction band Conduction band
T>0K T-300K
x\.< Valence band •<>> <Valence band

—■----------- -~--e
(a) (b)
fig. 10.15 (a) Energy bahd diagram of n type icmK undue lur at i 0, At I • 500 K
Instead of adding a pentavalent impurity to an otherwise pure crystal, a trivaleru impurity say
ooron is added and the corresponding problem may now be discussed.
$$3/ Souo State Physics
Conduction band
E,
® ^Hole
( •J ° Electron from
T = 0K
© band
(Si) Ea
E.
Valence band
(«) (*)
Fig. 10.16 (a) Representation of p-type silicon, (b) Energy band diagram at 0 K"
Conduction band Conduction band
Ee------------------------------------------
T>0K T = 300K
Acceptors have accepted

/ electrons from valence band
■C\V' v '■ X ' ■ \ O O O O

.Valefl6e band ' ' Y4
\v.X'.cw>.c,.....
Valence band
...
(a) (b)
Fig. 10.17 (a) Energy band diagram of p-type semiconductor at T > 0, (b> at 100 If
The three valence electrons enter into covalent bonding, but a region of stress exists where the
fourth bond ought to be, and any stray electron in the vicinity can be trapped by the impurity centre
which then becomes negatively charged. The region from which the electron came is positively charged.
In effect the trivalent impurity has injected a hole into the crystal. Such an impurity is called an acceptor
impurity since it accepts electrons into the impurity centre. Silicon or germanium doped in this way ha*
many holes as charge carriers and is therefore termed a p-type semiconductor. In a p-type semiconductor,
the holes are the majority carriers and thermally generated electrons are the minority carriers. LU* *
n-type semiconductor, a p-type semiconductor also satisfies the relation,
pn=pln, = n „2l
In the case of p-type semiconductors also, for each impurity atom, there is a free hole in the
valence band but there is no corresponding generation of free electron in the conduction band. Thos,
p > pi but n < nr
Physics of Semiconductors < 543
Conclusion: In an n-type semiconductor electrons arc in the majority and are called majority
carriers. Some holes exist owing to the lormation of electron-hole pairs at room temperature; these are
called minority carriers. Alternatively, in a p-type semiconductor, holes are the majority carriers and
electrons the minority carriers, The number of charge carriers available determines the resistivity. Most
of the germanium and silicon crystals used in devices has a resistivity of 0.001 fi-m to 0.1 Q-m after
die impurities have been added.
^STATISTICS Of EXfttiN^C SEMICONDUCTORS
The salient feature of integrated circuit technology is the control of the conductivity of silicon that is
achieved by the controlled introduction of electrically active elements into the lattice.
We will now use the following symbols:
Nd = density of donor atoms
Nj = density of ionised donor atoms

Na = density of acceptor atoms
N~ = density of ionised acceptor atoms

n = the general symbol to represent the density of free electrons in the conduction band
p = the general symbol to represent the density of holes in the valence band and
n. = density of intrinsic holes and electrons (density of intrinsic carriers)
CHAPTER 10
We have seen that the introduction of
impurities in pure semiconductors increases the
density of one type or another type of charge
ttt
E.
carriers. But the product of hole and electron
concentrations, n?, is a constant at a given
temperature and for a particular semiconductor.
So the added impurities should not affect this
product. Let pn represent the concentration of
holes in an n-type material; since all the holes
present in the n-type material are as a result of
the break of covalent bonds, we have
n'=Pn
Fig. 10.18 Energy level diagram for n-type
Let Nd and Nj be the concentrations of
donor impurities and ionised donor atoms.
n represents the free electrons density due to impurity atoms.
. 2
Now (n + n )pn = n.
ie., (J>„+W)pn=
Pt +PnNd = nt
pt = nt -PnNd
(10.29)
Pn<ni
This tells that as a result of the doping, the
hole concentration has decreased from its level in
the intrinsic case; the net effect then of doping a
semiconductor with a n-type impurity is to increase
the free electron concentration and to decrease the
hole concentration.
Similarly np represents the concentration of
electrons in ap-type material; since all the electrons
present in the p-type material are as a result of the
break of covalent bonds, we have
P' = nP
Let Na and N~ be the concentrations of

acceptor impurities and ionised acceptor atoms. Let Fig. 10.19 Energy diagram for p-type
p represent the free hole density due to impurity semiconductor
conduction.
Now P~Na
Thus, (p + p')np =
W + np) np = n?
n2p + N~(np) = nt
n2p = nt ~npN;
np<n. (10.30)
This indicates that as a result of doping, the electron concentration has decreased from its level
in the intrinsic case; the net effect of doping a semiconductor with p-type impurity is to increase the free
hole concentration and to decrease the electron concentration.
In an n-type semiconductor, if the donor atoms are ionised, they each contribute a free electron
which then has energy corresponding to some value near the bottom of the conduction band. So some of
the free electron states in the conduction band are filled by the donor contributed electrons.
As far as the probability of the break up of covalent bonds is concerned, in order to become free,
an electron in a bond must now acquire more energy, since all states near the bottom of the conduction
band are already filled. In effect this means that at the room temperature, fewer bonds will be broken
through thermal agitation in the case of n-type semiconductor than in the intrinsic case^Therefore
lowering of the hole concentrulion is justified. Another way of looking at the same mechanism is to say
,h>, the introduction of the donor atoms has changed the Fermi probability occupancy of Ferm, level.
Fermi Level in an Impurity Semiconductor
The general equations for the concentrations of electrons and holes in an extrinsic semiconductor am
given by
n = CT312 exp [(Ef- Ec)]/kgT]
p = CT312 exp [(Ev - Ef)\/kBT\
Therefore in order to have an increase in the electron density and decrease in the hole concentration,
the Fermi energy level must be different from that of the intrinsic one.
For n-type of material
(Ec - Ef) (g/-gy)

CT312 exp > CT3n exp
kBT kBT
i.e., -(Ec-Ef)>-(Ef-EJ
{Ec-Ef)<(Ef-Ev) (1031)
This shows that the Fermi level shifts upward, closer to the conduction band in a n-type
semiconductor. The magnitude of the shift is proportional to the doping level.
Similarly, the Fermi level shifts downward, closer to the valence band in a p-type semiconductor.
General Equation for an Impurity Semiconductor
Let us now consider a semiconductor doped with

Conduction band
both types of impurities. As the temperature
increases, electrons are first excited from the
donor levels to conduction band and from the
valence band to the acceptor levels. The electrons
leaving the donor levels leave behind positively
ionised donor atoms; similarly the electrons
mu:
leaving the valence band make the acceptor
atoms negatively charged and leave behind holes E, N
in the valence band. As the temperature is further E,
o
increased, electrons are able to go over to the
conduction band from the valence band.
Valence band
Let n be the density of electrons in the
conduction band, p be the density of holes in the Rg. 10.20 A semiconductor with
both type of impurities
valence band, N~ be the density of ionised
acceptors and Nd be the density of ionised donors. Let Nd and Na be the densities of donor and acceptor
impurities.
546 Souo State Physics /
For charge neutrality,

(ne+ N;e) = (pe + Nje)
«+ N~ = p + Nd (10.32)
"a
«.=",n«j=1+exp[(£<_E/)/ttrl
Similarly, Nd = JVJ1 - F(Ed)]
1 - F(E,) = 1----------------- !--------------

d l + exp[(E</-Ez)/kBT]
exp[(Erf -Ez)/fcfiT]
1 + exp [(Ed — Ef)[kBT\
_____1______
1 + exp [— (Ej — Ey)/ kBT]
Substituting these values in equation (10.32), one gets

312 ■
2nmekBT Ef~Ec N,
2 exp
h2 kBT J l + exp[(Eo-E/)/jlBT]
• -|3/2
2nmpkBT Nd__________
exp (10.33)
l + exp[- (Ed-Ez)/fcBT]
Ef-Ec
Wcexp +------------- ___________
kBT l + exp[(Ea-Ez)/fcBT]
= lVvexp (10.34)
l + exp[-(E,-Ez)/*BT]
2nm’kBT
h2
Fermi Level in an n-Type Semiconductor at Very Low Temperatures

The simplest model for zi-type semiconductor consists of a conduction band below which there are
donor levels/m3 having energy Ed as shown in Pig. 10.21. This model may be considered at relatively
low temperatures.
PHtsics of Semiconductors D"rZ
At 0 K all the donor levels are filled with

electrons. When the temperature is slightly increased
such that only a small fraction of donors is ionised, we
wpect the Fermi level to lie only half way between
the donor level and the bottom of the conduction band.
Tlie position of Fermi level at various temperatures
can be obtained as follows:
At very low temperatures,
n = NdF(Ec)
Nd
1 + exp «EC - Ef)/kBT] " N“ eXp Êf~EcW
When T is small, [1 - F (Erf)] means an electron Fig. 10.21 Fermi level in an n-type
missing in the Ed state. semiconductor at 0 K
J l + e*p[(Ed-Ef)/kBT]
_ e*p[(Ed-Ef)/kBTl
1 + exp [- (Ef - Ed)/kBT]
~e\p[(Ed-Ef)lkBT\
CHAPTER 10
’Ed-l
Thus !V;=^[l-F(E</)]=N</exp ——
ksz
But n = Nd
Substituting for n and Nd and equating
Ed-Ef
Aêxp = Ndexp
kBT
Ef~ Ec- Ed- Ej

2Ef=Ec + Ed
E,
(1(135)
*■*- at very low temperature Ef lies mid way between Ec and E^

Theory of n-Type Semiconductors
Equation (10.34) is
Nc exp [(Ef-Ec)/kBT] + --------------- - = N exp [(E - E)lk„T\ +------------------------------ -

l + exp[(Ea-£y)/^T]----- - PH v b i \ + ^[{Ef-Ed)lkBT]
If we assume that the temperature is not very high, n » p and hence

p = Nv exp [(£v - E^!kBT] can be neglected; and Na = 0.
Nd
\exp[(E/-Ec)/fcBn =
1 + exp [(Ey — Ed)!kBT]
Le., Nc exp [(Ey- Ec)/^7] + Ncexp [(Ey-Ec + Ef- Ed)/kBT ]-Nd = 0

or exp (2EflkBT) {Nc exp [-{Ec + Ed)/kgT]} + exp (Ef/kBT) {Nc exp (- EJkBT) }-Nd = Q
exp (E Ik J) = ~ Nc eXp(~ Ec/keT) ± e^-2EcM + 4NcNd exp[-(Ec + Ed)/kBT]}112

s 2Ncexp(-Ec/kBT)exp(-Ed/kBT)
The R.H.S. is,
f 4N2N
-JVcexp(-Ec/fcgT)±^ IN2 exp(-2Ec/kBT) + —exp(-2Ec/kBT)exp[(Ec -Ed)/fcsT]
2NC exp(-Ec/kBT)exp(-Ed/kBT)
। 1/2
4AZ
-! + l + ^-KE.-EJ/^T]
or exp (Ef!kBT) = (10.36)
2 exp (—Ed/kB T)
There are two limiting cases. Either the first term under the radical is small or second term is
small.
Cate 1
Second term is small
4\,
i e., exp [(Ec - Ed)lkBT] « 1
This implies small Nd or high T, which is a bad approximation; because we do not know how
small or large they have to be and if either Nd is too small or temperature is too high, the assumption
about the hole suppression becomes untrue. The only argument is:
lWng(l“|W=l+2-'reh,w
X 4\
eip((£f -
2 V
2exp(-£rf i,D
exp (E/kBT) = (NJN) exp (£/k^T) (1037)

Nj = Nc exp [(Ef-E^kBTl (1038)
>
ie.. Ndd= n
In other words all the donor atoms are ionised. This result is dependent on Ef and therefore
affected by whether or not p is suppressed, so there can be a conflict of interest as far as low or high
temperatures are concerned. So long as equation (1037) holds; however, all the impurities will be
ionised.
The is the situation that is of interest in electronic engineering. For silicon and germanium at
room temperature, the impurity concentrations of lO^-lO22 belong to this range. We can confidently
predict that if we dope a crystal with 1022 donors/m'', we have a density of 10“ electrons.
Equation (1037) can be written as
Ef E<
----
kBT
= t—
kBT
+ in >»
Nc
CHAPTBR 10
Nj . Ne I
Ef=Ec + kBT}n-/^=Ec- Vln^- . (1039)
At T = 0, this formula is not valid since we assumed T is large. If T —»again it is not valid
because of the disappearance of hole suppression. The only valid information from equation (10.39) is
Ey drops as T increases. E^> EgH if kBT »(£c - E^. All this means is that intrinsic carriers, which
’re produced in equal concentrations of holes and electrons eventually swamp the impurities and make
•be material essentially intrinsic again if the temperature is high enough.
*»«ration
(0 Temperature is 300 K
00 \= flp/m3
(«0 The donor level lies at 0.02 eV below the conduction band.
Equation (10.39) is.
Nc
Ec-Ef^(kBT)\n
N,
'Wx*2xl0M'
= 0.025 x In
10"
i.e., Ec-E/ = 0.203 eV
But Ec - Ed = 0.02 eV
Now Ed-Ef=(Ec-EJ)-(Ec-Ed)
i.e„ Ed - Ef= 0.203 - 0.02 = 0.18 eV
If Nd and Nd' are the ionised and unionised atoms respectively, then
Nd' = (Nd- Nd) = with n = Nd
Nd
l + exp[(£d - Ef)/kBT]
________ 1022
" 1 +exp (0.18/0.025)
Le., Nd' = 7.5 x 1018
But N^ + Nd'=Nd
n+Nd'=Nd
i-e., n = Nd-Nd'
n = 1022 - 7.5 x 1018= 1022- (7.5 x lO^/lO4
r ■ ■
n=1022 ^1022. (10.39a)
I L io4.
But at 300 K, ni in an intrinsic semiconductor is approximately 1017.
Case 2
exp [{Ec-Ed)/kBT] » 1
"e
This implies large Nd or low T. Here there are no limiting problems as in Case 1, but there may
be some practical difficulties.
Equation (10.36) becomes,
^NdINcf2Êc-Ed)l2kBT]
exp (EflkBT) =
2 exp (~Ed/kBT)
exp (Ef/kBT) = (NJNêxp [(£f + EdV2kBT\ (10.40)

Ec + Ed Nd
+ (1/2) In (10.41)
kBT 2kBT
At T - 0, Ey= (Ec + Edyi Le., Fermi level lies exactly half way between the donor level and
bottom of the conduction band. As T increases, Fermi level drops. Also for a given temperature, the
Penni level shifts upward as the concentration increases. This is shown in Fig. 10.22.
The general equation for density of electron is
n = /Vcexp[(£f-Ecyilgn
n = Ncexp (Eflk^T) exp (-EJk^T) (10.42)
Ef
Substituting the value of exp from equation (10.40) in equation (10.42), one gets
kBT
n = N'WJN,?'1 exp \(Ec + EJTZkJ} exp (~EJkBT)
exp [- (Ec - EJKkJ’l (10.43)
*8- 10.22 The variation of Fermi level with temperature for different concentrations CHAPTER 10
It is evident from equation (10.43), that the density of electrons in the conduction band is
proP°rtional to the square root of the donor concentration. Another important conclusion is that as the
^Perature increases, the Fermi level falls below the donor level and it approaches the centre of the
bidden gap which makes the substance an intrinsic semiconductor. The conductivity of intrinsic
^conductor is smaller than the n-type or p-type of a semiconducting device. Equation (10.43) can be
Written as
lnw=_<£r-_g£)^.(1/2)ln(Nc^
2kBT
A graph is pJoaed with In n and l/T winch gives a straight line with a slope - (E, - EJlk^ ff j
becomes sufficiently high so as to excite electrons from valence hand to reach directly to the conduction
band (intrinsic excitation) then the slope changes to -EJZkg.
Theory of p-Type Semiconductors

If we assume that the temperanrre is not very high.
P»n and hence in equation (1033), the term
can be neglected, and Nd = 0.

Thus equation (1034) becomes
L l+exP[(E.-E/)/EaT|
Thus Nr exp {(Er - E^fkJ}

Kg. 1(L23 Variation of In a with tEmperanre. In the
+ Nrexp {(Et- Ef+Ea-E^kBT}-Na^0
order, 1, 2, 3 curves correspond to samples with
Le., exp (~2Ef/kJ) [Nrexp [(Er+ E^kJ]} increasing donor concentration
+ exp (-Ef/k^T) {Nr exp (EJkJ)} - Na = 0
-N, exp(EJkBT) ± (N; exp (2Er/kBT)+4NaN, exp[(£, + EJ/^T]}*-

or exp (-EjJ kJ) =
ZAêxpK^ + EJ/tgTI
-1 + {1 + (41V«/Arr) exp[(Ea - EJ/^T])1^

Le., exp (—EjJkJ) = (10.44)
2 exp (Ea!kBT)
There are two limiting cases. Either the first term under the radical is small or second term is
small.
Gne1
Second term is small
4N
Le., -^-exp[(Ea-EykB-n«l
Using (1 + x),/2 = 1 + ”, we have
+ {l + ^Na/Nt)exp[(Ea - EJ/kBT]
exp (-EflkBT) =
2exp(EJkBT)
exp (-Ef!kBT) = êxp (-E/ kJ) (10.45)

Na = Nexp [(Ev-Ef)/kBT]
all acceptor atoms are ionised. Equation (10.45) can be written as
Ev , Ng
- -— + In
kBT Nv
N
-Ef=-Ev-kBTln-f-
iy a
■.EÊ^k^h^ (10.46)
At T - 0 K, this formula is not valid since we assumed T is large. If T —> <» , again it is not valid
because of the disappearance of electron suppression. The only valid information from equation (10.45)
is that Ej. moves upward as T increase. Ej E^2 if kBT » (Ea — Ev). All this means that intrinsic
carriers, which are produced in equal concentrations of holes and electrons, eventually swamp the
impurities and make the material essentially intrinsic again if the temperature is high enough.
lllustradon
(0 Temperature is 300 K
00 Na = lO^/m3
CHAPTER 10
(Hi) The acceptor level lies at 0.011 eV above the valence band.
Equation (10.46) is
Ef-Ev=kBT\n^
4.83 x 5.2 x 1024

= 0.025 x In
1021
- =0.25 eV
Now (Ef-Ea) = (Ef- Ev)-(Ea-Ev)
Ef- E = 0.25 - 0.011 = 0.239 eV.
and Na' are ionised and unionised acceptor atoms respectively, then
Na'=(Na-N-a)
Na' = No [1- F(Ea)]

1 - F(EJ = 1----------------------------------
l + exp[(Ea-Ez)/fcB7']
exp[(Ea - Ef)/kBT]
l + exp[(Ea - Ef)!kBT\
___________ 1__________ =_________ 1________

~ l + exp[(Ez-Ea)/JtBT] " 1 +exp (0.239/0.025)
= 7 x IO"5
Thus, Na' =Na x 7 x 10~5 = 1021 x 7 x IO-5
= 7x 1016
But Na’ = Na-N-a
or N~ =Na - Na‘ with N~ =p

i.e., p = Na- Na' = 1022-7 x IO16 = lO2^ 1 - (7/106)]
Le., p = 1022
n= 1022[l-^-L1022
in4
But at 300 K, n. in an intrinsic semiconductor IO17.
Case 2
4^-exp[(Ea-E„)/^7]»l
This implies large Na or low T. Equation (10.44) can be written as
, r „ ~ 2(Na/Nv^2 exp [(Ea - Ev)/2kB T]

exp (-EJkrT) =------------ - ----------------------—-—
f B 2exp(Ea/ifln
i.e., exp (-Ef!kBT) = exp [-(Efl + E)l2kBT\ (10.47)
Ej__ (Ea+Ev)
or -k.T- 2k,T
(E„ 4- E,) p,T] N„

LvJV
Ea + Ev r^r-
In^- (10.47a)
Li: 2
■.
.2
. g
Na
= Ej= (Ea + Ev)/2 i.e., Fermi level lies exactly half way between the acceptor level and
of the valence band. As T increases, Fermi level shifts upward. Also for a given temperature the
t0P . |eve| shifts downward as the concentration increases. This is shown in Fig. 10.24. The general
Zon for density of holes is
p = Nyexp [(Ev-Ef)/kBT]
Substituting the value of exp (~Ef/ kBT) from equation (10.47), one gets,
P = «W“ “P (- + E,Y2kBT] exp (EJk,T>) N,
(10.48)
It is evident from this equation that the

density of holes in the valence band is proportional
to the square root of the acceptor concentration.
Another important conclusion is that as the
temperature increases, the Fermi level moves
upward, crosses the acceptor level and approaches
the centre of the forbidden gap which makes the
substance an intrinsic semiconductor.
Illustration
(i) Sample used, n-type germanium.
(ii) Donor impurities used, 1022 germanium Fig. 10.24 The variation of Fermi level with
atoms/m3. temperature for different concentration
(iii) Temperature, 300 K.

(iv) Forbidden energy gap, Eg = 0.67 eV.
Number of electrons reaching the conduction band from donor level is
n=N+=Nd-Nd
n = Nd-NJ(Ed)
But n is also equal to CT3'2 exp [(£y- Ec)/kBT]
exp [(£z- Ec)/kBT] = Vd[l - F(Ed)]
4.83 x 1021 x 3003/2 x exp [-(£c - Ef)/kBT] = 1022 1 - __________ 1__________ = 1022
l + exp[(£d-£z)/fcBrj
exp [(£c - Ef)/kBT\ = 24 91602210 - = 24.96 x 102

E,. - Ef
- In (2496)
k„T
Ec - Ef = 0.025 x In (24.96 x 102)

Ec-Ef = 0.196 eV
Now the number of electrons coming from the valence band to the conduction band is
«' = Pn = (-UkBT)
= 24.96 x 1024 exp (- 0.474/0.025)
i-e., n' = pn= 1.5 x 1017 Ec ----------- ,-----------------------------------
Hence n p = 1022 x 1.5 x 1017
" 0.196 eV
= 1.5 x 1039 (A)
with n = N. = 1022 Ef -----------*---------- ------------------------
a
The density of intrinsic charge carriers if it
is an intrinsic semiconductor wiU be L = 0.67 - 0.196 = 0.474 eV
n^Wexpf-E^T)
= 24.96 x 1024exp (- 0.67/0.05)
n,. = 3.78 x 1019 Ev ---------------------- ------------------------
Fig. 10.2S Impurity and intrinsic carriers in an n-type
= 1.43 x 1039 (B) semiconductor
Equations (4) and (B) are the same.
Variation of Carrier Concentration with Temperature

The temperature variation of n and p for an n-type
semiconductor is shown in Fig. 10.26. There are three
different regions corresponding to three different
ranges of temperatures. At very low temperatures,
very near absolute zero, the Fermi level is in between
the donor level and the lower edge of the conduction
band and the donor ionisation is about to start. As
the temperature is raised the donor atoms get ionised
and the electrons go to the conduction band crossing
the small impurity gap quite easily. The electron
concentration in the conduction band steadily
increases, and this region is called the impurity range.
The Fermi level moves towards the donor level. At
Fig. 10.26 Variation of the electron and bole
about room temperature all the donor atoms are
concentration in an n-type semiconductor with
ionised and so the concentration of the electrons in
the reciprocal of the absolute temperature
the conduction band remains constant over a certain
temperature range. This region is called the exhaustion range and in this range Fermi level crosses the
•/ Physics
donor level. Hence the conductivity must be essentially constant over this region. In fact there will be a
slight decrease in conductivity with increasing temperature in this region, because of the decrease in
electron mobility.
As the temperature is still further raised, the thermal ionisation of the atoms in the valence band
starts and electrons cross the forbidden gap thereby increasing the electron concentration in the conduction
band considerably. As the valence band is an inexhaustible source of electrons unlike the donor level,
more and more of the electrons from the valence band reach the conduction band and completely out
number the donor electrons.
The Fermi level keeps on its downward trend until it comes to the middle of the forbidden gap.
The material practically becomes intrinsic at this temperature. The hole concentration follows the dotted
curve as the temperature increases and over the intrinsic range both the hole and electron concentration
curves overlap, since they become equal in number. In practical devices it is necessary to operate either
in the impurity range or in the exhaustion range to take full advantage of the properties introduced by
the impurities. Consequently the temperature at which the intrinsic conductivity becomes dominant,
determines the highest possible operating temperature. For Ge (Eg = 0.7 eV), it is about 100°C and for
Si (Eg = 1.1 eV), it is about 200°C. The flat region is observable only if Nd is small enough. If Nd is large
the low temperature impurity region passes to intrinsic region without passing the flat region. Thus we
find the lower donor densities have larger flat region.
Conductivity of Extrinsic Semiconductors

The conductivity of semiconductors is more complicated than that of metals; besides the electron
scattering processes being temperature dependent as in a metal, the actual number of current carriers n
CHAPTER 10
and their energy distribution also vary with temperature.
We know that,
p = 1/g = 1/nep
In p = In------ In n (10.49)
JU
The mobility of charge carriers is essentially a measure of the ease with which the carriers can
”*°ve under the influence of an electric field. It is proportional to the inverse of the scattering probability,
ne mobility is assumed to be independent of temperature in this equation. This is not strictly true.
0 ihty is determined by scattering of the current carrying particles. One mechanism by which scattering
oûrs is due to the vibration of the lattice atoms. This type of scattering is called lattice scattering,
pother way in which charges are deflected or scattered is by interaction with impurity atoms. This is
impurity scattering. Both impurity and lattice scattering lower the mobility of charge carriers and
Cnce cause the material to have higher resistivity if scattering is absent.
tn a metal, the density of current carriers is the density of electrons. This number is substantially
v and consequently any variation of resistivity in a metal with temperature is due to mobility
of J1100 In m°St metals»1116 main tyP6 of scattering is ,attice scattering which increases with increase
tem mperature and hence mobility decreases and hence resistivity of a metal increases with increasing
A semiconductor is characterised by the activation of current carriers, either intrinsically or from
impurities, or both. This activation has been seen to be an exponential function of temperature. No
doubt lattice scattering reduces the mobility of charge carriers in a semiconductor as the temperature
increases, but its effect is not so strong compared with the exponential addition of new charge carriers
to the conduction process with increasing temperature. Consequently, even though the mobility decreases
the increase of charge density results in an overall decrease of resistivity with temperature.
The general expression for resistivity is.
~ 1 ~
p = — :■
;: nep n
In a metal, n is constant, and p increases with
temperature because of mobility variation. In a
semiconductor, however, n increases with
temperature faster than |1 decreases, hence p
decreases with increasing temperature.
The graph (Fig. 10.27) shows qualitatively
the temperature dependence of the conductivity a
of a semiconducting crystal containing a moderate
number of impurity atoms. In the region A, the
impurity atoms alone are ionised and hence o is low.
As the temperature is increasing, the number of
atoms ionised will be increasing and a increases.
The slow increase in o is due to large impurity
scattering and small amount of carriers, usually the Fig. 10.27 Variation of conductivity in an n-type
impurities are completely ionised at 200 K. The slope semiconductor with the reciprocal of the absolute
temperature
1
of In G vs — in the region A is related to the
ionisation energy of the impurity.
In the region B, there is no increase in o due to impurity conduction and the temperature is not
high enough to allow very many atoms to jump directly from the valence band to the conduction band;
here a remains relatively constant. In fact o shows a slight downward trend in this region; since the
mobility decreases slightly because of the predominance of lattice scattering when all the impurities are
ionised. In the region C, the temperature is high enough to allow carriers arising from the valence band
to the conduction band generation to dominate and the semiconductor behaves as an intrinsic material.
The slope of the curve in the region C can be related to the energy gap Eg. The onset of C in Ge is 150°C,
while for Si it is about 250°C.
When no external field is applied to a semiconductor each carrier (electron or hole) moves in a random
way owing to its thermal energy. The frequent change in direction of the pqth of the carrier occurs due
to scattering by the vibrations of the lattice atoms and by the coulomb field of the ionised donor and
acceptor atoms. Application of an external field superimposes on the random motion of the earners a
drift velocity. In the steady state, the rate of momentum gained from the field equals the rate of loss of
n-type semiconductor and (,7) nX^X"™' ‘ ‘°
0 Current Flow in a Biased w-Type Semiconductor

An n-type semiconductor has (z) electrons as majority carriers, (ii) an (almost) equal number of immobile
positive ions, and (iii) holes as minority earners. Assume that the hole contribution to current is negligible.
Consider an n-type semiconductor placed between a pair of electrodes across which a voltage is
applied. Due to the field produced by the voltage there will be a steady drift of the free electrons
towards the positive electrode. The electrons reaching the positive terminal disappear at the metal of the
electrode and the immobile positive ions in the vicinity of the negative electrode remain unneutralised
due to the drift of the free electrons. These ions immediately attract electrons. Thus a continuous flow of
electrons from one terminal of the voltage source to the other terminal via the semiconductor takes
place. The rate of flow of electrons from the negative electrode to the semiconductor and from the
semiconductor to the positive electrode is determined by the applied voltage and the conductivity of the
semiconductor which accounts for the current flow.
Fig. 10.28 Biased n-type semiconductor 1i

IAPTER
Current Flow in a Biased p-Type Semiconductor

A P'type semiconductor has (i) holes as majority carriers, (ii) an (almost) equal number of immobile
■tegative ions, and (iii) electrons as minority carriers. In this case the electron current is considered
Eligible.
When a p-type semiconductor is placed between a pair of electrodes, across which a voltage is
applied, there will be a constant drift of the holes towards the negative electrode. On reaching the
negative electrode they combine with the electrons coming out of the metal of the negative electrode
^d disappear. At the same time, an equal number of holes is generated near the positive electrode. This
« because as the holes drift away from the positive electrode they leave behind the unneutralised immobile
negative charges. These charges and the positive elects give rise to an electric field which causes the
•onising electrons to leave the acceptor atoms and come to the positive electrode where they are lost.
_____
By losing an electron in the above process the acceptor atom attempts to steal an electron from an
adjacent bond A hole is thus formed. The generation of holes takes place at the rule equal to the rate nt
which they disappear at the negative electrode. This rate is again determined by the magnitude of the
applied voltage and the conductivity of the semiconductor. Note that the current inside the /Mypc
semiconductor is due to the motion of the holes whereas in the external circuit it is due to the motion of
electrons.
XL GENERATION AND BECOMRIN^nkl1' '?' ■ ......... .....
At a fixed level of excitation, electron-hole pairs are continually being created or generated as the
supplied energy enables some electrons having valence band levels of energy to gain sufficient energy
to break free from their parent nuclei and to take part in conduction through the crystal. The excitation
of electrons from the valence band to the conduction band leaves holes in the valence band which also
contribute to conduction. At the same time the free carriers are being generated, the reverse process of
recombination is also taking place whereby free electrons and holes meet, annihilating each other. In
physical terms, recombination is the process whereby a free electron travelling through the crystal is
captured by an atom having an incomplete bonding structure. The captured electron completes the
structure and is then no longer free to take part in conduction.
The direct transition of an electron from the conduction band to the valence band is unlikely,
however, since a free electron and a hole will only recombine if momentum is conserved in the system,
that is, if the electron and the hole initially have nearly equal and opposite momenta. The probability for
this in germanium and silicon is low, and another recombination mechanism must be invoked.
The majority of recombination events are found to take place at the site of an impurity atom or a
lattice defect in the crystal. Such a location acts as a trap or recombinations centre and is, in effect, a
third body which can satisfy the momentum requirements in the electron-hole collision. Figure 10.30
shows as trap which is located approximately in the centre of the forbidden gap. The electron moves
from the conduction band into the trap level and remains there for a short time before passing down into
the valence bond. Once an electron is in the trap it is not free to move and does not contribute to the
conductivity.
Electron
Conduction band
-- Recombination centre
° Valence band
Hole
(«) (b) (c)
Fig. 10.30 (a) Generation of an electron-hole pair (fe) Direct recombination of an

electron and a hole (c) Recombination through a recombination centre
Non-uniformity also occurs at an interface between two crystals and at the surface due to the
change or termination of the regular array of atoms. Such non-uniformities upset the periodic nature of
the electric field in the crystal causing regions which tend to capture or trap free carriers. In the energy
band model these disturbances in the electric field create levels in the energy gap range which have a
high probability of capturing an electron, a hole or both types of carriers (Fig. 10.31).
Fig. 10.31 Band model representation of generation and recombination in a semiconductor
Such levels corresponding to energies approaching conduction band energies are termed electron
traps as they have a high probability of capturing free electrons, while those having energies near
valence band levels are called hole traps, having a high probability of capturing a hole. During its life as
_ ____________________________________________ _
a free carrier, an electron or hole is trapped by such levels many times, being freed to the adjacent band
by energy absorption. While trapped, electrons and holes cannot take part in conduction and may be
considered as being out of circulation for a brief time. Trapping levels corresponding to energies near
the centre of the energy gap have a high probability of capturing both an electron and hole resulting in
annihilation (recombination) of the trapped carriers; such traps are termed recombination centres. The
average time that an electron or hole remains free after generation is known as its lifetime (t).
The discussion of homogeneous semi
conductors has been confined to thermal equilibrium
conditions. However, semiconductor devices, in
general, operate under non-equilibrium conditions.
For example, a bar of n-type germanium acting as a
photodetecting device is not in equilibrium in the
presence of light. When the bar is illuminated, excess
charge earners (above the equilibrium numbers) are
produced in the material and the electrical
conductivity of the bar increases. This is illustrated
in Fig. 10.32.
Let a bar of semiconductor be illuminated
Fig. .10.32 Uniform illumination of a semiconducting
uniformly over one face. The illumination creates bar connected in a current-measuring circuit
hole-electron pairs, and if the sample is say,
predominantly n-type, an excess hole concentration p is built up by the light. These holes and the equal
density of excess electrons present will increase the current through the bar. Another way to express this
is to say that the excess carriers modulate the conductivity of the material.
Th'is process is usually referred to as minority carrier hole injection, since this positively charged
earner is greatly outnumbered by the electrons or mojority carriers present in thermal equilibrium. In
transistors minority carrier introduction or injection takes place by the supply of electrical energy instead
of light energy, via a p-n junction. Nevertheless, this type of carrier injection is basically the same and
charge neutrality is normally maintained (/.£., for every hole injected an electron must be introduced).
Minority Carrier Lifetime

Under thermal equilibrium conditions the product of electrons and holes in any semiconductor must be
a constant at any temperature. The value of this constant will depend on semiconductor parameters such
as the energy gap. When carriers are injected via the energy of an electric field or light, equilibrium is
disturbed and carriers in excess of the equilibrium np product are introduced. For reasons of electrical
neutrality, the numbers of electrons and holes so introduced must be equal; we shall also assume that
their number is small compared to the equilibrium number so that quasi-thermal equilibrium occurs.
This possibility of introducing excess carriers, yet maintaining electrical neutrality, distinguishes
semiconductors from metals and results from the two-carrier nature of the semiconductor. This accounts
for the fact that transistors utilising two electric erriers (bipolar transistors) are fabricated from
semiconductor materials and not metals.
our interest now lies in the discussion about the lifetime of the minority curriers in an extrinsic
^conductor. For example the life of positive hole in an n-type material may be discussed. It should
ûnderstood that in therm equilibrium generation and recombination of carriers are constantly taking
place, but on the average or every electron excited into the conduction band one recombines or drops
back into the valence band. Let the generation rate be gT carriers /m '-sec. and the tvcombination rate
be/?. For a particular semiconductor (in the absence of the field), the thermal generation rate gr is a
function of temperature alone (the value of gT is an empirical quantity of the material and varies with
impurity density, imperfection in the crystal, deformation, etc.). In other words, it is not a unique property
of say germanium, but is a unique quantity for a particular sample of germanium). The recombination
rate/? depends upon how frequently an electron in the conduction band encounters a vacant slate (hole)
in the valence band, i.e., the rate is proportional to the concentration of holes and electrons. The more
holes there are, the sooner they will encounter an electron.
Thus, R<*np
i£ j R = r np (10.50)
where r is the constant of proportionality called recombination coefficient. The net rate of change of
hole concentration in n-type semiconductors without minority carrier injection is
dp (10.51)
^-Sr-rnp
Under equilibrium conditions is zero, and the rate of formation of electron-hole pairs is i
equal to the rate of recombination. ®

Thus, gT=rnoPo (10.52) g '|j
where n0 and p() refers to the equilibrium concentration of electrons and holes respectively. If now the £
crystal is slightly disturbed from equilibrium by a few excess holes Ap and an equal number of electrons
An, the net rate of excess hole-carrier recombination (or loss) at any instant is given by O
J(Ap) ij
~ dT = f("o+ A”)(P° + Ap) (10>53)

This assumes r is unchanged since the density of excess carriers introduced is small. Thus equation
(10.53) becomes
- = r [nopQ + n^ + Anp0 + AnAp - nQp0]
By neglecting (An) (Ap)

= r [n0Ap + PoAn]
d(Ap)
—- =-rAp(n0 + PQ) (10.54)
at
The quantity l/r(n0 + p0) is usually defined as the minority carrier lifetime T, and equation
UO-54) is then written as
d(fy) _ Ap _ (P~PO)
as Ap = (p-p0) (10.54a)
dt r T
d(Ap) dt
t
Integrating both sides, we get
In Ap = - -+ In C
T
Ap = Ce~^
when r = 0, Ap = (Ap\, = C
Thus. (Ap) = (Ap)0 (e^ (10.55)
where (Ap^ is the initially injected number of holes at t = 0 and Ap is the number of holes left at the
instant r. It is apparent now that the excess of holes injected decay exponentially with time, i.e., if the
initial hole concentration is (Ap)0, the fraction of holes left after time t is (Ziplo^1- If a time t = t hat
elapsed since concentration (Ap)0 existed, the concentration of holes will be (Me)th(Ap)0 or (Ap)f/2.1]9
= 37% of (Ap)0. We say that t is the time necessary for the hole concentration to decay (Me)th its initial
value. Thus the carrier lifetime is defined as the time in which the excess carriers fall to Me of its initial
value or 37% its initial value.
(a) 0)
Fig. 10.33 (a) The decay of excess hole concentration with time
(/>) Logarithm of the concentration vs time
Measurement of lifetime is of importance because it indicates how long minority carriers can
exist free in a semiconductor. It is found that the lifetime in a very pure semiconductor with no lamce
defect is comparatively long, as 2000 to 3000 p. sec. The presence of structural defects, unwanted
impurities such as copper, and even the crystal surface itself enhance recombination.
p'or example, the rate of recombination at a specially treated surface may be one-tenth that at a
x>thly elehed surlacc or one-fiftieth that al a sandblasted surface. On the other hand, the presence in
,fl\minnium crystal of a density ol as little as IO17 or 10IH copper atoms per cubic metre can decrease
îZme^KXXHolnsorta.
A distinction is made between bulk lifetime, i.e., the lifetime as it might be measured in an
infinite crystal, and surface lifetime due to the presence of condition of the sample surfaces. In an actual
crystal.
Ap = (Ap)0 exp (~t/xB) exp (-//?,) = (Ap)0 (exp H(I/T B + 1/t,)]}
Ap = (Ap)0^
i.e.,
where xB= bulk lifetime
Ts = surface lifetime
x = observed lifetime
Obviously
1 _ _L _L (10.56)
T Xg Xg
In making lifetime measurements on a sample, the bulk lifetime xB is measured by observing x
for a variety of surface treatments or dimensional changes so that xs is varied. After having a curve for
various values is obtained, xg can be found by extrapolating the curve to zero xs.
CHAPTER 10
WMOBitnrrcpeciiaiesiT e^weia" ~
The conductivity of a solid has been previously expressed as c - nep, where the mobility p. is the
average velocity acquired by a carrier in a unit electric field. This concept can be examined more
closely. First of all the electrons and holes in a semiconductor are in a rapid random motion because of
their thermal energies. It is the additional velocity introduced by an external electric field which constitutes
the electric current observed. The net velocity due to the field is called drift velocity. Secondly an
electron in a perfect crystal experiences an acceleration I----- I in a field E which implies that its drift
velocity continuously increases. This connot be the case because according to Ohm s law, o = j/E
(nevd A
I constant. This means that the average velocity vd must be a constant. Hence it is necessary to
assume that the electron loses energy in collisions with the crystal structure so that it has a' constant
average velocity or mobility, p Suppose that the average time between such collisions is T and
that at each collision the electron loses all the energy it gained from the field subsequent to the previous
Elision. For simplicity let us assume that t is independent of electron velocity. Then the number of
collisions per second is 1/t and the rate of change of velocity is ““J- Under steady state conditions this
rate of change must be equal to the acceleration due to the field, or eElm = vd lx - ftEtx. Therefore,
|1 = exhn. The parameter T is called relaxation time.
In a perfect crystal, the conduction electrons move in an ideally triply periodic potential fjeld. In
order to explain the origin of collisions it becomes necessary to postulate that deviations from ideally
perfect lattice occur in crystals. There are several kinds of imperfections including substitutional and
interstitial atoms, missing atoms or vacancies, dislocations etc. In addition to these built-in defects the
thermal vibrations of atoms at temperatures above absolute zero produce instantaneous displacements
which also disrupt the ideal periodicity in a crystal. All these imperfections disrupt the periodicity of
atomic array and cause the electrons to be scattered. The two important causes of scattering in
semiconductors are (i) atomic vibrations (phonons) (ii) ionised impurity atoms. The effect that these
imperfections have on the mobilities of electrons or holes can be determined most easily by calculating
the corresponding relaxation time. In performing such calculations it is necessary to consider the energy
values that the electrons can have and it is convenient to average the relaxation times over the entire
energy distribution. An actual calculation of the mobility due to scattering by phonons is the T3'2
temperature dependence. Similarly the mobility due to ionised impurities scattering p.7 is T*2 temperature
dependence. The actual mobility is given by
1 __L 1
U ~ Ik + lb
1 a _
(10.57)
Drift and Diffusion

The current that flows across a semiconducting crystal has two components:
1. Drift current 2. Diffusion current.
1. Drift Current
In a perfect (defect free) crystal the periodic electric field enables electrons and holes to move freely as
if in a vacuum. In this case the wave model of the electron is more appropriate than the partide model.
The defects in real crystals cause the periodic electric field to be disturbed and, for T > 0 K, rtwrmal
energy can be considered to cause the lattice ions to vibrate. These imperfections cause scattering of the
free carriers resulting in finite conductivity.
By considering the free electrons in a semiconductor to be analogous to the molecules in a low
pressure gas, the kinetic energy of a free electron due to its thermal energy is 15 from winch its
mean (thermal) velocity can be estimated to be of the order of 10s m/s. In the absence of any externally
applied electric field, the random motion of free carriers within a crystal does not result in a net transfer
of charge since charge movement in any direction is balanced by charge movement in any other direction.
When a voltage is applied across the material, each carrier experiences a force attracting it to one end of
the material, electrons being attracted to the positive potential due to their negative charge and holes to
the negative potential This net movement in charge carriers, termed drift is superimposed on the random
thermal movement and results in current flow through the crystal. The electric current density is green by
J - nevd
, the drift velocity. Since the usual statement of Ohm’s law is J = aF, where G is the electrical
tfhere »s crystal, this conductivity is
cOtiductlVlty (s = JIE= (nevJE)
o ;= (nelE) (eElim) with vd= (eElim)

i.e-> o - (ne2i/m) (10.58)
x is the relaxation time between collisions

whet®
vdocE
Again
vd=pE
h re the parameter p is the mobility of charge carriers within the crystal
Thus, J = nevd - ne\lE

O = JIE - ne\x
or
or in terms of resistivity p (Q-m),
p = I/O = (l/nep) (10.59)
If the material is a semiconductor, the current flow would be due to electron and hole movement
Correspondingly the current densities due to electron drift and hole drift are:
Jn (drift) = n\LneE ■ — (10.60)
Jp(drift) = p^peE ,/<<'.’" (1°'61)
respectively. Although these charge movements areinopposite directions, the electron movement is
7
negative charge movement while the hole component is positive charge movement and so the total drift
CHAPTER 10
cunent is the sum of the two components, thus
- J (drift) = Jn (drift) + Jp (drift)
i.e., 1 J (drift) = neftnE + pe \lpE (10.62)
Comparison with J = aE shows that the conductivity of a semiconductor is given by
o = ne[Ln+ pe[Lp
For an intrinsic semiconductor, n = p = nf and so the intrinsic conductivity is- given by
’ (10.63)
For extrinsic semiconductors with typical dopant levels, the minority carrier component is
negligible at normal operating temperatures.
Conductivity is a function of temperature. If an increase of temperature causes an increase in
free charge, the conductivity of the material is increased. However, temperature increase also causes
uicreased vibration of the lattice ions which causes increased scattering, reduced carrier mobility and
hence reduced conductivity. The variation of conductivity of a material with temperature depends on
which of these effects dominates. For a conductor there is not a significant increase in free charge with
^crease of temperature and therefore the increased scattering causes the conductivity of a conductor to
. as the temperature increases. Alternatively, the free carrier density of an intrinsic semiconductor
tncreases rapidly with temperature resulting in increased conductivity. A conductor is said to have a
Positive temperature coefficient resistance since its resistance increases with temperature while an intrinsic
emiconductor has a negative coefficient.
___________________
At normal operating temperatures an extrinsic semiconductor has properties similar to those of a
conductor. An increase of temperature does not significantly change the free earner density since most
of the dopant atoms are already ionised; thus increased scattering causes conductivity to fall. However,
as the transition temperature is approached, the generation of electron-hole pairs does cause the free
carrier density to increase significantly and the material takes on intrinsic properties. Thus an extrinsic
semiconductor has a positive temperature coefficient of resistance at normal temperatures changing to
a negative coefficient near the transition temperature.
2. Diffusion Current
In addition to the drift motion of the carriers under the influence of an electric field the carriers in
semiconductors may move by diffusion. Diffusion occurs whenever there is a non-uniform concentration
of charge carriers at some places of the crystal.
The free electron density in a homogeneous semiconductor in the absence of an applied electric
field is uniform at equilibrium due to a combination of the random thermal motion of the electrons and
the repulsive force between them caused by their like charge. If excess carriers are introduced locally
within such a semiconductor, either by causing carrier generation by heating or incident radiation or by
injecting carriers into the material via a surface contact, a non-uniform distribution is created. Ignoring
the process of recombination which is an additional phenomenon, the excess carriers move from the
region of higher density to regions of lower density tending to produce a uniform distribution. The
transport mechanism is called diffusion and it take place in addition to drift caused by an applied electric
field.
Let us suppose that the concentration An of electrons varies with distance x in the semiconductor,
the concentration of gradient being
3 (An)
8x
Partial derivatives are used here as An is a function of both time and distance. Fick’s law states
that the rate at which earners diffuse is proportional to the density gradient and the movement is in the
direction of negative gradient, the rate of flow of electrons is proportional to
3 (An)
3x
from which the rate of flow across unit area is got, equal to
3 (An)
■D-ar
where Dn is the diffusion coefficient for electrons in the semiconductor concerned. Partial derivatives
are used in equation (10.63a) as An is a function of both time* and distance. This flow constitutes an
electron diffusion current density and since conventional current is the rate of positive charge
(diffusion) = - (e) (rate of flow across unit area)
■ (10.64)
If an excess hole concentration is created in the same region, hole diffusion takes place in the
same direction at a rate per unit area
n 3(M
" p dx
resulting in a hole diffusion current density
~ ■" •' '■■■H lit I !■<>'
Jp (diffusion) = + (e) (rate of flow across unit area)
(10.65)
dx
. D is the hole diffusion coefficient.

If there is an electric field E and a concentration gradient in the x-direction, the total hole-current
is the sum of the drift current (pe)np and the diffusing cunent given by equation (10.65).
Thus, Jp = Jp + (diffusion)
r
Jr = pe^p -eDp-^~ (10.66)
Similarly for the electrons, the total current density
d(An)
Jn = ne\t
• n + eDn (10.67)
3x
Einstein Relation
Although the carrier transport mechanisms drift and diffusion have been considered independently,
they are both dependent on the scattering processes responsible for hindering the flow of carriers in a
semiconductor. Einstein showed that the parameters describing the two processes, mobility p and diffusion
coefficient D respectively, are directly related. At equilibrium with no applied electric field, the free
electron distribution is uniform and there is no net current flow. Any tendency to disturb the state of g ' |
equilibrium which would lead to a diffusion current, creates an internal electric field and a drift current
balancing the diffusion component. Under equilibrium conditions, therefore, the drift and diffusion AC
currents due to an excess density of electrons, and from equations (10.60) and (10.63a) H
d(An)
ÊêDn^- (10.67a) §
The force F on excess carriers restoring equilibrium is given by the product of excess charge and
electnc field, thus from equation (10.67a).
Soud State Physics • '1
F = (An)eE = [eDn I ] —— (10.68)

This force also depends on the thermal energy of the excess carriers. By making an analogy
between the excess carriers in a semiconductor and gas molecules in a low pressure gas, the force
corresponding to the pressure gradient is equal to (kBT) — (An), as from the kinetic theory gases, gas
pressure is equal to nkBT where n is the molecular concentration. Comparing this force term with
equation (10.68) gives
= e£>n/pn
Dn= \lnkBT/e (10.69)
The relation between diffusion coefficient and mobility of a charge carrier is termed Einstein's
relation:
Now a. _ kBT
e
DP kBT
and
M-p e
Dn Un
DP
At T - 300 K, kBT/e = 26 mV. Using this relation the electron and hole diffusion coefficients for
various semiconductors can be calculated from the mobility.
The values for silicon are Dn = 3.6 x 10-3 m2/s and Dp = 1.3 x 10-3 m2/s while those for germanium
are Dn = 0.01m2/s and Dp = 5 x 10-3 m2/s.
The Continuity Equations

The behaviour of excess carriers in a semiconductor is due to the combined effects of generation,
recombination, drift and diffusion. The mathematical relations combining these effects are termed the
electron and hole continuity equations which can be derived by considering the combined time rate of
change of the excess carrier density within an elemental volume (Fig. 10.35). The number of excess
electrons in such a volume is An (ASx) and the rate of increase of this number is
9(An)
x (A 8x)
This rate of change is due to three effects: The net rate of electron recombination and movement
due to drift and diffusion.
Net Recombination Rate

Equation (10.54o) is a first order representation of the net rate of increase of the number of excess of
electrons in the volume due to the difference between the rates of recombination and generation, thus
(10.71)
Fig. 10.35 Excess electron density
Rate of Increase due to Drift

Due to the applied electric field E, electrons drift into the volume at plane 2 and out at plane
CHAPTER 10
Plane 1 Plane 2
/
E=-
E —
dx
Electron drift
Fig. 10.36 Electron drift in elemental volume due to an applied field
The excess electron density at plane 1 is An and so’ ^1„) where A is the
electron drift is An (eE^) and the current leaving the ... + §{An) so current
cross-sectional area of the element. At plane 2 the e^C increêof±enumber of excess electrons
entering the volume is [An + 5(An)] (e E Ap.n). The ne
in the volume due to drift is thus
[An 4- 5(An)] A - (An41„ E)A =

e
d(An)
but &r
Therefore (10.72)
Sr ... dx
Rate of Increase due to Diffusion

The change of excess electron gradient across the element causes a net increase of electrons in the
volume since the rate of diffusion into the volume at plane 2 is greater than the rate of diffusion out of
the volume at plane 1. Equation (10.63a) relates the rate of diffusion to the excess electron gradient and,
as diffusion is in the negative x-direction in this case, the respective rates of diffusion into and out of the
volume are
d(An) । d fd(An) &
dx dx v dx
d(An)
and
dx
The net rate of increase of electrons in the volume is therefore
D d F^)]
n----
dx L dx
d(An) d2(An)
thus, (10.73)
di diffusion
1 Electron gradient
Excess electron _.5(An) d ra(An)lST
density distribution dx dx L dx J
in vicinity of
elemental volume
5 (An)
Electron gradient
d (An) x x + 5x
dx
Electron diffusion
Fig. 10.37 Electron diffusion in elemental volume due to a non-uniform excess density distribution
The total rate of increase of excess electrons in unit volume is given by the sum of the increases
given by equations (10.71), (10.72) and (10.73) resulting in
d(An) An rd(An)1 [d2 (An)
” ---- + K# (10.74)
"dT T " dx. - . L a*2 d
which is the continuity equation for excess electrons. For excess holes the corresponding equation is
d(Ap) Ap d2(Ap) (10.75)
’b.£L dx . dx2
Phywcs of Semiconduct^^7|
The sign difference between equations (10.74) and (10.75) is due to the different directions of
jrift of electrons and holes in an applied field.
These equations describe the general behaviour of excess minority electrons and holes in a
semiconductor and are the basis of analytical work on device performance at a physical level. The
equations shown are strictly valid only for low levels of minority carrier injection, that is, An « np or
bp « Apn, as no account has been taken of the effect of the excess carrier densities on the internal
electric field.
The combined current density due to excess electron drift and diffusion is
d(An)
J n= (An) e|i E + eDn (10.75a)
x dx
dJn d(An) d2(An)
i.e., (10.76)
3x n dx n dx
d(An) d2(An)
or (10.77)
dx dx2
Substituting this in equation (10.74), one gets
(10.78)
dr dx
The corresponding equation for holes is
(10.79)
CHAPTER 10
■ ■ & ’ ' TO
Diffusion Length
If excess carriers are injected into a semiconductor they diffuse away from the point of injection. As
they diffuse they recombine at a rate described by their lifetime and within a certain distance the excess
carrier density falls to zero. As some semiconductor devices rely on the injection of minority carriers
into a semiconductor and their subsequent collection, the decay of the excess carrier density with distance
is of particular importance. This decay is described in terms of the carrier diffusion length for the
semiconductor. The injected electrons diffuse in the x-direction recombining as they do so, the density
at the injecting contact (An)0 being maintained by the carrier source. The resultant electron distribution
is given by the solution An (x, t) of the continuity equation for excess electrons (equation 10.74). At
steady-state a continuous flow is established and the time rate of change of the electron density in the
semiconductor [d(An)/dr] is zero.
Under these conditions the variation of the excess electron density with distance An(x) is given
by the solution of
d2(An)~ d(An) An
D. + »nE — =0 (10.80)
dx2 . dx .
If the semiconductor can be assumed to be neutral, that is, there is no applied electric field and
the level of injection is low, drift effect can be neglected and equation (10.80) reduces to
(An)
(10.81)
Dnxn
An(x)
t
Let the solution of the equation (10.81) be of the form
(An)x = A exp
x = O,(An)I = (An)o=A
(10.82)
(An)x = (An)oexp (10.83)
where
is the electron diffusion length. The variation of the excess electron density with distance from the
injecting contact is shown in Fig. 10.37.
At x = L*, An = 0.37 (An)0
and so Ln can be defined as the distance from the injecting surface to the point at which the excess
density is 37 per cent of the injected density.
Similarly for excess holes in an n-type semiconductor, the hole diffusion length Lp is given by
For silicon Dn = 3.6 x 10-3 m2/s at 300 K and so for a typical electron lifetime of one p sec, the
electron diffusion length is 60 pm.
Equation (10.83) is
(An)x = (An)0 exp
(An).
= exp
(An)0
Refer equation (10.75a).
(diffusion) = (eD ) —
’ dr
-*£>,( An)0
—exp (10.83a)
/.atx = 0is-^4^
Thus.
These equations are useful in the study of the operation of the p-njunctions and bipolar transistors.
The diffusion length of injected earners is important in determining certain dimensions in
semiconductor devices. In a bipolar junction transistor for example, excess carriers injected from the
emitter into the base are collected at the collector-base junction. For efficient operation, the width of the
base resnon must be small compared with the diffusion length of the injected carriers otherwise a large
proportion of them would be lost by recombination before reaching the collector-base junction.
It is often necessary to determine whether a material is n-type or p-type. Measurement of the conductivity
of a specimen will not give this information since it cannot distinguish between positive hole and
I*
electron conduction. The Hall effect can be utilised to distinguish between the two types of carriers, and
it also allows the density of the charge carriers to be determined.
If a piece of conductor (metal or semiconductor) carrying a current is placed in a transverse cc it
h
magnetic field, an electric field is produced inside the conductor in a direction normal to both the
current and the magnetic field. This phenomenon is known as the Hall effect, and the generated voltage E I
is called the Hall voltage. See Fig. 10.39. $ ■i
<
i'
k
1
The Hall effect may be explained by reference to Fig. 10.40 which shows the from face of the
slab only.
Assuming that the material is an n-type semi
conductor, the current flow consists almost entirely of
electrons moving from right to left. This corresponds to the
direction of conventional current from left to right as in
Fig. 10.39.
If v is the velocity of electrons at right angles to the
magnetic field, there is a downward force on each electron
of magnitude Bev.This causes the electron current to be
deflected in a downward direction and causes a negative Fig 10.40 Motion of electrons in an n-type
semiconductor
charge to accumulate on the bottom face of the slab
(face 1). A potential difference is therefore established from top to bottom of the specimen with bottom
face negative. This potential difference causes a field EH in the negative y-direction, and so there is a
force of eEH acting in the upward direction on the electron. Equilibrium occurs when
eEH = eBv
Eh = Bv (10.84)
If Jx is the current density in the x-direction, then
Jx = nev
where n is the concentration of current carriers.
Thus (10-85)
The Hall effect is described by means of the Hall coefficient RH, defined in terms of the current
density Jx by the relation
Eh ~ RiJJ*
r,
OF (1086)
ie> Rh=^ (10.87)
In this case RH =------ (10.88)
Negative sign is used because the electric field developed is in the negative y-direction.
Eh 1
Ru =-------- - — .-----
H BJX ne
All the three quantities Epr B and Jx can be measured, and so the Hall coefficient and carrier
density n can be found out.
Figure 10.41 shows the conditions that exists in a similar p-type specimen when the current is
entirely by holes. In this case
Physics of
Fig. 10.41 Motion of positive holes in a p-type semiconductor
R _ 1 (10.90)
H BJX pe
where p is the positive hole density.
Determination of the Hall Coefficient

The Hall coefficient is determined by measuring the Hall voltage that generates the Hall field. If VH is
the Hall voltage across the sample of thickness t, then
Substituting for EH from equation (10.86), one gets

= ' (10'9!)
If & is the width of the sample, then its cross-section will be bt and the current density
Jx = Ix/bt
Hence R„=^ <10.92)
Note that the polarity of VH will be opposite for n- and p-type semiconductors.
Experiment
A rectangular slab of the given material having a thickness t and width b is taken and a current lx ampere
is allowed to pass through this sample by connecting it to a battery Bv The slab is then placed between
tWo Pole pieces of an electromagnet such that if the current direction coincides with the x-axis, the
^gnetic flux density B coincides with the z-axis, as shown in Fig. 10.42.
The Hall voltage VH is then measured by placing two probes at the centres of the bottom and top
faces of the sample. If the magnetic flux density is B weber/m2 and the Hall voltage is VH volt, then RH
18 obtained from equation (10.92) in m3/ coulomb.
Fig. 10.42 Set-up for the measurement of Hall voltage
The analysis given above applies only when the charge carriers are free of attractive forces in the
energy bands and when they move with a steady drift velocity vd. This is not the case in a semiconductor,
and a computation of the average speed leads to the conclusion that
_
"
3k
—--
8ne
= 1.18
—ne-
For n-type of material, the conductivity is given by
= ne^
n = = GnRH (10.93)
n ne 1.18
For p-type of material
<''c'A
- A= (10.94)
pe 1J8
There is another interesting quantity called the Hall angle (0H) defined by the equation,
tan Qh = Eh/Ex
„ JXB nevxB
But (10.95)
" ne ne
i.e., Eh = ExvJUEx
(10.96)
where p ip( the mobility of the charge carriers
Thus, tan 0,, = —H-

* E.
I
^plications of Hall Effect
Determination of Semiconductor Type
For an n-type semiconductor the Hall coefficient

Tfinc thp don nf thm Hau ■
is negative wherea«fnr.
5«*uve wnereas K
for a p-type • a
semiconductor it is
positive, Thus. the stgn the Hall coefficient can be used to detcimine whether a given semiconductor
is n- or p-type.
(H) Calculation of Carrier Concentration
The Hall voltage V„ is measured as usual by placing the two probes at the centres of the top and bottom
faces of the sample. If the magnetic flux density is B wb/m2, then
1
n =------
e^H
where R ri “ “
H ne IB
(iii) Determination of Mobility
If the conduction is due to one type of carriers, e.g., electrons, we have
Le., O = ne[ln
= ct/ne = gRh
10*
Le., knowing ct, the mobility pn can be determined.
(/V) Measurement of Magnetic Flux Density
CHAPTER
Since Hall voltage V is proportional to the magnetic flux density B for a given cunent fr through a
sample, the Hall effect can be used as the basis for the design of a magnetic flux density meter.
(v) Measurement of Power in an Electromagnetic Wave

in an electromagnetic wave in free space the magnetic field H and the electric field E are at right angles.
Thus, if a semiconductor sample is placed parallel to E it will derive a current I in the semiconductor.
The semiconductor is subjected simultaneously to a transverse magnehc field Hproducmg a Hall voltage
across the sample. The Hall voltage will be proportional to the product E and H ..e„ to the magnitude of
the Poym/ng Xrwr of the electromagnetic wave. Thus, the Hall effect can be used to deremnne the
power flow in an electromagnetic wave.
(w) Hall Effect Multiplier
hthe magnetic flux densityflis produced by passing a current f through an airniore coil, BwiU be proportional
to r. The Hall voltage is thus proportional to the product of 1 and f. This forms the basis of multiplier.
.. . semiconductors. The vacuum devices like diode,

Most of the devices in electronics today built from
are u„;it from semic transistors Th
Wode, etc. have been replaced by semiconductor dev.ces hire p-o juncuon diodes. transistors, etc. The
advantages of semiconductor devices over vacuum tubes are the following.
(i) As the name indicates, vacuum tubes require vacuum, but semiconductors do not require
vacuum.
(ii) Vacuum tubes have filaments, and so require supply for heating the filament. Semiconductors
do not have filaments.
(iii) Semiconductor devices are smaller in size, lighter in weight, and are mechanically very rugged.
(iv) Operation of semiconductor devices requires low-voltage power supply. The power
consumption is also smaller than that of the corresponding vacuum tubes.
(v) The semiconductor devices require very small warm-up time and, therefore, operate
immediately after the supply voltages are switched on.
(vi) The performance of semiconductor devices is more reliable than that of vacuum tube devices.
(vii) The operating life of a semiconductor device is appreciably longer than that of its equivalent
vacuum tube.
A semiconductor device can be defined as a unit which consists, partly or wholly, of semiconducting
materials and which can perform useful functions in electronic apparatus and solid state research.
Examples of semiconductor devices are semiconductor diodes (p-n junction), transistors, integrated
circuits, etc. Almost all semiconductor devices are comprised of a single crystal semiconductor
incorporating two or more semiconducting regions of different impurity density. The difference in the
electric fields and carrier densities associated with differently doped regions, called junctions, permit a
wide range of essentially non-linear conductivity effects in devices incorporating two, three or more
distinct regions. Most semiconductor devices can be understood through the simplest of such functions,
called p-n junction, which is a system of two semiconductors in physical contact, one with excess of
electrons (n-type) and the other with excess of holes (p-type).
A p-type or n-type crystal when used separately conducts just like any poor conductor without
asymmetry, and this phenomenon by itself is not very important. Almost all the semiconductor devices
in use today are combinations of the two types of extrinsic crystals, the p and n types. The simplest
semiconductor device is a combination of one p-type and one n-type crystal called the p-n junction.
It should be emphasised at this point that it is not possible to make a p-n junction by placing
p-material in contact with n-material. One reason is that even the most smoothly polished surfaces
pressed against one another have only relatively small areas of contact. Furthermore, it is impossible to
get surfaces absolutely clean, and the effect of drift or other contaminating agents on the surface is such
as to reduce the area of contact and cause other deleterious effects.
The fabrication ofjunctions between p- and n-type materials, which have become of great technical
importance, will now be described. A p-n junction is, in a sense, an internal boundary within a single
crystal. On one side donors and on the other side acceptors are in excess. Ordinarily, the transition is not
completely sharp and the width over which the conductor changes from n-type to p-type is the most
important parameter. Double junctions such as a p-n-p arrangement can also be formed on the same
principle.
Experimentally there are three principal ways of preparing p-n junction devices; the grown junction
method, the alloying method and the diffusion method. In the grown junction method, a crystal o
semiconductor is grown, for example, from an initially n-type melt, which while the crystal is being
I
_______________________________
.■irtned, is counterdoped by adding enough acceptor impurities so that the subsequently grown portion
f the crystal is p-type- The resulting junction is usually graded rather than abrupt. Although accurate
control can be maintained over the impurity concentrations on either side of the junction by this method,
difficulty of locating the junction in the grown crystal and the difficulty of attaching leads to narrow
grown junction regions has prevented widespread adoption of the technique in manufacturing.
In the alloying method an alloy pellet or foil is melted upon a semiconductor base crystal. The
alloy pellet contains impurities which will give rise to the conductivity type opposite to that of the
original crystal; after it has melted the temperature is raised to a value high enough to allow the molten
alloy to dissolve away the underlying semiconductor crystal to some extent. The liquid phase is then a
solution of the semiconductor material in the liquid alloy which is approximately saturated at the
maximum fabrication temperature. Since the equilibrium solubility of the semiconductor in the liquid
metal normal increases with temperature, when the device is slowly cooled the solution will become
supersaturated with respect to the solute and some of the dissolved semiconductor atoms will recrystallise
at the liquid-solid interface, continuing the single-crystal structure of the substrate. Since the liquid
phase contains impurities associated with the conductivity type opposite to that of the original crystal,
the regrown material will be of the opposite conductivity type, and there will be a p-n junction at the
interface between original and regrown material. Upon further cooling the entire alloy phase solidifies;
it is then a simple matter to make electrical connections to the original crystal and to the resolidified
alloy pellet. The alloying process generally produces junctions that are quite abrupt. Although it is
sometimes difficult to exercise the strictest dimensional control over devices made by the alloying
process, the ease and simplicity of the technique has led to its widespread use as a production method
for many different types of devices.
In the diffusion method, an impurity element is diffused at an elevated temperature into a base
crystal whose conductivity type is opposite to that which is produced by the presence of the diffusing
CHAPTER 10
impurity in the crystal lattice. The depth of the junction below the surface of the crystal and the impurity
concentration gradient at the junction can be controlled by controlling the diffusion time and temperature
and the surface concentration of the diffusing impurity. Diffused junctions may be either graded or
quite abrupt, depending upon the diffusion time, surface concentration and base crystal impurity density.
Although the attachment of leads to diffused layers presents some technical problems, the ease and
accuracy with which the thickness of diffused layers can be controlled has resulted in the widespread
use of diffusion as a manufacturing technique.
Let us now begin the discussion of the characteristics of a p-n junction by assuming that a
junction has just been made in a crystal-growing furnace. Figure 10.43 shows such a crystal, which we
will assume is at room temperature.
The uncircled charges on each side of the junction represent the free carriers, i.e., the plus signs
on the p side represent free holes, and the minus signs on the n side represent free electrons. These holes
and electrons are present because of the thermal ionisation of the donors and acceptors.
The charges shown in circles represent the ionised impurities, which cannot move. On the p side,
the acceptors are shown with negative charge. This is because the thermal energy associated with room
temperature causes electrons from the valence band to be activated into the empty bands of the acceptor
atoms. The acceptor atoms are negatively charged because of the presence of the extra electrons.
On the other hand, the donor impurities on the n side are positively charged because they have
supplied electrons to the conduction band. ,
On the p-side of the junction, a high concentration of free holes exists. On the n-side, a high
concentration of free electrons is present. Because of thermal vibration, these concentrations on either
side would like to spread out. The spreading-out process due to random velocity and scattering is known
as diffusion. Its effect on the charge distributions is to spread or disperse it in a manner similar to the
spreading or diffusion of ink by capillarity when a drop is put on a blotter. Thus holes from the p-side of
the junction diffuse over to the n-side, and electrons from n-side diffuse into the p-region because of
thermal agitation.
Fig. 10.43 Newly made p-n junction. Diffusion and recombination have not yet occurred
However, when either type of charge penetrates the boundary region into the other side, it finds
itself surrounded by earners of the opposite sign. Recombination is very likely under such conditions.
For this reason, quite soon after a junction is made, the boundary region between the p- and the n-sides
becomes devoid of holes and electrons because both readily find carriers of the opposite type with
which to recombine.
Away from the boundary, toward the outside of either of these regions, free carriers still exist,
and the charged impurity atoms are still effectively neutralised by the space charge of free carriers of
opposite sign around them. But right near the junction region, the impurities have no neutralising space
charge present, because the free carriers in this region have been annihilated. This leaves ionised acceptors
(-) near the junction on the p-side and ionised donors (+) near the junction on the n-side. Both are
without compensating free-carrier charge. When a sufficient number of donor and acceptor ions are
uncovered, further diffusion is slopped. It is because now, a barrier is set up against further movement
of charge carriers. This is called potential barrier or junction barrier. The potential barrier is of the
order of 0.1 to 0.3 volt. Figure 10.44 shows the electrostatic potential difference across the p-n juncuoa.
How this potential barrier is developed? When a sufficient number of donor and acceptor ions is
uncovered, further diffusion is prevented. It is because now positive charge on n-side repels holes »
cross from p-type to n-lype and negative charge on p-side repels free electrons to enter from n-type »
p-type. Because of this a difference in potential exists between the two sections, which inhibits further
electron-hole combinations at the junction, and the Fermi level of the two sides is in the same level»
shown in Fig. 10.45. The region across the p-n junction in which the potential changes form positive »
negative is called the depletion region. The width of this region is of the order l0 M m. Since this region
has immobile (fixed) ions which are electrically charged, it is called as the space-charge region. Oucsate
this region on each side of the junction, the material is still neutral. The potential barrier for germanium
p-n junction is about 0.3 volt. This potential barrier discourages the diffusion of majority carriers across
the junction. However, the potential barrier helps minority carriers to drift across the juncuoa. But
electric current cannot flow as no external electric field is applied to the system. The voltage developed
across the junction may be represented by a ficticious battery having a voltage Vr
1
p-lypo [ n-lypo
O o' O ; 0 0 0
O' O, o : 0 0 0
< \ .o O 0 0 0
p 'o o : o 0 0
’I?)"
’ CHAPTER 10
Fig. 10.44 (a) Diagram showing the position of earners in a p-* junction
(b) Variation of concentration of immobile ions
(c)Charge density
(d) Space charge
(e) Potential hi|l caused by charge distribute
A question will arise whether this space charge equivalent battery will be able to del.ver any
current when connected in a circuit containing no other battery. In order to answer this, consular the
energy level diagram of a (pm> junction. The Fermi levels in the two samples are al dtffaent pasimsns
with respect to Ute band edges. Fermi level is something like potentuU and so u must be at the same
level in a system in thermal equilibrium. At the insunt pm junetton is formed Ferm, level m n-type ts
« a higher level than in p-lype. Because of this difference the electrons wtll flow from matenal whtch
has a higher Fermi level to a material which has a lower Fermi level unul they «un a common level.
The band edges in the two samples shift until they attain a common level. The band edges m the two
584ÔLID STATt PHYSTCS ________________________________________ _______________ _______
samples shift themselves to make this alignment possible. The conduction band of p-type is shifted
upwards by eVB over the conduction band of zi-type where VB is the potential barrier developed across
the junction.
From the energy level diagram we find that the minority electrons in the conduction band of
p-type crystal is at a higher energy than the majority electrons in the conduction band of n-type crystal.
The electron flow from p to n and from n to p are governed by the following factors. The electron
—>
current Ie form p to n is proportional to the product of electron density in the p-region and the probability
factor. In this case the probability factor is unity since the electrons on p-side are having energy higher
than electrons on zi-side. The only difficulty is that the number of electrons in the conduction band of
p-type is very small and is proportional to exp (- E/kBT) where E is the energy difference between the
lower edge of the conduction band of p-type and Fermi level.
Thus, ' 4 = C exp (—ElkBT) (10.97)
Let us now calculate the electron current from right to left (n-side to p-side). The density of
electrons is proportional to exp [(Ef- Ec)/kBT] or exp [- (Ec - Ef)lkBT\. The probability that the electron
will have sufficient energy to climb up the energy ladder of height [E - (E - E,)] is proportional to exp
[-(E-Ec + Ef)/kBT\.
Thus, 4 = C exp [- (Ec - Ef)/kBT] exp [- (E - Ec + Ef)/kBT\
Ie =C exp (~E/kBT)
i.e., t = Z ' (10.98)
Thus we see that no net current flows across the junction because of the space charge equivalent
battery. The same argument holds good for holes also.
Physics w SkMK^cuCTtms.^^1
The potential difference (or the barrier potential VB) due to accumulation of an excess of immobile
charge in each layer near the junction, under the equilibrium condition at the temperature T degree
kelvin may be obtained as follows: When no external voltage is applied to the p-n junction crystal, no
current passes through the external circuit even when the p and the n-regions are shorted as shown in
Fig. 10.46. Thus, the net current through the junction must be zero separately both for free electrons and
positive holes. Considering only the free electron current at the p-n junction of Fig. 10.46, one finds that
there are two components of current density flowing across the junction. Jn is the component of the
current density that flows down the potential barrier with the electron flowing from p-region to n-region
and it is the drift current density due to the free electrons under the influence of the field on account of
the potential barrier and Jn may be written as
Jn = ne VnE
where E is the electric field intensity caused

due to the potential barrier voltage VB and n
is the density of free electrons.
The current density component Jn'
owes its origin to the flow of electrons from
the n-region where the free electrons are the
majority carriers to the p-region where they
are minority carriers and this current flows
CHAPTER 10
due to diffusion. Thus
,, dn
=eD — (10.99)
n dx
where Dn is the diffusion constant for electron
is the gradient of the electron
density in the x-direction (length of the crystal Fig. 10.46 (a) A p-n junction whose p and n-regions are
is along the x-direction). When the externally shorted (6) Potential distribution along the length of
applied voltage is zero, the sum of the the p-n junction
components is equal to zero. Hence

r dn
0 (10.100)
Dn dn
-Edx = —x —
n .
b
dn
n
Soud State Physics
where nn and np are the densities of the free electrons in the n-region and p-region respectively,
P'n
where Va and Vb are the potentials at the locations a and b respectively.
Hence barrier potential,

kBT
VB = —
d & {In
v (nIn )}J
x n p' (10.100a)
nn = npCXP <~eVlJkBr) (10.101)
Considering the hole current and using the relationship
ni , .
pn = —; we can show that
nn
or . pp=pnexp(eVB/kBT) . (10.102)
For a typical germanium p-n junction with p- and n-regions doped to the order of 1022 impurity
atoms/m3, the barrier potential at room temperature is about 0.3 volt.
îrWfDrtrOF&EPl.feTrOlQ'LAVLROI- rHfep-nldNlllUN.... ■■
We have seen that the space charge on the n-side is positively charged and on the p-side it is negatively
charged. Figure 10.44 shows the space charge region in the two sides of the junction and the consequent
potential variation. Let and X2 be the widths of the space charge region in the p and n sides respectively.
The area of the depletion layer in each region depends on the concentration of the impurities in the
regions. The effective area of the depletion layer can easily be calculated with the help of the Poissons
equation which states that the second derivative of the potential with respect to the distance is proportional
to the charge density. In the simple one-dimensional case when the voltage varies only in the ^-direction
along the length of the crystal, the Poisson's equation may be written as
d2V _ p
dx2 e
where V is the voltage and p is the volume density of charge in the material of permittivity e. In the
portion of the depletion layer situated in the p-region near the junction the charge density may be given
by
P = " eNa
where Na is the density of the acceptor atoms and the negative sign is used since the acceptor atoms are
negatively ionised. In order to determine the width of the depletion region X, in the p-region, we shall
apply Poisson’s equation in this region.
dV _
On integration, x+A (10.104)
dx . £
x2
V= — + Ax + B (10.105)
and £
where A and B are arbitrary constants and may be determined by the boundary conditions. At the right
hand side of this portion of the depletion layer in Fig. 10.44 we assume that V= 0 when x = 0 so that all
voltages are measured with respect to the potential at the boundary between the p-type and n-type
materials. Using this boundary condition in equation (10.105), one gets
B=Q (10.106)
In the p-type semiconducting material the potential is constant at the end of the depletion region
(Fig. 10.44). Thus, the depletion region may be assumed to end at a point x = - X{ where dV/dx = 0, so
that we can realise that at this point the field strength is zero. Using the second boundary condition in
equation (10.104), one gets
On substitution of the values of the constants A and B in equation (10.105),

eNax2 eNaX,x
V=(l/2)—^—+ aJ-
e £
CHAPTER 10
If V = -V1atx = -X1
or _v (10.108)
1 2e
In a similar way the Poisson’s equation may be applied for the portion of the depletion layer
situated in the n-region near the junction. Considering that the charge density in this region is due to the
positively ionised donor atoms, we may write the Poisson’s equation for this portion of the depletion
layer as
d2V eNd
dx2 ~ £
where Nd is the density of the donor atoms in the n-region of the p-n junction.
On integration, +C (10.109)
dx e
and V= (-l/2)“-~~ + Cx+D
The boundary conditions are now applied as follows.

(i) When x = 0, V = 0, one gets D = 0
(n) When x = X2, dV/dx = 0, one gets
eNdX2
(10.110)
e
eNdX2x
Thus, V = (-1/2)g -
£ e
If V = V2 at jc = X2, one gets
'eNdX2' eNdXj
V2 = (-1/2)
e £
eNdX2'
V2 = (l/2)
£
Here V2 is the potential at the point x = X2 where the depletion layer in the n-region ends.
Thus, the potential barrier at the junction,
€
t*- = (10.111)
The equation of charge neutrality is
NgX,
or (10.112)
Nd
On substitution of the value of X2 in equation (10.111), one gets
n2x2
r,,
|_
n.
N„
(10.113)
If this value of X, is substituted in equation (10.112), one gets,
X2 = «W
2eVfl
( N }
eA/ 1+—
I A/J.
d
(eN2 / ai\
, /N N
i +^
V Nd
(eNa/Nd)(Na+Nd)] (eNd/Na)(Na + Nd)j
-il/2
{KW“ + <Wnl>
nl/2r 1
2eVb (Nd + Na)
e(Na+Nd)\ \_(NaNd)1'2.
(10.115)
CHAPTER 10
Thus, the width of the depletion layer can easily be determined if the value of the potential
barrier VB and the densities of the donor and the acceptor atoms in the n-type and the p-type regions o
the p-n junction are known.
The portion of the depletion layer situated to the left of the junction contains a certain amount of
negative charge, while the portion of the same situated to the right of the junction contains an amount of
Positive charge. The potential developed across these two portions is equal to the barrier potential VB.
Therefore, there exists a certain amount of capacitance at the junction. If Q is the quantity of charge
contained in each portion of the depletion layer, then
q - e NaX^S = e NjX2S (where S is area of cross-section)
Substituting for Xj from equation (10.113)
2e2N2S2 e VB
Q= (
(Na + Nd) .
Thus the junction capacitance for unit area is
C=-^ eeNaNd
J dVB
= [vflr1/2 2(Na + Nd)
590 Physics
eeNaNd
2VB(Na+Nd)
eNaNd
2tVB(Na+Nd\
S E
C. = ——— [farad per unit area of cross-section]
J Xj + X2
%IX. VOLT-AMPERE CHARACTERISTICS?!

LfcLi^wjs,
The p-n junction possesses rectifying properties just like a vacuum tube diode and it offers an extremely
low resistance to the flow of electric current in one particular direction and a very high resistance to the
current flow in the opposite direction. It has already been pointed out that the barrier potential VB
developed across the junction is of such polarity that it tends to oppose the movement of the positive
holes due to diffusion from the p-region to the n-region (see Fig. 10.45) and that of free electrons due to
diffusion from the n-region to the p-region. Again, all the charge carriers in any semiconducting material
do not possess the same amount of kinetic energy but have a range from a very high value to an extremely
low value. It has already been mentioned that the distribution of kinetic energy or velocity to different
charge carriers is decided by Fermi-Dirac statistics. Due to the diffusion of charge carriers, as the
potential barrier across the p-n junction slowly develops, it becomes impossible for more and more
charge carriers to cross the junction. The ones that have highest kinetic energy may be able to surmount
the potential barrier. The process of crossing the junction may continue till an equilibrium condition is
established and no free carrier, however large its kinetic energy, is able to cross the junction. After
reaching equilibrium the only mechanism by which the free carriers can be made to cross the junction is
to increase its kinetic energy by some external means, such as by the application of an external eunl.
across the junction. The band diagram of an unbiased p-n junction is shown in Fig. 10.47.
Electron
energy
Fig. 10.47 Energy band diagram of a p-n junction

PHYSICS OP
type semiconductor the Fermi level lies near the conduction band edge Ec and for
F°r j tnr it is near the valence band edge E . When ap-n junction is formed, under equilibrium
p-typesem penni level attains a constant value throughout the sample as shown in Fig. 10.47. Clearly,
cond'tiont C. t:on band edge Ec) of the p-type will not be at the same level as E^ of the n-type.
then the con uc in From p.g 10 47, we find
Sbnil«ly.£»W _ = _ x
t-'B ^cp cn vp ^vn VB (10.117)
• the barrier energy, e is the electronic charge and VB is the barrier potential. Note that
where Es ,s
E„A
jdxwchapotential VB- — exists at the p-n junction a voltmeter connected across p-n junction will
e
notread this potential. The reason for this is as follows:
If this is possible, let us assume that a current flows due to the barrier voltage in a short-circuit
unction diode. This current will heat the connecting metal wire. Since there is no external source of
energy the heating of the wire must take place with a simultaneous cooling of the p-n junction diode.
But under thermal equilibrium this situation cannot exist. Hence we conclude that the current through
the circuit is zero. This means that the barrier voltage must be balanced by the metal-to-semiconductor
contact potentials at the ends of the diode. A voltmeter connected to the terminals of the diode shows
zero voltage reading.
On the other hand when the positive terminal of a battery is connected to the p-type side and the
negative terminal to the n-type side of a p-n junction, the junction allows a large current to flow through
it In this case, the p-n junction, is said to be forward-biased. When the terminals of the battery are
reversed, i.e., the positive terminal is connected to the n-type side, and the negative terminal to the
CHAPTER 10
p-type side, the junction allows a very small current to flow through it. Under this condition the p-n
junction is called reverse-biased. This behaviour of a p-n junction makes it suitable for use as a rectifier.
The potential energy difference (E -E&) between (see Fig. 10.47) free electrons in the conduction
band on either side of the junction is just equal to eVB, so we can now relate VB to the electron
concentrations on either side by the following general equations
nn = TV exp [- (Ecn - E}/kBT\
and
np = Ncexp [- (Ecp - E^lkBT]
Thus (Ec - Ecn) eVB

Tv. . • nP L k*T J wJ
lakmg logarithms
= In (nJnV
kBT n p
kBT
g 111 (n'np'
Vgd ~ ---- Jnr)
kBT
= —In (NdPp/np Pp)
k T
-~Y^(NdNaln^) (10.118)
Pically, in silicon we may calculate VB for Na = 1022 and Nd = 1024 with n. = 1.4 x 10l6/m3
Pmyks
VB = 0.82 volt at 300 K

Using equation (10.67a)
dn
and neU.E = - eDn —
" dx
dV • ,
Putting, E = - — [and rearranging]
dx
(10.118a)
dx L dxj
V. n
pv =(DA)
o "»
',s = (DA)i"W <l0119)

This looks very like equation (10.100a) indeed use of Einstein’s relation £>z/|ln = kBHe shows
that they are identical.
This is a comforting result, as this proof of equation (10.119) is dubious, since the occurrence of
diffusion within the junction region is not obvious: The mean free path is normally no smaller than the
thickness of the depletion layer. The importance of equation (10.119) is that the same equations are
needed for discussing the theory of the junction when a bias voltage is applied across it.
—---------
In Fig. 10.48, the circles with negative sign in the depletion layer represent acceptor ions and the circles
with positive sign represent donor ions. It may be noted
Depletion layer
that there are no free or mobile charge carriers in the
depletion layer. But it contains only immobile positive and
negative ions. It has been observed that an electric potential
is developed across the p-n junction due to charge separation
on its either side. This electric potential is known as barrier
potential and represented by the symbol VB. The value of
this barrier potential at room temperature is about 0.3 volt
for germanium and 0.7 volt for silicon. It has been observed
that there is no further diffusion of electrons or holes across
the junction due to the barrier potential unless an external
field is established across the p-n junction.
A voltage or p.d. across ap-n junction may be applied
in any one of the following two methods: (i) Forward biasing
(//) Reverse biasing.
PHVSiCIC*
0 Forward Biasing
For a current to flow through the junction, a battery must be connected to the diode to overcome the
potential barrier. And the po arity of the battery should be such that the majority carriers in both sections
ait driven toward the junction. When the battery is connected in this way, it provides forward bias
causing forward or high current to flow, because it allows the majority carriers to provide the current.
To apply forward bias, positive terminals of the battery is connected to p-side and negative
terminal to n-side as shown in Fig. 10.49 (a). The applied forward potential establishes an electric field
which acts against the potential barrier field. Obviously, the resultant field is weakened and the barrier
height is reduced at the p-n junction. Since the potential barrier height is very small, a small forward
voltage is sufficient to completely eliminate the barrier. Obviously, at some forward voltage the potential
barrier at the p-n junction can be eliminated altogether. Then the junction resistance will become almost
zero, and a low resistance path is established for the entire circuit. Thus a large current is generated in
the circuit even for the small potential difference applied. Such a circuit is called forward bias circuit
and the current is called forward current. The salient features of the forward bias circuit are summarised
below:
Fig. 10.49 (a) Forward biasing

(b) Symbolic representation of p-n junction
(0 The p-n junction offers low forward resistance to current flow.

(ii) The magnitude of current in the circuit due to the establishment of low resistance depends
upon the applied forward bias.
««) Al some forward voltage, the potential barrier is eliminated altogether.
The current flow may be understood as follows.
When the electron hole combination takes place near the junction, a covalent bond near the
l**iUve terminal of the battery breaks down. This causes the liberation of an electron whtch enters the
’“Hive terminal. This action creates a new hole which moves towards the junction. For each electron
“'•■region that combines with a hole from p-region. an electron enters the crystal Irom the negative
terminal. The constant movement of the elections towards the positive terminal and the holes towards
the negative terminal produces a high forward current. As the applied voltage is increased further, the
elections and holes having lower energy will be able to cross the potential barrier and the current will
increase further.
(m) Reverse Biasing

Here, the positive terminal of the battery is connected to n-region and the negative terminal to p-region
as shown in Fig. 10.50. In this case, the applied reverse voltage establishes an electric field in the same
direction as that of the field due to barrier potential. As a result of this, the resultant field is strengthened
and the barrier height (Vfl) increases as shown in Fig. 10.50. It has been observed that the increased
barrier potential prevents the flow of charge carriers across the junction.
Fig. 10.50 (tf) Reverse biasing

(b) Symbolic representation of p-n junction
Thus a high resistance path is established for the entire circuit, and the current does not flow
through the junction, i.e., the effect of reverse bias is to increase the potential barrier, thus allowing a
very little current to flow. When the junction is reverse biased, the electrons in n-type semiconductor
and holes in p-type semiconductor are attracted away from the junction under the action of the applied
voltage. Since there is no recombination of electron-hole pairs, the current is negligibly small, i.e., the
junction has a high resistance.
V-l Characteristics of a p-n Junction

The volt-ampere characteristic of a p-n junction is a curve between the voltage across the current through
it. Usually, the voltage is plotted along the horizontal axis and the current along the vertical axis.
Of a forward
In voltage currentp-n
andbiased junction, the
respectively. voltmeterRand
A resistance ir
is aZhTT connec,ed ">
current through the p-n junction as shown in Fig. 10.51 (aj dlhecircuit lo control the Row of
voltageInitially,
is increased applied voltage
whenby(headjusting is zero,
the potential no current
divider Rh »n‘™’S.!.hrou«h the circuit. But as the applied
AS the applied voltage ts further increased, the current increase' . n°wi"S in circuit,
initially when the applied voltage is small, the entire volt™ P Z "ls bccause of the fact that
potential. However. once the applied voltage exceeds the bXT,™*! “ overco™"8 the barrier
junction reduces and the current increases sharply if we „> ° Potent,al’ the resistance of the p-n
„„ent in (mA) along the y-axis, we obtain a curve as shown ta pfn m oo alo"g d,e
^CHAPTER 10^
1
r
Rg. 10.51 (a) Circuit for a forward biased p-n junction
(fe) V-l Characteristic for a forward biased p-n junction
In a reverse biased p-n junction, the battery connections are opposrte to those in fprward biasing.
Ute voltage and milliammeter are connected to record the values of voltage and current respective y.
Initially, when the applied voltage is zero, no current flows through the circuit. But as the voltage is
““eased a small current starts flowing in the reverse direction due to opposite battery connections, the
>
’’"trier potential at the junction is increased. As a result of this, the junction resrstance becomes very
Wgh, and practically no current flows through the circuit. However, a very small current (microampere)
in the circuit. This current is due to the flow of minority carriers and known as reverse saturauon
As the voltage is further increased the value of reverse saturation current does not increase.
,, But it has been observed that at a particular voltage, the breakdown of the junction occurs and
£ averse saturation current increases to a large value. The voltage, at whreh dus sudden merease of
takes place, is known as breakdown voltage (V„,). Now if we plot a graph with voltage dong the
axis and current in (pA) along the vertical axis, we obtain a curve as shown m Fig. 10.52 (M.
RECTIFIER equation
net PUrr
j -p, en* density across a p-n junction can be analysed in terms of the tour components J,. Jy
c04ndu e Currem density J, is due to the flow of minority electrons on the conduction band of p-region
Ct‘On band of n-region. Since electrons carry a negative charge, the How of free electrons
Fig. 10.52 (a) Circuit for a reverse biased p-n junction
(b) V-l Characteristic for a reverse biased p-n junction
from the p-region to the n-region is equivalent to a conventional current flow from the n-region to the
p-region, i.e., flows from right to left.
The majority electrons in the conduction band of the n-region can flow to the conduction band of
the p-region giving rise to a current density J2 flowing from left to right.
The majority holes in the valence band on the p-region can flow to the valence band on the
n-region giving rise to a current density J3 flowing from left to right.
The minority holes in the valence band on the n-region can flow to the valence band on the
p-region giving rise to a current density J4 from right to left (see Figs. 10.49 and 10.53). Hence the net
current density J flowing from left to right is given by
J=(J2 + J3)-(J1+J4) (10.120)
We can now evaluate these four components. Jj is the current density caused by the flow of
electrons from the p-type down the energy hill to the n-region. In a typical p-n junction this current is
very small and is also a constant for the following reasons. The minority electrons are scarce in the
p-region and so the current carried by them also must be small. Their motion through the bulk material
to the junction boundary is mainly by diffusion, since the applied electric field is only across the barrier
region and not in the bulk region. Once the electrons is at the junction boundary it will be swept away
through the junction, down the potential hill into the n-region. The diffusion of the electron from the
bulk to the junction boundary is not affected by the applied voltage whether in the forward direction or
in the reverse direction. Again the potential hill across the junction is always downward for the electron
flowing from left to right whether the biasing is forward or reverse. Hence J, is practically constant and
for this reason it is called the saturation current density. J2 is caused by the flow of the majority electrons
from the conduction band of the n-region to the conduction band of the p-region. The conduction band
provides a copious supply of electrons, but the potential barrier VT = (V - V) is the only impediment
Only those electrons which have sufficient energy to overcome the potential barrier VT will flow across
the junction to the left. The current density J2 is given by
J2 = C, exp (-(1012l)
CHAPTER 10 ’
I
Mtmmhp** ——*
where Cj is a constant. A similar argument can be used to find the flow of holes in the valence band
JA is the saturation current density which docs not depend on the applied voltage. J3 is the hole current
which flows up the potential hill and is given by
Jy - C2 exp (- cV.,lknT) (10.122)

where C2 is another constant. When there is no applied voltage (V = 0), the net current density in each
band is separately zero. Current flow in one band is independent of the flow in the other band since
there cannot be any accumulation of charge in cither band under equilibrium conditions. Applying these
conditions C] and C2 can be evaluated.
When V = 0, VT = VB, then J2 = J, and ./3 = J4
Substituting these values of J2 and J2 in equations (10.121) and (10.122) we get
J| = Ci exp (— eVJkBT)
and J= C2 exp (- eV^kBT)
or C| = J x exp [eVJkBT\
C2 = J4exp [eVl{/kBT]
Substituting the values Ct and C2 in equations (10.121) and (10.122) one gets
J2 = Jj exp [e(VB - VT)/kBT] (10.123)
and J3 = J4 exp [e(VB - VT)/kgTJ (10.124)
J2 + J3= {(J, + J4) exp [e(VB - VT)/kBT])
Thus equation for J is given by [Refer equation (10.120)]
/=(/,+ J4) {exp [e(VB - VT)/kBT] - 1}
But (J, + J4) = JQ represents the total saturation current density and (VB - Vr) = V is the applied
voltage. The net current density becomes
J=J0[exp (eV/kBT)-l] (10.125)
Equation (10.125) is known as the rectifier
equation. V is positive when the applied voltage
biases the junction in the forward direction and V
is negative when the biasing is reverse. The
experimental circuit for studying the diode
characteristic and the graphical plot of equation
(10.125) are shown in Figs. 10.54 and 10.55. In
the positive quadrant when a forward bias voltage
Fig. 10.54 Circuit for studying‘diode characteristic

is applied of magnitude V > exp (eVlkBT)
» 1 and J becomes equal to Jo exp (eVlkBT) i.e., J increases exponentially with applied voltage. In11,6
negative quadrant when a reverse bias voltage of magnitude - V » kBTte is applied, exp (- eVlkfl
« 1 and J becomes practically equal to J(). That is, the reverse current remains constant at the smaU
p-Region negative p-Region positive
Fig. 10.55 Graphical plot of equation (2.125)
CHAPTER 10
Zener Diode
We have seen that a junction diode, when subjected to a large reverse bias, breaks down. In this breakdown
region the reverse current increases very rapidly. This breakdown is attributed to two main causes,
namely, the avalanche breakdown and the Zener breakdown. In the avalanche breakdown, the conduction
band electrons make ionising collisions with the atoms of the crystal. These collisions produce further
electrons, which in turn collide with further atoms. The cumulative effect of such collisions results in
the breakdown of the junction, called the avalanche effect. Zener breakdown occurs when the applied
electric field is so high that the valence band electrons are pulled out to the conduction band in large
numbers resulting in the breakdown. This phenomenon is also called the field emission of electrons.
The voltage at which the Zener breakdown occurs can be carefully controlled by adjusting the doping
concentrations of the junction materials. When the junction materials are heavily doped, the depletion
region will be thin and even at low voltages a strong electric field of the order of IO5 volt/cm appears,
resulting in the Zener breakdown or field emission. When the junction materials are lightly doped the
depletion region will be very wide and at a higher voltage (not strong enough to cause field emission)
*e carriers will be accelerated enough, to cause ionisation by collision resulting in avalanche breakdown.
1 ls found that such breakdowns will be nondestructive provided, the excess heating is prevented by
Ruting the junction current. The current voltage characteristic in the breakdown region or the Zener
^8‘0n as u is called, is practically vertical and this property is very useful as voltage reference. A
J nCUon diode used in the Zener region is called the Zener diode and its action is similar to that of
voltage regulator gas tubes. Zener diodes have the advantage of lower dynamic resistance and a higher
voltage and current range.
UATION
Since the action of semiconductor devices like the diode and the transistor depend on the generation and
transport of excess minority carriers, it is necessary to have an equation governing their motion in a
semiconducting crystal. This equation is known as the continuity equation. The continuity equation is
nothing more than a mathematical way of expressing the principles of conservation of particles inside a
given volume of semiconducting crystal. Such an analysis is made taking into account the following
processes for holes and electrons separately.
1. The electrons and holes generated by thermal processes or otherwise have a finite lifetime. The
generation and recombination of the electrons and holes must be considered. From equation
(10.54a) we see that the rate of change of excess hole concentration in a given volume element
is given by the ratio of the excess concentration to the carrier lifetime
J(Ap) Ap
r.e., —-— = - —
dt t
putting Ap = p-pQ where p0 is the equilibrium density and p is the concentration at the instant t,
we get
^(P-Po)"-—(10.12®
. dp _ <J>y^P) .
t.t-., ------ —
dt XP
pjxp gives the generation rate and pKp gives the recombination rate and so (dp/df) gives the net
rate of change of hole density due to generation and recombination.
2. Let the volume element considered have unit area in the y-z plane and a length dx along the
x-axis as shown in Fig. 10.56. Let E be the applied electric field along the x-axis. The drift
current density Jc in the positive x-direction is given by
J* = epvpE (10.126a)
where the superscript + indicates that the current is due to positive holes and subscript c indicates
that.the current is due to conduction or drift motion in the electric field.
The diffusion current density for positive holes is given by
J*—dig- (10.127)
pdx
The sum of the drift and diffusion currents is given by
J = Jc + Jd = epy.pE -
Unit area
J
4—* J + dJ
x
x + dx
Fig. 10.56 Drift and diffusion current in a volume element
Considering only the drift and diffusion motions, the rate of change of hole density with time
from the given volume element dx is given by f — |
dx. If the corresponding current density that
\dt)
is responsible for this change in the hole density is dJ, then
dJ = -e dx (10.128)
Le., (10.129)
The negative sign indicates that the excess concentration will decrease with time:
CHAPTER 10
dp .
or — is negative.
dt
dp dJ r dp j2„
Thus,
dt dx
(10.130)
3. Lastly there may be sources and sinks for excess minority carriers in the volume element. A
reverse biased p-n junction acts as a sink for minority carriers. Photo emission of minority carri
ers is also possible. Let the rate of change of hole density due to such processes be given by G.
Then the complete continuity equation becomes
(10.131)
In three-dimensions the equation becomes
dP = Pq_Z_P _h £Vp + OV2p + G

(10.132)
dt Xp p
Pmkb
From similar arguments we can write the continuity equation for electrons as
dn n„ -n dn d2 n _
— = ----- + n E — + D +G (10.133)
dt xn n dx " cbc
In order to find the current density due to the contribution of the different carriers, the appropriate
continuity equation has to be solved taking into account the suitable boundary conditions.
Let us now apply the continuity equation to calculate the current components J{ and J4 in a
biased p-n junction. The current Jx consists of minority electrons moving by diffusion on the p-side and
falling down at the junction due to the potential well, i.e., the junction acts like a sink for the electrons.
Far away from the junction boundary the electron density n0 is the normal equilibrium value. At
the junction boundary the electron density is zero. So there is a concentration gradient for the minority
electrons in the p-region as shown in Fig. 10.57.
fig. 10.57 Concentration gradient for the minority electrons in the p-region
Because of this concentration gradient the minority electrons diffuse to the junction boundary *
giving rise to the current Jv The appropriate equation is given by
(l0134)
CM
dh (dn\
[— = 0 under steady state conditions. uE — = 0 since there is no electric field in the bulk region.
" \dx J
<7 = 0, since there are no sources or sinks in the bulk material].
The solution of the equation (10.134) is of the form
n - n0 = A exp [± x/y]Dnxn ] (10.135)
since (n - n^) cannot increase with distance, the negative exponent is in admissible. So the admissible
solution is
--------------------------- —------------------------------------------------- PhYMCS OF 603
n-n() = A exp\xJ^f)nxn J--------------------(10.136)

AjUnct’on to ,M' a sârP one al x = 0, we have at x = 0, n = 0 and so A = - nQ. Thus
equation (10.36) becomes u
" = /,o-«o <cxp J) (10.137)
= «0 f 1 - exp (x/4bnxn )] (10.137a)
Since ylDnxn has the dimension of length, it is called the diffusion length for the electron (£„).
'îen x = “ ^n’n ~ no p ~ ~J • Thus diffusion length is defined as the distance at which the concentration
increases to p J of its final value. Thus equation (10.137) can be written as
n = n0[l -exp(x/Ln)] (10.138)

n0 must be substituted as n” indicating the equilibrium density of electrons in p-type.
n°p -e*p(x/Ln)±-
Thus, = -n°p/Lr (10.139)
L x=0
Thus, = eD — at x = 0 (10.140)
n\dx)
CHAPTER 10
J^^nn°pILn (10.141)
From similar arguments we can show that
J4 = -eDpP°n/Lp (10.142)
The total saturation current
Jo = + J4 = - [eDnn°p/Ln + eDp P°n/Lp] (10.143)
The negative sign indicates that the current is opposite to the positive x-direction. Since Pn and
np arc small, the saturation current is small and is also constant. Substituting this value of JQ in equation
(10.125) one gets,
(10.144)
Conclusion
From the above rectifier equation we see that in a forward biased p-n junction the currents are carried by
the injected minority carriers. The component is due to the holes injected into the n-region where
they become minority carriers. Similarly the component is due to the electrons injected into the p
region where they become minority carriers. These injected earners increase minority carrier densities
close to the depletion region, and so begin to move by diffusion to regions of lower concentration away
’Scuo Swt Physks
from the depiction region. These minority carriers suffer recombination and at a distance approximately
equal to 4 times the diffusion length, the carrier concentrations come to the normal equilibrium values.
In devices it is preferable to have efficient injection of minority carriers in one direction only. For
example, in a p-n-p transistor the injected hole current J3 must be appreciable compared to the electron
current injected from n to p. In the n-p-n transistor the injected electron current from n to p must be
appreciable compared to the hole current injected from p to n. This can be done by proper doping of the
samples. We define a parameter called the minority carrier injecting efficiency or simply the emitter
efficiency (y) to describe the characteristic of a good emitter. In a forward biased p-n junction the ratio
of the hole current to the sum of the hole current and the electron current is called the emitter efficiency
of the p-material. That is
' (A + /3)
eDpP°n/Lp
[eDnn°p/Ln+eDppon/Lp]
________________ 1 ___________
“ [eDnn°p/Ln + eDpP°n /Lp]/eDpP°n/Lp
___________ 1_________
- \ + eDnnQ
pLpIeDpP°nLn
__________ 1________
7" \ + Dnn°pLplDpp°nLn (10.145)
(10.146)
(10.147)
Thus, and (10.148)

CP
Thus referring equations (10.70) and (10.57)
OmW.
So for greater emitter efficiency

(10.149)
Smaller on means, smaller conductivity, higher resistivity and hence smaller doping levels for
the n-type material. Smaller Lp means, smaller diffusion length for the injected holes in the n-region and
longer Ln means larger diffusion length for the injected electrons in the p-region. Greater op means
higher doping levels in the p-region. These factors will be important in the design of efficient transistors.
Physics or StMICOHOUcroW. 605
~XXllL SOME
* ............. '■'•
SPECIAL *b-n 'JUNCTION
........'-- ; ~
DlODE?"*
-T-T' .~j----.i
—
.'nrj.MhMiiif- rfir~iii'i' *rttrr-J*_ wrt
We have already seen that the depletion region around a p-n junction contains immobile positive charges
on the w-sidc and immobile negative charges on the p-side. Also we know that, the application of a
reverse voltage to a p-n junction causes these uncovered charges to increase. This may be considered as
a capacitive effect and the junction is assumed to exhibit a capacitance, called the junction capacitance.
This capacitance is not a constant, but decreases with the increase in reverse voltage. This property of
the p-n junction finds application in a special type of diodes, called varactors or varicaps. Such diodes,
among others, are discussed below.
Varactor Diode
It is a device whose reactance can be varied in a controlled way with a bias voltage. We have seen that
a p-n diode has a voltage-dependent junction capacitance. Therefore, p-n junction diodes find applications
as varactors, also called varicaps.
For an abrupt p-n junction, the junction capacitance varies inversely as the square root of the
reverse bias voltage. For a linearly graded junction, this capacitance varies inversely as the one-third of
the reverse bias voltage. The voltage sensitivity of the junction capacitance is thus greater for an abrupt
junction than for a linearly graded junction. By using special growth techniques, the junction capacitance
may be made to vary inversely as the square of the reverse bias voltage. When such a junction capacitor
is used with an inductor in a resonant circuit, the resonant frequency will vary linearly with the applied
voltage. Such varactors are useful in frequency modulation.
Varactor diodes may be used to replace the bulky variable capacitors in the tuning stage of a
radin receiver or in a TV tuner. This makes the circuit compact and improves its performance. Varactors
CHAPTER 10
are also used in self-balancing bridge circuits, in special type of amplifiers (called parametric amplifiers),
in harmonic generators, in microwave frequency multipliers, and in active filters.
Breakdown Diode
When p-n junction diodes are operated in the saturation portion of the reverse-voltage characteristic
(Fig. 10.55), they are called breakdown diodes.
The following two mechanisms are responsible for breakdown in a p-n junction diode:
(/) As the applied reverse bias in a p-n junction increases, the field across the junction increases
correspondingly. At some value of the bias, the field becomes large so that a thermally
generated carrier while traversing the junction acquires a large amount of energy from the
field. This carrier is then able to disrupt covalent bond and create a new electron-hole pair
while colliding with an immobile ion. The new carriers again pick up sufficient energy from
the applied field and collide with other immobile ions generating further electron-hole pairs.
This process being cumulative in nature, results in generation of an avalanche of carriers
within a very short time. This mechanism of carrier generation is referred to as avalanche
multiplication. The result of the process is the flow of a large amount of current at some
value of the reverse bias.
(n) Zener breakdown takes place when the reverse-bias field across a p-n junction is such that
the field may exert a strong force on a bound electron to tear it out from a covalent bond.'
Thus, a large number of electron-hole pair will be generated through a direct rupture of the
covalent bonds. The electron-hole pairs so generated increase the reverse current. Note that,
By twill Bmo
contrary to avalanche multiplication, in Zener breakdown, the carrier generation is not due to
the collisions of carriers with the immobile ions.
For breakdown voltages below 6 volt true
Zener breakdown occurs. For higher voltages the
avalanche multiplication is predominant. In spite
of the two distinct mechanisms, breakdown
diodes arc ordinary called Zener diodes. The Fig. 10.58 Symbol used for a Zener diode
symbol for a Zener diode is shown in Fig. 10,58.

The voltage-current characteristic of a Zener
diode is given by the dashed portion of the
characteristic curve in Fig. 10.55.
The Zener characteristic is almost parallel
to the current axis indicating that the voltage
across the diode remains almost constant although
the current through it may vary. The voltage
across a Zener diode thus serves as a reference
and the diode is referred to as a reference diode.
A typical application of a Zener diode as
a reference diode is given in Fig. 10.59. The Fig. 10.59 Typical application of a Zener diode
voltage V and the resistance R are determined so that the diode current is within the specified limit and
the diode is operated in the breakdown region. The voltage Vo across the load resistance RL is a constant
here although the supply voltage V and the load resistance RL may vary. The upper limit of the diode
current is determined by the power dissipation rating of the diode.
In Fig. 10.59, if / be the current drawn from the source, and A and IL be the currents through the
Zener diode and load resistance respectively, then Kirchhoff’s current and voltage laws give
I = IZ + IL (10.150)
and VO=V-1R (10.151)
Also Vo= IlRl (10.152)
Let the supply voltage V remain constant and the load resistance Rl be varied. Since the Zener
voltage tends to remain constant, equation (10.151) gives dl = 0. We then obtain from equation
• (10,150)
d! = dlz + dlL = 0
i.e., dl^-dIL (10.153)
Thus, when the load resistance is Increased but the supply voltage is fixed, the current 1L decreases
and the current /z increases by an equal amount so that the total / remains constant.
Now suppose that the load resistance RL is fixed and the supply voltage V is varied. Since Vo
tends to remain constant, we obtain from equation (10.151)
dV - R dl
__________ __ ________ _ __________ ___ ___________ Physics of SowcowwCMiS Ji
We also know from equation (10.152), dl, = 0, and from equation (10.150), d! = dlr. That is,
when the supply voltage is altered but the load resistance is kept fixed, the total current / and the Zener
current I. change equally to keep the load current constant.
Note that though the Zener voltage is fixed, the Zener current I7 may vary. Hence the DC
resistance ol the zener diode, i.e., V()//z is not a constant. The Zener dynamic resistance rz is given by the
inverse of the slope of the characteristic, i.e., by dVJdx. As the Zener characteristic is nearly parallel to
the current axis, dVJdx = 0, i.e., rz « 0. In practice, rz has a finite value, but it must be small for a good
Zener diode.
Tunnel Diode
When the concentration of impurity atoms is very large
(about 1024 to 1025/m3 ) in both p- and n-regions, the
barrier-width of a p-n junction diode becomes very small
(=10 nm). The typical volt-ampere characteristic of such
‘a diode is shown in Fig. 10.60. The characteristic shows
a region of negative slope when operated in the forward
direction. Note that the occurrence of this negative slope
cannot be explained by the mechanism discussed in
Section XX. The quantum mechanical process, known
as tunneling, gives a satisfactory explanation of the above
characteristic. Hence the diode is called a tunnel diode. Fig. 10.60 A typical tunnel diode characteristic
The negative slope, i.e., the negative differential resistance (the differential resistance of any
CHAPTER 10
point in the volt-ampere characteristic is given by the reciprocal of the slope of the characteristic at that
point. If the slope is negative, evidently the differential resistance is negative) exhibited by a tunnel
diode can be utilised in the construction of amplifiers, oscillators or switching devices. Since the tunneling
process is very fast, tunnel diode devices can work at very high frequencies (about 10 GHz).
Photo Diode
When a light radiation is allowed to fall on a reverse-biased p-n junction diode additional-hole pairs are
created in both p-and n-regions. This produces a very small change in majority carrier concentration
and a very large change in minority earner concentration. These additional minority earners enhance
the reverse current since they fall down the barrier potential. It is found that the current through the
diode varies almost linearly with the light flux. The diodes designed to operate on this principle are
called photo diodes. Such diodes are used in light detection, in light operated switches, reading of
computer punched cards and taps.
Light Emitting Diodes (LED)

When a p-n junction diode is forward biased, carriers are injected across the junction to establish excess
carriers above their thermal equilibrium values. These excess carriers recombine and release
electromagnetic energy. In the case of GaAs, the energy appears in the form of infrared radiation. For
the alloy semiconductor, GaAS । - Px, the energy appears in the form of visible light. The p-n junction
diode constructed with such semiconductors is called the light-emitting diode (LED). Here we get
optical energy from the biasing electrical energy. The electrons that are injected in the p-side make a
downward transition from the conduction band to the valence band and recombine with holes, emitting
photons with energy h\) - Eg. The corresponding emission wavelength is given by
where h is Planck’s constant, c is the velocity

of the electromagnetic wave and Eg is the band e e o q
gap. Light emission in the n-side of the junction WAWZ— hv
takes place similarly except that here the holes
are excess carriers. The downward transition
of electrons from the conduction band to the
valence band and subsequent emission of
Kg. 10.61 Electron-hole recombination in a
photons due to recombination with holes are
p-n junction diode
shown in Fig. 10.61.
Diodes built with GaAslx - P are most commercially available because of lower cost and easy
fabrication. GaAslx - P light-emitting diodes are used in the manufacture of signal and displays. The
infrared LED is a potential source for optical fibre communication. Under some conditions the emitted
light is coherent. Such a diode is referred to as an injection junction laser.
Solar Cell
The solar cell is basically a p-n junction diode that converts sunlight directly to electricity with large
conversion efficiency. The action of the solar cell is explained as follows:
(i) When a p-n junction diode is exposed to light, photons are absorbed and electron-hole pairs
are generated in both the p-side and n-side of the junction, as shown in Fig. 10.62 (a). The
electrons and the holes that are produced over a small distance from the junction reach the
space-charge region X by diffusion [Fig. 10.62 (ft)].
(ii) The electron-hole pairs are then separated by the strong barrier field that exists across the
region X. The electrons in the p-side slide down the barrier potential to move to the n-side
while the holes in the n-side move towards the p-side [Fig. 10.62 (c)].
(iii) When the p-n junction diode is open-circuited, the accumulation of electrons and holes on
the two sides of the junction gives rise to an open-circuit voltage Vo. If a load resistance is
connected across the diode, a current will flow in the circuit [Fig. 10.62 (a)]. The maximum
current, called the short-circuit current is obtained when an electric short is connected across
the diode terminals. Note that the current flows as long as the diode is exposed to sunlight
and the magnitude of the current is proportional to the light intensity.
Solar cells are used extensively in satellites and space vehicles as most important long-duration
power supply. Solar cells are constructed with silicon, gallium arsenide, cadmium sulphide and with
many other semiconductors, and in various device configurations.
(0
Fig. 10.62 (a) p-n junction solar cell with load resistance, RL
(b) Diffusion of electrons and holes
(c) Energy band diagram corresponding to (b)
(d) Formation of the open circuit voltage 1/Q ■
CHAPTER 10
1. Breaking of a covalent bond produces a free electron, which moves about the lattice in a random manner.
(a) true (h) false
2. A semiconductor is damaged by a strong current
(a) true (&) false ’
X Intrinsic concentration of charge carriers in a semiconductor varies as
(a) T (b)^
(c) T3'12 4 5 (fl VT
4. The dependence of the mobility of charge carriers in a semiconductor is given by
(a) jt * irr (b)[k<x i/r3/2
(c) fl °c T*2 (d) li °c T2
5. In an intrinsic semiconductor, the Fermi level lies almost midway in the forbidden gap
(a) true <*) false
$10 Squd StMI Physks
1
The slope of the straight line drawn between Inp and ol a semiconductor gives
A_
7? W 2kB
ri') tfi (d) 2 kB

7. Minority carriers in a p-type semiconductor are
(a) electrons (b) holes
S. The electronic configuration of silicon is
(a) Is2.2s2. 2p6. 3s2, 3p4
(b) Is2.2s2. 2p6. 3s1, 3p6
(c) Is2.2s2, 2p6, 3s2, 3p2
(d) Is2.2s2. 2p6, 3s°, 3p2
9. The forbidden energy gap of carbon in diamond structure is
(a) 0.7 eV (b) 1 eV
(c) 0.01 eV (d) none of these
10, Iffflp > me. the position of the Fermi level in an intrinsic semiconductor
(a) lies midway between the valence band and conduction band and independent of temperature
(b) will be raised slightly with increase of temperature
(c) will be lowered slightly with increase of temperature
II. The Fermi level in an n-type semiconductor at 0 K lies
(a) below the donor level
(b) half way between the conduction band and donor level
(c) coincides with intrinsic Fermi level
12. When boron atoms are added to pure silicon, one gets
(a) p-type semiconductor (b) n-type semiconductor
13. In a p-type semiconductor, as the density of acceptor atoms Na is increased, the Fermi level shifts towards
the valence band
(a) true (b) false
14. In an n-type semiconductor, as the density of donor atoms Nd is increased, the Fermi level shifts towards
the conduction band
(a) true (b) false
15. Room temperature resistivity of pure germanium in Q-m is
(a) 47 (b) 4.7
(c) 0.47 (d) 0.047
16. A semiconductor exhibits negative temperature coefficient of resistivity
(a) true (b) false
17. In a semiconductor at a given temperature, the rate of generation of electron-hole pair equals the rate of
recombination
(a) true (b) false
When a free electron recombines with a hoiTZ 611
(a) generation of energy ’lhere results
(b) release of energy
(c) no change of energy
19. The density of carriers in a pure semiconductor is nr ■
(a) exp (- Eg/kBT) Proportional to
(c) exp (- Eglk^ {b) exP 2£AD
The energy needed to detach the fifth valence 1^
20.
germanium atoms is approximately 6006 & eCtr°n fr°m the arsenic imPurity atoms surrounded by
(a) 0.001 eV
r(c)\ n0.1i eV
w °-01 eV
_ . (d) 1.0 eV
21. Donor type tmpurity is formed by adding impurity of vakncy
W3 (0)4
(C) 5 M) 6
22. The diffusion current is proportional to
(a) square of the applied electric field
(b) applied electric field
(c) concentration gradient of charge carriers
23- The ratio of the diffusion constant for hole (Dp) to the mobility for hole is proportional to
(a) temperature T , (fe) T1
(c) 1/T (d) independent of temperature
24. In step graded junction, a contact potential gets developed due to difference in the doping of the two
regions
(a) true ' .. (b) false
25. The depletion region in an open circuited p-n junction contains
(a) electrons
(fe) holes
(c) uncovered immobile impurity ions
(d) neutralised impurity atoms
26. The reverse saturation current in a p-n diode
. , . (b) decreases
(a) increases
(c) remains constant with increase of reverse bias
27. The reverse saturation current in germanium diode is of the order o
.., A m pa
(a) 1 nA
(d) 1 ampere
1 ... diode is of the order of
28. The reverse saturation current in s
(b) 1 pA
' nA (d) 1 ampere
(c) 1 mA
EL MBSkoePwma
29. In a junction diode, the transition capacitance (C) is proportional to

(a) X (b) X111
1 1
(c) y (<0 x2
where X is the width of the depletion layer.

30. In a reverse biased p-n diode, the density of minority carrier holes in the n-region at the junction equals
(a) thermal equilibrium concentration, p®
(b) zero
(c)(p°/2)
31. The Einstein relationship between the diffusion constant D and mobility p for electron is
2kBT D„ e
(fl) —= ~JL~ (b)-^ = —
m e m W
Dn kBT Dn
(c) — = (J) — = kBT-E
liilfil
1. Though silicon and aluminium have the same atomic density and mass density, the difference in their
electrical resistivity is very high. Why?
2. Explain the different quantum numbers associated with electron orbit.
3, Give the graphical representation of the energy band model of carbon and silicon.
4. Compare the variation of conductivities with temperature in metals and semiconductors.
5, What are density of energy states in semiconductors?
6. Enumerate some of the properties of a semiconductors.
7, What is an intrinsic semiconductor? Give examples.
8. Explain why the conductivity of a pure semiconductor increases with temperature while that of a metal
decreases.
9. When does an intrinsic semiconductor behave as an insulator?
10. What is a hole in a semiconductor and how is it formed?
11, State and explain the mass action law.
12, Give the resistivities of germanium and silicon at room temperature.
13, What is the characteristic difference between metals and semiconductors from the consideration of
temperature coefficient of resistivity?
14. Explain with the help of suitable diagrams how free electrons and holes contribute towards electric current.
] 5. Write down the expression for the density of carriers in a pure semiconductor in terms of temperature,
Boltzmann constant and forbidden energy gap E.
w many free electrons does one donor atom contribute?
Physics of Sbmicomctk^ws^/6^
17. How n-type and p-type semiconductors are produced?

18. Write down as many as you can of the ways in which n-type and p-type semiconductors differ from an
intrinsic semiconductor.
19. Write down the equation relating mobility of charge carriers in a semiconductor with temperature.
20. What is the magnitude of ionisation energy of impurity arsenic in germanium?
21. Explain the terms mobility of charge carriers and Hall effect.
22. Explain how Hall coefficient is used to determine the mobility of charge carriers.
23. Explain the term Donor exhaustion graphically in an impurity semiconductor.
24. Explain diffusion charge carriers in semiconductors.
25. Get Einstein’s diffusion equation.
26. Give the expression for the diffusion hole current density.
27. Discuss the drift and diffusion phenomena in semiconductors.
28. Differentiate between drift and diffusion currents in semiconductors. Which is more often present in
semiconductor devices?
29. Define diffusion constant for electrons. Give its dimensions.
30. Write the continuity equations for holes and electrons.
31. Define mean lifetime of carriers.
32. Give the principle of Hall effect multiplier.
33. What is meant by potential barrier across a p-n junction?
34. Explain the changes that take place when p-n junction diode is (i) reverse biased (ii) forward biased
externally.
35. Write the continuity equation for holes. Give the physical meaning of each term in the equation.
CHAPTER 10
36. Plot the volt-ampere curve for a p-n diode and explain the nature of this curve.
37. Write a note on Zener diode.
38. A small quantity of indium is incorporated in germanium. Is the crystal n-type or p-type?
39. Why a semiconductor is damaged by a heavy current?
40. What is the difference between hole-current and electron flow?
41. Why is silicon usually preferred to germanium as a transistor material?
42. Distinguish between Zener breakdown and avalanche breakdown.
43. Sketch the experimental set up for measuring Hall voltage.
1. What are semiconductors? How do they differ from conductors? Why an increase in temperature decreases
the resistivity of a semiconductor?
2. Explain with suitable diagrams the conduction band, valence band and the forbidden band and hence
explain the behaviour of conductor, semiconductor and insulator. Explain the contribution of electrons
and holes to electrical conduction.
3. What are intrinsic semiconductors?
Discuss the statistics of intrinsic semiconductors and obtain the expression for the conductivity.
fek Sq^Statt Physics________ ____________________________________________________
4. Write down the expression for density of electrons and holes in an intrinsic semiconductor. Equate these
two equations and arrive at an expression for the Fermi level. Discuss the significance of this equation.
Obtain an expression for the carrier density of an intrinsic semiconductor.
Explain how the resistivity of an intrinsic semiconductor varies with temperature.
6. How is the band model helpful in explaining the various properties of semiconductors?
Give the theory of intrinsic semiconductors.
7. Obtain the equation for the conductivity of an intrinsic semiconductor in terms of earner concentration
and carrier mobilities. Suggest a method for evaluating the energy gap of a semiconductor.
Distinguish between thermal velocity and drift velocity of carriers. Which is normally the larger?
Which controls the mean time between collisions with the crystal lattice? How does a rise in temperature
affect each velocity in a semiconductor?
9- Contrast the energy level diagrams of a hydrogen atom and a metallic solid. Give approximate values for
the separation between energy levels in each case.
10- Distinguish between intrinsic and impurity semiconductors with suitable examples. Discuss the theory of
intrinsic conductivity of a semiconductor.
H- Mark the Fermi level for (i)an intrinsic semiconductor (ii) n-type semiconductor and (iii) p-type
semiconductor. Describe the behaviour and properties of conductors, insulators and semiconductors on
the basis of band theory.
12. What are n-type and p-type semiconductors? How are they produced?
Show that the density of electrons in the conduction band of an n-type semiconductor is proportional to
the square root of donor concentration.
13. What are n-type semiconductors?
“At a given temperature, the product of the electron density and hole density is the same for the intrinsic
and extrinsic semiconductors”. Is this statement true? Can you explain your answer with examples?
14. Discuss how the resistance of an intrinsic semiconductor varies with temperature. Explain further how
such a study could be used to measure the energy gap of the semiconductor.
Is- Distinguish between metals, semiconductors and insulators.
Assuming the Fermi-Dirac distribution, derive the expression for the number of electrons per unit volume
in the conduction band of an intrinsic semiconductor. Discuss how this number depends on temperature
and energy gap.
16. Obtain the quadratic equation for the Fermi level in an n-type semiconductor. Solve it for low temperature
range and hence show that the density of electrons in the conduction band is proportional to the square
root of donor concentration.
1 7* Derive an expression for the density of holes in an intrinsic semiconductor. Suggest a method for evaluating
the energy gap of the semiconductor.
18- Distinguish between intrinsic and impurity semiconductors. Give an example for each class of
semiconductors.
Indicate on an energy level diagram the conduction and valence bands, donor and acceptor states. What
are the positions of Fermi levels for
(a) an intrinsic semiconductor?
(b) a n-type semiconductor?
(c) a p-type semiconductor?
___ ___________________ ___________________ Physics of Semiconductors 6iS
'.g ■ atically show the energy levels of a pure semiconductor, semiconductor with donor impurity
, . C°n ?ctor W'^ accePtor impurity. Write down the expression based on Fermi statistics for the
' , , ln ln^r'ns’c semiconductor. Explain its dependence on the energy gap between the conduction
band and valence band and temperature.
_(. Derive expressions for the densities of electrons and holes in the conduction and valence bands respectively
in an intrinsic semiconductor. Show that the Fermi energy level in an intrinsic semiconductor lies
approximately half way between the top of the valence band and the bottom of the conduction band.
21. Distinguish between intrinsic and extrinsic semiconductors. Obtain an expression for the carrier
concentration for an intrinsic semiconductor.
When does an extrinsic semiconductor become an intrinsic semiconductor?
22. How are p-type and n-type crystals obtained? “When donor-type impurities are added to a semiconductor
the concentration of holes decreases” — Explain with reasons.
23. Explain with necessary theory the concept of minority carrier lifetime in an impurity semiconductor.
24. Give the theory of direct recombination of carriers in semiconductors and hence obtain the expression for
the decay of minority carriers injected into a semiconductor.
25. Explain the term Donor exhaustion graphically and hence discuss the variation of conductivity with
temperature of an n-type semiconductor. Write a note on direct recombination of carriers in semiconductors.
26. Explain the phenomenon of diffusion of charge carriers in semiconductors. Define Diffusion constant and
give its units. What is Einstein’s relationship?
27. What is Hall effect? Briefly discuss the physical origin of Hall effect. What are the uses of this effect?
28. What is Hall coefficient ? Show that for a p-type semiconductor the Hall coefficient RH is given by
1
R"h = —
pe
CHAPTER 10
Describe an experimental set-up for the measurement of the Hall voltage.
29. What do you understand by drift and diffusion currents in the case of a semiconductor? Deduce Einstein
relation relating to these currents.
30. Light falls on one end of a long open-circuited extrinsic semiconductor bar. Sketch the steady minority
carrier concentration as a function of distance. Define the symbols in the equation describing the sketch.
31. The barrier potential across a p-n junction assists the flow of holes from n-region to p-region. But the net
hole current flow under thermal equilibrium is zero. Explain.
32. Discuss the drift and diffusion phenomena in semiconductors.
Explain the mechanism of current flow through a forward biased junction diode and draw its V-I
characteristics.
33. Explain qualitatively how a p-n junction functions as a rectifier.
34. Give the circuit for studying diode characteristics, and obtain the equation for saturation current in terms
of temperature.
35. Define diffusion potential connected with p-n semiconductor junction. Explain how it arises. Compute the
value of the diffusion potential in a p-n junction in terms of the impurity concentrations and doping levels.
36. Point out the importance of the continuity equations. Deduce the continuity equation for the electrons in a
p-type material,
37. Explain the term depletion layer across a p-n junction. Obtain the expression for the width of the depletion
layer in terms of the impurity concentrations and barrier potential.
Explain how a semiconductor diode can be used as a rectifier.
Discuss the operation of a p-n junction diode.
39. What is the effect on the space charge width at a p-n junction when the junction is (i) forward biased, and
(if) reverse biased. Draw the circuit diagrams of (a) a forward biased p-n junction, and (6) a reverse biased
p-n junction.
40. Draw the energy band diagram of an unbiased p-n junction. Explain the terms: Barrier energy, barrier
potential, and depletion region, as applied to a p-n junction.
41. What is breakdown diode? What are its uses? Describe how breakdown in a p-n junction occurs.
42. What is drift current and diffusion current in a semiconductor? Write an expression for the total electron
current density in a semiconductor.
43. Explain the working of a p-n junction. Discuss forward and reverse biasing of p-n junction diode.
44. Explain with diagrams forward and reverse biasing of a p-n junction. What is meant by avalanche
breakdown?
45. Draw the (V-I) characteristics of a tunnel diode and discuss its applications.
46. Show that for the condition where the acceptor density in the p-type region is greater than the donor
density in the n-type region, the total depletion width of the p-n junction when there is no applied voltage is
r iV*
=---... —=
1- For an intrinsic semiconductor with gap width Eg = 0.7 eV, determine the position of Fermi level at
T — 300 K if mp =6me. Also calculate the density of holes and electrons at 300 K. How do these quantities
alter if E = 7 eV?
g
2. Calculate the intrinsic concentration of charge carriers in germanium at 300 K. Eg for germanium is
0.67 eV. Given m*/m0 = 0.12 and m*p/mQ = 0.28.
3. Mobilities of electrons and holes in a sample of intrinsic germanium at 300 K are 0.36 m2 V-ls-1 and
0.17 m2 V 1 s 1 respectively. If the resistivity of the specimen is 2.12 £2-m, compute the forbidden energy 8aP-
4. The following data are given for intrinsic germanium at 300 K
n, = 2.4 x 1019/m3
p, = 0.39 m2 V-’s-1
pp = 0.19 m2 V-’s-1
Calculate the conductivity of the sample.
5. The band gap of an alloy of semiconductor gallium arsenide phosphide is 1.98 eV. Calculate the wavelength
of radiation that is emitted when electrons and holes in this material recombine directly. Mention the
colour of the emitted radiation.
6. Calculate the current produced in a small germanium plate of area 1 cm2 and of thickness 0.3 mm,
a potential difference of 2 volt is applied across the faces. Given: Concentration of free charge carried 1 (
germanium is 2 x 10l9/m3 and the mobilities of electrons and holes are 0.36 m^'s-1 and 0.17 m2 V s
respectively.
"!• Compare the density of charge carriers in a pure silicon crystal at the two temperatures 27°C and 57°C. E
for Si is 1.1 eV. *
8. The variation of the resistivity of intrinsic germanium with temperature is given by the following table:
T (K) 385 455 556 714
p(Q-m) 0.028 0.0061 0.0013 0.000274
Determine the value of E .
8
9. Find the resistance of an intrinsic germanium rod 1 cm long, 1 mm wide and 1 mm thick at 300 IC For
germanium n. = 2.5 x 1019/m3, |ie = 0.39 n^V^s"1, = 0.19 m^-’s-'at 300 IC
10. In an intrinsic semiconductor the effective mass of the electron is 0.07 mQ and that of the hole is 0.4 m0
where mQ is the rest mass of the electron. Calculate the intrinsic concentration of charge carriers at 300 IC
Given : Eg = 0.7 eV.
11. Intrinsic semiconductor material A has an energy gap 0.36 eV while material B has an energy gap of
0.72 eV. Compare the intrinsic density of carriers in these two semiconductors at 300 K. Assume that the
effective masses of all the electrons and holes are equal to the free electron mass.
12. A specimen of germanium is doped with 0.1 atomic present of arsenic. Assuming that at room temperature all
the arsenic atoms are ionised, find the electron and hole densities in germanium. The intrinsic earner density at
room temperature in germanium is 2.37 x 1019/m3. The density of germanium atom is 4.41 x lO^/m3.
If the electron and hole mobilities at room temperature are 0.38 and 0.18 m2V-1s-1 respectively, calculate
the resistivity of (a) intrinsic germanium and (b) germanium containing 0.1% arsenic.
13. A sample of germanium is made of p-type material by adding acceptor atoms at a rate of one atom per
4 x 108 germanium atoms, n. = 2.5 x 1019/m3 at 300 K and all the acceptor atoms are ionised at 300 K. The
density of germanium atoms in 4.4 x lO^/m3. Compare the density of holes with that of intrinsic charge
carriers. >
14. Calculate the position of Fermi level Ef and the conductivity at 300 K for a germanium crystal containing
5 x 1022 arsenic atoms/m3. Also calculate the conductivity if the mobility of the electron is
0.39 n^V-V1.
15. Consider a sample of n-type silicon with Nd = lO^/m3. Find n and p at 300 K. Number of intrinsic carriers
at 300 K is 9.8 x 1015.
16. A sample of intrinsic germanium at room temperature has a carrier concentration of 2.4 x 10,9/m3. It is
doped with antimony at a rate of one antimony atom per million atoms of germanium. If the concentration
of germanium atoms is 4.8 x 1028/m3, find the hole concentration and die conductivity of the semiconductor.
Assume complete ionisation of antimony atoms.
Given: \in = 0.35 m2V-1s-1.
17. In a semiconductor the effective mass of the electron is 0.07 m0 and that of a hole is 0.4 where is the
free electron mass. Assuming that the average relaxation time for the holes is half that for the electrons,
calculate the mobility of the holes when the mobility of the electrons is 0.8 n^V's"'.
18. If a sample of silicon is doped with 3 x 1023 arsenic atoms and 5 x 1023 atoms of boron, determine the
electron concentration if the intrinsic charge earners are 2 x 10l6/m3.
19. In an n-type semiconductor, the Fermi level lies 0.3 eV below the conduction band at 300 K. If the
temperature is increased to 330 K, find the new position of the Fermi level.
$18 Solid State Physics
20. The intrinsic carrier density for silicon at 300 K is 1.5 x l0I6/m3. Find the equilibrium majority and
minority carrier density at 300 K when silicon is uniformly doped with IO16 phosphorus atoms/m3. If the
resulting extrinsic semiconductor is then uniformly doped with 2 x 1016 boron atoms/m3, what are the
final free carrier densities at 300 K?
Assume charge neutrality exists throughout.
21. In a n-type semiconductor, the Fermi level lies 0.4 eV below the conduction band. If the concentration of
donor atoms is doubled, find the new position of the Fermi level. Assume kgT = 0.03 eV.
22. In a p-type semiconductor, the Fermi level lies 0.4 eV above the valance band. If the concentration of
acceptor atoms is tripled, find the new position of the Fermi level. Assume kgT = 0.03 eV.
23. The energy gap of Si is 1.1 eV. Its electron and hole mobilities at room temperature are 0.48 and
0.013 m2V-1s-1 respectively. Evaluate its conductivity.
24. A silicon crystal is made n-type by introducing Nd donor levels /m3. The donor energy level and the Fenni
level coincide at 0.1 electron volt below the bottom of the conduction band Ec. Calculate the electron, hole
and donor densities for the crystal. Given: Eg = 1.11 electron volt, T = 300 K.
25. Find the conductivity of intrinsic silicon at 300 K. It is given that the density of intrinsic charge carriers at
300 K in silicon is 1.5 x 1016/m3 and the mobilities of electrons and holes in silicon are 0.13 m2V-1s-1 and
0.05 m2V-ls-1 respectively. Also calculate the conductivity if donor type impurity is added to the extent of
one impurity atom in 108 silicon atoms.
26. Germanium has a donor type of impurity added to the extent of one atom per 108 germanium atoms. What
effect does this have on the conductivity of the material at 27°C ? Given : pn = 0.39 m2V-1s-1 and
pp = 0.19 m2V*'s-1 for intrinsic germanium. Electron mobility of the doped germanium is 0.38 m2V-1s-1.
Eg = 0.067 eV.
27. Prove that in the case of extrinsic semiconductors, the product of the majority and minority carrier densities
is equal to the square of its intrinsic concentration of carriers. Take a sample of n-type semiconductor at
27°C with 1022 donor atoms/m3.
2S. A silicon crystal is doped with indium for which the electron acceptor level is 0.16 eV above the top of the
valence band. For silicon the energy gap is 1.1 electron volt and the effective masses of holes and electrons
are 0.39 and 0.26 respectively. What impurity density would cause the Fermi level to coincide with
impurity level at 300 K and what fraction of the acceptor level will be filled ?
Calculate the minority carrier concentration in the crystal.
29. Calculate the intrinsic conductivity at 300 K for germanium. Calculate also the dependence of conductivity
on temperature about room temperature.
Eg = 0.72 eV;
pm = 0.39 m2 V-,s-1; and
pp = 0.19 m2 V-'s-',
30. An n-type semiconductor has IO20 donor atoms/m3 which are completely activated at 300 K. The electrons
in the conduction band may be represented by Ne = 2.5 x 10s available levels/m3 at the bottom of the
conduction band Ec with the probability of occupation equal to exp [- (E - E)lkgT]. Determine the
position of the Fermi level. Also calculate the density of holes due to intrinsic semiconductor for an
energy gap of one electron volt.
3 J. A pure semiconductor has an energy gap of 1 eV. For temperature of 0 K and 300 K respectively, calculate
the probability of an electron occupying a state near the bottom of the conduction band.
32. Compute the concentration of electrons in an intrinsic sample of Si at room temperature. Given ■
m’ = 0.7 m0 and mp - m0 and Eg = 1 eV.
Physics of Semiconductors 619
33. Calculate the resistivity at 300 K for pure germanium from the following data:
Eg = 0.72 eV
pn = 0.39 m2V-1s-1
pp = 0.19 m2V-1s-1.
34. Germanium crystallises in the diamond cubic structure with eight atoms in the unit ceil. From X-ray
measurements the edge of the unit cell is found to be 0.562 nm. Calculate the density of germanium.
35. Calculate the density of donor atoms which has to be added to intrinsic germanium to produce n-type
material of resistivity 0.19 X 10-2 Q-m. It is given that the mobility of electrons in the n-type semiconductor
is 0.325 m2 V-1s-1.
36. Germanium crystallises in the diamond structure with eight atoms in per unit cube. From X-ray
measurements the edge of the unit cube is found to be 0.562 nm. Calculate the concentration of germanium
atoms.
37. Electrons in an n-type germanium have a mobility 0.36 m2 V-1s-1 at room temperature. Assume that the
effective mass of an electron in the conduction band is (l/4)m0, where mQ is the mass of the electron.
Calculate the time between collisions with the lattice.
38. A specimen of an extrinsic p-type silicon material has the following dimensions: Length 5 mm; width
2 mm; thickness 1 mm. Calculate the impurity concentrations of the specimen if the electrical resistance is
100 Q. The electron and hole mobilities may be taken as 0.12 and 0.25 m2 V-1s-1 respectively and the
intrinsic carrier density is 2.5 x 1016/m3. Determine the ratio of conductivities of electrons and holes.
39. Crystalline pure germanium has 4.5 x 1028 atoms/m3. At 300 K, one atom in 2 x 109 is ionised. The
mobilities of electrons and holes at 300 K are 0.4 and 0.2 m2V-1s_1. Determine the conductivity of pure
germanium Also estimate the conductivity of germanium doped by the addition of one part in 107 of a
CHAPTER 10
trivalent element at 300 K.
40- Compare the free electron densities in the intrinsic germanium and silicon at 50°C and 100°C with those
at room temperature (300 K). Assume that the effective densities of states in the conduction and valence
bands, N and N respectively, are independent of temperature. The energy gaps of Ge and Si may be taken
as 0.7 eV and 1.1 eV respectively at the above temperature. Neglect the temperature variation of the
mobilities. The intrinsic resistivities for germanium and silicon are 0.5 Q-m and 100 £2-m respectively at
300 K.
41- A semiconducting crystal, 12 mm long, 5 mm wide and 1 mm thick, has a magnetic flux density of
0.5 weber/metre2 applied from front to back perpendicular to largest faces. When a current of 20 mA flows
lengthwise through the specimen, the voltage measured across its width is found to be 37 pV. What is the
Hall coefficient of this semiconductor? What is the density of the current carriers?
Estimate what the above voltage (37 pV) would have been if a specimen of copper of similar dimensions,
and with the same 20 mA current flowing along its length, had been placed in the same field.
42. The conductivity of germanium at 20°C is 2 fl"*m”'. What is its conductivity at 40°C ? Eg = 0.72 eV.
43. Silicon has a conductivity of only 5 x 10 4 (I'm1 in its pure form. An engineer wants it to have a
conductivity of 200 Q 'nr1 when it contains aluminium as an impurity (p-type). Calculate the mass of
aluminium to be added per m3 of the crystal in order to get this conductivity p p = 0.05 m2 V_|r'.
44. Using the general equation for p, show that (dp/dE) is maximum in the valence band at Ev - E ~ (kBT)T2.
620 ôu^;Sjim Physics ’
45. A cadmium sulphide photo detector crystal is irradiated over a receiving area of 4 x IO-6 m2 by light of
wavelength 0.4 x 10-6 metre and intensity 200 watt/m2.
(a) If the energy gap of cadmium sulphide is 2.4 eV, confirm that electron-hole pairs will be generated.
(b) Assuming each quantum generates an electron-hole pair, calculate the number of pairs generated per
second.
(c) The increase in the density of electrons is given by the product of number of electrons produced per
sec and the lifetime of the electron carriers. Calculate the increase in conductivity for an electron of
lifetime 10~3 sec and an electron mobility of IO-2 m2V-1s-1.
46. Obtain an order of magnitude ratio of two resistivities at room temperature: One exhibited by pure silicon,
and the other containing 0.001 atomic percentage of phosphorus. Lattice parameter for Si is 0.5431 nm.
47. Assuming that in an intrinsic silicon at room temperature, 10% of the free electrons recombine with holes
each second, calculate the approximate rate of release of energy which results. Given n. = 6 xl015/m3,
=1.15 eV.
48. Calculate the resistance at 300 K of a block of silicon of length 0.5 cm and cross-section 3 x 10“7 m2 doped
with 4 x IO22/™3 phosphorus atoms. What current flows when 1 V is applied along its length. The mobility
of the majority charge carriers is 0.14 m2 V-1s-1.
49. An electric field of 100 V/m is applied to a sample of n-type semiconductor whose Hall coefficient is
- 0.0125 m3/coulomb. Determine the current density in the sample assuming pn = 0.36 m2 V-1s-1.
50. The room temperature electron mobility in GaAs is 0.08 m2V-1s-1, Calculate the diffusion constant for
electrons.
51. The resistivity of a semiconductor was known to be 0.00893 Q-m at room temperature. The flux density
Bz in the Hall model was 0.5 weber/metre2. Calculate the Hall angle for a Hall coefficient of 3.66 x 10~4
m3/coulomb.
52. The Hall coefficient of a certain specimen of silicon was found to be -7.35 x 10-5 m3 C-1 from 100 to
400 K. Is this semiconductor intrinsic or extrinsic at room temperature, and is it n-type or p-type? The
electrical conductivity at room temperature was found to be 200 Q-1 nr1. Calculate the density and
mobility of charge carriers at room temperature.
53. The resistivity of a doped silicon sample is 8.9 x 10-3 £2-m. The Hall coefficient was measured to be
3.6 x l(L4m3/C. Assuming single carrier conduction, find the mobility and density of charge carriers.
54. Find the diffusion coefficients of electrons and holes of a single crystal at 27°C, if the mobilities of
electrons and holes are 0.17 and 0.025 m2V-1s-1 respectively at 27°C.
55. We have a bar of silicon which is 2 cm long and has a cross-sectional area of 1 cm2. The crystal is n-type
with a donor concentration of 1023/m3. If we put some good contacts over the ends of the bar and measure
a resistance of 10 ft, what is the electron mobility?
56. A rod of semiconductor 2 cm long, 2 mm wide and 1 mm thick has contacts at each end to which 20 V d.c.
is applied. The rod is exposed to a uniform beam of radiation, the absorption of which increases the
current by 2.5 mA. When the beam of the radiation suddenly cut off, the current decreases initially at the
rate of 21.5 amp/sec. If = 0.39 and = 0.19 m2 V-ls-1, find (a) the minimum frequency of the
electromagnetic radiation (/>) the equilibrium density of electron-hole pairs due to the exposure to radiation
(c) the minority carrier lifetime and (J) the excess density of electrons and holes remaining 0.5 millisecond
after the radiation is cut off. Eg for the semiconductor is 0.72 eV.
Physics
57. At t = 0 sec, the injected density of holes in a bar of germanium is 102o/m3. Ten microsecond latter the
density decreased to 10l9/m3. What is the lifetime of the hole in the bar?
58. A semiconductor contains acceptors and the hole concentration is lO^/m3. Assume that the density of
states in the valence band Nv is lO^/m3.
(a) How far above the valence band in eV does the Fermi energy level (£p lie at 300 K?
(h) Consider a semiconductor, germanium, with a band gap E = 0.66 eV and equal density of states in the
conduction and valence bands.
i .e., Ng = Nv = lO^/m3. The temperature is 300 K.
(i) What is the value of intrinsic carrier concentration, n.?
(») If the number of electrons n is lO^/m3, what is the value of the hole concentration, p?
59. If the carrier mobility of a sample is 0.2 m2V-1s-1 at 0°C, what is the diffusion constant at the same
temperature?
60. The minority carrier lifetime in p-type Si material is 10-7s. The mobility of electron in silicon is
0.15 m2 V-V1 at 300 K.
(a) What is the diffusion length, Ln ?
(b) If IO20 electrons/m3 are injected at x = 0, what is the diffusion current density at x = 0?
(c) If there are 1021 holes/m3, what electric field will be required to give the same current as in part (i>)?
Given Lt = 0.045 m2V-1s-1.
rp
61. In one particular experiment, the lifetime of electrons at room temperature in an n-type germanium crystal
with a general surface is found to be 78 |£s, whereas with an acid-etched surface it is 340 ps. Assuming an
electron mobility of 0.36 m2V-’s-1, find the diffusion length of the electron in both specimens.
62. A semiconductor AX compound with an np equilibrium constant of lO^/m6 is made into two forms:
CHAPTER 10
(a) Intrinsic with an excess carrier lifetime of 600 p. sec and
(h) p-type with an equilibrium hole concentration of 1019/m3 and an excess carrier lifetime of 200 ps. A
light source which induced 3 x 1018/m3 excess carriers is turned off. Compare the number of excess
conduction electrons and holes as a function of time.
63. A junction has a built-in potential difference of 0.8 V and a forward bias of 0.55 V is applied, What is the
potential difference across the depletion regions? What is its value if the bias is reversed ?
64. Compare the built-in voltage in junctions made in Si and Ge having the doping concentrations Nd= 1020
and Na = 1023 at 300 K. Given: n,. for germanium is 2.4 x 10l9/m3 and n for Si is 1.4 x 10,6/m3.
65. The conductivities of the p-region and the n-region of a germanium p-n junction are 1000 fiT'm1 and
200 £2-1m-1 respectively. The cross-section of the crystal is 0.05 cm2 and the relative dielectric constant
for germanium is 16. Calculate the width of the depletion layer and the junction capacity when the p-n
junction is (a) unbiased, (b) when it is forward base by 0.1 V, and (c) when it is reverse biased by 10 V.
Assume the junction is an abrupt one, |ip = 0.19 m2V-1s’1 and pB = 0.39 m*V’s-1 and n( = 2.15 xl09/m3.
66. A germanium p-n junction diode has 1022 donor atoms/m3 of the n-region and 2 x IO21 acceptor atoms/m3
of the p-region. Find the value of the barrier potential developed across the unbiased junction at room
temperature. Calculate the total width of the depletion layer and the junction capacity if the p-n junction
is abrupt one. The relative dielectric constant for germanium is 16 and the area of cross-section of the
•diode is 0.01 cm2. (kBTle) = 0.026 V. Show that the major portion of the depletion layer is situated In the
p-type. Given n, = 2.4 x 1019/m3.
67. Find the static and the dynamic resistance of a p-n junction germanium diode if the temperature is 27°C
and /0 = 1 |xA for an applied forward bias of 0.2 volt.
Physics of Semiconductors 621
§7 . At t = 0 sec, the injected density of holes in a bar of germanium is 102°/m3. Ten microsecond latter the
density decreased to 10l9/m3. What is the lifetime of the hole in the bar?
58. A semiconductor contains acceptors and the hole concentration is 1022/m3. Assume that the density of
states in the valence band Nv is 1025/m3.
(a) How far above the valence band in eV does the Fermi energy level (Ej) lie at 300 K?
(b) Consider a semiconductor, germanium, with a band gap Eg = 0.66 eV and equal density of states in the
conduction and valence bands.
i .e., Ne = Nv= 1025/m3. The temperature is 300 K.
(i) What is the value of intrinsic carrier concentration, n.?
(ii) If the number of electrons n is 1023/m3, what is the value of the hole concentration, p?
59. If the carrier mobility of a sample is 0.2 m2V-1s-1 at 0°C, what is the diffusion constant at the same
temperature?
60. The minority carrier lifetime in p-type Si material is 10-7s. The mobility of electron in silicon is
0.15 m2 V-’s’1 at 300 K.
(a) What is the diffusion length, Ln ?
(b) If IO20 electrons/m3 are injected at x = 0, what is the diffusion current density at x = 0?
(c) If there are 1021 holes/m3, what electric field will be required to give the same current as in part (b)?
Given = 0.045 m2V-ls-1.
61. In one particular experiment, the lifetime of electrons at room temperature in an n-type germanium crystal
with a general surface is found to be 78 |xr, whereas with an acid-etched surface it is 340 Jis. Assuming an
electron mobility of 0.36 m2V_,s"1, find the diffusion length of the electron in both specimens.
62. A semiconductor AX compound with an np equilibrium constant of 1036/m6 is made into two forms:
CHAPTER 10
(a) Intrinsic with an excess carrier lifetime of 600 |1 sec and
(b) p-type with an equilibrium hole concentration of 1019/m3 and an excess carrier lifetime of 200 (is. A
light source which induced 3 x 1018/m3 excess carriers is turned off. Compare the number of excess
conduction electrons and holes as a function of time.
63. A junction has a built-in potential difference of 0.8 V and a forward bias of 0.55 V is applied, What is the
potential difference across the depletion regions? What is its value if the bias is reversed?
64. Compare the built-in voltage in junctions made in Si and Ge having the doping concentrations Nd= 1020
and Na = 1023 at 300 K. Given: nt for germanium is 2.4 x 1019/m3 and n. for Si is 1.4 x 1016/m3.
65. The conductivities of the p-region and the n-region of a germanium p-n junction are 1000 fT'm1 and
200 Q-'m*1 respectively. The cross-section of the crystal is 0.05 cm2 and the relative dielectric constant
for germanium is 16. Calculate the width of the depletion layer and the junction capacity when the p-n
junction is (a) unbiased, (b) when it is forward base by 0.1 V, and (c) when it is reverse biased by 10 V.
Assume the junction is an abrupt one, = 0.19 m2V_,s_| and pn = 0.39 m2V *s 1 and n. = 2.15 xl09/m3.
66. A germanium p-n junction diode has 1022 donor atoms/m3 of the n-region and 2 x 10-1 acceptor atoms/m3
of the p-region. Find the value of the barrier potential developed across the unbiased junction at room
temperature. Calculate the total width of the depletion layer and the junction capacity if the p-n junction
is abrupt one. The relative dielectric constant for germanium is 16 and the area of cross-section of the
diode is 0.01 cm2. (kBT/e) = 0.026 V. Show that the major portion of the depletion layer is situated m the
p-type. Given n(.= 2.4 x 1019/m3.
67. Find the static and the dynamic resistance of a p-n junction germanium diode if the temperature is 27°C
and /Q = 1 pA for an applied forward bias of 0.2 volt.
Solid State Physics
68. In a Zener diode circuit the supply voltage is 9 V and the Zener voltage is 6 V. If the maximum Zener
current that can safely flow be 20 mA, determine the value of series resistance R. If a load resistance Rt of
1 kQ be connected across the Zener diode, calculate the load current and the Zener current. Also calmly
the minimum value of RL that can be employed.
69. For what voltage will the reverse current in a p-n junction germanium diode attain a value of 90% of its
saturation value at room temperature?
70. Calculate the applied voltage for a current across a p-n junction of 1 mA. Room temperature is TFC. The
value of saturation current is IO-6 ampere.
71. You have an abrupt p-n junction with 1024 donors Zm3 and 1022 acceptors Zm3 with a junction potential of
0.6 V (VB) at 300 K.
(a) With no applied voltage, what is the electron concentration in the p-type material?
(b) The electron mobility is 0.1 m2V-,s-1 and the lifetime is 10"6 sec; under forward bias if the injected
electron concentration at the edge of the depletion region is lO^/m3, what is the electron current
density?
(c) If the area of the injection is KT6 m2 and the dielectric constant is IO-10 farad Zm, what is the capacitance
of the p-n junction with 10 V reverse?
72. An abrupt Si p-n junction is doped with 1021Zm3 boron atoms in the p-region and lO^Zm3 phosphorus
atoms in the n-region. Calculate at 300 K:
(a) VB, the barrier potential.
(b) The depletion layer thickness in each side when -10 V is applied.
(c) The capacitance with -10 V bias, if the area is IO"8 m2. Given e = 12 and n. = 1.6 x 10l6An3.
73. Find the magnitude of the barrier in an abrupt silicon junction in which the p-side is doped with one boron
atom for each 106 silicon atoms, and in which the n-side is doped with one phosphorus atom for each
5 x 107 silicon atoms.
Take the temperature to be 300 K, the density of silicon to be 2400 kgZm3, its relative atomic mass to be
28.1 and the intrinsic charge carrier density to be 1.5 x 10,6Zm3.
74. Find the value of the applied forward voltage for a p-n junction diode if ZQ = 30 micro ampZcm2 and
I = 2 ampZcm2 and e/k.BT = 39 voir1.
75. The approximate value of p-n junction current under forward bias is given by I = Zo exp (cV/tg7T Show
that the incremental resistance Re, defined by
(AV7AI) is equal to I —— I at room temperature. Given (elkJT) = 39 V-’.
76. Silicon wafar is doped with 1021 phosphorousZm3. Calculate

(a) concentration of majority carriers,
(b) minority carrier concentration and
(c) electrical resistivity at 300 K.
Given n( at 300 K is 1.5 xl0l6Zm3; mobility of holes is 0.035 mÎM-n and mobility of electrons is O-Otf
m2ZV-s.
Dielectrics and Related Properties j
I. INTRODUCTION —---- -
So far, we have been largely concerned with the properties of charge carriers in metals and semiconductors.
However, there are many other materials with very few electrons to take part in normal electric
conductivity. Such materials have dielectric properties and so it is possible to conceive the ideal insulators
which would have no free electrons. A dielectric material has interesting electrical properties because
of the ability of an electric field to polarise the material to create electric dipoles. A dipole is an entity in
which equal positive and negative charges are separated by a small distance, the electric dipole moment
is given by
\l = qdl (11.1)
The electric dipole is a vector. In its simplest model, a dipole moment consists of two point
charges of opposite sign, +q and -q separated by a distance dl.
Choosing the origin of the coordinate system to coincide with the negative charge, the dipole
moment in this case has a magnitude equal to q dl, and is represented by a vector pointing from the
negative charge in the direction of the positive charge, as shown in
Fig. 11.1. The unit of electric dipole moment is the Debye (1 Debye = -q di +q
3.33 x IO-30 coulomb-metre). In spite of being poor conductor of
jl = qdl
electricity, or perhaps because of it, the dielectrics are most interesting
and useful electrical engineering materials. The extensive applications
as insulators and capacitors and their properties can predetermine the Fig. 11.1 Separated cnarges
forming a dipcle
electrical performance and quality of such devices.
It is a fundamental experimental result, first discovered by Faraday, that the capacitance of a
condenser is increased if the space between the conductors is filled with a dielectric material. If CQ is the
capacitance of the condenser with the region between the conductors evacuated and C its capacitance
when the region is filled with a dielectric, then the ratio
is found to be independent of the shape or the dimensions of the conductors and is solely a characteristic
of the particular dielectric medium used, e is called the relative permittivity or the dielectric constant of
the medium. In the S.I. system of units the permittivity of the medium is defined as
e = eoer (11.3)
623
pr Soub State Physics
where £0= 8.854 x 10~12 Fnr1 and is an electric constant which represents the permittivity of VMuum
whilst £r is the relative permittivity of the material. The term dielectric constant is sometimes used
both £ and £r. Since this causes confusion the terms permittivity and relative permittivity arc to he
preferred. The dielectric constant of a material is a macroscopic quantity that measures how effective art
electric field is in polarising the material.
In this Chapter we wish to develop our model of the solid by associating electric charges, electric
dipole moments, and possibly higher order electric moments with the lattice points. By so doing, we
hope to account for the observed electric and dielectric properties of non-metals.
Insulators or dielectrics are substances which do not possess free electric charges under ordinary
circumstances. This does not mean that they cannot modify the electric field into which they are
introduced. In fact the most important property of dielectrics is their ability to become polarised under
the action of an external electric field. The atoms and molecules of dielectrics are influenced by an
external field and hence the positive particles are pushed in the direction of the field while the negative
particles in the opposite direction from their equilibrium position. Hence dipoles arc developed and
they produce a field of their own. The process of producing electric dipoles out of neutral atoms and
molecules is referred to as polarisation.
•1A'.TirVIEW'OFBASICLFORinULA'F,”'~" 1 ■■
Coulomb's law is the experimental foundation upon which the theories of electromagnetic phenomenon
and electrodynamics are based. This law expresses the mechanical force between charged bodies in
terms of the magnitude of the charges, q{ and q2 (in coulomb), and their separation, r (in metre).
i-e., F=--'-2-r2 newton (114)

4tc e r
where, ir is a unit vector directed from the centre of charge of one body to the centre of charge of the
other body E = E0Er. Table 11.1 gives the relative permittivity of a number of dielectric materials; the
values given are for static or low frequency (< 1000 Hz) fields. The relative permittivity of a material is
a directly measurable quantity which expresses on a macroscopic scale the overall result of the interaction
which occurs on a microscopic scale between an externally applied field and the atoms or molecules of
the material. The interaction is referred to as polarisation.
The force on a charged body in an electric field is
F = (Ê) newton (11.5)
where, q{ is the charge on the body expressed in coulomb. A combination of equations (11.4) and (11.5)
determines the electric field, E, arising from a point charge, q2:
E = - -■* 2 i volt/metre (11.6)

4rterr
By definition, the electric field is the negative gradient of the potential distribution in the region.
Dimcrwa and
dV = -E Jr
b
vb - V
V ya =
1_2 (11.7)
4ite|_rfc ra
Let the reference point for measuring the potential be the point a; further, let point a be relatively
long distance from the charge, qr Locate the origin at the charge q2 and mathematically let r «»; then
the potential at point b is
K=--^- (H.8)
b 4n e rb
A dimensional analysis of equation (11.6) yields
I” coulomb metre coulomb

[E] = _______ x_____ =---------------
. metre2 farad J metre farad
The ratio of charge to voltage is defined as capacitance

measured in farad (Q/V = C). Therefore
[E] = [volt/metre]
In the rationalised m.k.s. system of units, one line of force
or one flux line originates on each unit charge. Hence a charge
qi will send q{ lines of forces and this will be received by an
area Anr2. The number of fines of forces received by unit area is
called flux density or electric displacement, D.
Thus, D = T^ (11.9) Fig. 11.2 Unes of forces from a charge <?.

4 nr
Let us now consider an electric field produced by the charge qv Consider another chaige q2 at a
distance r from qv Let the force experienced by the charge q2 be F. Now
„ F
E= —
<h
Substituting for F, one gets
F _
E=
<h 4a e r2q2
i.e., <l\
E=
4nera
Table 11.1 The relative permittivity of some selected substances nt .’(>(
Dielectric er Dielectric Dielectric e,
Vacuum 1 (by definition) Polyethylene 2.25 Cotton 5
Air 1.0006 Polyvinyl chloride (PVC) 6 Hydrogen chloride 1.003

Paraffin 2.2 Epoxy resin 3.6-11 Chloroform 5.1
Benzene 2.284 Glycerine 50 Ethyl alcohol 25.8
Ice at -5°C 2.9 Water (distilled) 81 Nitrobenzene 36.5

Rubber 2.94 Calcite 6.1 Potassium chloride 4.8
Amber 2.7 Noeprene 7 Rock salt 6
Quartz 3.8 Bee wax 2.7 Calcite 6.1
Bakelite 5 Barium titanate 1200 Hydrogen 1.00027
Glass 5-10 Liquid ammonia (-78°C) 25 Oxygen 1.00055
Mica 3-6 Sodium chloride 25.62 Nitrogen 1.0006
Germanium 16 Transformer oil 2.2 Ethylene 1.00138
Marble 10-15 Viscous vaseline 2.2 Carbon tetrachloride 2.24
Diamond 5.5 Polystyrene 2.6 Benzene 2.28
Porcellian 5.5 Ammonia 1.00072 Tbluene 2.39
(11-10)
or
i.e., EEo£r=D (ll.H)
PgEep (11.12)
or
with er= 1
Thus, DxeeJ-^- x-^-

L metre metre.
is the unit of D.
Thus, the unit of electricflux density is coulomb/metre2.
Gauss Theorem
It states that the total normal electric induction through a closed

surface is equal to the charge enclosed by the surface.
Figure 11.4 is a sketch of a point charge, q, surrounded
by a closed surface of any desired shape. The electric flux
passing through a differential area is
Rg. 11.3 Electric field intensity
dig = DdA (11.12a)
The unit vector may be written as the vector r

divided by its magnitude or r/r. With this substitution,
the electric flux is
q CrdA"]
¥=^Lv"J
The term in parenthesis is the differential solid

angle, d(0, subtended at the charge q by the differential
CHAPTER 11
area, dA. fig. 11.4 An illustration of rhe resuhs of Gauss's
law of electrostatscs
q
Thus, dig = — das
T 4n
The total electric flux that emanates from the charge q is found by integrating over the entire
closed surface, A
628 SM» StaTB PHYSK3
V= (11.13)
This result is very important. By combining equations (11.12a) and (11.13)
V = J D dA = q (11.14)
Equation (11.14) is often referred to as Gauss law. But

D = Ee
Hence, 6 E dk.-q (11.15)
This is the other way of writing Gauss law.
Dielectrics and Gauss Theorem

Let us apply Gauss theorem to a parallel plate condenser without a dielectric and then with a dielectric.
In the first case, when no dielectric is present, the electric ______________ ;________________ + q
held Eq at any point on the gaussian surface is given by
EodA= —
Gaussian surface
Le.,
(11.16)
In the second case, when dielectric is present, the Fig. 11.5 A parallel plate condenser
net charge within the gaussian surface is q - q', where q with no dielectric
is the induced surface charge, and the field E is given by
jE JA = (11.16a)
EA = — -—
eo eo
E=-*---£
(11.17)
A Eq A Eq
---------- ------------------------ ------- ------- --------- ----------- Dielectrics ano Related Properties
Equation (11.17) indicates that the induced rh™
which reveals itself as a reduction in the potential dT * ‘° 'E<E()'
respectively, then t^êrence when dielectric is present and not present
e K, (11.18)
The corresponding expressions for capacitances are:
r Ae0 Q
0 d Vo
and AE0Er Q
d Vd
Co ' H
-------------------------------------------------- —_*~-q
Fig. 11.6 A parallel plate condenser with a dielectric
CHAPTER 11
Er
Substituting for Eo from equation (11.16), we get
- - £= — =9- ----
Er AE0Er (11.19)
Comparing equation (11.19) with (11.17), we get
<7 <?
Asoer A £q A Eq (U. 19a)
e, (11.20)
630 Souo Swe Physics
.. - --- - ----
This shows that the induced charge q' is less than the free charge q and is zero when Er = 1 or the
dielectric is absent.
Thus equation 11.16 (a) is
i.e., eoerjEdA = ^
This is nothing but the Gauss law in the presence of the dielectric.
Electric Flux Density and Polarisation

Owing to the polarisation of the medium, charges are induced at the surfaces of the dielectric, the
charge due to electric polarisation at the boundary near the positive plate of the capacitor being negative
and vice versa. If q is the charge on the plate and q' is the induced charge on the boundary of the
dielectric, then we can write equation 11.19 (a) as
? _ g 4
A <Aer A
ie" +*A
** C-qC>^ xl
The last term of this equation gives induced surface charge per unit area, called the electric
polarisation, P.
Substituting, E = (^/Aeoer) from equation (11.19), in equation (11.21), we get,
q „a
— =Ee0 + P with-y-=D
A A
i .e., D = E e0 + P
Since P and E are vectors, D must also be vector, thus we have
D = Ee0 + P (11.22)
In free space, where there is no dielectric and thus P = 0, we have
D = E Eo with D = q/A
_ _ q £0ero
Thus equation (11.22) becomes,

E e = E e0 + P
P = E Eo£/. — E Eq
P=E£0(Er-l)
(11.22*)
where % is electric susceptibility of the dielectric medium.
Dipole Moment and Polarisation

As pointed out earlier, insulators or dielectrics are materials whose electrons are bound to the nucleus
by strong forces and hence they are not free under the influence of an external field. Dielectrics may be
broadly divided into non-polar materials and polar materials. In non-polar materials the molecules,
which are usually diatomic and composed of two atoms of the same type, may be represented as positive
nuclei of charge q surrounded by a symmetrically distributed negative electron cloud of charge —q. In
the absence of an applied field the centres of gravity of the positive and negative charge distributions
coincide. When the molecules are placed in an external electric field the positive and negative charges
experience electric forces tending to move them apart in the direction of the external field. The distance
moved is very small (IO-10 m) since the displacement is limited by restoring forces which increases
with increasing displacement. The centres of positive and negative charges no longer coincide and the
molecules are said to be polarised. Each molecule now forms a dipole whose movement is defined as
ji = $dx
where, dx is the distance between the two centres of the charges and is a vector pointing from the
negative to the positive charge. Dipoles so formed are known as induced dipoles since when the field is
removed the charges resume their normal distribution and the dipoles disappear. For molecules e will be
of the order of the electronic charge (10-I9C) and dx of the order of molecular dimensions (IO-10 m) so
p will be of the order of 10-29 C-m = 3 Debye unit
In considering a dielectric material from the macroscopic point of view, we restrict our attention
to average values over volumes which are sufficiently small in comparison with the dimensions of the
material specimen but large enough to contain a sufficient number of molecules for the purpose of
averaging. Thus the sum of the dipole moments in an element of volume Av is
VAv _ CHAPTER 11
X g, = NAv Jl =PAv
1=1
where, p. represents the average dipole moment of each molecule and N the number of molecules per
unit volume. The vector P is the dipole moment per unit volume and is called the electric polarisation.
In polar dielectrics the molecules, which are normally composed of two or more different atoms,
have dipole moments even in the absence of an electric field, that is, the centres of their positive and
negative charges do not coincide. Normally these molecular dipoles are randomly oriented throughout
the material owing to thermal agitation, so that the average moment over any macroscopic volume
element is zero. In the presence of an externally applied field the molecules tend to orient themselves in
the direction of the field in such a manner that the elementary volume has a net dipole moment given by
NSv _
X = N Av g = PAv
t=l
In some polar materials a spontaneous dielectric polarisation can exist even in the absence of an
applied electric field. Such materials are known as ferroelectrics.
Dielectric polarisation is nothing but the displacement of charged particles under the action of the
electric field to which they are subjected. Devices based on this manifestation are numerous. They
range from condensers and switch-gear equipment in power and distribution installations to rectifiers,
resonators, amplifiers and transducers—convertors of electrical energy to other forms of energy—in
communication technology. They include memory devices used for storage of information in modem
computers.
The above said displacement of electric charges results in the formation of electric dipole moment
in atoms, ions or molecules of the material. The three important types of polarisations are (i) electronic
polarisation (ii) ionic polarisation and (iii) orientational polarisation.
(/) Electronic Polarisation

Why should the application of an electric field produce a dipole moment in materials with no free
electrons? The possible mechanism can be deduced by consideration of the much oversimplified classical
model of an atom in such a material shown in Fig. 11.6 (A).
fig. 11.6 (A) (a) An atom without any field (b) Electronic polarisation
The type of polarisation has been explained with the help of rare gases atoms, in which it is
assumed that the interaction among the atoms is negligible. Here the nucleus of charge Ze is surrounded
by an electronic cloud of charge - Ze distributed in a sphere of radius R. Thus charge density, p is given
by
»-(d^=-(3/4)[>] <112”
When this system is subjected to an external field of intensity £, the nucleus and the electron
eXperienee Lorcntz f°rces °f magnitude ZeE in opposite directions. Therefore the nucleus and electron
cloud are pulled apart. As they are pulled apart, a coulomb force develops between them, which tends to
counter at the displacement and hence the actual magnitude of the displacement is of the order of IO"17 m
lor a field 30 kV/m. Let the small displacement be x. To calculate the induced dipole moment in the
atomic model it is firstly assumed that only the electron cloud is displaced by the field.
Lorentz force = - ZeE
Charge enclosed in the sphere of radius, x

and Coulomb force = Ze x
4keox2
The charge enclosed is
= (4/3) K?p = (4Z3)s? [-

L k z? J
Zex3
Zf3
Hence coulomb force is
Ze Sex3 _ Z2g2x
4k Eq X2
(11.23a)
Z?3 ~ 4n e0 Z?3
In the equilibrium position, the two forces are equal.
Z2e2x
-ZeE = --------- -5-
4k e0 Zr
E 4n £0 Zf3
4g£0Z?3E
(11-24)
Ze
The displacement of the electron cloud is proportional to the applied field E.
CHAPTER 11
Thus, the two electric charges +Ze and -Ze are now displaced by a distance x under the field
constitute an induced electric dipole moment given by
Ze4K£0Z?3E
^ = Zof =------- Ze
- 4k Eo Zf’E
pr°c E
<* (11.25)
where at = 4kEqZ?3 is called electronic polarisability. Thus the induced electronic dipole moment is
proportional to the applied field. The dipole moment for unit volume is called electronic polarisation.
ir. P, = Ma, = MxJE •'
where N is the number of atoms/m3
But P, = E Eq (er - 1) [Refer equation (11.22a)]
E£0(Er~l) = NaeE
Na,
e - 1 =----- (11.26)
E0
(it) Ionic Polarisation

When atoms form molecules, electronic polarisation is still possible but there may be additional
polarisation due to a relative displacement of the atomic components of the molecule in the presence of
an electric field. Consider, for simplicity, a sodium chloride molecule; it is composed of Na+ ions bound
Cl" ions and their interionic distance is r0, say. It is evident that such molecules have a built-in permanent
dipole moment, equal to rQe which exists even before the field is applied. Such materials are said to be
polar. Note all the molecules are polar since an essential requirement is that the centres of gravity of
negative and positive charge in the molecule should not coincide and this is not true for all materials, for
example in an oxygen molecule. We can estimate the permanent dipole moment of the NaCl molecule
by assuming an interionic separation of 0.1 nm; the dipole moment is then of the order of IO-29 C-m.
-------------- E
Na Cl Na Cl
O----- ro----- O O--------------- x--------------- -O
Fig. 11.7 Ionic separation in a field
When a field is applied to the molecule, the sodium and chlorine atoms are displaced in opposite
directions until ionic binding forces stop the process, thus increasing the dipole moment.
Again it is found that this induced dipole moment is proportional to the applied field and an ionic
polarisability at, is introduced to account for the increase, giving
|l, = azE
Of course, the individual ions experience polarisation in addition. For most materials, the ionic
polarisability is less than tilt electronic and typically, a, ■ 0.1a .
(Hi) Orientation Polarisation

This type of polarisation only occurs in polar substances. The existence of a permanent moment is
purely a matter of molecular geometry. The permanent molecular dipoles in such materials can rotate
about their axis of symmetry to align with an applied field which exert a torque in them. This additional
polarisation effect is accounted by an orientational polarisability term, a^.
With electronic and ionic polarisation processes, the force due to the externally applied field is
balanced by elastic binding forces, but for orientation polarisation no such forces exist. In thermal
equilibrium with no field applied the permanent dipoles contribute no net polarisation since they are
randomly oriented. When a field is applied, dipole alignment largely offset by thermal agitation. However,
since it is observed that the orientational polarisation is of the same order as the other forms of polarisation,
Dttiowa **
------------------------------------------- .------------------------ ------------ •----- _------ -- • , ^___ ,..___ ■.Ji.iii.. '„
nly necessary for one dipole in 105 to be completely aligned with the field to account for the effect.
•* ’S °reas the orientational polarisability, a0, is temperature dependent, since the higher the temperature
ater is the thermal agitation and the lower is c^, the distorting polarisability factors, ae and a( are
^Sons of molecular structure and are largely independent of temperature.
-« LANGEVIN’S ThEbtfOf i»OLAftjSATidfQ in I>6lar OifiJECflacf

a^rw****’-
Debye in 1927 conceived the idea that molecules such as HC1, H20 may possess a permanent dipole
moment due to some kind of asymmetry in their structure. Thf action of an electric field on them are
twofold.
(i) It tends to align molecules so that their electric axes are in the direction of the field.
(n) It causes a displacement of the electrons in each atom relative to the nucleus of the atom.
In the absence of an applied field, these molecules point in random directions and the net
polarisation of the dielectric is zero. If an electric field is applied, the expression for the polarisation can
be obtained from Langevin-Debye theory, which is as under:
When the polar dielectric is subjected to an electric field the individual dipoles experience torques
which tend to align them with the field. If the field is very strong, we may assume all dipoles to be
aligned completely and the polarisation may achieve the saturation value.
P5 =Wu
”771
where N is the number of molecules per unit volume. This electric field will also produce induced
dipole effects. For the moment, we shall ignore this contribution.
Table 11.2 Dipole moment of some selected-molecules
Dipole moment j
Molecules
{Debye unit) C x
NO 0.1
HC1 1.04
CO 0.11 CHAPTER 11
co2 0
CC14 0
cs2 0
HjO 1.84
At fields generally applied, the polarisation of a polar dielectric is very small in comparison to
its saturated value. It decreases with the increase in temperature. This deviation from saturated value is
due to the thermal energy to the molecules, which produces random dipole orientations. Statistical
mechanics gives the probability of finding a molecule with particular molecular energy W at temperature
T is proportional to exp (- W/kBT).
Here the system is subjected to a field E applied along the x-direction. The potential energy
associated with each dipole may be obtained as follows:
Couple = (qE) BC
T - q El sin 0
Therefore potential energy is.
e e
JTdQ = jqEl sin 0 t
90 90
W = - )im E cos 0 (11.27)

But the number of molecules (dN) having inclinations 0 and (0 + dQ) and energy value ty j$
proportional to
exp (- WlkgT) sin 0 d0
dN = C exp (- W/kJ) sin 0 dQ
(by kinetic theory and distribution laws)
dN =C exp cos Q/kBT] sin 0 tZ0
Let, a = \LmElkBT
dN = C exp [a cos 0] sin 0 dQ (11.28)
Thus, N = fce^(-dx)
Fig. 11.8 Polar molecule in an electric field
Le., £_
a
e -e
N=C
a
aN
<>'*>
Now for the molecular dipole of moment incUned at an angle 0 to the field, the resolved
component of its moment in the direction of the field is cos 0.
Therefore, the resolved components of all the dN molecules inclined at an angle 6 will be
dM = dN cos 0
— \t electric dipole moment due to all the N molecules lying between 0 and K contained
Henced*"* * nentational polarisation.
. volume gi'csmc
jflutm
=/>o=j^-CO80dA/
o
it*
for dN from equation (11.28)
Substituting
X
0 = J Hi cos 0 C exp [o cos 0] sin 0 dQ
= Qim J exp [a cos 0] cos 0 sin 0 d0

o
X = cos 0
Let,
dx = - sin 0 d0
-i
= CU.pe“‘fc
Substituting for C- from equation (11.29), one gets
F<,=
(e — e ) J,
= _ML_ [xe"]^- je^dx

(ea-e~a)
’(ea+e'fl)
(11.30)
Po~^ (ea-e-a)
'•e., The orientational polarisation,
P„ = njl (“>' A* - <“)

(11.31)
*here L (a) is known as Langevin function.

SSt Souo Swi Pwvnct
In equation (11.31), N\xm represents the dipole moment per m3 when all the molecules are turned
in the direction of the applied electric field and hence it gives the saturation value of PQ say Pf. This P
is a constant depending upon the nature of the gas.
Pn ( , n
Thus, — =L(a)= cot ha— (11.32)
This relation can be graphically represented by Langevin curve. Taking different arbitrary values
for a, the correponding values of ^cot/ia —J = = L(a) can be calculated and a graph is drawn.
When a becomes large that is, at very low temperatures, the function reaches a saturation corresponding
to a maximum alignment of the dipoles along the field direction. i.e., at very high fields or at very low
temperatures.
When a = is large, the Langevin function L (a) = PJPs approaches unity, i.e., Po = P,
= nJ'/ and so one approaches complete or maximum alignment of the dipoles along the field direction.
The second characteristic of the curve is important for many practical purposes. That is, at high
temperatures or for small fields.
pmE
a = —~ « 1 and in such a case
kBT
.. . I .i. I] ea+e~a 1
L(a) = cot ha — = —------ - -----
L aJ ~e~ a
„ _ l + (q2/2) i
«TT+(^6)f ~~
= 3a2-a2
«H + (a2/6)] =641 + (a2/6)]
L(a) = (2 a2/6 a) (neglecting higher powers of a]
~ = L(a) = a/3
a
The initial part of the curve {i.e., for small values of a) is sensibly linear and coincides with the
tangent to the curve at the origin whose slope is 1/3.
Now, =
Now, Po = =
i.e., the orientational polarisation is inversely proportional to the absolute temperature and directly
proportional to the applied field E. Thus
' . , PD. .
Ka) = /=a/3 ■
■■
or ^>=1/3
CHAPTER 11
i.e., the slope of the Langevin function for small values of a is 1/3. Also note that this derivation shows
clearly that the tendency of the extended field to align the dipoles is counteracted by the thermal motion,
resulting in a decreasing value of Po with increasing T.
Now, the total polarisation of a polyatomic gas is given by
P = Pe + Pi + po
p = NEae + NEaj + NEa^ = Ee^ (er - 1)
x ^4 z.™
or eo(£r_i) = N (ae + at)+ (11.36)
b
e0(er-l) = a+ T
where a = N (ar + a,)
. M
and
■ M,
— — -
Now, E0(€r-I) = a + -
This is the equation of a straight line. The dielectric constant of the gas is determined
at different
temperature and £$ (er- 1) is then plotted against 1/T.
Hie result would be a straight line whose slope is given by
(11.38)
is evaluated from this equation. The intercept at 1/T = 0 would give the sum of the electronic and
ionic polarisabilities provided the number of molecules per m3 is known. Electric and ionic polarisation I
are almost invariably present in most dipolar substances and the total polarisation of a dipolar substance
is given by the sum of the three contributions. In general, dipolar contribution exists in materials having
high static dielectric constant (e.g., water with e = 81).
It may be mentioned that equations (11.36) and (11.37) hold if and only if the separation between
atoms or molecules is so large that there is no interaction between the dipoles and hence the field seen
by a dipole is just the applied field. Hence equation (11.37) is valid only for gases and liquids. Thus
equation (11.36) becomes
P = Ee0 (er- 1) = NE (ae + a. + cQ
r
= NE a„+a,+-t-a- M-2
L w
JV
Therefore, (11.39) ’j
eo . 3k*T.
' j
Permanent Dipole Moments of Gaseous Molecules
The deciding factor for the existence of the orientational polarisation, of course is, simply whether or j
not the molecules have a permanent dipole moment. The existence of a permanent dipole moment is . j
purely a matter of molecular geometry. Thus, CO2 molecule has no permanent dipole moment whereas
CO molecule has a small, permanent dipole moment. Since the CO2 molecule has zero dipole moment, >
the two bonds of the molecule must make an angle of 180° with each other and the molecule must have
a centre of symmetry. Since H2O and NO2 molecules have a large permanent dipole moment, their two
OH and ON bonds must take an angle which is other than 180°. It is evident that molecules such as 0,.
H^, N2,... which consist of similar atoms and have a symmetrical charge distribution carry no permar s
dipole moment and are thus non-polar; CC14, CH4, CS2,... are some non-polar polyatomic molecules
having zero dipole moment.
The electric field which an atom sees or the total electric
field at the atom site is called the internal field or the
local field, and this field is not the macroscopic field
which we have defined in the case of gases. As long as * S/ope- O&
the density of molecules is high, field acting on a given
molecule consists partly of the applied field and partly
of the field resulting from the mutual intersection of the N(at + a,)
other molecules, polarised under the influence of the
external field.
--------* 1
T
Rg- 11.10 Plot Of e (F r,
eo (- 1) as a function of./T
—* 1000/T
Fig. 11.11 Temperature variation of the static dielectric constant of some vapours
The model used by Epstein to calculate the local field in the case of one-dimensional atomic
array is shown in Fig. 11.12.
F'g- 11.12 String of atoms

This Figure shows an array of equispaced atomic dipoles separated by a distance a. Suppose an
electric field E is applied from left to right The aim is to find the local field E. which a representative
atom A sees. If is the induced dipole moment in each atom due to the applied field E, the internal field
seen by an atom A is the sum of the applied and the fields produced by Mind of all other atoms P, Q,
lying on the left of A and R. S,... lying on the right of A.
The components of the field produced by a dipole moment in the direction of unit vectors a and
âre
„ I 2LLCOS0
Er=--------- ~3—a,
r 4n e0 r3 r
The field produced at A by at P is obtained by the above equations if r = a and 8 = 0. Thus
Similarly £«= "T”-with 9= 180°andr = -a

M 4ne0 (-a)
Tbe contributions of the field due to atoms P and R at A is obtained by adding EM> and EM'
+ a 3
JI <,Q U
In a similar way
—- --------------------------- --------------- - -----------
The internal field at atom A is
£'(4) = £+~T +---- ~-t+ (11.40)

K£o“ ne0 (2a)3
fyAM+JLL’l 1
"M3 L 23 3’ J
£,=£+^M
with n as an integer.
But £4 ”1.2
n=i n
Equation (11.41) can be written as
E,= E+—4 (11.42)

n e0 a
In a three-dimensional case, the calculation of the internal field would be very complicated and
would depend upon the crystal structure. By analogy with equation (11.42) one expects that the internal
field in a crystal would involve similar terms. In a three-dimensional case (1/a3) may be replaced by N,
the number of atoms per unit volume, and (1.2/rc) by a constant y, which depends upon the type of the
structure. Hence
£.= £+^
As ATjt. = P
(11-43)
y is called the internal field constant.

Now, P = NaEL
Also P = E £o(er-l)
(11.43a)
Evaluation of the Local Field for Cubic Structure

To evaluate the local field we must calculate the total field acting on a certain typical dipole, this field
being due to the external field as well as the other dipoles in the system. This was done by Lorentz as
follows.
The dipole is imagined to be surrounded by a spherical cavity of radius r and centre A. such that
the radius r is lame compared with the intermolecular distance so that the sphere contains many molecules
but small compared with the dimensions of the whole dielectric. If this dielectric is placed between two
ScMoSiwniPwwci_______________________________________
charged plates, the electric field experienced by a molecule of the dielectric, if assumed to be placed $
the centre of the cavity, is given by
E; = E, + E2 + E3 + E4
where
(i) E( is the field intensity due to charge density on the plates of the capacitor (i.e., with no
dielectric).
(if) E, is the field at the atom due to the polarised charges (induced charge) on the plane surfacei
of the dielectric (i.e., depolarising field).
(iff) E3 is the field due to polarised charges on the surface of the spherical cavity.
(iv) E4 is the field due to all the dipoles inside the spherical cavity.
Now, D = E, e0 = E e0 + P * ]
E = —=E + — (11.44) j
e0 < Eo
„ r i
E2=------- =-------- [taking E = 0 in equation (11.44)] 1
eo eo .1
E3 is the field intensity at A due to other atoms contained in the cavity. We are assuming a cubic 1
structure, so E3 = 0 because of symmetry. ’
E4 is the field intensity due to polarisation charges on the surface of the cavity and was calculated :
by Lorentz as given below:
Computation of E4
The enlarged view of the cavity is shown in Figure
11.14. If dA is the surface area of the sphere of radius
r lying between 0 and 0 + d0, where 0 is the direction
with the reference to the direction of the applied field,
then dA = 2n (PQ) (QR)
But sin 0 = pQlr, PQ = rs\nQ
and dQ = QR/r, QR - r dQ
Hence, dA = 2nr sin 0 r df) = 2KF2 sin 0 df)
The charge dq on the surface dA is equal to the
normal component of the polarisation multiplied by
the surface area. Therefore.
dq = P cos 0 dA = P (27tr*8in 0 cos 0 d0)
Y Z 31 /) J
' fry &
The field due to this ei-..,-,,

the direction 6 = 0 is C c-< j 3; a M denoted in
J।
dE = *lxc°s0
4 4rtEor2
- P cose27tr2 sin fl de cos fl

4ne0r2
P
= 7— cos2 e sin e de
Rg, 11.14 Cavity enlarged
ZEo
Thus the total field E4 due to the charges on the surface of the entire cavity is obtained by
integrating
f dE4 = f cos2 e sine de

J 2e00 J0
p f ,
= -—J cos2 e d(-cosfl)
2eo o
p cos3e
2e0 _ 3
' •' P : ' V i
fp p J • p '” • p
? E, = E + — - — + 0 + — ; E£=E + — (11.44a)
c. . • e0 £0 -3Sq ' 3Eq
Equation (11.44a) shows that the internal field at an atom in a cubic structure is of the form of
CHAPTER 11
equation (11.43) with y= (1/3). E£ is called Lorentz field. It has been assumed in this derivation that the
region outside the sphere is continuous whose dielectric constant is Er. It should be noted that the field
intensity at the atom, i.e., the Lorentz field is larger than the applied field by an amount that is directly
proportional to the polarisation density.
It is now oossibleto relate the dielectric constant of an insulator to the polarisability of atoms comprising
it The dipole moment of single atom is proportional to the local field. i.e.. dipole moment - oEt where
a is the polarisability of the atom. If there are N atom per umt volume, the electnc moment per umt
volume which is called Polarisation is given by
p = /VaE£
From equations (11,43a) and (11.26)
P^ÊCe,.- i) = /VaE/
EerE0-Eel)=/VaE,
E erE0= /V aE/ + E Ejj
From equation (11,44a)
„ „ P „ NaEt
E, = E+ — = E + ——-
3e0 3e0
NoEl I Na
or e = el-
36q 3 £0
E, I
E " [1-(Mx/3e0)]
Substituting Et/E in equation (11.45)
er
Ef -1
£r + 2_
Na/e0 _ Na.
3 3 Eq
er -1 /Vet
e, +2J 3e0 (11.47)
This is Clausius-Mosotti relation which relates the macroscopic dielectric constant wit
microscopic polarisabilities.
Multiplying both sides of equation (11.47) by the molar volume, one gets
E, - 1 Na Ma , . .t
-------- , where M. is the molecular weight
£. + 2 P 3e0J p 4
W,
But -----
p = NAa
Hence,
Cr-1 = nac
1p
E_ + 2 P 3e0 m
called molar polarisation. In the presence of orientational ploarisation, the Clausius-Mosotti equation
can be written as
£,-1 Ma Na r
£ +2 P = IT
V fcoJ
e.-l "N , ■ , - .3
er+.2 —
P ’ TT(a
This equation is called Debye’s equation and it
forms the basis for the method of determining permanent
dipole moment. Dielectric constants are measured at
different temperatures and a graph is drawn between
Er-1 MA , 1
£_ + 2 T 311 T
It is found to be straight line. Equation (11.48) can

be written as
er -1 NAa' NAa0
er+2j I P 3e0 + 3e0
NAa'
—-— + — _L
e
3e0 3e•o( L 3kBT
er -1 m
er +2 p. T
where the slope
— 2^
9 jt
r' a
• *\
P»=3x (11.48a)
Thus H.can be found our using the above equation (11.481 In any case if the permanent dipole
wmeat is renx the diekctric constant like the polarisation is independent of temperature. In such cw
d»e straight hne is paralkd k» the x-axis. The accuracy of measurement of the dipole moment by means
cf the atove method is determined by the precision with which the slope is determined, lb obtain |
accurate result « is necessary to carry out the measurements in sufficiently wide temperature ranges.
I
Relation between Dielectric. Constant and the Refractive
Index (Lorentz-Lorenz formula)
The idea that there exists a definite relation between dielectric constant and refractive index comes
from the propagation of electromagnetic waves through a medium. The electromagnetic waves as
devckpedby Maxwell by the idea that electromagnetic induction consists of varying electric and magnetic J
fields with time. The electric and magnetic vectors in such waves are perpendicular to each other and .
also perpendicuiar to the direction of propagation. Maxwell has shown that the velocity of propagation
of such waves far an unbounded metfium is given by 2
■ .......... 1
Tn E :
where p b the n^nrric ptnraMin of the medium and € is the ofantare perauamry. The permeability .1
t
i 4
far nt—yrir medfa is Hence the velocity in such a medium is ”n,e refractive index of 4
the meh—n is given by

Veiodty of waves in vacuum }
~ Velocity of waves in medium
1/Ui, _
•= (i/m £)w = ve,£« * VCr 4
Tins n = wtere e, is the telative permittivity. Using this value of Erin equation (11.47)
(11.49).
V+2 3«a
k ii. < ■ n—■ —I
Ths refation is known as Lorena-Lorenz equation.
—-------- —__ Dtnecrttg ano Related 649
constant of solids and liquids ~

Three classes of materials may be identify r
1 Solids exhih f- 08 aS *** êlectric behaviour of solids is concerned:
2 . 2 8 °f y eleCttOnk POlmSab1"1’ - -Hd dielectrics.
3 Sol d h‘ h mmi K1 electron,c and '“I'd polarisabilities - ionic non-polar dielectrics.
' solids. P°SSeSS °nenta'“’"a1' well as electronic and ionic polarisabilities - polar
1. Elemental Dielectrics
These are materials consisting of single type of atoms such as diamond, sulphur, germanium, etc. Such
materials contain neither ions nor permanent dipoles and thus exhibit only electronic polarisation. If af
is the polarisability per atom in such materials, we have polarisation,
P =Pe=NaeEL
Ee^- l) = Mxe£L
Substituting for EL from equation (11.46), one gets
(6,-1)=^ (e,-l)= Na‘ -s

1 Na _ Na,
3e0
er -l~l rMl] = NACL'

(11.50)
Er+2 P. 3Eq
2. Polarisation of Ionic Crystals

In ionic crystals such as alkali halides, the total polarisation is electronic and ionic in nature. These
solids contain more than one type of atoms, but no permanent dipoles when the crystal is considered as
a huge molecule. The behavior of such a material is complicated, the internal field at the positive sites,
CHAPTER 11
for example, is different from that at negative ion sites. The static relative constant erj is related to P by
the expression.
Table 11.4 Dielectric constant of some elemental dielectrics
Material . . ‘ .r • •
Diamond 5.7
Germanium 16
Silicon 12
Sulphur 3.5
P<+Pj = E(e„-l) (11.51)

It may be of interest to point out that the ionic polarisation P, usually constitutes a considerabi
fraction of the total polarisation. Experimentally this has been established as follows: When one measure6
the dielectric constant at frequencies of approximately 5 x 1014 Hz, corresponding to the visible part of
the electromagnetic spectrum, the relatively heavy positive and negative ions can no longer follow the
rapid field variations. Consequently, one measures in that region only the electronic polarisation P
Since a measurement of the static dielectric constant gives Pe+ P., it is thus possible to find P and P
separately. If ere represents the dielectric constant measured at optical frequencies, one may write 1
e0(£„-l)E = Pe (11.52)
From equations (11.51) and (11.52), it is obvious that the difference between erj arid £ is a
measure of the ionic polarisation. The values of £rs and ere given in Table 11.5 for alkali halides illustrate
clearly that the static dielectric constant of these materials contains an appreciable contribution from the
displacement of positive ion lattice relative to the negative ion lattice in an external field. It should be
mentioned here that in the optical region of the elelctromagnetic spectrum, one measures the dielectric
constant by determining the index of refraction n. According to Maxwell’s theory of electromagnetic
waves, = n2 for materials with a magnetic permeability equal to that of vacuum.
Table 115 Static and optical dielectric constant of alkali halides; n is the index of refraction
Solid ere = rfi Solid £rs 6 = rfl

LiF 9.27 1.92 KC1 4.68 2.13
LiCl 11.05 2.75 KBr 4.78 2.33
LiBr 12.1 3.16 KI 4.94 2.69
Lil 11.03 3.80 KF 6.05 1.85
NaCl 5.62 2.25 RbF 5.91 1.93
NaBr 5.99 2.62 RbCl 5.00 2.19
Nai 6.60 2.91 RbBr 5.00 2.33
3. Polar Solids
In solids whose molecules possess permanent dipole moments, the total polarisation has all the three J
components and is written as P = Pe + P( + PQ. Unlike the molecules of a liquid or a gas which can rotate |
freely, the molecules of a solid are often constrained by the stability of the structure and the directional
character of the bonding. No accurate theory exists to relate Po to its stimulus (field) in the case of
solids. The alignment of the permanent dipoles with the electric field depends upon the shape of the 4
solids and the interaction of the molecules. More symmetrical molecules can rotate more freely.
Non-polar solid methane (CH4) which is highly symmetrical exhibits this feature and so does
solid hydrogen. However, less symmetrical molecules, such as H2S and HC1 do not exhibit this behaviour.
One example of polar solids is solid nitrobenzene (C6H5NO2). Figure 11.16 shows the variation of £, as
a function of temperature for nitrobenzene. It is observed that as the material freezes, the dielectric
constant er decreases abruptly from a value near 35 to a much lower value. It is also observed that in the
solid state er is independent of temperature, whereas in the liquid state it decreases with increasing
temperature. These observations can be explained as follows;
In the liquid state, is determined by the electronic, ionic and orientational contributions. The
decrease of £ with increasing temperature must evidently be ascribed to the fact that the orientational
g Relative dielectric constant of nitrobenzene as a function of temperature
contribution decreases with temperature, as it does in

the case of gases. The sudden drop in erat the melting
point is interpreted as meaning that even though the solid
contains permanent dipoles, these are 'frozen' in the solid
state and no longer be aligned by an external field. Thus,
in the solid state one only measures the contributions to
Er associated with electronic and ionic polarisation. This
also explains the fact that in the solid state the temperature
dependence of er has disappeared. However, in some
solids, the permanent dipole moment may still contribute
to the polarisation, although their motion may be strongly
inhibited. The behaviour of HC1 is shown in Fig. 11.17.
HC1 freezes at about 160 K. At this temperature, er
fig. 11.17 Er versus 1 /T for HC1
increases suddenly by a small amount; this is due to the
change in density upon solidification. However, in the s lid state, Er keeps increasing with decreasing
temperature, indicating the presence of orientational polarisation. It is not until a temperature of 100 K
has been reached that e drops sharply, a result of the fact that the dipoles have become immobile. In
CHAPTER 11
general, e will decrease with increasing temperature as a result of a reduction in the orientational
polarisation. If there are no permanent dipoles present, er is nearly independent of temperature.
UI J JWWIU. - JLJRJlJljy ii
iWMMiaa&usnaia'ti
Below a certain temperature it is found that some materials spontaneously acquire an electric dipole
moment By analogy with the magnetic case these materials are called ferroelectrics. Just as with
ferromagnets these crystals exhibit a hysteresis curve P versus E and this can be explained by a domain
hypothesis. These domains are quite easy to observe with polarised light in some materials.
The transition to the ferroelectric state is a cooperative phenomenon which is accompanied by
specific heat anomaly or by a latent heat and it appears that at the transition temperature the crystal
lattice spontaneously distorts to a more complicated structure which possesses a permanent electric
dipole moment.
There are three main types of crystal structure which exhibit ferroelectricity: (1) Rochelle salt
structure, typified by Rochelle salt. NaK (C4H4O6). 4H2O, (2) the perovskite group, consisting mainly
of titanates and niobates, of which barium titanate, BaTiO3 has been the most extensively studied one,
and (3) the dihydrogen phosphates and arsenates, e.g., KH2PO4 (*K DP).
In ferroelectric materials the electric flux density D is not determined uniquely by the applied
field but depends upon the previous history of the material. Just as feiromagnetics have regions with
aligned magnetic moments, so also in ferroelectrics there are large regions which are characterised by
the"alignment of the electric field. For this reason the electric field turns the whole of such region in the
direction of the field and overcomes the thermal agitation that tends to scatter the electric dipoles in
different directions. The aligned electric fields of such regions of a ferroelectric combiner with the
external electric field increasing the flux density thousands of times. The charge of a condenser is
increased the same number of times when a ferroelectric is used instead of air. The lower the temperature
and the stronger the electric field the more predominant is the effect of the latter over the random
thermal agitation. In sufficiently strong fields, the electric dipoles of all regions of the ferroelectric are
practically in the direction of the field. This produces the greatest possible charge density. Condensers
made of BaTiO3 and other ferroelectric materials concentrate considerable quantity of electric energy
with in a small space as ferrites concentrate magnetic energy.
When an electric field is applied to a specimen of a ferroelectric crystal, the polarisation first
rises rapidly with applied field to a value above which the dependence is linear. Linear extrapolation to
zero field gives Ps, the saturation or spontaneous polarisation. On subsequently reducing the field to
zero, remanen (residual) polarisation Pr remains. The negative field to reduce the polarisation to zero is
called the coercive field and represented by Ec. The existence of a dielectric hysteresis loop in a dielectric
material implies that the substance possesses a spontaneous polarisation and the value of P (depending
upon the shape of the hysteresis loop) depends upon a number of factors such as the dimensions of the
specimen, the temperature, the texture of the crystal, the thermal and electrical properties of the crystal.
The hysteresis loop of a ferroelectric material changes its shape as the temperature is increased.
The height and width decrease with increase of temperature. At a certain temperature known as
ferroelectric Curie temperature, the loop merges in to a straight line and the ferroelectric behaviour of
the material disappears.
Table 11.6 Properties of some ferroelectric materials at room temperature
Crystal Curie temperature, K Spontaneous polarisatidn,

er in wedk fields
Pf (coulomb / m2)
Rochelle 297 to 255 0.24 x 10"2 200
BaTiOj 391 26 x 10~2 1000 to 1700
kh2po4 123 4.95 x IO"2
KNbOj 708 26.6 x 10~2 -
kd2po4 213 9 x IO'2 -
Spontaneous polarisation in a ferroelectric material disappears above the Curie temperature. If

the temperature is below the Curie temperature, the polarisation or dielectric constant is not a linear
function of the field and er is not a constant and so the equation P = Ee0 (Er - 1) cannot be applied
directly. In such cases Er for a ferroelectric material may be defined for the virgin curve as a differential
quantity.
DlELKTWCS AND RiUW
dP (11.53)
dE =e0(£r~ 0
We know that the internal field

Ei = E^
Co
and
Le.,
Hg. 11.18 (,) Hysteresis loip ferroelectric materials, (8) M relation above Cori, temperature
p 1-^6 = NaE CHAPTER 11

or
«o J
NaE (11.54)
P=
£o .
0, one gets a non-vanishing solution for P and therefore there exists the
possibility of spontaneous polarisation.

We may conclude now that with (N ap/%) = 1. the dielectric constant will become infinite and
the substance will become spontaneously polarised. 0 = 1/3 for cubic structure.
<S4 Souo SwiPwwa
Dipole Theory of Ferroelectricity

The interaction between adjacent dipoles in a ferroelectric material is large and a dipole moment has a
tendency to align itself in a direction parallel to that of its neighbour. Assuming that the permanent
dipoles are responsible for spontaneous polarisation, we can write.
P = Po= Na0Et = N \iinL(a)
For higher temperatures.
a= is small
kgT
and hence L (a) = a/3
Ml2
Thus, p = pn=-p^ = E.
0 3kBT ‘
p = p =^\e + ^-
0 3fcflT [ e0 J
r_N\L2mE
3kBT + 3eofcflT
1 M^P '
3e0£bT 3kBT
P_ _ ^2m/3/cfi m/3kB
^2
(11.56)
£_r.T M^P~ [T-Qc]
3fcB £0 _
where, 0( = "n2P
3^b e0
and is known as ferroelectric curie temperature.
L = Ceo
E (T-Gc)
c_ ^2m _et.
Eq P
P c
Now,
Ee0 4 (11.57)
This equation is known as Curie- Weiss law and we have shown with the help of simple theoij
that a ferroelectric material obeys this equation at sufficiently large temperatures
---------------------- ----- — _____ tteucrwa mo Jtadi* RmWM ‘ Ml
The Curie point for Rochelle salt is about 24°r onzi u L ~~
r Qkn..f an°r u- . • ‘24 C and th,s substance has a very narrow temperature
range of about 40 C within which it is ferroelectric.
We shall now show that soontan<.™i<. ■ .•
Curie temperature. Polanaauon >s possible in a ferroelectric material below the
We know that, P = P, = (a) ()15g,

For very low temperatures, a is large (or for high electric fields, and hence L <a) I. The
polarisation is called the saturation polarisation P
When a is large, L (a) - 1 and N|lm = p, is known as saturation polarisation.
P = P/(a)
P
~^=L(a)
But L(a) = L
=L (11.59)
Spontaneous polarisation exists if there is a non-vanishing solution for P in equation (11-59)

with the applied field E = 0.
Hence for spontaneous polarisation.
' = £ -Hngq
P, LVeoJ
£ =L (x) = [cot hx-(l/x)J

i.e., (11.60)
MP
CHAPTER 11
with
Eq
and so (11.61)
P _ P
Now,
i.e.,
iww ifcW.
p
" ri;
(11.62)
LhW W
wt _ _ ____ ____ __________
Thus we obtain two simultaneous equations (11.60) and (11 62), which determine the conditi0tl
of spontanea polarisation m fcnvdcctric crystals. Equation (11.60) gives the Langevin curve, whilc
the second one a straight hnc passing through the origin whose slope is (7739) and is equal to (773) (3^
M*.p) « UtJ andlhc sl°Pc increases with temperature.

The Langevin curve intersects with the first line at the point A. They intersect each other at the
origin 0 and at another point A, so that the solutions are (PIPS) = 0 or AN. But (P/PT) = 0 cannot be a
true solution. because there is spontaneous polarisation. Hence the only possible solution is (PIP*) =
that is io sav, a point of intersection of the two curves other than origin. As the temperature increases the
degree of spontaneous polarisation decreases and at very high temperatures (T> 9), there is no spontaneous
polarization. because the straight line does not intersect the L (x) curve. Measured values of p are
Rochelle sah 2.1; BaTiO, 0.044; KH2PO40.37.
Fig. 11.19 Langevin curve
The spontaneous polarisation, which is the most characteristic property of a ferroelectric material,
usually vanishes above a certain temperature 9c called the ferroelectric Curie temperature. In the
ferroelectric region, i.e., below 0t, the dielectric constant is evidently a function of the field strength and
is no longer a constant. One can, of course define differential relative dielectric constant on the basis of
equation (11.53).
. . dP
(11.1
Generally (he derivative is taken for the virgin curve at the origin. The dielectric
*- a. defined by equation <11.631 may become extramely high n. the temperature approaches 11
foroelecoic Cone temperature, a. evident from Fl,. 11.20 showing the variation of dielectric const.
trTT'B*TThcchaindolted •«‘ f'"d
HOOOOyolt/m while the solid curve refera io a field of 3600 voWm.lt may be seen that in the ferroelecn
reôn. i.e m die temperature range below 8, ihe dielectric constant E, is , fu„clion of r,eld. e bei
**"rfor higher value, of field. However, for mmperatures exceeding the ferroelectnc Curie tempû
0^, er does not vary with field.
Dielectrics and Related I
constantFor
e= temperature exceeding the
er^ with temperature ferroelectric
is given by the Curie temperature
Curie-Weiss law: theVanat,on of ^solute dielectric
C
p = ---------
(T-0)
than is a constant Curie

wheretheC ferroelectric and 0 is the characteristic
temperature 0c. temperature for the material’ nnlv
y * êw de
a 8rees smaller
Classification of Ferroelectric Materials

Ferroelectric materials may be classified into the following three groups depending on their chemical
composition and structure:
(a) Tartrate group
(b) Dihydrogen phosphates and arsenates alkali metals
(c) Oxygen octahedron group.
Table 11.7 indicates some of the materials which possess ferroelectric properties.
Fig. 11.20 Dielectric constant of barium titanate ceramic as a function of temperature
Table 11.7 Properties of some ferroelectric materials
Curie temperature Spontaneous polanwtio*

Material Chemical formula
(°Q lO-’^Qh*2 ,.z
Rochelle Salt Na K upper +23 0.25

lower-18
KDP-dihydrogen phosphate kh2po4 -150 4.95
Barium titanate BaTiO3 + 120 26.0
Sodium nitrate NaNO2 +160 7.0
£58 StwoSwVtPHffitcs
(rt) Tartrate Group

A typical example of ferroelectric material of this group is Rochelle salt, which is the sodium-potassiurn
salt of tartaric acid NaK (C4H4Oft). 4H2O. This material was probably the first solid known to exhibit
ferroelectric properties. This material has the unique property that it is ferroelectric only in the temperature
range extending from -18°C to 23°C. Thus this material has two transition regions instead of one.
Figure 11.21 shows the variation of spontaneous polarisation Ps of Rochelle salt with temperature
Other materials belonging to this group of ferroelectric materials are those in which a part of Na in the
Rochelle salt has been replaced by NH4, Rb or Ti.
(b) Dihydrogen Phosphates and Arsenates of

Alkali Metals
A typical example of this category is KH2PO4. Figure
11.22 shows the spontaneous polarisation versus
temperature curve of this material. In this case, there
is only one Curie temperature namely 123 K.
(c) Oxygen Octahedron Group

Probably the best-known ferroelectric material is 290
barium titanate BaTiO3; it is a representative of the so T(K)
called oxygen octahedron group of ferroelectric
Rg. 11.21 Variation of spontaneous polarisation of
materials. Above the Curie temperature (120°C),
Rochelle salt with temperature
BaTiO3 corresponds to the cubic structure presented
in Fig. 1L23. In this structure, the Ba2+ ions occupy
the comers of a cube; the centres of the cube faces are
occupied by O2- ions. The oxygen ions form an
octahedron, at the centre of which the small Ti4+ ion is
located. The Ti44 ion is considerably smaller than the
space which is available inside the oxygen octahedron.
It thus brings with it a high ionic polarisability for two
reasons: (/) It has a charge of 4e and, (b) it can be
displaced over a relatively large distance. We shall see
that this may be the explanation for the occurrence of
spontaneous polarisation in BaTiO3. Fig. 11.22 Spontaneous polarisation of KH2PO. as
There is an intimate relationship between the
ferroelectric properties and the atomic arrangement in ferroelectric materials. Above 120°C, BaTiO31
has the cubic structure as in Fig. 11.23. When the temperature is lowered through the critical temperature
of 120°C, the material becomes spontaneously polarised and at the same time the structure changes, 1
The direction of spontaneous polarisation may He along any of the cube edges, giving a total 6 possible
directions for the spontaneous polarisation. Along the direction of spontaneous polarisation of a given
domain, the material expands, whereas perpendicular to the polarisation direction it contracts. Thus, the
material is no longer cubic, but corresponds to a so-called tetragonal structure. BaTiO3 has two more
transition temperatures: One at 5°C, where the spontaneous polarisation changes its direction from one
Dielecttocs and RaxnsD Pmomkins
of the cube edges to a direction corresponding to
a face diagonal in Fig. 11.22; and one at -80°C e-(— -
where the spontaneous polarisation changes from . © B«2
a direction corresponding to a face diagonal to one
along a body diagonal. Associated with each of
these ferroelectric transitions is a change in the
crystal structure of the material. These thrfee w-------
transition temperatures are reflected in the Fig. 11.23 The cubir vu'.ture of Ba'iO
dielectric constant and in the spontaneous above the fcnoeleciric Curie temperature
polarisation of the material, as may be seen in
Figs. 11.24 and 11.25.
The spontaneous polarisation represented
in Fig. 11.25 was measured along a cube edge
over the whole temperature range. Thus the
magnitude in the region between 193 K and
278 K is obtained by multiplying the value given
in Fig. 11.25 by V2(P in that region is directed
along a face diagonal). Similarly, to obtain the
magnitude of Ps in the region below 193 K, one
should multiply the value in Fig. 11.24 by 73 (Ps
directed along body diagonal in this case). Fig. 11.24 The dielectric constant oFBaTiO,. as
a function of temperature
Antiferroelectricity
These are some dielectric materials which
show the phenomena of antiferroelectricity,
which is quite analogous with anti
ferromagnetic materials. Unlike the
ferroelectrics, antiferroelectrics have no
permanent moment, because of the geometry
of the spontaneous polarisation. The CHAPTER 11
neighbouring dipoles are antiparallel to each
other. Lead zirconate (PbZrO3) is an example,
which is ferroelectric in high fields but not in
low field. These solids have an
antiferroelectric Curie temperature above Fig. 11.25 The spontaneous polarisation of
which the effect does not exist Er in such BaTiO, measured along a cube eage
materials, generally lies between 50-150.

Table 11.8 indicates the properties of the
antiferroelectric materials.
I able ILS 1 Vv penics ot Mime and ferroelectric materials •i
J
Material Chemical formula Curie temperature (°C)
Lead zirconate PbZrO3 + 233
Sodium niobate NaNbO3 + 638
ADP NH.,H2PO4 - 125 ‘i
Rgtyw p^lEM
-■> • Ir'h lift? rt f l tit tr r
While most dielectrics are only weakly anisotropic, weakly nonlinear and weakly sensitive to mechanical i
strain, electromechanical effects are still large enough to be of practical value in electrically driven •
acoustical resonators. The entire phenomena of electromechanical phenomena in dielectrics is termed)
piezoelectricity. It is evidenced by an induced polarisation and an electric charge appearing on the
surface of a mechanically strained dielectric. ]
Fig. 11.26 Displacements of the ions under an electric field

• ■ -1
We have seen that an applied electric field in inducing an electric dipole moment in a dielectric,
displaces ions relative to each other. The structural dimensions of the crystal have been changed by the j
applied field. In Fig. 11.26 an ion array is indicated with and without applied field. The dimensions of ]
the crystal have increased in the field direction. The physical property is called electrostriction. So
electrostriction can be defined as the phenomenon in which a strain is produced in a solid on the application ]
of the external field which is proportional to the square of the applied field and independent of the field-
direction. The electrostriction occurs in all materials regardless of their state of aggregation but the|
effect is very small except in high fields. Its cause has been stated to be the attempt of atoms or molecules
to take up an orientation that will cause the free energy of the system to be at a minimum.
Now let us consider the effect on the polarisation of changing the dimensions of the crystal by j
means of a mechanical strain. We consider two kinds of crystals namely, those with a centre of symmetry ‘
and those without. If a unit cell of a dielectric is such that we can draw from a central point a vector to;
one charged ion and on drawing an equal and opposite vector from the point we also find a similar ion'
then the structure has a centre of symmetry. Of the 32 crystal classes (point groups) twelve have centre ,
of symmetry. In Fig. 11.27 we use a two-dimensional model of an ionic solid to demonstrate that ;
piezoelectricity cannot occur in crystals having a centre of symmetry. In the figure the position of the ■
ion A is obviously a centre of symmetry. When the array has been compressed by a mechanical force, <
(a)
(b)
Fig- 11.27 (<j) Ionic
structure with a centre of
v - D u u U StrUCtUre C°mPress*d
symmetry
a force. No net' change of pot
an sat j on
the ion B has been moved closer tn inn a .k j
has also been moved closer to ion A u/hi-h h S decreas,ng the BA diP°le moment However, the ion C
opposite direction to the decrease in RA deCTeaseS CA diP°le moment by the same amount in the
mechanical deformation of a " P°“
gu 8 gives a structure without centre of symmetry. The dipole moment is determined

using an ion plus a fraction of each of its nearest neighbours (here we take one third of each of the
c arges o e ee nearest neighbours). When strained, this structure develops net dipole moments due
to each ion and its neighbours.
fig. 11.28 Ionic structure without a centre of symmetry
Since both the strain and polarisation are characteristically directional in a crystal, complex
relationships exist between these quantities. For example, quartz crystals cut in wafers whose faces are
parallel to the basal plane (X-cut) will contract or expand in a direction parallel to an electric field CHAPTER 11
perpendicular to the faces.
A few of the many uses of piezoelectric behaviour in crystals will now be briefly mentioned. A
piezoelectrical crystal will vibrate naturally in several mechanical modes, the frequencies of vibration
being dependent on the dimensions of the specimen and the elastic constants of the material. If the
crystal is placed between the electrodes and an alternating voltage at one of the reasonant frequencies is
applied the amplitude of oscillation will build up at this frequency. The stability of the oscillator system
will be controlled by the constancy of the elastic constants of the crystal. Specially cut quartz discs are
generally used for this purpose, the stability being high since the coefficient of thermal expansion is
low.
Another application of piezoelectric oscillations lies in the conversion of mechanical pulses into
electrical ones and vice versa. The crystal here is used as a transducer. Acoustic pulses are used in
underwater search and other applications. In almost all such cases the acousuc pulses are produced by
£ Soud Sime Phvsks
piezoelectric transducers. Another important application is the use of piezoelectric materials as de] i
lines. If an electrical signal is converted into an acoustic one at one end of a quartz rod the signal
pass along the rod as an acoustic wave. It will travel in quartz with appropriate sound velocity 'rv j
reaching the end the acoustic wave may be picked as electrical signal. The initial electrical signal h '
thus been delayed. 1
IX. PROPERTIES OF DIELECTRICS IN ALTERNATING FIELDS ’r

.......................... ............................ “ ; ' ............. - --
We now take up the study of the behaviour of dielectrics in alternating electric fields. Here again we
make use of the same basic atomic models used earlier and study the behaviour of this model in alternating
electric field. This study reveals that the dielectric constant under these conditions is a complex quantity.
The imaginary part of this complex dielectric constant determines the dielectric losses of the material.
In the macroscopic theory of isotropic dielectrics under static fields, the electric flux density D is
proportional to the electric field intensity E, so that D = E E, where £ is a constant defined as the electric
permittivity and is a property of the dielectric.
When a dielectric material is subjected to an alternating field the orientation of the dipoles, and 1
hence the polarisation, will tend to reverse every time the polarity of the field changes. As long as the |
frequency remains low (< 106 c/s) the polarisation follows the alternations of the field without any 1
significant lag and the permittivity is independent of the frequency and has the same magnitude as in a 1
static field. When the frequency is increased the dipoles will no longer be able to rotate sufficiently 1
rapidly so that their oscillations will begin to lag behind those of the field. As the frequency is further ’
raised the permanent dipoles, if present in the medium, will be completely unable to follow the field and !
the contribution to the static permittivity from this molecular process, the orientation polarisation ceases;
this usually occurs in the radio frequency range (106 - 1011 Hz) of the electromagnetic spectrum. At still
higher frequencies, usually in the infrared (1011- 1014 Hz) the relatively heavy positive and negative :
ions cannot follow the field variations so that the contribution to the permittivity from the atomic or ;
ionic polarisation ceases and only the electronic polarisation remains.
The above effects lead to fall in the permittivity of a dielectric material with increasing frequency, j
a phenomenon which is usually referred to as anomalous dielectric dispersion. J
■
Dispersion arising during the transition from full atomic polarisation at radio frequencies to ;
negligible atomic polarisation at optical frequency is usually referred to as resonance absorption. J
Dispersion arising during the transition from full orientational polarisation at zero or low 1
frequencies to negligible orientational polarisation at high radio frequencies is referred to as dielectric |
relaxation. |
When a dielectric is subjected to an alternating field the polarisation P also varies periodically with time ]
and so does the displacement D. In general however P and D may lag behind in phase relative to E so 4
that for example if E - Eo cos ox, we have ]
D = Do cos (cor - 8) (11,64) ‘
= Do cos 8 cos cor + Do sin 8 sin (at
= Dt cos (at + D2 sin ox
where 5 is the phase angle, Di = Do cos 8 and D2 = DQ sin 8. For most dielectrics Do is proportional to
£o but the ratio (D(/£o) is generally frequency dependent. To describe this situation one may thus
introduce two frequency dependent dielectric constants.
e, Pl = —COS 0
Eo
e, Pl = -^-sin 8
^0
It is frequently convenient to sum these two constants into a single complex dielectric constant.
E* = £r - ier" (11.65)
Thus, D = er Eq e ‘w = E* Eo (cos cor + i sin cor) (11.66)
£ "
Also we see that, tan 8 = ——
er
Because both £r' and t" are frequency dependent the phase angle 8 is also frequency dependent.
We shall now show that the energy dissipated in the dielectric in the form of heat is proportional
d(Z>)
to Er". The current density in the capacitor is equal to & .
Thus, I = co(- Oj sin cor + D2 cos cot)

The energy dissipated per second in the dielectric is given by
z \ 2n/a>
( CD 1 f
W= — \IEdt
\2ltJ J
o
Substituting for 1 and E, one gets
r2k/<o
W = — J co(- £>j sin at + D2 cos cor)Eo cos (or dt
L o
CHAPTER 11
2it/<o 2n/o»
= — —of E0D1 sin cor cos cor dt + co | Eo D2 cos2 cor dt
J J
The value of integral containing Dl is equal to zero.

W = (co/2) DJE0
W = (tiJ/2)E&" (11.67)
The energy losses are thus proportional to sin 8 since e = (DJE^) sin 8. For this reason sin 8 is
called the loss factor and 8 is the loss angle (but it is customary) to call tan 8 as the loss factor; this is
correct only for small values of 8 because tan 8 = sin 8 = 8. The dielectric loss at low frequencies is
mainly due to d.c. resistivity. But at high frequencies the dielectric loss is mostly due to dipole rotations
or to ionic transitions from the lower energy states to higher energy states. Because of the upward
transition the energy is absorbed from the applied field. The losses which fall on the infrared region are
referred to as infrared absorption and in the optical region are referred to as optical absorption.
It should be possible to explain the frequency dependence of the dielectric constant directly in terms of
the electronic structure. It is well known that the refractive index varies with the wavelength of light in
the optical region, the phenomenon being known as dispersion. Dispersion can be explained on the
basis of classical theory which assumes that atom contains electrons vibrating at certain natural
frequencies characteristic of the atom and that the application of an alternating field sets such electrons
into forced vibration. Since the molecules in a dielectric are represented as dipoles on bound charges,
there must be equal number of positive charges and negative charges because the dielectric is an uncharged
medium. When an electromagnetic wave impinges on this bound charge it is caused to oscillate and
therefore to radiate. If the frequency of the wave is not equal to the natural frequency of the bound
charge the forced oscillation will have a small amplitude the radiation is very weak. This corresponds to
molecular scattering. If the frequency of the wave is equal to the natural frequency of the bound charge,
there is resonance and a much larger energy from the wave goes into the charge. In solid, liquid or gas
at high pressure there is strong intermolecular action and friction type forces causes heavy damping
with the result that the dipole energy is quickly dissipated. This corresponds to true absorption. In a gas
at low pressure there is no damping and the dipole radiate strongly. This is resonance radiation. The
absorption of an electromagnetic wave by a conducting medium is easily explained because the conduction
has a large number of free electrons. When the wave arrives its energy makes the charge move. The
moving charge constitutes current and the usual dissipation of energy by the current explains the
absorption of energy.
At optical frequencies the permittivity is almost entirely due to the electronic polarisation. To
determine the dependence of the electronic polarisability on the frequency of the applied field we shall
use the classical model of an electron elastically bound to the atom.
Consider the original atomic model with a nucleus of charge +e and a single orbiting electron,
the latter being represented by a spherical electron cloud of radius r0. The centre of this sphere coincides
with the nucleus in the absence of an electric field. If the electron cloud be displayed by an amount x
relative to the nucleus and then the system be left to itself, then the force tending to drive the centre of
the cloud at any instant is given by
f ^2x
F = -A.
where / = - ------ r
4ne0r03
where x is the displacement at that particular instant, F is called the restorting force and/the restoring
force constant. Hence, if there is no damping, the equation of motion of the electron will be identical to
a harmonic oscillator whose equation of motion is given by
+A = o
^+4-0
dr m
«■•<»>
2 f e2
w't*1 M° m 4rce0r03m
The solution of equation (11.69) is
x = x0 sin (o)ot + 5)
where x0 and 8 are integration constants and (00 = f(f/m) is the natural or resonance angularfrequency
of the electron cloud (i.e., the electron will show resonance absorption at this frequency). For
r0 = IO'10 m and m = 9.1 x 10-31 kg, 0)0 = 10I6rad/sec. Hence, the frequencies we are talking about lie
in the ultraviolet part of the electromagnetic spectrum.
Hence the electrons in an insulator absorb radiations in the visible and ultraviolet parts of the
electromagnetic spectrum only. Since the electrons absorb energy only in the visible and ultraviolet
regions, the electronic polarisation may be considered as instantaneous and frequency independent for
all frequencies of interest in electrical engineering and applied physics. Accordingly, the electron cloud
would go on oscillating for an indefinite period of time about its field free static position, x = 0. It is not
so in practice. Equation (11.69) is incomplete in the sense that it does not take into account the emission
of electromagnetic radiation by an oscillating charge according to field theory. This along with the
collisions among the electrons leads to damping. In mechanical system, damping of the oscillating
particle would result from the viscosity of the medium and this damping leads to a term proportional to
the velocity of the particle in the equation of motion. In the electrical case under consideration, the
CHAPTER 11
damping due to radiation may be represented in a similar way and the equation of motion can be written as
m —5- = —fx -2b —

dt2 dt
where 2b - {^(s^Kxtzmc) in which p() is the permeability of free space (= 4n x 10~7 henry/metre) and
is the natural frequency and c is the velocity of light. Substituting numerical values, one may find
that (2bhn) « <o0 a result which will be used later.
When an external alternating field of frequency © represented by £0cos car = Real [£0 acts
on the electron, the Lorentz force on the electron cloud is - e£0cos (at and the resulting motion is
j2
m — = -fx-2b — -eE0cos(i)t (11.70)
where £0 is the amplitude of the field acting on the electron. Once the displacement of the electron
cloud at any instant is determined, the induced dipole moment may be obtained by multiplying - e with
x (/).
The equation of motion is
d*x dx
+ 2b~ + rôcos 031 ~ 0 (H.71)
d^x
+ (Iblm)
r y-j + (eEJm)cos (Dt = 0
(11.72)
This equation can conveniently be solved for x(t) using complex notation.
Let the solution be of the form
x (0 = Re [A* e““] (11.73)
where *Re’ means real part and A‘ is a complex amplitude. The electric field E0cos oat can be written as.
Re
dx *
Now, — = Re [A icoe'(“] ‘
ul
d2x
—r=Re[A‘e«“(iCD)2]
at
.
13
5
= Re [-A* (D2ei<“] . i
Substituting these values in equation (11.72), one gets 4
Re [(-tfA* + (Jim)A* + i (2h(o/m)A* +(e/m) Eo} ?<“] = 0
This is possible only if the quantity within the serpentine bracket is zero.
i.e., -A*<i?+A*(flm) + A’ i (2bti)/m) + (elm) EQ = 0 j
Substituting | | we get
A* [(Do - cd2 + i(2&©/m)] = -

m
________ -eE0/”» 44
[(Wq - (D2 ) + i (2btD)/m) (11-74) $
Now the induced dipole moment as a function of time is t
MO = - ex (0
Substituting the values from equations (11.73) and (11.74)
/x „ F (e2/m)£oe“ 1 ;
” [((D2 - (D2) + i(22xD/m)] (lt75) 1
This is the relation between the induced dipole moment and the applied field.
The coefficient of electric field (£T/“), which is polarisability, is a complex quantity a* (»
static field|ita = a£)
Thus, M'> =Rc (11.75-0
where a* is the complex electronic polarisability and its value is given by

'________ (g2/rc)
CX _ — .9 9 (11.76)
(C0(}-CO2)-i(2M"0
Separating the real and imaginary parts
(cog - co2)2 +(4b2co2/m )
(cog-co2)_______________ i(2bw/m)______
a’ = (e2/m) (11.77)
(cog - to2)2 + (4b2G)2/m2) (cog - to2)2 + (4b2(B2/m2)
ae = a/ - iae" (11.78)
where a/ and a" are respectively the real and imaginary parts of polarisability.
Equation (11.77) may be extended to calculate the value of electronic polarisation and relative
dielectric constant due to electronic polarisation. Electronic polarisation in an alternating field can be
written as
Pe(r) = Re[Ara;E/«q (11.79)
where N is the number of atoms per cubic metre. Expanding equation (11.79)
Pe(t) = Re [jV (a/ - iae")E0 (cos cor + i sin cor)] (11.80)
= N ae' Eo cos cor +N ct"E0 sin cor (11.81)
Substituting the value of a/ and a" from equation (11.77), we get
(cog -co2)E0coscor
Pe(t) = (Ne2!m)
(cog - co2)2 +(4b2©2/m2)
(2bm/m)E0sin(Dt
+ (Ne2/m) (11.81a)
(cog - co2)2 +(4b2co2/m2)
The first part of electronic polarisation is in phase with applied field and the second part lags the
applied field by 90°.
As the electronic polarisability,ex,,, is a complex quantity this can be correlated to a complex CHAPTER 11
dielectric constant £* (= e'- <£/'). In an alternating field
Pe(r)= RefATÊ/"]
= Re [e0 (£*- DE/0*] (11.82)
or ®o(e> l) = Nae
Substituting for ex* from equation (11.76), we have
._______ N(e2/m)
60 Er “ (cog - co2) + i (2b(0/m)
. _______ Nje^/m)______ _
Ef = 1 + eo[(G>o -®2) + i(2bti)lm)] (11.83)
Equation (11.83) is true for bound electric charges.

Equations (11.77). (11.81).(11.81 a) and (11.83) have been derived on the basis that the atom has
a single electron charge. However, for an actual atom with Ze charge, e in these equations will be
replaced by Ze. where Z is the atomic number of the element.
We shall now discuss the frequency dependence of electronic polarisability, a* [Equation 11.77],
The variation of real and imaginary components of a’ with frequency is shown in Fig. 11.29.
Fig. 11.29 Real and imaginary parts of electronic polarisability as a function of angular
frequency, for a single electron
O’) For (o = 0 (i.e., for static field), the imaginary part vanishes and the real part
, e2 e2m . e
< =---- 2 = — [Equations (11.69) and (11.77)] with f= —~
m(Jio mf 4ne0r03
e1
“/ = '2/4™ r3 = 4jce0'0 > toe Static value ae
(it) For (0 < (00 both the real part (a') and the imaginary part (a") of the polarisability are positive.
For (i) > (t)0 the real part is negative and the imaginary part is positive.
.2b .
(Hi) Since — «(00, a remains almost constant from zero frequency up to values of to comparable
with <o0.
(iv) When co = <u0, the real part is zero and the imaginary part has maximum value which equals
e2
——. In the region where to nearly equals <o(), the behaviour can be discussed conveniently
by introducing the variable

Aco = ©0 - co with Aco «coo
;■■ ■■ iiii.iiT-i ■'Mi.r.irliii । ik>. ■» rtf rlltihi if i ■
Now, w2 - w2 = (®0 + co) (®0 - ©) = 2w()Aw
ên the real part becomes
2®0Am
a/ =(e2/m) (11.84)
4o>o(A(o)2 + (4b2®o/«\
2®0A®/4®p
(A®)2+(b2/m2)
A©/2©0
a/ = (e^m) (11.85)
L(A®)2 + (b2/m2)
Equation (11.84) can be written as

2b©0
where P =------- and x = 2®^®
d (x2+p2)-x(2x)
Thus, (x2+P2)2
„ (P2-*2)
(x2+P2)2
[ (x2 +p2)2(—2x) —(P2-x2)~(x2 + p2)2
________________ dx_________
(X2+P2)4
-2x(x2+p2)2 '
a' when x -P
(x2+P2)4
a, is negative when x is positive
CHAPTER 11
and 2®0A® = 2ba\/m
or A® =+{b/m) (11.86)
Therefore a/ is maximum when A® = ®0 - © = «b/m). Similarly, a'e is positive when x is
negative. Hence o,e' will be minimum when A® = ®q ~ ~(b/m).
This is best illustrated in the graph. The damping coefficient (2b) is thus a measure of the separation
between the maximum and minimum in the dispersion curve [see Fig. 11.29].
The imaginary part a," vanishes for © = 0 as well as for ® -> In the vicinity of © = ^ we may
write by introducing the variable A®.
_ J. 2b®0/m
Thus,
l<$70 Souo State Physics
2ba)0
4Wq(Aco)2 +(4fe2(Oo/m2)
2co0 e2b
4m2©2 [(Aco)2 + (b2/m\
a» e2!>/2m2(O0
‘ [(Aco)2+(fe2/m2)]
Thus, a" exhibits a maximum for Aco = 0; i.e., for co = ®0 and
,, e2bm2 e2
ry — —--------------- — ______
e(max) 2m2d)0b2 2m0b
Hence, „ _ e
ae(max)-4^b
1
Again
(Aco)2+(62/m2)
Put Aco ± blm
„= e2f> 1
2m2C00 _(Z>2/m2) + (ft2/m2)
a" = ——______ _
2m2co0(2Z? Im2)
e2
a/' = (l/2)a,'(lliax) when A© = ± (b/m) (11.88a)
In other words, the width of the bell-shaped portion of the curve for ae" corresponding to half
the maximum value is readily found to be (2b/m).
In the above discussion, we have used a model with one electron in the orbit. In a general case,
however, every atom contains several electrons, each electron having its own restoring force constant/
and damping constant b. Hence, the atom will, in general, have several values of ©Q. Then the a/ versus
© curve and a/' versus © curve will have the shapes as shown in Fig. 11.30.
’W. ionic ÔLARi’SATOffiVTtS'TtTtJFJCTiCTrSPTÔTCRCF^™™' 1

The phenomenon of ionic polarisation is analogous to electronic polarisation when the alternating fields |
are considered. Here the restoring force tending to derive the displaced ions back to their equilibrium
position may be taken approximately as proportional to the displacement. Hence following the method >
used in assessing the frequency dependence of electronic polarisability, we find that in this case also the ’
Frequency -------- — <o
Fig. 11.30 Variation of (Xt and a"with angular frequency in the case of a multiefectron atoms
forces are harmonic. However, in the present case, the masses of the particles are those of the atoms
rather than those of the electrons. Because of this increased mass, the natural frequencies of ionic
vibrations lie in the infrared part of electromagnetic spectrum and to0 = IO14 radians per second. Hence,
in this case also, ionic polarisability of a molecule is also complex in form and may be expressed as
a* = a.' - ia"
The plots a.' and a" as a function of frequency are similar to those of a' and a", respectively;
the difference being only in the natural frequency of oscillation.
The expression for ionic polarisation may be written as
P(.(t) = Re [TV a* P/0*]
= Na-Eq cos a)Z + Na"E0 sin tor (11.89)
This relation is similar to equation (11.81) for non-polar substance.
OFTMm^Pdi^RSoDDS
CHAPTER 11
In the case of non-polar solids, there are no permanent dipole moments, so the polarisation components
present are electronic and ionic. It has been studied that in the case of solids in static field, the field at an
atom of the solid dielectric is the internal field or local field. Taking the Lorentz internal field relation
[equation (11.44a)] for non-polar solids when they are subjected to an alternating field, we have
P{t)
EL(t) = E(t)+~ (11.90)
where P(t) is the electric dipole moment per unit volume at the time instant t. In accordance with
equation (11.90), considering both the electronic and ionic polarisabilities, we may write,
KO = N Ke {(a* + of') Ey? (1L90O)
where E0L* is the complex amplitude of the internal electric field, and <n is the angular frequency of the
applied field.
In general P (/) is not in phase with either the applied field E (/) or the internal field E (/)
Hence for umc-varying applied field, the following relation valid for d.c. field no loneer •>
aPpliec.
P = E„(E,-DE
Instead P (t) and the applied a.c. field Eo cos tot or Re [E0e/to/] are related by a complex relalive
constant er*. as given below.
P(n = E0Rel(<-DEneiw] (,19|) \
Combining equations (11.90) and (11.91). we get

i . !
Et(t) = Re {EoeltM} + - Re [(£, - 1) E()e,“'] .
= Re [E0e,to,(l + (e* -1)/3}]

n f(er + 2)E0eiwl 1 j
"Ke I 3 (11.92) I
or EL(t) = Re[E;LetoT j
where F* — -j
wncre £ol - (11.93) |
Substituting the value of E0L from equation (11.93) into equation (11.90a), we get,
P(t) = NRe (ae* +a?‘)|-y j(e; + 2)e't“ (n.94)

Combining equations (11.91) and (11.94) and rearranging, we get
|H^=(M3E0)[ae* + a*]
(11.95)
Equation (11.95) relates the complex dielectric constant E* under a.c. operating conditions to the
atomic quantities of the material. This equation is similar in form to the Clausius-Mosotti expression
given by equation (11.47) which gives the dielectric constant Er with the atomic quantities under d,q.
field conditions. Both equations (11.47) and (11.95), however, apply for the Lorentz field conditions, f-
Le., with y- (1/3).
We conclude from equation (11.95) that the complex dielectric constant £* of non-polar solids
depends on the complex polarisabilities a, and a, and hence the variation of real and imaginary parts
of £* with frequency will depend on the variation of real and imaginary parts of a* and a* with frequency.
We may thus express the complex dielectric constant Er in the following form:
e’=e/- is." (11.96)

The nature of variation of e/ and £r" with frequency depends on the frequency range under
consideration. From earlier articles it is apparent that a’ and a* are real up to infrared frequencies.
Hence, for the dielectrics under study, the e’ remains essentially real up to microwaves and has the
same value for static fields. In practice, however, several solid dielectrics contain ions which may be
Dmccnadi jMfr
j over distances exceeding one or more interatomic distances when subjected to external electric
r -id Such a condition exists in glassy materials and to a small extent even in crystalline materials.
,e. such a condition, the dielectric constant develops imaginary component, i.c., becomes complex
■ÎPbLAkRf^TOS
We have so far taken into consideration the frequency dependence of electronic polarisability a, and
ionic polarisability a’ and have neglected the frequency dependence of orientational polarisability. For
several materials, typically liquids and glassy solid dielectrics, this frequency dependence orientational
polarisability becomes significant, and results in dielectric losses even at frequencies below the infra
red region, ie., in the frequency range extending from zero to several thousand megahertz.
The principal effect in the materials (solids and liquids) which contain permanent dipole moments,
when the material is subjected to an alternating field, is termed dipole relaxation. The physical picture
of this relaxation is as follows: Let a static field E is applied to a crystal at time t = 0 and held constant
thereafter. The dipoles in the crystal may have one of the two responses. They align rapidly with E,
depending upon the temperature, of gradually assume the final alignment. Rapid alignment of the dipole
along E is the static response discussed earlier. In the second type of response E and P are not in time
phase. The mathematical treatment of the problem is discussed below for permanent dipole moments
rotating in liquids.
Let the liquid understudy contain N dipole/m3 and let each dipole has a dipole moment Pp. We
assume that the material has been subjected to a d.c. field E for sufficient time and under the equilibrium
condition so reached, let the orientational polarisation be PQ. Let the d.c. field be suddenly switched off
at time instant t = 0. The polarisation will not then become zero instantaneously since it takes some time
for the dipoles to rotate. Let the decay of polarisation with time follow the following exponential law:
Po(t) = Poe-^ (11.97)
where t is called relaxation time.
Figure 11.31 shows the decay of the orientational polarisation of a liquid after switching off the
external field at time t = 0. The relaxation time t of a liquid increases with the increase of its viscosity.
^•8- 11.31 Decay. of orientational polanwtion of * liquid after switching off the field at time t - 0
■. -
The rate of change of polarisation is given by

IPO(O1 = - (7-) d 1.98)
The rate of decay is a function of instantaneous value of the polarisation. At t = <», P0(t) becomes
zero. Hence we may write equation (11.98) as below,
(11.99)
di v
Let us now consider the build up process of orientational polarisation. Suppose that the dielectric
field E has been absent for a long time and at t = 0, it is switched on. The orientational polarisation after
sufficient time will rise to its ultimate value of PQ, and at any time t after r=0, orientational polarisation
may be expressed as in (Fig. 11.23).
P0(t) = P0{l - exp (—r/T)}
The rate of increase of orientational polarisation is given by
~ : -r.
='(i/t)[P0-P0(r)] J
; ' =(l/T)[P0(oo)-P0(t)] (11.100) |
Fig. 11.32 Growth of orientational polarisation with time after switching on the field at time r » 0 a
It may be seen that equations (11.99) and (11.100) have the general form.
Inspection of equations (11.99) and (11.100) make clear that during decay as well as during
build up, the rate of change of P0(r) is, apart from the factor (1/t), equal to the ultimate value corresponding |
to the field E, minus the instantaneous value P0(r). I
For the given dielectric, the equilibrium value of the orientational polarisation in a static field £
may be expressed as, J
= eo ~ . I
------ :_ z___ 2_j
l i
i
where ero is that part of the relative dielectric constant which consider only the orientational polarisation
OfCTWCT AND faWftMM)
Next let us apply an alternating fiHd t.-

P (,y? To find this value Pdt) we refer to eou°i nd,e,CC‘"C Whal w,,‘,hcn ** ,hc valuc of
both decay condition as well as the build un ‘’J/.”* This » “ *L'ncral ctluallon Whtable for
Sd also At the time instant r, ext ma ±7 r T* Z
. , d elcctnc field is £ cos (nt, and hence at that instant the
n £v() cos (nt. Now the corresponding differential equation
dipoles are aiming at Po„ (°°) equal to e0 <ie q, ~ 1)
for P0(t) may be written as,
dt po^ = (1/t) [e0 (ero - l)£0cos mt - P0(/)J (II.101)
With a.c. field, in general, there exists a phase difference between P^l) and E (t). Hence, we
may express Po (t) as below introducing the complex dielectric constant £*,
£0(t) = e0Re [(6* -!)£,/"] (11.102)

d >
Hence, - [£0(r)] = £0 Re [(e,o - 1) Eo io elu>r]
Re [e0£0ko- 1)] = (1/t) Re [£oeo(£fo - 1) - 1)J
i.e., im (ej, - 1) = (1/t) [ (efo - 1) - (ej. - 1)]
or ion (e* - 1) + (e* - 1) = (ero - 1)
(e* - 1) (1 + ion) = (ero - 1)
• ^'0 “ F 1 - ion
^0 -1)~ (1 + ion) -1\1 + oj2t2 (11.103)
From equation (11.103) we conclude that for a.c. field, e’ . i.e., the orientational part of the
dielectric constant becomes complex and is a function of the static value E, and on. Separating the real
and the imaginary parts, equation (11.103) may be written as,
CHAPTER 11
1 on
(<-D = (e.-D 1 + coV Il + <o2t2 (11.104)
Substituting this value of s‘ in equation (11.102), we get the following expression for PQ(t).
(coso# + sin ox )(6,#

£qW - £o p0
cos tot arts into/

+ (o2t2 + i + arr2
(11.105)
SOUu STAre PHYSICS
From equation (11.105), we find that P0(t) contains two terms: The first term on the right hand
side of equation (11.105) which is in phase with the external field and the second term which lags
behind by 90°. The amplitude of the first term is proportional to 1/(1 + oA2) while that of the second
term is proportional to ojt/(1 + <o2x2). Figure 11.33 shows the variation of these quantities 1/(1 + cd2^
and m/(l + (O2^2) with angular frequency co. It is observed that the in-phase component of P0(r) begins
to disappear when (OT becomes comparable to unity. For lor = 0 and cot « 1, the in-phase component
namely 1/(1 + cd2!2) is approximately unity. At cor = 1, the in-phase component reduces to one half of its
d.c. value. It is also observed that the in-phase component of P0(t) begins to decrease when on becomes
comparable to unity. When on » 1, the dipoles cannot follow the field variations and hence the
polarisation vanishes. The variation of the out of phase component depends upon on/(l + co2!2), which
has a maximum value of 1/2 at on =1.
The decrease in the in-phase component with frequency may be interpreted as follows. At low
frequencies the dipoles can respond to the variation of the electric field and move with the field direction.
As the frequency increases, the dipoles can no longer cope with the changes in the direction of the field
and hence the effective polarisation falls to very low values, r may vary from 10"6 to 1O“10 sec and as
such, the frequency range affecting the behaviour of orientational polarisation lies between 106 to IO10
(radio frequency region) and hence is very important for electrical engineers.
Fig. 11.33 Variation of 1/(1 + (O2T2) and 0H/(1 + CO2!2) with frequency co
Table 11.9 Variation of t with temperature for propyl alcohol
Temperature (°C) 20 0 -20 -40 -60
106 T (sec) 0.95 1.7 3.2 7.5 26
This table indicates that in the case of propyl alcohol, as the temperature reduces the relaxation
time T increases and hence the frequency for which gjt = 1 decreases.
With high frequency applied fields the dielectrics absorb energy and behave as loosy dielectrics. In the
proceeding sections we discussed the frequency dependence of the electronic, ionic and orientational
contributions to the polarisation.
Since these contributions are additive, a material may be characterised by a complex dielectric
constant given as, £, — (£r - iEf ) in which the real and imaginary parts £rz and e" incorporate all the
three contributions. In the present section we shall show that the imaginary part gives rise to absorption
of energy by the material from the alternating field. For this purpose, consider a parallel plate condenser
filled with a material characterised by £r; the functions £/((0) and £r/z(co) are assumed to be given. With
the alternating fields the electric flux density has to be expressed as
D(t) = Re [ê; E0^<oq (11.106)

There is a variation of electric flux density with time, so there will be a flow of current and the
current density will be
J(r) = ^=Re[eoe;,tOEo^«r]
Taking Er = (£.'- tEr") and €“* = [cos cor + i sin ax]

we get J (r) = (aE0 eq Re [/ (cos cor + i sin cor) (£/ - is")]
J(t) = (QE0E0[Er"cos(at-er'sin(Dt] (11.107)
This shows that there are two components of the current density, one in-phase with the applied
field and the other out-of-phase.
From equation (11.107) we observe that
(z) The imaginary part e" of the complex dielectric constant determines the in-phase component
of current.
(n) The real part e' of the complex dielectric constant determines that the component of current
which is 90° out of phase with the field.
(iii) The term containing £ ', being in phase-quadrature with the applied a.c. field does not result
in absorption of energy.
(iv) The tern* containing £ " being in-phase with the applied a.c. field results in absorption of
energy. CHAPTER 11
The instantaneous power/m3 absorbed by the medium equals J (r) £(t). Hence the energy/m3
absorbed by the material per second (energy density) is given by
W(t) = f2’ J(t)E(t) J«nt) (11.108)

2it Jo
Substituting the value of J (/) and E(t), we get
J- j2x (e/'cos cot - £/sin cnt)E0 cos car d(cot)

W) =
- -L-j2*(oEqEq (e/'cos2<at - s/sin (at cos co/) d(cw)

678 SOUD SlXTE PHYSICS
or W(O = (oV2)eo£;'£o2 Hl.1Q9)
Equation (11.109) tells that the amount of energy absorbed by the medium is proportional to the
imaginary part e" of the complex dielectric constant. The energy so dissipated in the dielectric medium
is referred to as the dielectric loss. It can be seen that £r is the imaginary part of the relative dielectric
constant and hence one could conclude that the absorption of energy depends upon the out-of-phasg
component of ionic, electronic and orientational polarisations. The absorption of energy is possible in
the ratio frequency range if orientational polarisation or permanent dipole moments are present. The energy
density W(t) is responsible for the losses in a dielectric, and these losses are called dielectric losses.
Resultant
current vector
Fig. 11.34 Illustrating the vector relationship between the field vector ElV the current vector okq£' Eg which leads the
field by 90 degree and the current vector (0CC1E''£n which '» in-phase with the field. The loss angle 6 is indicated
To derive a circuit analogue of the phenomenon of dielectric losses a parallel-plate capacitor

with unit area of cross-section of the plates and separated by a metre as in Fig. 11.34 is considered. If the
applied voltage is £0 cos cor, then
J (r) = co e0 Eo (e"cos cor - E'sin cot) [Refer equation (11.107)]
which shows that the dielectric may be considered to be made up of a parallel combination of resistance
and capacitance. If R is the resistance and C is the capacitance of the dielectric,
,z. Encos©t „ .
J (0 = —----------- £0© C sin ©r (11.110)
R
with R =----------- and C = £n£' with the general expression for capacitance as
£oe/'©
■£oeM
C L d .
where e" —> 0, R —> «>. The loss angle tan 8 is defined as E.'r'lE' and is a measure of the dielectric losses.
r X Zr 1
tan 8= —7“ =
e' CRta
The physical significance of the angle 8 becomes evident from equation. (11.107).
DfELKnacs and Raxno Pttowmw 679
I'hus with no losses. Er = 0 so that the current density J(t) equals coe0£0 t' cos (ax + 90°)
•fying that the current J (t) leads the field by 90°. In such a case, 5 = 0. However, if there are losses
Sl«n' non-ze”1 and there is a current component in-phase with the field. The resulting current no longer
âds app'ied field by 90 but leads by (90° “ S) as shown in FiS- 1134-
The dielectric losses in the radio frequency region are usually due to dipole rotation or ions
jumping from one equilibrium position to another. The dielectric losses associated with ions, the
frequencies of which fall in the infrared region, are usually referred to as infrared absorption. Similarly,
insses in ic optical region, associated with the electrons, are referred to as optical absorption. The
occurrence of absorption in the optical region is the source of the colour of the material. For example a
rvstal of NaCI is transparent in the visible light; this means that there is negligible absorption for the
corresponding frequencies. However, after the NaCI has been exposed to X-rays, one finds that it has
turned yellowish brown. The reason for this is that, after irradiation with X-rays, a relatively small
number of electrons, which have been transferred to positions in the lattice where they are not bound so
strongly as they were before, giving rise to resonance frequencies lying in the visible part of the spectrum.
When white light passes through the crystal, a fraction of the light corresponding to a narrow frequency
region is absorbed, and the transmitted one is therefore coloured. The centres which are responsible for
this particular type of absorption are called F centres; they consist of electrons occupying positions in
which negative ions are missing. This type of colour centre occurs in all alkali halides as well as in other
ionic crystals.
(a) Dielectric Relaxation

Dielectrics take a finite time for the polarisation to reach its maximum value. This is due to the forces
between adjacent molecules which tend to prevent the alignment along the external field. The average
time for relaxation varies from substance to substance, values from IO-10 sec to several days.
Due to this relaxation, capacitor connected to a potential difference V acquires charge at a finite
rate. Discharging process is also slow. If a capacitor is charged and discharged quickly and then left
with terminals open, it will be found to have acquired a potential difference between its plates.
Phenomenon of hysteresis with alternating field is also the consequence of the relaxation time.
(b) Dielectric Absorption

On account of the finite conductivity of the dielectric materials noticeable energy loss is observed in the
form of heat. This loss and the hysteresis loss are referred jointly as dielectric losses. Similar to the
relaxation phenomenon, absorption effect is observed in capacitors. If an initially charged capacitor is
discharged by short circuiting it, it is found that the capacitor still retains a charge when the short circuit
is removed. This is due to electric absorption. It is when the dielectric is not perfectly homogeneous.
For a perfectly homogeneous dielectric, this residual charge should not occur. Thus a gas or a perfectly
homogeneous crystal like calcite shows no residual charge.
If the capacitor is repeatedly charged and discharged, dielectric absorption causes heat to be
produced. If the process is rapid, as with high frequency a.c„ energy losses in the dielectric are low, Le.,
the dielectric absorption is small, as the molecules are unable to rotate to any extent in this very short
time.
(c) Dielectric Breakdown
It is the most important property of real dielectrics. For any material there is a maximum field intensitv
• beyond which damage occurs that results in conduction, sparking and other breakdown phenomena. At
relatively high fields, the electrons in the dielectric gain enough energy to knock other charged particle*
and make them available for conduction. This multiplying process occurs along certain paths in the
material. Along these paths, local heating also occurs and a permanent damage occurs.
The breakdown phenomena in solids is the most complicated one and is least understood
Although, many theories exist regarding the breakdown of solids (intrinsic, thermal, etc.) the failure of
solid insulation in practice is almost always due to entirely different reasons. Electric strength of solid
dielectrics depend on many extraneous factors, such as
(0 defects and inhomogeneity of the material,
(ii) thickness area and volume of the specimen,
(Hi) the surface condition and the method of placing the electrodes,
(iv) the type and application of test voltage and test duration and
(v) moisture and other contaminations^
By testing a pure homogeneous material under carefully controlled atmosphere and avoiding i
the field concentration at the edges of the electrodes, a number of fundamental breakdown mechanisms ■
in solids can be distinguished.
(i) Intrinsic breakdown - electronic in nature and depends on the presence of electrons
capable of migrating through the lattices.
(it) Thermal breakdown - when the local heat generated by losses exceeds that, what can
be dissipated by the dielectric.
(Hi) Discharge breakdown - depends upon the presence of voids, etc.
Intrinsic Breakdown
In a perfect dielectric there are no free electrons and the conductivity is almost zero. In general, all
crystals contain imperfections of one or more of the following types.
(i) Vacancies or interstitials — vacancies are lattice sites, i.e., points where atoms should be but
are missing. Interstitials are ions displaced with respect to regular array of atoms.
(ii) Non-stoichiometry - in an impure crystal some atoms may be extra which can take interstitial
positions or lattice, may rearrange to have vacancies.
(Hi) Imperfections — due to the presence of foreign atoms.
The impurity atoms or molecules act as traps for the conduction electrons up to certain ranges of 1
field/temperature above which the trapped or conduction electrons would be released for conduction. <
In a pure dielectric the valence band is separated from the conduction band by a very large '
energy gap, the electrons cannot acquire enough energy to jump ttfthe conduction band. To remove an 3
electron from the atom, a field of the order of 108 V/cm is required. But normally, breakdown occurs |
much below this field. The above said impurities contribute free electrons in solid dielectric at ordinary
temperatures which are responsible for this low value of breakdown field. Even at room temperature the
thermal energy is sufficient to eject electrons from the traps into the conduction band, because of the
small energy gap between the trapping levels and the conduction band. Thus the crystal will always be
expected to have some conduction electrons, although the more perfect the crystal the smaller these will j
be in number. All the intrinsic breakdown theories use these conduction electrons in their development- ,
(a) Hiffi temperature breakdown: When a field is applied to an imperfect crystal, electrons in
the conduction band gain energy form it and due to collisions between them, this energy is
shared by all the electrons. As in the imperfect crystal collision between electrons
predominates, the electrons gain energy more rapidly than they lose it. Hence, the electrons
temperature will be relatively higher than the lattice. The effect of increased temperature is
to eject more electrons to the conduction band, increasing the conductivity. As the electron
temperature continues to rise, a condition will be reached when complete breakdown occurs.
(h) Low temperature breakdown: Under this condition, the number of electrons will be few and
the interaction of electrons with the lattice will be predominant. When an electric field is
applied, these electrons gain energy and after collision with the lattice, lose their energy to
the lattice.
Thermal Breakdown
Thermal breakdown occurs in a dielectric when the rate of heat generation is greater than the rate of
dissipation. Electrothermal breakdown in solid dielectrics consists on its destruction but to the heating
produced by dielectric losses. This heat goes partly to increase the temperature and the rest is dissipated
to the ambient media. The increase in the temperature of the dielectric results in increased conductivity
and also loss to the ambient. Thus the temperature stabilises when the heat generated is equal to the heat
lost by the ambient. Clearly, a critical temperature may be envisaged below which a stable condition
can be reached and above that limit an unstable state results with a limitless temperature rise, conductivity
and collapse of voltage. This mode of dielectric breakdown is known as thermal breakdown. Obviously,
for a given material, a thermal breakdown voltage can be specified. Also this phenomena sets the upper
limit for improving breakdown voltage by increasing the insulation thickness unless extraneous means
of heat removal are used. This mechanism of breakdown is more dominant in insulating systems using
alternating voltages, where the heat generated per unit volume in a given dielectric in unit time is given
by
Er tan 5
W=£2v watt/cm3
1.8 x IO12
where E is the uniform electric field in volt/cm, v is the frequency of the applied voltage, 6 is loss angle
and Er is relative permittivity. H H31dVH0
For d.c. voltage
E2
W= —
P
where E is the uniform electric field in volt/cm and p is the resistivity of the insulation in ohm-cm.
The chief characteristics of thermal breakdown are:
(i) It occurs at high temperatures.
(ii ) The breakdown field strength depends on the size and shape of the insulation sample, and on
the geometry and the thermal properties of the electrodes and the ambient medium.
(Hi) The breakdown time is of the order of millisecond or much longer.
(iv) In alternating fields the breakdown strength is lower than the d.c. breakdown strength as the
power loss increases with frequency.
Discharge Breakdown
Breakdown of solids by gas discharges is usually classified as external (surface breakdown) or intern^
External breakdown is generally caused by a glow or corona discharge. Such discharges are normals
confined to the vicinity of the electrodes, especially at sharp edges where relatively high stresses are
present. These stresses initiate local gaseous discharges which gradually cause deterioration of the
adjacent solid dielectric. Because of the organic nature of the majority of dielectrics, such deterioration
is usually accompanied by the formation of carbon so that the damaged areas become conducting.
These areas constitute extensions of the electrodes so that eventually a conducting path will be formed
leading to a power arc and the complete failure of the dielectric. Surface breakdown, also known a*
'tracking may be caused by the contamination of the dielectric surface by conducting impurities such
as dust, moisture, salt sprays, etc.
Breakdown by internal discharge is associated with the presence of gas or liquid filled void* or
cavities within the solid dielectric. Such cavities or voids may be formed either during the process of
manufacture of the dielectric or as a result of operating conditions such as thermal expansion* and
contractions under cyclic electric loading, overstressing or mechanical bending, or by the decomposition
of moisture under the action of electric stress. The electric stress across such cavities will be high, due
to the difference in permittivity between the gas and the surrounding solid dielectric, whilst their inherent
electric strength is low relative to the solid insulation. As a consequence partial discharges (corona)
may occur in such cavities at otherwise acceptable working stresses and these will then cause a progressive
deterioration of the adjacent solid insulation. The breakdown mechanisms in the cavities themselves is i
essentially a gaseous discharge initiated by an electron avalanche. The by-products of such discharges
(energetic electrons and ions, ultraviolet light, free radicals, ozone, etc.) are deleterious to both the electric
and mechanical properties of the dielectric and will lower its performance characteristic and service life.
Electrochemical Breakdown
Chemical and electrochemical type of breakdowns are very much related to thermal breakdown
Temperature rise in an insulating material (due to losses, etc.) accelerates the chemical deterioration.
Electrochemical deterioration is due to the presence of ions and their mobility in the insulation, which
are responsible, for leakage current and energy loss in the material. In most of the cases the final
breakdown resulting from electrochemical deterioration is thermal breakdown.
Chemical deterioration is a progressive process and can occur in the absence of an electric field
due to number of reasons:
1. Some materials oxidise under the presence of air or ozone. Rubber is one such material
which oxidises and cracks in the presence of ozone. Polythene oxidises in strong day light. J
2. Some of the materials, mostly organic in nature, show chemical instability as they are operated
under high temperature. J
3. Cellulose esters, and other polyesters lose their electrical and mechanical properties when
they are moist and hot.
4. Some of the insulating materials get contaminated when they come in contact with other '
chemical substances, when in use in an electric equipment. Rubber and polypropylene age
rapidly at elevated temperature when in contact with copper. Cellulose degrades rapidly in 4
the presence of traces of acidic substances.
5. Glass fabrics made from glass of high sodium content lose their mechanical strength under
warm and damp conditions. Sodium being very mobile leaches to the surface of the fibre5
and the strong alkali formed with the moisture present, leads to deterioration. 4
Diubctmci -amd Awm*1*0
Many insulating materials have I rec ions, which arc responsible for leakage current in the presence
electric field' Such ions after reaching the electrodes reduce (heir charge and may also attack the
-trode metal evolving some gas, or some other substance may be deposited on the electrodes. Such
e et< of activities ot the ions are chemically or electrically harmful and tnany times lead to rapid failure
''population. The rate ol electrochemical deterioration is determined by the magnitude of leakage
l. rrent and other factors like concentration ot ions in the insulation, temperature, and whether the
latcrial is polar one or not. To avoid electrochemical deterioration: (/) The impurities should be avoided
the insulating materials, (ri) it should not be operated at elevated temperature. (Hi) care should be
taken to avoid contamination in polar materials, which otherwise will result in high leakage currents.
materials
The requirements of good insulating materials can be classified as electrical, mechanical, thermal and
chemical. Electrically the insulating material should have high resistivity to reduce the leakage current
and high dielectric strength to enable it to withstand higher voltage without being punctured or broken
down. Further the insulator should have small dielectric loss.
Since the insulators are used on the basis of volume and not weight, a low density is preferred.
Similarly a uniform viscosity for liquid insulators ensures uniform thermal and electrical properties.
Liquid and gaseous insulators are used also as coolants. For example, transformer oil, hydrogen
and helium are used both for insulation and cooling purposes. For such materials good thermal
conductivity is a desirable property. The insulators should also have small thermal expansion to prevent
mechanical damage. Further it should be non-ignitable or if ignitable it should be self-extinguishable.
Chemically, the insulators should be resistant to oils, liquids gas fumes, acids and alkalies. The
insulator should not absorb water particles, since water lowers the insulation resistance and the dielectric
strength.
Insulating materials should have certain mechanical properties depending on the use to which
they are put. Thus when used for electric machine insulation, the insulator should have sufficient
mechanical strength to withstand vibration. Good heat conducting property is also desirable in such
cases.
;R 11
Materials with large electronic and ionic polarisabilities and therefore large permittivity are used
for making dielectric capacitors. Titanium oxide which has a permittivity of about 100 is a good example
of such a material. The use of molecules with a permanent dipole moment is not desirable because of
the possibility of large dielectric losses at high frequencies.
As a matter of fact the insulating materials may be solids, liquids or even gases. But here we shall
discuss the solid insulating materials only. Though there are a number of solid insulating matenals. yet
the following are important from the subject point of view.
Sm* Spat IM^ks
— - . ... —
Glass
It is an inorganic insulating material, which comprises of complex system of oxides. Silica (SiO i •
most essential constituent of many commercial glasses. It is fused with alkali (like potash, soda^^
and some base (like lime, lead oxide etc.). The silica glass (having 100 per cent SiO2) is the
insulating materials. Its dielectric constant varies between 3.7 and 10. loss tangent between 0.0003
0.01 and dielectric strength between 2.5 and 50 kV/mm.
Glass is widely used as an insulating material to form and envelop for electric bulbs, electron-
valves, mercury switches. X-ray tubes etc. It is also used as dielectric material in capacitors.
Mica
It is an inorganic compound of silicates of aluminium, soda potash and magnesia. It is crystalline in
nature and can be easily split into very thin flat sheets. The two important types of mica are muscovite
and phlogopite. The muscovite mica is known to one of the best insulating materials. Mica has a good
dielectric strength and mechanical strength. Its dielectric constant varies between 5 and 7.5, loss tangent
between 0.0003 and 0.015 and dielectric strength between 700 and 1000 kV/mm.
This mica is widely used as an insulator for commutator segment separator in electrical machines,
switchgears, armature winding, electrical heating devices like electric irons, hot plates etc. It is also
used as a dielectric material for high frequency applications.
Ceramics
These are generally non-metallic inorganic compounds such as silicates, aluminates, oxides, carbides,
borides, nitrides and hydroxides. These materials are brittle in nature and may be crystalline or amorphous.
The ceramics used as dielectrics may be broadly described as porcelains, alumina, ceramics, titanates
etc. The ceramics have excellent dielectric and mechanical properties. The dielectric constant of the
commonly used ceramics varies between 4 and 10.
The ceramics are widely used as insulators for switches, plug holders, cathode heaters, vacuum
type ceramic metal seals etc. These are also used as a dielectric materials in capacitors. These capacitors
may be operated at high temperatures and can be moulded into any shape and size.
Asbestos
It is an inorganic material, which is used to designate a group of naturally occurring fibre material. The
asbestos generally consists of magnesium silicate composition. The asbestos has good dielectric and
mechanical properties.
It is widely used as an insulator in the form of paper, tape, cloth and board. It is also used in
dielectric applications where it is impregnated with a liquid or solid. It is also used to manufacture panel
boards, insulating tubes and cylinders used in the construction of air cooled transformers.
Resins
These are organic polymers and may be natural or synthetic. The natural resins are derived from plant,
animal sources etc. The resins have very little applications in engineering industry. The synthetic resins
are produced artificially. The commonly used synthetic resins are polyethylene, polystyrene, polyvinyl
chloride, acrylic resins, teflon, nylon etc. The resins have good dielectric and mechanical properties.
The dielectric constant of resins varies between 2 and 4.5, the loss tangent between 0,0002 to 0.04 and
dielectric strength is quite high.
The resins are widely used in engineering industry as dielectric and insulating materials. They
used as an insulating material in radio, television, power and submarine cables. They are also
1S° dielectric material in d.c. and high frequency capacitors.
used as a
Rubber
orp aiSo organic polymers and may be natural or synthetic. The natural rubber is obtained from
ThPSC
tree. The natural rubber has limited applications because of its resistance to low and high
^peratures. The synthetic rubbers are produced artificially by copolymerisation of isobutylene and
• rene. These rubbers have good electrical and thermal properties. The dielectric constant of rubber
vines between 2.5 and 5, and loss tangent between 0.01 and 0.03.
The rubbers are widely used as an insulating material for electric wires, cables, tapes, coatings,
transformers, motor winding etc.
Transformer Oil
Transformer oil is a special mineral oil with high dielectric strength. This oil is used for insulation and
cooling of transformers. The oil should be perfectly free from moisture, because presence of even trace
of water in it reduces its insulation strength considerably. The oil must undergo dehydration periodically
to remove moist contents from it. Sludge formation takes place in the oil due to moisture, dirt or some
foreign matter in the oil which is harmful. So the oil is to be tested at regular intervals to know its
qualities.
The transformer oil serves the following two purposes:
(a) It transfers heat by convection from windings and core to cooling surfaces.
(b) It maintains the insulation of the windings.
Table 11.10 Experimentally determined value of permanent dipole moment of a few dielectrics in gas phase
Molecule (lm (Debye unit) Molecule (Debye unit)
H2O 1.84 CO 0.11

ch3ci 1.15 NO 0.10
HC1 1.04 co2 0 CHAPTER 11
H2S 0.93 cs2 .0
no2 0.40 ch4 0
Table 11.11 Dielectric strength of some materials
Dielectric strength
Material Permittivity tan 8
(kV/mm)
Bakelite 22 6 0.02
Bitumen 14 4.5 -
Cotton 4 5 0.20
Ebonite 25 2.8 0.01
Empire cloth 15 2 -
Fibre 5 6 —
Glass 8 ft. 5 0004
Rubber 17 4 0.01 ft
Marble 6 8
Muscovite 95 ft 0.0003
Dry paper 7 3 0.005
Paraffin wax 8 2.2 0.0003
Porcelain 15 ft 0.002
Shellac 13 3 0.008
Slate 3 ft —
Mineral oils 30_______ 2 0.0002
While the oil is in service in the transformer, a sludge is formed which is an oxidation produce
Sludge formation is accelerated by the contact with air and temperature. Sludge is also caused by the
presence of acids and alcohols. Sludge formation produces the following effects:
(u) Rate of heat transfer is reduced.
(b) Ducts are clogged.
(<•) Operating temperature increases.
1. Net outflow of flux through a closed surface enclosing a charge q is

(«) q (b) l/q
(< »<?/€,) (d) q/4 7te0
2. Newton/coulomb equals volt/metrc
(a) True (b) False
3. The unit of dipole moment/unit volume is
(a) coulomb/mctrc (b)coulomb/metre2
(< i coulomb/metre' (</) coulomb
4. When a monoatomic gas atom is placed in a uniform electric Held E, the displacement of the nucleus it
proportional to
(a) E1 (b) E
(c) £3 4 5 6 7 (c/) independent of E
5. The flux density is related to the electric field as
(<i)D = e + £ (b)D = e-£
(c)D = eJE (d)D = eE
6. When a monoatomic gas atom is placed in a uniform electric field E, the resulting induced dipole momeoi
is proportional to
(a) E W
(t.) £t (</) independent of E
7. The electronic polarisability ar of a monoatomic gas atom is
(a) 4neu 4ft£0R
(c) 4rc(/?3 (</)
where R is the radius of the atom
ijxccl number <4 atoms per unit volume, the dielectric constant of rnonoatomic gas is essentially
K. independent ol temperature
th) False
m) True
■ntalional polarisability per molecule in a polyatomic gas is proportional to
The onci
(b)T1
(«) I
(</) l/T2
«) 1/T
The orientational polarisability per molecule in a polyatomic gas is given by
10.
u2
Um (b) -~-
,t0 3kHT 3kuT
H2
Um
(c) 3kBT
11 Ina solid or liquid dielectric, with external applied electric field, as the electronic polarisability a, increases,
the internal field £.
(a) increases (b) reduces
(c) remains unaltered (d) none of these
12. For an elemental solid dielectric the total polarisation is given by
NaE N2aE
(fl) (o)
yNa j yNa
1-------
. eo J . eo .
N2E r NaE2
(c)
yNa 1_
. eo . . eo .
13. The dipole moment per unit volume of a solid is the sum of all the individual dipole moments and is called
(a) polarisation of the solid (b) permittivity of the solid
(c) electrostatic moment (d) none of these
14. The polarisation Pina solid dielectric is related to the electric field E and the electric flux density D by the
relation
(a)E = EQD + P (b')D = E+E0P
(c)D=Ee0 + P (d)D = Eq(E + P)
15. For a given dielectric, as the temperature increases, the ionic polarisability
(a) increases (b) decreases
(c) remains unaltered (d) none of these
,,
10. —---- Na js
-1 -- ------
er + 2 3e0
(a) Lorentz relation (b) Clausius-Mosotti relation
(c) Einstein relation (d) none of these
17. Condition under which spontaneous polarisation in a dielectric occurs is
NaB2 Na2p
(a)-----— = 1 (b)------ -- = 1
eo eo
N2aP ' Nap

(c)------ - = 1 (d) —- = 1
£o eo
18. For a given dielectric, the electronic polarisability, ae
(a) increases with temperature
(b) decreases with temperature
(c) is not affected by temperature change
(d) may increase or decrease with temperature
19. In a dielectric, the polarisation is
(a) linear function of applied field
(b) square function of applied field
(c) exponential function of applied field
Cd) logarithmic function of applied field
20. In a ferroelectric material, as the applied electric field is gradually reduced to zero, the polarisation still
left is known as
(a) coercive polarisation (b). remanent polarisation
(c) zero polarisation (d) positive polarisation
21. In a ferroelectric material, the spontaneous polarisation vanishes above a certain temperature called
(a) Transition temperature (b) Debye temperature
(c) Fermi temperature (d) Curie temperature
22. The factor responsible for spontaneous polarisation is
(a) free electrons (b) atoms
(c) permanent dipoles (d) none of these
23. Piezoelectric effect is the production of electricity by
(a) chemical effect (b) varying field
(c) temperature (d) pressure
24. Above Curie temperature, the hysteresis loop of a ferroelectric material merges into a
(a) parabola (b) straight line
(c) point (d) ellipse
25. The losses in a dielectric subjected to alternating electric field are determined by
(a) real part of the complex dielectric constant
(b) imaginary part of the complex dielectric constant
(c) both real and imaginary parts of the complex dielectric
(d) none of these
26. At frequencies around 5 x JO14 Hz, the ionic polarisation becomes
(a) zero (b) unity
(c) infinity (d) negative
,7 In a dielectric, the power loss is proportional to
(a) co (b) w2
(<•) 1 / co (</) 1 / co2
I. What is meant by polarisation mechanism in dielectrics?

2. Get the relation between flux density and intensity of electric field.
3. State and prove Gauss theorem in electrostatics.
4. Show that P = E Eg (Er - 1) where P is the electric polarisation.
5. Explain electronic polarisation and orientational polarisation in dielectrics.
6. Discuss local field in solid dielectrics.
7. Write down Clausius-Mosotti equation. Explain the symbols.
8. Discuss the relation between dielectric constant and refractive index.
9. What are the chief characteristics of ferroelectric materials?
10. What are antiferroelectricity and piezoelectricity?
11. Explain the terms dielectric loss and dielectric breakdown.
12. Describe the spontaneous polarisation of Barium titanate crystal.
13. Discuss the mechanism that lead to dielectric breakdown.
14. Explain the phenomenon of spontaneous polarisation in ferroelectric material.
15. Explain dielectric relaxation.
16. What is meant by complex dielectric constant?
17. Explain absorption of energy in dielectrics and dielectric loss.
18. Discuss electrochemical breakdown in dielectrics.
19- Give the function of transformer oil in transformers.
1 • What is meant by polarisation mechanism in dielectrics? Discuss the different polarisation mechanisms in
dielectrics and explain their temperature dependence.
Explain what is meant by polarisation in dielectrics. Amve at the relation between the dielectric constant
and atomic polarisability.
3- Obtain Clausius-Mosotti equation and explain how it can be Used to determine the dipole moment of a
polar molecule from the dielectric constant measurements.
Explain the terms dielectric loss and dielectric breakdown.
Briefly describe the mechanisms leading to dielectric breakdown.
3- What are the chief characteristics of ferroelectric materials? How does the dielectric constant of a
ferroelectric crystal vary with temperature?
Mention some of the uses of ferroelectric crystals.
What is meant by local field in a solid dielectric?
Deduce an expression for the local field for structures possessing cubic symmetry.
7. How are the insulators classified? Give the details of their classification.
What is meant by dielectric breakdown? Explain how it can be prevented?
State the nature and applications of two materials of high dielectric constant
8. Explain “internal field” in a solid dielectric. Obtain Clausius-Mosotti formula relating mi
dielectric constant with microscopic polarisabilities.
9. Describe the various dielectric polarisation mechanisms. What is complex dielectric
it vary with frequency of the applied Geld?
10. What is meant by dielectric loss? State its importance.
Discuss the mechanisms that lead to electric breakdown.
11. What is orientational polarisation? Derive an expression for the mean dipole moment when a polar material
is subjected to an external electric field.
12. What are the chief characteristics of ferroelectric materials? How do you establish the existence of
ferroelectricity in a material? i
13. On what factors does the breakdown voltage of a dielectric material depend? What is the mechanism of
thermal breakdown? i
. . - i
How does the dielectric constant of a solid vary with frequency of the applied voltage?
14. Explain the terms complex dielectric constant and dielectric loss.
What is the use of transformer oil? What are its characteristics that should be tested so that it could be used
when the transformer is in operation?
15. Explain electronic polarisation in atoms and obtain an expression for electronic polarisability in terms of
the radius of atom.
16. Discuss Weiss theory of ferroelectricity. Give some applications of ferroelectric materials
17. Explain how the dielectric constant of a ferroelectric crystal varies with temperature.
Name two ferroelectric materials. What are the applications of ferroelectric materials?
18. Show that the dielectric constant of a polar molecule varies inversely as the first power of temperature.
19. How does dielectric constant of a solid containing permanent dipole vary with temperature? Illustrate
your answer with an example.
20. Define the term “polarisation density”. Derive an expression for electronic polarisability in a dielectric. ;
21. Explain what is meant by polarisation in dielectric. Arrive at the relation between the dielectric constant
and atomic polarisability of an isotropic solid. *
22. Distinguish between polar and non-polar substances. Describe the behaviour of a polar substance in an
alternating field. Explain the term dipole relaxation and loss angle.
23. On what factors does the breakdown voltage of a dielectric material depend? What is the mechanism of
thermal breakdown?
24. Explain the different types of polarisation mechanisms in dielectrics and sketch their dependence ou the
frequency of the applied electric field.
25. What is meant by local field in a dielectric and how is it calculated for a cubic structure? Deduce Clausius-
Mosotti relation and explain, its use in predicting the dielectric constant of solids.
26. What is dielectric breakdown? Summarise the various factors contributing to breakdown in dielectrics.
State why the simple dipole theory fails to explain ferroelectricity. Describe the ionic displacement theory
and show how it explains the ferroelectric nature of Barium titanate.
,g What does complex polarisation signify? What are the possible losses in a dielectric? How do they vary?
Write an essay on dielectric breakdown mechanisms in insulators.
W What is dielectric breakdown? Summarise the various factors contributing to breakdown in dielectrics.
u Discuss in detail the theory of dielectrics in alternating field. Obtain an expression for the dielectric
constant in terms of the frequency and relaxation time.
12. Define “polarisation density”. Obtain an expression for Lorentz field in a dielectric material and hence
derive the Clausius-Mosotti equation.
3^, Give a schematic sketch of the variation of the total polarisability of an atom as a function of the frequency,
explaining the physical origin of the various contributions and the relevant frequency ranges.
34, At what frequency the real and imaginary parts of the polarisability become dominant?
Illustrate their distribution around that frequency. Show that the imaginary part of the dielectric constant
is a measure of the dielectric loss.
35. Consider a gas containing N similar atoms/m3 of polarisability a. Show that the dielectric constant of the
gas is given by
_* _, . Ne2!m^ j
CP —■ 1 ~r n n J
(cDq - (a ) +ilbissjm I
-.................................................................................................................
1. A parallel plate condenser has a capacitance of 2 pf. The dielectric has permittivity £r = 100. (a) For an
applied voltage of 1000 volt, find the energy stored in the condenser as well as the energy stored in
polarising the dielectric (b) A field strength E is applied to a dielectric. Show that the stored energy in the
polarised atom is equal to (1/2) ocE2, where a is the polarisability.
2. Two parallel plates have equal and opposite charges and are separated by a dielectric 5 mm thick, of
dielectric constant 3. If the electric intensity in the dielectric is 10° V/m, calculate (a) the free charge per
unit area on the conducting plate, (b) the bound charge per unit area on the surfaces of the dielectric (c) the ''
polarisation P in the dielectric (d) the displacement in the dielectric and (e) the energy density in the JZ
dielectric. Ki
-.' nJ
3. If a dielectric is introduced between the plates of a parallel plate capacitor, show that the induced charge fc- ■
varies with the dielectric as , . ’ ' ” 1
x i
r o'Y* J °
E =1------ where a is surface density.
v •••■•!
4. If all the molecular dipoles in a 0.1 cm radius water drop are pointed in the same direction, calculate the
intensity of polarisation. Dipole moment of the water molecule is 6 x IO7-30 C m.
5. Argon gas contains 2.7 x 1025 atoms /m3 at 0°C and at one atmospheric pressure. Calculate the dielectric
constant of argon gas at this temperature, if the diameter of the argon atom is 0.384 nm.
6. Assuming that the polarisability of Kr atom is 2.18 x 10“*° F m. Calculate the dielectric constant of Kr at
0°C and at one atmosphere.
7. Find the total polarisability of CO2, if its susceptibility is 0.985 x 10 3. Density of carbon dioxide i8
1.977 kg/m3.
8. The relative permittivity of argon al 0°C and one atmosphere pressure is 1.000435. Calculate the
polarisability of the atom.
9. Prove that the gravitational force is negligible in comparison to electrostatic force in the hydrogen atom in
which the electron and the proton are about 0.53 x 10"10 m apart. G = 6.7 x 10~11 Nm2/kg2.
10. The dielectric constant of helium, measured at 0°C and at one atmosphere is er = 1.000684; under these
conditions the gas contains 2.7 x 1025 atoms/m3. Calculate the radius of the electron cloud (atomic radius).
Also calculate the displacement x when a helium atom is subjected to a field of 106 volt/m.
11. Two pith balls, each weighing 100 mg and suspended from the same point by silk threads, 30 cm long, are
equally charged and repel each other to a distance of 10 cm. What is the charge on each ball?
12. Calculate the induced dipole moment per unit volume (density of polarisation) of He gas if placed in a
field 6 x 105 V/m. The atomic polarisability of helium is 0.18 x Iff40 F m2 and the concentration of helium
atoms is 2.6 x 1025 /m3. Also calculate the separation of positive and negative charges in each atom.
13. If all the atoms of diamond are polarised alike and produce a polarisation density of 1.32 x 10~5 Cm2,
calculate the shift of the centre of negative cloud of 6 electrons on each atom from the nucleus. Given:
Density of carbon = 3500 kg/m3, atomic weight of carbon = 12 and Avogadro’s number = 6.02 x 1026.
14. An atom of oxygen on being polarised produces a dipole moment of 0.5 x HT22 C m. If the distance of the
centre of negative charge cloud from the nucleus be 4 x 10"17 m, calculate the polarisability of the oxygen
atom.
15. Calculate the average radius of the atom of an air molecule if the polarisability of atoms in the air molecules
is 9.7 x 10"41 Fm2. Also compare this result with the relative displacement of the nitrogen nucleus and
electron cloud at a field of strength 3 x 106 V/m.
16. The polarisability of NH3 molecule in gaseous state, from the measurement of dielectric constant is found
to be 2.5 x 10-39 Fm2 and 2 x 10~39 F m2 at temperatures 300 K and 400 K respectively. Calculate the
contribution to the polarisability because of deformation of molecules and the contribution because of
permanent dipole moment at each temperature.
17. There are IO27 HC1 molecules per cubic metre in vapour. Determine the orientational polarisation at room
temperature if the vapour is subjected to an electric field of 106 V/m. The permanent dipole moment of
HC1 molecules being 1.04 Debye unit. Show that at this temperature and for such a high field the value of
a (a = îÊ/kgT) is very much less than unity.
18. The dielectric constant of helium at 0°C and 1 atmosphere pressure is 1.000074. Calculate the dipole
moment induced in each helium atom when the gas is in an electric field of intensity 3 x 104 V/m.
19. The polarisability of NH3 molecule is found experimentally by the measurement of dielectric constant as
2.42 x 10"39 F m2 and 1.74 x 1(T39 F m2 at 309 K and 448 K respectively. Calculate for each temperature
the polarisability due to permanent dipole moment and due to deformation of molecules.
20. A capacitor uses aluminium oxide as the dielectric with = 8. An effective surface area'of 360 cm2 gives
a capacitance of 6pF. Calculate the field strength and the total dipole moment-induced in the oxide layer if
a potential difference of 15 volt exists across the capacitor.
21. The polarisability of neon gas is 0.35 x Iff40 Fm2. If the gas contains 2.7 x 1025 atoms/m3 at 0°C and one
atmosphere pressure, calculate its relative dielectric constant. Also solve for of krypton having
a, = 3.54x Iff40Fm2.
There are 1.6 x IO2' NaCl molecules /m3 in a vapour. Determine the orientational polarisation at room
temperature if the vapour is subjected to an electric field 50W V/cm. Assume that the NaCl molecule
consists of Na+ and HC1" ions separated by 0.25 nm.
H Oue gram molecule of a certain polar substance is dissolved into 1000 cm’ of a non-polar liquid. The
liquid itself has a dielectric constant of 3.000 at 27°C, whereas the solution has a dielectric constant of
3.200 at that temperature. Calculate the dipole moment of the polar molecules.
24 An elemental dielectric material has Er = 12 and it contains 5 x 1028 atoms/m3. Calculate its electronic
polarisability assuming Lorentz field.
25. A solid dielectric material has 5 x 1028 identical atoms/m3. If the polarisability is 3.6 x Ifr40 Fm2, calculate
the Lorentz field normalised with respect to the external electric field, i.e., find EJE.
25. Three identical atoms in a string are subjected to a homogeneous electric field E volt/m along the line
joining their centres. If the polarisability is 2.5 x IO-40 Fm2 and the centre to centre spacing is 0.3 nm, find
(£./£j at the position of the centre of the atom.
27. A charge of Q coulomb is elastically bound in an equilibrium position and separated by a distance of
d metre with an equal and opposite charge. If the system has a force constant of (f) newton/m, find an
expression for its polarisability.
28. The centres of two identical atoms of polarisability a = 2 x IO-40 farad m2 are separated by a distance
5 x 10-,° m. A homogeneous electric field E is applied in a direction to the line joining the centres of the
two atoms. Calculate the ratio between the internal field, and E.
29. The bakelite is found to have the real part of its complex relative dielectric constant as 4.36 with a loss
tangent of 2.8 x 10-2 at a frequency of 1 MHz. Calculate the complex polarisability of the material assuming
Lorentz field. Assume N = 4 x 1028 /m3.
30. A parallel plate capacitor has an area of 8 cm2 with a separation of 0.08 mm. The space is filled with
polystyrene. The real part of the relative dielectric constant is 2.56 and the loss tangent is 0.7 x 10"* al a
frequency of 1 MHz. Calculate the capacitance and the equivalent parallel loss resistance.
3L A parallel plate capacitor has an area, 20 cm2 and separation between the plates, 0.2 mm. The space
between the plates is filled with a dielectric having the real part of the dielectric constant, £r' = 2.5 when
subjected to a 2 volt alternating voltage at 1 MHz. The loss tangent at this frequency is 4 x IO"4. Find the
elements of an equivalent (/) parallel R-C circuit (z7) series R-C circuit
32. The following data refers to a dielectric material £r = 4.94, n2 = 2.69, where n is the index, of refraction.
Calculate the ratio between electronic and ionic polarisabilities of this material.
33. Design a parallel plate capacitor using mica, which will give a capacitance of 0.0252 pF. The main mica
sheets are available only in 1 x 10-4 inch thickness. Dielectric constant of mica = 7 and the dielectric
strength is4x K^V/in.
ki *wws
sfci Mm’SJ’Or®'
The presence of lattice defects or the inclusion of impurities in a solid can give rise to optical absorption.
The starting point of such absorption is either the excitation of vibrational modes or the promotion of
electrons from a given set of energy states to others of higher energy. Analogous effects occur in perfect
crystals. Simply because the density of impurities and defects in a crystal is usually small compared
with the density of lattice atoms, the most prominent features of the absorption of a solid are characteristic
of the host lattice, and impurity absorption bands are usually observable only if they occur in those
spectral regions in which the host material is transparent. The emission of light from solids, on the other
hand, is usually dominated by impurities even when their density is as low as in 106. Thus a solid can
absorb photons of one energy due to electronic transitions characteristic of the host lattice and in
consequence emit photons of different (usually lower) energy to a transition between impurity levels.
The call “optical properties” usually implies that the size or dimensions of the sample under
consideration and examination are large compared with the wavelength. The mean free path of photons
can then be large and their wave vector well defined. Hence in an interaction with a non-localised
excitation of the crystal the wave vector conservation rule applies and is used extensively. Arbitrarily
we have chosen a frequency of 3 x 1011 Hz, corresponding to a wavelength of 1 mm (photon energy
1.23 x 10“3 eV) as the lower limit of the optical frequency range. At the high frequency end of the
spectrum, technical difficulties become severe in the ultraviolet region above about 3 x 1015 Hz (100 nm ■
wavelength, photon energy 12.3 eV) and this provides an effective upper limit. This wavelength is,
however still large compared with atomic dimensions which allows optical properties of a solid to be .
explained in terms of macroscopic “optical constants”, the refractive index and extinction coefficient
which are, of course, not really constant at all as they vary with frequency.
The optical properties of solids are of considerable importance. One of the many striking
developments of the last three decades has been the extension of optical techniques and relatively high
resolution spectroscopy throughout the spectral range from visible light to microwaves. Solid State
Physics has both contributed to, and profited from the development of this subject. The important
contribution has been in the field of photoconductive detectors: Semiconducting elements that decrease
in resistance on illumination, Photoconductive can arise from the promotion, on absorption of a photon,
of an electron from a bound state of an impurity to the conduction band where it is free to move through
a lattice and carry a current. Photoconductivity can also result from the promotion of electrons from a
filled energy band to the conduction band, two mobile charges (an electron and a hole) being produced
per photon in this case. The spectral response of a photoconductive detector in an optical property of the
solid, being determined by the photon energy necessary to promote an electron. However, the magnitu ,
694
________________________________________________„•. „ •.\
f resultant photo current and the rate at which it can respond to changes in illumination level
depend respectively on the ease of electron (or hole) movement through band states and the probability
of electron recapture by an impurity, or hole. By suitable choice of doping impurity, fast and sensitive
detectors can now be constructed for use at any desired wavelength throughout the infrared spectral
region. Light detectors and light emitters are the most important optical solid state devices but they also
provide filters, polarisers, modulators, non-reciprocal devices, frequency changers, etc.
The optical response of the solid material is characterised by the complex refractive index
(n~n{ - w^'c^ may be expressed in terms of two optical constants namely, the dielectric constant
-2 = e = e, + ie2 and the optical absorption coefficient, a =---- — (or the optical conductivity,
tij
<5 = an,), and by Maxwell’s equation in the presence of matter
dZ)
curIH=——+J (12.1)
At
curlE = -p0— (12.2)
where E and H are the electric and magnetic field vectors, respectively, and J is the current density. In
the Maxwell’s equations, optical constants may be introduced by relating E to the displacements D via
D = P + Ee0 = EE0£r (12.2a)
P = Ee0(er-l)
^-«=-Er=z- (12-3)
and the current density due to mobile charges is related E via
J = oE (12.4)
The optical absorption coefficient is perhaps the most obtainable one on simple experimental
determination. When a beam of light of intensity Io goes normally through a slab of a medium of
thickness x, the beam of light attenuates in accordance with the exponential law, I = Zo exp (- ax).
Consequently, a can be obtained simply by measuring -y- of the intensities impinging and emerging
from the sample.
simplest possible theojy of the response of a solid to an oscillating external electromagnetic field
Was provided by the Drude model. The starting assumption is that the optical conductivity and the c\i
êlectric constant can be determined by considering the motion of free electrons. In the presence of
collisions, the equation of a free electron in an electric field is
(12.5)
where m is the mass of electron, x is its displacement and t is the relaxation time.
If both x and E have the time dependence of the form exp (- i(ot), then
dx , d2x .
- - (i®x) = - i®x and —x- = - ®zx
dt dr
i®xm
,
- md)~x --= -------
-eE
T
( 2 imrn'X
-x m® +------ = -eE
eE eE
2 iwm (12.6)
ni® +------ m® ®+—
T k T.
To obtain the optical conductivity we may suppose that x = vr, where v is the mean velocity of
the electron and T is the relaxation time for electron collision. The current density is
nxe
j = nev =------
ne eE
j (12.7)
T |_ mco{<x> + (i/t) }
ne2
or E ~°“ m®t{® + (i/T)} (12.8)
In the limit ®t» 1, i.e., when the collision frequency — is small compared with the frequency
® of light wave (in the absence of collisions), equation (12.8) reduces to
ne2 e£
o = mco2T Wlt^ X = mo2 êêr e<Iuatlon (12.6)] (12.9)
This is known as the Drude formula for the optical conductivity. The real part of the dielectric
constant may similarly be calculated as follows:
The electric polarisation is
ne2E P
P = - nex = - ■y = y £ en as v = ——
ma 2 j x, -o x £Eo
from which it follows that
ne 2 1
E,= l+X = 1- as(e,- l) = x
mw2e0
(12.10)
1 ©
r ne 2
where, = _me0J is the electron plasma frequency.
Thus the complex dielectric response function is, e = £, + i e2 with = ------ ; i.e., a = £, to £(,
(0£0
1 ne2
• u <=
w,th 2 (12.11)
CD£0 m(O2t
1 p -«>ho
-------
®£0 tO2T (03t
, ®P i(0P (12.12)
E = E, + ie, = 1-—%- +
12 (02 art
When an » 1, i.e., when the collision frequency — is small compared with the frequency of the
T
light wave, 2 2 will be very small compared with 1.
_ _ . (OpT 1
US’ £ (02 _l + (l/COT)
Wp
e = £1 + i£2=1-—---- —— (12.12a)
1 2 0)[a) + (i/T)]
The real part of the dielectric constant, the optical conductivity and -imaginary part (negative
Fig. 12.1 The Drude model optical constant

The physical significance of the two optical constants, e) and e2 or the conductivity 0 r
explained as follows: Electromagnetic waves incident on a medium can propagate through the
only if the real part of the dielectric constant is positive, but they are totally reflected from the med?Um
if the real part of the dielectric constant is negative. This behaviour may be characterised by the refl e<û01
(/?) given in terms of n = e1/2 by Ce
2
1-n
R= (12.13)
1+n
which is shown as a function of — in Fig. 12.2.
The plasma frequency is the dividing line between propagation through the medium and total
reflection at the surface of the medium. At the plasma frequency, the medium is transparent to light of
wavelength X =----- and [- imaginary part of (E-1)] exhibits a resonance peak, m = —— = kc

P Up L Xp
.J
In simple (nearly free-electron) metals, such as the alkali metals, with about 1028 electrons/m3,
co is of the order of 1016 rad/sec and X of the order of 0.1 itm (0.1 x IO-6 m). For this reason the metal ’
p p J •
reflects visible light but is transparent to ultraviolet light. These qualitative observations can be explored
and then explained in detail by using the optical dispersion relation, which can be derived from solutions
of Maxwell’s equations in the form involving only the electric field:
V2E = p0e|^ + (12J4) |
The last term of this equation describes the absorption of electromagnetic radiation and is often ;
called the dissipation term. J
On substituting a wave like solution of the form
E = Eo exp [i(k.r - co/)] (12.15)
led to the dispersion relation
- k2 = - goe co2 - |i0 iaxj
1
Letting Po eo _ ’ one gets
• I*/2
„ eco icon (0 E IC
kr =------ 5- +------ 7; or k = (12.16)
£0 cl £0 cl c [e0 e0 co.
co 2tvu 2n . r _ .
The standard relation k = — =------ = — is thus modified by the complex index of refraction,
c c K
- kc • •>
_E_ icr ।
— = n=n + in, Eq CO J (12.17)
-co c 1 ,eo
e io
(n + in,)2 = n2 + 2 n in. - n? = ----- 1--------- (12.18)
e0 e0 co
Equating the real and imaginary parts of the above equation, one gets
2 2 j G. .
-n. = — and nn, = --------- (12.19)
Eq ' 2 Eq CO
A is a complex propagation vector. In free space, k = —, as the ordinary light; but, in a dispersive
c
medium, there is a dispersion.
In such cases the dielectric constant is
E iC
E (CO) = — 4.-------
Eq Eq CO
‘kc?
with the assumption = £(C0)
.(0.
Thus the dispersion takes the form
co2 E (co) = kPc2

Restricting our attention to real part, one gets
co2 = C0p + (Refer equation 12.10)
The polarisation defined as the dipole moment per unit volume is (Refer equation 12.9)
P = -nex = --^T£ (12.20)

mco
The dielectric function at frequency co is
D(w) P(o»
e (co) = —= 1 +
£0 E(co) Eo E(<0)
Comparing equations (12.20) and (12.21), one gets
ne2
£ (co) = 1----------- y
£0 mti)
The plasma frequency is given by
7 ne
i &P e0»"
A plasma is a medium with equal concentration of positive and negative charges, of which at
least one charge type is mobile. In a solid the negative charges of the conduction electrons are balanced
by an equal concentration of positive charge of the ion cores. We now write the dielectric function
[equation (12.22)] as
CO2
£ (co) = 1 - -f- (12.23)
co
Ionic conductivity caused by the motion of ions in an ionic insulating crystal is called ionic conductivity.
In a perfect crystal the ions are bound to each other with no freedom of motion. But under certain
circumstances the thermal energy at room temperature is sufficient to release a few ions. These ions
move through the crystal in a random fashion by hopping over to the various defect centres in the
structure. The ion cannot move if the structure is free from defects and so defects are essential for ionic
conduction in crystalline solids. Hence ionic conductivity is an important factor in the investigation of
defects. Ionic motion is possible in diffusion and also by an applied electric field. If p is ionic mobility,
N is the number of ions/m3 and q is the ionic charge, then
O = Nqp. (12.24)
Einstein's diffusion equation tells that
<7
Im? A Q J
or a=TF (1225)
But D is related to the excitation energy E by the relation

D = Do exp [~E/kBT] (12-26)
where Dq is a constant and E is the excitation energy which is defined as the energy required to produce
a lattice vacancy and causing the subsequent diffusion of the ion into that vacancy. Hence the conductivity
expression is
Fig. 12.3 Dispersion relation for transverse electromagnetic waves in a frce-electron gas
&— , T [Po exp (—E/kgT)} (12.27)

x.Kb* J
From field theory
c = Vyllir e
where v is the phase velocity of the electromagnetic wave in the given dielectric medium, c is the
velocity of light, ef is the relative dielectric constant and |ir is the relative permeability. The refractive
index n is given by the ratio of the velocity of light in vacuum to the velocity of light in the given
medium as
n=- = Jv^ (12.28)
v
For Pr = 1, =£ .Ln the case of alkali halides the polarisation is made up of electronic polarisation
and as well as ionic polarisation. A d.c. measurement of Er will give Nag + Na. and we have by the
Clausius-Mosotty relation.
e.-1 (Nae+Na j)
(12.29)
3 Eq
Measurement of retractive index will show that e. depends only on Na. since the ionic contribution
is negligible Hence, we get the relation
(12.30)
Th
a. Kn 6 equation is called the Lorentz-Lorenz equation, substituting the value of n, we can calculate
Wln8 Er, a. can be calculated from the relation (12.29).
iWriifilfclaiM
It is found that the metals are generally opaque to electromagnetic radiations from low frequenc'
the middle of the ultraviolet, where from they become transparent. Insulators are found to be trans^8
over most of this region. The metals have not only high opacity but also high reflectivity. Accordi
the quantum free electron theory, metals have a series of quasi continuous energy level and so h
electrons in the Fermi level can accept any value of the photon energy and get accelerated. Two thin 6
can happen in this process. If the electrons have only a small chance for collision with the lattice ions
during the period of the impinging wave, the energy absorbed is re-radiated without any dissipation and
the metal is transparent. This is probably so at high frequencies above the ultraviolet. If the period of the
impinging wave is large, the electrons will suffer large number of collisions during a cycle and the
energy gained may be dissipated. Dissipation will be cent per cent only if the excitation and the response
are exactly in phase. In general the excitation and the response will be out of phase. This condition leads
to negative dielectric constant over a certain region of the spectrum. Negative dielectric constant gives
rise to complex refractive index, which means, that the incident wave is reflected. For most of the
metals the complex refractive index lies in the visible region and so it is, metals in general are good
reflectors. Opacity arises because of the out of phase component and the polarisation.
The ionic insulators are transparent for almost all
frequencies up to the point called the fundamental
absorption frequency. This shows that the electrons in Fundamental
absorption'“"J
the topmost filled band do not have allowed energy values
immediately adjacent to them as in the case of metals. At B
Restrahl Impurity Exciton
the fundamental absorption frequency, photons have & absorption absorption absorption
sufficient energy to excite the electrons from the valence
band to the conduction band across the forbidden gap.
Since the fundamental absorption frequency, is in the
ultraviolet region, where the photons have energy greater
than 4 eV; it is clear that insulators have band gap greater
than 4 eV. The material is opaque to all frequencies above Frequency ------ -
this. Below this frequency there are absorption peaks as Fig. 12.4 Absorption peaks
shown in Fig. 12.4.
These are not due to excitation across the band gap. Absorption in the infrared region or the restrahl
frequencies arise because of the ionic polarisation mechanism having the same relaxation frequency as the
applied field. Absorption in the visible region arise because of the impurity energy levels, colour' centres or
exciton levels which invariably lie in the forbidden gap. Their excitation energy falls in the visible region
and so it is, the material exhibits absorption in the visible region which gives rise to characteristic colours
in the case of impurity doped ionic crystals. In the case of semiconductors the band gap is small, of the
order of 0.5 eV to 1 eV and so the fundamental absorption frequency associated with intrinsic excitation of
electrons from the valence band to the conduction band across the band gap lies in the infrared region
(wavelength about 2 micron). Beyond this wavelength, the crystal is relatively transparent. The infrared
absorption spectra of semiconductors are more complex because of the very many mechanisms leading to
the absorption. The simplest is the absorption associated with the excitation of the electron from the
valence band to the conduction band across the band gap. Free carrier absorption, absorption due to
excitation of lattice vibrations, absorption due to localised states of impurities in the band gap, absorption
due to exciton states are some of die complex mechanisms in operation in semiconductors.
____________________________ OrncM
_____.___—. ■ ___ _ -.^7 >-T'-'^ jt^reJK
Electron photon interaction and absorption due to this are very important in semiconductors.
Such an interaction is common at long wavelengths with photons of energy less than E . The physical
meaning of the electron-photon interaction is that the free electrons act as a set of linear oscillators with
a resonance frequency. When the frequency of the incident radiation coincides with this frequency,
absorption results due to resonance. Ionic polarisation mechanism becomes operative if there is an ionic
contribution to the bonding, so an absorption like restrahal occurs in the infrared region. The study of
the absorption spectra enables us to know about the energy band structure of semiconductors.
■CTUHife .. .....-1 ... " 111 '____ zr

Insulators that are transparent because of the large band gap appear coloured sometimes. This colour
results from selective absorption of some portion of the visible spectrum by imperfections in the crystal.
Such imperfections in a crystal which selectively absorb certain colours in the visible spectrum are
called colour centres. These colour centres give rise to energy states in the forbidden gap. The commonly
studied colour centres are the F centres produced by excess metal ions in alkali halides. Suppose an
alkali halide like KC1 is heated in excess potassium vapour,-some K+ ions are deposited on the crystal
surface. The Cl" ions from the interior migrate to the surface to combine with the K+ ions. These create
Cl" ion vacancies in the interior. In order to preserve the charge neutrality of the crystal, free electrons
get trapped in these anion (Cl) vacancies. The electron bound to a -ve ion vacancy is called F centre.
Figure 12.5 explains the formation of F centres.
oooooo
0(00000
oooooo
OOO(0OO
oooooo
oooooo.
Rg. 12.5 A is an anion vacancy. B is an anion vacancy associated with
a free electron which is identified as F centre
CHAPTER 12
The other method of producing F centres is exposing Ute ionic crystal Io high energy radiation
hglnSXnon in th^F centres am excited to the conduction band with the consequent ab^rption of
the red colour So the crystal appears violet. Similarly L.F contammg excess Lt looks ptnk. NaO w.th
excess Na looks brownish yellow. The F band optical absorption ts the ehamctensbc ol the crystal and
not of the vapour. The 'F band in K.C1 is almost the same whether the crystal is heated in Na or K
vapour. The role of the alkali vapour is to produce an 'F centre in the host crystal. Usually the excess
alkali atom concentration of the order of 10” to l(P/m3. Coloured crystals are less dense than uncoloured
crystals. That agrees with the experimental results. The colour centres can be removed by irradiating the
crystal with light of wavelength in the absorption band. This is known as bleaching. Bleaching is attributed
to the ionisation of 'F centres, and is accompanied by photoconductivity. Other colour centres are also
possible. For example, a hole bound to a cation vacancy gives rise to ‘ V* centres which absorb ultraviolet
light.
Exciton is a bound electron-hole pair. An electron in the vicinity of hole need not annihilate itself by
recombination. It can occupy any one of the energy levels available to it and bind itself with the hole
and behave like a neutral hydrogen atom. Similar to the hydrogen atom has different energy levels, the
exciton also has different energy levels. The energy of formation of an exciton is less than the band gap
and so its energy levels lie in the band gap.
The conditions favourable for the formation of excitons are, that the medium must have a large
dielectric constant, so that the energy for formation may be small. This means that the excitons can be
produced by incident photons having energies less than the band gap. The excitons are neutral and so
their movement do not give rise to electrical conductivity. Low energy photons absorbed by the excitons
do not give rise to photoconductivity since the electron-hole pair move as a single entity to higher
energy states. Of course if the incident photons have energies greater than the ionisation energy of the
excitons, free carriers will be produced giving rise to photoconductivity. The exciton absorption spectra
appear as small peaks near the expected intrinsic absorption (Fig. 12.4).
MMM
Materials which can absorb photons through their energy levels can also emit them back, and if the
radiation lies in the visible region, the phenomenon is called luminescence. If the time delay between
absorption and re-emission is less than 1(L8 s the material is said to be fluorescent and if longer the
material is phosphorescent. In luminescence the exciting photons have generally greater energy than
the emitted photons. For re-emission to take place effectively, producing luminescence phenomenon,
there must be suitable energy levels in the band gap and such levels are produced by impurities are
called activators and co-activators. Activators have energy levels near the valence band, whereas co
activators have energy levels near the conduction band. For example, in ZnS, Cu is used as the activator
and CI as the coactivator. The activator provides intermediate energy levels for the emitting electrons to
fall. The co-activator acts as a trap for the electrons thereby governing the delay time between the
absorption and the emission process. So luminescent phosphors for different applications can be produced
by a careful mixture of the activator and the coactivator impurities. Luminescence excited by photons is
called photoluminescence, when excited by high frequency electric fields, it is called electroluminescence,
when excited by bombardment of electrons; it is called cathodoluminescence, when excited by certain
chemical reactions it is called chemiluminescence.
,4
|A•
maser aNDLASER .....
radiowaves, microwaves and heat, is a form of electromagnetic energy. We are concerned
Li?ht. ’ .jaljon in the optical part of the spectrum which extends from the ultraviolet region to the far
b^1** including the visible region. The ultraviolet end of the spectrum is limited by the availability of
infrared an(j limited transmission of materials including air. The infrared region extends
near infrared at the end of the visible part of the spectrum to the far infrared at millimetre
^lengths corresponding to microwave frequencies and has been extensively studied. The visible
**'e ”-»niv a small part of the total optical spectrum.
ôn is oni> *
Microwave Amplification by the Stimulated Emission of Radiation (MASER) and Light
; Ufication by Stimulated Emission ofRadiation (LASER) are spectacular optical phenomena exhibited
certain class of solids, especially the impurity doped semiconductors. In view of their immense
tentialities in practical applications like, satellite communications, radio astronomy holography, etc.
the study of maser and laser has assumed great importance.
When there are energy levels in a solid separated by frequencies corresponding to microwave,
infrared and visible radiations, the solid exhibits emission and absorption spectra characterised by discrete
lines in different regions. In the case of metals, the energy levels are quasi-continuous and so their
spectra are not characterised by discrete lines. Band to band transitions do not give rise to discrete lines
but only a band of frequencies in the different regions. In the case of semiconductdrs and insulators, the
situation is different. We know that the impurity energy levels are always situated in the forbidden gap
of semiconductors and insulators. When the impurities are small, so that their mutual interaction can be
neglected, we will get a set of discrete levels in the forbidden gap. If the impurity concentrations are
large, they may interact with others giving rise to bands, instead of discrete energy levels. Transitions
between the energy levels in the forbidden gap can give rise to emission and absorption lines in the case
of semiconductors and insulators. It is found that the transitions between the energy levels of some
impurity atoms give rise to the spectacular phenomena of maser and laser. Discrete energy levels are
essential for the laserand maser action, and such levels are available in gases (the gaseous atoms do not
interact with each other) and in certain impurity doped semiconductors and insulators.
In every non-interacting atomic system, there
discrete energy levels. If the atom is in the upper
and the electron makes a transition to the lower
energy can be emitted in the form of
ôn of frequency
^2 ~ El
U= (J2.31)
I R
the energ'dradiation of energy hv exactly equal to
£2taJlon t}^lfterenCe êtween îe tw0 levels E{ and
level may system’ atom >n the lower energy
energy levj S°rt> t*Tat ener8y and g° to the higher
T*1'8 Process^ ÛS ann‘âte incident photon.
tad*aiion inJ *S CaHe(l absorption. So in general
racts *n the following ways:
IX. MASER AND LASER
Light, like radiowaves, microwaves and heat, is a form of electromagnetic energy. We are concerned
herewith radiation in the optical part of the spectrum which extends from the ultraviolet region to the far
infrared including the visible region. The ultraviolet end of the spectrum is limited by the availability of
suitable sources and the limited transmission of materials including air. The infrared region extends
from the near infrared at the end of the visible part of the spectrum to the far infrared at millimetre
wavelengths corresponding to microwave frequencies and has been extensively studied. The visible
region is only a small part of the total optical spectrum.
Microwave Amplification by the Stimulated Emission of Radiation (MASER) and Light
Amplification by Stimulated Emission ofRadiation (LASER) are spectacular optical phenomena exhibited
by certain class of solids, especially the impurity doped semiconductors. In view of their immense
potentialities in practical applications like, satellite communications, radio astronomy holography, etc.
the study of maser and laser has assumed great importance.
When there are energy levels in a solid separated by frequencies corresponding to microwave,
infrared and visible radiations, the solid exhibits emission and absorption spectra characterised by discrete
lines in different regions. In the case of metals, the energy levels are quasi-continuous and so their
spectra are not characterised by discrete lines. Band to band transitions do not give rise to discrete lines
but only a band of frequencies in the different regions. In the case of semiconductors and insulators, the
situation is different. We know that the impurity energy levels are always situated in the forbidden gap
of semiconductors and insulators. When the impurities are small, so that their mutual interaction can be
neglected, we will get a set of discrete levels in the forbidden gap. If the impurity concentrations are
large, they may interact with others giving rise to bands, instead of discrete energy levels. Transitions
between the energy levels in the forbidden gap can give rise to emission and absorption lines in the case
of semiconductors and insulators. It is found that the transitions between the energy levels of some
impurity atoms give rise to the spectacular phenomena of maser and laser. Discrete energy levels are
essential for the laser and maser action, and such levels are available in gases (the gaseous atoms do not
interact with each other) and in certain impurity doped semiconductors and insulators.
In every non-interacting atomic system, there
are discrete energy levels. If the atom is in the upper
state and the electron makes a transition to the lower
state, then energy can be emitted in the form of
radiation of frequency
u= (12.31)
h
CHAPTER 12
Let a radiation of energy hx> exactly equal to

the energy difference between the two levels E{ and
E2 fall on the said system, an atom in the lower energy
level may absorb that energy and go to the higher
energy level, and thus annihilate and incident photon.
This process is called absorption. So in general
radiation interacts in the following ways:
1. When an aioin is in the lower energy state, the energy of the striking radiation may be absorbed
thereby raising the atom to the higher energy slate. If nothing further happens to the atom it
may fall again spontaneously to the lower energy state re emitting the photon which it ha*
absorbed earlier. This process is called spontaneous emission. This spontaneous emission is
a statistical process and hence we cannot say when exactly a particular transition will take
place. Wc can only say about the probability of spontaneous transition and hence it resembles
the phenomenon of spontaneous radioactivity.
2. If the photon strikes an excited atom, that is, an atom in the higher energy state, it may
stimulate the atom to emit its stored energy by falling to the lower energy state, provided the
energy difference between the two states is exactly equal to the energy to the impinging
photon. The process is called stimulated emission and it is this process that is important in the
Maser action.
Now there are two very important points about stimulated emission upon which the properties of
laser light depend. First the photon produced by stimulated emission is of almost equal energy to that
which caused stimulated emission and hence the light waves associated with them must be of nearly the
same frequency. The other one is the light waves associated with these photons are in phase and hence
they are said to be coherent. In the case of spontaneous emission the random creation of photons results
in the waves of random phase and the light is said to be incoherent.
Population Inversion
Consider an atomic system placed in a radiation field of energy density E (d) under equilibrium conditions.
Let E, and E2 be the energy levels occupied by and N2 atoms respectively. The photons corresponding
to the transition from the level E2 and E( will have energy, E2 - E, = hx>.
There are three possible processes taking place in the atomic system. Spontaneous transition
from the level E2 to E} may take place. Let A2l be the spontaneous emission transition probability per
unit time. Secondly absorption of energy hv can take place resulting in the atom being raised from level
E] and E2. It is reasonable to assume that such absorption transitions per unit time is proportional to the
energy density E (u). So the induced absorption transition probability per unit time will become
B12 E(v) where B)2 is the absorption probability per unit time per unit energy density. Thirdly the
radiation field may interact with an atom in the higher energy state E2 and induce it to fall to the energy
slate Er It is again reasonable to assume that the probability of induced emission is proportional to the
energy density of radiation field. So the probability of induced emission per unit time can be written as
B2] E (V) where the constant B2} represents the induced emission probability per unit time per unit
energy intensity. If there are N2 atoms in the level E2 the number of atoms that fall from the level E2to
E| per unit time is equal to [A2J + B2} E (1))] N2 and the number of atoms that rise up from the level
dN
to E2 per unit time is BI2 E (v) Nx. So the net rate of change of atoms —1 in the level E2 per unit time
dt
is given by
= Bl2 E (V) N, - [A2I + 521 Eft))] N2 (12.32)
Under equilibrium condition the net rate of changes of atoms in any level must be zero. So
^=0
dt
or B|2£fU)/V, s|A2| +fl2i £(u)]/v2 (12.33)
■^g. , B,2£(v)
[A21+B2,£(d)1
Boltzmann has shown that the atomic population at different energy levels at a given temperature
7" is given by the relation
N2 = Ni ^p [- (£, - E^/kgT]
ie' N2 = Ni exp (- h\)lkBT) (12.34)
Under normal conditions the population in the lower energy level is greater than the population
in the higher energy level. Substituting the value of from equation (12.34) in equation (12.33), one
gets
Bl2 E(v) exp (hV)lkBT) = 421 + B21 £ (v)
_______ (^21/£12)_______
£(u)= [exp(Av/ABT)-(£21/£12)] (12.35)
The energy density of radiation at a given temperature as per Planck’s radiation formula is
' "rr\ [SaWI f " ■ 1 :
n ~L,< J
One gets on comparison of the two relations (12.36) and (12.35),
_ 8jiAv3
(12.37)
and ~~ = 1 (12.38)
#12
These relations were first obtained by Einstein in 1971. The constants A^, fl21 and fl12 are called
Einstein coefficients. Substituting the value of fl21 / £12 fr°m equation (12.38) in (12.35), one gets the
relation between the spontaneous emission probability and the induced emission probability, when the
matter is in equilibrium with radiation
Spontaneous emission probability A2) Av
eXP [ ~kfT) ~ 1 remembering #12 = s2i (12.39)
Induced emission probability £21 E(v)
Spontaneous emission is much probable than induced emission for Av > k T. This holds good in
the case of electron transitions in atoms and molecules and in the case of radioactive transitions in
nuclei. If hv < k T induced emission or stimulated emission may become important and this is possible
CHAPTER 12
in the case of atomic transition in the microwave as well as in the visible region.
The conditions under w . . . rslfiiat;ve emission
radiation andcan be induced
matter or stimulated
are in thermal continuously
equilibrium there is
can thus be discussed. We ave see number of absorption and emission transitions per unit time is
no net absorption or emission si probabilities for absorption is considerably less than the
he same. Though the ,nd“^ emission, absorption equals the emission because of the large
spontaneous transition proba y energy Such ^15^ conditions
number of atoms in the lower energy level
are not suitable for maser action.
In the case when matter is being continuously bombarded by the photons and non-equilibni
ium
conditions prevail, we can write the ratio of the emission rate to the absorption rate as
Emission rate B,t E(v))A^ Bj + A,,
Absorption rate Bu E(v)N\ Nx Bl2 B2i E(v) (12.40)
= [| + -A<_
L (12.41)
( ho
If the energy difference between the two levels is small such that is small, the quantity
_ A2L.„'|
B:i E(v) J becomes very small when compared to unity as seen from the equations (12.38) and (1239)
and so equation (12.41) becomes
Emission rate
Absorption rate <1X42)
At any fixed temperature the atomic population N2 in the higher energy level E2 is always less
than the atomic population /V( in the lower energy level E(. If by some methods we effect population
inversion so that N2 > Nt, we can maintain the emission rate higher than the absorption rate. This means
that, when a radiation of energy density E (v) passes through a system in which N2> Nv the radiation
comes out with more photons of frequency v than that are incident on the system. This situation is
referred to as the wave amplification by stimulated emission of radiation. If the radiation is in the
microwave region, the phenomenon is the MASER, and if the radiation is in the visible region of the
electromagnetic spectrum, then the phenomenon is called LASER. Since more atoms jump to the lower
energy state than the atoms which reach the higher energy state, the upper levels gets depleted and the
amplification decreases. In order to maintain the amplification level constant, the population ratio must
be maintained at the same level by pumping the atoms at the lower energy level to the higher energy
level. Though the phenomenon of stimulated emission was known as early as 1917, yet a practical
device could be constructed only in 1954 and the credit for this discovery goes to Prof. C.H. Townes of
the Columbia University. The necessary conditions for sustained maser action are as follows:
1. There must be at least a pair of energy levels (Ej > Ex) separated by the desired radiation
which is to be stimulated.
2. There must be means of inverting the population of the two energy levels so that the population
N2 at the higher energy level E2 is always kept greater than the population at the lower
energy level E(.
3. There must be an electromagnetic system which can retain the photons of energy (E^ - E|)
with low losses so that they can be used for stimulation.
It was believed that a photon could interact with an atom in only two ways until the idea of
stimulated emission of radiation originated from Albert Einstein 1916. The two ways are: The photon
could be absorbed and excite the atom a level of higher energy or be emitted as the atom dropped to >
lower energy level. Einstein proposed a third probability — that a photon with energy corresponding to
that of an energy level transition could stimulate an atom in the upper level to drop to the lower level, io
the process of stimulating the emission of another photon with the same energy as the first Under
normal circumstances, stimulated emission is unlikely because at thermodynamic equilibrium more
atoms are in the lower energy levels than in higher ones. Thus a photon is much more likely to encounter
an atom in lower level and be absorbed than to encounter one in a higher level and stimulate emission-
________________________ ______ _____ ____ _ Optical Pfto«imE* O#SO«t» 70$
The first evidence fw^mulated etn’ssion was not reported until more than two decades thereafter,
emulated emtss on seemed little more than a laboratory curiosity. The efforts to use stimulated emission
initially were in wave region and led to the invention of the maser (microwave amplification
hy the stimulated emission of radiation).
The first stimulated emission amplifier to operate was a gaseous one. The device employed
ammonia gas. e ammonia molecule NH3 the three hydrogen atoms lie in the plane at the comers of
a triangle and the nitrogen atom occupies one or other pyramidal position on either side of the triangle
as shown in Fig. 12.7.
Kg. 12.7 Ammonia molecule
The potential energy function of the nitrogen molecule is shown in Fig. 12.7. It has an energy
minimum on either side of the plane of the hydrogen atoms and the potential barrier, which has a
maximum value in the plane of the hydrogen atoms. The nitrogen atom can tunnel through the plane of
the hydrogen atoms and such a transition is calledinversion. The transition between these inversion
levels by the nitrogen atom gives rise to a very strong line of frequency of 23870 MHz. Classically we
can picture the nitrogen atom flipping back and forth with a characteristic frequency 23870 (MHz). In
the quantum picture this is described as transition between the inversion energy levels. At any temperature
the nitrogen population in the two energy levels is given by Boltzmann formula,
N2 = exp {- (E2- ExVkBT]= A, exp (- hv/kBT) . (12.43)
where N2 is the number of nitrogen atoms in the level E2 and is the number of nitrogen atoms in the
level Er The above equation suggests that under normal conditions N2 < Nv Population inversion is
obtained by segregating the lower energy molecules from the higher energy molecules by an ingenious
device. The difference in the dipole moments of the ammonia molecule in the two energy states enables
us to separate the higher energy molecules by applying a non-homogeneous electric field. The essential
parts of the ammonia maser are shown in Fig. 12.8.
Ammonia gas from an oven kept at room temperature is allowed to flow at a uniform rate at a
pressure of 1 mm into an electrostatic focuser. A non-uniform electric field is produced by specially <M
shaped charged metallic plates as shown in Fig. 12.8. The inhomogeneous electric field acting on the q-
anunonia molecules aligns the higher energy molecules along the axis and pushes the lower energy MJ
molecules away from the axis. These lower energy molecules are readily removed by a vacuum pump. flu
The higher energy molecules enter a resonant microwave cavity which is tuned to the same frequency
as the energy separation of the two energy levels of the ammonia molecule. The maser operation can be Q
explained as follows: The molecules entering the cavity have a small but finite probability of induced
or stimulated emission. In addition there is an even smaller probability of a downward spontaneou
transition. The small amount of the emitted radiation from these transitions is reflected by the walls of
the resonant cavity. The reflected waves then act on other molecules to stimulate transitions. The radiation
is once again reflected and becomes available for further stimulation of emission. Thus a rapid build u
of the oscillations occur. It is important to note that the cavity configuration must be such as to provide
high 'Q' (Q is the factor of merit of the cavity which is given by the ratio of the rate at which the enerev
is stored to the rate at which the energy is lost in the cavity). A poor cavity will reflect a smaller fraction
of the microwave energy and hence more molecules will be needed to obtain the oscillation conditions
Again the microwave radiation must be properly polarised for stimulating the molecular transitions
Output Input
| Focuser j
—
Gas
oven
Microwave cavity
[ Focuser [
Cross-section
of the focuser
Vacuum pump
Fig. 12.8 Ammonia maser
The minimum number of molecules N that must flow per square cm per second is called the
minimum flux and this is calculated as
hV
N=------------- (12.43a)
4n2p.2t2Q
where V is the volume of the cavity, t is the average time that a molecule spends in the cavity, p. is the
dipole moment of the ammonia molecule and h is Planck’s constant. In terms of the cross-sectional area
A, the length L of the cavity and the average velocity v, the minimum flux N is given by
(12.44)
47t2p2Lg
3k T
where v is calculated from the kinetic theory formula v2 = ——. An approximate value for v is about
m
IO5cm/sec at about 300 K. The cavity dimensions are 0.96 cm diameter and’12 cm long. The Q value is
about 10*. By substituting these numerical values in equation (12.44) one gets the threshold flow rate of
molecules to establish oscillation is found to be 1013 molecules per second. The above flux requirement
can be easily obtained by the focussing arrangement designed in the device by Townes. This maser is
not quite suitable for practical applications since it can operate only at one frequency with no means of
tuning. Its great value lies in the demonstration of maser action which enabled further progress in this
field.
The population inversion in ammonia maser is obtained by segregating the molecules of higher
energy from the molecules of lower energy by a painfully complex process. This method may not be
suitable or s0 1 ' 0 er mel ° 0 achieving the population inversion is to irradiate the material
with «i ia ia ion o energy precise y equal to the energy separation between the two maser levels so that
the atoms a e ower energy eve may absorb the energy of the incident radiation and go to the higher
energy eve , t us pr uemg population inversion. This method is called pumping. But it can be shown
from t eoretica consi erations t at any amount of radiation intensity can never invert the population
jV] and N2 ctween t e two energy levels in a material which is in thermal equilibrium. At the most N2
can be ma e equa to ( ut maser action requires N2> N.. So Bolenbergen suggested an ingenious
device to overcome is t eoretical limitation. Suppose the material has 3 energy levels. There are two
possible schemes of obtaining maser action between any two levels.
Es ........ Long-lived state Short-lived state

—-Stimulated emission Spontaneous emission
e2- J------------- Short-lived state E ■” Long-lived state
Pumping Pumping
radiation Spontaneous emission ----- Stimulated emission
radiation
E, - E,-l—
- Ground state Ground state
(a) (b)
Fig. 12.9 Pumping radiation
In Fig. 12.9 (a) the atoms are elevated from the level Et to E3 by a pumping radiation. The atoms
are stimulated at the level E3 to drop to the level E2 by another stimulating radiation resulting in the
maser action. Relaxation or spontaneous emission process cany the atoms from the level E2 to the level
E{ very quickly. They are then pumped back to the state E3 in a continuous maimer. Under normal
conditions N3<N2<NV Due to pumping action N3 = Nv Since N2 lies between N3 and N3 becomes
greater than N2, provided the atoms falling to level E2 are cleared very.quickly by spontaneous transitions
to the lower level E{ or by any other relaxation process. In the scheme shown in Fig. 12.9 (b), the atoms
are pumped from the level Ex to level E3 by a suitable radiation. By a rapid relaxation process the atoms
are brought to level E2. Stimulated emission is effected between the levels E2 and Ev In the pumping
process N3 becomes approximately equal to /Vj. But most of the atoms fall to the level E2. So in the level
E2 there are more atoms than in the level Ev This makes maser action possible between the levels E{
and E2. In summary we can say that if atoms relax rapidly in the unused transitions, e.g., (E2- Ej) in
Fig. 12.9 (a), few atoms will remain in the state E2 and there will be more atoms in the state E3. In Fig.
12.9 (b) more atoms will be in the state E2 with only few atoms in states E( and E3. The presence of
(£ — E )
radiation field at the desired frequency D2i = —~~ will stimulate emission. This will try to reduce
N2 - Nv But the pumping radiation and the proper relaxation process can restore the conditions for
continuous maser action. Bloenbergen found that the required energy levels are easily available in the
electron paramagnetic spectra of certain doped crystals like pink ruby. We will now briefly discuss what
is electron paramagnetic resonance (EPR) and how the EPR spectra of materials enable us to select
suitable maser materials. The EPR spectra give the frequencies of the strong resonant absorption lines
in non-interacting paramagnetic systems. What will happen if the paramagnetic systems interact? A
non-interacting system will have discrete energy levels separated by a large quanta of energy. If the
systems interact, the discrete energy levels will spread into bands and the energy values within the
allowed band will be practically continuous. Continuous energy levels are unsuitable for maser action, •:
and so it is, a non-interacting system with a set of discrete energy levels is chosen for maser action. ‘
Energy levels which are susceptible for resonant absorption must also be susceptible to resonant emission
712 Souo StKrt IhMcs
or a stimulated emission phenomenon. So it is, the EPR spectra of materials reveal the energy ]ev
available for maser action. Of course all materials showing EPR spectra may not be suitable for maser
action, since the other factors like relaxation time, pumping method, etc. also have to be favourable
Resonance mainly occurs when the natural frequency of oscillation of a system coincides with
the frequency of the external forcing system. Consider a magnet of moment |1 freely suspended jn
magnetic field of intensity H. When the magnet is turned through an angle 0, it is acted on by a torque
is given by
T = PH 02.45)
The torque acting on the magnet is the product of the moment of inertia of the system I and the
. - . d:0
angular acceleration —y
dt
d2$
Le- =gxH (12.46)
= p/7sin0 (12.47)
= p H 0 when 0 is small
The natural frequency of oscillation of the above magnetic system is given by
1 [pJi .
(12-48)
When H = 0, the couple vanishes and hence the angular momentum as well. The system by itself
has no natural frequency of oscillation. Its frequency of oscillation is determined by the external field H
and varies with it So no resonant oscillations can be excited in such a magnetic system. The case is
different in an atomic magnet The atomic magnetism itself is due to the angular momentum of the
electron spin motion or orbital motion. In fact the atomic magnet has a freely rotating angular momentum
vector. This angular momentum vector is intrinsic to the electron and is present irrespective of the
magnetic field in which the atomic magnet is placed. Any system with a freely rotating angular momentum
vector is gyro. Suppose such an atomic magnet is placed in an external field H. The field exerts a torque
T given by
T = pH
dL
But T = — where L is the angular momentum
dt
ge
and p = y L where y=~—
2mc
where ‘g ‘ is the spectroscopic splitting factor, e the electronic charge, m mass of the electron and c is the
velocity of light
Therefore T = yL x H
or 7^LxH (12.49)
This is the famous equation of the gyroscope where the angular momentum vector L rotates or
processes about magnetic field vector H with a frequency coL given by
O)L = yH (12.50)
______--------------------------------- — . .___________ _ 0* &»»
*S Ca*’ei1 l^C Larmorfrequency. It is this Larmor frequency that is experimentally

determined from observations on the EPR spectra. From the Lannorfrequency the spectroscopic splitting
factor's can be calculated from the formula
ge/7
(12.51)
The energy level difference in the magnetic system is given by
= (12.52)
EPR can be explained classically as follows: When an atomic magnet is placed in a magnetic
field, it processes about the field direction with a frequency called the Larmor frequency. If a rotating
magnetic field, with precisely the same frequency as the Larmor frequency of the atomic system is
applied to it, resonance is said to occur. That is the atomic system absorbs large amount of energy from
the external field. Therefore a meter which measures the strength of the applied field shows a dip, when
the frequency of the applied field coincides with the Larmor frequency of the atomic system. This
means that the Lannor frequency of the atomic magnet is known, and hence the spectroscopic splitting
factor and the different energy levels in the system which are susceptible to strong resonant absorption.
In this way the EPR studies of materials enables us to find the suitable materials for maser action.
According to quantum mechanics the resonant absorption occurs when the atomic system goes to an
allowed higher energy level from an allowed lower energy level. This means that atomic system has
discrete energy levels, which can be exploited for maser action.
A non-interacting paramagnetic system is obtained by doping A12O3 with about 0.05% Cr. This
is the ruby crystal. The Cr+++ ions replace some of the Al444 ions from the A12O3 crystal lattice. The
Al444 and O ions are non magnetic, where as the Cr444 ions are magnetic because each ion has three
unbalanced spins. Magnetic moments due to orbital motions are all quenched leaving only the spin
magnetic active. The three spin magnets of each chromium ion cannot orient themselves in any direction
they like. However wave mechanics imposes some restrictions in their orientations and so they can
orient themselves only in any one of the four states as indicated in Fig. 12.10 (a).
CHAPTER 12
Rg. 12.10 Orientation of spin magnetic moments
Since each spin has a moment | the magnetic moment of the four states work out to + + 1,
- - and - 1 respectively. In the absence of any external magnetic Held all the four states must have the
i energy. That is. the magnetic system here is four fold degenerate. But due to an internal field
called the crystalline field the four states split into two energy levels £p and E2 as shown in Fig. 12 jq
(b). The spin states ± —, are identical as also the states ± . When external magnetic field is applied the
orientations of the spin magnets change giving rise to new energy levels. It is also found that the enerev
of each state increases with the increase of the external applied magnetic field in a different way jn
other words we have now obtained four energy states with varying energy differences at different points
The change in energy level differences with the applied magnetic field means that we can get different
resonance frequencies for different external fields. That is the maser can be tuned. Though three energy
levels are enough for obtaining maser action we have now four levels to exploit. We have seen that for
maser action the excited energy levels must have different life times. Fortunately the three excited
states have different life times.
How the maser action is obtained with the said four energy levels? The energy level differences
between the various levels correspond to photons at microwave frequencies. Let us now inject a photon
having a frequency corresponding to the energy difference between the levels 1 and 3. Some electrons
in the levels 1 are pushed to the level 3 by the absorption of the incident photon. The surplus electrons
in that level try to come back to the ground state 1. This they do in steps, i.e., they first fall to the level
2 and then they fall to the level 1, instead of falling straight to the level 1. What we want to establish is
a surplus of electrons in the level 2 as compared to the level 1 at any instant. If the electrons from the
level 2 drop out as fast as the newcomers arrive we cannot establish the population inversion between
the level 1 and 2. The problem is similar to that of filling a water tub with the drain open. Unless the
water at the input comes faster than it is drained at the output, we cannot have any appreciable water
level in the tub at any instant i.e., the output must be delayed with respect to the input, to have appreciable
water level in the tub at any instant. A similar things happens in the level 2. The level 2 has longer life
time than the level 3. So the electrons stay in the level 2 for a longer time. So at any instant the population
in the level 2 will be more than the population in the level 1. This can be further augmented by cooling
the crystal to liquid helium temperatures. Suppose a photon of precisely the same frequency corresponding
to the energy difference between the levels 1 and 2 is incident on the sample, stimulated emission
occurs and this is the maser. A typical ruby maser operating between the levels 1 and 2 at 3.7 kG
magnetic field gives maser beam of wavelength 7.14 cm or 4.2 x 109 Hz. One great advantage in the
three level maser is that the pumping frequency is different from the resonant emission frequency and
so there will not be any interference. In order to obtain the optimum maser operation at the desired
frequency one needs to choose the proper field and the proper direction of the crystal. The sample must
be placed in a microwave resonant cavity, which is resonant both with the pumping frequency as well as
the signal frequency. This requires special cavity designs. Well designed maser amplifiers are used for
amplifying very weak signals up to microwatt level with very little introduction of noise in the process.
Noise is produced by spontaneous emission of radiation of the active ions in the upper energy state and
thermal radiations from the walls of the cavity. The former is negligible at microwave frequencies and
the latter is reduced by working at liquid helium temperatures, (about 4 K) when the thermal radiation
in the cavity is very low.
A large number of crystals containing paramagnetic ions can be employed as microwave masers.
The paramagnetic ion must of course, have a suitable zero field splitting with the separation of the
levels preferably greater than the maser transition. The atoms of the host structure should have low
nuclear magnetic moments in order not to interact with the paramagnetic ions. Such an interaction
would split the levels and increase the number of transitions. The pumping power would have to be
increased to produce the necessary population inversion. The crystal matrix must be strong and chemically
stable. Large single crystals which can withstand the necessary reduction of temperature are advantageous-
T9Rf IVWWII
MfeiMNikMSaMi
Summary of Basic Principles

The type of laser selected for a particular application may be the result of experimenting with various
wavelengths to determine adaptability, particularly if laser radiations to be an integral component of
permanent installation. The three possible interactions of electromagnetic radiation with atomic levels
are:
(i) An atom in an excited state may give up energy and fall back to the ground state. This
process is called spontaneous emission (Fig. 12.11a). The equation to represent this process
is
atom* atom + photon
The asterisk indicates the excited condition of the atom.
(ii) An atom in the ground state may absorb a photon of appropriate energy and get raised to an
excited state. This is called induced absorption (Fig. 12.11b). The equation to represent this
process is
atom + photon —> atom*
Spontaneous Induced
emission absorption
(a)
Fig. 12.11 Interaction between atoms and electromagnetic radiation
(Hi) A passing photon of just the right energy may induce an atom in the excited state to emit a
photon and thereby make a transition to the ground state Left to rtself the exerted atom
would have emitted the photon and made a transition to the ground state. But the incident
photon hastens the process. The equation is symbolically
atom* + photon -> atom + 2 photon
This type of transition with the emission of photons is called stimulated emission (Fig. 12 1 Ie).
The characteristics of this stimulated emission is that the two photons that are emitted have exactly the
CHAPTER 12
same energy, exactly in the same direction and perfectly in phase

Let us consider a group of atoms all in the same excited state. A passing photon may cause
stimulated emission in one of these atoms. The results in the enusston of two photons. Each of these
photons may cause induced emission in two other excited atoms. This process may continue in a chain
reaction (Fig 12 12) The result will be an intense beam of photons moving in the same direction and all
are coherent. This is the basic principle of operation of lasers, laking the first letter of each word in light
amplification hy stimulated emission of radiation coins the word laser.
Kj. till X ate.' e".S5 • O’
The above said process is not practicable far the reasons listed now. The life of an atom in an
excited state is of the otder of l(H s. This means that before an excited atom can be stimulated to emit
a photon it is most likely to make a spontaneous emission. The photons emitted by spontaneous emission
are not coherent. The number of excited atoms (.V^) and the number of atoms in the ground state (N) is
related by the equation.
Na = Nexp(-EfkBT)
where £ is the energy difference between the ground and the excited state. kB is the Boltzmann constant
and T is the temperature in degree kelvin. For radiation by atoms. £ is usually much greater than k^T.
Hence at thermal equilibrium the population of higher states is very much lower than that of the ground
state.
Suppose ratfiation of appropriate energy is incident on a mixture of unexcited and excited atoms.
The probability of induced absorption by an unexcited atom is exactly the same as that of stimulated
emission by an excited atom. The population of unexcited atoms is much larger than that of excited
atoms. The lifetime of the excited atoms is very short Because of these two said reasons most of the
photons of the incident ratfiation cause induced absorption. There will be very few stimulated emissions.
The model devised to find a solution to the above said problem in an atom which has three
energy levels is shown in Fig. 12.13.
225 eV ------- J-------------------------- -------------------- S

I
। Radiationless
| transition
1.79 eV -------- j--------------------------- L-------------- M
Optical | |
pimpins ! I Laser radiation
(550 on) ! | (6943 nm)
Ground sore -------------------------------------- 1------- G
Kg. 12.13 Metastabie state
The atoms that are originally in the ground state are raised to the higher excited state S by
external agency. The excited state is short-lived. The atoms cannot remain in the state S for a longer
_ Optical Pnoramei or Scuta 717
time Hence they rapidly fall (or decay) into an intermediate state M called a metaslahle state. This
method or process of transferring atoms from the ground state to the metastable state is usually called
optical pumping- 10 sec is the life time of atom in the metastable state. This is much larger compared
to the lifetime of the atom in the excited state 5 (which is about IO-8 s). A passing photon produces
lasing transition from M to the ground state. The above process in which the ratio of the population of
the atoms in a higher state (Af) to that in the ground state is increased considerably is called population
inversion.
-The Ruby Laser

Laser action was first reported in ruby by Mai man in 1960, and both technique and theory have since
been extensively developed. Ruby laser rods are grown from sapphire (A12O3) doped with 0.01 to
0.05% chromium oxide (by weight) to form a synthetic ruby crystal coloured red or pink. Rods are up
to 20 cm long 3 to 2.5 mm in diameter. Ruby resists optical damage at normal power level if its surface
is clean, and conducts heat better than glass.
The ends of the ruby rod are optically flat and parallel. The rod is surrounded by a glass tube.
Upon the rod is wound a coiled flash lamp filled with xenon gas which acts as the opucal pumptng
system.
Working- As mentioned earlier the ruby rod is a crystal of aluminium oxide (A12O3) doped with
0.05% chromium oxide(CrO,), so that someof the Al* ions are replaced by Cr* ions. Thesettmpunty
chromium ions give pink colour to the ruby and give rise to the laser action. The energy-level dtagram
of chromium ions is shown in Fig. 12.15.
It consists of an upper short-lived energy level (rather energy band) E above i« ground state
energy tevel E„ the energy difference (E, -£,) = *» corresponding to a wavelength of 550 nm. There
is an intermediate excited-state level E2 which is metastable (a state relattvely long-hved one) havtng a
lifetime of 10”3 s about 10’ times greater than the lifetime of Ey Usually most o the chromium tons are
in the ground state £,. When the flash of light (which lasts only for about a milhsecond) falls upon the
ruby rod, the 550 nm radiation photons are absorbed by the chromtum tons whtch are pumped (raised) -
to the excited state £,. The transition 1 is the (optical) pumping transttton The exctled tons gtve up. by g
collision, pan of their energy to the crystal lattice and makes a transttton or decay to the meustable state P
e2. The transition from £, to E, (transition 2) is thus a radialtonless trans,non. As the hfe lane of the $
«ate E2 is much longer, to number of ions in this state goes on tncreastng du. to pumptng, while the
"ootbeJ in to ground state £, goes on decreasing. By this population mverarm » aclueved between to
g
e*cited metastable state £2 8roun^ slaê
Fig. 12.15 Energy level diagram of chromium ion
When an excited ion passes spontaneously from the metastable state E2 to the ground state
(transition 3), it emits a photon of wavelength 694.3 nm. This photon travels through the ruby rod and,
if it is moving parallel to the axis of the crystal, is reflected back and forth by the silvered ends until it
stimulates an excited ion and causes it to emit a fresh photon in phase with the stimulated photon. This
stimulated transition 4 is the laser transition. (The photons emitted spontaneously, which do not move
axially, escape through the sides of the crystal). The process is repeated again and again because the
photons repeatedly move along the crystal being reflected from its ends. The photons thus multiply.
When the photon-beam becomes sufficiently intense, part of it emerges through the partially-silvered
end of the crystal. The drawbacks of the ruby laser is:
The laser requires high pumping power because the laser transition terminates at the ground
state and more than one-half of the ground state atoms must be pumped up to the higher state to achieve
population inversion. Moreover, ions which happen to be in their ground state absorbs the 694.3 nm
photons from the beam as it builds up. The ruby laser is a pulsed laser. The active medium (Cr*44 ions)
is excited in pulses, and it emits laser light in pulses. While the xenon pulse is of several millisecond
duration; the laser pulse is much shorter, less than a millisecond duration. It means enhanced instantaneous
power.
Helium-Neon Laser
In gas lasers, the atoms are characterised by sharp energy levels compared with that in solids, the
electric discharge method is usually employed to pump the atoms to the higher energy states. He-Ne
laser is the first one to be operated successfully. It is a four level laser and population inversion is
achieved by electric discharge. The laser tube is approximately 5 mm in diameter and 0.5 m long. It
contains a helium-neon mixture, in the ratio 5 : 1 at a total pressure of about 1 torr (= 1 mm of mercury).
The ends of the tube are plane and parallel. One end of the tube is heavily silvered. The other hand is
partially silvered.
An electric discharge is produced in the gas mixture by electrodes connected to a high frequency
electric source.
The collisions of the helium and neon atoms with the electrons from the discharge excite (or
pump) the helium and neon atoms to metastable states. The metastable state in helium is 20.61 eV
above the ground state. That in neon is 20.66 eV above the ground state. Some of the excited He atoms
transfer their energy to ground state Ne atoms by collisions, with the 0.05 eV of additional energy being
provided by the kinetic energy of atoms [the advantage of this collision process is that the lighter He
atoms can be easily pumped up to their excited states; the much heavier neon atoms could not be raised
efficiently without them]. Thus He atoms help in achieving a population inversion in the Ne atoms.
When an excited Ne atom passes spontaneously from the metastable state at 20.66 eV to state at 18.70 eV,
it emits 632.8 nm photon. This photon travels through the gas-mixture, and if it is moving parallel to the
axis of the tube, is reflected back and forth by the mirror ends until it stimulates an excited Ne atom and
causes it to emit a fresh 632.8 nm photon in phase with the stimulating photon. This stimulated transition
from 20.66 eV level to 18.70 eV level is the laser transition. This process is continued and a beam of
coherent radiation builds up in the tube. When this beam becomes sufficiently intense, a portion of it
escapes through the partially-silvered end.
From the 18.7 eV level the Ne atom passes down spontaneously to a lower metastable state
emitting incoherent light, and finally to the ground state through collision with the tube walls. The final
transition is thus radiationless. Obviously, the Ne atom in its ground state cannot absorb 632.8 nm
photons from the laser beam, as happens in the three level ruby laser. Also, because the electron impacts
that excite the He and Ne atoms occur all the time, unlike the pulsed excitation from the xenon flash
lamp in the ruby laser, the He-Ne laser operates continuously. Further, since the laser transition does not
terminate at the ground state, the power needed for excitation is less than that in a three-level laser.
Properties of Laser Beam and Uses of Lasers

Properties: The laser beam has certain characteristic properties which are not exhibited by beams obtained
from other sources.
O') The laser beam is 100% spatially coherent, with the waves all exactly in phase with one
another. An interference pattern can be obtained not merely by placing two slits in a laser
beam but also by using beams from separate lasers.
(«) The laser light is almost perfectly monochromatic, i.e., highly temporally coherent.
Ou) The laser rays are almost perfectly parallel. Hence a laser beam is very narrow and can travel
to long distances without spreading. It can be brought to an extremely sharp focus.
Mr WV awl FM99U
Collision
20.66 eV
Metastable stale
20.61 eV
632.8 am (Laser
‘ Mctatfable 632.8 nm
transition)
■ state
18.7 eV
I Spontaneous transition
Radiationless
transition
Ground state -
0 0
Fig. 12.17 A four-level laser
(iv) The laser beam is extremely intense. It can vaporise even the hardest metal. Because of its
high energy density directional property, a laser beam can produce temperatures of the order
of (10*)oC at a focused point.
Uses: The laser is used in holography, radio communication in outer space, piercing botes in
metals, detecting and ranging objects at great distance, welding, surveying and delicate surgery.
Semiconductor Lasers
A semiconductor laser consists of a flat junction of two pieces of semiconducting materials, each of
which has been treated with a different type of impurity. On passing an electrical current through such
a device, laser light emerges from the junction region. Low cost, small size and relatively high efficiency
make these lasers well suited for microelectronic adaptation, and applications are almost unlimited in
high-technological uses, for example, fibre optics communications though the power output is limited.
These lasers are similar in construction to a transistor or a semiconductor diode. They are usually
infrared pulses with power on the order of watts and can be produced with good efficiency, especially a
low temperatures. The activation mechanism can be a voice or television current signal, thereby producing
laser beams modulated with these signals. Silicon and germanium conduct electricity better than insulators
but not so well as true conductors. These semiconductor materials allow construction of complex
microelectronic circuits by carefully controlling the composition making it possible to build many useful
structures to accommodate the desired use. Advances made in this field since 1975 have resulted at
room temperature lifetime of 100 years for continuously emitting semiconductor lasers. It is now possible
in producing beams of high quality and low diversion angles with millions of years of useful lifetime
Using of materials such as indium and phosphorus in addition to the standard gallium, arsenic and
aluminium (which emit wavelengths of 0.8-0.9 pm in the infrared region), has resulted in longer
wavelengths of 1.1-1.6 pm, which increases efficiency of light transmission in optical fibres. Also
being developed are shorter wavelengths, such as in the visible (red, particularly) and, even in <1*
ultraviolet (0.4 pm) region.
—-----„*U ■>• (‘.wk . Hg
Gas Lasers
Gas lasers produce coherent light atom beams bv an । a- u . • .
**S2K:ta rxxxxs
ftncnon, (/»the wtde varietyofwavelength., available, (c) they are less expensive. (d) some, for example,
the CO., are very efficient (30/o) and (e) very high power outputs are available from relatively small
units, as asers can e exp ame by the following parts: The gas cavity, excitation of the gas by
electnca c argej an stimu ate emission of the laser light on discharge of the electric pulse. A variety
of pumping met o s are used in gas laser technology whereby the atoms or molecules of the lasing gas
are excited. In some gas mixtures, such as the most popular of all, helium-neon, the electrical discharge
excites the helium atoms which transfer the energy to the neon atoms which emits red light. Other gas
mixtures, such as carbon dioxide, nitrogen and argon, are energised by the CO. molecules absorbing the
electrical energy and vibrating at a high energy level.
The helium-neon laser cannot produce much power, typically only a few milliwatt, but this
versatile laser can emit laser light continuously for many thousands of hours and has a plethora of uses.
The CO2 laser can be used to produce terawatt (IO12 W) in pulses of ultrashort pulse widths
(10-12 s). Amplification is possible by making multiple passes of the beam through the huge gas cavities
developed to produce clusters of beams of several feet in diameter. Continuous beams of CO2 lasers of
high intensity are also available for such applications as welding or cutting metals. Other popular gas
lasers are the argon and krypton lasers which emit in the green and red portions of the spectrum,
respectively. Mixed together, the resulting emissions can be controlled to provide four individual and
separate wavelengths in the visible range. One application popular with this combination is in the
entertainment field-light shows, movies, etc.
Liquid Lasers
Though several liquids have been used to produce laser beams, the organic dye laser is the most popular
one. It consists of solid dye materials dissolved in an organic solvent such as alcohol to form a solution.
Organic dyes have energy levels so closely spaced that a number of these levels can produce a wide
range of wavelengths in the visible portion of the spectrum, 0.4-0.7 pm. Using an appropriate optical
arrangement, a single wavelength emitting from the dye solution can be selected for use on the process
at hand. For example, these lasers are used in applications involving chemical analysis and identification
of atomic species. Because of the wide range of wavelength available in a variety of dye solution, dye
lasers are described as ‘tunable’.
Solid lasers may suffer damage at high power levels due to the intense heat generated within the
solid material and by the pumping lamp. The liquid laser is not susceptible to such damage. A dye
identified as Rhodanine 6 G was the first dye for which contmuous rather than pulsed operation was
achieved, making possible the production of a continuous beam of tunable laser Itght. Another dye,
r 12
, * p , □ ... „ uri can be made of lase at wavelengths varying across the

•hethylumbeliferone, with the addmon of HO
:
hghtspectrum from uhrav,inletto,ydX^^ûhOdegmeofiucimumfe^.

range. In one strangest d,sc-shaped laserjtgn^ # J
n this device, the circumference w pumped by another laser. One of the inventors c
cavity. At the centre of the lasei was a make a spherical laser, one that would emit
Cheves it should be possible to extend his tecnmq
laser light from the entire surface of a ball-shape vic
TIM Scud SWrt Physics
Rf- 12.18 Diagrammatic sketch showing (a) excitation of gaseous laser medium (i.e., electrical discharge),
(b) reflection of photons during stimulated emission, and (c) exiting photons in a laser beam
Free Electron Lasers

The first free electron laser as the most tunable one was emerged in 1985 able to successfully test-fire
6000 watt beams of light at a variety of wavelengths spanning the infrared portion of the spectrum.
Free electron laser (FEL) represent a totally new concept in the quest to develop powerful light
sources for strategic defence, industry and basic research applications.
They produce light beams with the aid of electrons, the same subatomic particles that travel
through household wiring to meet daily electricity needs. In the case of FEL, the electrons are generated
by accelerators and then directed through an array of 340 magnets, 3 feet in length, arranged with
alternating north-south poles. The negatively charged electrons passing through the array are then forced
to ‘wiggle’ as the alternating magnetic poles deflect these tiny particles left and right. This wiggl‘nS
causes the electrons to emit light, a phenomenon well known to us. Light is reflected back and forth
between two small morrors spaced 23 feet apart, gaining strength on each pass through the wigg,er
Optical
magnets. Each round trip between mirror takes about 46 billionths of a second. During a test shot, 2000
n ips are made.
We can literally dial a wavelength. The wavelength produced by the free electrons is related to
the particles energy. As a result, we are able to dial up a specific wavelength by choosing an accelerator
known to supply electrons at energy levels that radiate certain laser wavelengths when wiggled. This is
a key advantage that FELs have over conventional lasers that emit only a single wavelength beam when
their medium is excited to produce light.
Another attractive characteristic of such lasers is the high-quality beam emitted free electrons
when they move through a magnetic field. For example, the beam from a spotlight, consisting of light
from a variety of wavelengths, would be spread about 2000 miles across by the time it reached the
moon. By comparison a laser beam of perfect optical quality, such as an FEL, would be only 200 yards
in diameter at the same spot because it is made of only one specific wavelength, and the beam divergence
is low. The first free electron laser was tested in Stanford University in 1976.
Phosphors in Fluorescent Lights

Phosphors are solid which absorb energy and re-emit it as light. As in lasers we have just described the
?mitter is usually an impurity ion in a host lattice. However, for the uses to which phosphors are put it
s not necessary to produce intense, coherent beams of light, and the emitting process is spontaneous
ather than induced. There are many applications of phosphors, for example, television pictures are
)roduced by phosphors that are bombarded with an electron beam. In terms of tonnage produced, one of
he most important applications is fluorescent light tubes.
Fluorescent lights produce radiation in the ultraviolet (254 nm) by passing an electric discharge
hrough a low pressure of mercury vapour. The tube is coated inside with a white powder which absorbs
he ultraviolet light and emits visible radiation. For a good fluorescent light, the efficiency of the
onversion should be high and the emitted light should be such that the appearance of everyday objects
iewed by it should resemble as closely as possible their appearance in daylight. Most phosphors for
luorescent lights have been based on alkaline earth halophosphates such as SCag (PO4)2, CaF2. As in
isers, the usual dopants are transition metal or lanthanide ions, but more than one impurity ion is
ceded to approximate the whole visible spectrum. Not all the impurity ions need to be capable of
bsorbing the exciting radiation, however, as the host lattice can act to transmit the energy from one site
> another. For example, in a phosphor doped with Mn2+ and Sb3+ ions, the ultraviolet radiation from
ic mercury lamp is only absorbed by the antimony (Sb3*) ions. The excited antimony ion drops down
»a lower excited state via a non-radiative transition. Emission from this lower state produces a broad
and in the blue region of the visible spectrum. Some of the energy absorbed by the antimony travels
trough the host crystal and is absorbed by the manganese ions. The excited Mn2+ ions emit yellow
ght and return to the ground state. The two emission bands together produce something close to daylight,
hosphors have been introduced which are more efficient and give a closer approximation to daylight,
good approximation is, for example, given by a combination of blue from barium magnesium aluminate
>ped with divalent europium (Eu2+), green from an aluminate doped with cerium (Ce3*) and terbium
T>3+) ions, and red from yttrium oxide doped with trivalent europium (Eu3*).
In these phosphors and in the ruby laser, light was absorbed and emitted by electrons localised
i an impurity site, but in other optical devices, the radiation is emitted by delocalised electrons.
/ &uo$rAltftftMc$
light-Emitting Diodes (LEDs)

They are effectively the reverse of photovoltaic cells, hi photovoltaic cells, light is used to produce an
electric voltage; in LED’s a voltage is applied across a p-n junction to produce light. Fig. 12.19 shown
a p-n junction in a semiconductor such as GaAs.
E Electric field direction
fig. 12.19 Energy bands near the junction in a p-n junction
The band structure shown in for the junction in the dark and with no electric field applied. Now
suppose that an electrical field is applied so that the n-type is made negative relative to the p-type.
Electrons will then flow from the n-type to the p-type. An electron in the conduction band moving to the
p-type side can drop down into one of the vacancies in the valence band on the p-side, emitting a photon
in the process. This is more likely to happen if the transition is allowed, so that semiconductors with
direct band gaps are usually used in such devices. To use the LED as a display, for example, it is then
wired so that an electric field is applied across the parts making up the required letters or numbers.
Different colours can be produced by using semiconductors of differeing band gap. GaP produces red
light, but by mixing in various proportions of aluminium to form Ga1;t A1J* green or orange light can
be produced. It should be noted that semiconductors with indirect band gaps are used far LEDs but in
these cases, impurity levels play an important role. Thus GaP is used although it has an indirect band
gap. Silicon, however, is not suitable because there is a non-radiative transition available electrons at
the bottom of the conduction band and these electrons donate thermal energy to the crystal lattice rather
than emitting light when they return to the valence band.
When the electric field causes conduction electrons to move across the p-n junction, the resulting
situations is one in which the population in the conduction band is greater than the thermal equilibrium
population. An excess of electrons in an excited state is essential feature of lasers and there are several
semiconductor lasers based on the p-n junction. The best known of these is the GaAs laser.
'XI.’WWJUHIUNW UStRS'
iiiiWtiiiiriwn II nit
Industrial Applications of Lasers

Materials Processing
For mechanical and metallurgical engineers, a knowledge of laser technology relating to metal working
techniques is a requisite. Laser can cut, drill, weld, remove metal from surfaces, and perform the#
operations even at surfaces inaccessible by mechanical methods. It is not necessary that users of lasers
for these operations understand all the technical details of the laser system, but knowledge of the beam
characteristics and material absorption qualities is essential in proper adaptation of the beam to obtain
the desired result.
Cutting and Drilling
Because CO2 lasers, which produce 10.6 gm wavelength beams, can be manufactured with extremely
high continuous wave (CW) power densities, this laser system is the most commonly used in industrial
cutting and drilling operations not only with metals but also such nonmetals as ceramics, plastics, cloth,
paper, glass and so on. Gas jetting is usually associated with industrial metal cutting either to enhance
removal with a reactive gas, such as oxygen, or with a protective (inert) gas to protect flammables.
Typical metals that are efficiently cut or drilled with CO2 systems are steel, aluminium and titanium.
Cutting speeds reach rates from 20 inch per minute for one-inch carbon steel sheets to 100 inch per
minute for one-half-inch aluminium alloys. Laser energy supplies all the energy needed to cut or drill
non-metals, but often coaxial gas jets serve to protect the treated surfaces and coaxial vacuum can be
included to direct toxic fumes away from the operation.
Welding
Several advantages over gas or arc welding are possible with laser-welding techniques; (a) purity of the
materials involved is not altered, (b) localised heating by the small spot size can be accurately controlled,
even programmed, by computers to reproduce exact characteristics, and the laser beam can be transmitted
through windows of a closed container to permit welding (or other operations) in a controlled atmosphere.
Heat Treatment
Although induction heating has served the metal processing operations for many years in providing
surface treatments, for hardening steel particularly, the versatility of the laser beam has proven very
useful in the treatment of many metal surfaces. Cost saving is one consideration, because less energy is
required, heat losses are reduced, and the time involved is considerably lessened. Steel and aluminium
surfaces can be hardened or alloyed by methods established for production line applications. A less
expensive substrate can be used in some applications so that metal powder layers can be coated and
then processed thermally by the laser beam in precise locations.
Communication Using Fibre Optics

Lasers play the essential role in using thin strands of glass fibres to transmit light signals that can be
received and translated into a communication format. Here the laser beam is reflected to low angles
down the fibre core. Some light is absorbed, of course, or lost, so that the ‘signal’ must be reinforced at
some length down the fibre. However, the technology has advanced to the point whereby ‘repeater’
stations are not required for many kilometres and the development of unproved fibres and research with
various solid state lasers will undoubtedly increase the distance a signal can propagate. These distances
are so great now the need for reinforcing the signal will not restrict installing fibre cables under (Keans
to provide new communication systems between countries separated by large bodies of water.
The method of signal transmission, which is superimposed on the beam, includes a process
called modulation. The light signal is transmitted though fibre to a decoder, or demodulator, that receives
the digital photon signal, converts it to an electrical signal, amplifies it, and sends it on for interpretation
by a communication network. The contribution which fibre optics has made in the field of communication
and other technologies employing electronic or optical signals has been extensive, from replacing control
wiring jn automobiles to replacing essentially all telecommunication cables, local and international.
_________________ _____ .________________
Advantages of signals transmitted by photons in fibres versus electrons in metal wires are many
most obvious ones arc the reduced size and weight, the reduced cost of hardware, and the increased
signal capacity. Because the optical system is not electrical, static or noise, is not encounted. Also no
sparks arc generated and hence can be used in chemical industries also. Also, light emitting diodes
(LEDs) can be used instead of lasers for short hauls, such as automobiles, computers, printers, etc
Astronomer’s Measurements
By bouncing light from a newly developed laser off reflectors left by astronauts on the moon, astronomers
have taken new measurements of the constantly changing distance between the earth and moon. The
scientists said they believed the measurements, across perhaps 230000 miles of space, were accurate to
within an inch, ten times more accurate than any made in the past. The astronomers used a special
80-lens telescope (University of Hawaii) to receive the new short-pulsed laser beams. The new
measurements, combined with old ones provided detailed records of day-to-day changes in the rotation
of the earth and the slight wobbles it makes as it spins on its axis. They are also recording lunar motions
caused by subtle gravitational effects arising from the influences of relativity. By analysing the new
data, scientists were able to gain better understanding of the forces deep within the earth that set off
great earthquakes, as well as the variations in the earth’s rotation that have been linked to such devasting
effects as a cyclical warm water ocean current that is believed to cause weather anomalies.
Medical Applications of Lasers

The developments of the free-electron laser by John M.J. Madey in 1971 excited research groups
throughout the world who have recognised the potential of the concept, especially with respect to medical
applications. The free-electron laser is considered to be the most exciting medical machine of the next
several years. It was considered as a major breakthrough in the treatment of diseases such as cancer,
without the liability of harming healing tissue.
The free electron-electron laser is a relatively young device that differs sharply from any other
laser equipment It requires access to a high-energy electron accelerator. Indeed, medicine is just one of
a gaggle of applications cited as promising fields for the free electron laser; other include spectroscopy,
IR imaging, chemical processing, welding and metal working, laser fusion, communications and directed
energy weapons. The medical applications of lasers in some of the important areas are now discussed
briefly.
Surgery
In medicine as in science fiction, lasers are mostly regarded for their ability to vaporise matter with a
concentrated blast of energy. Surgeons use them to bum up brain tumours and remove tattoos. Experiments
with lasers to weld tissue, hoping to bring a new delicacy to surgical techniques were Successful-
Reconnecting blood vessels with laser welding is much quicker for the surgeons than using traditional
sutures. The key difference between using a laser to blast away tissue and using it to rejoin or mould it
lies in the amount of energy used. Laser welding will result in fewer postoperative infections than
sutures because the laser introduces no foreign materials into the body.
Another technique involving the use of lasers is the treatment of paralysis, where an He-Ne laser
is used to stimulate the nerves in the wrists and ankles. Apparently this procedure has the unique ability
to stimulate the part of the brain that controls motor responses and causes dramatic changes in nerve
reactions. Success has been achieved in restoring hand movement after spinal cord injury, reduction of
stiffness and spasms in paralysed limbs, and a major recovery of body movement in some patients
prt-vKHisly classified as permanently paralysed. Relief of pain by this technique has also been reported.
Though by pass surgery' gives ten years of healthy life, in a countable number of cases, artery disease
cxMitinues to narrow the artery'. Such patients could be helped by laser angioplasty which could be
probably be repeated whenever needed.
Ophthalmology
The four most common sight-destroying diseases among people over the age of 45 are: Muscular
degeneration, glaucoma, diabetic retinopathy, and cataract, and states that new therapies have simplified
much eye surgery so that many operations can be performed on an out patient basis. Millions of people
suffer from glaucoma, a potentially blinding disease in which pressure builds up inside the eye the
pinches the optic nerve. The pressure comes from a backup in the flow of fluid. Watery fluid normally
enters and exists the eye at all times, but it gets backed up when something clogs up the ‘drain’ called
the trabecular meshwork. With too much inflow and too little outflow pressure mounts. Three out of
four glaucoma patients can control this pressure with special eye drops. For the rest an ophthalmologist
might suggest 80 to 100 bursts of argon laser.
There is a rarer form of glaucoma, called angle-closure glaucoma, for which the laser has been
used. While open-angle glaucoma progresses without symptoms, angle closure causes blurry vision,
red eyes and pain. To treat it, ophthalmologists use the laser to puncture the iris—the coloured part of
the eye—so that fluid flows freely between two chambers in the front of the eye and pressure drops. If
you catch this early enough, the laser will cure it. However, more work is needed in this area.
Dermatology
Dr. Leon Goldman, a dermatologist, was a pioneer in developing removal of skin irregularities at the
University of Cincinnati Medical School Laser Laboratory. The treatment of portwine strains and deep-
red birth marks on Caucasian skin has become a clinical procedure. Also, removal of unwanted growths
including carcinomas (skin cancerous cells), have become routine laser treatments.
Lasers acupuncture is becoming a popular treatment for some disorders and for the relief of
pain. Being painless, fast and hygienic, laser treatment is becoming more popular in China and Western
Europe than needle techniques.
M— ____ -____ ---__ ■ ■ ■- ■
Introduction
Optical fibres are best known for their use in signal transmission for communications. They were originally
developed to serve as optical elements. Optical fibres are used to transmit light in the way that metal
wires are used to transmit electricity. However, optical fibres have greater advantages over copper wire
f°r communication purposes.
1. Much greater bandwidth
2. Immunity from electromagnetic interference
3. Smaller and lighter
4. Stable or declining price.
There are disadvantages in getting signals into and in joining fibres, but these are relati vely
ltlOr Problems. The frequencies of optical waves, microwaves and radio waves are l0‘5 Hz, lO‘o Hz
SouQSwaPwvsci _____
and IO6 Hz respectively. Because of the extremely large frequencies, a light beam can easily act as a
carrier wave and can carry far more information than radio waves and microwaves. Since the demand
for die flow of information traffic will be so high that only a light wave will be able to cope with it. In
order to have an efficient and dependable communication system, one would require a guiding medium
in which the information carrying light waves could be transmitted. This guiding medium is the optical
fibre which is hair-thin structure and guides the light beam from one place to another. In addition to the
capability of carrying a huge amount of information, fibres fabricated with recently developed technology
arc characterised by extremely low losses (0.19 dB/km) as a consequence of which the distance between
two consecutive repeaters could be as large as 250 km.
Optical Fibres
A telephone call can be sent along an optical fibre in the form of a series of light pulses from a laser. The
intensity, time between pulses and length of pulse can be modified to convey the contents of the call in
coded form. In order to transmit the information over useful distances the intensity of the light must be
maintained so that there is still a detectable signal at the other end of the fibre. The important requirement
is that the laser beam keeps within the fibre. Laser beams, diverse less than conventional light beams so
that using laser light is a help, but even so there is some tendency for the beam to stray outside the fibre.
Therefore, fibres are usually constructed with a variable refractive index across the fibre. The beam is
sent down a central core. The surrounding region has a lower refractive index than the core so that light
deviating from a straight path is totally internally reflected and hence remains in the core.
Communication Using Fibre Optics

Dispersion is the term given to phenomena which tend to spread out an optical signal over time and
frequency. In binary pulse-code modulation (PCM) system, the energy in a light pulse which is ‘on’ is
spread out so that if ‘on’ pulses are too close together they cannot be separated. There are two chief
sources of dispersion in optical fibres: Modal (or intermodar) dispersion and intramodal dispersion
(made up of material and wave guide dispersions). We shall deal first with modal dispersion in two
types of fibre.
Step-Index Fibres
A step index fibre consists of a cylindrical central core with refractive index (RI) = n, cladded by a
material of slightly low RI, say rij. Modal dispersion is much the most important source of dispersion in
these fibres and arises because there are many different paths down the fibre for the light rays.
The refractive index distribution in the transverse direction is given by
n(r) = n} 0<r<a in the core
= n2 r> a in the cladding
where a is core radius. For a ray entering the fibre, if the angle of incidence at the core-cladding interface
is greater than the critical angle 0t = | sin (n^ )j, then the ray will undergo total internal reflection at
that interface. Further, because of the cylindrical symmetry in the fibre structure, this ray will suffer
total internal reflection at the lower interface also and therefore get guided through the core by repeated
total internal reflections.
The energy of the light ray, and hence its signal content, moves with the group velocity of the
ray, vg, so the group delay in a fibre of length, L for this ray will be x = — .The dispersion in arrival
times because of multimode propagation will be the difference between the*longest and shortest group
Oftkai Rwtomu wlMWf
delays. It turns out that the longest group delay is for rays which travel entirely in the central region for
»hKl> •>. - and the shortest group delay is for evanescent rays which travel in the cladding with
group velocity. V = —. The dispersion is then

n2
At= — - A =^nl (12.53)
v,, v» c
For a fibre 1 km long, with n( = 1.52 and n2 = 1.50, the model dispersion works out to 67 ns. In
fibres rather longer than 1 km, the dispersion given by equation (12.53) is too great, because defects and
kinks allow slower modes to catch up so that
At= AijTf
where At1 is the dispersion for 1 km. The maximum bit-rate, R, for PCM (pulse code modulation)
signals is given by
R = (4At)-1
Rg. 12.20 Sketch showing method of transmitting laser beam energy within special glass fibre
while the bandwidth for AM signals is roughly -. Thus over a 50 km length of the fibre in this example,
Ax ' 67 x Tso - 474 ns K - 530 kbit/s, a modest bit-rale. Monomodal step-index fibres can be
730 PHVSICS
made to eliminate modal dispersion, but the rather small core diameter makes joining and signal insertion
much more difficult. A better approach is the use of a RI which varies in the core material.
Graded-lndex Fibres
The modal dispersion of step-index fibres can be reduced by using several cladding layers and making
multi-step index fibres, but enormous reductions in modal dispersion may be achieved by having a
continuously changing RI from the centre of the fibre to the cladding. These are called graded-index
fibres. Because the RI changes gradually as a ray passes through the core to the cladding, it does not
change direction abruptly, but gradually, so that rays of longer pathlength spend a greater proportion of
their time in a medium of lower RI and hence travel faster; this is the secret of the low model dispersion
in graded index fibres.
The RI is the central zone of the fibre can be written
n(r) _ Jn1A/l-2(r/a)aA r<a
1^2 r> a
where r is the distance from the centre of the fibre, a is the radius of the core, A = ———. n. is the RI
ni
at the centre, is the RI of the cladding and a is the grading parameter, (a = 1 for linear grading, a = 2
for parabolic and a = °° for step-index fibre). Figure 12.21 shows n(r) for various values of a. The
optimal value for a is given by
«opt = 2(l-A)
that is, a little less than two. For optimal a the dispersion is given by
Fig. 12.21 RI profiles for some values of the grading parameter, a
Ln, A2
At . = —-g—
nun c
________________ ____________ *_________ OrncM Prereatagof
When a is little different from its optimal value, the dispersion is
Suppose n. = 1.5 and A = 0.01, then a = 1.98, = 63 ps/km, and if a = 2,— = 0.25 ns/km.
opt L L
The dispersion has a very sharp minimum at a which is easily missed in manufacturing the fibre.
The number of modes supported by the graded-index is approximately given by
(kxafuA
" (a + 2)
where, k{ = . When a = 2, N is haff that for a step-index fibre, which leads to half the energy input
A
to it compared with the step-index fibre, as the energy in each propagating mode is the same.
intramodal Dispersion
Intramodal dispersion is made up of material dispersion and waveguide dispersion. The former is caused
by the RI being a function of wavelength, and would occur regardless of the fibre dimensions. Waveguide
dispersion is caused by variation in the propagation constants of the waveguide with frequency. Since
waveguide dispersion is proportional to —, where a is the fibre radius, it is most important for
monomodal fibres. Waveguide dispersion is negative while material dispersion is positive, so in these
fibres it is possible to eliminate intramodal dispersion at a particular wavelength.
In silica fibres, the material dispersion is negligible at 1 = 1.3 gm, and it is roughly
At < 30 (AX) (I) in gs
elsewhere in the wavelength region 1 to 2 gm, where Ak is the spectral width of the light source. There
is no y[L dependence for long fibres. Intermodal and intramodal dispersions are not directly additive,
but must be combined as follows:
■At=7(At;ÂtJ)]
where At and At are the respective intramodal and (inter) modal dispersions for the entire length of
the fibre. Intramodal dispersions can be reduced by using a source of narrow spectral range, such as a
laser.
CHAPTER 12
Attenuation in Optical Fibres

At first, attenuation was the most important obstacle to the use of optical fibres, since about 1000 dB/
km was the best obtainable one in the 1960s. Subsequent improvements have resulted in an attenuation
coefficient for silica fibres as shown in Fig. 12.22, which is very close to the theoretical minimum. The
long-wavelength limit in the infrared is caused by electronic lattice tansitions, especially the strong
w Souo State Physics
absorption around 10 pm. which has a large ‘tail’ down to 1.5 pm. This limit is an intrinsic property of
silica, and can only be overcome by changing to other materials, such as alkali halides or fluoride
glasses, which have no infrared absorption up to longer wavelengths than 10 pm. The absorption peak
at 1.4 pm is due to hydroxyl ions in the silica, which cannot be eliminated. At short wavelength the limit
is set by Rayleigh scattering. Silica is a glass and as such consists of small volumes in which the atoms
(about a dozen in number) are correctly positioned, joined to other such groups of atoms in haphazard
way. These groups scatter light because of micro-variations in the RI. The scattering losses go as X4
amounting to 4.5 dB/km at 0.6 pm and 0.3 dB/km at 1.2 pm. With reasonable sources and receivers,
losses of 0.3 dB/km mean that repeaters are not necessary in fibres up to 100 km long. Coupling and
bending losses are more significant in most cases.
Rg- 12.22 Attenuation against wavelength for silica fibres
The Manufacture Optical Fibres

The basic process is simple in principle. The core material is melted in a container with a hole in the
bottom which is centrally placed in another vessel containing the molten cladding material as in Fig.
12.23. Graded index fibres may be obtained by adding dopants as GeO2 to the molten SiO2 which
diffuse into the central core by an amount which depends on the temperature and time taken to cool. The
RI profile is not easily controlled. A second process offering potentially greater control of RI profile is
a CVD (chemical vapour deposition) process in which doped SiO2 is deposited on the walls of a tube of
pure silica under the influence of heat which can be applied to a narrow moving zone of the tube.
Volatile reactants such as SiCl4 and GeCl4 are used to transport germanium and silicon, which
are oxidised by oxygen at 1200°C to (Ge, Si) O2 of the desired RI. Repeated passes with differing gas
compositions can be made to give the desired profile. The finished tube is then heated to beyond its
softening point (about 1800°C) so that it collapses into a solid rod, which can then be drawn down to the
desired diameter. This is largely determined by the temperature of the undrawn fibre (through its very
pronounced influence on viscosity), though the draw-rate is also important and can be controlled by
feeding back thickness information to the drum motor. Deposition can also be carried out on the outside
of a rod or lube in much the same way to produce the required index gradient.
Optical Properties of Soum 733
Fig. 12.23 An apparatus for producing cladded fibres
Features of Fibre Optics Communication Systems

Very large information transmission capacity and large repeater spacing are the main features of fibre
optic communication systems. They also offer many advantages compared with the usual metallic
transmission process. Since the fibres are composed of dielectric materials they are totally immune to
extraneous interfering electromagnetic signals. There is virtually no signal leakage from the fibres and
therefore cross-talks between neighbouring fibres are almost absent while this is very common in the
conventional systems. Since signals do not leak away from the fibres they are resistant to intrusion and
are accordingly highly suited to secure good results in defence communication networks. Since these
fibres are immune to electromagnetic interference and do not pick up line currents, they can be safely
used in a power station, and can be laid alongside metallic power cables.
They are also much smaller in size than an electrical line of equivalent band width and thus
would occupy much less duct space. Also the raw material used in the fabrication of low loss fibres is
silica, which is abundantly available in nature (of course in an impure form), whereas copper or aluminium
constitutes the basic raw material in coaxial cables. Cost surveys indicate that coaxial cable price will
continue to rise due to an almost continuous increase in the price of copper but the prices of fibres will
come down as the production volume increases.
Holography
Holography is lensless three-dimensional photography. A conventional photograph is only a flat record
of a real image projected onto a photographic film. Information about the three-dimensional character
CHAPTER 12
of the object is almost entirely lost during the photographic recording process. Only the blurring of the
images of objects that are not within the depth offield of the camera preserves any record of the location
of the object relative to the camera. A hologram on the other hand is a special ‘photograph’ of an object
that retains information about the phase of waves coming from the object. Holography has a much
longer history than that of the laser, although it was the invention of the laser that made the production
of high quality holograms a reality.
734 SoudStatxPhys.cs
In 1947. Denis Gabor was looking for a way to improve the quality of images that could be
obtained with an electron microscope. Although the electron microscope of that day should have been
capable of resolving down to the atomic scale, aberrations of the electron optics prevented them from
doing so. Gabor conceived the idea of recording an electron hologram, which would contain amplitude
and phase information, and then reconstructing a corrected image of the object by optical means. He did
succeed in producing holograms and performing image reconstruction, but the optical sources available
to him were not sufficiently temporally coherent to allow high quality images to be achieved. For his
pioneering work he was awarded the 1971 Nobel prize for Physics.
The high degree coherence obtainable with a large has made the production of holograms and
applications of holography into a large subject in its own right. The principles underlying holography
share much in common with the phenomena of interference and diffraction.
In conventional photography the photographic emulsion becomes dark according to the local
intensity of the real image falling on it. The emulsion is a mixture of silver halide crystals of different
sizes, predominantly silver bromide, in a gelatin matrix. Incident light frees electrons from the halide,
but the electrons become trapped. Addition of developer reduces the silver ions in an exposed crystal to
silver atoms, leading to a strongly absorbing region where exposure levels were high. This is how a
photographic negative is produced. We make a hologram, and preserve phase information in the
photographic record, by allowing temporally and spatially coherent light to illuminate the object. Light
reflected and scattered from the object falls on a photographic film together with a reference wave
supplied directly to the film with the same laser as is used to illuminate the object. The schematic way
in which this is done is shown in Fig. 12.24.
Light emitted by a laser splits into two paths, one to create an object beam and the other to serve
as a reference beam. It is intersecting, or interference, of the two beams and the resultant beam projected
onto a photographic film that forms the holographic image. Because every location on the object is
illuminated by the object beam, the reflection of these waves intersects the reference pattern and the
resulting image appears suspended in space so that as the viewer around the image a three-dimensional
object is visualised.
The developed hologram does not contain a recognisable image of the object as a conventional
photograph does. The hologram generally appears as a collection of bright and dark lines with bright
and dark patterns of concentric circles. The stored image can be regarded as a representation of the
diffraction pattern of the object. The hologram formed by exposure of a film and the production of a
Complex pattern of transmission is called amplitude hologram. However, it is possible to process the
film chemically by bleaching so that the dark silver atoms are converted into silver salts that are transparent
but have a different refractive index than the surrounding film. This converts the records hologram into
a pattern of phase information and is called a phase hologram.
Volume Holograms
The holograms that we have been considering so far are called plane holograms because we have been
tacitly assuming that interference of object and reference waves writes the hologram in a particular
plane. We are neglecting the thickness of the photographic emulsion. However, since actual emulsions
can be up to 20 pm thick it is possible, and is in many cases desirable, to write a volume hologram in
which interference fringes are written throughout the emulsion. The hologram can be thought of as a
continuous distribution of plane holograms at different values of z through the emulsion thickness. Just
as the simple plane hologram produced by the interference of two plane waves was a planar diffraction
Fig. 12.24 Diagrammatic sketch illustrating technique with a laser to produce a hologram on film
grating the volume hologram produced in this way will have a structure where the regions of bright and
dark are distributed in a series of parallel planes in the recording medium.
Industrial applications of holography include non-destructive testing (NDT) techniques to find
flaws in structural parts. Called holographic interferometry, this method of examining materials for
flaws, dimensional exactness, effects of heat or vibration, or other physical aspects has revolutionised
NDT, replacing radiography in many instances and supporting other methods of quality control to
accuracies not available until the laser was adapted to holography and developed to its present state of
the art.
Other applications include data storage, whereby written information can be reduced to such
small dimension that one source claims that all the material in a library could be stored on a medium
about the size of a regular-size sugar cube. In the operation of a robot, recognition of patterns stored in
a rhemory bank could help in a robotic decision making. Holographic logos are being used to foil credit
card counterfeiters. Holography gives doctors a 3D view of the inner workings of the body organs
without side effects. The beating heart, the foetus of a pregnant woman, flowing blood are now available
from “motion holography".
An instrument called an ophthalmic laser interferometer has been developed by eye researchers
so that the results of certain eye surgery can be predicted. “The pre-surgical prediction of the potential
retinal visual acuity allows the clinician to make a more confident qualitative and quantitative
determination as to the cost/benefit ratio for the patient as reported in the journal Laser Optics. This
instrument is, therefore, valuable for patients with optical media problems such as lenticular cataract
or aberration, or cloudy vitreous which cloud or degrade images. The laser interferometer can also
serve as a predictor of multiple sclerosis by determining if the eye being examined maintains the same
<36 towSMiftwo
decimal acuity throughout constant monitoring during a five minute period as a healthy eye would, a
suspected acuity would decrease with time. Holography helps to visualise subatomic particles. It js
reported that scientists are looking with holograms to find the elusive fundamental particle of matter
the quark.
Laser Plasma
Short pulse, high energy laser pulses when focused produce extremely high energy flux, electric and
magnetic fields. For example, a 1 kJ one ns rectangular laser pulse focused to a spotsize of 1 pm
produces an energy flux of 6.4 x IO23 W m-2, an electric field of 2.2 x 1013 V m-2, and a magnetic flux
density in free space of 73 k tesla. Fields substantially smaller than this can strip outer and inner shell
electrons from the atoms of a target material. Consequently, intense focused lasers have found widespread
use in the production of plasmas from the surface of target materials. These laser produced plasmas can
be copious producers of X-rays, which can be relatively coherent. Such X-rays have significant potential
for high resolution holography and lithography. Because diffraction limits resolvable feature size in a
microscope or lithography system, the shorter the wavelength being used the finer the resolution. Most
laser-induced plasma generated x-radiation is coherent because of amplitude spontaneous emission
(ASE) effects. The rapid ionisation of a target material, frequently a thin metal foil, irradiated with an
intense laser pulse, can lead to a short-lived population inversion on energy levels of the resultant
multiply ionised ions. In many ways the process is an energetic analog of the excitation processes in
self-terminating pulsed gas lasers such as copper vapour and nitrogen.
The irradiation of various materials at very high laser fluences (Jm-2) has, in and of itself, provided
a fruitful means for studying matter at very high temperatures and pressures. However, much of the
impetus for such studies has been provided by the desire to demonstrate laser-driven, inertial confinement,
nuclear fusion. Nuclear fusion occurs in stars and hydrogen bomb explosions, and there has been work
for several decades on the controlled production of such thermonuclear reactions on a laboratory scale
for nuclear power generation.
Optical Terminology
Light is electromagnetic radiation with a wavelength between 0.1 nm and 100 pm. Of course, this
selection of wavelength range is somewhat arbitrary; short wavelength vacuum-ultraviolet light between
0.1 nm and 10 nm (so-called because these wavelengths-and a range above up to about 200 nm-are
absorbed by air and most gases) might as easily be called soft x-radiation. At the other end of the
wavelength scale, between 100 pm and 1000 pm, the sub-millimetre wave region of the spectrum, lies
a spectral region where conventional optical methods become difficult, as do the extension of microwave
techniques which are easily applied to the centimetre and millimetre wave regions. The use of optical
techniques in this region, and even in the millimetre region, is often called quasi-optics.
Table 12.1 summarises the important parameters that are used to characterise light and the media
through which it passes. A few comments on the table are appropriate. Although the velocity of light in
a medium depends both on the relative magnetic permeability pr and dielectric constant e of the medium,
for all practical optical materials pr = 1 so the refractive index and dielectric are related by
n=
Ofdcai fhtoMxnril'or --jFST.
-------„ w,ri ,- - —• - '■ |-rfliir
Table 12.1 Fundamental parameters of electromagnetic radiation and optical media
Physical quantity Symbol Value Unite

(Parameter)
— ■— ■ ■
1
Velocity of light C° a/UoEo 2.99792458 x 10s mtr1
in free space/vacuo
Permeability of free Uo 471 x 10~7 Hnr1

space
Permittivity of free 8.85416 x 10-12 Fm-‘
space
I
Velocity of light in a - ms-1
medium
Refractive index *=7^ - dimensionless
Relative permeability of usually 1 dimensionless

a medium
Dielectric constant of a 6r - dimensionless

medium
C
Frequency - Hz
109 Hz = 1 GHz (gigahertz)
1012Hz = 1 THz (tetrahertz)
Wavelength in vacuo - m
h=~
41«
....
Wavelength in a medium — m
II
II
1
p
10-3 m = I mm (millimetre)
Kfr6 m = 1 pm (micrometre)
10-9 m = 1 nm (nanometre)
10-12 m = 1 pm (picometre)
1 A (angstrom) 1010 m
1 p (micron) = 1 pm
1 mp (millimicron) = 1 nm
CHAPTER 12
-l< <
Wave number cm-1 (Kayser) or nr’

IP
II
Wave vector 2n
k,lkl = v nr1
A
(Conn/...)
Physical quantity
Symbol Value Units
{Parameter)
Photon energy E = hv - J
1 eV (electron volt)
= 1.60202 x 10-19 j
Electric field of wave E Vnr1
Magnetic field of wave H Am-1
Poynting vector P = ExH Wm"2
IEI2
Intensity Wnr2
Ex Ey 1——■,
Impedance of medium ^-=-^- = 7^0^60 Q
Impedance of free space Zo = 7Po/eo 376.7 a
When light propagates in an anisotropic medium, such as a crystal of lower than cubic symmetry,
n and e, will, in general, depend on the direction of propagation of the wave and its polarisation state.
The velocity of light in vacuo is currently the most precisely known of all the physical constants—its
value is known within 4 cm-1. A redefinition of the metre has been adopted based on the caesium atomic
clock frequency standard and a velocity of light exactly 2.99792458 x 108ms-1. The velocity, wavelength
and wavenumber of light travelling in the air have slightly different values than they have in vacuo.
A plane electromagnetic wave travelling in the z-direction can, in general, be decomposed into
two independent, linearly polarised components. The electric and magnetic field pairs associated with
each of these components are themselves mutually orthogonal and transverse to the direction of
propagation. They can be written as (Ex, Hy) and (£y, Hx). The ratio of the mutually orthogonal E and H
components is called the impedance Z of die medium
£l=_^L=Z =
7/y Hx y ere0
The negative sign in the above equation arises because (x, y, z) is not a right-handed coordinated
system. The Poynting vector S, where
S = ExH
is a vector which points in the direction of energy propagation of the wave. The average magnitude of
the Poynting vector is called the intensity I.
IEI2
I = <ISI>-sslf
The factor 2 comes from time-averaging the square of the sinusoidally varying electric field-
OmcM Psomwt* •***■ 7W
The wave vector k points in the direction perpendicular to the phase front of the wave (the
surface ot constant phase). In an isotropic medium k and S are always parallel. The photon flux
corresponding to an electromagnetic wave of average intensity, I, and frequency, u, is
hvt ch
For a wave of intensity of 1 Wm’2 and wavelength 1 pm in vacuo N = 5.04 x 10” photons
s'1 nr2- Photon energy is sometimes measured in electron volt. A photon of wavelength I pm has an
energy of 1.24 eV. It is often important, particularly in the infrared, to know the correspondence between
photon energy and thermal energy. The characteristic thermal energy at 300 K = k^T = 0.026 eV.
1. Discuss absorption of light by semiconductors. What are excitons? Describe the different colour centres
present in a crystal.
2. Discuss the principles involved in the working of lasers. Explain in detail the working of a solid state
laser.
3. Explain the terms spontaneous emission and population inversion. Describe the construction and working
of a laser.
4. Explain the terms inversion ofpopulation and stimulated emission as applied to Masers and Lasers. Describe
the construction and operation of a Ruby Laser.
5. What is population inversion? How can it be achieved? Describe the principle of Laser action. Discuss
briefly the various uses of Laser.
6. Explain under what conditions stimulated emission of radiation can take place? What are the characteristics
of such radiation? Describe the construction and operation of Ammonia maser.
7. Describe stimulated emission of radiation from explaining the role of Einstein coefficients. Write down
the rate of equations of a three level atom and bring out the conditions for laser action.
8. Describe the kind of statistics used for understanding the population densities distribution. Explain the
terms the spontaneous and stimulated emissions and population inversion. Describe the construction and
working of a laser.
9. Explain the terms stimulated and spontaneous emission. State the conditions for laser action in crystals.
Explain the construction and action of Ruby crystal. Mention some of the important applications of laser
in industry.
10. Discuss the salient features of optical absorption in the case of metals, semiconductors and insulators.
Explain under what conditions stimulated emission of radiation can take place? What are the characteristics
of such radiations? Describe the construction and operation of the Ammonia maser.
11. Derive an expression for the complex dielectric constant giving the optical properties of a metal of electron
CHAPTER 12
concentration n and constant relaxation time r. How are the real and imaginary parts e, and Ej relaxed to
the conductivity?
12. Discuss the classical theory of the response of a solid to an oscillating electromagnetic field and obtain an
expression for the dielectric function in terms of the plasma frequency.
13. Discuss population inversion in an atomic system and hence obtain the relation between the spontaneous
emission probability and the induced emission probability in terms of Einstein's coefficients when matter
is in equilibrium.
—TOcr jdum&Nr A^»'*»-• ■ ■ 4k* '-o-■>* j*s■ «*»-wM
Problem
1. In a material at 300 K two energy levels have a wavelength separation of 1 pm. Determine
(a) The ratio of upper to lower level occupation densities when the material is in thermal
equilibrium.
(b) The effective temperature when the levels are equally populated.
(c) The effective temperature when the upper level is twice as densely populated as the lower
(Assume unit degeneracy for each level).
Indicate briefly the relevance of population inversion in the operation of lasers and describe
one way by which inversion is achieved.
Solution
At normal temperature, the lower energy level in a material is more densely populated than a higher
energy level N2 according to Boltzmann equation (assuming unit degeneracy) as
N^N.expl-^-E^T]
Nx ________ 1________
N2 ~ exp [(E, - E2)/kBT] ~ exP [(£i “ E2)/kB^
Since Ez > E, and N} > N2, the temperature is positive as illustrated in Fig. 12.Pl(o).
0 N1 N,
—Population density —* Population density
(o)
Fig. 12.P1
However it is possible under certain conditions to make N2 > with E2 > Ev This is known as
population inversion and form the expression for T given below, it will be seen that T has a negative
value and the effect is therefore equivalent to a negative temperature. This is illustrated in the figure.
n2 1
(a) exp[(£ 2-£()/^T]
and for the transition between the energy levels, (£2 - EJ must be hv
ch
i.e., ^2 - £,) = /m =
X
(E2 -£;) _ ch 3x 108 x 6.626 xlO’34 _180l
kBT X kBT 10-6 x 1.38x10"23 x 300
N,
Thus, ^-==xp(- 48.01) = IO"21
■sr
jc‘- Answer (a)
i
TV,
(b) ^-=exp[- (£2-£1)/kB7] = l
(I'2 1^=101 =
.e., - 0
>T
; r->± « Answer (b)
।
- — In
in 27
^B T
or (£2-£1) = -kflTxln2
i.e., /n) = = - kBT In 2

K
ch
- T=---------------
lx£sTln2
3xl08 x 6.626 x IO'34
or T~~ 10"6 x 1.38x 10'23 x0.693
T=-21000 K; Answer (c)
Conclusion
To obtajn laser action, the energy spacing between the levels must be large, so that stimulated emission
occurs in the optical region. For stimulated transitions to occur, the population density in one of the
1^ler energy levels must be increased at the expense of a lower level. This is known as population
Souo Sixts Phywcs
inversion. A large number of transitions can then be stimulated from the higher level to the lower level
with the emission of coherent radiation. A typical material such as ruby has three energy level and in
order to obtain population inversion, a white flash-light source is used to raise the population in level
three. Laser action with the emission of red light then occurs due to stimulated transition from level two
to the ground state.
In a four-level laser with a material like neodymium-doped glass, population inversion is more
readily obtained than in a three-level laser. Hence, less optically pumping is required to produce laser
action between level three and level two.
2. The core of silica optical fibres contains some B2O3, GeO2 and P2O5. How do these impurities
increase the refractive index?
Answer: The oxides contain small highly charged ions. These have low polarisability and hence
impart high refractive indices.
3- A single crystal of copper contains a low angle tilt boundary on (0,0, 1) with a tilt axis parallel
to (0, 1,0) plane. Calculate the tilt angle if the spacing of the dislocation in the boundary is
3 x HP m and their Burger’s vector is 0.4 x HP m.
L
Solution: 0=—
D
With b = 0.4 x 10-9 m
D = 3x 10~6m
0.4 x 10"9
Thus, 0 = 3Xiq_6 = L33 x 10"4 radiation
i.e., 0 = 1.33 x 10-4 radiation

4. The lattice constants for KBr and NaCl are respectively 0.66 nm and 0.56 nm. Calculate the
(a) F-centre absorption energies and (b) F-absorption wavelength.
Solution:
The formula used is
vF ro2 = 0'5 x IO"4 m2s-1
l)f r02= 0.5 x 10-4 m2s-1

„ 0.5 xlO’4 0.66
For KBr vF =------ j----- Wlth ro = “Z~ nm
ro 2
0.5 xlO’4
V'’(M3xl0-’)’ = 004<X10
„ , 6.626 x 10“34 x 0.046 x 1016
and Ef = hvF =----------- t6X10-w----------- eV = 1.9 eV
E,«1.9eV I Answer («)
Ofdcai PROR-mFs or Souos 743
Again c ~ ^f^f
. c 3xlO8
Xf=uF = 0.46x10“ =652nm
Xf = 652nm Answer (b)
For NaCl
r0 = 0.28 nm
0.5 xlO"4
™*s (0.28x10-’/= 0 064X 10
, 6.626x 10"34 x0.046xlO16

= hv'-------- iTTlcF7’
Ef = 2.6eV Answer (a)
c=
c 3xl08
1 = — =------------- 7T- = 468 nm
F nF 0.064 xlO16
XF = 468 nm | Answer (b)
5. The figure shows the energy level of Nd3* in yttrium aluminium garnet 0GAl5O12) which are
involved in the laser action of this crystal (known as NdYAG laser). Describe the processes that
occur when the laser is working.
Answer: Radiation from a lamp excites electrons from the ground state G, to states B, C, D.
Electrons in states C and D undergo non-radiative transitions to state B. Radiative transitions
from B to lower states are forbidden and so a large population of electrons in state B builds up.
Eventually a photon is emitted and an electron goes to state A. This photon induces further
emission from B to A, eventually producing a beam of laser light. Transitions from B to both A
and G must be forbidden for a large population to build up in B, but the transition B -> A must
be less forbidden than the transition B —> G as it is B —> A that gives rise to laser action, and
hence must be the more likely to occur.
How do you expect the formation of colour centres to affect the density of the crystal?
Answer: A crystal with F-centres contains anion vacancies. We could expect, therefore, that the
density would be lower than that of the colourless crystal.
7- In an oxide MnO, Mn2* ions occupy octahedral holes in an oxide lattice. The degeneracy of the
3d levels of manganese are split into two, as for If1*. The five d electrons of the Mn2* ions
occupy separate d-orbitals and hence parallel spins. Explain why the absorption Unes due to
transition between the two 3d levels are very weak for Mni(.
Answer: In Mn2+, an electron can only go from one 3d level to another if it changes its spin.
Transitions in which an electron changes its spin are forbidden and so give rise to weak spectral
lines.
8. Calculate the dislocation spacing in a symmetric 1° tilt boundary in a copper single crystal
Solution:
, „ b .
9 = — with b = 0.26 nm
9=I^radim
it b 180 xb 180 x 0.26 xlO-9

i .e., -----= —; D =------------- -----------------------
180 . D n 314
5 . D = 15 run
9. A phosphor commonly used on television screen in ZnS doped with Cu2*. This is more efficient
at transferring energy to the impurity sites for emission than are the phosphors based on phosphates
as host. ZnS is semiconductor. Suggest a reason for the efficiency of transfer in this solid.
Answer:ZnS is a semiconductor with a full valence band and empty conduction band. When the
phosphor is illuminated electrons are promoted to the conduction band. Since the orbitals in this
_________________________ Oimcw
band are delocalised, the energy can easily he transferred to the other parts of the crystal, in
particular to the dopant atoms.
KI Outline the processes leading (photographic process) to the formation of a silver atom when red
light is absorbed by a given crystal of AgBr with an indirect band gap. Explain why this is
useful? Compare the processes you describe with those in phosphors.
Answer: The sensitiser acts like an impurity. It absorbs the radiation and goes to an excited
state. The excited electron undergoes a radiation less transition to a level in the conduction band
of AgBr. Since it is now a delocalised one, the electron can travel through the crystal until it
combines with an interstitial Ag+ ion to form a silver atom. The indirect band gap helps by
reducing the probability of the electron in the conduction band dropping into a vacancy in the
valence band. The process is similar to that of phosphors. However, with phosphors it is the light
emitted by the impurity that is important whereas photography it is the light absorbed by the
sensitizer that matters.
11. Explain why silicon is used for solar cells but not for LEDs.
Answer: Silicon is an indirect band gap solid with an available non-radiative pathway from the
conduction band to the valence band. In photovoltaic cells, electrons are promoted from the
valence band to the conduction band and then are used to electric work. The promoted electrons
do not return directly to the valence band either by emitting energy or by a non-radiative pathway.
In LEDs it is the return of the electrons to the valence band by emitting light that is important.
This return has low probability because of the indirect band gap and the electrons use the non-
radiative pathway instead. Promotion to the conduction band in the solar cell will also be low
probability but there is no competing non-radiative route.
12. A laser beam of wavelength 740 nm has coherence time 4 x 10~5 s. Deduce the order of magni
tude of its (a) coherence length, (b) spectral half-width and (c) the purity factor.
Solution:
(a) The coherence length,
I = xc
= 4 x 10~5 x 3 x 108 = 12 x 103 m
I* 12 km
■ --• . -
(6) The spectral width
with X = 740 nm and I» 12 km
Now Al«= 2^ X|V. « 0.45 x IO"16 m

12X103
Al-0.45 x l0"‘6m
(c) The purity factor,
Q=—
* AX
740 xl0~9
= 1.6 x IO10
0.45 xlO-16
= 1.6 x IO10
| e=i.6 x io10 |
13. A laser source of wavelength 6 x 10~7 m, coherence width 8 x IO 3 m and power 10 mW shines
on a surface 100 m away. Deduce the illumination. Compare it with that due to a collimated
beam from a torch filament of diameter 0.1 cm, lens of focal length 10 cm and power 10 W.
Solution:
The semi angle of cone of laser beams,
X 6xl0~7
= 7.5 x IO5 radian
a ~ 8 x 10'3
_ ... , Aj n(r0)2 -
Solid angle, Ato = -y = —,— = jtf)2
r r
= n x (7.5 x IO"5)2 = 176.6 x IO*10
Areal spread, AA = rÂco) = 1002 x 176.6 x 10“10 = 176.6 x IO-6
Illumination,
'. =---- = 10 x ------ —-------

= 56.6 W/m2
AA 176.6x10” 6
X = 56.6 W/m2
For the torch, the angle subtended by the filament size at the lens
O' = ^ = 10-2 radian
Areal spread, A A' = 7c(re')2 = 3.14 x 1002 x Ifr4 = 3.14

Illumination,
F 10
r2 = 777 = 777 =3.2 W/m2
2 AA 3.14
i.e., I2= 3.2 W/m2
(Zj/ZP = (56.6/3.2) = 17.7
i.e., 1^2=™
Optical Properties of Souos 747
14. A fibre-optic link is operated at a wavelength of 1.3 gm. Find the maximum bit-rate of a 25 km
line made from a multimodal step-index fibre. Given n, = 1.47 and n2 = 1.46.
Solution:
The dispersion for 1 km is
A M"!-";)
c
1000 x 0.01
= " Tv in8 = 3,3 x 10-8 or 33 nm
Thus the dispersion for 25 km is
At = At, VZ
where At, is the dispersion for 1 km
Now At = 33^25 = 165 nm
The maximum bit rate
R = (4At)-1
1 1
- (4At) “ 4xl65xl0‘9
i .e., R = 1.5 x 10*

15. What will be the critical angle for a ray in a step-index fibre for which = 1.53 and which has
a cladding whose RI is 2.5 per cent less.
Solution:
Formula used
0 = sin-1 —
|_ni J
2-5x1.53 -0 038
100
n2= 1.53-0.038 = 1.492
= 1.53
0c =77.2°
_____ _
CHAPTER 12
16. The angle of incidence for a ray in a step-index fibre for which nI = 1.5 is 11°. Compute the
refractive index of the cladding material.
Solution: i + 0C = 90°
Now
79° = sin-1
or [ —1= sin 79° = 0.982
n2 = n, x 0.982= 1.51 x 0.982
\ = 0.982
17. The refractive index of the core in a step-index fibre is 1.50 and the relative refractive index
difference between the core and the cladding of the fibre is 1.8%. Estimate (a) the numerical
aperture (NA), (b) the critical angle at the core-cladding interface within the fibre.
Solution:
(a) An = = 0.018 and n. = 1.50

1
n2 = 1.50-0.018 = 1.482
NA = [(«! + n2)(n}- nJ]”2 = 0.23
The numerical aperatttre of the fibre is 0.23 - <
1-482
(b) sin 0 = — = —— = 0.988;
c H] 15
0C = sin-1 [0.988] = 81°

The critical angle at the core
Cladding interface is 81°

Miscellaneous Topics
Gaseous Insulating Materials

Air, nitrogen, hydrogen, neon and argon are some important insulating materials available in nature.
Electronegative gases such as freon and sulphur hexafluoride are also used. They are cheap and are
easily available. Nonflammable and non-explosive. Air is the most commonly used dielectric and is
used as insulator in the following applications:
(z) Overhead transmission lines.
(zz) Air condensers.
(Ui) Plugs, switches and various electrical machines and apparatus.
Liquid Insulating Materials

Insulating liquids are generally used as an insulating and heat transfer medium or purely dielectric
purpose in order to eliminate air or other gases and there by obtaining improved dielectric strength.
Generally, insulating liquids are used in conjunction with solid insulation. Broadly, the liquid insulating
materials may be classified as
1. Minerals oils (petroleum oils)
2. Askarels
3. Silicon liquids
4. Fluorinated liquids
5. Synthetic hydrocarbon liquids
6. Organic esters
7. Vegetable oils.
-20°C to 150°C is the temperature range under which the above liquids are used as insulating
materials.
Minerals oils are derived from crude petroleum. After distilling off the lighter fractions (gaso-
lm, petroleum, naptha, kerosene) in the process of crude oil distillation 'masulf, a petroleum residue is
obtained which renders various oils after further distillation. Thus mineral oil is the final product of
refining a certain oil fraction. Among the important electrical insulating products derived from the
Crude petroleum are the insulating oils (used in cables, capacitor, transformer and switch-gear application),
electrical grade impregnating waxes and petroleum and asphaltic compounds, varnishes and sealing
compounds. The said oil in transformers is some times known as transformer oil.
740
_—
Transformer Oil
The transformer oil in the transformer has a vital role in the performance and life of the unit. Some
requirements of the oil are as follows:
(0 To provide high dielectric strength.
(ii) To permit good transfer of heat i.e., heat dissipating media.
(iii) To be of low viscosity.
(iv) To have high flash point
(v) To prevent corrosion of insulating material of the transformer.
(vi) To ensure long life and chemical stability.
Transformer oil is a special mineral oil with high dielectric strength. This oil is used for insulation
and cooling of transformer. The oil should be prefectly free from moisture because presence of even a
trace of water in it reduces its insulation strength considerably. The oil is undergone the process of
dehydration periodically to remoe moisture contents from it. Sludge formation takes place in the oil due
to moisture, dirt or some foreign matter in the oil which is harmful. So the oil is to be tested at regular
intervals to know its qualities.
The transformer oil serves the following two main purposes:
(a) It transfers heat by convection from the windings and core to the cooling surfaces.
(b) It maintains the insulation of the windings.
While the oil is in service in the transformer, a sludge is formed which is an oxidation product.
Sludge formation is accelerated by the contact with air and temperature. Sludge is also caused by the
presence of acids and alcohols. Sludge formation produces the following effects:
(a) Rate of heat transfer is reduced.
(b) Ducts are clogged.
(c) Operating temperature increases.
Properties of Transformer Oil
(0 Dielectric strength 40 kV per mm when applied for one minute.
(ii) Flash point 160°C.
(Hi) Sludge value per cent 1.2 (the percentage of insoluble matter formed when the oil is heated
and oxidised).
(iv) Pour point 40°C.
(v) Specific gravity 0.88.
(vi) Dielectric constant 2.2.
(vii) Acidity after oxidation 0.5.
The transformer oil should possess the following properties:
(i) Non-inflammable.
(ii) Non-sludging.
(iii) High insulation resistance.
(iv) Low evaporation.
(v) Better mobility and penetrating quality.
(vi) Easily available in sufficient quality.
(vii) Low cost.
(viii) High thermal conductivity.
_______ MtscaiANtous Toho 751
I he following laboratory tests may be curried out on the transformer oil for determination of its
r 13
properties:
(i) Moisture test.
:
(ii) Acidity test.
(Hi) Dielectric strength test.
(iv) Sludge resistance test.
When insulating oil is in circuit breakers it serves two purposes i.e., it provides insulating property
and helps in quenching the arc produced when the contacts are opened or closed. It acts as a fire
extinguishing media. Nowadays synthetic oil is used as an insulator in transformers in place of transformer
oil (mineral oil) because synthetic oils are very much resistant to oxidation and fire hazards.
Fibrous Insulating Materials

These materials are having alongated particles called fibres in their structure. They are mechanically
very strong and cheap. They are textile materials. They are having high hygroscopicity and this is the
drawback. Some examples are wood, papers, cardboards, cotton, jute, silk, rayon, nylon, adhesive tapes,
asbestos, fibre glass. Some of them are discussed here.
Wood
Density of wood is 103 kg/m3 and its tensile strength is 800 x 1300 x 104 kg/m2. It is frequently used for
low voltage installation. It is very hygroscopic and after absorbing moisture tends to lose markedly its
mechanical properties. Because of the above limitations wood in rarely used as such. Whenever it has to
be used as an insulating material it is impregnated in oil. Because the wood is cheap, easily available
and easily fabricated, it is used as structural material for transmission and distribution poles. It is also
used for switch boards, round blocks, casing and capping and handles of tools.
Paper and Cardboard
The paper is manufactured form coniferous wood. The organic contamination like lignin and pantosans
must be properly removed. Some alkaline reagents are added in the crushed wood which is then boiled.
The material is then formed in to papers. The process is called sulphate process. Unimpregnated paper
is used in telephone cables and capacitors. Cardboards are sheets of shorts fibres. They are either resilient
or stiff. They are used for slot liners in electrical machines, coil frames and as insulation in oil immersed
transformers.
Asbestos
ft is a mineral (naturally occurring) material of fibrous structure. The larger the fibre, the higher is the
grade of asbestos and greater is its cost. These fibres are strong and flexible and some varieties are
CVen suited for spinning into different textiles. Asbestos finds extensive use in electrical machines
because of its ability to withstand very high temperature. It can bear a temperature of about 400°C
without any considerable change. Asbestos is also used for making cloth types, paper boards for
•Mutation purposes. Asbestos materials are impregnated because it absorbs moisture. Its dielectric
“trength is 3-5 k V/mm. The main applications of asbestos:
(0 In low voltage work as insulation in the form of rope, tape, cloth and board. For these purposes
asbestos is properly impregnated with a liquid or solid like resin. Proper impregnation improves
the mechanical and electric properties.
_____
(if) It is used as insulation in wires and cables under high temperature conditions, in coil winding
and in end-cum insulation in motors and generators, and layer insulation in transformers.
(in) It is used as arcing barrier in switches and circuit breakers, etc.
Cotton and Silk
Cotton is combustible and chars when heated, even without the presence of sufficient air or oxygen. It
is a porous material and soaks water rapidly. Moisture or humid air can also make it moist. Hence it is
not a good insulator. However it is used where flexibility is an important factor, very high temperature
are not reached and the atmosphere is not humid. Cotton covered wire is extensively used for winding
of small magnet coils, armature windings of small and medium sized machined, chokes.
Silk is more expensive than cotton but takes up less space and is, therefore, used for covering
windings in fractional horse power machines. Silk is less hygroscopic and has a higher dielectric strength
than cotton, but like cotton it requires impregnation.
Fibre Glass
Fibre glass products are less hygroscopic, possess good electrical and mechanical properties and sufficient
flexibility to get moulded into required shapes. For many applications fibre glass is impregnated with
materials like synthetic resin.
Adhesive Tapes
These tapes are widely used in wiring systems to cover the conductor where its original insulation is cut
out They must bear a temperature of 75°C for 24 hours. They should not have sulphur content otherwise
it will react with the copper conductor.
Impregnated Fibrous Insulating Materials

Almost all the fibrous materials used insulation are impregnated. Impregnation reduces hygroscopicity,
chemical and thermal degradation by which the fibrous materials become more useful for insulation.
Usually oils are used for the purpose of impregnation. Resins, drying oils, varnishes are also used for
impregnation of insulating materials. Oils used for this purpose are selected carefully depending on
requirements.
Insulating Resins or Plastic Insulating Materials

Plastic is an organic material and is found in many varieties. It can be easily moulded into any shape
through application of heat and pressure. Resin is the substitute word normally used in insulation
technology in place of plastic. The most common definition for plastics is that they are natural or
synthetic resins or their compounds. Most of the plastics are of organic nature composed of hydrogen,
oxygen, carbon and nitrogen. Natural resins are derived from plant and animal sources. The use of
plastic insulating materials is so common that probably it amounts to more than that of the use of all
other insulating materials combined together. Standard forms in which plastics available include moulding
powers, sheets, rods, tubes films and liquids. The properties common to most of the plastics are Io*
price, a wide range of colours, toughness, water resistance, low thermal conductivity, low electrical
conductivity, light weight.
Plastics or Resins can be of Two Types
1. Natural resins
2. Synthetic resins.
Natural Resins: 1 hey are available in nature and arc derived from plant and animal sources.
Simple purification or sometimes a little chemical modification is all that is required to make use of
natural resins in electrical insulations. Examples of natural resins are lac, cosein, amber, shellac, wood
resin etc.
Synthetic Resins: The resins which are prepared artificially by the recurring chemical reaction
of a simple organic compound are called synthetic resins. During the reaction the molecules of the
simple organic compound combine together to form a high molecular weight composition. This reaction
is called polymerisation.
Classification of Synthetic Resins (Plasties)
Resins are divided into two main groups:
1. Thermosetting resins (it is hard, rigid and does not soften when heated).
2. Thermoplastic resins (it is soft and melts easily when heated).
1. Thermosetting Resins
The thermosetting resins are formed by the intermedia products which under the influence of heat,
pressure etc. undergo chemical changes of condensation and polymerisation to form a rigid final shape.
They require heat and pressure to mould them into shape. When heat is applied, they first becomes soft
and plastic and on further heating they undergo change and set hard. The process is called thermosetting
or thermohardening, when a material is thermoset, it is permanently set and does not soften to any
appreciable extent when being heated. However, intense heating will being about the breakdown of the
material by burning.
The thermosetting materials under a chemical change when moulded and cannot be resoftened
by heating to reshape them. Compared to thermoplastics, thermosetting materials are harder, mechanically
stronger and are suitable for use at higher temperatures. These materials are less flexible and have heat
resisting properties. The moulding temperature for the thermosetting are usually considerably higher
than for thermoplastics. They are widely used for telephone receivers, radio and television cabinets,
switch boxes and electrical outlets. Proper fillers and reinforcing materials are added to thermosetting
to improve various properties. Commonly used fillers and reinforcing materials are wood, flour, rag
fibres, chopped glass fibre, mica, clay, magnesium oxide, aluminium oxide, etc.
2. Thermoplastic Resins
These materials are those resins or plastics which soften on the application of heat, with or without
pressure but they require cooling to set them to shape. When heated thermoplastics begin to soften at
temperatures as low at 140°F and then can be moulded without any change in chemical structure.
Plastics materials which soften and melt retain certain flexibility and are called thermoplasts,
^y are produced artificially from original substances like oil and coal products. Filler like soot, mica,
textile, wood, glass fibres are often added to achieve certain desired properties. They are widely used
Ôr floor tiles, walls, fluorescent light reflection, lenses etc.
A composite is an admixture of two or more materials to achieve a combination of properties not

()tberwise possible by using any of the materials alone. For example, the properties needed in most
754 Souo State Physics
structural materials are high strength or high modulus and low weight along with good toughness. High
strength or high modulus and light weight are attained in glass, silica, carbon, boron etc., in the form of
fibres. But they may not possess high toughness or ductility. They easily undergo fracture which is
caused by a rapid progress of a small crack. If, however, high quality fibres of these materials are
produced and embedded in a ductile matrix (like a metal or plastic matrix) the composite has a combination
of high toughness with high strength and low weight. The soft and ductile matrix protects the surface of
the fibres from acquiring cracks and also arrests the propagation of cracks already present. Such composite
materials are called fibre reinforced composites. In addition, composites can be developed by dispersing
particles in a matrix (particulate composites) or by constructing a structure with layers or sheets of
different materials (lamellar composites or laminates). There are many natural or organic materials
which can be classified as composites. Wood, bamboo, bone and tooth are typical examples.
Fibre Reinforced Composites

In these, fibres usually of length, 1 to 10 pm, are the load bearing component. The matrix mainly
transmits the load to fibres. It further protects the fibres from formation of cracks on the surface. The
matrix being soft prevents the spreading of the crack from one fibre to the next. The interfacial bond
between fibre and matrix must be strong.
The volume fraction of the fibres can be as high as 90%. The strength ac and Young’s modulus
Ee of a composite can be calculated from the following formula:
Ec =EJf Vjf+Emm
V
V=l-y
m_________ J ■ .
where the subscripts f and m refer to fibre and matrix respectively. It is assumed that the fibres are
aligned in the direction of loading.
Fibrous composites can retain their strength up to very high temperature, usually 0.9 times the
melting point of the matrix in degree kelvin. The combinations of fibre and matrix are glass and epoxy;
boron and epoxy, carbon and aluminium, boron and aluminium. Important applications of glass fibre
reinforced plastics (GFRP) are used in boats, helmets, rifle tubes and helicopter rotor blades.
Particulate Composites
Here the matrix is the load bearing constituent. The hard or stiff phase that is dispersed strengthens the
matrix and makes plastic deformation difficult. Typically the particle size would be 0.01 to 0.05 pm.
The volume fraction of the hard particles is low, usually about 2 to 5%. The disper solid increases the
recrystallisation temperature of the matrix. Particulate composites or dispersion hardened materials can
withstand very high temperatures (0.7 - 0.8 times the melting point of the matrix). Typical examples of
such composites are sintered aluminium powder (SAP) with dispersion of A12O3 particles in aluminium
and thoria - dispersed nickel (T D nickel).
Problem
Calculate the Young’s modulus of a composite with glass fibres reinforced in phenol formaldehyde
plastics. The volume fraction of plastics is 33.3%. The modulus of glass fibres is 6.9 x 104 MPa and that
of polymers 6.9 x I02 MPa.
Miscellaneous Topics 755
Solution
CHAPTER 13
EcL = VE+ Vmm
J j
£
2 1
= - x 6.9 x 104 + - x 6.9 xlO2
= 4.6 x 103 MPa
Laminated Composites
Laminates are thin sheets of one material bonded to a second material to form a layer composite. Such
composites have good mechanical properties in all directions of the plane. For instance in plywood
layers of wood are stacked so that grain direction of one layer is at right angles to the directions in
adjacent layers. The layers are then bonded with epoxy resin. Since wood has greater strength along the
grain compared to the strength across the grain, wood does not have uniform properties in a plane. By
forming plywood we are able to achieve a product of uniform or non directional strength. Another
example is laminated plastics where woven mats of fibre glass are bonded by a resin.
Undirectionally Solidified Eutectics

Certain alloys of eutectic composition on solidification in a slow manner can develop a structure in
which one of the phases get aligned in a direction in the form of rods or plates. For instance it is possible
to produce rods with particles of a phase aligned along the length of the rod. Such composites can attain
high strength in certain directions. A typical example is an alloy aluminium with 33% copper in which
CuA12 particle is aligned in a particular direction.
Wood
Wood is a natural composite. It consists of numerous cells with cell sap and cell walls. The cell walls
contain basically cellulose and lignin. Both cellulose and lignin are organic polymers with high molecular
weight. During the growth process, the cells are elongated in the longitudinal direction of the wood.
Further wood can absorb moisture. The important characteristics of wood are the anisotropy or
directional nature of its properties such as Young’s modulus and dimensional change due to absorption
of moisture and tensile strength. The properties are usually measured in the directions longitudinal,
radial and tangential. As an example, Young’s modulus along these directions are approximately as
follows:
E,long = 7000 - 14000 MPa
£rad. = 550 - 1000 MPa
£tan = 400 - 700 MPa
The properties of wood can be improved by several methods. One method is the formation of
Plywood. Another method is to fill the pores in cells with a polymer resulting in impregnated wood.
“This piece of the review work on Nanomaterials is absolutely on the basis of data collected by the
author of this book from many journals and several standard textbooks on this subject. The author does
not claim any right over the subject matter presented here for the use of undergraduate students in
Science and Engineering pursuing their course in Indian Universities”. The field is new to him and he
is away from centres doing some work on this area. Hence, the author is doubtful of the format of the
consolidation of this topic and its justification.
In the line of Thirukkural "Nanotechnology is the science of understanding the structure and
behaviour of materials at the atomic or molecular level”. It is the world of atoms, molecules,
macromolecules, quantum dots, and macromolecular assemblies.
Abstract’. Prefix denoting 10“9 is called nano. The symbol used
is n. Thus 1 nanosecond (ns) = 10"9 second. Similarly, 1 nanometre (nm)
= IO-9 metre. Technology involving sizes of only a few nanometres is
nanotechnology. A form of carbon in which the atoms are linked by a
cylindrical framework with diameter of only a few nanometres is a
nanotube. It is also known as a bucky tube.
Any one of several forms of carbon made up of many atoms
bonded together in a polyhedral structure of pentagons and hexagons of
60 (70, 240, 540, etc.) carbon atoms is called buckminister fullerene.
The illustration shows one with 60 carbon atoms. The substance was
first discovered by Richard Smalley and associates in 1985, when graphite was blasted with high-power
laser. The module, C^, was named buckministerfullerene in honour of Richard Buckminister Fuller,
who built a geodesic dome with a similar structure at the Expo’, 67 in Montreal. Informally, the molecules
are known as buckyballs or fullerenes. The substance is a yellow crystalline solid called fullerite.
Derivatives of fullerene have been made, the more known being buckytubes.
In the IT field, Nanotechnology is expected to revolutionize the development of nanoscale
components through which we can have smaller and faster computers with larger memories. This may
be possible through hardware components like carbon Nanotubes, Scanning Probe Microscopes (SPMS)
and Atomic Force Microscopes (AFMs). Another area which can benefit through Nanotechnology is IT
Security.
Preamble-. In 1959, the great physicist of our time Prof. Richard Feynman said that nothing in
the laws of physics prevented us from arranging atoms the way we want: " ... it is something, in
principle, that can be done; but in practice, it has not been done because we are too big. He was particularly
interested in the possibility of denser computer circuitry and microscopes that could see things much
smaller than is possible with “scanning tunnelling microscope’’, and there are other important examples.
Although Feynman’s talk did not explain the full concept of nanotechnology, it was K.E. Drexler who
envisioned self-replicating ‘nanobots’, i.e., self-replicating robots at the molecular scale, in engines of
creation.
interest”# Observation of Dr Pillai on Prof. Feynman
CHAPTER 13
On receiving the Nobel prize Feynman visited the school where he studied. He requested “that time
principal to show him the old records of his performance during his stay in that campus. The Principal
with reluctancy replied that he was poor in all the subjects at all times. Feynman joked that one of the
conditions to earn Nobel prize is that one should be poor in his school career. Since it is a joke we take
it easy; otherwise it is untrue in many cases.
Introduction
All about rearranging atoms whichever way we want is nanoscience. The technique used for manipulating
atoms and molecules to fabricate materials, devices and systems is known as nanotechnology.
The common method used to understand the chemistry and physics of materials till recently was
studying large and complex structures, and then investigating the size and shape of the fundamental
building blocks of the structure that are usually simpler and smaller; this basic approach is sometimes
called ‘top-down’ science.
However, high power scanning microscopes and special types of probes help the scientists to
have clean observation of individual atoms and molecules. Thus, it has become possible to manipulate
and move atoms and molecules to form new structures, and, thus design new materials that are built
from atomic level constituents. It is also known as materials by design. This ability with utmost care in
arranging atoms provides opportunities to develop mechanical, electrical, magnetic and other properties
that are not otherwise possible. This is term ‘bottom up’ approach and the study of the materials is
‘nanotechnology’. The prefix nano tells that the dimensions of these structural entities are on the order
of a nanometre (10-9 m). Less than 100 nanometre is approximately 500 atom diametre. The one common
example of a material of this type is carbon nanotube.
Nanoscience and Nanotechnology
When we talk about “materials science”, we normally mean ceramics or crystalline materials, glasses
or non-crystalline materials, polymers or heavy chain molecular materials and metals or cohesively
bonded materials with applications in diverse fields.
However, the world of materials is rapidly progressing with new and trendiest technologies, and
obviously novel applications. Among modem and sophisticated technologies, nanotechnology may yield
more than the expected results.
Nanoscience and nanotechnology will take you with all confidence through a world that exists at
nanoscale. This technology offers us to minimise the dimensions of many devices and circuit systems to
nanoscale range making them even smaller but with greater efficiency. The techniques emanating us for
manufacturing products from atoms or molecules instead of form bulky materials. One common basic
Principle is that many of the physical properties of the products from such microscopic particles (atoms/
molecules) wholly depend on how the small cluster of atoms are lined up or arranged. One may get
diamonds from coal, if the atoms of this black coloured solid are arranged in a particular manner.
Computer chips are got by rearranging the atoms of sand by adding a pinch of suitable impurities. In
shon, the one main fundamental principle of nanotechnology is high position control. No doubt at the
Molecular level, the proposal of holding and positioning of molecules is new and shocking. However,
long ago as 1959 Richard Feynman, the Nobel prize winning physicist, said it is possible but not with
easiness.
758 Sooo State Physics
It is guessed that nanomechanics will be in use in the next one or two decades to manufacture
consumer goods at the molecular level, piecing one atom or molecule at a time to make baseballs,
telephones, etc. Nanotechnology is an umbrella term that covers many areas of research dealing with
objects that are measured in nanometre. A billionth of a metre is a nanometre or a millionth of a millimetre
is one nanometre.
Synthesis of nanoparticles, processing of the nanomaterials and the study of their properties and
applications is given the emigration name nanotechnology. Particles of sizes between 1 and 100 nm are
usually called nanoparticles or generally nanomaterials. Let us discuss on example: 10"9 metre is
1 nm = 10 A. Hence, 1 pm (1 micron) = IO-6 metre or 1000 nm. The radius of an oxygen ion in oxide
materials is 0.07 nm or of diameter 0.14 nm. Hence, seven oxygen ions in a linear direction will make
alert 1 nm which is the lower side of the nano range. Therefore, about 700 oxygen ions in a spatial
dimension will be the limit of the nano range materials (higher side).
In the usual and habitual language, when we talk about “materials science” and materials
technology, we normally mean ceramics or crystalline materials and metals or cohesively bonded
materials. In the case of the material ceramics, the trend is always to prepare finer powder for the
ultimate processing and better sintering to achieve dense fine grained microstructure of the particulates
with better and favourable properties for different applications. Usually, the degree of fineness goes up
to atomic of molecular level i.e., up to 1 nm-100 nm by special processing techniques. More is the
fineness, more is the surface area which in turn increases the reactivity of the material. Thus, the
densification or consolidation occurs very well at lower temperature than that of conventional ceramic
systems, which is finally “cost effective” and also improves the properties of materials like abrasion
resistance, corrosion resistance, mechanical properties, electrical properties, and a host of other properties
for applications in diverse fields. The deviation of phase diagram of nanomaterial form that of bulk
phase diagram is being exploited for forming some selected compositions of alloys. Another interesting
information is that the thermal stability of interfacial regions is typically less than that of the bulk
material: Thus the nanophase materials are often sintered or undergo phase transformation at temperatures
below those of the bulk material. This characteristic property, has numerous applications to material
processing. It is also found that nano phase materials have wide applications in the study of thin films,
electronic devices, photonics, bioceramics, biotechnology and medical instrumentation. However, one
should know that a knowledge of quantum mechanics is absolutely essential to know more about the
behaviour of nanoparticles and handle them to our taste.
Nanostructured Materials
Nanoclusters are clusters of atoms consisting-of typically hundreds to thousands on nanometre scale.
Such small groups of atoms (clusters) go by different names such as nanoparticles, nanocrystals, quantum
dots and quantum boxes. Extensive study of the nanomaterials over the past decade brings out remarkable
variations in fundamental electrical, optical and magnetic properties that occur as one progresses from
an “infinitely extended” solid to a particle of material with a countable (smaller) number of atoms or
molecules. The conclusion is that nanostructured materials has opened a new chapter and several
applications for short, medium and long term. Quantum wires, electron field emitters for ultra thin TV
screens, high resolution tips for scanning and atomic face microscopes, nanoelectronic devices.
_ __________________ ____ Miscellaneous Topics ■
nanoprobes, s^ns”rs; u'trahigh strength composites, gas storage, nanodevices, and parts of nanomachines
are some of the devices possible using nanostructured materials.
CHAPTER 13
Graphite
The crystal structure of graphite is distinctly different from the structure of the glittering diamond. Also
graphite is more stable than diamond at ambient temperature and pressure (see Fig. 13.2). Graphite is
formed by flat hexagonal layers of carbon atoms separated by 0.34 nm. The C—C distance is about
0.142 nm. a = 0.245 nm is the lattice constant and c = 0.680 nm. The inference is that structurally its
interplanar spacing (0.34 nm) is quite large compared to the plane interatomic spacing (0.142 nm).
Physically, its stiffness along the plane is quite large because of strong o bonds and in the perpendicular
direction it is weak because of the van der Waal’s force. The graphite structure is composed of layers of
hexagonally arranged carbon atoms; within the layers, each carbon atom is bonded to three coplanar
neighbour atoms by strong covalent bonds. Carbon when sp2 hybridised contains three strong 7t-bonds
which lie in a triangular plane with bond angle of 120° between them and one weakly bonding K-bond
perpendicular to the plane. Each carbon atom in the plane is covalently bonded to three others in plane
with strong o bonds of the sp2 hybridisation, this network forms a continuous sheet of carbon. The
fourth bonding electron participates in a weak van der Waals type of bond between the layers. As a
consequence of these weak interplanar bonds, interplanar cleavage is facile, which gives rise to the
excellent lubricative properties of graphic. Also, the electrical conductivity is relatively high in
crystallographic directions parallel to the hexagonal sheets. Graphite has metallic conductivity along
the plane and semiconducting property perpendicular to the plane. The anisotropy in conductivity is
about 103. The favourable property of graphite is, it is highly anisotropic solid.
Fig.13.2 Structure of graphite, illustrating sheet molecules connected by metallic bonds
Some Selected Properties of Nanomaterials

The sizes of the atom clusters (nanoparticles) that constitute the material decide the properties of
nanomaterial. It is possible to produce new materials with unique properties, if one can control the sizes
of nanoparticles. Atomic clusters, grain boundaries and interaction between the atomic clusters are the
sources to have unique properties.
Mechanical Properties
Most metals used for different purposes are made up of small crystalline grains. The boundaries between
the grains slow down or arrest the propagation of defects when the material is stressed, thus giving it
strength. If these grains can be made very small, or even nanoscale in size, the interface area within the
material greatly increases, which enhances its strength. For example, nanocrystalline nickel is as strong
as hardened steel.
Chemical Properties
As the nanoparticle size decreases, the inter-particle spacing decreases in metals and the surface area
increases. As a result, material properties change; for example, the melting point decreases with size.
The electronic properties are also affected leading to large changes in catalytic properties. Therefore,
nanoparticles can be arranged into layers on surfaces, providing a large surface area and hence enhanced
activity, relevant to a range of potential applications such as catalysts.
Magnetic Properties
A normal ferromagnet contains domains each containing several thousand atomic spins; within the
domains the spins are aligned in a straight direction while different domains point in different directions.
However, nanostructured magnetic materials exhibit totally new class of magnetic properties.
As the particle size decreases, the formation of domain wall becomes energetically unfavourable
and the particles are called single domain particles with a critical diameter. In this situation the
magnetisation changes do not take place through domain wall motion but require the coherent rotation
of spins resulting in large coercivities. Magnetic materials possess some type of anisotropy, which
affects their magnetic behaviour. The coercivity of magnetic material is proportional to the anisotropy
and so the high anisotropy of materials are preferred for high coercivity applications.
Fullerenes (Carbon 60)

Hary Kroto and Richard Smalley around 1980 discovered a new class of carbon material called carbon
60 (Cw). In the case of fullerenes, graphite acquires curvature due to the presence of pentagonal rings in
the hexagonal graphite sheet. The term fullerenes is given to any closed carbon cage. Generally, Cw are
spherical molecules about 1 nm in diameter, comprising 60 carbon atoms. In other words fullerenes
exists in discrete molecular form and consists of a hallow spherical cluster of 60 carbon atoms; a single
molecule is denoted by Cw. Each molecule is composed of groups of carbon atoms that are bonded to
one another to form both hexagon (six-carbon atom) and pentagon (five-carbon atom) geometrical
configurations. One such molecule (see Fig. 13.3), is found to consist of 20 hexagons and 12 pentagons
which are arrayed such that no two pentagons share a common side; the molecular surface thus exhibits
the symmetry of soccer ball. The material composed of CWJ molecules that contains sixty carbon atoms
in a network of sp2 bonding which forms a spherical structure, is known as buckministerfullerene, frorn
a number of perspectives, a molecule almost custom built for nanoscience. Discovered in 1985 by
Kroto et al., Cwis approximately Inm in diameter. The term fullerene is used to denote the class of
materials that are composed of this type of molecule. In general fullerenes are made up of hexagonal
and pentagonal rings o carbon arranged exactly as of an Indian football. Today we find the presence or
CHAPTER 13
existence of the fullerenes C%, C70, CW(, C|W based on fullerenes and few more members of geometrically
permitted fullerene family. These fullerene molecules differ in the number of hexagonal rings present.
When the number of carbon atoms change the shape of the molecule also changes. The C70 looks like a
ruby ball and C)20 takes a dumbbell shape. Diamond and graphite are what may be termed network
solids, because all of the carbon atoms form primary bonds with neighbouring or adjacent atoms
throughout the entirety of the solid. The common synthetic graphite is usually manufactured as
composites.
(b) (c)
(a)
Fig. 13.3 (a) The structure of C60 molecule (fe) Structure of fullerene C,o (c) Buckyball 60 atoms
At present, many methods are available to prepare molecules in large quantities, so the study
of this molecular form of carbon is advancing in all areas. As a pure crystalline solid, this material is
electrically insulating. However, with proper impurity additions, it can be made highly conductive and
semiconductive. Presently, we know that doped with alkali metals become superconducting with Te
- 50 K. Fullerene research has got immense scope in nanoscience and technology. They find use in
catalytic chemistry, biomolecular recognition, as molecular sieves, nanoreactors, etc.
Carbon Nanotubes
A form of carbon in which the atoms are linked by a cylindrical framework with diameter of only a few
nanometre is known as carbon nanotube. It is also known as buckytube. In the experiment, on the arc
discharge between graphite electrodes, along with the collected shoot particles there were some fine
'nbe like structures This on careful examination and analysis revealed that they are carbon nanotubes
<CNTs). Its structure consists of a single sheet of graphite, rolled into a tube, both ends of which are
«pped with C„ fullerene hemispheres. The tubes can be either open at their ends or capped at one or
b°d> ends with half a spheroidal fullerene. The following indicates a schematic representation of a
natbon nanotube:
(0
Kg. 13.4 The structure of carbon nanotubes
(a) metallic, (b) and (c) semiconducting
A nanotube is completely specified by what is referred to as a roll of vector which identifies its
helical nature and diameter.
Conclusion
Carbon nanotube (CNT) is a new form of carbon configurationally equivalent to two-dimensional
graphene sheet rolled into a tube. It is grown by different methods in the laboratory with a few nanometre
in diameter and several microns long. CNT exhibit extraordinary mechanical and electrical properties.
The Young’s modulus is about 1 tetra pascal. It is very stiff like diamond. The estimated tensile strength
is 200 Giga Pascal. CNT can be metallic or semiconducting and offers amazing possibilities to create
future nanoelectronic devices.
Some Production Processes of CNTs

Some well-known methods of producing CNTs are discussed below:
(a) Arc discharge
(b) Pyrolysis
(c) Laser vaporisation
(<f) Electrolysis.
(a) Arc discharge: The Fig. 13.5 given below supplies some details of producing CNTs by arc
discharge method. Here, the pressure used is 500 torr (while it is 100 torr in fullerenes), and secondly,
the nanotubes are found deposited in the cathode and not in the soot. This method produces well-
ordered multi-walled CNT (MWCNT) with diameters from 2 nm up to 30 nm. The separation between
graphite layers is around 0.34 nm, which is very close to that of graphite 0.335 nm. The length of these
nanotubes can be up to 30 p. The optimum conditions for generating nanolubes with this method consist
of using currents of 150 amp, voltage of 25 volt and graphite electrodes between 6 mm and
8 mm in diameter with a separation between them of 1 mm under helium atmosphere. The electric arc
reaction is too violent, so it is very difficult to control the formation reaction.
Helium in Manometer
Rg. 13.5 Arc discharge set up
(b) Pyrolysis method: This method consists of heating a hydrocarbon on a precursor which
contains carbon under the presence of a catalyst such as nickel, cobalt or iron. It was a kown fact that
carbon fibres could be obtained by pyrolytic methods using hydrocarbons (prior to the discovery of
C^.
It must be noted that carbon fibres are not nanotubes since the fibres are bigger in diameter and
exhibit a great amount of defects and impurities. One must note that the application of carbon fibres is
widespread, showing a strength comparable to steel.
It was found that (in 1994) carbon nanotubes could be aligned by embedding them in a polymer,
thus forming a composite material. When the polymer was cut, it was observed an aligned arrangement
of nanotubes. In this context,, a better alternative is to use laser ablation of cobalt thin films and then
pyrolyse them with an organic precursor such as 2-amino 4,6-dichloro-S-try azine. The nanotubes obtained
in this way are aligned in bundles which can grow up to 40 p and diameters between 30 run and 50 nm.
(c) Laser vaporisation method: The laser vaporisation method involves firing a high power
laser towards a graphite target inside a furnace at 1200°C. The condensation of material generated by
the laser is responsible for the nanotube formation. If we add nickel or cobalt to the graphite target, we
obtain Single-Walled Carbon Nanotubes (SWCNT). The SWCNT has diameter around 1.4 nm forming
a two-dimensional crystal with a lattice constant of 0.17 nm.
(d) Electrolysis method: Graphite electrodes inside a molten salt such as lithium chloride (700°C)
under an argon atmosphere is the basis of this method. Depending on conditions 20% to 30% consists of
nanotubes. The depth of the cathode and the current (3-10 amp) play an important role in the formation
of nanotubes.
Carbon: Symbol C. A non-metallic element belonging to group 14 (formerly IVA) of the periodic
table; Z = 6, MA = 12.011, m.p. = 3823 K. b.p. = 5100 K. Carbon has three main allotropic forms.
Diamond: (r.d. = 3.52) exists as very hard crystals with high refractive index and is prized as a
precious stone. It is also used in many cutting tools. It occurs naturally but can be produced synthetically.
The hardness is a result of the crystal covalent tetrahedron structure.
Graphite: (r.d. = 2.25) exists as a soft black slippery substance (also called black lead). It occurs
naturally but can also be synthesised. It has many uses such as conductors of heat and electricity, solid
lubricant, and in pencil lead (mixed with clay). The third crystalline allotrope is fullerite. There are also
various amorphous forms of carbon, e.g., charcoal. Carbon has two stable isotopes (nuclean number 12
and 13) and four radioactive ones (10, 11, 14, 15).
Semiconductor and Semiconductor Nanoparticles

A crystalline solid (e.g., silicon or germanium) with electrical conductivity between that of a conductor
and insulator, i.e., in the range about 105-10-4 siemen/metre. In a semiconductor, the energy bands
contain a narrow forbidden band across which electrons in the valence band can cross-over to the
conduction band when thermally excited. The electrons are thus mobile under the influence of an external
electrical field. The crossing-over of the electron leaves a positive hole in the valence band. The hole
behaves as though it were a “positively charged electron”, i.e., it is mobile under an electric field. In
effect, electrons and holes are the charge carriers in a semiconductor.
Semiconductor nanocrystals are the most important materials amongst the nanophase materials
due to their exotic band gap engineering behaviour. Silicon is the prime material in semiconductor
industry and is widely used in manufacturing of integrated circuits. However, because of indirect band
gap property it exhibits very weak luminescence and hence cannot be used for making optical devices.
In 1990, the nanocrystalline silicon was produced successfully from bulk silicon by electrochemical
anodisation. This silicon exhibits direct band gap type properties and was seen to emit light in the
presence of UV excitation at room temperature. This silicon is known as porous silicon. The porous
silicon emits light on excitation in the visible region corresponding to the band gap varying between 1.6
and 2.0 eV. Porous silicon finds numerous applications because of its optical properties and high surface
area. Porous silicon has very interesting biological applications because it is bio-inert i.e., it is biologically
stable and has a low degree of biotoxicity. It has also found its use in glucose monitoring systems.
The electric current in a semiconductor is carried by both ‘electrons’ and holes in semiconductors.
These electric charge carriers move differently through semiconductors with different compositions, so
we can make different sorts of semiconductor structure. Since the electrons and holes have opposite
charges they can attract each other and form ‘excitons’. These carriers do not move freely through the
semiconductor. The crystal lattice of atoms does affect their motion by making them more likely to
travel at certain speeds, but a perfect crystal will not cause them to be deflected. However, their motion
is affected by imperfections in the lattice, as well as by the phonons.
Maceuêovs Topics 76S
isjanoelectronics
CHAPTER 13
The Semiconductor Structures
If wc put two different semiconductor materials side by side, it is found that the electrons and holes will
have preference of one material over the other. If we visualise the electrons to be residing on a ‘cage ,
then we will find that electrons from one cage in one material can easily fall into an adjacent partially
filled cage on a lower band from another material, so that we can say that the electrons ‘prefer’ some
materials over the others. It is a kind of ‘friendship’ of the electrons in a cage of a given material with
the case of a second material. The holes also can do this, but since they are voids or gaps, they simply
fall upwards. By putting a piece of preferred semiconductor next to another, we can make a device
where the electrons will only want to travel in the direction of the preferred material thereby creating a
'diode*. By surrounding some preferred semiconductor by a different semiconductor, the ‘traps’ can be
created for the electrons and holes that lead us to a “quantum well”, a “quantum wire”, or a “quantum
dot”.
The Quantum Wells

A “quantum well” is a potential well that is obviously very small. This ‘well’ is like a cage in which the
carrier particles (z.e„ the excitions) can be trapped, in much the same way that light can be trapped
between the mirrors. By creating “layers of different semiconductors”, it is possible to make particular
‘layers’ to act as ‘traps’ for excitions. These “trapped particles” can be considered to be in “quantum
confinement”. (
Due to this particle trapping, the “quantum confinement effects” naturally restrict the motion of
the carriers in same way, i.e., restrictions on what the particles want to do. In a “quantum well”, the
excitons can move freely side ways in the plane of a “this layer”, but they might like to move in the
forward and/or backward directions as well. These particles are constrained or confined in the forward
backward directions i.e., a 2D confinement. For any particular sideways motion, there could now be
various ways in which the carrier is confined in the layer giving rise to quantum wells. These “quantum
wells” have many useful properties, since it is possible to exactly engineer the forward-backward
confinements, and since they are relatively easy to make. As a result, they are widely used to make
‘Semiconductor Lasers” and other useful devices. This “quantum confinement effect” can be taken
further and make semiconductor structures—that brings us to the “quantum wires" and “quantum
dots”.
Quantum Wires
Froni “quantum well”, we can go ahead one step further in the semiconductor structure* i.e., by making
not a ,ayer but only a thin ‘wire’ of the preferred semiconductors (i.e., a chain like structure). These
raPped excitons can now be considered to be in ID “quantum confinement”. In this case, an exciton is
1 y free to choose its trajectory along the wire.
General Properties of Carbon Nanotubes

are^1 °bservalion using high resolution transmission electron microscopy (HRTEM) reveals that CNTs
uiechXlra°rdinarily flexib,e- For example, they can be bent mechanically by an ultrasonic bath, by
an,cal milling, and by using a polymeric resin. Theoretical calculations predict this flexibility. The
first attempt to determine the stiffness of carbon nanotubes was when Treacy et al., used HRTEM to
measure the amplitudes of the vibrating tubes, to calculate indirectly the Young’s modulus. They found
that MWCNTs exhibit Young's modulates of the order of 1.8 tcra Pa (1 tera Pa = 1 x 1012 Pa), which is
higher than conventional carbon fibres (Ca 800 giga Pa). Direct measurement using Atomic Force
Microscopy (AFM) reveal that the Young’s modulus of MWCNTs is around 1.28 tera Pa. This high
Young’s modulus makes the nanotubes a very strong structure.
The first measurement of the electrical conductivity of CNTs were made using gold micro contacts
attached to the CNTs by lithographic techniques finding that the resistance depends on the temperature
and that in the range between 2 K and 300 K the tubes were semimetallic. Conductivity measurements
on aligned MWCNTs show that the material behaves as a nanoconductor. Also it has been confirmed
that depending on the diameter and helicity, carbon nanotubes can be conductors or semiconductors.
Single-Walled Carbon Nanotubes(SWCNTs) around 1.4 nm diameter exhibit quantum conductivity.
We may note that the atomic arrangement, i.e., the geometry of the structure, determines the mechanical
and electronic properties of CNTs. Nowadays, nanocrystals have been prepared. Ductility and strength
are the central mechanical properties of any material. They are determined by the physical nature of
plastic deformation, which is conventional, coarse-grained metals is mainly carried by dislocations line
defects of regular crystal lattice within individual grains. Study suggest, however, that the mechanism
of plastic deformation in nanocrystalline materials may be different and so may lead to novel mechanical
properties. Hardness or high strength are noticed in many nanomaterials. However, in most cases
nanomaterials have very low ductility, i.e., they fail when their shape is changed. Some even become
brittle when a deforming load (force or stress) is applied.
Luckily in 2002 Wang et al., reported their finding is engineering an unusual nanocrystalline
material that combines two useful properties that are often mutually exclusive strength and ductility.
They created a copper nanostructure by rolling the metal at temperature below 77 K and then heating it
to around 450 K. The result was a ‘bimodel’ structure of micrometre sized grains (at a volume fraction
of 25%) embedded in a matrix of nanocrystalline grains. The material showed extraordinary high ductility,
but also retained its high strength. The reason for this behaviour seems to be that while the nanocrystalline
grains provide strength, the embedded larger grains stabilise the tensile deformation of the material.
Processing nanomaterial to achieve both strength and ductility can enhance the material’s resistance to
fatigue. More than anything else, it is fatigue that at present limits the lifetime, and hence the range of
applications, of many advanced materials.
Scope of Applications
Nanocrystalline materials are three-dimensional solids composed of nanometresised crystallites or grains
on account of their unique structure, which is characterised by ultrafine grains and a rather high density
of crystal lattice defects, these materials have extra ordinary fundamental properties that could be exploited
to make “next - generation" superstrong materials.
The central mechanical properties of any material is its mechanical properties which are
determined by the physical nature of plastic deformation. The deviations from the bulk phase diagram
may be exploited to form certain compositions of alloys that are otherwise unstable in the bulk form. In
addition, the thermal stability of interfacial regions is typically less than that of the bulk materials: Thus
_ ___________________ _ __ ■Miscellaneous
the nanophase materials are often sintered or undergo phase transformation at temperatures below those
CHAPTER 13
of the bulk material. This is a characteristic property which has numerous application to material
processing.
By improving the properties of nanomaterials, we may be able to find better applications as
varied as semiconductor electronics, sensors, special polymers, magnetics, advanced ceramics, and
membranes. It is necessary to improve our current understanding of particles size control and
methodologies for several classes of nanophase materials and address the issues of their characterisation.
We should also explore the fields such as (i) Electronics of thin films, electronic devices like MOSFET,
JFET and in electrical ceramics (n) Bionics, (Ui) Photonics, (iv) Bioceramics, (v) Biotechnology, and
(vi) Medical instrumentation, etc.
Importance of Nanotechnology
The body of airplanes are made from aluminum despite the truth that the well-known diamond has a
strength to weight ratio about 50 times that of aerospace aluminum. Diamond is expensive, we cannot
make it in the shapes we want, and it shatters. It is untrue today. Nanotechnology will let us inexpensively
make shatter proof diamond (with a structure that might resemble diamond fibres) in exactly the shapes
we want. This may help us make a Boeing 747 whose unloaded weight was 50 times lighter but just as
strong.
We are well aware that travel in space today is very expensive and booked for an elite few or for
those who enjoy travel grants whether it is air planes or airships. But nanotechnology will amazingly
reduce the costs and increase the capabilities of space ships and space flight. The strength to weight
ratio and the cost of components are absolutely critical to the performance and economy of space ships.
The inventions in nanoscience and their applications will improve both the above said parameters by
one or two orders of magnitude. The benefits in these two parameters alone will improve the overall
cost/performance ratio by over three orders of magnitude leaving other advantages of nanotechnology.
Beyond inexpensively providing remarkably light and strong materials for space ships, nanotechnology
will also provide extremely powerful computers with which to guide both those ships and a wide range
of other activities in space. If you want the computer hardware revolution to continue at its current pace,
in another five to ten years you have to move beyond lithography to some new post lithographic
manufacturing technology. Making patterns on a resist and spraying chemicals around simply cannot
arrange atoms with the ultimate precision that should be feasible. More precise methods will be needed.
Ultimately, each logic element will be made from just a few atoms. Designs for computer gates with
less than 1000 atoms have already been proposed but each atom in such a small device has to be in
exactly the right place. To economically build and interconnect trillions upon trillions of such small and
precise devises in a complex three-dimensional pattern one may need a manufacturing technology well
beyond today’s lithography: One needs nanotechnology. With it, we should be able to build mass storage
devices that can store more than a hundred billion bytes in a volume equal to the volume of a sugar
i cube.
We know that, as on today ‘smart’ weapons are big and heavy i.e.. we have the “smart bomb’’
but not the “smart bullet”. In the years to come, even weapons as small as a single bullet could pack
more computer power than the largest supercomputer in existence today, allowing them to perform real
time image analysis of their surrounding and communicate with weapons tacking systems to acquire
and navigate to targets with greater precision and control. We will also be able to build weapons both in
expensively and much more rapidly, al the same time taking full advantage of the remarkable materials
properties of diamond. Rapid and inexpensive manufacture of great quantities of stronger more precise
weapons guided by massively increased computational power will alter the way we fight wars. Coal
and oil from the ground, dam across falls and river and nuclear fuels are the main sources to generate
power today. But the sunshine all around us in the most part of the earth for several months in a year can
provide orders of magnitude more power than we use. The principles of making efficient solar cells are
of high cost. But low cost solar cells and battery is beyond our reach now. But nanotechnology will cut
costs both of the solar cells and the equipment needed develop them. Solar power will then become
economical.
The other interesting point is, it is not the modem medicine that does the healing(always). but
the cells themselves. If we had surgical tools that were molecular both in their size and precision, we
could develop a medical technology that for the first time would let us directly heal the injuries at the
molecular and cellular level that are the root causes of disease and ill health. With the precision of drugs
combined with the intelligent guidance of the surgeon’s scalpel, we can expect a quantum leaps in our
medical capabilities.
Nanoscience, Nanotechnology and Medicine

It is the known practice of keeping clinically dead human body or brain at an extremely low temperature
in the hope of later restoring it to life with the help of future medical technologies. Cryonics is the
practice of preserving organisms, or at least their brains, for possible future revival by storing them at
cryogenic temperatures where metabolism and decay are completely stopped. Though still controversial,
it has greater potential to save lives than any other method that we can use today.
Generally, sicknessfor disease) and ill health are caused largely by damage at the molecular and
cellular level. Surgical tools and instruments used now are large and crude. From the view point of a
cell, even a fine scalpel is a blunt instrument more suited to tear and injure than heal and cure. Modem
surgery works just satisfactorily only because cells have a remarkable or wonderful ability to regroup
themselves, bury their dead ones and heal the wound or injury.
Manufacturing technology of the 21st century (nothing but nanotechnology) may help u-
economically build a wide range of complex molecular machines. Fleets of computer controlled molecular
tools much smaller than a human cell and built with the accuracy and precision of drug molecules. Such
tools will let medicine, for the first time, intervene in a sophisticated and controlled way at the cellulin
and molecular level. They could remove obstructions in the circulatory system, kill cancer cells, or take
over the function of such cellular organelles. Just as today we have the artificial heart, so in the future
we could have the artificial mitochondrion.
Bodies of beings one filled with intricate, active molecular structures. When those structures arc
damaged, health suffers. Modem medicine can affect the workings of the body in several ways, but
from a molecular viewpoint it remains crude indeed. But molecular manufacturing can construct
range of hospital instruments, machines and devices with far greater abilities. The body is actually
huge complex world of molecules. We can learn a lot to repair it with nanotechnology. The human bod)
can be considered as a work yard, construction site, and a war-field cum battle ground for molecular
CHAPTER 13
machines. It works or functions remarkably well, using systems so complex that medical science still
does not understand many of them. When we chew and swallow, muscles drive our motions. Muscle
fibres contain bundles of molecular fibres that shorten by sliding past one another. In the stomach and
intestines, the molecular machines we call digestive enzymes break down the complex molecules in
foods, forming smaller molecules for use as fuel or building blocks. Molecular devices in the lining of
the digestive track carry useful molecules to the blood stream.
In the lungs, molecular storage devices called hemoglobin molecules pick up oxygen. Driven by
molecular fibres, the heart pumps blood laden with fuel and oxygen to cells. In the muscles, fuel and
oxygen drive contraction based on sliding molecular fibres. In the liver, they drive molecular machines
that build and breakdown a whole host of molecules. The tale continues through all the work of the
body. Except for tooth filling and other artificial implants, everything in the human body is constructed
by molecular machines. They clear away structures that are old or out of place, sometimes using machinery
like digestive enzymes to take structures apart. Failures in reconstruction increase as we become aged.
We have to remember that the immune system does not respond to all invaders or responds
inadequately. Malaria, tuberculosis, herpes, and AIDS all have their strategies for evading destruction.
Cancer is a special case in which the invaders are altered cells of the body itself, sometimes successfully
masquerading as healthy cells and escaping detection.
The other part is that the immune system sometimes over responds attacking cells that should be
left alone. Certain kinds of arthritis, as well as lupus and rheumatic fever, are caused by this mistake.
Between attacking when it should, the immune system often fails, causing suffering and death even.
We are aware that diagnostic procedures vary widely, from asking questions to patient, looking
at X-ray shadows, through exploratory surgery and the microscopic and chemical analysis of materials
from the body. Doctors can diagnose many illness, but others remain mysteries. The two main forms of
treatment are surgery and drugs. From a molecular perspective, neither is sophisticated. Surgery is
direct, and manual. Surgeons tom tissues and skin to enable healing, cut out cancer, clear out clogged
arteries, and even install pacemakers and replacement organs. It is direct, but not safe always; anaesthetics,
infections, organ rejection, and missed cancer cells can all cause failure. The body works by means of
molecular machines, most working inside cells. Surgeons can see neither molecules nor cells, and can
repair neither cent per cent. Antibiotics- like penicillin are selective poisons. Viruses are a harder case
because they are simpler and have fewer vulnerable molecular machines. Cancer is the most difficult of
all and many a time they poison healthy cells of the patient while treatment. Drug molecules bind to
molecules in the human body and change the behaviour. Some decrease to secrete stomach acid, others
stimulate the kidneys, many affect the molecular dynamics of the brain.
Developments in nanotechnology will result in improved medical sensors. As protein chemist
Bill DeGrado notes, “Probably the first use you may see would be in diagnostics: Being able to take a
tiny amount of blood from somebody, just a pinprick, and diagnose for a hundred different things". In
the longer term, though, the story of nanotechnology in medicine will be the story of extending surgical
control to the molecular level.
MrH1 . .■■»«■*■■■»■*—■■ ■ *■■ ■■■ ■ ■ <■*' - ------------------------ ---- --------
Conclusion
A nanometre (nm) is one-billionth of a metre; a nm is about the width of six bonded carbon atoms
About a million nanometre will reach across the head of a pin. Our fingernails grow approximately
nanometre per sec.
Somr Sflecled Relations
• 1 inch = 25.400,000 nm
A red blood cell is 7(XX) nm in diameter and 2(XX) nm height.
A virus is 100 nm.
• Intel will be manufacturing devices by 2007 with feature sizes about 20 nanometre across.
• In two dimensions we could stack about 250,000 components in the same space as a red
blood cell,
• If the trends continue as far as 2017, which may be the end-point of "Moore’s Law”, we
could be looking at a manufactured device the size of the red blood cell with 256,000
components.
• If we add the third dimension, that could translate into 65,536,000,000,000,000 components.
• Somewhere along the way, we are talking about the raw technical capability to produce a
rather sophisticated robot small enough to wander around through your body doing whatever
it has been programmed to do.
• If we make the robot —the volume of a red blood cell, we are still talking about 655,
360,000 components, which is arguably perhaps enough to embody this machine with the
ability to think, move and do whatever we have programmed it.
Some Examples of Nano particles

L Nanoparticles of Tin Dioxide: The details of this important work is discussed here. The
emission intensity of the peak at 612 nm of the Eu3+ ions due to 5D0 -» 7F2 transition, activated by SnO,
nanocrystals were found to be sensitive to the nanoenvironment for both doped and coated samples.
The luminescent efficiencies of nanocrystals of SnO2-*doped’ by Eu?O were compared with those of
SnO2 ‘coated’ by Eu2O, and the intensities were found to be significantly higher for coated materials. It
was found from the measured luminescent intensity that Eu3+ ions occupy “low symmetry” sites in the
nanocrystals of SnO2 coated by EiÔ with relaxation rate much higher in the coated sample than in
doped sample due to the asymmetry of Eu3+ ions.
2. Nanoparticles of Cuprous Oxide: The Cuprous Oxide (Cu?O) particles coated with poly
acrylamide having diameters in the range from 4.8 nm to 8.6 nm were prepared by a chemical method
The optical absorption of these particles was found to be characterized by excitons with corresponding
energies varying from 2.6 to 2.25 eV in the above particles size range. A second optical absorption
maximum signifying surface states within the band gap is exhibited by the specimens with relevant
energies varying from 2.6 to 1.77 eV in this particle size range.
____ Muoujimbm Tones . 771
J. Nanoribbons of Zinc Sulphide: One-dimensional nanostructured materials set the pace of
CHAPTER 13
the recent trend in nanomatcrials research due to their wide range of potential applications in many
nanoscale devices. It is known that ZnS is an important semiconductor used as “phosphorus materials”.
Hence, some efforts have been made into controlling the size, morphology and crystallinity of the ZnS
crystals in order to fine-tune their physical properties.
4. Nanoparticles of CdS: 1 he optical and microstructural properties of nanocomposite thin
films based on the systems CdS-ZnO and CdS-AIÔ, were studied. These nanomaterials were synthesised
by solgcl technique. The molar ratio of CdS with ZnO and AI2O^ were varied within the range of 20 : 80
to 50 : 50. The nanoparticles of CdS that are highly confined with radius 1.8 nm to 4.7 nm. which were
estimated from the blue shift of the absorption edge, were obtained by using ZnO matrix, whereas for
A1,O, matrix the size varied from 2.8 nm to 7 nm. The microstructural characterisation by high resolution
revealed well-resolved crystalline nanoparticles in both cases.
1. Distinguish between atomic clusters and nanoparticles.

Answer: The general practice used by scientists for investigating the materials is to break them
into fundamental building blocks and grouping them (atomic clusters) and study them at each
stage. From the understanding of the basic interactions of atoms, attempt is made to explain the
structure and properties of bulk materials.
Nanostructured materials may be defined as those materials whose structural element, crystallites
or molecules have dimensions in the 1 to 100 nm range. Clusters of atoms consisting of typically
hundreds to thousands on nanometre scale are called nanoclusters (nanoparticles): others with
much greater dimensions are simply called clusters.
2. What is nanotechnology?
Answer: Here manufactured products are from atoms. The properties of those products depend
on how those atoms are arranged. If one rearranges the atoms in coal, he gets diamonds. If one
rearranges atoms in sand (and adds a pinch of suitable impurities), he gets computer chips.
3. Discuss the special properties of nanomaterials.
Answer: Many properties of nanomaterials are drastically different from the normal bulk materials
for two main reasons. First, nanomateriais have a relatively larger surface area when compared
to the same mass of materials produced in bulk. This can make materials more chemically reactive
and affect their strength or electrical properties. Secondly, quantum effects can begin to dominate
the behaviour of matter at the nanoscale affecting the optical, electrical and magnetic behaviour
of materials.
4. What are carbon nanotubes?
Answer: A carbon nanotube is a cylindrical rolled up sheet of grapheme, which is a single layer
of graphite atoms arranged in hexagonal pattem. Their hexagonal structure gives them great
tensile strength and elastic properties. The tubes are tough and when bent or squeezed, they
spring back to their original shape. They also transfer heat very efficiently. They can be made to
exhibit either metallic or semiconductor characteristics depending on the way they get folded.
5. What are nanostructured materials?
Answer: Nanostructured materials may be defined as those materials whose structural element,
clusters, crystallites or molecules have dimensions in the 1 to 100 nm range. Clusters of atoms
consisting of typically hundreds to thousands on nanometric scale are commonly called as
nanoclusters. These very small groups of atoms, is generally go by different names such as
nanoparticles, nanocrystals quantum dots or quantum boxes.
6. Give the salient features of nanotechnology.
Answer: Nanotechnology will offer greatly improved efficiency compared with electricity and
computers in every facet of life. It has dual use many commercial uses and military uses for
making more powerful weapons and tools of surveillance. Thus, it represents not only wonderful
benefits for humanity, but is also a matter of grave risk.
The important understanding of nanote clogy is that it offers not just better products, but a
vastly improved means of production. A computer can make copies of data files essentially as
many copies as you want at little or not much cost.
7. Explain the role of nanorobots when injected into human body.
Answer: A typical nanomedical treatment will consist of an injection of perhaps a few cubic
centimetre of micronsized nanorobots suspended in fluid (probably a water/saline suspension).
A typical therapeutic dose may include up tol-10 trillion (1 trillion= 1012) individual nanorobots,
although in some cases treatment may only require a few million or a few billion individual
devices to be injected. Each nanorobot will be on the order of perhaps 0.5 micron up to perhaps
3 microns in diameter.
The adult human body has a volume perhaps 100,000 cm3, and a blood volume of 5400 cm3, so
adding a mere 3 cm3 dose of nanorobots is not particularly invasive. The nanorobots are going to
be doing exactly what the doctor tells them to do, and nothing more. So the only physical change
you will see in the patient is that he or she will very rapidly become well again. Most symptoms
such as fever and itching have specific biochemical causes which can also be managed, reduced,
and eliminated using the appropriate injected nanorobots. Major rashes or lesions such as those
that occur when you have the measles will take a bit longer to reverse, became in this case the
broken skin must also be repaired.
Explain the Following Terms:
CHAPTER 13
$ Diamondoid, Assembler, Molecular manufacturing and Nanomachine.
Answer: Diamondoid: Structures that resemble diamond in a broad sense, strong stiff structures
containing dense, three-dimensional network of covalent bonds, formed chiefly from first and
second row atoms with a valence of three or more. Many of the most useful diamondoid structures
will in fact be rich in tetrahedrally coordinated carbon.
Assembler. A general purpose device for molecular manufacturing capable of guiding chemical
reactions by positioning molecules.
Molecular manufacturing: Manufacturing using molecular machinery, giving molecule by
molecule control of products and by products via positional chemical synthesis.
Nanomachine: An artificial molecular machine of the sort made by molecular manufacturing
9. How nanorobots be retrieved from the body?
Answer: Some nanodevices will be able to exfuse themselves from the body via the usual human
excretory channels; others will be designed to allow ready exfusion by medical personal using
apheresis like processes or active scavenger systems. It is very design dependent.
10. Explain with crystal structures the salient features of graphite and fullerenes.
11. Discuss two methods of synthesis of nanomaterials.
12. What are the different methods for the production of CNTs? Briefly discuss them.
13. Mention some important mechanical and electronic properties of CNTs. Discuss briefly quantum
wells, quantum wire and quantum dot.
*■*1 iiiiJ-iiitritiiiii'iiiinj-WLJiLJjijmm! urn i. .wiwimiix jjiiiim
1. L. Pauling, General Chemistry, Dover, New York (1988).

2. S. Kar, S. Biswas and S. Chandhuru, Zinc Sulphide Nanoribbons, Proc. Natl. Conf, on Nano Science and
Technology, Kolkata (India), January, 2005.
3. M.S. Dressethas, et al.. Science of Fullerenes and Carbon Nanotubes (San Diego, CA: Academic 1996).
4. P. Moriarty, Nanostructured Materials, Rep. Prog. Phys. 64, 297 (2001).
5. S.L. Kakani and Amit Kakani, Materials Science, New Age International (P) Ltd.. New Delhi, 2006.
6. BPS Publications, New Delhi, A Future Technology with Visions (2006).
Note: Thirukkural is an ancient treasure provided by the virtuous poet Thiruvalluvar with 1330 verses
each in two lines in his mother tongue (Tamil) with the sole purpose of inculcating in us rationalistic
habits with all goodness to practise.
Tables
Thble 13.1 Temperature coefficient of permittivity of some substances
Material Temperature dependence of permittivity, Tce
Methyl alcohol - 0.0059 / K

Ethyl alcohol - 0.0057 / K
Chloroform -0.0041 /K
NaCl + 8.4 x 10-4/K
KC1 + 3.03 x 10-5 / K
Table 13.2 Electronic polarisability of some selected atoms
Sl.No. Material Electronic polarisability ae in 10“ 40
1. He 0.12
2. Ne 0.35
3. Ar 1.43
4. Kr 2.12
5. Xe 3.54
Table 133 The electric strength of some materials
Material Electric strength kV/metre ., s

Air 3000
Mineral oil 15000
Impregnated paper 15000
Polysterene 20000
Hard rubber 21000
Bakelite 25000
Glass 30000
Fused quartz 30000
Mica 200000
Table 13.4 Properties of some ferroelectric materials
SLNo. Material Curie temperature Electronic polarisability

‘ <• • ae in 10^> ' j
1. NaK (CÔ^. 4 H,0 290 8000
2. KH2PO4 123 16000
3. > Ba Ti O3 380 78000
4, KNbO3 708 80000
5. WO3 220 .—
6. Cd Nb2 O7 185 5400
MisdeuANGOi* Tdmc*
Table 15.5 General properties of mineral insulating oils
CHAPTER 13
Oils used in paper insulated Oil used in transformers,
properties Oil used in capacitors
cables switches, circuit breakers
Specific gravity 0.93 0.885 0.885
Flash point 235°C 165 °C 135°C
Pour point -5°C - 45°C - 45°C
Resistivity (Q cm) (I to 10) x 1012 (50 to 100) x JO12 (1 to 10) x 1012
Dielectric strength 30 kV 30 kV 30 kV
(kV/mm)
Power factor at 1OO°C 0.001 0.001 0.001
at 50 Hz
Specific heat 0.412 0.4252
Table 13.6 Properties of polyethylene
Properties Low density polyethylene High density polyethylene
Dielectric constant (at 10 Hz) 2.28 - 2.32 2.25 - 2.32

Dielectric strength (kV/mm) 20-160 20-160
Power factor (at 60 Hz) (1 to 5) x 10-4 (2 to 6) x 10-4
Tensile strength (kg/cm2 x 10~3) 0.09-0.16 0.16-0.365
Surface strength (£2) 1014-1017 1014-1015
Volume resistivity (Q cm) 1017-1019 1015-1016
Water absorption (%) Less than 0.01 Less than 0.01
Elongation (%) 110-160 40 - 300
Softening temperature (°C) 94-110
Specific heat 0.55
Relative density 0.91-0.925 0.95 - 0.97
Crystalline melting point (°C) 110-1160 126 - 136
Table 13.7 Properties of polystyrene resin
Properties ‘ ’ Value .
Dielectric strength (kV/mm) 20-28

Power factor (60 Hz) 10 to 30 x 10~5
Dielectric constant (60 Hz) 2.55
Insulation resistance 1017- 1019
Tensile strength (kg/cm2 x IO-2) 0.35 - 0.65
Compressive strength (kg/cm2 x IO-2) 0.78-1.12
Elongation % 1-3.5
Maximum temperature for continuous use (°C) 65-80
Molecular weight 6 x 104 - 50 x 104
Water absorption % 0.03 - 0.06
Specific heat 0.32
Specific gravity 1.06
Table 13.8 Properties of polyvinyl chloride
Properties Value
Temperature of use (°C) 60 - 90

Insulation resistance (Q cm) IO12 - IOn
Brittle temperature (°C) 30
Softening temperature (°C) 12.0
Dielectric constant 5-6
Dielectric strength (kV/m) 30
Table 13.9 Properties of polyamide resins
,.3Properties ./i < • .. /. . Value

Tensile strength (kg/cm2) 0.5 x itr3
Dielectric strength (kV/mm) 20
Dielectric constant (60 Hz) 4-6
Maximum continuous strength 132-150
Melting point (°C) 200 - 255
Table 13.10 General properties of two main types of mica
A '■ >;V- Muscovite-mica

Specific gravity 2.7 - 3.2 2.6 -2.8
Tensile strength (kg/cm2 x 10r3) 0.35 - 0.7 -
Maximum operating temperature 500 - 600 800 - 900
Moisture absorption Low Low
Resistivity at 25°C (Q cm) 10l5-1016 1012 - 10’4
Dielectric strength (kV/mm at 25°C) ' 80 60
Power factor at 27°C________________ 1 x IO"4-3 x 10*4 io x i(r4-5Qx itr4
Table 13.11 Properties of some types rubbers
- >------- - •*.- .'.I.- ,
Natural Nitrile
Properties Hard rubber Butyl rubber Neoprene Silicon Hypalon
k . rubber -j butadiene
i. Maximum service 75 60 80-90 90 - 175 - 200 150

temperature (°C)
2. Water absorption % 1-2 0.2- 1.0 0.3 - 0.5 3-4 - 0.5 - 2.4 -
3. Specific gravity 0.93-1.6 1.1 - 1.4 0.9- 1.3 1.09-1.6 1 0.5 - 2.4 -
4. Tensile strength 0.21 - 0.32 0.28-1.12 0.05-0.21 0.14-0.26 0.19-0.32 0.09-0.12 0.11 -0.26
5. Dielectric strength (kV/mm) 18-24 12-28 16-32 4-20 16-20 12-28 16-24
6. Dielectric constant 2.7-5 2-16 2.1-4 7.5-14 3.9- 10 2.8 - 7.0 5-11
7. Power factor 0.05-2 x IO'2 0.5-2 x 10~2 0.3 - 8 x IO2 1.0-6 x IO"2 3-5x 10~2 0.1 - I x IO"2 2-9x (O'2
8. Volume resistance (Q cm) IO15 - 1017 1014 1014 — IO16 1011 - 1012 1012 - IO15 10,J- 1017 IO13 - IO15
9. Surface resistance (Q) IO14 — IO*5 - 1013- 1014 10" - IO'2 1012- 1015 IO13 10u
CHAPTER 13
7^8 Soud Swoe Pwwks
Tahir 13.12 Insulating materials for different applications
SLNo. Application Insulating material used
1. Heating element of an oven Nichrome
2 Fuse holder Porcelains
3. Switch for domestic purpose Bakelite
4. Commutator Mica
5. Cable joint box Bitumen compound
6. Electric iron Mica
7. Low voltage cable Rubber
8. Flexible wire Plastic
9. Distribution board Wood
10. Laminating insulating boards Epoxy resins
Table 13.13 Questions with answers in Yes or No
SLNo. Question Answer
1. Brass can stand more mechanical above that copper and is used for No
making flexible wire
2. Steel is not used as conducting materials in domestic switches Yes
3. Nichrome is preferred for winding chokes in tube lights No
4. P.V.C. insulation does not absorb moisture Yes
5. Hydrogen is used mainly as a coolant No
6. Mumetal is an alloy of iron and copper used as magnetic material No

for small electric motors
7. Lead is an alloy used as filament in bulbs No
8. Aluminium can be soldered more easily than copper No
9. A fuse material can be soldered more easily than copper No

Table 13.14 Properties of important ceramics
SI. High voltage Low voltage

Properties Alumina Steatite Ziroon
No. porcelain porcelain
1. Specific gravity 3.1-3.9 2.35-5.1 2.7 - 2.4 2.5-2.9 3.1 -3.8
2. Water absorption 0.0 - 0.2 0.0 - 0.5 0.5 - 2.7 0.0 - 0.03 0 - 0.02
3. Dielectric constant (60 Hz, 25°C) 8-9.5 5.7 5.5-7.0 5.7 - 6.5 7.1 -9.1
4. Power factor (x 103, 25°C, 60 Hz) 0.5- 1.5 8-25 7-20 1.2-2.0 5 - 36.0
5. Tensile strength (kg/cm2 x 103) 0.56 - 3.5 0.2 - 0.56 - 0.52- 1.05 0.9-1.04
6. Compressive strength (kg/cm2 x 102) 5.6-3.0 1.75-5.6 1.75-4.2 4.2 - 30.5 6-7.0
7. Volume resistivity (£2 cm, at 25°C) 1014- 1016 1012 - 1014 1011- 1014 1012- 1015 1013- IO15
8. Softening temperature, °C 1450-2000 1300- 1335 1300 - 1335 1300 - 1450 1300- 1550
9. Structure limiting temperature, °C 1400- 1802 1000- 1200 1000- 1100 1000- 1180 1000- 1300
10. Heat conductivity 7-50 2-8 3.4-4 5-8 _____ 7-'5
CHAPTER 13
Some Useful Informations
1.SPEC1ALTABLES
Table 14.1 Electron configuration of some selected elements
Atomic Name of Atomic K L M N O

number element Symbol weight s s p spd spdf spdf
8 Oxygen O 16.0 2 2 4
10 Neon Ne 20.18 2 2 6
11 Sodium Na 22.99 2 2 6 1
13 Aluminium Al 26.98 2 2 6 2 1
14 Silicon Si 28.09 2 2 6 22
17 Chlorine Cl 35.45 2 2 6 25
24 Chromium Cr 52.00 2 2 6 265 1
26 Iron Fe 55.85 2 2 6 266 2
29 Copper Cu 63.54 2 2 6 2 6 10 1
32 Germanium Ge 72.59 2 2 6 2 6 10 22
47 Silver Ag 107.9 2 2 6 2 6 10 2 6 10- 1
Table 14.2 Various series of hydrogen spectrum
SLfto. Series observed , ; Value of ■, <-’■ Position in the spectn»

1. Lyman series 1 2, 3, 4,... oo Ultraviolet
2. Balmer series 2 3,4, 5,... oo Visible
3. Paschen series 3 4, 5, 6,... oo Infrared
4. Brackett series 4 5. 6, 7,... oo Infrared
5. Pfund series 5 6, 7, 8,... oo Infrared
780
SOME
.... ■ .. ...... » -A >.7
Table 14.3 Shortest and longest wavelength tn the different series of hvdrogen spectrum
SI.No. Series Longest (nm) Shortest (nm)
1. Lyman series 121.8 91.1
2. Balmer series 655.9 364.9
3. Paschen series 1876.1 821
4. Brackett series 4053.4 1459
5. Pfund series 7461.9 2280.1
Table 14.4 Bonding energies and melting temperatures of some selected substances
Bond energy
Melting
Bonding type Substance
kJ/kmol in eV/atom, ion or temperature °C
103 molecule
Ionic NaCl 640 3.3 801

MgO 1000 5.2 2800
Covalent Si 450 4.7 1410

C (diamond) 713 7.4 3600
Metallic Hg 68 0.7 -39

Al 324 3.4 660
Fe 406 4.2 1538
W 849 8.8 3410
van der Waals Ar 7.7 0.08 -189

ci2 30.8 0.32 -101
Hydrogen nh3 35 0.36 -72
— h2o 5 0.52 0
Table 14.5 Bond lengths and bond energy of some diatomic molecules
*' Molecule - Bond length (nm) 'Band energy (eV)
NaCl 0.236 4.4
LiH 0.160 2.5
NaBr 0.250 3.8
KC1 0.267 4.3
Nai 0.271 3.2

table 14.6 Physical pioperlies ol sonic ionic solids
Nearest Lattice energy kJ/kmol

Bulk modulus, Repulsive
Ionic neighbour (in 103) Melting
K in exponent n
solids separation. temperature °C
10'° Nlm1
r0(nm) Experimental Calculated
NaCl 0.2820 2.40 8 788 747 800
NaBr 0.2989 1.99 8.5 736 708 742
KC1 0.3147 1.74 9 717 676 770
KI 0.3533 1.17 10.5 617 605 682
LiCl 0.2570 2.98 7.0 862 807 614
Lil 0.3000 1.71 8.5 732 695 440

RbCl 0.3291 1.56 9.5 687 650 717
Table 14.7 Covalent bond lengths and associated binding energies
Binding energy in kJ/k Binding energy in

Band Bond length (run) Bond Bond length (nm)
mol (in 103) kj/kmol (in 103)
H—H 0.074 436 0=0 0.121 498

O —H 0.097 463 N —N 0.100 390
C —C 0.154 348 H —Cl 0.128 431
C=C 0.134 615 Si —O 0.183 368
c—a 0.177 327 C—H 0.108 414
Table 14.8 Work function and threshold frequency of some photosensitive cathodes
Threshold
Source Metal Work function (eV)
frequency (Hz)
Beryllium 9.4 x 1014 3.89

Titanium 9.4 x 1014 4.10
Ultraviolet Gold 1.16 x 1013 4.51
radiation Palladium 1.21 x 1013 4.80
Mercury 1.09 x 1013 5.01
Cesium 4.6 x 1014 1.91
Rubidium 5.3 x 1014 2.18
Visible radiation Sodium 5.9 x 1014 2.46
Barium 6.1 x 1014 - 2.51
Calcium 6.5 x 1014 2.70
Table 14.9 Wavelengths of elections under selected voltages
Voltage applied (volt) Wavelength, X (nm)
44 0.18
54 0.17
74 0.14
too 0.1227
Some Useful InnmmxAcM 7fl3
Liblv 14.10 Wavelengths ,v| protons acceleialcd by some selected voltages
Voltage applied (volt) Wavelength. X (nm)

25 0.008
36 0.0066
49 0.0057
100 0.0004
Table 14.11 Magnitude of the wave functions and probability of finding the particles at well known
positions ot electrons in a one-dimensional box of side a for n = 2
n=2 V lyl2
x=0 0 0
a <? 2
X= 4 a
a
X=2 0 0
3a
X=T -f. 2
a
x= a 0 0
Table 14.12 Enthalpy of formation of vacancies in some crystals
Crystal Ev (kJ/kmol) in 103 Ev eV/vacancy
Zn 49.0 0.51
Al 68.0 0.70
Mg 56.0 0.58
Kr 7.7 0.08
Cd 38.0 0.39
Pb 48.0 0.50
Ag 106.0 1.10
Cu 120.0 1.24
Ni 168.0 1.74
Table 14.13 Equilibrium vacancies in a metal
Approximate fraction of
Temperature aC
vacant lattice sites
500 1 x 10 10
1000 1 x ID-’
1500 1 x 104
2000 I x 10~3
labfc 14.14 ( <-. ->(.>1 -triittijrt ?iw! M-lect.-d properties >'f repre x-ntatr.e elements
Atomic Density in Crystal Lattice constant Atomic

Element Symbol Afe/bng prww °C
weight IO» (kg/rf) stmetun (2D°C) (nm) radius (nm)
Aluminium Al 26 97 2.7 fee 0.4049 0.1428 660.2

Cadmium Cd 112.41 8.65 hep a = 0 2979 0.1489 320.9~~
c = 0.5617
Carbon C 12.01 2.22 de 0.3564 0.0770 3700 "
Chromium Cr 52.01 7.19 bee 0.2885 0.1249 1890
Copper Cu 63.54 8.96 fee 0.3615 0.1278 1083
Germanium Ge 72.59 5.36 de 0.5658 0.1224 937
Iron (a) Fe 55.85 7.87 bee 0.2866 0.1238 1539
Lead Pb 207.21 11.34 fee 0.4949 0.1750 327
Magnesium Mg 24.32 1.74 hep a = 0.3209 0.1594 650
c = 05210
Potassium K 39.10 0.86 bee 05339 0.2312 63.7
Silicon Si 28.09 2.34 de 0.5428 0.1176 1430
Silver Ag 107.88 10.49 fee 0.4086 0.1444 9605
Sodium Na 22.99 0.97 bee 0.4281 0.1857 97.8
Zinc Zn 65.38 7.13 hep a = 0.2664 0.1332 419.5
c = 0.4945
Table 14.15 Root mean square velocities of molecules of some well known gases at 0°C
Velocity,cialS^mls -r
Oxygen 4.22
Hydrogen 16.92
Helium 12.01
Carbon dioxide 3.61
Chlorine 2.86
Nitrogen 4.52
Argon 3.81
Table 14.16 Physical properties of some selected metals
- n1. ; "-J w.t ' ' V !Ur.~ ••gi
Young's Linear *
Atomic Atomic Density p
Metal modulus in 10*° expansivity a Poisson's ratio
number Z weight a M (kg/m3)
(N/m2) inlO^(r’)
Aluminium 13 27 2700 7.0 2.4 0.34
Chromium 24 52 7100 2.5 0.85 -
Copper 29 635 8930 12.0 1.6 0.29
Iron 26 55.8 7860 22.0 1.2 0.30
Lead 82 207.2 11301 1.49 2.9 0.44
Nickel 28 58.7 8900 20 1.3 0.30
Potassium 78 39.1 21400 16.6 0.92
Silver 47 107.9 10500 7.9 1.9 0.38
Tin 50 118.7 7300 5.5 2.7 0.33
Tungsten 74 183.9 19300 36 0.43 -
SCXME JNKWWnKMS itSt,
fable 14.17 Ihcnnai pr<ip.:rUe> <4 r t.jl-:
Specific heat Thermal Specific latent Temperature coeffi

Metal Melting point
capacity, conductivity heal in 105 cient of resistance a
(TJUC)
CJJlkgK) ttT(Wnrx K~') (Mg) (Rl)
Aluminium 900 200 933 3.9 4.2 x KT’
Cobalt 420 70 1769 2.6 62 x 10-’
Copper 410 390 1335 2.1 4.3 x 10-’
CHAPTER 14
Iron 450 75 1810 2.75 6.5 x IO’
Mercury 140 10.4 234 0.12 0.92 x 10-’
Nickel 450 70 1730 3 632 x 10-’
Molybdenum 260 140 2890 2.9 431 x 1(T’
Silver 230 422 1234 1.05 3.9 x 10-’
Tin 220 65 505 0.59 43 x 10 ’
Zinc 390 110 692 1.12 4.1 x 10-’
Table 14.18 Classical velocity of free electrons at different temperatures
Temperature °C Root mean square velocity, c,(pds)
0 1.11 x 105
27 1.17 x 10s
40 1.19 x 10s
55 1.22 x 10s
75 126 x 10s
100 1.30 x 105
Table 14.19 Selected electrical properties of some familiar metals
Debye Lattice
Resistivity at Number of temperature Hall coefficient at 293 Crystal
Metal parameters
(fC(Orm) atoms!nr1 KRH(mi/c) structure
M*) (a, c) (nmi)
Cu 1.55 8.5 330 - 0.55 x IO"10 fee 0.3615

Ag 1.49 5.8 224 + 0.85 x 10-'° fee 0.4086
Au 2.04 5.9 175 - 0.722 x 10-'° fee 0.4078
Zn 5,52 6.6 213 - 033 x 10-'° hex 0.2659,

03936
Pb 1.92 33 85 + 0.085 x 10-*® fee 0.4949
Fe 8.9 8.5 419 + 0244 x |0-‘® bee, fee 02867
Co 9.0 400 - 1.340 x MT1® fee. hex 0.2507,

6.25
0.4070
Ni 476 - 0.612 x 10-’® fee 0.3524

6.7 9.0
(Comd...)
Souq Simrt Pmvsk3
Debye Lattice
Resistivity at Number of Hall coefficient at 293 Crystal
Metal temperature parameters
0°C (Q-m) atoms/m' K Rfl (m3lc) structure
e0(*) (a, c) {nm)
W 5.0 6.3 334 + 1.18 x 10 10 bee 0.3150
Al 2.5 6.0 395 -0.30x IO'10 fee 0.4041
Table 14.20 lerini enei>:\ aiui other related parameters lor some selected elements
Electron
Fermi energy at 0 Fermi Fermi temperature
Valency Metal concentration
KEF(eV) velocity at OK (m/s) tf(K)
n (Im3)
1 Li 4.72 x 1028 4.71 1.29 x 106 5.48
Na 2.66 x IO28 3.24 1.67 x 106 3.75
Ag 5.86 x 1028 5.48 1.39 x 106 6.37
Au 5.90 x 1028 5.51 1.39 x 106 6.39
Cu 8.50 x 1028 7.05 1.57 x 106 8.12
2 Mg 8.61 x 1028 7.13 1.58 8.28

Ca 4.60 x 1028 4.68 1.28 5.43
Ba 3.16 x 1028 3.65 1.13 4.23
3 Al 18.06 x IO28 11.63 2.02 13.49

In 11.49 x 1028 8.60 1.74 9.98
Table 14.21 Electrical conductivity and other transport properties of some selected metals
Electrical Concentration of
m
Metal conductivity free electrons, n XF m
a (ohm~} m~]) (/m3)
Li 1.07 4.62 0.90 x 10~14 1.21 x 106 10.8 1.2
Na 2.09 2.65 3.20 x IO"14 1.11 x 106 34 1.2
Cu 5.76 8.50 2.7 x 10~14 1.60 x 106 53 1.01
Al 3.64 18.06 0.71 x IO"14 2.02 x IO-'4 14.1 0.97
Ag 6.14 5.9 4.11 x IO’14 1.41 x 10-14 57.1 0.99
Zn 1.69 13.1 0.41 x 10-14 1.98 x IO-'4 7.8 0.85

Some Umma,
........... .. ~ . .-'.xZ*
Table 14.22 I oicni/ number ol some u .ciiil metals
Electrical Thermal Lorentz number, L

Metal conductivity, conductivity,
p (Q-m) <ST(Wm~' K~l) atlTiKW^K^ at 313 K W£1K~2
------------- -
Al 2.74 x 10~8 422 2.01 x 10-8 2.06
Cu 1.72 x IO’8 388 2.23 x IO8 2.33
Ag 1.60 x 10~8 231 2.31 x IO-8 2.37
CHAPTER 14
Zn 5.92 x 10-8 129 2.31 x IO-8 2.33
Pb 2.08 x IO"8 36 2.47 x KT8 2.56
Cd 7.69 x 10“8 101 2.42 x 10-8 2.44
Au 2.23 x 10-8 295 2.35 x IO-8 2.40
Table 14.23 Critical temperature Tc and critical field Hc (at 0 K; of some superconducting materials
Ho
Material TC(K)
(Amp/m) (gauss) I
Hg 4.12 33 x 103 413 I
Sn 3.72 24 x 103 306 I
Al 1.196 7.9 x 103 99 I
Zn 0.79 3.8 x 103 45 I
Pb 7.175 6.4 x 103 803 1
V 5.1 105 x 103 1300 I
Ga 1.09 0.41 x 104 51 I
Ta 4.48 67 x 103 829 n

Nb 9.25 156 x 103 1950 n
Nb-44%Ti 10.5 9.5 x 103 120 ii
Nb3AI 18 3.2 x 107 400 x 103 u

V3Ga 16.5 2.8 x 107 350 x 103 ii
Nb3Sn 18.5 1.6 x 107 200 x 103 n

Table 14.24 Superconducting transition temperature of some alloys and metallic
compounds compared with their constituent elements
Table 14.25 I lien's pap al I* K lol '><>1111 suprir rnidiii lots
Eg(0)
Element Eg (0) [2 A(0)] (eV) Tt(K)
kuTc
Aluminium 3.4 x IO*4 3.3 3.3
Tin 11.6 x IO"4 11.6 3.6
Niobium 30.5 x 10^* 9.5 3.7
Tantalum 14.0 x 10M 4.46 3.6
Lead 27.3 x 10-4 7.18 4.4
Mercury 16.5 x 10-4 4.16 4.6
Zinc 2.4 x 10-4 0.9 3.1
Gallium 3.3 1.09 3.5
Table 14.26 Some properties of I 2 3 compounds
Superconducting London penetration depth Lattice constant

coherence length (T = 0 K) (T=0/0
In plane 1.2 - 1.6 nm 150 nm 0.4 nm

Along c-axi/ 0.13 - 0.3 nm 700 nm 1 nm
Table 14.27 Penetration depth A. and the coherence length cn of some selected superconductors
Material X (nm) e0 (nm)

Sn 34 23
Al 16 1600
Nb 39 •38
Pb 37 83
Cd 110 760
Nb-Ti 300 4.0
V3Ga 90 2.0
Nb3Sn 65 3.0
NbjGe 90 3.0
Table 14.28 Diamagnetic volume susceptibilities ol some materials
Material X
Cu - 0.95 x 10-5
Si - 0.40 x 10“5
He - 0.50 x IO"9
Ar -HxlO-9
CHAPTER 14
Kr - 16 x 10-9
Xe — 25x IO"9
Au - 3.7 x 10-5
Ge - 0.8 x IO"5
Table 14.29 The susceptibility of some paramagnetic materials at room temperature
Material x=(u-D
Oxygen 0.19 x IO"5
Platinum 35.5 x 10-5
Air 0.035 x IO-5
Nitrogen 0.0012 x IO"5
Tungsten 7.5 x 10-5
CoO 585 x IO-5
MnSO4 360 x IO-5
142 x 10-’
Fc2°2
FeC^ 372 x IO'5
NiSO4 122 x IO-5
Table 1430 Saturation magnetisation and paramagnetic (0^) and ferromagnetic

(0p curie temperatures for ferromagnetic materials
. .........
M^ at 300 K MâtOK
Bohr magneton per atom j
Material
(amp/m) (amp/m) %
Nickel 0.475 x 106 0.5 x 106 630 646 0.612
Iron 1.710 x 106 1.763 x 106 1044 1047 2.21
Cobalt 1.45 x 106 1.446 x 106 1400 1503 1.70
Gadolinium 1.0 x 106 1,970 x 106 228 - 7.10
Table 1431 Classification of magnetic materials
Permanent
Classification Interaction between neighbouring ions
dipoles
Diamagnetic No -
Paramagnetic Yes Negligible
Ferromagnetic Yes Parallel orientation
Anti-ferromagnetic Yes Anti-parallel orientation of equal moments
Ferrimagnetic Yes Anti-parallel orientation of unequal moments

Table 1432 Neel and Curie temperature for anti-ferromagnetic materials
Paramagnetic tn x(fr)
Crystal Tn(K) TC(X)
ion lattice TC x(r0)
2
MnO fee 610 122 5.0
3
FeCl2 hep 48 23.5 2.0 <2.0
FeO fee 570 198 2.9 0.7
CoO fee ■ - 291 - -
NiO fee - 523 - -
Table 1433 Saturation magnetisation and the Curie temperature of some selected ferrites
Maximum
Material Curie temperature
\ magnetisation .
Fe 1750 1043
MnOFe2O3 358 783
NiO Fe2O3 240 893
CuO Fe2O3 290 728
MgO FejOj 143 523
Table 1434 Magnetic characteristics of some typical hard materials
------------------------------- ——----------
Coercive field Remnance
Name and composition BH (Jfa?)
(amp/m) (weber!m2)
Fe 75 1.5 100
Tungsten steel (6% W, 1% C and 93% Fe) 5000 1.0 3000
Remalloy (12% Co, 17% Mo and 71% Fe) 2000 1.0 ‘ 12000
Alnico II (10% Al, 17% Ni. 12% Co, 6% Cu and 55% F) 5000 1.7 1700
Alnicov V (8% Al, 14% Ni, 24% Co, 3% Cu and 51% Fe) 50000 1.2 45000
SOMC UMM. hWWMMtom tty
table 14.35 i atbun Inc «»««n ma> hm.ibh «!(>»■, ■ 1 \li>. * >
Alnico 2 Alnico 5 Alnico 6 Alnico 7

10 Al 8 Al 8 Al 8.5 Al
IO Ni !4Ni 15 Ni I8 Ni
12.5 Co 24 Co 24 Co 24 Co
6 Cu 3 Cu 3 Cu 3.25 Cu
CHAPTER 14
Table 14.36 I he magnetic characteristics of some of the soft materials
Name and Saturation P Hysteresis Uses

composition magnetisation in 105 Q.-m loss
(amperetum/m) Jlkglcycle
Fe 17.5 5000 10 x 10-8 0.03
98% Fe and 2% Si 16.7 7500 35 x IO"8 0.02
96% Fe and 4% Si 15.5 30000 55 x 10-8 0.005 Motors, high quality
Hypemik (50% Ni 12.7 60000 45 x 10-8 0.003 transformers and audio

and 32% Fe) transformers
78 - Permalloy (78% 8.7 100000 16 x 10-8 0.0005

Ni and 32% Fe)
Supermalloy (79% Ni, 7.0 1000000 60 x 10-8 0.0001

5% Mo and 16% Fe)
Mn-Zn Ferrite 3.1 2500 20 x KT6 0.001

___ ^n0.5 ^no.s
Table 1437 Mobility and minority concentrations for n-type and p-type samples of germanium
Given: = 036 m2 V"' s'1, p;) = 0.17 m2 V\1 and n, = 2.5 x IO”7mJ
p-rype samples n-type samples
* c ohnr' m~l n(/mi') p(/m3) a ohm~l m~l ntfm3) pf/w3)
104 1.70 x 105 3.68 x 1023 104 1.75 x 1023 3.57 x 1015
102 1.70 x 10'7 3.68 x 1021 102 1.75 x 1021 3.57 x 10‘7
______ 10 1.70 x 1018 3.68 x 1020 10 1.75 x 1020 3.57 x l0lM

FM lout* liwn Fhvwci
-- - . .-
l.ddr I 1 »N fl n ■ |. ll plopi lb. • ,.i '.i uni <n id nine 1 ompomid
IrttliCf h'lectnni Mole mobility

MnhMril iWMfINt
K, ill .MX)
K (r V)
IHdhllilV III al 300 A
Dielectric
constant e,
4
m, $
mt
(HHt) MX) A (Hta/V.<) (ni^Vs)
InNh 0.648 0.1 OK 7.8 0.074 17 0.0115 0.5

(»v 0.566 oooo 0.39 0,181 16 - -
SI OMI 1.120 0.15 0.062 U.K - -

AlSb 0.014 1.0 0.02 0.042 11.4 0.39 0.8
(ini’ 0.345 2.24 0.01 7.5 x 10 * 10 0.34 0.5
(InAs 0.505 1.35 0.H5 0.044 12.4 0.070 0.5
(InSb 0.010 0.07 0.41 0.140 15 0.048 0.38
Ibhlc 14..W llipnle moment ol some selected molecules

Dipole moment Dipole moment
Molecule Molecule
(Debye unit) (Debye unit)
NO 0.1 CO, 0
HC1 1.04 cs, 0
CO 0.11 H,0 1.84
HBr 0.79 h2s 0.93
HI 0.38 ch4 0
NO, 0.40 CHjCI 1.15
Ibblc 14.40 Diclecliic constant ol'gns molecules at 0"C
Dipole moment Dipole moment

Gas (er-1> x 10s Gas (8,-1) X103
(Debye unit) (Debye unit)
He 0.071 0 c2»4 1.38 0
h2 0.270 0 CO 0.692 0.10
0.531 0 N,0 1.08 0.17
\ 0.58K 0 nh2 8.34 1.45
CO, 0.998 0 SO2 9.93 1.50
CH, 0.948 0
‘Ihblc 14.41 Properties ol some widely used dielectrics
Dielectric constant Dielectric strength Resistivity

Material Density (kghn*)
•r (kVhnm) (ohm metre)
Glass 4-10 20- 32 2200 - 4000 10"- 10‘6
Mica 4-5.6 60-125 2500 - 2700 10u- 10”
Asbestos - 2 2300 - 2600 2 x 107
Bakelite 4-4.5 10-40 1.2 ~ ——

(Contd-)
Some Useful iNrotwanota 799
Dielectric constant Dielectric strength Resistivity

Material Density (kglm3)
e. (kV/mm) (ohm metre)
Ebonite 4-4.6 25 1.3 1 x IO20
Polystyrene 2.2-2.8 25-50 1.05-1.65 5 x 1013 - 5 x 10”
Polyvinyl 3.1 -3.5 50 1.38 -
chloride (PVC)
Rubber (soft) 2.6-3.0 4 x 1015
CHAPTER 14
15-25 1.7 - 2.9
ruble 14.42 Insulating materials for different applications

Application Insulating material used
Heating element of an oven Nichrome
Fuse holder Porcelain
Switch for domestic purpose Bakelite
Commutator Mica
Cable joint box Bitumen compound
Electric iron Mica
Low voltage cable Rubber
Flexible wire Plastic
Distribution board Wood
Laminating insulating board Epoxy resins
Thble 14.43 Relative permittivity of some selected substances

■: Dielectric . £.
Vacuum/Air 1 (by definition) 1.0006
Benzene 2.284
Glass 5-10
Paraffin 2.2
Ice at -5°C 2.9
Quartz 3.8
Bakelite 5
Mica 3-6
Marble 10-15
Porcelain 5.6
Polyethylene 2.25
Polyvinyl chloride (PVC) 6
Epoxy resins 3.5-11
Water 81
Calcite 6.1
Bee wax 2.7
Barium titranate 1200
Transformer oil 2.2
Viscous vaseline 2.4
Polystyrene 2.6
Toluene 2.39
: lM****«
K Table 14.44 I h vtiK.ll and mmh.nm.il piopcilics <«l three scumomlm.l<>rs
SLNo. Property Ge Si GaAs Units
1. Melting point 937 1415 1240 "C

2. Density at 25°C 5320 2330 5310 kg/rn1
3. Thermal expansion 6.1 x 10 6 4.2 x 10 4 5.9 x 10 4 /kelvin
4. Thermal conductivity 630 840 520 Wm 'K 1
5. Specific heat 310 760 361 Jkg 'K 1
6. Atomic weight 72.66 28.09 144.6 number
7. Lattice constant 0.5657 0.5431 0.5654 nm
8. Atoms/m3 4.42 x 1028 4.99 x IO28 4.34 x 1028 number
9. Dielectric constant 16 11.8 11.1 number
10. Band gap energy 0.67 1.106 1.4 eV
11. Intrinsic resistivity at 300 K 46 2300 3.7 x IO6 Q-m
12. Electron mobility 0.39 0.15 1 m2V',s'1
13. Hole mobility 0.19 0.05 0.045 m2V’*s'1
14. Intrinsic charge density 2.4 x 1019 1.5 x 106 1.4 x 109 Zm3
15. Electron diffusion constant at 300 K 0.01 0.0038 0.031 m2/s
16. Hole diffusion constant at 300 K 0.0049 0.0013 0.00115 m2/s
Table 14.45 Room temperature resistivity and energy gap of elements of the fourth group
Element C (diamond) Si Ge Sn(gray) Pb

p (Q-m) 1014 3000 0.47 2x 10-6 2 x IO'7
Eg (in eV) 5.2 1.21 0.75 0.08 0
Table 14.46 Classes of semiconductors
Crystal Lattice Fundamental energy

Material
structure spacing (nm) g“P, Eg (eV)
Si Diamond 0.542 1.08
Ge Diamond 0.562 0.65
Sn (gray) Diamond 0.646 -
GaP Zinc blende 0.545 2.24
GaAs Zinc blende 0.565 1.38
SiC Wurtzite 0.435 2.86
Cd S Zinc blende 0.583 2.40
Zn S Zinc blende 0.541 3.70
PbTe Rock salt 0.645 0.32

Some Um
Table 14.47 Dopands ionisation cnvrgv
Semiconductor Dopant (type) Ionisation energy (eV)

B(p) __________ 0.010___________
Al(p) 0.010
Ge Ga(p) 0.011
P(n) 0.012
As(n)
CHAPTER 14
0.013
Sb(n) 0.0096
B(p) 0.045
Al(p) 0.057
Ga(p) 0.065
Si P(n) 0.044
As(n) 0.055
Sb(n) 0.039
Table 14.48 Physical properties of important dielectrics
Maximum
Thermal
Dielectric Dielectric strength working Density
Material conductivity tan 8
constant (kV/mm) temperature (kglm3)
(milliwattJmlk)
°C
Air 1 3 — 1.4 0.25 -
Alcohol 2.6 — — 794 180 -
Asbestos 2 2 400 3000 80 —
Paraffin 2.2 12 35 882 270 0.0003
wax
Dry paper 3.2 5 90 822 132 0.007
Porcelain 5.7 15 1000 2400 1000 0.008

Mica 6 45 750 2880 600 0.02
Quartz fused 3.5 13 1000 2200 1200 0.002
Ebonite 2.8 50 80 1402 155 0.005
Rubber 4 10 70 1520 260 0.01

(vulcanised)
Flint glass 6.6 6 — 4555 1100 —
Grown glass 4.8 6 — 2200 602 0.02
Resi 3.0 — — 1100 — —

iflsS Souo State Physics
Tabic 14.49 Properties <>l some Icrroeleetric materials
Curie Spontaneous
Material Chemical formula temperature °C polarisation
Rochelle salt NaKC4H4O4.4H2O Upper +23 0.25

Lower -18
KDP (dihydrogen phosphate) KH2PO4 -150 4.95
Barium titanate BaTiO3 +120 26.0
Trihylene sulphate (Nl^CHjCOOHj) H2SO4 +4 2.8
Sodium nitrate NaNO2 +160 7.0
Table 1430 er and tan 6 of some dielectrics at 300 K
Material £r tan 5
Alumina 10 (5 - 20) x KF4
Porcelain 5 75 x KF4
Silica (Quartz) 3.8 2 x 1CF4
Mica 5.4 3 x KF4
BaTiO3 500 140 x KF4
PZT 1000 40 x icr4
Nylon 3.1 220 x KF4
Perspex 2.6 145 x 10”4
Polyethylene 2.3 2 x KF4
Polystyrene 2.6 0.8 x KF4
PTFE 2.1 2.0 x KF4
Polycarbonate 3.1 10 x KF4
PVC 3 162 x 10-4

Somc Useful - 797
•able 14.51 DuJcdiu piopeitivs of B.ifiO.
Permittivity er
Temperature °C Frequency (Hz) Temperature °C tan 3
At 1.5 MHz Permittivity e.r
20 400 1000 1500 0 0.24
60 500 1 1490 40 0.20
100 600 107 1375 80 0.16
CHAPTER 14
115 2000 109 1000 120 0.06
120 (curie point) 4900 10" 200 160 0.04
140 2800
145 2000
180 1500
.yyvli9WWPIWT
i)‘j—M'AiB <r, ■Grtar - i~W "Wu u ..‘j tHfrHrtww r .ifwiimb'î MtaotMiM—M
Metric Prefixes
Prefix ■. Symbol Factor
ultra U 1015
tetra T 1012
giga G 109
mega . M 106
kilo k 103
hecto h 102
deka d 10*
— — 10°
deci d icr*
centi c io~2
milli •m 10~3
micro 10^
nano n KT9
10-12
pico P
femto f 10-'5
a KT’8
atto
■! wm*hw
mnstRivED siuNrrs' il'*h<7ii 'r —n ■■“■■ --—--rii'Ml
Derived SI Vnits having Special Names and Symbols
Name of Symbol for SI derived unit

Physical quantity (and symbol)
SI unit and definition of unit
Frequency (v) Hertz Hz (= s’1)
Energy (U) Joule J (= kg m2 s“2)
Force newton N (= kg m s-2 = J nr1)
Power watt W (= kg m2 s-3 = J s’1)
Pressure (P) pascal Pa (= kg nr1 s~2) = N nr2 = J nr3
Electric charge (Q) coulomb C (= As)
Electrical potential difference (V) volt V (= kg m2 s-1 A-1 = J A-1s-1)
Capacitance (C) farad F (= A2 s4 kg-1m-2 = A s V-1 = A2 s2 J-1)
Resistance (R) ohm Q (= V A’1)
Conductance (G) siemen S (= A V-1)
Magnetic flux density (B) tesla T (= V s nr2 = J C1 s nr2)
IV. WHY SI UNITS? - ------------------------—-
Advantages of SI Units
(0 It is comprehensive in the sense that its seven base cover all disciplines of science and
technology.
(ii) The system is coherent as the unit of a derived quantity can be obtained as the product or
quotient of two or more fundamentals.
(Ui) It is now internationally accepted.
Differentials
1. d (u + v - w) = du + dv - dw 2. d (uv) = udv + vdu
3. d (e*) = e* dx 4. d(eax) = aea'dx
5. J (log x) = x~'dx 6. d (sin hx) = cos hxdx
7. d (cos hx) = sin hxdx 8. d (tan hx) = sec h2x dx
_ .(u\ vdu-udv
9. d (cot hx) = - cosec h2x dx 0. d - =-------5------
\v) v
Some Useful (nfomwions <
Indefinite Integrals
f . (ax + />)" + l r dx 1
'■ + 0(„ + |) •"‘-1 2. -------- = - log {ax + b)
J ax + b a
f dx _ 1 10 x 4. f J{ax + b)dx = — {ax + b)*1
3’ J x {ax + b) b g {ax + b)
J 3a
e dx 2y/ax + b
J y]ax + b a
CHAPTER 14
Exponential and Logarithmic Expressions
1 I ax
1. [eaxdx = ~eax 2.\baxdx=——
J a J a logo
3. Jxn eaidx= —x"e“- —Jx71-1 e^dx, n positive
f ax e<a
4. Ie sin bxdx = —~—r?~(a sin bx - b cos bx)
J {a2 + b2)
5. Jlog axdx = xlog ax-x 6. Jxlogax = log (log ax)
Definite Integral
oo t 2
fsin x t n sin ax
if a > 0
0
71 71 K
3. ^sin2axdx=jcos2axdx = —
0 0
5. J x" er^dx = -^r, if n is a positive integer, a > 0

o a
6. lx2" = l-3-5- (2n- l) 7. U
J e 2n + ian J 2a V a
.. f logx , n, n
1^7 ôe
APPENDICES
A.l. List of Physical Constants with their Units
SI. No. Quantity Symbol Magnitude Unit

1. speed of light in vacuum c 2.997925 x 108 metre/sec ms'1
2. charge of electron e 1.6021 x IO'19 coulomb c
3. rest mass of electron me (m) 9.109 x 10~31 kilogram kg.
4. proton rest mass mP 1.6725 x IO’27 kilogram kg
5. neutron rest mass mn 1.6748 x IO'27 kilogram kg
6. atomic mass unit mu 1.6604 x 10"27 kilogram kg
7. electron radius re(r) 2.818 x IO"15 metre m
8. electron volt eV 1.602 x 10~19 joule J
9. energy equivalent to electron mass mec2 0.511 million electron volt MeV
10. energy equivalent to proton mass mpc2 938.25 million electron volt MeV
11. energy equivalent to neutron mass mnc2 939.55 million electron volt MeV
12. 1 Angstrom unit A io-10 metre m
13. proton to electron mass ratio mPlmc 1836.1 — —
14. specific charge of electron elme 1.75879 x 10" coulomb/kilogram Ckg-1
15. specific charge of proton elmp 9.583 x 107 coulomb/kilogram Ckg-1
16. Avogadro’s number Nz 6.02252 x 1026 (kilomol)"1 kmol'1
17. Boltzmann constant 1.38054 x IO’23 joule/kelvin JK-1
18. thermal energy at 300 kelvin kBT 4.14 x 1021 =0.0258 joule J
electron volt eV
19. Planck’s constant h 6.626 x 10’34 joule sec Js
(Contd...)
APPENDICES
Sl.No. Quantity
Symbol Magnitude l/nlt
to*
20. unit atomic angular momentum (h/2n) - h h
1.05459 x l(rM joule sec
(reduced Planck's constant)
21. permeability of free space 4n x 10’7 henry/metre Hm"1
Mn
22. IO"9
permittivity of free space - 8.854 x 10*12 farad/metre Pm'
% 36ji
23.
«m»m
mass of neutral hydrogen atom — 1.0081422 atomic mass unit amu

24. radius of first hydrogen orbit (Bohr radius) 0.529 x IO*10 metre m
rB
25. energy of ground state hydrogen atom 2,175 x IO"18 joule J
(Rydberg energy) electron volt eV
26. Rydberg constant for hydrogen 1.0967758 x 107 metre"1 nr*
rh
27. Bohr magneton (electron magnetic moment) 9.2732 x IO"24 amp metre2 Am2
28. proton magnetic moment 1.410 x IO" 26 amp metre2 Am2
29. I Debye unit D 3.33 x ItT30 coulomb metre Cm
30. wavelength of photon having 1 eV energy (hc/e) 1240 x IO"9 metre m
= 1240 nanometre nm
31. ' acceleration due to gravity at sea level on equator g 9.8118 metre/sec2 ms"2
32. universal constant of gravitation G 6.6732 x 10"11 newton metre2 NnPkg2
kilogram2
33. Faraday constant (change of one kilomole of F' 9.649 x 10-7 coulomb/kilomol Ckmoi"1
electrons)
34. Loschmidt’s number (number of molecules/m3 L' 2.686 x 1025 — —
of gas at STP)
35. universal (or molar) gas constant 8.3143 x 103 joule / Jkiuol * K
kilomol kelvin
36. root mean square velocity of hydrogen CH 1.84 x 103 metre/sec ms"1
molecule at STP
37. volume of one kilomol of perfect gas at STP - 22.41 metre3 m3
38. standard atmospheric pressure p, 1.013 x 105 newton/metre* Nm"2 1
2.1 The distribution of electrons in the various states, 29
2.2 Electronic configuration of elements, 31
2.3 Periodic table, 36
3.1 Energy absorbed and energy released in the formation of NaCl, 53
3.2 Bond lengths and bond energies of some diatomic ionic molecules, 55
3.3 Physical properties of some ionic crystals, 63
3.4 Covalent bond lengths and associated binding energies, 67
3.5 Comparison between ionic bonds and metallic bonds, 76
3.6 General properties of various bonds, 78
3.7 Bonding energies and melting temperatures of some selected substances, 79
4.1 Seven basic crystal systems with their characteristics, 93
4.2 Absence of five-fold rotation axis, 97
APPENDICES
4.3 Possible glide planes, 99
4.4 The seven crystal systems and the fourteen Bravais lattices, 102
4.5 Comparison of cell properties of some crystal structures, 114
4.6 Crystal structures and selected properties of some representative elements, 116
4.7 Crystal structures of representative compounds, 117
4.8 Enthalpy of formation of vacancies in some crystals, 128
4.9 Equilibrium vacancies in a metal, 132
5.1 Ratios between interplanar distances, 169
6.1 Parameters connected with Fermi energy for metals, 239
6.2 Electrical conductivities and other transport parameter for some selected metals, 251
6.3 Electrical and thermal conductivities of some metals at 300 K, 264
6.4 Linear expansion coefficients of some selected solids at 300 K, 267
6.5 Hall coefficient and mobilities for some metals at 300 K, 275
6.6 Thermionic constants, 280
6.7 Susceptibilities of some monovalent and divalent metals (room temperature) 288
7.1 Experimental thermal properties of some substances at room temperature and at atmospheric
pressure, 334
7.2 Debye temperatures of some materials, 350
7.3 Deviations from T3 law, 350
8.1 Properties of some selected superconducting elements, 358
8.2 Critical temperature Tc and critical magnetic field Ho (at 0 K) of some compounds and alloys,
359
8-3 Energy gap at 0 K for some superconductors, 370
8.4 Penetration depth at 0 K, 371
8.5 Applications of superconducting materials in some important fields, 402
9.1 Directions of electrons moments in a filled 2p shell, 444
9.2 The spin states of three representative elements, 445
9.3 Spin distribution and magnetic moment in the first long period, 445
9.4 Diamagnetic susceptibility of some materials. 446
9.5 Susceptibilities of some paramagnetic materials at 300 K and under a field of 1 tesla, 464
9.6 Values of S and for unpaired 3d electrons, 465
9.7 Magnetic susceptibilities of some paramagnetic materials at room temperature, 472
9.8 Distribution of 3d electrons in iron atom, 473
9.9 Some physical properties of ferromagnetic elements, 476
9.10 Values of the magnetic moment for different numbers of/electrons, 478
9.11 Electronic configuration and spin moment of iron group of elements. Calcium and copper have
been added for comparison, 479
9.12 Two important properties of a few permanent magnetic materials, 480
9.13 Properties of some high permeability materials, 481
9.14 Saturation magnetisation and paramagnetic (0) and ferromagnetic (0^ temperatures for
ferromagnetic materials, 493
9.15 Some antiferromagnetic materials and their properties, 506
9.16 Distinction between magnetic materials, 509
9.17 Magnetic units, 510
10.1 Comparison of the properties of Al and Si at 300 K, 522
10.2 Electrical characteristics of some selected semiconductors, 538
10.3 Electrical and mechanical characteristics of Ge, Si and GaAs, 539
10.4 Intrinsic carrier density in silicon and germanium calculated as a function of temperature. Values
are quoted/m2, 539
10.5 Ionisation energy from donor and acceptor states in silicon and germanium, values are quoted in
eV, 540
11.1 The relative permittivity of some selected substances at 20°C, 626
11.2 Dipole moment of some selected molecules, 635
11.3 Electric dipole moment of some molecules, 642
11.4 Dielectric constant of some elemental dielectrics, 649
11.5 Static and optical dielectric constant of alkali halides; n is the index of refraction, 650
11.6 Properties of some ferroelectric materials at room temperature, 652
11.7 Properties of some ferroelectric materials, 657
11.8 Properties of some antiferroelectric materials, 660
11.9 Variation of t with temperature for propyl alcohol, 676
11.10 Experimentally determined value of permanent dipole moment of a few dielectrics in gas phase,
685
11.11 Dielectric strength of some materials, 685
12.1 Fundamental parameters of electromagnetic radiation and optical media, 737
I<I feaqw*™* of penmttiv ity of some substances. 774
152 I'kvtrvMUC poUnsaNhty of some selected atoms. 774
153 The ekrctrk strength of some materials, 774
l\4 IVêrt*** of «o<«e fenwlectric materials. 774
155 General properoes of mineral insulating oils. 775
156 Priêrtres of (Mlyethylene. 775
15” properties of polystyrene resin. 775
15$ Properties of polyvinyl chloride. 776
154 Pmperries of polyamide resins. 776
1510 General properties of two main types of mica. 776
15H Properties ofsome types rubbers. 777
1512 Insulating materials for different applications. 778
1513 Questions with answers in Yes or No. 778
APPENDICES
1514 Properties of important ceramics. 779
151 Electron configuration of some selected elements. 780
142 Various series of hydrogen spectrum. 780
143 Shortest and longest wavelength in the different series of hydrogen spectrum, 781
154 Bonding energies and melting temperatures of some selected substances, 781
143 Bond lengths and bond energy of some diatomic molecules, 781
156 Physical properties of some ionic solids, 782
157 Covalent bond lengths and associated binding energies, 782
14.8 Work function and threshold frequency of some photosensitive cathodes, 782
14J Wavelengths of electrons under selected voltages, 782
14.10 Wavelengths of protons accelerated by some selected voltages, 783
14.11 Magnitude of the wave functions and probability of finding the particles at well known
positions of electrons in a one-dimensional box of side a for n = 2,783
14.12 Enthalpy of formation of vacancies in some crystals, 783
•4.13 Equilibrium vacancies in a metal, 783
14.14 Crystal structure and selected properties of representative elements, 784
14.15 Root mean square velocities of molecules of some well known gases at 0°C, 784
1516 Physical properties of some selected metals, 784
*517 Thermal properties of some metals, 785
1518 Classical velocity of free electrons at different temperatures, 785
Selected electrical properties of some familiar metals, 785
14JO Fermi energy and other related parameters for some selected elements, 786
14 21 Electrical conductivity and other transport properties of some selected metals, 786
14 ~~ Lorentz number of some useful metals, 787
1423 Critical temperature Tc and critical field Hc (at 0 K) of some superconducting materials, 787
14.24 Superconducting transition temperature of some alloys and metallic compounds compared with
their constituent elements. 787
14.25 Energy gap at 0 K for some superconductors, 788
14.26 Some properties of I 2 3 compounds. 788
14.27 Penetration depth X. and the coherence length e0 of some selected superconductors, 788
14.28 Diamagnetic volume susceptibilities of some materials, 789
14.29 The susceptibility of some paramagnetic materials at room temperature, 789
1430 Saturation magnetisation and paramagnetic (Op) and ferromagnetic (Oy) curie temperatures for
ferromagnetic materials, 789
1431 Classification of magnetic materials, 790
1432 Neel and Curie temperature for anti-ferromagnetic materials, 790
1433 Saturation magnetisation and the Curie temperature of some selected ferrites, 790
1434 Magnetic characteristics of some typical hard materials, 790
1435 Carbon free non-machinable alloys (Alnico), 791
1436 The magnetic characteristics of some of the soft materials, 791
1437 Mobility and minority concentrations for n-type and p-type samples of germanium Given: p, =
036 m2 V-1 sr1, Up = 0.17 m2 V’s"1 and n( = 2.5 x 1019/m3,791
1438 Physical properties of Si and Ge of some compounds, 792
1439 Dipole moment of some selected molecules, 792
14.40 Dielectric constant of gas molecules at 0°C, 792
14.41 Properties of some widely used dielectrics, 792
14.42 Insulating materials for different applications, 793
14.43 Relative permittivity of some selected substances, 793
14.44 Electrical and mechanical properties of three semiconductors, 794
14.45 Room temperature resistivity and energy gap of elements of the fourth group, 794
14.46 Classes of semiconductors, 794
14.47 Dopands ionisation energy, 795
14.48 Physical properties of important dielectrics, 795
14.49 Properties of some ferroelectric materials, 796
14.50 e, and tan 8 of some dielectrics at 300 K, 796
14.51 Dielectric properties of BaTiO3, 797
(0 Derive the equation for the momentum and energy of a particle in one-dimensional box with
impenetrable walls, for n = 1 and n = 2. Assume that potential energy is zero. Find the corresponding
values for an electron in a box of length 1 A. Refer equation (6.76).
k2h2
2m
But
fc2 2—.2
a
nnh
nh h2 ( k2 )
For n = 1, momentum, p( = — and E] = — I I
APPENDICES
„ 2M jr7 h2 (2k2
For n = 2, momentum, p2= and E2 = — I
For n = 1 and n = 2 and a - 0.1 nm

h - G-62 x io34 = 3.31 x IO"24
P] ~ a ~ 2na ~ 2n ” 2x10"’°
Pj = 3.31 x IO-24 kg m/s
2 a 2lta a
’ 2m(a2J {4K2mJ [a2 J 8/na2
E1 (662 x 10-34)2 = 6622 x 10~a

8 x 9.1 x IO"31 x IO'20 ’ 723 x IO'5*
= 6O.4xlO-t9J
_ 60.4x10 ” _ 37 7 cV
" 1.6 x IO'*9
£j = 22^1 = 150.8 ey
«0 Show graphic^ me vLuon of !he w.ve funcuon < W fa vah^ of qu^ munben I ■
* 3.4 io caae^rfae panicle in a one-done.u.ooal box. Hence expfan <he m«nmg of a node «1
an antinode in terms of probability density.

(a) In the case oft a ______ _ in
free particle in a„ nnr dimensional box and the value of W (x) u given by the
one-oimcnsiuiia
*ave function
where a is the length of the box . A node corresponds to (x) = 0. for nth quantum state the nodes occur
. nnx _ hXa
when sin----- = 0, or----- = mil, i.e., x
a a
Thus the nodes are located
An antinode corresponds to the maximum value of (x). Since the maximum value of sin
= 1, for an antinode
Therefore for the nth quantum state the antinodes occur when
. nnx , nttx z_ , n a(2m + l)
sm----- = 1 or------ = (2m + 1) — or x = —----------
a a 2 2n
a 3a ( 2n -1A
Thus the antinodes are located at x = — —,—-— la
2n 2n I 2n J
When n = 1, nodes occur at x = 0 and x = a and antinodes occur atx = ~

2
a a 3a
When n = 2, nodes occur at x = 0; x = — ;x = a and antinodes occur at x = —; x = —
2 4 4
a a
When n = 3, nodes occur at x = 0; x = x = a and antinodes occur at x =
3 6’
_ 3a _ 5a
X= ~6'X~ ~6
When n - 4 nodes occur at

_ a 2a 3a
x = 0;x = -;x= —;x = —;x = a
4 4 4
and antinodes occur at
a 3a 5a la
x» —;x = —;x = —;x= —
8 8 8 8
These are shown in the graphs.
(h) In terms of probability density an antinode is a point of maximum probability density and a
node is a point of zero probability density. We, therefore, find that for the nth quantum state, there are
n antinodes, i.e., there are n equally probable positions in the box at which the panicle is most likely to
be found. Similarly, there are (n - 1) nodes, each node lying in between two antinodes, it., there are
(n -1) equally spaced positions where the probability of finding the particle is zero. Of course, the two
positions x = 0 and x = a are permanent positions of nodes.
In the ground state n = 1, the position of maximum probability is given by x «(a/2). For the fin*
excited stale n = 2, the probability is maximum for x = (ci/4) and x = (3a/4) but the probability for
x - (a/2) is zero. According to the classical theory the probability of finding the panicle is the same s*
every point in the box but according to quantum theory there is a greater probability of finding the
particle at some points than at others. The probability of locating the particle
the walls is always zero. These are shown in Fig. A.3. at * — o, or x = a, i.e., near
appendices
Fig. A.3
A .4. Conversion Table
To convert SI to To convert Gaus

Quanta? Symbol Gaussian unit SI unit
Gaussian multiply by sian to SI multiply by
Capacitance c statfarad farad 8.99 x 0" 1.11 x IO"*2
Charge statcoulomb coulomb 3.00 x 109 3.34 x 10-'°
Conductivity Q (statohm-cm)-1 (ohm-m)-1 8.99 x 109 1.11 x 10-w
Electric ament I statampere ampere 3.00 xlO9 3.34 x IO-10
Electric cunent density J statamp/cm2 amp/m2 3.00 x 105 3.34 x 10*
Energy E erg joule 107 IO-7
Electric displacement D statvolt/cm coulomb/m2 12k x 10s (12k x IO5)-’
= 3.77 x 106 = 2.65x IO-7
Electric field strength e statvolt/cm volt/m 333 x IO* 3.00 x 10*
Electric potential ♦ statvolt volt 333 x 10-3 3.00 x 102
Magnetic field strength H oersted amp/m 4k xlO-3 (4k x 10-3)-1
= 1.26 x IO"2 = 7.96x 10
Magnetic flux 0 maxwell weber 108 io*
Magnetic induction, magnetic B gauss tesla = weber/m2 10* io*
flux density
Inductance L abhenry henry 109 IO*
Permeability of free space Mo (unitless) henry/m (4k x 107)-’ 4k x IO-7
= 7.96 x 10s = 1.26x IO-6
Benmttivity of free space (unitless) farad/m 36k x 10? (36k x IO?)*
= 1.13 x 10” = 8.85 x IO-12
Power P erg/sec watt 107 IO-7
Resistance R statohm ohm 1.11 x IO-12 8.99 x 10”
Resistivity P statohm-cm ohm-m 1.11 x IO-10 8.99 x IO9
Dielectric polarisation P statcoulomb/cm2 coulomb/m2 3.00 x 10s 333 x 10*
Magnetisation M gauss amp/m 136 x IO2 7.96 x 10
------------------—-------- - - 8
ANSWERS TO OBJECTIVE QUESTIONS
CHAPTER 2
2- (4) 3. (fl) 4. (a) 5- (4) 6. (c)

1. (a)
8- (d) 9. (b) 10. (a) 11- (c) 12. (4)
7. (fl)
14. (a) 15- (c) 16. (a) 17. (c) 18. (4)
13. (a)
20. (a) 21- (6) 22. (6) 23. (fl) 24. (c)
19. (d)
25. (a) 26. (a) 27. (a) 28. (b) 29. (a)
CHAPTER 3
2. (a) 3- (c) 4. (b) 5. (fl) 6. (b)

1. (b)
8- (c) 9- (fl) 10. (b) 11. (4) 12. (4)
2. (a)
13- (c) 14. (6) 15. (a)
APPENDICES
CHAPTER 4
2. (fl) 3- (b) 4. (d) 5. (a) 6. (fl)

1- (c)
7- (b) 8. (c) 9- (4) 10. (a) 11- (fl) 12. (c)
13. (c) 14. (a) 15. (d) 16. (b) 17. (b) 18. (b)
19. (a) 20. (b) 21. (c) 22. (a) 23. (a) 24. (fl)
25. (c) 26. (c) 27. (fl) 28. (a)
CHAPTER 5
3. (b) 4- (c) 5. (d) 6. (d)

1- (b) 2. (fl)
7. (fl) 8. (c) 9. (fl) 10. (d) U. (b) 12. (b)
13. (c) 15- (c) 16. (c) 17. (b) 18. (d)
14. (a)
19. (b) 20. (c) 21. (a) 22. (b) 23. (b) 24. (b)
25. (b) 26. (a) 27. (d) 28. (b) 29. (fl)
CHAPTER 6
1- (c) 2. (fl) 3. (fl) 4. (b) 5. (c) 6. (c)

7- (a) 8. (4) 9. (a) 10. (c) H. (4) 12. (a)
13. (a) 15. (b) 16. (c) 17. (6) 18. (d)
14. (d)
19. (d) 20. (c) 21. (fl) 22. (4) 23. (6) 24. (a)
25. (fl) 26. (a) 27. (d) 28. (a) 29. (a) 30. (b)
31- (fl) 32. (a) 33. (a) 34. (fl) 35. (o) 36. (b)
37. (a) 38. (b) 39. (d) 40. (fl) 41. (o) 42. (b)
43. (c) 44. (c) 45. (a) 46. (b) 47. (b) 48. (b)
(a) 50. (fl)
*14 Solid State Physics
CHAPTER 7
1. (a) 2. (b) 3. (c) 4. (a) 5. (c) 6. (fl)

7. (c) 8. (fl) 9. (a) IO- (a)
CHAPTER 8
1. (c) 2. (d) 3. (c) 4. (d) 5. (fl) 6. (b)

7. (6) 8. (a) 9. (c) 10. (b) 11. 12. (c)
13. (c) 14. (d) 15. (a) 16. (*) 17. (fl) 18. (fl)
19. (6) 20. (d) 21. (a) 22. (a)
CHAPTER 9
1. (c) 2. (b) 3. (c) 4. (d) 5. (c) 6. (c)

7. (c) 8. (c) 9. (d) 10. (a) 11. (b) 12. (c)
13. (a) 14. (b) 15. (6) 16. (b) 17. (b) 18. (d)
19. (d) 20. (b) 21. (fl) 22. (c) 23. (b) 24. (c)
25. (c) 26. (d) 27. (d) 28. (d) 29. (fl) 30. (c)
31. (d) 32. (d) 33. 34. (c)
CHAPTER 10
1. (a) 2. (a) 3. (c) 4. (b) 5. (fl) 6. (b)

7. (a) 8. (c) 9. (d) 10. (b) 11. (b) 12. (fl)
13. (a) 14. (a) 15. (c) 16. (a) 17. (fl) 18. (b)
19. (d) 20. (b) 21. (c) 22. (c) 23. (fl) 24. (a)
25. (c) 26. (c) 27. (b) 28. (a) 29. (c) 30. (b)
31. (c)
CHAPTER 11
1. (a) 2. (a) 3. (*) 4. (b) 5. (d) 6. (fl)

7. (c) 8. (a) 9. (c) 10. 0) 11. (fl) 12. (fl)
13. (a) 14. (c) 15. (e) 16. (6) 17. (d) 18. (c)
19. (a) 20. (*) 21. (d) 22. (e) 23. (d) 24. W
25. (b) 26. (fl) 27. (fl)
ANSWERS TO PROBLEMS
CHAPTER 2
1. 2.187 x 106 ms1,0.0529 nm and 1.519 x 10 ‘6 s

2. 2.19 x 106 ms-1 3. 2 and 3, 121.6 nm 102.6 nm
4 9.5 nm 6. 8.2 x 10’
5,16.53 eV. 3654 x IO,2m. 0.0106 nm. 340 eV. - 680 eV and 10.5 x 10 ” Js
8. 4,5 x IO14 Hz and 1.524 x IO6 m 1 9. 485.4 nm
10. 13.6 volts 11. 365 nm and 121.7 nm
13. 1215 nm, 103.5 nm and 690.2 nm 14. 9.27 x 1024 amp metre2
16. 1 x IO28 and 8.5 x IO28 17. 9.274 x IO24 amp metre2
18. 4.5 x 1014 s'1 and 1.524 x IO6 nr1 20. 10.2 eV. 121.7 nm
CHAPTER 3
4. P log,B
M N_
N-M'
’ N1n-m A M\n-m
5. AM i- ,N-M■ .-^[N-M], rt = r0 and Fmax,
nJ ~n)
r0 Jf.
APPENDICES
6. 16 ’ r‘ ~ nm ^max = 0 024 N
and r, = r0
m +1
8. — I unit and r, = 0.121 nm 9. 0.408 nm and 4.33 x 10"2 eV
10. a = 7.2 x IO"38 J-m2, b = 9.4 x 10-“5 J m2,0.238 x 10* N and 0.353 nm
13. 6.9 eV or 667 x 103 kJ/kmol 14. 3.49 x IO" m2/N
15. 7.76 eV/molecule, 748 x 103 kJ/kmol and 78 x 103 kJ/kmol
16. 8.1 eV and 780 x 103 kJ/kmol 17. 7.48 x 10-" m2/N
18. 781.6 kg or 20 kg-atom 19. - 1.9. eV
20. -7.2 eV 21. 0.5 eV and 2.88 nm
22. - 3.065 eV/atom 23. - 2.05 eV/atom
24. 2.04 eV and 0.7 nm 25. 4.37 x IO3 kg/rn3
CHAPTER 4
1. 0.155 r 2. 0.414 r
t 3 i ft ^3
3. 2 4. a3 1--------- and R = 0.29 r
8
MB JPitofrBwrFwwBCi
5. 3540 kg/m3 and 3500 kg/m3 6. 0.282 nm

7. 0.124 nm 8. 8.98 x 103 kg/m3
9. 4.373 x IO3 kg/m3 10. 0.362 nm and 0.097 nm
11. 121.2 x 10~3 m3,0.7 nm and 0.866 nm 12. 4.7 x 1022 cells, 1.9 x 1023 atoms and 4 atoms
13. 9.35 x IO-29 m3 and 6968 kg/m3 14. 0.0725 nm
15. 7.68 x IO-30 m3 and 0.0362 nm 16. 1.21 x IO13, 1.72 x IO13 and 2.10 x IO13
17. 8.2 x IO12, 5.8 x IO12 and 9.5 x IO12 18. (3 6 1)
b CA
( <2----
19. 22. (6 3 2)
I 2 37
23. 0.4927% 25. (4 3 0)
26. 1.12x10“* 27. 3.75 x 10“*
28. 0.126 nm 29. 6:3:2, 75:72 and 1 : 71
30. 72:75 31. (634)

32. 8.413 x 10-7 33. 0.132 nm
CHAPTER 5
1. 6° 24' 2. 0.87 x IO-3 nm
3. 0.00996 nm 4. 1.81 x 10"5m
5. 14° 6' 6. 13° 30'
7. 1.84 x IO3 8. 12xlO^s
9. V 10. 3.9%
11. 4.7% 12. 0.0635 nm
13. 0.33 nm and 0.1078 nm 15. 7.3 x IO5 m/s
16. 2.409 x 10-" m 17. 2.598 x 108 ms-3
18. 1.1 x 10^ m 19. 1.33 x IO"20 kg-m/s and 0.33 MeV
20. 20° 55' 21. 17° 24' and 26° 36'
22. 0.0381 nm 23. 58° 25'
24. 0.2816 nm 25. 1.25 x 1016,4.15 x IO7 m/s and 0.2483 nm
26. 13° 307 and 0.098 m 27. 1485 Js-‘ and 33.8°C
28. (1 1 1),(T 1 0),(0 1 6),(1 1 0), (2 3 12), (1 0 4)
29. (2 1 2),(1 2 1),(1 0 3) 30. 0.00323 nm
31. 0.178 x lO-’m 32. 19 photons/minute and 4 x 1017
33. 0.0871 nm 34. 0.145 nm
hv
35. ——T and 9.77 x KPcV
Imc1
36. 3.82 x IO"23 kg-m/s, 0.0173 nm, 5.78 x IO10 nr' and 2.7°
CHAPTER 6
L 0.726 x KT2 m1 V 's'1 2. 2.84 x IO-'4 s and 3.28 nm
3. 0.427 x 10-2 m2 V'1 s"1 and 2.42 x IO*14 s
4 0.396 ms'1.3.96 x IO-3 m2 V'1 s*', 2.3 x 1(T14 s and X = 2.65 nm
6. 1.12 x 10 s WQK 2
5. 497.6 x 10* amp/m2 and 3.6 x IO-4 m/s
7. 4.46 x 104 fl-m 8. 1.03 x 10-2
9. 1.91 x 10‘um 10. 150 eV
11. 9.4 eV, 37.6 eV and 84.6 eV 12. 9.3 x KT31 kg
13. 2.05 MeV 14. 225 eV and 17.4 x 105 K

15. (1 1 1), (1 1 2), (1 2 2), (11 3), (2 2 2), (1 2 3)
The first and the fifth are non-degenerate; 2nd, 3rd and 4th are three-fold degenerate and the
sixth is six-fold degenerate. Their energy values are:
APPENDICES
362 6A2 9/t2 HA2 12A2 14A2
8ma2 ’ Sma2 ’ 8/nzz2 ’ Sma2 ’ 8ma2 ’ 8zna2
16. (6 1 1), (1 6 1), (1 1 6), (5 3 2), (5 2 3), (3 5 2), (3 2 5), (2 5 3) and (2 3 5) give the same energy
level; therefore, the level is nine-fold degenerate.
17. (a) cos hx - i sin x (A) - 2 i sin x (c) ie-^^
18. (i) cos2 hx + sin2x (it) 4 sin2x an<i (Hi) N2
19. (o2V7
20. 0.4 21. J2k and 0.0158
22. Zero
24. HF'4 26. 4.5 x IO21

27. 1.23 x IO-7 eV 29. 0.269
30. 1264 K 31. 5.7 eV
33. 2.67 x IO-'4 s, 7 eV, 1.57 x 106 m/s and 41.9 nm
34. 2.47 x 1026 t.. 35. 0.36
37. 0.012 and 0.98 38. 0.074 eV and 2.5%
39. 5.1 x 1023 40. 414.9 N/m2
41. AV™ where A = (2/5) (h2/2m) (3N/8JO273 42. 6 eV, 4.638 x 104 K and 1.5 x IO6 m/s
43. 0.018,0.98, 0.24 and 0.76 44. 3.3 eV, 2.56 x 104K and 1.08 x 106 m/s
45. 9.84 x 109 46. 9.4 eV
47. 3.3 x IO-4, 1,0, 1,0.089 and 0.91 48. 291 K
49. 4.53 x IO27
50. 1.62 x IO2 J kmol4 K'1 and 0.675%, 1.45 and 0.608%
51. 5.27 x 1028/m3, 1.39 x 106 m/s, 4.2 x 10"l4s, 58.3 nm and 0.74 m/s
52. 1.8 x 102 J kmol'1 and 3 x 102 J kmol1 K~*
53. 7.02 eV and 7.019 eV and 6.999 eV

54. 21.6 J kmol’1 K-1 and 4.6 x 103 J kmol-' K_|
55. 2.321 x IO-8 WQK2
56. 2.09 x 10-8 Q-m and 0.35 x IO"2 m2 V-'s"1
57. 4.18 eV and 2.758 x 1015 Hz

58. 1.13 x 10~14 eV
59. 2.04 J kmol 1 K-1 and 1.51 x 102 kmol K“’ 60. 1.39 x 106 m/s and 2 x 108 V m’1
61. 0.8% and 0.36% 62. 6.60 x 104 N
63. 1,0.856 and 0.12 64. 290 K
65. 5.51 x 10-8 Q-m 66. 1.1 x IO"6 Q-m
67. 1.92 x IO"8 Q-m and 0.42 xlO"8 Q-m 68. 1-54 m/s and 2.18 x IO-30 J
69. 0.732 70. 455 W nr1 K-1 and 52.5 W nr1 K-1
72. 5.84 x IO"8 Q-m and 22.4% 73. 4.34 x 10-8 Q-m
74. 159 GHz 75. 11.4 eV
76. 0.969 x 10* Q-m 77. 0.37 x 10-8 m
78. 0.37 79. 2.5 x 1028/m3, 0.0061 m2 V1 s1
80. 0.245 x 10"9 m3 C"1, 4.07 x IO4 m3 O,1 2.49 x IO9 V and 4.07 mV
81. 39.3 mA, double the value 82. 37.49 W
83. 59.9 x IO”16 m 84. 4.5 x 108 Vm-1
85. 0.11x10* 86 421 x IO"8
87. 2.81 x IO-3 Bohr magneton 88. 2
89. 4.1 eV 90. 0.86 x 106 m/s
91. 4.25 x 104 K 92. 9.7 x 10-25 kg-m/s
93. 3 x IO14
CHAPTER 7
I 1*56 * 10” Hz, 345 x 10’1* ' 2 *47 / 1<? kJ kwA '
t 62,67 J/kmol K and 1,6 x IO1 kJ/kmol K
4 H,44x 10” Hz. 74 x IO*2 Hz, Ihevitxatumal frequency <Xalum*nmm atom m 64 x 1022 Hz and
it comparable
5, 616.6 K 6 34* K
7, Al 3.2 K (he electronic «pecific heat and lattic specific heat are comparaMe,
[C,|,z » 1.97 x 10 4 R* and (CJto » 1,95 x 10 4 R,
H. 3,53 x HJ* K 9. 2<6*xl0»J
10. [CJ,, » 22,7* J/kmohK and II. 3905 K
|CJto * 4,6 *
12. 1.328 Wkmol'1 K’
naioNadav
CHAPTER*
1. 24,81 A X 4,139 K
3. 1.16 mm 4. 1,71 x 10* A/m2
5. 0,02*2 A/m 6. 14,5 K, 20,7 x 10s A/m, 18.9 x 10* A/m
7. 53 nm, ICP/m2 g. 0X10I5 nm

10. 4,2 x 10* A/m II. 2.13 K
12. 29.3 nm, 34% 13. 7,193 K, 39 om
14. 0.39 x l(T* m IS. 3,15 x 10” Hz
16. 34 x J(HeV If. 43.9 J/m2
CHAPTER 9
1. 203 A/m, 17,3 X 1.26 WWm2 - 8 A/m2
3. 1,259 Wm3, 1500 A/m 5. 0X15 A/m

6. 07)196 Am2,2,5 x 10’ Nm 7. - 3 x 10’ A/m, 1.257 x I07 teda
*. tOOWb/m2 9, 041 Bohr magneton

10. -5x 10* |j. 19,95 Am2
12. S^xlO’r’ 13. 3.28 x 104,242 x 10* A m2

14., 043 x 10* 041 Bohr magneton IS. 2.2 Bohr magneton
16. 1,736 Bohr magneton 17. 0,196 x 10 2,1 A m2 or 0.021 Bohr magnetos
1*. 4.36 Bohr magneton 19. 3,6 x 10 21 joule
26. 34 K 21. 241 x 10 ’ Bohr magneton

22/ 34 tctla 23. 24 x I027 A m2, 50%
820
24. 15.8 x IO5 Am-', 0.66, 1580, 3135 tesla 25. 4 Bohr magneton
26. 8.7 x IO-5, 87 A/m . 27. 2.72 x IO"3 Bohr magneton/spin
28. 1.517 Bohr magneton 29. - 0.88 x IO-9
31. 2.7 x 1022 Bohr magneton, 5.1 x 106 A/m 32. 5 x 107 A
33. 3.7 x ICT29 A m2 34. 1489 W/m2
35. 6.78 x 103 A/m 36. 1.7xl05A/m2
37. 2.3 x 10~3 38. 0.016 x IO-6
CHAPTER 10
1. Ef - Ev = 0.385 eV, 3.5 x 1019 /m2, 8.6 xl0~34/m3
2. 5 x 10,8/m3 3. 0.72 eV
4. 2.22 fl-1 nr1 5. 625 nm, Red
6. 1.13 A 7. 0.128
8. 0.648 eV 9. 4.31 x 103 fl
10. 23 x 1018/m3 11. 1015
12. 4.41 x lO^/m3, 1.27 x 1013/m3, 0.47 fl-■m, 3.73 x 10 7 fl-m
13. 0.22 14. Ec - Ef= 0.16 eV, <sx = 3120 fl-1 nr1
15. n = lO^/m3, p = 9.6 x 1010/m3 16. 1.44 x 1016/m3, 2.24 x 103 fl W
17. 0.07 m2 V-1 s"1 18. 2 x 109/m3
19. Ec-Ef- 0.33 eV 20. p = 1016/m3, n = 2.25 x 1016/m3
21. Ec = E' = 0.379 eV 22. Ec-E’ = 0.367 eV
23. 5.488 x 1(H fl-1 nr1 24. 4.6 x lO^/m3, 7 x 107/m3, 0.92 x lO^/m3
25. 4.32 x 10"4 fl-1 nr1,10.4 fl1 nr1 26. a, = 3.53 fl-1 nr1, = 7.6 fl-1 nr1
28. 2.03 x lO^/m3, 1022, 1.56 x 108/m3 29. 1.3 fl-1 nr1, 0.0603 fl1 nr1 K-1
30. Ec - Ef= 0.32 eV, 3.8 x 1013/m3 31. O.and 2.1 x IO-9
32. 3.95 x 1016/m3 33. 0.91 fl-m
34. 5.46 x 103 kg/m3 35. 1.01 x lO^/m3
36. 4.5 x lO^/m3 37. 0.51 x 10-12s
38. 6.24 x lO^/m3, 7.7 x IO-11 39. 2.16 fl-1 nr1,142 fl-1 nr1
40. 15.9, 7.25, 0.07 fl-m 41. 3.7 x 10-* C"1 m3,0.74 x IO-9 volt
42. 1.82 fl-1 m-' 43. 11.25 x IO"4 kg/m3
45. 16 x 1013 pair/s, 1.6 x IB*10 fl1 nr1 46. 0.8 x 108
47. 11 x IO"2 watt 48. 0.054 A
49. 2880 A/m2 50. 0.00208 m2/s
51. 1.17° 52. 8.5 x lO^/m3, 1.47 x KT2 m2 V"1 s'1
Appendices 821
ca 0.0344 m2 V-1 s-1, 2.04 x lO^/m3 54. 44 x IO-4 m2 s-1 and 6.47 x Ifr4 m2 s_|
55. 1.25 x 10“3 m2 V'1 s'1
% 1.74 x 1014 s’*, 1.34 x 1019/m3, 115 gs, 1.73 x 10,7/m3
57> 4 3 ps 58. 0.173 eV, 4.6 x 1019/m3, 2.12 x 10,6/m3
59. 0.0047 x m2 s-1 60. 1.97 x IO"5 m, 3.15 x IO3 A/m2, 4.4 x 102 V/m
61. 8.5 nm, 17.8 nm

62. 1.56 x 1018/m3, 1.0075 x 1019/m3, 1.83 x 10,7/m3
63. 0.25 V 1.35 V 64. 2.5
65. 4 3 x 10"7 m, 165 p.|if, 35.1 x 10-8 m, 202 p.|if, 2500 nm, 28 jigf
66. 0.271 V, 5.3 x IO-7 m, 0.8|l|if, Xj = 5 Xj 67. 88 ft, 11.4 ft
68. 150 ft, 6mA, 14 mA, 300 ft 69. 0.0166 V
70. 0.178 V 71. 7.8 x 1013/m3, 8.15 x 102 A/m2, 0.87 jif
72. 0.514 volt, 1.1 x 10 6 m and 1.1 x 10-5 m, 0.0878 ji|xf
APPENDICES
73. 0.68 V 74. 0.285 V
CHAPTER 11
1. 1 joule, 0.99 joule 2. 26.55 |iC/m2, 17.7 gC/m2, 13.28 J/m3

4. 8.4 x 10~7 C/m2 5. 1.0024
7. 3.24 x KT40 Fm2 8. 1.43 x lO^Fm2
10. 0.0587 mm, 7.03 x IO"17 m 11. 1.35 x KT8 C
12. 2.81 x 1O~10 C/m2, 3.4 x l(r17m 13. 7.8xl0"14m
14. 6.9 x 1(H5 Fm2 15. 9.6x 10-nm,2.6x 10“16m, — =3.7x IO5
X
16. 0.5 x IO-19 Fm2, 2 x IO 39 Fm2, 1.5 x 10“ 39 Fm2

17. 9.66 x IO-7 C/m2, a = 0.836 x 10“3
18. 7.3 x IO-37 cm
19. 2.2 x 10~39 Fm2, 1.52 x 10'39 Fm2, 0.228 x 10“39 Fm2
20. 3.537 x 107 V/m, 3.35 x 10“11 Cm 21. 1.000108, 1.00108
22. 10-’1 C/m2 23. 0.355 x IO"29 Cm
24. 4.17 x lO^Fm2 25. 3.105
Q2
26. 1.5 27. — Fm2
UJ
28. 1.029 29. IO-40 (3.5-1 0.06)
30. 226 pgF, 10 Mft
31. 1.8 Mft, 221.4 jigF, 0.287 ft, 221.4 miF
32. 1.735
Bibliography
iMiiiMMMIttfciMiMiiiMM m iwihriiiii.
Solid State Chemistry, N.B. Hannay, Prentice Hall. Inc., N.J. (1967).
2* Introduction to Properties of Materials, Daniel Rosenthal and Robert M. Asimon, Affiliated
East-West Press Pvt. Ltd., New Delhi (1974).
Solid State Physics, A.J. Dekker, Macmillan, London (1958).
Solid State Physics, GI. Epifanov, Mir Publishers, Moscow (1979).
5* Introduction to Solid State Physics, C. Kittel, Wiley Eastern Limited, New Delhi (1985).
** Solid State Physical Electronics, Aldert Vander Zeil, Prentice Hall of India Private Ltd., New
Delhi (1971).
Science of Engineering Materials, C.M. Srivastava and C. Srinivasan, New Age International
(P) Ltd., Publishers, New Delhi (1987).
Solid State Theory, W.A. Harrison, Tata McGraw-Hill, New Delhi (1970).
** Elementary Solid State Physics, R.Ramasamy, Lakshmi Publishers, Madurai (1971).
Electronic Properties of Materials, Rolf E. Hummel, Springer-Verlag, New York (1985).
The Physics ofEngineering Solids, T.S. Hutchison and D.C. Baird, John Wiley, New York (1987).
12. Quantum Theory of Crystalline Solids, Alexander O.E. Animalu, Prentice Hall, New Jersey
(1977).
ri ri ri ri
Physics of Semiconductors, S.M. Sze, Wiley Eastern Limited, New Delhi (1988).
Superconductivity, T.V. Ramakrishnan and C.N.R. Rao, Wiley Eastern Limited, New Delhi (1992).
Properties of Electrical Engineering Materials, G.C. Jain, Harper and Row, New York (1967).
Lectures on the Electrical Properties of Materials, L. Solymar and D. Walsh, Clarendon Press,
Oxford (1970).
si
A Guide to Superconductivity, David FishLock, Macdonald, London (1969).

ri
Physical Principles of Magnetism, F. Brailsford, D. Van Check Nostrand Company, London

(1966).
ri ri a
Polar Dielectrics, Jack C. Burfoot, MacMillan Private Ltd., New York, (1979).
Magnetic Materials, J.C. Anderson, Spottiswoode Ballantyne and Co. Ltd., London, (1978).
Thermal Conduction in Semiconductors, D.M. Rowl and C.M. Bhandari, New Age International
(P) Ltd., Publishers, New Delhi, (1980).
Jiri
Iasers and Electro-optics, Christopher C. Davis, Cambridge University Press, London (1999)-
Electronic Devices, ER. Connor, Edward Arnold (Publishers), London (1994).
822
Index
attenuation coefficient, 368

A
in optical fibres, 731
a.c. Josephson effect, 393
avalanche breakdown, 599
resistivity, 362
effect, 599
absence of five-fold rotation, 97
average speed, 181
absolute permeability, 429 axis of symmetry, 94
absorption frequency, 702 azimuthal quantum numbers, 14
acceptor impurity, 542
acoustic attenuation, 368 B
activators and co-activators, 704 BCS ground state, 387
adiabatic demagnetisation, 465 theory, 382, 385, 388
allotropy, polymorphism, 123 Balmer, 4
amorphous solids, polycrystalline materials, 87 series, 10
ampere’s hypothesis, 430 band structure of semiconductors, 524
angular coordinate, 13 structure, 525
momentum vector, 436 theory of solids, 291
Bardeen, Cooper and Schrieffer, 359, 385
momentum, 13, 436
barrier energy, 591
anion, cation, 52
basis, pattern, 88
anisotropy energy, 498
Blackman and Kellerman, 351
annealing, 136
Bloch, 293
annihilation, 562
wall, 499, 500
anomalous dielectric dispersion, 662
Gruneisen law, 253
expansion, 266
Bohr magneton, 430, 435, 438
antiferroelectricity, 659
model of atom, 4
antiferromagnetism, 502
radius, 8
application, 27, 579
Sommerfeld atom model, 23
applications of lasers, 724
Bohr’s correspondence principle, 225
of superconductivity, 398
frequency condition, 5
of superconductors, 402
theory of hydrogen atom, 5
asymptotic curie temperature, 503
atom, structure, 3 bond energy, 53
atomic oscillators, 334 bonding force, 48

Bondings in solids, 47
packing factor, atomic radius, 105
823
;ss • •■WvuhCS
bonds, 73, 74, 76 cohesion of atoms, 48

Bom, 56 cohesive energy, bonding energy, 50
Haber cycle, 62 collision time, 194, 195
Madelung theory, 55 colour centres, 703
Bom’s probability, 163 combination of symmetry elements, 98
Brackett series, 11 complex dielectric, 671
Bragg, 165 dielectric constant, 662
Bragg’s equation, 170 compositional defects, 131
law, 166 conclusion, Rutherford model, 4
planes, 162 conductivity at high frequency, 269
X-ray spectrometer, 167 continuity equation, 570, 600
Bravais lattice, 87, 90 cooper pair, 360, 385, 386
breakdown diode, 605 coordination number, 100, 105
Brillouin function, 463, 487 correction, 171
zones, 303, 305 correspondence principle, 225
building blocks, 89 Coulomb’s law, 3, 48, 624
Burgers vector, 133 coulombian force, newtonian centrifugal force, 5
covalent bond, 65
c bonds or compounds, 71
caesium chloride structure, 112 substances, 71
calculation, 50, 57, 59 critical current, 364
of rn and En, 8 or transition temperature, 358
carrier lifetime, 563 cross over point, 525
cartesion positive integer coordinates, 345 ciyotron, 403
centre of symmetry, inversion centre, 94 crystal field and quenching, 473
centrifugal force, radial acceleration, 3 lattice, space lattice, 87
classical free electron theory of metals, 181 momentum, 308
model-Drude model, 695 physics, 87
susceptibility, 287 planes, directions, 118
theory, Langevin-Curie law, 440, 446 system, 90
wave equation, 198 symmetry, 92
quantum theories, 197 crystalline anisotropy energy, 498
theory, 190, 334 crystals, 64
classification, 657 Curie constant, 451, 459, 486
of ferroelectric materials, 657 law, 459
Clausius-Mosotti relation, 645 molecular constant, 453
closest packing, 107 temperature, 427, 455, 652, 656
coercive field, 652 Weiss law, 455, 483, 485, 654
force. 475, 480, 495 current loop, Ewing, 430t 437
coercivity, 475
coherence length, 366, 386, 388
D distribution of atoms, 120
4.c. Josephson effect, 391 domain model, 496
pavisson-Germer, 161 structure, 500
de Broglie hypothesis, 158 wall energy, 499
wavelength, 159 domains, 491, 498

dopants, donor, 540
Debye, 623
drawbacks of Bohr-Sommerfeld atom model, 23
Scherrer, 169
Debye's temperature, 180, 253 of classical theory, 190
approximation, 346 of Rutherford model, 4
equation, 647 drift, diffusion, 566, 568
frequency, 346 velocity, 185, 187
temperature, 348 Drude, Lorentz, 186

ductility, malleabillity and softness of pure metals, 124
theory, Langevin theory, 635
theory, 343
E
degenerate, non-degenerate, 230
eccentricity, polar equation, 14
delta iron, 123
edge dislocation, 132
density of energy states, 233
effect of magnetic field, 361
of vibrational modes, 345
effective mass, 530
depletion layer, 589
mass of electron, 309
diad axis, 96
number of Bohr magneton, 461
diamagnetism, 288, 365, 439
effects of dielectrics, 679
diamond cubic structure, 110
eigenvalues of energy, 221
dielectric constant, 624
Einstein relation, 569
absorption, 679
Einstein’s coefficient, 707
constant and refractive index, 648
mass-energy relation, 158, 200
loss, 676, 678
theory of specific heat, 340
in alternating field, 662, 664
electric flux density, electric displacement, 625, 630
Dielectrics, 623
properties of metals, 180
diffraction, 165
electrical resistivity, 189
diffusion coefficient, 568
resistance, 267
current density, 568
electrodynamics, 373
length, 573, 574
electron configuration, 30
dipole, 666
in a periodic field, 294
moment, 623, 631
paramagnetic resonance (EPR), 711
directional nature of a covalent bond, 68
scattering, 252
dispersion bonds. 74
electronegative element, 52
dipole bonds, dispersion forces, 75
electronegativity, 52
dissociation energy, 62
electronic defects, 131
distinction between metals and insulators, 312
$600 Stare Physics
polarisation, 632 ferroelectricity, 651

specific heat, heat capacity, 191, 239 ferroelectrics, 632
ionic polarisation and orientational polarisation, 634 ferromagnetic curie temperature, 485
electron-lattice scattering, 184 domains, 493
elliptical orbits for hydrogen, 13 ferromagnetism, 474
emission coefficient. 280 field strength, 430
current, 280 fine structure of Ha line, 23
energy gap, 536 flaky structure, 70
of dissociation, 50 flip-flop, 403
entropy, 366, 382 flipping, 286
Epstein, 641 fluid model, two-fluid model, 363
equation for stationary states, 202 flux density, electric displacement, 625
equilibrium concentration, 563 density, magnetic induction, 376, 428, 429, 436
energy, 57 exclusion, 364
spacing, 49, 525 forbidden energy gap, 526
evaluation of the local field, 643 forward biasing, 593
exchange forces, 483 free-electron theory, 197
interaction, 492 particle, tunnel effect, 208, 209
excitation energy, 700 Frenkel defects, 126, 129
excitons, 704 frequency dependence of ionic polarisability, 663, 670
exhaustion range, 556, 557
experimental demonstration, 500
G
extinction coefficient, 694 G.P. Thomson, 161
gamma iron, 123, 124
F gaseous molecules, 640
face centred cubic structure, 107 gauge factor, 269
failure of Sommerfeld’s free electron theory, 292 Gauss theorem, 627, 628
F-centres, 703 generation and recombination, 560
fermi curve, 238 geometrical construction, 139
distribution function, 237 Germer, 161
energy, fermi level, 233, 235, 137, 241 Giaever, 389
level in impurity semiconductors, 545 glancing angle, 166
surface, 249, 250 glide plane, 98
temperature, fermi velocity, 237, 287 Goudsmit, 24
Dirac statistics, 194, 232 Gouy method, 468
ferrimagnetism, ferrites, 505, 506 graded-index fibres, 730
ferroelectric curie temperature, 652, 654, 656 grain boundaries, 135
materials, 654, 657 gyromagnetic ratio, 432
scattering, lattice scattering, 557
H
induced dipole moment, 666
HsP mgk.578
dipoles, 631
oicflkient 275. 576
inductive impedance, 363
effect 273. 575
reactance, 363
field. 577
insulating materials, 683
roltage. 273
insulators, 521
^d magnetic materials, 511
interatomic forces, 47
fcp structure. 108
separation, 48
ctfw-ity of electron, 239
intermolecular bonds, 74
edacity, electronic, 191, 239
field, 486
of dissociation, sublimation, 62
internal field, 481, 486
Heisenberg. 163
field and exchange interaction, 491
Weiss. Ewing, 485
field constant, 643
Hriynherg's uncertainty principle, 163
local field, 641
Heitler-Loodon model, 492
molecular field, 481
hemochromatosis, 407
interstitial atoms, 566
Herbert Frohlich, 383
impurity, 131
heiropolar bonding, homopolar electron pairing, 65
interstitialcies, Frenkel defects, 126
high resistivity materials, 291
intramodel dispersion, 731
hole diffusion coefficient, 569
intrinsic activation, 529
holography. 735
and extrinsic semiconductors, 527, 528
homopolar, or electron-pairing bond, 65
excitation, 552
Hooke's law constant, 334, 339
semiconductors, 529
Hand rales. 472
ionic bonding, heteropolar, 52
hybrid bonding, 69
hybrid orbitals, 70 conduction, 186, 700
hybridization, 70 polarisation and orientational polarisation, 634
hydrogen atom. 8 solids, 64
bonds. 76 ionisation energy, 9

potential, 38
spectrum, 9
by*rr»u, 474, 500 isotope effect, 369, 385
>wp. 652 isotropic scattering, 272

H« hae, 10,22
J
I
J. Bardeen, W. Brattan and W. Shockley. 521
^“1 naistivity, 258 John Bardeen, 384
‘®P«fccuon in crystal, 124 Josephson's tunneling, 390

UBPw'ao« of Schrodinger equation. 204 Joule heating, 357
•“•PurMy conduction, 539 Joule’s law. 271
'**• exhaustion range, 556, 557

K low resistivity materials, 289
Kamarlingh Onnes, 358 temperature superconductors, 405
kinetic thermal motion, 182 lower dynamic resistance, 600

velocities, 181 luminescence, fluorescent, 704
Kronig-Penny model, 294 Lyman series, 10
L M
Lande factor. 460 macroscopic quantum interference, 394

g factor, gyromagnetic ratio, 438 Madelung constant, 56, 58
Langevin function, Langevin curve, 450, 638 magnetic dipoles, 427
theory, 446, 635 induction, 429, 436
Langevin's formula, 443 orbital quantum number, 24, 25
function, 450, 637 permeability, 428
theory of polarisation in polar dielectrics, 635 polarisation, 442
Larmor frequency, 439, 713 powder pattern, 500
precession, 439 properties of materials, 427
theorem, magnetic moment, 442 quantum number, 431
lasers, 715 spin quantum number, 24
different types-of lasers, 717 - 722 susceptibility, 428, 437
lattice energy, 55 moment, 441
parameters, 89 magnetism in metals, 285
planes, 115 magneto caloric effect, 467
points, space lattice, 87 encephalography, 409
scattering, 557 resistance, 181, 273, 276
vibration, 255 magnetostrictive energy, 500
Laue, 165, 169 magnetoencephlography, MRI, 409, 410
Lenz’s law, 439 majority carriers, 540
Leon Cooper, 384 manufacture of optical fibres, 732
levitation, 404 masers, 705
light emitting diodes, 607, 724 and lasers, 705
line imperfections, 132 mass action, 534
local field, internal field, 641 energy relation, 158
London equations 373, 374 matter waves, 159
penetration depth, 376 Matthiessen's rule, 181
Lorentz field, 644 Maxbom, 206
force, 274, 441, 665 Maxwell's equation, 374
field, 645 mean collision time, 181
number, 194, 264 energy of the electron, 241
Lorenz equation, 648 free path, 191
loss angle, 678 mobility, 189
mechanical effect on electrical resistance, 267 terminology, 736
mechanism in superconductors, 359 conductivity, 695
mechanism of current conduction in semiconductors, constant, refractive index, 694
558 fibres, 727
Meissner and Ochsenfcld, 364 properties of solids, 694
effect, 361. 364. 370 terminology, laser plasma, 736
Mendelyeev, 30 orbital angular momentum, 433
metallic crystals. 73 gyromagnetic ratio, 431
method of images, 282 orientation polarisation, 651
Miller indices. 112 origin of ferromagnetism state, 476
minority carriers lifetime, 562 of magnetism, 433
mobility. 527 other cubic structures, 110
of charge carrier, 275, 565
molar electronic specific heat, 191 P
polarisation, 647 parallel and antiparallel dipoles, 456
molecular field coefficient, 454, 481 paramagnetic curie temperature, 484
field constant, 486 susceptibility, 455
magnet, 448 volume susceptibility, 451
moment of current loop, 438 particle in a rectangular three-dimensional box, 225
momentum space, 278 Paschen series, 11
Pauli’s exclusion principle, 27, 232
N
penetration depth, 370
Neel and Bitter, 502 pentavalent impurities, 541
INDEX
temperature, 502, 505 periodic potential, 294
new superconductors, 395 table, 30
non-degenerate energy state, 300 permanent dipole moment, 635, 640
polar materials, 631 permittivity of free space, 3
polar polyatomic molecules, 640 Pfund series, 11
Nordheim's rule, 261 photo diode, 607
normalization of wave function, limitations, 200, 207, photoconductivity, 704
222
physical significance of the wave function y, 205
n-type semiconductors, 543 physics of drift, 537
nuclear magneton, 433 piezoelectricity, 660
Planck’s constant, 5
O
quantum theory, 200
Ohm’s law, 180, 182
plane of symmetry, 94
one-dimensional box, 220
p-n junction, 580
optical, 694
point defects, 125
absorption coefficient, 695
group symmetry, 92
absorption in metals, insulators,
polar and non-polar bonds, 71
semiconductors, 694, 701, 702
•iid non polar materials, 651 relation between the density of crystal material and
dielectrics, 635 lattice constant, 110
solids. 650 between electrical conductivity and thermal

polarisability. 634 conductivity, 192
in ionic crystals, 649 relative dielectric constant and refractive index, 701
ionic. 634. 649,652,670 permeability, 429
polarisation. 624 permittivity, 623
polycrystalline materials, 87 relativistic correction, 160
population inversion, 706 relaxation process, 188
potential applications, 402 time, 185, 194, 566, 567
barrier, 209, 585 remanence, 494
function, 282 remanent flux density, 480
powder crystal method, 169 repulsive exponent, 56, 59
power applications of superconductors, 410 residual resistivity, 257
pramagnetic curie point, 455 resistivity, 180, 257, 362
primary bonds, secondary bonds, 52, 74 restoring force constant, 664
primitive cell, 90 reverse biasing, 594
principal quantum number, 6, 14 permeability, 494
probability density, 205 Richard-Dushman equation, 280
properties of ionic solids, 64 root mean square velocity, 182
pseudo constant, 531 rotating crystal method, 170

rotation symmetry, 94
Q rule of two, 71
quantum mechanics of simple problems, 207 Rutherford model of the atom, 3
numbers, 5, 24 Rydberg constant, 9
theory of ferromagnetism, 485
theory of free electrons, 197
s
theory of paramagnetism, 459 saturation in covalent bonds, 68
tunneling, 389 induction, 495
Quincke’s method, susceptibility, 470 polarisation, 475
sc, bcc, fee, hep structures, 113
R scattering cross-section, 260
radial coordinate, 13 Schottky defects, Frenkel defects, 125, 126
momentum, 13 effect, 281
randomizing effect, 476 plots, 284
reciprocal lattice, 138 Schrodinger wave equation, 200
reciprocal lattice parameters, 144 time-dependent wave equation, 202

Schubnikov, 372
recombination coefficient, 563
screw axis, 98
reflection coefficient, 218
dislocation, 133
probability, 218
symmetry, 94 secondary bonds, 74
Index 831
'lection of electrical engineering materials, 288 Strak effect, 13

structure of ferrites, 506
rules. 12
Semiconductors, 521, 535,-557 sublimation energy, 62
shortcomings of Bohr’s theory, 12 substitutional impurity, 131

superconducting gyroscope, 404
Silsbee effect, 372
Silsbee’s rule, 364 state, 356
susceptometer 408
skin depth, 379
sodium chloride structure, 112 superconductivity, 181,' 356
soft magnetic materials, 508 superconductors in a.c. fields, 377
solar cell, 608

supercurrent density, 374
solid substance, 455 superelectrons, normal electrons, 363, 373

some special p-n junction diodes, 605 surface imperfections, 135
Sommerfeld’s relativistic correction, 22 susceptibility determination, 468
relativistic atom model, 13 symmetry elements, 92
space groups, 99 operation, 92

quantisation, 433, 434
spatial quantisation, 24, 431
T
specific heat, 333, 366, 381 technical magnetisation curve, 493
spectral series, 10 temperature coefficient of resistance, 567

spectrometer, 167 effect on charge carriers, 556
spectroscopic splitting factor, 713 tetrad axis, 96
spin aligning energy, 476 the basis and crystal structure, 88
energy gap, 368
INDEX
angular momentum, 432, 434, 435
gyromagnetic ratio, 432 penetration depth, 370
magnetic moment, 432 theory of electronic polarisation, 633
paramagnetism, 285, 465 of ferromagnetism, 476
spinning of electron, 24 ' thermal agitation, 527
emission, 706 conductivity in metals, 262
polarisation, 652 conductivity, 262, 367, 368
magnetisation, 481, 486 excitation, 528
SQUID, 405 - 409 expansion, 265
stable lattice, 49 motion, 181
stacking defect, 136 movement, 566
Stark effect, Zeeman effect, 13 properties of solids, 333
stationary state, 203 properties, 366
orbits, 5 vibration, 125, 356
statistics of extrinsic semiconductors, 543 thermionic emission, 276
steady state drift velocity, 189 thermodynamics of superconductors, 380
stcp-index fibres, 730 tilt boundaries, 136
stimulated emission, 705, 706
JfWw- W3M» FoV>»C5 .
_ --' /■■-■■ h- . ■. . •-------
total electric flux. 627 virtual phonon, 385
molar specific heat, 351 Volt-ampere characteristics of p-n junction, 590

transducer, 662 volume defects, 137
translation symmetry elements, 99 hologram, 734
transmission coefficient, 215 imperfections, 137
probability, 210, 213, 215 susceptibility, 443, 451
traps, lifetime, 561, 562
triad axis, 96
w
trivalent impurities, 541 wave function, 208
tunnel effect, tunnel diode, 209, 210, 607 functions in a band, 307
tunneling, 209, 282 mechanical concept of the atom, 38
twin boundaries, 137 nature of matter, 158
two fluid model, 363 number, 9
Type I and Type II superconductors, 371 Weiss molecular field, 486
and Type n, 359 theory, 454
theory of paramagnetism, 454
u width of depletion layer, 586
Uhlenbeck and Goudsmit, 24 Wiedemann-Franz law, 181, 192, 264
unit cell and lattice parameters, 89
universal gas constant, 181
X
X-ray diffraction, 165
V spectrometer, 167
vacancies, Schottky defect, 125 X-rays, 166
valence band, 524
van der Waals, 62 z
and hydrogen bonds, 52 Zeeman effect, Stark effect, 24
forces, 71, 72 Zener breakdown, 599
Van Laer and Keesom, Varactor diode, 380 diode, 599
variation of resistivity with temperature, 255 zigzag motion, 186
vector-algebraic discussion, 140 zinc blende structure, 111, 112
atom model, 24 Zurich superconductors, 397
vibrational energy, free energy, 186
modes in a continuous medium, 343

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Revised Sixth Edition

(NEW REVISED SIXTH EDITION)

NEW AGE INTERNATIONAL (P) LIMITED, PUBLISHERS

Copyright C 2005. 2002, New Age International (P) Ltd,, Publishers

Al! rights reserved.

Typesetter: Print Tex India.

PUBLISHING FOR ONE WORLD

NEW AGE INTERNATIONAL (P) LIMITED, PUBLISHERS

4835724, Ansari Road, Datyaganj, New Delhi - 11<XXn

Preface to rhe Sixth Edition vii

IMTERAT C FORCES AND BONDING IN SOLIDS

Calculation of Repulsive Exponent from

Properties of Ionic Solids

Examples of look Solids

XIV Covalent Bond

XVI Direction^ Nalurc.uf a C.Qvuli:nt Bond

XY11I Properties of Covalent Compounds

xxm Dipok Bonds

Hl : The Basis and Crystal Structure

VII : Crystal Symmetry (Symmetry Elements in Crystals)

IX : To Show ih^fiviToldKotaiimAxis isntx

Com patible with a La ft i ce

X : Combination of Symmetry Elements

XIII : Space Groups

XL¥ : The Bravais Space Lattices

XYH : Other Cubic Structurcs

XIX : Important Features of Miller Indices of Crystal Planes

XX : Important Planes and Directions in a Cubic crystal

XXII : Separation between Lattice Planes in a Cubic Crystal

XXV : Reciprocal Lattice

1___ WAVE NATURE OF MATTER AND X-RAY DIFFRACTION

IV Experimental Study of Matter Waves

V TheDavisson-Germ erExpen ment

VII X-ray Diffraction

Bragg's X-ray Spccirameter

in Drawbacks of Classical Theory

Relaxation Time, Collision Time and Mean Free Path

Classical Wave Equation

IX Importance of Schrodinger Equation

Physical Significance of the Wave Function y

Limitation s on y j nd Norm ah sat ion of Wave Function

XIV Fermi-Dirac Statistics and Electronics Distribution in Solids

i:ul eimi DuiribuhoaEimGiion

xvu Heat Capacity of the Electron Gas

XVIII Mean Energy of Eteccron Gas at Absolute Zero

Effect of Temperature of Fermi Distribution Function

XXI Electron Scattering and Sources of Resistance

XXIII : Resistivity of Alloys

XXV : Thermal Conductivityin Metals

XXIX : Joule's Law

XXX : Effect of ihe Magnetic Fields

XXXU : Schottky Effect

XXXIV ; A Note on Selection of Electrical Engineering

xxxx Monon of Electrons m a OneJJimcnsmnalJ •VtT<

7. THERMAL PR0PERT1ESDF SOUDS

n Lattice Specific Heat

in Classical Theory (Dtdong and Petit Law)

IB An Account of the Mechanism o ~ Superconductors

IY Effects of Magnetic Field

YUI Thermal Properties

I ype I and Type H Superconductors

Xii rhermodynamics of Superconductors

9. MAGNETIC PROPERTIES OF MATERIALS