MONOGRAPH

ON
APPLIED PHYSICS - II
(PH-1007)

BY
ANAMOL GAUTAM
RAJESH MOHNI

AKAL COLLEGE OF ENGINEERING AND TECHNOLOGY

VIA RAJGARH DISTT. SIRMOUR
HIMACHAL PRADESH

1
 Preface

There is a great relation between physics and engineering

and most of the technological developments and their
advancements have been the result of joint efforts of physicists
and engineers. Therefore, the subject physics is very important
and indispensable for engineering students.
Students face problems in this subject because there is
no well defined book on the subject which covers all the topics.
So we have gleaned this material from various sources for you
people. This monograph will serve the purpose very well.
There is a list of books given at the end of this monograph, all
these books are available in the library and you can still find
many more books to remove lacunae in your knowledge.
We are thankful to Dr. Prabhakar, Principal ACET. Dr.
Atwal, Director, higher Education, kalgidhar Trust; for providing
us this opportunity. We are also thankful to all faculty members
and staff members for their encouragement and co-operation.

Anamol Gautam
&
Rajesh Mohni

2
 Syllabus
Section A

Crystal Structure: Space lattice, unit cell and translation vector, miller indices, simple
crystal structure, bonding in solids, experimental x-ray diffraction method, and powder
method.

Free electron theory: Elements of classical free electron theory and its limitations,
quantum theory of free electrons, Fermi level, density of states, Fermi-dirac distribution
function , Thermionic emission , Richardson’s equation.

Section B
Band Theory of Solids: Origin of energy bands, Kronig Penney model (qualitative), E-K
diagrams, Brillouin zones, concept of effective mass and holes, classification into metals,
semiconductors and insulators, fermi-energy and its variation with temperature.

Section C
Photoconductivity and Photovolatic: Photoconductivity in insulating crystals, variation
with illumination, effect of traps, application of photoconductivity, photovoltaic cell and
their characteristics.

Properties of Solids: Atomic magnetic moments, orbital diamagnetism, classical theory

of paramagnetism , ferromagnetism molecular field theory and domains, magnetic
circuits, its comparison with electric circuit and its application, superconductor
(introduction , types and application), hall effect.

Section D
Laser: Spontaneous and stimulated emission, laser action, characteristics of laser beam-
concept of coherence, types of laser based on pumping techniques, He-Ne laser ,
Semiconductor laser (simple ideas) with applications.

Fibre Optics: Optical communication: communication through open space optical wave
guides with special reference to propagation of light fibres, numerical aperture, single
mode and multimode fibres, applications

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CONTENTS PAGE NO.

SECTION A

CHAPTER 1 CRYSTAL STRUCTURE 1-23

CHAPTER 2 X-RAY DIFFRACTION 24-29

CHAPTER 3 FREE ELECTRON THEORY OF METALS 30-49

SECTION B

CHAPTER 4 BAND THEORY OF SOLIDS 50-68

SECTION C

CHAPTER 5 PHOTOVOLATIC 69-77

CHAPTER 6 DIA- PARA- FERROMAGNETISM 78-91

CHAPTER 7 SUPERCONDUCTIVITY 92-98

SECTION D

CHAPTER 8 LASER 99-111

CHAPTER 9 FIBRE OPTICS 112-122

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 CHAPTER 1

CRYSTAL STRUCTURE
The three states of matter are solids, liquids and gaseous. Solids have used shapes
while the other two states do not have any shape. Solids further exist in two states
crystalline and amorphous. The crystalline solids show periodicity in the arrangement of
atoms while amorphous solids are irregular in shape. The crystalline solids are further
divided into two types single crystal and poly crystalline solids, if the entire solid consists
of only one crystal i.e. the periodicity of the arrangement of atoms extend up to infinity,
the crystal is termed as single crystal. In polycrystalline materials a number of aggregate
crystallites are separated by well defined boundaries. The small crystallites are known as
grains and the boundaries are known as grain boundaries. Materials like rubber, glass etc.
are amorphous. Diamond, rock salt, mica, quartz etc. are crystalline. Many properties of
materials are found to depend upon the structure of the crystal. For this reason in this
chapter we will study basic concepts and simple structures of solids.
Crystallography
The study of the geometric form and physical properties of crystalline solids by
using X-Rays electron beams and neutron beams etc. constitutes the science of
crystallography.
Since in crystalline solids the atoms and molecules are arranged in regular and
periodic manner, so most of the solids are crystalline in nature because energy released
during the formation of ordered structure is more than that released during the formation
of a disordered structure. Thus crystalline is the low energy state and most of the solids
preferred this state.

Crystal Lattice And Translation Vectors

Atoms in a crystal are arranged in the form of periodic array. This array consists
of a representative unit of the structure, usually a group of atoms or molecules which are
also referred to as “motif”. If these representative units in the array are replaced by
simple mathematical points, the resulting collection of points is called a lattice. Thus, a
space lattice may be defined as an infinite array of points in three dimensions in which
every point has identical surroundings. The term identical surroundings means that the
lattice has the same appearance when viewed from a point r→ in the, lattice as it has
when viewed from any other point ŕ→ w.r.t. some arbitrary origin. Fig.1 shows a finite
two dimensional square array of points. Similarly, we have three dimensional space
lattice. However, it must be noted that environment about each point in lattice is same its
shown in fig.1. Third dimension is difficult to show on the paper, so only two
dimensional lattice is shown.

5
 Fig.1 Crystal Structure

To define space lattice, let us consider point O as origin and two vectors a→ and b→,
called fundamental translational vectors in two dimensions. To obtain any point P, we
draw a vector T→ from O to P. Then
T = n1 a→ + n2 b→
where n1 and n2 are integers.
Similarly, in three dimensional lattice
(1)
The application of this operation (1) to any point r→, results in the point r→

(2)
Such translational vectors which produce a translation operation containing
integral coefficients are called primitive translational vectors.
If point r→ is obtained by using equation

Such translation vectors which contain non-integral coefficients are called non-primitive
translation vectors.

Basis And Crystal Structure

Lattice is simply the network of points in space, until we associate these lattice
points with one or more atoms (i.e. unit assembly of atoms of same composition) we do
not get crystal structure. This unit assembly which make the given lattice a crystal is
known as basis (pattern or motif). Thus basis is the assembly of atoms, ions or molecules
which when repeated in three dimensions generates a crystal structure. A basis may be a
single atom (eg. Cu crystal) or group of atoms or molecular ions (eg. NaCI consists of
Na+ and Cl- ).Thus a crystal lattice combined with a basis generates the crystal structure.
Mathematically
Crystal structure = space lattice + basis.
Crystal lattice is purely a geometrical conception consisting of a periodic
arrangement of points such that by placing different atoms (or groups of atoms) on these
points, we obtain the actual crystal.

6
 The generation of a crystal from two dimensional lattice and a basis is as shown
in fig.2. The basis consists of two atoms, represented by O and • having orientation as
shown in fig.2. To obtain the crystal structure the basis is placed on each lattice point
such that the centre of the basis coincides with the lattice point. The number of atoms in a
basis may vary from one to several thousands, but the number of space lattices possible is
only 14. Hence due to different types of basis available, a large number of crystal
structure can be obtained from just fourteen lattices.

Fig.2. Crystal Structure

Unit And Primitive Cell

Consider a two dimensional lattice array as shown in fig.3. We find that if the
parallelogram ABCD is repeatedly translated by the vectors a→ and b→ along AB and AD
we obtain the same lattice of which this parallelogram is a part. Thus, ABCD is called a
unit cell. The choice of unit cell is not unique; some other unit cells are also shown in the
fig.3. In three dimensional case we parallelepipeds as unit cells.

Fig.3 Two dimensional lattice and different unit cells.

7
 Consider the unit cells ABCD and EFGH displace these portions towards any
direction we find that only one lattice point can lie in the area of the parallelogram.
Displaced parallelograms are shown by dotted lines and are containing points C and F
respectively. Such unit cells which contain only one lattice point are known as primitive
cell. A primitive cell is also a minimum volume cell.
The other unit cells viz. MNOP and PQRS are not primitive since these contain
more than one lattice points.
Therefore, we conclude that the entire lattice can he derived by repeating a unit
cell by means of translation vectors as edges of the unit cell.

Lattice Parameters Of A Unit Cell

Crystallographic Axis
The lines drawn parallel to the lines of inter-section of any three faces of a unit
cell, which do not lie in the same plane are called crystallographic axis. In figure 4 OX,
OY and OZ are crystallographic axis.
Interfacial angles
The angles between the three crystallographic axis are called interfacial angles.
In fig.4 α, β and γ are interfacial angles.

Fig.4 Unit Cell

Primitives
The three sides of the unit cell are known as primitives. In fig.4; a, b and c are
called primitives.

TYPES OF LATTICES
Bravais in 1848 introduced the concept of space lattice to describe the structure of
crystals. According to him there are five lattice types or unit cells in two dimensions and
fourteen in three dimensions.
(1) Two dimensional lattice
There are in all five Bravais lattice types in two dimensions, i.e. oblique, square,
hexagonal, rectangular and centred rectangular. These are shown in fig.5(a).

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 Fig. 5(a) Bravais lattice types in two dimensions

(ii) Three dimensional lattices

There are seven crystal systems in three dimensions namely triclinic, monoclinic,
cubic, Tetragonal, orthorhombic, trigonal and hexagonal. These seven types of crystal
systems generate 14 types of Bravais lattices in which triclinic lattice is of general type
and other 13 are of special type. These space lattices are shown in fig. 5(b) and table 1
gives the seven systems and fourteen lattices.

Table 1.The Crystal System

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Fig.5 (b) space lattice and crystal system.

10
From different crystal structures given above we find that
1. In triclinic arrangement
(i) No two of the three axis are at right angle to each other.
(ii) Repetitive intervals along each axis are different.
2. In trigonal (rhombohedral) arrangement
(i) The three axis are equally inclined to each other at angles other than a right angle
(ii) The repetitive intervals along the three axes are equal.
3. In hexagonal arrangement
(i) The three axes in one plane are 120° from each other and the fourth axis normal to this
plane
(ii) The repetitive intervals along the three coplanar axis are equal but the interval along
the fourth axis is unique.
4. In a simple monoclinic arrangement
(i) One of the axes is at right angle to the other two but the other two axis are not at right
angles to each other
(ii) The repetitive intervals along each axis is different.
5. In a simple tetragonal arrangement
(i) The three axes are at right angle to each other
(ii) the repetitive intervals along two axes are equal and the interval in the third direction
is different from that in the other two.
6. In simple cubic arrangement
(i) The three axes are at right angle to each other.
(ii) The repetitive intervals along the three axis are equal.
7. In Orthorhombic arrangement
(i) The three crystal axes are at tight angle to each other
(ii) The repetitive interval along each axis is different,

MILLER INDICES (Crystal directions and planes)

Many physical properties of crystalline solids are anisotropic i.e. depend upon
directions within the crystal. For this reason, to specify planes and directions in crystal is
an important aspect. For this purpose Miller devised a system which is known as Miller
indices.
The crystal directions are specified by the following method. First whole
numbered point (x, y, z) is determined through which each of the direction passes and is
enclosed in a square bracket. For example in fig.6, OA and OB directions are represented
as [110] and [0l0] respectively and OC is represented as [111]. If there is a negative
component along any axis such as -1, it is represented as ī and read as bar one. It may be
noted that equivalent directions of [l00] are [010], [001], [ī 00], [0 ī 0] and [00ī]. These
six directions are grouped together in the symbol < 100 > i.e. the angular brackets enclose
a family of equivalent directions. There are eight equivalent directions in < 111 > and
twelve in < 110 >. Hence in general a direction is denoted by three integer number [uvw]

The Miller indices of a plane are determined as follows.

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 Fig. 6 Crystal directions

Consider the plane shown in fig.7

(i) Find the intercepts of the plane along the a, b and c axis in other words determine the
coordinates of the intercepts

(ii) Express the intercepts as multiples of a, b, and c

3 2 2
(iii) Reduce these reciprocal into the smallest set of integers in the same ratio.

(iv) Enclose into parentheses

(233)
In general Miller indices of a plane are denoted by (hkl). If n1a, n2b and n3c are
the coordinates of the intercepts made by the plane on the three crystallographic axes, the
Miller indices are given as

Fig. 7 A crystal plane making intercepts 3, 2 and 2

on a, b and c axis respectively.

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Important features of Miller indices
(1) In cubic crystals the direction [hkl] is perpendicular to the plane (hkl), but this
is not true in other crystal systems.
(2) When Miller indices are of double digit, these are separated by commas e.g.
(5, 12, 15).
(3) If a plane is parallel to a coordinate axis then the intercept of the plane is
infinity and hence index is zero.
(4) If a plane passes through origin then the Miller indices are defined for another
plane parallel to this plane and making non-zero intercepts since all the parallel equally
spaced planes have the same index numbers (hkl).
(5) The planes (2 2 6) and (1 1 3) represent the same plane i.e. ratio of the indices
is only important,
(6) The crystall directions of a family < hkl > need not be parallel to each other
similar is the case with members of a family of planes {hkl} some important planes with
their Miller indices are shown in fig.8

Fig.8 Miller indices of some planes.

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 DISTANCE BETWEEN LATTICE PLANES IN A CUBIC CRYSTAL
Let oa, ob and oc are mutually perpendicular lines and form the Cartesian system
of coordinates as shown in fig.9. Consider two planes parallel to each other one passing
through origin (not shown) and other plane parallel to this plane is ABC. If this plane is
represented by Miller indices (hkl), then the coordinates of A, B and C will be (a/h,0,0),
(0,b/k,0) and (0, 0, c/l) respectively.

Fig. 9 An (hkl) plane at distance d from another similar

parallel plane passing through origin.

Let ON = d be the distance between the two planes. Now equation of plane ABC
in intercept form can be written as

(3)
and perpendicular distance of a point O (0, 0,0) from this plane is given as

we have, used the formula that perpendicular distance of point (x1, y1, z1 ) from plane

(4)
Hence distance between two parallel lattice planes is

(5)

Alternative method
Let α, β and γ be the angles made by ON with oa, ob and oc axes respectively.
Hence we can write
(6)
From fig. it is clear that

Now

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 (7)
Hence from eq. (6) & (7) we get

(8)

(9)

(10)

CRYSTAL STRUCTURE
Face-centered Cubic or Cubic Close-packed Structure
The above close packing of cubic symmetry leads to face-centred cube. Here also
the fraction of the total volume filled is 0.74. In this case the first two planes go in the AB
sequence; the third however is displaced relative to both A and B into positions C. A
fourth plane has the A position and the repetition cycle ABCABC……is established. A
unit cell of this crystal structure is shown in fig.10 (a).
This cell is not the smallest possible cell, but it does have one convenient feature ;
the cell is a cube. An atom occupies each corner of the cube and the centre of each face ;
hence the name face-centred cube (fcc). This structure is symmetrical with respect to
rotation by 900 about any one of the cube edges. The more conventional way to draw this
cube is pictured in fig.10(b). The face-centered cubic structure is also close-packed, each
atom having 12 nearest neighbours.
12 is the maximum value of the coordination number in a structure of identical
atoms. In other words no structure with coordination number greater than 12 is possible.
Packing fraction in this ease is also 0.74 as proved below.

(a) (b)
Fig. 10

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 The atoms are in contact along the diagonal of the faces. Let R be the radius of
sphere, then diagonal of the face
= 2R + R+ R = 4R.
Number of spheres in one unit cell =6/2 + 8 * 1/8 = 4

Hence volume of the cube =

= 0.74

Fig. 11 Fig.12 Position of atom centers of bcc lattice

Since fraction of the total volume filled is the same in hcp and fcc structures
hence these are the closest packed structures.
The atoms are in contact along the diagonal of the faces. Elements having face-
centred cubic structure are Cu, Ag, Au, Ca, Al, Pb and Pt.

Body Centred Cubic Structure

All metallic elements do not crystallize in close -packed structure. Li, Na, K, Cr,
Mo, W and ordinary modifications of Fe as well as a number of others have a body-
centred cubic structure. The body-centred cubic is sketched in fig. 12. This unit cell is
cubic with an atom at each corner and an atom in the centre of the cube. This structure is
not close-packed since each atom has only eight neighbours. Note that atoms are in
contact along body diagonals.
Here 8 spheres are attached at each corner of the cube and one atom at the centre
of the body.
Number of atoms in one unit cell = 8 * 1/8 + 1 = 2

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 Say BC = a
Now from triangle ABD

If R is the radius of sphere, AC = 2R + R + R = 4R for closer packing

Hence this structure is not so close packed as hcp or fcc.

Simple Cubic Structure
Another possible structure is the simple cubic arrangement of the atoms. The unit
cube of this structure has atoms only at the corners of the cube, and the atoms therefore
touch along cube edges, fig.13 This structure is loosely packed; each atom has only six
neighbours.
Only one element Po (in a certain temperature region) exhibits this crystal
structure. The simple cubic structure is intrnduced mainly because its simple geometry
simplifies later semi-quantitative calculations and discussions.
Many other cubic unit cells bear a simple relationship to the simple cubic cell.
Some can be reduced to sets of interpenetrating simple cubic sub-lattice. A body-centred
cubic lattice can be considered to contain two identical simple lattices. One consists of
the corner atoms, the other of the centre atoms. Face-centred cubic lattices can be
considered to contain four identical simple cubic lattices properly disposed with respect
to one another.

Fig. 13 Positions of atom corners Fig. 14 Diamond structure

on sc lattice

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Diamond Structure
The diamond structure is a combination of two inter-penetrating face-centred
cubic sublattices. The unit cell is sketched in fig.14. One sub-lattice has its origin at the
point 0, 0,0, the other at a point one quarter of the way along the body diagonal (at the
point a/4, a/4, a/4). The diamond cubic structure is loosely packed, since each atom has
only four nearest neighbours.
Number of spheres in one unit cell =8.
Now the diagonal is 8R where R is radius of sphere. In diagonal there are two half
spheres.
If ‘a’ is a side of the cube then diagonal will be √3 a.

Obviously diamond structure is loosely packed.

If an atom is imagined to be at the centre of the regular tetrahadron, then its
neighbours are on the four corners. Ge, Si and C, (in the diamond phase) crystalline with
diamond structure.

BONDING IN SOLIDS
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.
These bonds are made of attractive and repulsive forces that tend to hold atoms (i.e., ions,
radicals, molecules) or atomic units at a different spacing such that the opposite forces
just balance; and the process of holding them is known as bonding.
Since the particular bonding pattern within a material plays a large part in
determining the physical, chemical, and electrical properties of that materials, the
materials engineer must possess a sound working knowledge of the types of bonding
found in engineering materials.

FORCES BETWEEN ATOMS

The forces between atoms can be of two kinds: forces of attraction and forces of
repulsion. 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
their 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 electrical
charges, one of 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 interatomic separation r. The net potential energy is the sum of both terms:

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 (11)
where α is the proportionality constant or attraction and β for repulsion. The solid curve
in Fig.14(a) show the potential energy.

Fig.14 Energy and Forces between atoms

` (a) Energy curve (b) Force curve

The forces between the atoms can be derived directly from Eq.11 by recalling that the
force is the derivative of potential energy. This is expressed as:

(12)
The net force is represented by the solid curve in Fig.14(b).
At large separations, the atoms do not interact with each other, so that V=O and
F=O. As the atoms approach each other, they exert attractive forces on each other,
primarily because of the positive and negative charges in the atoms. When the atoms are
separated by only a few atomic diameters, the repulsive forces between the like charges
of the nuclei, however, start to assert themselves although somewhat more slowly. At
some separation, called the equilibrium separation, re, the forces of attraction just equal,
the forces of repulsion, and the potential energy is at a minimum.
The forces of repulsion are the result of interpenetration of outer electron shells
between atoms, ions, and molecules when they approach one another at interatomic or
intermolecular distances. The forces of attraction are due to the interaction between outer
electrons of the two atoms, resulting in the formation of a sufficiently stable aggregate
which can be considered as an independent molecular species.

TYPE OF BONDS AND THEIR ENERGIES

The nature, strength and directionality of chemical bonds can be explained by
reference to the movements and locations of the electrons involved. According to the
strength, chemical bonds are grouped into primary and secondary bonds. Primary bonds
by virtue of their nature are interatomic bonds, whereas secondary bonds are
intermolecular bonds.

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 The attractive forces in primary bonds are directly associated with the valence
electrons. The outershell, which contains the valence electrons, is in a high energy state
and is relatively unstable. If it can acquire more electrons to bring the total up to eight, or
lose all its electrons to another atom, it can become stable. This is how atomic or primary
bonds are formed. In fact, each is a direct consequence of the exchange or sharing of
valence electrons which lie in the s-and p- orbitals. In other worth, a primary bond is
formed only if there is a pronounced lowering of the energies of the electrons involved
during the formation of the bond. Since a primary bond does involve a substantial
lowering of the energies of the bond electrons, it follows that such a bond must be
stronger and more stable than secondary bonds.
There are three principal types of primary bonds ionic, covalent, and metallic.
These bonds are distinguished on the basis of the positions assumed by the bond electrons
during the formation of the bond. vander Wads bonds and hydrogen bonds are typical
examples of secondary bonds and they result from intermolecular (dipole) attractions.
The natures of the first four types of bonding in solids are illustrated in Fig.15
Few materials have pure bonds of one type or the other. In fact mixed bonds are mostly
found in common materials.

Fig.15.Nature of the four types of bonding

(a)Metallic bonding (b) Ionic bonding
(c) Covalent bonding (d) Vander Waals bonding

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BOND ENERGIES
The bonding energy or the cohesive energy is defined as the energy of formation
of one mole of a substance from its atoms or ions. It is 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 ions at the equilibrium spacing in the crystal structure, using the state of infinite
separation of the atoms or ions as the zero of 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. If we measure the heat of vaporization of one
kilogram mole this must be the energy used in breaking N bonds (N0 =Avogadro’s
number) Figures derived in this way are tabulated in Table 2 together with the type of
bonding for the solid concerned. It is clearly seen from this table that primary bonds are
stronger than secondary ones as referred to earlier.
The melting points and the boiling points of the elements are dependent on the
strength of the bond. Generally, the stronger the bond, the higher are the melting and
boiling points.

Table 2 Types of Bonds & their Energies

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IONIC BOND
An ionic bond is rarely the attractive force existing between a positive and a
negative ion when they are brought into close proximity. These ions, of course, are
formed when the atoms involved lose or gain electrons in order to stabilize their outer
shell electron configuration. Elements are classified as either electropositive or
electronegative, depending upon whether they tend to lose or gain electrons in order to
achieve this stable outer-shell electron configuration. The definition of ionization
potential provides that ionization energies or potentials measure the amounts of energy
required to remove the successive outer electrons from an atom. The first I.P. of various
elements listed in Table 3 shows that, in general, it requires less energy to strip one
electron from a metal atom than from a nonmetallic atom. This rule also applies to the
removal of the second and subsequent electron in most cases. Thus, metals are termed
electropositive while nonmetals are electronegative, these terms referring to the abilities
of the elements to form positive and negative ions respectively under favorable
conditions during them chemical reactions.

Table.3 First Ionization potential of some elements (kJ/mol)

Let us consider the combination which takes place between the metal sodium and
nonmetal chlorine to form sodium chloride (common salt). The sodium atom has a single
electron in its outer shell and this transfers to join the seven electrons in the outer shell of
the chlorine atom as illustrated in Fig.16. This type of atomic interaction, involving the
outright transfer of one electron from one atom to another, leads to the formation of ions
which are held together by electrostatic attraction. Because of the electrostatic nature of
the binding force, the bond between atoms is said to be ionic or electrovalent, and the
valence exhibited is said to an electrovalence.
Besides this attraction, the process of adding an extra electron to the chlorine
atom is accomplished by an appreciable decrease in the potential energy.
Ionic bonds are nondirectional, so that in a crystal, a cation tends to surround
itself by as many anions as possible and vice versa. The Coulomb term for a crystal i then
dependent on the mutual attractive as well as repulsive interaction or a given ion with all
the other ions in the crystal.
The major requirement in an ionically bonded material is that the number of
positive charges equals the number of negative charges. Thus, sodium chloride has a

22
composition NaCI. Magnesium chloride has composition of MgCI2, because the
magnesium atom can supply two electrons from its valence shell but a chlorine atom can
accept only one. Other solids having ionic bonding are potassium oxide (K2O) and
lithium hydride (LiH).
Yet other examples of ionic bonding occur in the compounds: cupric oxide
(CuO), chromous oxide (CrO2) and molybdenum fluoride (MoF2) showing that metallic
element need not be from Group I or II of the periodic table but that any metal may
readily become ionized by losing its valence electrons.

Fig. 16.Nature of an ionic bond

COVALENT BOND
A covalent, homo polar or electron-pair bond is formed when pairs of electrons
are shared by several atoms (rather than by electron transfer to make two different ions)
and have their energies lowered as a result of this sharing. Stable covalent bonds are
formed between many nonmetallic elements since the atoms of these elements usually
possess half-filled outer electron shells which resist the direct electron transfer required
for the formation of an ionic bond. An excellent example of covalent bonding is found in
the chlorine molecule. Here, the outer shell of each atom possesses seven electrons. Each
chlorine atom would like to gain an electron, and thus forms a stable, octet. This can be
done by sharing of two electrons between pairs of chlorine atoms, thereby producing
stable diatomic molecules. In other words, each atom contributes one electron for the
sharing process.

Fig.17 Nature of a Covalent bond

The natures of the covalent bonds in the molecules of chlorine, nitrogen, and
hydrogen fluoride are illustrated in Fig.17. All molecules with halogen atoms (e.g., Cl, F
Br, I, etc.) exhibit the same phenomenon.
In line with modern ideas involving probability distribution of electrons, the
covalent bond maybe considered to be a region of high elctron density existing between
two atoms. This can be best demonstrated in terms of hydrogen molecule (Fig.18). When
two hydrogen atoms are very far apart, they do not interact and the lone electron of the
atom stay in their respective 1s ground states. When the atoms are brought together, the
two electron-density-distribution clouds start to overlap. The electron of one atom comes
under the influence of the positive charge of the nucleus of the other and vice versa. This
results in a change in the electron density distribution around the two nuclei. The

23
quantum-mechanical calculation is roughly equivalent to adding these two atomic
orbitals (AO) to give the bonding, that is molecular orbital (MO). With the formation of
the molecule, the density of electron distribution, which is a measure of the probability of
finding an electron in any spherical shell, increases at points between the nuclei along the
internuclear axis. In other words, the electrons spend more time between the two nuclei
where they are commonly shared by the positive charge. The Fig.19 illustrates another
covalent bond in a chlorine molecule seen as a region of high electron density between
the two chlorine atoms.

Fig. 18 Covalent bond in a hydrogen molecule showing region of high

electron density clouds and over-lapping of two atoms

This concept of sharing of electron between neighbouring atoms is basic to the

understanding of the covalent bond. This kind of bonding is possible whenever such
sharing results in a lowering of the total potential energy of the system. Sharing of
electrons with a decrease in the potential energy of the system is most readily achieved,
when there are unfilled quantum states in the outermost principal shell.

Fig.19 Covalent bond in a chlorine molecule.

24
 Since pairs of electrons are shared in covalent bonds there is some degree of
orbital overlap between the bonded atoms (Fig.18). This overlap is limited by the
electrostatic repulsion of the positively charged nuclei, the resultant shapes of the bond
orbitals determining whether the bond will be directional or nondirectional in space with
respect to the nuclei (or ion cores). The greater the degree of orbital overlap the stronger
the bond, since extensive overlap means greatly lowered energy levels of the bond
electrons.
In atoms that have certain energy levels close together; these levels sometimes
interact as a preliminary to the formation of molecule with other atoms and exhibit a
bonding phenomenon known as hybridization, which is an important feature of the
molecular-orbital theory. The molecular orbitals of methane, diamond, graphite, ethylene
having carbon in each of them illustrate hybridization and directional bonding.
The covalent bond found in a wide variety of materials since it can be formed
between atoms of the same or different elements. Stable covalent bonds are formed in the
solid state primarily between. Non-metallic atoms like nitrogen, oxygen, carbon and
chlorine families. Other elements like silicon, germanium, arsenic, and selenium form
bonds that are partly covalent, partly metallic; the transition metals (Columns IIIb-VIIb in
the periodic table) are also thought to have a certain amount of covalent character to their
bonds. They also include many of the organic compounds such as benzene, alcohol,
turpentine, chloroform, and members of the paraffin series which contain mainly the
elements carbon, hydrogen and oxygen. An important example of covalent bonding is
found in polymeric materials which include rubbery elastomers, high-strength fibres, and
a variety of structural materials denoted by the term plastics.
Generally speaking, the number of covalent bonds that can be formed by an
element is determined by the number of electrons that can be added to the valence shell
without exceeding 8. According to this rule the maximum number of covalent bonds is
(8-N),where N is the number of valence electrons.
A covalent bonding is very strong so that the cohesive energy of a solid such as
diamond, which is entirely carbon, very large and in agreement with this fact valency
solids are usually very hard and have high melting points.
The strength of individual bonds in covalent molecules depends on such factors as
degree of ionic character, bond order (single bond, double bond, etc., indicated by the
sign —), and resonance of bonds between alternative positions. Table.4 gives some
examples of experimentally determined bond energies for neighbouring atom pairs in
typical molecules. Using these values one can estimate the total bonding energy of
materials such as polymers and judge their relative stabilities.
METALLIC BOND
As its name signifies, metallic bonding is the principal force holding together the
atoms of a metal. This type of bond is characteristic of the elements having small number
of valence electrons, which are loosely held; so that they can be easily released to the
common pool. The bonding results when each of the atoms of the metal contributes its
valence electrons to the formation of an electron cloud (frequently referred to as an
‘electron gas’) that pervades the solid metal. The electrons are pictured not as definite
points but as a “cloud” whose density represents the probability that electrons will be
found at the given position in the atom. It is seen that the ten innermost core electrons

25
tend to be concentrated in the vicinity of the nucleus, while two valence electrons have
their most probable positions near the surface of the atom.

Table 4 Bond Energies and Bond Lengths

At the simplest level, in metallic bond the metal ions are bound together in a solid
metal by the interaction of all the valence electrons—the electron cloud or gas that may
be considered to move freely. A schematic picture of the metal ions and that of the
electron cloud is illustrated in Fig.20. Valence electrons occupy a definite energy level
and move about freely in the crystal structure of the metal. Therefore, a metal crystal
should be considered to consist of positively charged ions, and surrounded by a cloud of
free electron. Since the negative electron cloud surrounds each of the positive ions that
make up the crystal structure, strong electrical attraction holds the metal together.

Fig. 20 Schematic picture of a metallic bond

A metallic bond, thus conceived can exist only between a large aggregate of
metallic atoms and must therefore be nondirectional. This type of bond causes a
significant lowering of the energy levels of the electrons involved since they are in close
proximity to several ion cores at all times. Another view of the metallic bond is to regard
it as a covalent bond brought about by atoms in close proximity alternately sharing and
losing electrons in their outer orbitals.
In general, the fewer valence electrons an atom has and the more loosely they are
held, the more metallic the bonding. However, the transition metals, such as ‘iron, nickel,
and tungsten exhibit a fair degree of covalence due in part to their incomplete “d”
electron orbitals. A special characteristic of metal bonding is the fact that every positive

26
23ion is equivalent. Thus, the metal can behave in a definite ductile fashion under stress
because a group of positive ions break their bonding at one location, slip to a new
position and establish their bonds.
This picture of the metallic state is essentially that proposed in the classical free
electron theory of Drude and Lorentz, formulated, before the advent of quantum
mechanics. More recent work has substantially modified the details of the above model
but the main assumption, i.e., the idea of “free” electrons in the metal is still useful.

COMPARISON OF BONDS
The comparision between various bonds are explained hereunder
Ionic And Metallic Bonds
In ionic bonding, a metallic element losses from the outer electron shell of its
atom a number of electrons equal to its numerical valency. These lost electrons are
transferred to the other electron shells of the nonmetallic atom or atoms with which the
metal is combining. In this a complete octet of electrons is left behind in the metallic
particle and completed in the nonmetallic particle. Thus, ionic bond results from an
electrostatic attraction between positive and negative ions which are derived from the free
atoms by the loss or gain of electrons, ideally, ionic bonds are formed by combining a
highly electropositive atom (metal atom which tends to lose electrons and become
positive ion) with electronegative atom (nonmetallic atom which tends to acquire
electrons and become negative ions). The bond itself is nondirectional since each positive
ion attracts all neighbouring negative ions and vice-versa; The bond in sodium chloride is
one of the good examples of ionic bond.
In metallic bonding atoms of the same metal loose their valence electron to form
an electron “cloud” throughout the space occupied by the metal atoms. The valence
electrons lie much further from the nucleus than do those in non metals. Thus the wide
orbits of the valence elections allow them to pass to regions remote from their parent
atoms. Likewise, they never associate with any one atom in the metal but drift through
the whole assembly as a kind of electron gas. Only the valence electrons behave in this
manner, for electrons in the inner shell lie much closer to the nucleus and are unable to
move outside its field of influence. Consequently, as far as the inner electrons are
concerned, an atom of a metal is much the same as an isolated atom, because these
electrons are held firmly within the atom and remain in their characteristic quantum shell.

Covalent Bond & Metallic Bond

In some respect, the metallic bond is similar to the covalent bond, and yet it is
quite different. In an elementary manner, the metallic bond may be considered as a
multiplicity of resonating covalent bonds. In metallic bonding the valence electrons
which hold the atoms together, are not bound to individual atoms or pairs of atoms but
move freely ‘throughout the whole metal. In the covalent bond, two atoms are limited
together by particular pairs of electrons shared between them.
Thus, the similarity to the covalent bond lies in a sharing of electrons. The
difference is that these electrons belong to the metal as a whole rather than to any
particular atom.

27
 CHAPTER 2

X-RAY DIFFRACTION
X-RAY DIFFRACTION
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 gratings 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
centers 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.

BRAGG’S LAW
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 depending on the path difference. When the path
difference (CB + BD) is a whole wavelength λ , or multiple of whole wavelength (nλ),
then the two rays will reinforce each other and produce an intense spot. Thus condition of
reinforcement is:
CB+BD=nλ
From fig.1 CB = BD = d sinθ
where, θ is the angle between the incident ray and the planes of reflection (glancing
angle). Therefore,
2d sinθ=nλ (1)

where d is the interplanar spacing of planes and n = 1,2, 3 ... stand for first order, second
order, third order... maxima respectively. Equation (1) is known as Bragg’s law. Different
directions in which intense reflections will be produced can be obtained by giving
different values to θ; i.e.,
for first maximum, sinθ1=λ/2d
for second maximum, sinθ2 =2λ/2d
for third maximum, sinθ3=3λ /2d and so on.

28
 Fig.1Reflection of x-rays from lattice planes in a crystal

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 extremely feeble
intensity.

BRAGG’S X-RAY SPECTROMETER

Bragg devised an apparatus known as x-ray crystal spectrometer where the crystal
was used not as a transmission grating, but as a reflection grating. x-rays from an x-ray
tube were allowed to pass through slits S1 and S2 so as to obtain a narrow beam which is
then allowed to strike a single crystal D mounted on a turn-table. The crystal is rotated by
means of the turn-table so as to increase the glancing angle at which x-rays are incident at
the exposed face of the crystal. The photographic plate or an ionization chamber is used
for measuring the intensities of the reflected rays. The angles, for which reflection
intensities are maximum, give the values of θ of equation nλ = 2d sin θ. The process is
carried out for each plane of the crystal. n = 1, creates the condition for the lowest angle
at which the lowest reflection occurs. n = 2, creates the condition for the next higher
angle at which maximum reflection occurs and so on. Thuss,
for n=1, λ=2dsinθ1, n =2, 2λ=2dsinθ2 ,n=3, 3λ=2dsinθ3, etc
where θ1, θ2and θ3 are glancing angles for n = 1, 2 and 3 respectively.
sin θ1 : sin θ2 : sin θ3 = 1:2: 3 (2)

29
 Fig. 2 Bragg’s X-ray spectrometer

Hence, by measuring glancing angles at which reflections occur, we can

determine the interplanar spacing knowing the wavelength of x-rays. If the above
proportionality is verified the assumption of Bragg’s theory that x-rays are reflected like
ordinary light, gets proved.
The structure of rock salt (NaC1) crystal was studied by using Bragg’s ionization
spectrometer and intensity or ionization current was determined for different glancing
angles. If a graph is plotted between intensity or ionization current and glancing angle,
the following intensity order of reflection diagram is obtained.
The experimental results from Bragg’s method have shown that if x-rays from a
palladium anticathode are used. The first order reflection maxima occurred at 5.9°, 8.40
and 5.20 for (100), (110) and (111) planes respectively. Now from Bragg’s equation,
nλ =2dsinθ
For first order reflection, n = 1

30
 Fig. 3 Variation of ionization current with glancing angle.

This procedure may also be followed for other crystal systems such as tetragonal,
hexagonal, etc. Table A gives the values of ratios between interplanar distance of the
planes (100), (110) and (111) for the cubic structures.

Table A. Ratios between interplanar distances

Thus we see that sodium chloride crystal has a face centered cubic structure.

POWDER CRYSTAL METHOD

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, with out 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.4.

Fig. 4 Powdered crystal spectrometer.

A narrow beam of these monochromatic x-rays suitably collimated by two lead

slits S1 and S2, falls on the powdered specimen S. The specimen is suspended vertically

31
on the axis of a cylindrical camera. The photographic film is mounted round the inner
surface of the camera, covering nearly the whole circumference in order to receive the
beams diffracted up to 1800.
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 wave length and a given value of d, there can be only one value of θ
(glancing angle) which satisfies the equation 2d sinθ= nλ where n = 1. Such reflected
beams emerge out from the specimen in all directions inclined at an angle 2θ 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 2 θ. The traces
obtained on the photographic film will be as in Fig. 5.

Fig. 5. Developed film.

Let L be the radius of the cylindrical camera. The direct beam strikes the film at θ.
Suppose a spectrum with glancing angle θ is found at A which is at a distance R from θ .
Then θ = R/2L. Using the value θ in the Bragg’s equation and knowing the value of λ, d
(spacing of the plane involved) can be calculated. The powder method has been
employed in the study of micro crystalline substances like metals, alloys, carbon,
fluorescent powders and other forms where single crystals are not available.
ROTATING CRYSTAL METHOD
In this method a small and well-formed single crystal is mounted perpendicular to
the beam. The film 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 structure
of ordinary and complex molecules.

Fig.6 ROTATING CRYSTAL METHOD

32
 LAUE’S METHOD
In this method a single crystal is held stationary on a goniometer so that θ remains
fixed. A beam of x rays of continuous wavelength is incident on this single crystal. The
crystal specimen have the dimensions of 1mm * 1mm * 1 mm and the beam x rays have
their wavelength varying from 0.2 to 2Å. A pinhole arrangement produces a well
collimated beam. The two flat films receives the diffracted beams. One receives the
transmitted and the other film receives the reflected x-rays. The arrangement is shown in
fig 7 (a). The diffraction pattern obtained on the films consists of a series of spots, fig.7
(b). The pattern will show the symmetry of the crystal. This method is widely used to
orient crystals for solid state experiments.

Fig.7 (a) Laue’s method of x-ray diffraction (b) Laue’s pattern

33
CHAPTER 3

34
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 Temperature

53
 CHAPTER 4

BAND THEORY OF SOLIDS

The free electron model of metals gives us good insight into the heat capacity, thermal
conductivity, electrical conductivity, magnetic susceptibility, and electrodynamics of
metals, But the model fails to help us with other large questions: the distinction
between metals, semimetals, semiconductors, and insulators; the occurrence of positive
values of the Hall coefficient; the relation of conduction electrons in the metal to the
valence electrons of free atoms; and many transport properties, particularly
magnetotransport. We need a less naïve theory, and fortunately it turns out that almost
any simple attempt to improve upon the free electron model is enormously profitable.
The difference between a good conductor and a good insulator is striking.
The electrical resistivity of a pure metal may be as low as 10-10 ohm-cm at a
temperature of 1 K, apart from the possibility of superconductivity. The resisitivity of a
good insulator may be as high as 1022 ohm-cm. This range of l032 may be the widest of
any common physical property of solids.
Every solid contains electrons. The important question for electrical conductivity
is how the electrons respond to an applied electric field. We shall see that electrons in
crystals are arranged in energy bands (Fig.1) separated by regions in energy for which
no wavelike electron orbitals exist. Such forbidden regions are called energy gaps or
band gaps, and result from the interaction of conduction electron waves with the ion
cores of the crystal.
The crystal behaves as an insulator if the allowed energy bands are either filled or
empty, for then no electrons can move in an electric field. The crystal behaves as a
metal if one or more bands are partly filled, say between 10 and 90 percent filled. The
crystal is a semiconductor or a semimetal if one or two bands slightly filled or slightly
empty.
To understand the difference between insulators and conductors, we must extend
the free electron model to take account of the periodic lattice of the solid. The
possibility of a band gap is the most important new property that emerges.
We shall encounter other quite remarkable properties of electrons in crystal.
For example, they respond to applied electric or magnetic fields as if the electrons
were endowed with an effective mass m*, which may be larger or smaller than the free
electron mass, or may even be negative. Electrons in crystals respond to applied fields
as if endowed with negative or positive charges, -e or +e, and herein lies the
explanation of the negative and positive values of the Hall coefficient.

54
Fig.1. Schematic electron occupancy of allowed energy bands for an insulator, metal,
semimetal, and semiconductor. The vertical extent of the boxes indicates the allowed
energy regions; the shaded areas indicate the regions filled with electrons, In a
semimetal (such as bismuth) one band is almost filled and another band is nearly
empty at absolute zero, but a pure semiconductor (such as silicon) becomes an
insulator at absolute zero. The left of the two semiconductors shown is at a finite
temperature, with carriers excited thermally. The other semiconductor is electron-
deficient because of impurities.

1.Nearly Free Electron Model

On the free electron model the allowed energy values are distributed essentially
continuously from zero to infinity. We saw in Chapter 3 that

(a)
where, for periodic boundary conditions over a cube of side L,

(b)
The free electron wave functions are of the form

(c)
they represent running waves and carry momentum p = ħk.
The band structure of a crystal can often be explained by the nearly free electron
model for which the band electrons are treated as perturbed only weakly by the periodic
potential of the ion cores. This model answers almost all the qualitative questions about
the behavior of electrons in metals.
We know that Bragg reflection is a characteristic feature of wave propagation in
crystals Bragg reflection of electron waves in crystals is the cause of energy gaps. (At
Bragg reflection wavelike solutions of the Schrodinger equation do not exist, as in Fig.
2.) These energy gaps are of decisive, significance in determining whether a solid is an
insulator or a conductor.
We explain physically the origin of energy gaps in the simple problem of a linear solid
of lattice constant a. The low energy portions of the band structure are shown
qualitatively in Fig. 2, in (a) for entirely free electrons and in (b) for electrons that are
nearly free, but with an energy gap at k = ± π/a. The Bragg condition (k + G)2 = k2 for
diffraction of a wave of wavevector k becomes in one dimension
(d)

55
 where G= 2πn/a is a reciprocal lattice vector and n is an integer. The first reflections
and the first energy gap occur at k ± π/a. The region in k space between -π/a and π/a is
the first Brillonin zone of this lattice. Other energy gaps occur for other values of the
integer n.
The wavefunctions at k = ± π/a are not the traveling waves exp(iπx/a) or
exp(-πx/a) of free electrons. At these special values of k the wavefunctions are made up
of equal parts of waves traveling to the right and to the left. When the Bragg reflection
condition k = ±π/a is satisfied by the wavevector, a wave traveling to the right is Bragg-
reflected to travel to the left, and vice versa. Each subsequent Bragg reflection will
reverse the direction of travel of the wave. A wave that travels neither to the right nor to
the left is a standing wave : it doesn’t go anywhere.
The time-independent state is represented by standing waves, We can form two
different standing waves from the two traveling waves exp( ±iπx/a), namely

(e)
The standing waves are labeled (+) or (-) according to whether or not they change sign
when -x is substituted for x. Both standing waves are composed of equal parts of right-
and left-directed traveling waves.

Fig.2.(a) Plot of energy ε versus wavevector k for a free electron. (b) Plot of energy
versus waveveetor for an electron in a monatomic linear lattice of lattice constant a,
The energy gap Eg shown is associated with the first Bragg reflection at k ± π/a; other
gaps are found at ± nπ/a, for integral values of n.

Origin of the Energy Gap

The two standing waves ψ(+) and (-) pile up electrons at different regions, and
therefore the two waves have different values of the potential energy. This is the origin
of the energy gap: The probability density ρ of a particle is ψ*ψ = |ψ|2. For a pure
traveling wave exp(ikx), we have ρ = exp(-ikx) exp(ikx) =1, so that the charge density is
constant. The charge density is not constant for linear combinations of plane waves.
Consider the standing wave ψ(+) in (e) for this we have

This function piles up electrons (negative charge) on the positive ions centered
x = 0 a, 2a, . . . in Fig. 3, where the potential energy is lowest.
Fig.(3a) pictures the variation of the electrostatic potential energy of a conduction
electron in the field of the positive ion cores. The ion cores bear a net positive charge
because the atoms are ionized in the metal, with the valence electrons taken off to form

56
the conduction band, The potential energy of an electron in the field of a positive ion is
negative, so that the force between them is attractive.
For the other standing wave ψ (-) the probability density is

which concentrates electrons away from the ion cores. In Fig.. 3b we show the
electron concentration for the standing waves ψ(+), ψ(-), and for the traveling wave.
When we calculate the average or expectation values of the potential energy over
these three charge distributions, we find that the potential energy of ρ(+) is lower than
that of the traveling wave, whereas the potential energy of ρ(-) is higher than the
traveling wave. We have an energy gap of the width Eg if the energies of ρ(-) and ρ(+)
differ by Eg. Just below the gap at points A in Fig. 2 the wavefunction is ψ(+), and just
above the gap at points B the wavefunction is ψ(-).

Fig.3 (a) Variation of potential energy of a conduction electron in the field of the ion
cores of a linear lattice. (b) Distribution of probability density ρ in the lattice for |ψ(-)|2
ά sin2πx/a ; |ψ(+)|2 ά cos2πx/a; and for a traveling wave. The wavefunction ψ(+) piles
up electronic charge on the cores of the positive ions, thereby lowering the potential
energy in comparison with the average potential energy seen by a traveling wave. The
wavefunctlon ψ(-) piles up charge in the region between the ions, thereby raising the
potential energy in comparison with that seen by a traveling wave, This figure is the
key to understanding the origin of the energy gap.

2.Kronig-Penney Model
The essential feature of the behaviour of electronic potential may be studied by
considering a periodic rectangular well structure in one dimension, which was first
discussed by Kronig and Penney in 1931. It is assumed here that the potential energy of
an electron, when it moves in one dimensional perfect crystal lattice, is represented in

57
the form of rectangular walls as shown in the fig.4. The period of the potential is (a +b).
In regions where 0 < x < a, the potential energy is assumed to be zero and in the regions
-b< x < 0, the potential energy is V. Though this is a highly artificial model but it is a
model for which the Schrodinger equation can be solved explicitly in terms of
elementary functions. The Schrodinger equation for the two region can be written as

Fig. 4

(1)

And (2)
Let the energy E of the electrons under consideration be less than V0, then let us put

(3)
Where α and β are real quantities. The two equations then become

(4)

(5)
Now from the Bloch theorem the solution of wave equation for a periodic potential will
be of the form of a plane wave modulated with the periodicity of the lattice of the form
(6)
where Uk (x) is the periodic function in x with period (a + b).
Since
So,

Substituting these values in (4) and (5), we get

58
 (7)

(8)
Now to solve these differential equations assume the solution of the form

So that

which on substituting in (7), gives

So that

(9)

Similar, (10)
where A, B, C, D are constants. These constants are so chosen that they satisfy the
conditions of continuity and periodicity of wave functions. Now because of continuity
at x = 0 the two wave-functions and their derivatives must have the same value at x = 0,

(11)
And (12)
and because of periodicity of function U (x), the values at x = a must be equal to those
at x = -b.

or
(13)

(14)
Now these four equations (11) to (14) have a solution only if the determinant of the
coefficients of A, B, C, D vanishes, i.e.,

59
This determinant on solving leads to the following equation

(15)
In order to express the relation in a more simplified form Kronig and Penney
suggested delta functions such that V0 →∞ and b→0 but the product V0b or β2b
remains finite. Such a function is known as delta function.. Within this limit equation
(15) reduces to

(16)
Between when b→0, sinh βb→ βb; cosh βb→1
Equation (16) is further written as

(17)
where the quality P is defined by the expression

(18)
since V0 tends to infinity i.e. P is a measure of the quantity V0b, which is the area of the
potential barrier.
The physical significance of this quantity is that if P is increased, the area of the,
potential barrier is increased and the given electron is bound more strongly to a
particular potential well. When P →0, the potential barrier becomes very weak which
means that electrons are free electrons. In this case we obtain from equation (17),

(19)
which resembles the result obtained by considering the Sommerfield model of a
metal.

60
Fig. 5. Graph showing the function [(P sin αa)/ αa] + cos αa plotted against αa for
P = 3π/2.

If a graph of the function is plotted against αa for P = 3π/2, a

curve as shown in

fig. 5 is obtained. Since the abscissa αa is a measure of energy and by

finding the value of αa at any point, the energy represented by the function at that point
is calculated. The values of αa satisfying equation (17) are obtained by drawing a line
parallel to αa axis at a distance cos ka from it and if we vary ka continuously from 0 to
π i.e. cos ka from + 1 to -1, we obtain all possible values of αa and hence that of energy.
These possible values of αa are drawn heavily in fig. 5. The following important
conclusions can be drawn from the diagram.
1.The energy spectrum consists of an infinite number of allowed energy bands
separated by intervals in which there are no energy levels. These are known as
forbidden regions.
The boundaries of the allowed ranges of aa correspond to the values of cos ka = ± 1 or
ka = nπ
i.e

2. When αa increases the first term on the left side of (17) decreases so the width
of allowed energy bands is increased and forbidden regions become narrower.
3. The width of allowed band decreases with the increasing value of P i.e., with
increasing the binding energy of electrons. When P is infinite, the allowed energy bands
are infinitely narrow and are independent of k because when P→∞, the allowed energy
ranges of α a reduce to points given by

(20)
i.e., E is independent of k.
The energy levels in this case are discrete and the electron is completely bound. It is
caught between the potential wells and moves only in one cell of width a.

61
 Hence we conclude that in one dimensional problem for the limiting case the
spectrum of permissible energy values is found to consist of continuous regions
separated by finite intervals. By varying the quantity P i.e. V0 b from 0 to ∞ we pass
from the case of free to that of bound electrons and can thus study the changes in the
allowed and forbidden ranges of energy and the wave function.
From (17) it is also possible to obtain the energy E as a function of the wave number k
which leads to the following conclusion.
The discontinuities in the E vs k curve occur at k = (nπ/a) where n = 1, 2, 3,….
These k values define boundaries of the I, II etc. Brillouin zones. From k = π/a to -
π/a there exists the first Brillouin zone. The second zone consists of two parts: one from
+ π/a to + 2π/a and the second from -π/a to -2π/a.

Fig.6. E as a function of wave no k.

Each portion of the curve may be called a band. The characteristics of the curves
are that:
1. They are horizontal at the top and bottom.
2. They are parabolic near the top and the bottom with curvatures in opposite
directions.
3. (d2E/dk2) is positive in the lower portion of the band and negative for the upper
portion.

3.Origin of Energy Gap

In order to consider physically the reason of forbidden bands, consider first the simple
problem of a linear lattice of lattice constant a. The low energy portions of the band
structure are shown in fig. 7 (a) and in fig. 7 (b) for electrons which are nearly free but
with energy gap at k = ± π/a.
The Bragg condition, (K + G)2 = k2, for diffraction of a wave vector k becomes in one
dimension

(21)

62
 Fig. 7. (a) Plot of B versus k for free electron.
(b) Plot of B versus wave vector k for an electron in a monatomic linear
lattice of lattice constant a. The energy gap Eg shown is associated with the first
Bragg reflection at k = ± π/a.

where G = ± (2nπ/a) is a reciprocal lattice vector. The first reflection and the first
energy gap occur at k = ±π/a, other energy gaps occur for other values of integer n in
(21)
The reflection at k = ± π/a arises because the wave reflected from one atom in the
linear lattice interferes constructively with the wave from a nearest neighbour atom.
The phase difference between the two reflected waves is just ± 2π for these two values
of k. The region in k space between -π/a and + π /a is called first Brillouin zone.
At k = ± π/a the wave functions are not the traveling waves eiπx/a and e-iπx/a of the
free electron model. We shall show that the solutions of these particular values of k are
made up equally of waves traveling to the right and to the left. The solutions are
standing waves. This can be understood in the following manner: When the Bragg
condition is satisfied, a wave travelling in one direction is soon Bragg- reflected and
then travels in opposite direction. Each subsequent Bragg reflection reverses the
direction of travel again. The only time-independent situation is formed by standing
waves. We can form two different standing waves from the travelling waves eiπx/a and e-
iπx/a

(22)
The standing waves are labelled (+) and (-) according to whether they are even or odd
when -x is substituted for x.
The two standing waves ψ(+) and ψ(-) correspond in a lattice to the different values of
energy. This is the origin of the energy gap. We recall that in quantum mechanics the
probability density ρ of a particle is |ψ|2. For a pure travelling wave ψά eiπx/a , so that ρ ά
eiπx/a .e-iπx/a =1, a constant. But ρ is not constant for linear combination of plane waves.
Consider linear combinations ψ(+) in (22); for we have ρ ά cos2πx/a. Fig. 8 (a) indicates
the variation of the electrostatic P.E. of the conduction electron in the field of positive
ion cores of monatomic linear lattice. The ion cores bear a positive charge, as in
forming the metal each atom has lost one or more valence electrons to form the
conduction band. The potential energy of an electron in the field of a positive ion is
negative. In fig. 8 (b) we sketch the distribution of electron density corresponding to the
standing waves ψ(+), ψ(-) and to traveling wave.

63
 The traveling wave eikx distributes electrons uniformly over the line: standing wave ψ(-)
ά Sinπx/a distributes electrons preferentially midway between the ion cores; and the
standing wave ψ(-) ά Cosπx/a distributes electrons on the ion cores, where the potential
energy is lowest . On calculating the average value of potential energy over the three
charge distributions, we expect to find the potential energy of ψ(+) lower than that of a
travelling wave, whereas the potential energy ψ(-) of is higher than that of traveling
wave. If the potential energy of ψ(+) and ψ(-) differ by an amount Eg , we have an
energy gap of width Eg between the two solutions at k = π/a or between the two at k = -
π/a. In fig. 7 (b) the wave function at A will be ψ(+) and the wave function at B will be
ψ(-).

Fig. 8(a) Variation of P.E. of conduction electron in the field of ion cores of
linear lattice.
(b) Distribution of probability density ρ in the lattice for |ψ(+)| 2 ά sin2 πx/a; |ψ(+)|
2
ά cos2πx/a. and for a travelling wave. The wave function ψ(+) piles up lowering the P.E.
in comparison with the average potential energy seen by travelling wave. The wave
function ψ(-) piles up charge in the region, between the ions and removes it from the ion
cores, thereby raising the P.E. in comparison with that seen by travelling wave.

4. Brillouin Zones.
We have seen in the Kronig Penney model that the energy discontinuities in a
monatomic one dimensional lattice occur when the wave number k satisfies the relation
k = nπ/a, where n is any positive or negative integer. Thus it is the value of wave
number which is important for the energy discontinuities. In one dimensional
monatomic lattice a line representing the value of k is divided up by energy
discontinuities into segments of length π /a as shown in fig. 9. These line segments are
known as Brillouin zones; the segment.
-π/a <k < π/a
is the first Brillouin zone, the two segments
- π/a <k <π/a and π/a < k < 2π/a

64
 Fig. 9

form the second Brilouin zone and so on.

All the results for a one dimensional periodic field apply equally to two or three
dimensional fields if we keep the other one or two of the coordinates fixed. (The axes
are supposed to be parallel to the sides of the square in two dimensional crystal and to
the three axes of a unit cell in three dimensions).
The zone description was introduced by Brillouin who pointed out that many
important and characterized features of electron propagation in periodic structures
could be described by considering the positions, in k-space, of the boundaries of zones,
these positions are independent of the details of the electron lattice interaction but are
mainly determined by the geometry of the crystal structure. Each crystal structure gives
rise to its own characteristic Brillouin zones. The first zone for two dimensional simple
square lattice will be a square ABCD the boundaries-of which will be given by the
relations
kx = ±π/a; ±ky=π/a
The boundaries of the second zone are given by the rations
±kx = ±ky = π/a
This is represented in the diagram by EFGH. The same principle applies to three
dimensional crystal structure. The first Brillouin zone of the simple cubic lattice is a
cube of edge 2π/a.

Fig. 10 Fig. 11 Fig.12

Fig. l0.Brilloujn zones in two dimensional. simple square lattice
Fig. 11. Relation between E and k for one direction of k space.

The meaning of these wave number diagrams is that if we start at the origin of k-
space and consider a series of states with continuously increasing k, then E varies
continuously with k as long as k lies within the zone, but when k reaches the surface of
the zone, there is an abrupt increase in energy. The explanation of this abrupt increase

65
of energy has already been discussed previously. For any one direction in k space the
relation between B and k is of the same general form as already studied but the position
and magnitude of the gaps, a1 b1, a2 b2 ... depend upon the direction concerned. This
gives the possible type of Brillouin zone.
(a) Zones do not Overlap
Here the energies of states at the top of the first band i.e., ar may for all directions
be less than the energy of any state for any direction at any bottom of the second band
i.e., as in fig. 12.
(2) Zones Overlap
Here the energy gap Eg is present at the top of the first band for any direction but
some of the states at the top of first band i.e., ar have energy values higher than those of
the lowest state situated at the bottom of the second zone i.e., br. This condition of
affairs is shown in fig.13.

Fig. 13

5.Number of Possible Wave Functions per Band

So far we have assumed the crystal to be infinite, but now it will be essential to
consider the consequences of imposing boundary conditions. For it, consider a linear
crystal of length L and the boundary conditions may be taken as

Now making use of the Bloch functions

and because of the periodicity of Uk we have

The boundary conditions thus require,

(23)

The number of possible wave functions (or k-values) in the range dk is

Since k is limited by relation k = it follows that the maximum value of n in 23 is given

by where N is the number of unit cells. This leads to the conclusion—

66
 The total number of possible wave functions in any energy band is equal to the
number of unit cells N.

6.Velocity of Electrons according to Band Theory

According to de Broglie, the motion of an electron with a velocity v may be
looked upon as the motion of a wave packet with the group velocity υG. equal to the
particle velocity. Let us suppose that the wave packet is made up of states near a
particular k value in a single band.
The general expression for the group velocity is

according to wave mechanical theory, where w is the angular frequency of de Broglie

wave and is related to the energy of the particle by the relation,

(24)

But

(25)
i.e. the velocity of free electrons is proportional to k.
Now on the band theory the energy versus k curve is shown in fig. 14. Because it is a
symmetrical curve having points of inflexion at M and N, the value of (dE/dk) is
different for different portions of the curve. Since the curve is horizontal at A, O and B

Fig.14 Fig. 15

we have for these portions (dE/dk) =0. At the points N and M, (dE/dk) is the maximum
but negative at M and positive at N. The velocity versus k curve can therefore be
obtained from the E versus k diagram which is of the type as shown in fig. 15. It is
important to note here that the absolute value of velocity reaches a maximum for k = k0
where k0 corresponds to the point of inflexion in the E - k diagram and beyond this
point the velocity decreases with the increasing energy which is quite different in
behaviour from that of free electrons.

7.Influence of Electric Field

To study the influence of an electric field ε on the motion of an electron in one
dimensional periodic field, let us consider that the Brillouin zone under consideration
contains only one electron which is initially in the state-k. When the field ε acts on the

67
electron for a time dt, the electron gains certain energy dE which is the work done on
the electron by the electric field in the time dt i.e.,

(26)
Because

Now

Which gives

(27)
Now if ‘a’ be the acceleration of the electron, we have

(28)
For free electron, we have

(29)
These two expressions (28) and (29) suggest that on the band theory, the electron
behaves as if it

(Note that if energy is given by E = (ħk2/2m)*, the same expression for m* can be
obtained). The effective mass is thus determined by (d2E/dk2). This shows that since for
the lower positions of E-K curve (d2E/dk2) is +ve, m* is +ve and it will have a –ve
value for the upper position. At the points of inflexion, (d2E/dk2) = 0 and hence m*
becomes infinite. Physically speaking this means that in the upper half of the band the
electron behaves as having a negative mass or behaving like particles with +ve charges.
One can arrive at the same conclusion by considering the v-k curve and making use of
27 when an electric field is applied,
the wave vector increases linearly with time. Until the velocity reaches its maximum
value, the electron is accelerated by the field; beyond the maximum the same field
produces a decrease in v, i.e., the mass must become negative in the upper part of the
band.

68
 Fig. 16.m*- k curve

Sometimes it is convenient to introduce a factor

This factor fk determines the extent upto which the electron in a k-state is a ‘free
electron’. If m* is large, fk is small, i.e., the particle behaves as a heavy particle. When
fk =1 then electron behaves as a free electron.

8. Distinction between Metals, Insulators, and Intrinsic Semi-

conductors
The distinction between metals, insulators and intrinsic semiconductors can be made on
the basis of band theory. For this, let us consider a particular energy band filled with
electrons up to a certain value k, as shown in fig. 17. As far as the influence of an
external electric field is concerned, we shall be interested in knowing that with how
many ‘free’ electrons the N electrons in the band are equivalent? If we could know the
answer to this question, it would be possible to draw conclusions regarding
conductivity associated with this band. The effective number of the “free” electrons in
the band according to preceding discussion is

Fig. 17. Energy band filled up to state k1.

(30)
where summation extends over occupied states in the band.
The number of states in the range dk for one dimensional lattice of length L is

(31)
In the shaded region of fig. 17. i.e., within limits - k1 to + k1.

(32)

69
 Since two electrons occupy each of the state, the term on the right hand side of
equation (32) is to be multiplied by 2. Hence,

From this expression the following important conclusions can be drawn —

1. The effective number of electrons in a completely filled band vanishes, because
(dE/dk) vanishes at the top.
2. The effective number of electrons reaches to maximum value corresponding to
the point of inflexion, where (dE/dk) is maximum.
From the above discussion it follows that a solid for which any zone or any allowed
band which has electrons in it is completely full, the other bands being completely
empty, is an insulator. In a completely full zone for every electron state with vector k
there is a corresponding one with - k. Consequently a full- zone cannot show
preponderance of electron waves in any preferred direction which means that there
cannot be any electric current. The substance behaves as an insulator under ordinary
potential differences in spite of the fact that the electrons are free to move through the
crystal. The reason for this is that electrical conductivity requires not merely freedom of
motion of the individual electrons but also the possibility of giving a swarm of
electrons as a whole, a resultant velocity in the direction of the field which can only
happen if there are unoccupied states into which the electrons can pass when the field is
applied. From the above approach of wave mechanics it is clear that if all the states in
the first zone are filled and there is a gap before the next zone the probability of an
electron passing from a state in the first zone to one in the second zone is negligibly
small -instead it suffers Bragg reflection in the lattice. Hence as all the states in first
zone are occupied, the applied field can produce no change in the motion of the
electrons as a whole and no current can be carried. On the other hand, a solid
containing an energy band which is incompletely filled has metallic character and on
the older theory can be called to have free electrons. it will be evident that this situation
can occur only at absolute zero, when the crystal is in the lowest energy state. At
temperatures other than zero, some of the electrons from the upper filled band will be
excited to the next empty band called conduction band and the conduction becomes
possible, If the energy gap is of the order of several e.v., the solid will remain an
insulator. For example in the case of diamond the forbidden energy gap is about 7 e.v.
But for a smaller forbidden gap say 1 e.v. the number of thermally excited electrons
will be appreciable and in this case we can speak of intrinsic semiconductor. The
examples of this case are Germanium and Silicon. As a matter of fact, all intrinsic
semiconductors are insulators at T = 0 and all insulators may be regarded as
semiconductors at T > 0. Thus it is quite obvious from these arguments that
conductivity of semiconductors increases with increasing temperature while the
conductivity of metals decreases with increasing temperature.
9. Direct Experimental Evidence for Band Structure
The band theory as a whole is supported mostly by indirect evidence but for more
or less direct evidence of the band structure of the energy levels we require:

70
 1. That the existence of the energy gaps ∆E between allowed band should be
somewhat confirmed.
2. We should get some experimental confirmation of the fact that allowed bands
are partly full in metals and completely full in insulators.
Study of resistivity variation with temperature, light absorption and photo-conductivity
in semiconductors and insulators indicate the existence of energy gap ∆E.
Confirmation of (2) comes from soft X-ray spectroscopy. Let us consider X- ray
emission first, using the energy level diagram 18 (a). ‘A’ represents the energy level of
a core electron say 1s (K-shell) state. Such core levels are sharp. Suppose a suitable
bombardment in an X-ray tube removes the core electron. The level can be filled from
the electrons in the higher ‘allowed’ band which is shown partly full.
For v > v2 there will be no emission; since there are no levels in higher band from
where transition can take place at v2, sudden emissions of all transitions will take place
which therefore becomes the emission edge. v1 <v <v2 will correspond to the emission
band; for v <v1 there will be no emission

Fig. 18. Transitions in Soft X—ray Spectroscopy

because again there are no possible transition levels. The observed emission band
width therefore measures the extent to which the allowed band is full. Now consider the
absorption of X-rays by the same substance. Fig. 18 (b) shows that for v <v2 there
should be no absorption; at v = v2 there should be an absorption edge’ at v > v2 there
should be an ‘absorption band’. Absorption therefore also gives the evidence for the
existence of the unfilled levels in the allowed band.
Absorption and emission edges coincide in frequency in metals.
Emission, bands for non-metals are different from metals and are what can be
expected from full zones. They have no sharp emission edges.
Emission bands in metals are also not perfectly sharp as transitions from filled to
unfilled levels occur in metals over a region proportional to kT at the Fermi levels. As a
consequence, the width of the emission edge also varies with temperature.

71
 PROBLEMS
1. Show that if in the potential model used in connection with the Kronig — Penney
calculation. V0 is allowed to become infinitely large and b is allowed to approach zero,
such that the product P = remains fixed, ten allowed energy values are given
by the solution of equation

Also show that this leads to allowed and forbidden energy bands.
While discussing Kronig —Penney model it has been shown that equations (11)
to ( 14) have non-vanishing solutions if and only if

(15)

Within energy range 0 < E < V0, ± β is imaginary and putting β = iγ. Noting that cos ix
= coshx and sinix = sinhx. Eqn. (15) can be written as

Substituting

Since b →0 sinhγb →γb and coshγb →1 in equation (1), we have

The plot of against α a is shown in fig. (5). Since α2 is

proportional to the energy E, the abscissa is a measure of energy. Furthermore, the right
hand side can accept values between -1 and +1 only as indicated by horizontal line, fig.
(5).
Thus, the energy spectrum of electrons consists of a number of allowed energy
bands separated by forbidden regions.

72
 CHAPTER 5

PHOTOVOLTIC
SOLAR CELLS AND PHOTODIDOES
Optoelectronic devices convert optical energy into electrical energy and vice
versa. The phenomenon of converting optical radiation into electrical energy is called
photovoltaic effect. Two important devices based on the photovoltaic effect are solar cell
and photo detector. The inverse of photovoltaic effect is termed electroluminescence, i.e ,
the phenomenon of light emission when subjected to electrical signal. The LEDs and
lasers found good examples of this effect.

PHOTOVOLTIC EFFECT
We know that if a photon with energy hν which is greater than or equal to band
gap Eg is incident on a semiconductor, absorption of light can take place with consequent
generation of an EHP. In other words, in order to generate EHPs in a particular
semiconductor, the wavelength of the incident radiation must be lower than a
characteristic value for the material, called the cut-off wavelength λc. The ability of the
material to absorb light is also dependent on another parameter, called the absorption
coefficient α. α has the unit of inverse of length while (1/ α) called the effective
absorption length, is essentially a measure of the material thickness within which the
incident photon is absorbed by the semiconductor. In fact, the fraction of the incident
radiation which is absorbed within a distance x from the surface is given by [1-exp(-αx)].
Therefore, if α is larger, more of the incident radiation is absorbed within the distance x.
Also, the fraction of the incident radiation absorbed within a distance (1/ α) is then
evaluated as [1-exp(-1)] = 0.632. An absorption coefficient of 104 cm-1 corresponds to an
absorption length of 1µm, which means that 63.2% of the incident radiation is absorbed
within 1µm from the surface. The absorption coefficients for different semiconductors
are plotted as a function of the photon energy in Fig.1 For indirect band gap
semiconductors, the value α a at a given photon energy is usually lower for materials with
higher Eg, as can be seen from the plots for Ge and Si. However direct band gap
materials (such as GaAs) have much larger values of α even though their Eg may be
larger than indirect band gap materials, as seen from the plots for GaAs and Si. This
means that for a given photon energy, a much thinner layer of GaAs (than silicon) is
needed to absorb the light.
When a p-n junction is illuminated with light of photon energy greater than Eg
photons are absorbed in the semiconductor and EHPs are generated both in the n-region
and the p-region of the junction. For the EHPs to contribute towards current in the
external circuit, the generated electrons and holes must be separated before they
recombine. This is achieved if the EHPs are generated in the depletion layer, where the
electric field sweeps away the electrons and holes in opposite directions. The photo-

73
 Fig. 1 Absorption coefficients as functions of photon energy for various
semiconductor materials

generated minority carriers, which are generated within one diffusion length from the
depletion layer edge, can also diffuse to the depletion region without recombining. They
are then swept across- the junction due to the electric field present in the depletion region
as shown in Fig. 2. Due to the direction of the electric field being from the n-region to the
p-region, the holes flow towards the p-region and electrons to the n-region. Since the
direction of this photo-generated current IL is opposite to that in a forward-biased diode,
we can write an expression for the total current in an illuminated diode as

(1)
In other words, the total current of the diode is lowered by an amount IL when
illuminated.
The I-V characteristics of an illuminated p-n junction diode are depicted in Fig. 3.
An interesting point to be noted is that the I-V characteristics pass through the first, third,
and fourth quadrants. Depending on the intended application, the diode can be made to
operate so that either power is delivered to the device (operating in the first or the third
quadrant) or supplied by the device to the external circuit (operating in fourth quadrant).
When the diode is used as solar cell, it is made to operate in the fourth quadrant and work
as a battery. On the other hand, to make use of the diode as a photodetector, it is usually
operated in the third quadrant. However, though the underlying principle is the same, the
actual structures are very different for these two devices

74
 Fig. 2 An illuminated p-n junction showing the generation
and subsequent separation of EHPs

Fig.3 I-V characteristics of an illuminated p-n junction.

Solar Cell
A solar cell is basically a p-n junction, which can deliver power to the external
circuit when illuminated. Arrays of such junctions are used to supply electrical power to
space satellites and also for remote and rural areas. Solar cells are preferred over
conventional batteries for these applications as they are environment-friendly and provide
maintenance-free services for long time. However, the high cost of solar cells has so far
curtailed its widespread use for terrestrial applications.
Solar cells are usually large area devices so that a greater amount of optical
energy is absorbed and output power is high. In order to increase the light-generated
current IL, a large number of the minority carriers generated outside the depletion legion
have to reach the edge of the depletion region. This requires the diffusion lengths Ln, and
Lp to be large. As seen from the discussion on fabrication of diodes, the top layer is
produced by diffusion or ion-implantation with a high impurity concentration. High
impurity concentrations create lattice damage which introduces recombination centres.
This makes the lifetime of carriers very short in the top layer and consequently the
diffusion length is small, hence, in a practical solar cell, the topmost layer is kept very
thin so as to allow more light to reach the base. On the other hand, the diffusion length in

75
the substrate (or base) is large and the carriers generated in this region mostly contribute
to useful photocurrent. Also, n+p structures, with the n+ layer at the top, are preferred.
This is because the diffusion constant of electrons in the p-base (Dn) is larger than that of
holes in the n-base (Dp) of a p+n junction. Larger diffusion constant means larger
diffusion length and therefore an improvement in IL as more carriers generated outside
the depiction region can diffuse to this high field region. Usually, in a practical solar cell
the surface concentration of the n-region is kept below 1020 cm-3 with a junction depth
less than 0.2 µm. The surface of the solar cell is coated with antireflection coating in
order to minimize reflection losses.In general, the antireflection materials used are Si02,
TiO2, and Ta205. The series resistance of the solar cell has to be made very small so that
power is not lost due to losses in the cell itself. To achieve this, thin contact fingers are
provided on the n-region. Fig.4(a) shows the structure of a solar cell.

Fig.4 (a) Structure or a solar cell (b) I-V characteristics of an illuminated solar cell
showing the point of maximum power.
Solar cells are usually calibrated at AMI or AMO illumination. The AMI
spectrum represents sunlight incident at the sea level on a clear day with the sun at the
zenith and the incident optical power in this case is about 92.5 mW/cm2. On the other
hand, the incident optical power tot AMO is 135 mW/cm2 and is considered to be the
intensity of the solar spectrum just outside the earth’s atmosphere. White AMO
calibration is generally used for solar cells in space satellites, AMI is usually meant for
cells in terrestrial applications.
The fourth quadrant 1-V characteristics of a solar cell is shown in Fig.4(b) The
three most important parameters of a solar cell are the open circuit voltage Voc, the short
circuit current Isc, and the fill factor FF. Since in a solar cell, current flows from the n-
region to the p-region, that is, in a direction opposite to that of a conventional diode,
putting V = 0 in Eq. (1) we obtain the short circuit current Isc, as

(2)
Again for I = 0, we have the open circuit voltage Voc from Eq (1) as

76
 (3)
However, no power is delivered when the solar cell is operating at either of these two
points. So, the operating point of the cell should be selected such that the output power
becomes maximum. The output power is given by

(4)
The condition for maximum power is obtained from dP/dV = 0. Hence, differentiating
Eq. (4) and equating it to zero, we get the expressions for the voltage and the current at
the point of maximum power as

(5a)

(5b)
The optimum load resistance Rop for maximum power is thus given by rearranging Eq.
(5b) as

(6)
The Fill factor of the solar cell is defined as

(7)
where Pm = VmIm is the maximum power output of the solar cell. For a well-designed cell,
FF usually lies in the range 0.7-0.8. The efficiency of the solar cell is given by

(8)
where Pin = incident optical power.
Thus, it is evident that to realize a solar cell with high efficiency, it is not only
necessary to have high Voc and Isc but also a high FF. Solar cells with η= 15% under
AM1 illumination are commercially available.
To improve the efficiency of solar cells IL has to be increased. This can be
achieved by increasing the collection of photo-generated carriers. One way of improving
the carrier collection is to heavily dope the back of the cell so as to realize an n+pp+
structure. The potential barrier at the back pp+ junction forces the minority carriers to be
confined to the p-region. The decrease in the availability of minority carriers reduces
recombination at the back contact and enhances the chance of collection of the generated
carriers. Other techniques employed to increase IL include surface texturing, use of solar
concentrators, and so on.
The efficiency of a solar cell depends, to some extent, on the material used. For a
material with larger band gap Voc is usually higher as Io reduces drastically with increase

77
in Eg see Eq. 3. On the other hand, with an increase in Eg, some part of the. incident light
for which hv is now less than Eg, no longer contributes to IL, thereby reducing ISC, see
Eq. 2. Therefore, there is an optimum band gap for the highest possible efficiency. GaAs
solar cells have higher efficiency than their silicon counterparts, and are therefore
preferred for space applications, where cost is not of much concern. On the other hand,
silicon is still preferred for terrestrial applications, for their lower cost. Very high
efficiency cascade solar cells, consisting of a series of junctions of materials with
different band gaps, which efficiently about different portions of the solar spectrum, have
also been demonstrated primarily for space applications.

Photodiode
In a photodiode the incident optical signal generates EHPs that gives rise to a
photocurrent. The diode is reverse biased at less than its breakdown voltage (Vr<VBR ) ,
so that under dark conditions, only a very small current flows, usually referred to as the
dark current of the photodiode. Now, when light is incident on the diode, a large
photocurrent flows. This change in current allows the photodiode to detect the presence
of light and hence the photodiode is also termed a photo detector. The dark current must
he made small and the photocurrent large as much as possible so that the photodiode can
detect weak signals and the signal-to-noise ratio (SNR) is large.
Most photodiodes have a thin p+ layer at the top unlike solar cells where the n+
layer is at the top. This is because a diode with the p+ layer at the top has a faster time
response compared to the diode with the n+ layer at the top (In a solar cell, the response
time is not important). For a well designed photodiode, most EHPs are generated within
the depletion region. Due to the electric field, the electrons move towards the n-region
and the holes towards the p-region. Now the mobility of boles is much less compared to
that of electrons. So with a p-layer at the top, the slower carriers (holes) have to move a
much shorter distance to the p-contact.
An important parameter of a photodiode is the quantum efficiency η, which is
defined as the number of useful EHPs generated per incident photon. The term ‘useful
EHPs, refers to those EHPs which do not recombine and therefore contribute to current in
the external circuit. The value of η may be less than 1 if all the light is not absorbed
within the depletion layer or a diffusion length from it. Another related parameter of a
photodiode is the responsibility R. It is the ratio of the photocurrent to the incident optical
power and is expressed in units of Amperes/Watt. If Poptical is the incident optical power
at a wavelength λ (corresponding to a photon energy hν), and IL is the photo-generated
current then η and R are expressed as

(9a)
And

(9b)

78
In Eq. (9a).
α = absorption coefficient
Wp, = thickness of the top layer.
W = depletion width, and
Lp = minority carrier diffusion length in the underlying n-layer.
It has been assumed that only those EHPs which are generated in the depletion
layer and one diffusion length away from it in the n-region contribute to the photocurrent.
From Eq. 9a), we see that for high efficiency, Wp must be small and the depletion layer
width W must he large. Physically this means that most of the incident photons are
absorbed within the depletion region rather than in the neutral p- and n-regions. As there
exists a strong electric field in the depletion region. as soon as anEHP is generated within
this region, electrons are swept into the n-region and holes into the p-region eventually
contributing to photocurrent. Also a large W results in a small capacitance and improves
the speed of response of the diode. However, if W is too large. the transit time delay of
the carriers dominates and hence a compromise has to he made.

HELP DESK 1
Equation (9b) suggests that for a given quantum efficiency, the responsivity increases
with wavelength. What is the physical reason for this?
let us consider two ideal photodiodes, P1 and P2, having quantum efficiency η
equal to 1. Let us assume that the same number of photons is incident on P1 and P2 per
unit time. Therefore, it follows that the photo-generated current is also the same in P1 and
P2, that is IL1= IL2. Let λ1 and λ2 be the incident wavelengths on P1 and P2 respectively,
and λ1 > λ2. Since each photon incident on P2 has higher energy than those incident on P1
the incident optical power on P2 (Poptical 2) is greater than the incident power on
P1(Poptical).

Now, since
And

it follows that R1 > R2

where R1 and R2 are the responsivities of diodes P1 and P2 respectively. Therefore for two
photodiodes having the same η, responsivity increases with increase in wavelength.
Also note that one photon can generate only one EHP. If the energy of the photon
hv> Eg. the excess energy (hv-Eg) does not contribute towards IL,, but is lost as heat in
the substrate. Therefore, reduction in wavelength below the cut-off wavelength only
increases the input power, without increasing output current, thereby reducing
responsivity.

A convenient way of tailoring the depletion layer width is to use a p-i-n

photodiode rather than a simple p-n junction. Most of the reverse bias appears across the
‘intrinsic’ layer, which need not be truly intrinsic, as long as the doping is low. As the
doping is low, the carrier lifetime is high in this region and most of the photo-generated
carriers are collected by the n- and p-regions. Figure 5.(a) shows the cross-section of a p-
i-n photodiode. The curvature at the junction edges leads to higher electric held intensity

79
and a smaller radius of curvature results in a smaller breakdown voltage. A guard ring of
larger junction depth is usually employed in p-i-n photodiodes as shown in Fig.5(a) to
increase the break down voltage and reduce the dark current.
Photodiodes, which are operated close to the avalanche breakdown voltage to
enable avalanche multiplication of photo—generated carriers, are called avalanche
photodiodes. The avalanche multiplication process increases the photocurrent and hence
the responsivity of the detector. However, since the avalanche multiplication process is
statistical in nature, there is a fluctuation in the responsivity due to the avalanche
multiplication noise.

Fig.5(a) Cross-section of a silicon p-i-n photodiode; (b) cross-section of a hetero

junction InP/InGaAs p-i-n photodiode

It is evident that the photodiode is extremely sensitive to the wavelength of the

incident light through the absorption coefficient. If the incident photon energy hv < Eg,
the light is not absorbed. On the other hand, if hv>> Eg, the photons get absorbed very
near to the surface where the carrier recombination rate is very high and as a result, the
photocurrent is small again. Therefore, it is necessary to choose a proper photodiode
material depending on the particular optical signal to be detected. Hetero junction
photodiodes, with multilayers of compound semiconductors are very useful in this regard.
The band gap of the absorbing layer can be tailored to match the wavelength of the
incident light. Also the quantum efficiency of a hetero junction photodiode is higher than
that of a homojunction device. This is because in a heterojunction diode, light can he
made to reach the absorbing layer through a higher band gap material (window), which
does not absorb the incident radiation so that surface recombination is avoided-.However,
such a diode may have a higher dark current due to lattice mismatch at the hetero
interface.

80
Example 1

81
 CHAPTER 6

DIAMAGNETISM, PARAMAGNETISM &

FERROMAGNETISM

Introduction
A charge separation constitutes an electric dipole and the polarization represents
the average density (per unit volume) of the electric dipole moment (a vector quantity) in
a given direction while the electric polarization has to do with the static positioning of
the charges, the magnetization is due the motion of these charges.
A plane current loop is equivalent to a magnetic dipole so far as the magnetic
effects both produced and experienced by them are concerned. Electrons in an atom move
in certain prescribed fashions about the nucleus of the atom. The electronic motion can be
described by assigning a certain angular momentum to each electron. Consequently the
magnetic properties of a substance are determined by the state of angular momentum
which the electrons may possess.
Let us consider an electron with rest mass m0 moving around the nucleus in a
circular orbit of radius a and angular frequency ω. The angular momentum of the election
about the z axis is

where is the unit vector in the z direction . Since the electron goes round every 2π/ω
second, the curent generated by the electronic motion is thus given by

Where Φ is a unit vector in Φ direction. The angular momentum associated with the
electronic motion is then given by

A substance therefore possesses permanent magnetic dipoles if the electrons of its

constituent atom have a net non-vanishing angular momentum.
The angular momentum of an electron according to modern atomic theory is
measured multiples of h/2π where h is Planck’s constant Thus the strength of a permanent
magnetic dipole can be expressed in terms of an atomic unit which is called the Bohr
magneton

82
 This is the value of an elementary permanent magnetic dipole.
Besides permanent dipoles, magnetic moments can also be introduced by the application
of an external magnetic field; the principle involved in the operation of a Betatron is that
the electrons are accelerated into circular orbital motions by a time varying magnetic
field and the magnetic moment is induced due to change in the orbital motion of the
electrons.
When a substance is placed in a magnetic field H, a magnetic moment M per unit
volume results; M is called the intensity of magnetization. For isotropic materials M and
H are parallel vectors and the susceptibility defined by M = χ. H is then a scalar quantity.
In anisotropic substances χ is a tensor.

Classification of Magnetic Materials

The magnetic properties of a substance depend upon
(1) Whether the substance has permanent dipoles.
(2) If it has, how these dipoles are oriented with respect to each other. Based on these
criteria, the magnetic materials are generally classified into the following five categories
I. Diamagnetic
2. Paramagnetic.
3. Ferromagnetic
4. Antiferromagnetic
5. Ferrimagnetic

Importance of Magnetic Materials In Solid State Physics

Many magnetic materials contain more than one kind of magnetic species because
magnetic ions located at different crystal sites may behave differently according to their
positions in the lattice. The interaction between neighbouring magnetic ions thus
becomes an important parameter for the studies of internal field and lattice.

Diamagnetism
Diamagnetism is associated with the tendency of electrical charges partially to
shield the interior of a body from an applied magnetic field. Classically, diamagnetism is
related to changes in the orbital motion of electrons known as Lamor precession that
occur when atomic systems are placed in a magnetic field. Atoms or ions in which the
orbital and spin angular momenta cancel in pairs have J = 0 and have no permanent
magnetic moment to cause Para magnetism.
It may be recalled that the current induced in a closed electrical circuit by a
magnetic field is always in such a direction as to tend to keep the total flux unchanged.
Thus the circuit has in effect a negative susceptibility. The effect is retained even in
systems of charges that must be treated by quantum mechanics and is responsible for
diamagnetism. Since all atoms or ions produce a diamagnetic contribution to the total
susceptibility, although it may be marked by the other types; it is a consequence of the
magnetic moment induced in the atoms by an external field, In this respect diamagnetism
may be compared with the electron polarization in an electric field. Both are essentially
independent of temperatures. There exists however an essential difference; in die
electrical case the induced moment lies along the direction of an applied field leading to

83
the positive electrical susceptibility; in the magnetic case the induced moment produces a
negative susceptibility.
Theory
Assume an arbitrary direction for the angular momentum vector Ma relative to the
magnetic field H.

Fig. 1

The magnetic dipole moment

(1)
The magnetic field produces a torque It µ X H on the dipole so that

(2)
This is the equation of motion of a vector Ma precessing about H with an angular
frequency

(3)
where ωL is called the Larmor frequency

The derivation is based on the assumptions that Ma is independent of H, i.e., it is

assumed that the orbit is not deformed under the influence of magnetic field, As a result
of the charge of electron the precession produces an induced magnetic moment with a
component opposite to that of H.

(4)
Substituting for ωL

(5)
2
where <ρ > is the mean square radius of projection of the orbit on a plane perpendicular
to H.
When the treatment is extended to solid containing Z electrons, one obtains for
diamagnetic susceptibility

(6)

84
 (7)
where it is assumed that the charge distribution of the atom is spherically

symmetrical, i.e
It should however be noted that the diamagnetic susceptibility is determined
essentially by charge distribution in atoms.
With the introduction of quantum orbital theory the Langevin’s expression was
corrected by substituting the value of <ρ >2 deduced on Bohr’s theory conception.
The value of <ρ >2 for hydrogen-like atom is

(8)
where a0 is the radius of inner most orbit in the hydrogen atoms (normal state) and
Z is the effective nuclear charge.
The atomic diamagnetic susceptibility is

(9)
where a0 =0.528 x 10-8 for hydrogen atom in normal state.

Paramagnetism
Paramagnetism is related to the tendency of a permanent magnet to align itself in
the direction of magnetic field such that its dipole moment is parallel to the field. In
atomic systems the permanent magnetic moment is associated with the electronic spin as
in atoms, molecules and lattice defects possessing an odd number of electrons, the total
spin cannot be zero. Thus a paramagnetic substance has a non-vanishing angular
momentum. It may also be the permanent moment of unfilled atomic shells that arises
from a combination of spin and orbital moment.

Origin of Permanent Magnetic Moment in Paramagnetism

Some atoms and ions have permanent magnetic moments. In the absence of a
magnetic field, these moments usually point in random directions and hence producing
no macroscopic magnetization. But in the presence of a magnetic field, the moments tend
to line up preferentially in the field direction and produce a net magnetization. Since the
moments line up in the direction of the field and enhance the external field, the
susceptibility is greater than zero.
Since paramagnetism depends upon magnetic moment of ions, the origin of these
magnetic moments is important. There are two chief origins for the moments: one from
the orbital motion of the electron and the other from the spin motion.
The orbital moment arises in principle because an electron in an orbit about an
atom can be considered to be a small circulating current about the nucleus. The magnetic
moment is related to the angular momentum by an important relation as follows—
The primitive magnetic moment µm of a circulating loop is given by
(10)

85
 Where i is the current in the loop and A is the area enclosed by the circulating
current. Imagine for simplicity that the current is caused by a single electron in a circular
orbit of radius r about the central nucleus.
Then the current around the orbit is the amount of charge which passes any point in the
orbit per unit time and is

(11)
The angular momentum of the electron in the circular orbit of radius r is
(12)
Then
(13)
Since the charge on electron is negative so µm and L are oppositely directed vectors. Thus
the relation between magnetic moment and angular momentum is

(14)
From this expression it is clear that magnetic moment and angular momentum are related
through a constant [e/2m] termed as gyromagnetic ratio.
Now further, since angular momentum of electron in its orbit was found to be a multiple
of (h/2π), the magnetic moment of an electron with angular momentum (h/2π) is called
Bohr magneton µB.

(15)

The orbital angular momentum can also be related to quantum numbers. Recall that the
quantum numbers l and ml refer to the electron in its orbit.
Total orbital angular momentum is given by

(16)
where l = 0,1,2….
The number m1 refers to the component of angular momentum in z-direction; it satisfies
the relation

(17)

Combining (16), (18) and (19). we get

(18)
and (19)
The spin of the electron also results in a contribution to the magnetic moment now
according to the hypothesis of Uhlenback and Goudsmit the electron has an intrinsic
magnetic moment due to this intrinsic angular momentum. The magnitude of this
moment µz, spin is found experimentally to be the same and is twice as predicted by
eq.14 , Thus

86
 (20)
where s is the spin quantum number. Since s has the value and +1/2 and -1/2 ; the

magnitude of spin magnetic moment is always i.e, spin moment always has the
magnitude of one Bohr magneton. Thus the energy split between Sz = 1/2 and Sz = -1/2
states in a magnetic field is found to be 2µBH in contrast to µBH as predicted in classical
model.
The magnetic moment of a multi-electron atom is merely the sum of the magnetic
moments of all the electrons including both orbital and spin moments. Each electron
contributes an independent vector quantity to the total magnetic moment of the atom,
Since all filled shells have zero total angular momentum, they also have zero total
magnetic moment. In particular atoms or ions which possess only filled shells have no
permanent moment and hence they cannot be paramagnetic.

Langevin’s Classical Theory of Paramagnetism

Langevin was the first to give an electron theory of paramagnetism. He
considered a paramagnetic gas in which each particle is associated with a permanent
magnetic moment µ. So when a mass of gas was placed in a field, each particle tended to
set itself along the magnetic field. Now at ordinary temperature the particles are subjected
to ordinary thermal agitation so the particles would be prevented from taking exact
alignment but a kind of statistical equilibrium will be set up. So the Maxwell-Boltzmartn
statistics was applied. Then potential energy of a particle making an angle θ with the field
H was calculated from this magnetic moment and then susceptibility was calculated.
If µ is the resultant magnetic moment then

(21)

But

(22)
If
(23)
Then

(24)
Or

(25)

87
Ferromagnetism
Ferromagnetics are qualitatively distinguished from other substances by the
following properties:
(1) They acquire a relatively high magnetization in weak fields. Thus, for instance, in a
field of 10 gauss, the specific intensity of magnetisation of antimony (diamagnetic) is
about - 0.8 x l0-6 and of cobalt (paramagnetic) is about 0.6 x 10-3 while for soft iron it is
about 200.
(2) They do not exhibit a linear proportionality between the magnetization and the field
strength.This means that their susceptibility χ is not constant but varies with the field so
that the magnetic properties of a ferromagnet cannot be specified in a simple manner as
in the case of para and diamagnets.
(3) Their magnetization is not a unique function of the field strength but depends also on
the field to which they have been subjected previously.If the field is varied cyclically, the
well known hysteresis curve is obtained.
(4) They can exit in a permanently magnetized state even when there is no external field
(residual magnetism
(5) They lose their spectral characteristic above a certain critical temperature and then
behave as paramagnetic substances. Early investigations had shown that a piece of iron
raised to dull red heat was not attracted by a magnet and that a magnet similarly heated
lost the whole of its magnetism. Hence it followed that iron loses its special magnetic
properties if its temperature is raised above a certain value.
Hopkins found the critical temperature for iron to be 740°C and for nickel to be
40°C. He also found that below the critical temperature, the susceptibility increased with
rising temperature in weak fields, but reverse was the case in strong fields. Curie and
others extending the observations far beyond the critical temperature found that
susceptibility of ferromagnetics varied both with field and the temperature in a
complicated way which could however be reduced to paramagnetics. Researches
conducted at very low temperature down to that of liquid air indicate that in the case of
Fe and Ni, if the magnetizing field is small the susceptibility decreases as the low
temperatures are approached: but the field is large it increases.
Hence ferromagnetism is probably to be regarded as a special manifestation of
Para magnetism limited to a range of temperature below Curie point.

Weiss Theory of Ferromagnetism

In order to explain the relation that exists between para and ferromagnetism as
well as to account for the special properties of ferromagnetics, Weiss gave his molecular
field theory. Weiss assumed that since in a real gas the molecules are mutually
influenced by their magnetic moments, there should exist within the gas a molecular
field, produced at any point by all the molecules in the neighborhood, proportional and
acting in the same sense as the intensity of magnetization.
If the internal field be represented by Hm = AI where A is molecular field constant, then
the effective field H may be regarded as the vector sum of external field H and internal
field Hm
(26)

88
 Considering a gm molecule of the substance and if ρ is the density ; M the
molecular weight : σ the gm. molecular magnetic moment and σ0 the gm. molecular
saturation moment, then according to classical Langevin’s theory,

(27)
And

(28)
When the external field is zero, i.e., H = 0,
Then
(29)

And also, (30)

But

(31)
Thus we obtain two simultaneous equations (27) and (31) which are solved
graphically. Considering the curves corresponding to the two equations, the equation (27)
gives curve (A) and equation (31) gives a straight line (B) of slope [RTM/Aρσ02].
The curves (A) and (B) intersect each other at the origin 0 and at another point S. so that
the solutions are σ/ σ0 = 0 or SN.
But σ/ σ0 = 0 cannot be a true solution since there is spontaneous magnetization.
Here the only correct solution is σ/ σ0 = SN, that is to say, a point of intersection other
than the origin. It can be easily shown that S corresponds to a stable state of spontaneous
magnetization because if the molecules in the domain assume the state C the local
magnetization is less than that corresponding to equilibrium.

Fig.2

So the magnetization and α will increase until the state indicated by SN is

reached. Similarly at the position D, the local magnetization is greater than that for
equilibrium value and hence the magnetization and α will decrease to SN. Thus the
condition for stable spontaneous magnetization is given by non-zero point of intersection
of two curves.

89
Domains Theory
In order to explain the fact that a piece of ferromagnetic material may exist in the
non-magnetized state, whereas a weak magnetic field may produce saturation
magnetization in the same specimen, Weiss introduced the domain hypothesis. Each
domain is spontaneously magnetized, the magnetization being appropriate to the
temperature T of the specimen. The over-all magnetization is given by the sum of the
domain vectors, and thus may vanish under certain circumstances; an example is given in
(Fig.3a). Magnetization of a specimen may occur either by the growth of one domain at
the expense of another, i.e., by the motion of domain walls (Fig.3b), or by rotation of
domains (Fig.3c). A representative magnetization curve is given in Fig.4, indicating the
predominant processes in the different regions. We may note here that originally it was
thought that the well-known Barkhausen jumps were due to the rotation of a complete
domain and that the size of the Barkhausen discontinuities was a measure of the size of
the domains. However, experiments by Williams and Shockley show that the Barkhausen
jumps are mainly associated with irregular fluctuations in the motion of the domain walls
rather than with domain rotation.

Fig.3. The domain structure (a) corresponds to the non- magnetized state; (b) represents
magnetization due to wall motion; in (c) the magnetization is due to rotation of the
domain vectors from an “easy” to a “hard” direction.
The most direct experimental evidence for the existence of domains is provided
by the so-called “Bitter powder patterns.” A drop of a colloidal suspension of
ferromagnetic particles is placed on the carefully prepared surface of the specimen; since
there are strong local magnetic fields near the domain boundaries, the particles collect
there and the domains may be observed under a microscope.

90
 Fig.4. Typical magnetization curve of a virgin specimen indicating the
predominant processes taking place in the different regions. When the field is reversed at
C, the dashed curve is obtained; Hc, is called the coercive force.
The physical origin of domains may be understood from the general
thermodynamic principle that the free energy E -TS of a solid tends to reach a minimum
value. As a result of the high degree of order in the magnetic system, except in the
vicinity of the Curie temperature, the entropy term may be neglected for our purpose;
thus, minimizing the energy E of the system should be sufficient to understand the
existence of domains. To illustrate the essential features of this point of view, we refer to
Fig. 6, representing a cross section through a ferromagnetic single crystal.

Fig. 5 The origin of domains

In (a) we have a single domain, i.e., saturation magnetization of the specimen.
Because of the free magnetic poles at the ends of the specimen, the expression for the
energy will contain a term (1/8π∫H2dV associated with the field outside the crystal. In a
configuration such as in Fig.5b on the other hand, the field energy is strongly reduced
because the spatial extension of the field is much smaller. Now, as we shall see below,
there is a certain amount of energy involved in producing a domain wall. Hence, one
ultimately arrives at an equilibrium situation with a number of domains such that the
energy required to produce one more domain boundary is equal to the resulting reduction
of the field energy.
A domain structure such as in Fig.5c has zero magnetic field energy. This is
achieved by introducing the triangular prism domains at top and bottom of the crystal:
such domains are called closure domains. Note that the wall between a closure domain
and a vertical domain in Fig.5c makes an angle of 450 with the magnetization directions
in both types of domains, hence the normal component of the magnetization in crossing
such a wall is continuous, i.e. there are no free poles and there is no field energy. The
energy required to produce a closure domain is essentially determined by the anisotropy
of the crystal, i.e., by the fact that ferromagnetic materials have “easy” and “hard”
directions of magnetization. For example, from the magnetization curves represented in
Fig.6 one sees that in iron, which is cubic, the easy directions of magnetization are the
cube edges.25 in ‘nickel, which is also cubic, the easy directions of magnetization are the
body diagonals. In cobalt the hexagonal axis of the crystal is the only preferred direction;
thus in a cobalt crystal with prominent domains magnetized along the hexagonal axis, the

91
closure domains are necessarily magnetized along a hard direction. In iron and nickel, on
the other hand, it is possible to have both the closure domains and the dominant domains
magnetized along easy directions.

Fig. 6. Magnetization curves at 38°C for a single crystal of iron for different directions of
the field relative to the crystal axes.
Summarizing the ideas discussed above we may say that domain structure has its
origin in the principle of minimum energy. It will be evident that the number of domains
and the 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 domains may vary
between, say,10-2 to 10-6cm3.

Hall Effect
Measurements of conductivity alone are not sufficient for determination of both
the number of conducting charges n and their mobility µ. Neither do they permit
determination of the sign of the dominant charge carrier. However it is quite fortunate
that a simple experimental procedure is available to measure the concentration of
majority carriers. This is the Hall Effect which gives additional Information required. If a
magnetic field is applied to a system in which a current is flowing there is a tendency for
the charge carriers to be deflected laterally. Now imagine applying an external electric
field E along the axis of the specimen, and then electrons will drift in the opposite
directions. If we apply a magnetic perpendicular to the axis of the specimen, the carriers
will then tend to be deflected to one side. At the surface of the crystal they will not drift
into a space but a surface charge will be developed. The surface charge then will give rise
to a transverse electric field, known as Hall field and this will cause a compensating drift
such that the carriers remain within the specimen.
Thus the Hall effect is observed when a field is applied at right angles to a
conductor carrying a current as shown in fig.7.

92
 The magnetic field gives rise to an electric field in a direction mutually
orthogonal to the direction of current and magnetic field. The reason for this effect is
apparent when the forces on the current carrier are considered. The electric field E which
produces the current I, causes a force of magnitude eE to act on the electrons. In the
presence of the magnetic field, a magnetic force proportional to the magnetic field
strength H and the electron’s average velocity v also on the electron. This force is at right
angles to the directions of H and v, and therefore each electron is deflected towards one
side of the conductor. When the electrons reach the surface of the conductor, an electrical
charge is built up there, which in turn produces an additional electric field. Under
equilibrium conditions, the sideways force on the moving carriers due to this field just
balances that arising from the field and the electrons can again move freely down the
conductor.

Fig.7

Consider a slab of material subject to an external field Ex along x-axis and a

magnetic field H along z-axis as illustrated in fig.7. As a result of the applied electric
field, a current density Ix will flow in the direction of Ex. For the moment let us suppose
that current is carried by electrons of charge -e. Under the influence of magnetic field the
electrons as discussed above will be subjected to a Lorentz force such that lower surface
collects a negative charge and upper surface a positive charge. Ultimately a stationary
state is obtained in which current along y-direction vanishes and a field is set up. If the
charge carriers were positive the upper surface would become negative and lower surface
positive i.e., Ey would be reversed. Thus measurement of Hall voltage gives the
information about the sign of charge carriers.
Now electric force on an electron having charge - e is - eE.
Force due to magnetic field H is (- e/c) v ΛH
Hence, total force on an electron is

But in the present case

(1)

Hall Voltage and Hall Coefficient

In the steady state, the force due to accumulation of electrons becomes equal to
the magnetic force and so the flow of electrons stops i.e., Ey = 0. Substituting this
condition in (1) , we get

93
 (2)
This Ey is called Hall voltage, where vx is average drift velocity.
Further, current density may be expressed in terms of number of electrons n per unit
volume

Substituting this value of v in eq.(2), we get

(3)
where RH is known as Hall coefficient. This expression for Hall coefficient is in e.s.u. and
in e.m.u. it will be

The Hall coefficient is determined essentially by the sign of charge carriers. It is

to be noted that the sign of the Hall coefficient is the same as the sign of the carrier. Thus
it is negative if the conduction is by electrons. If our calculation has been based upon
holes, the sign of the charge entering the Lorentz force would have been positive and
corresponding Hall coefficient would have been positive.
Mobility and Hail Angle
When current carrying particles acquire a velocity per unit electric field; the
velocity is known as mobility and is represented by µ i.e.,

(4)
Substituting this value of vx in eq.(2), we get

(5)
Equating the two values of Ey from (3) and (5), we get

(6)
And

Also
(7)

(8)
Or

(9)

94
 Importance of the Hall Effect
1. The sign of the current carrying charge is determined.
2. The number of charge carriers per unit volume can be calculated from the Hall
coefficient RH.
3. The mobility is measured directly.
4. It can be used to determine the electronic structure of the substance i.e., whether these
are metals, semi-conductors or insulators.
5. The knowledge of Hall voltage developed enables us to measure high unknown
magnetic field provided we know the Hall constant for the slab used for it.
6. It gives the concept of negative mass as suggested by Bleaney.
Experimental Determination of Hall Coefficient
We have

If i be the total current then

where b and d are the breadth and thickness of the specimen.

Thus,

(10)
Where VH is the Hall voltage.

Fig. 8. Experimental arrangement for the determination of Hall voltage.

Thus the value of Hall coefficient can be calculated by knowing i and Hz and by
measuring experimentally the Hall voltage, VH developed across C and D which is
measured either by sensitive galvanometer or better by means of a calibrated
potentiometer.
For accuracy of the measurement the length of the specimen should be large as
compared to its thickness.

95
 CHAPTER 7

SUPERCONDUCTIVITY

SUPERCONDUCTIVITY
Superconductivity was first discovered in 1911 by the Dutch Physicist Heike
Kamerlingh Onnes. Onnes observed that as purified mercury is cooled, its resistivily
vanishes abruptly at 4.15 K. Fig. I shows the result of the experiments conducted by
Onnes. Heike Kamerlingh Onnes was honored in 1913 with the Nobel Prize in physics
for superconductivity.
In many of the metals and alloys, dc electrical resistivity vanishes entirely below a
certain temperature, the temperature depending upon the substance. The zero resistivity is
known as superconductivity. The temperature at which the normal metal passes into
superconducting state is called the transition temperature or critical temperature Tc. The
materials whose resistivities become immeasurably small or actually become zero below
a critical temperature Tc. The known as superconductors. Fig. 2 (a) shows the resistivity
of normal metal and Fig 2(b) shows the resistivity of pure and impure superconductor.

Fig.1 Abrupt change of resistivity of liquified mercury observed by Onnes.

Above critical temperature Tc, the material is in the familiar normal state. But
below Tc it enters an entirely different superconducting state.
The most sensitive measurements have shown that the resistance of these
materials in the superconducting state is at least 1016 times smaller than their room

96
temperature values. Superconductors having a critical temperature Tc , above 77K
(boiling Point of liquid Nitrogen) are particularly interesting because they do not require
liquid helium (b.pt 4 K) or liquid N2 (b.pt 20 K) for cooling. There are some metals like
cesium that become superconducting only if a large pressure is applied to them.

(a) (b)
Fig. 2. Schematic representation of the resistivity of the
(a) Normal metal, (b) Pure and impure superconductor as a function of temperature T.

Properties of Superconductors
(1) At room temperature, the resistivity ρ of superconducting materials are greater than
other elements (as shown in Fig. 3).

Fig. 3 Comparison of ρ of superconductor and

normal metal at room temperature.

(2) All thermoelectric effects disappear in superconducting state.

(3) When a sufficient strong magnetic field is applied to superconductor below critical
temperature Tc its superconducting property is destroyed.
(4) When current is passed through the superconducting materials, the heating loss (I2R)
is zero.

Hence no heating losses.

97
Critical Field
The minimum applied magnetic field necessary to destroy superconductivity and
restore the normal resistivity is called the critical field Hc. When the applied magnetic
field exceeds the critical value Hc, the superconducting state is destroyed and the material
goes into the normal state.
Hc depends on the temperature. Fig. 4 shows the critical field Hc as a function of
temperature. A specimen is superconducting below the curve and normal above the
curve,
For a given substance, value of Hc decreases as temperature increases from T = 0 K to Tc

Fig.4 Schematic representation of the critical field Hc

as a function of temperature.

The curve is nearly parabolic and can be represented as:

(1)

where H0 is the critical field at 0 K.

Thus the field has its maximum value H0 at T = 0K

Eq. (1) is the phase boundary between the normal and superconducting
state,

98
Meissner Effect
Meissner and Ochsenfeld found that if a superconductor is cooled in a magnetic
field to below the critical temperature Tc (transition temperature), then at the transition,
the lines of induction are pushed out. “The expulsion of magnetic flux from the interior of
a piece of superconducting material as the material undergoes the transition to the
superconducting phase is known as Meissner effect.”
Fig.5 shows the normal sphere at T> Tc and superconducting sphere at T< Tc showing
the expulsion of magnetic lines of induction. Meissner effect is reversible, when the
temperature is raised from below Tc the flux suddenly penetrates the specimen after it

99
reaches Tc and the substance is in the normal state. i.e. a superconductor exhibits perfect
diamagnetism. Because of diamagnetic nature, superconducting materials strongly repel
external magnets. It leads to a levitation effect.

Fig.5 Meissner effect.

Type l and Type II Superconductors

Superconducting materials can he divided into two types, based on their magnetic
response. These two types are designated as type 1 and type II.
Type 1 or the ideal superconductors, while in the superconducting state are
completely diamagnetic, that is when these superconductors are placed in a magnetic
field, then all the lines of induction are pushed out from the specimen. (These
superconductors show Meissner effect). As magnetic field is increased, the material
remains diamagnetic until the critical value Hc is reached. At this point conduction
becomes normal and complete magnetic flux, penetration takes place.
Type II or hard superconductors are those in which the ideal behaviour is seen up
to a lower critical field Hc1 beyond which the magnetization gradually changes and
attains zero at an upper critical field designated as Hc2. The Meissner effect is incomplete
in this region between Hc1 and Hc2, this region is known as the vortex region as shown as
Fig.6(b). The normal behaviour is observed only beyond Hc2. The lines of induction
penetrate gradually from the specimen, as the field is increased beyond Hc1 and the
penetration completes at Hc2.Fig.6 shows the behaviour of Type I and Type II
superconductors as a function of -M and H.
From Fig 6 It is clear that for Type I superconductor upto Hc the magnetization of
the material grows in proportion to the external magnetic field and then abruptly drops to
zero at the transition to the normally conducting state.

100
 (a) (b)
Fig.6. Magnetization versus magnetic field for (a) Type land (b) Type 11
superconductors.

Variation of resistivity of a Type I superconductor and Type II superconductor as

a function of applied magnetic field is shown in Fig.7. In Type I superconductor, the
transition from superconducting state to normal state in the presence of a magnetic field
occurs sharply at the critical field Hc, while in Type II superconductor the transition from
superconducting state to normal state occurs gradually as the magnetic field is increased
from Hc1 to Hc2 as illustrated in Fig. 7(b),

(a) (b)
Fig.7 ρ verses H for (a) type 1 and (b) type 11 superconductors.

Isotope Effect
In 1950, CA. Reynolds and E.M. Maxwell found that the critical temperature
varies with the atomic mass ma, according to the relation:
maα . Tc = Constant
here α is a materials constant and is known as isotope effect co-efficient and is given as

101
 The value of α varies from 0.45 to 0.50 for many superconductors but there
notable exceptions to these values where the value of α is quite small like Nb3Sn, Mo etc.
Tc for mercury varies from 4.185 K to 4.16 K when m0 changes ma changes from 199.5
to 203.4 amu
Fig. 8 shows the experimental result for tin. Since Debye temperature θD, is proportional
to the velocity of sound which depends on ma -1/2; therefore the transition temperature can
be related to the Debye temperature i.e.

Fig. 8 Isotope effect for tin metal.

Applications of superconducting material

(1) These materials are used for producing very strong magnetic field of about 50
Tesla, which is much larger than the field obtainable from an electromagnet.
(2) High current densities with zero resistance properties of superconducting
materials make useful for strong electromagnets, e.g. in MRI (magnetic resonance
imaging) devices, used in medicine.
(3) In superconducting materials, heating loss is zero [ I2R = 0], therefore power can
be transmitted through superconducting cables without loss.
(4) These materials can be used to perform logic and storage functions in computers.
(5) Type 11 superconducting materials are mainly utilized for superconducting
solenoids.
(6) These are also used in high speed leviated trains (Meglev).
(7) SQUIDs are used in the field of medicine, it measures the very weak fields
generated by heart and brain.
(8) Recently superconductors have found applications in switching elements called
Cryotrons.

102
 CHAPTER 8

LASER

INTRODUCTION
The word LASER is an acronym for Light Amplification by Stimulated Emission
of Radiation. It is a device to produce a strong, monochromatic, collimated and highly
coherent beam of light and depends on the phenomenon of “stimulated emission’
The laser is the outgrowth of MASER which is a device that amplifies microwaves. The
first successful maser, an ammonia maser was built by Gordon, Zeiger and Townes in
1954. Townes, Basov and Prokhorov were awarded the Nobel Prize in Physics in 1964
for their invention of maser. In 1958, Schawlow and Townes showed that the maser
principle could be extended into the visible region and in 1960, T.H. Maiman built the
first laser using ruby as the active medium. Helium-Neon laser was developed by Au
Javan and his associates in 1961. This type of laser had been the dominant laser for the
next 20 years until cheap semiconductors have appeared. In these lasers the electric
discharge was used to create lasing. Also in 1961 the first semiconductor laser was
created by Robert Hall.

ABSORPTION OF RADIATION
If an atom is initially in a lower state 1, it can rise to a higher state 2 by absorbing a
quantum of radiation (Photon) of frequency v given

where E1 and E2 are the energies of the atom in the states 1 and 2 respectively, (Fig. 1).
This process is known as absorption of radiation

Fig.1 Absorption
The probable rate of occurrence of the absorption transition 1 — 2 depends
on the properties of states 1 and 2 and is proportional to the energy density u(v)

103
of the radiation of frequency v incident on the atom. Thus

where B12 is proportionality constant and is known as Einstein’s coefficient of radiation.

SPONTANEOUS EMISSION
Let us now consider an atom initially in the higher (excited) state 2. Excited state with
higher energy is inherently unstable, hence atom in excited state does not stay for longer
time and it jumps to the lower energy state 1 emitting a photon of frequency ν. This is
spontaneous emission of radiation. If there is an assembly of atoms, the radiation emitted
spontaneously by each atom has random direction and a random phase and is therefore
incoherent from on atom to another.

The probability of spontaneous emission 2 ! 1 is determined only by the properties of

states 2 and 1. This is denoted by A21
which is known as ‘Einstein’s coefficient of spontaneous emission of radiation’ In his
case the probability of spontaneous emissions is independent of it.

STIMULATED (INDUCED) EMISSION

According to Einstein, an atom in an excited energy state may, under the influence of the
electromagnetic field of a photon of frequency v incident upon it jump to a lower energy
state, emitting an additional photon of same frequency (v), Fig. 3.
Hence two photons, one original and the other emitted, move together This is stimulated
(or induced) emission of radiation. The direction of propagation phase, energy and state
of polarization of the emitted photon is exactly same that of the incident stimulating
photon, so the result is an enhanced beam coherent light
The probability of stimulated emission transition 2!1 is proportional the energy density
u(v) of the stimulating radiation and is given by B21 u(v)
where B21 is the ‘Einstein’s coefficient of stimulated emission of radiation’
The total probability for an atom in state 2 to drop to the lower 1 is therefore

104
 P21 = A21 + B21 u(v) (2)

Before After

Distinction between the Spontaneous and Stimulated Emission Processes

In the case of spontaneous emission, the atom emits an electromagnetic wave which has
no definite phase or directional relation with that emitted by another atom. In the case of
stimulated emission, since the process is forced by the incident electromagnetic wave, the
emitted light by the atom is in phase with that of the incident electromagnetic wave. The
emitted wave is also in the same direction as that of the incident wave.

RELATION BETWEEN SPONTANEOUS AND STIMULATED EMISSION

PROBABILITIES
Let us consider an assembly of atoms in thermal equilibrium at temperature T with
radiation of frequency v and energy density u(v). Let N1 and N2 be the number of atoms
in states 1 and 2 respectively at any instant. The number of atoms in state 1 that absorb a
photon and rise to state 2 per unit time is
N1P12 = N1B12u(v) .(3)
The number of atoms in state 2 that drop to state 1, either spontaneously or under
stimulation, emitting a photon per unit time is
N2P21 = N2 [A21 + B21 u(v)1 (4)
For equilibrium, the absorption and emission must occur equally. Thus
N1P12 = N2P21

(5)

105
Einstein proved thermodynamically that the probability of (stimulated) absorption is
equal to the probability of stimulated emission
i.e. B12 = B21
Thus , we have

The equilibrium distribution of atoms among different energy states is given by using
Boltzmann’s Distribution Law according to which

Consequently,

(6)

This is the energy density of photon of frequency v in equilibrium with atoms in

energy states 1 and 2, at temperature T. comparing it with the Planck’s radiation formula
(according to which the energy density of the black body radiation of frequency v at
temperature T is given as)

(7)
We get

(8)
This is the relation for the ratio between the spontaneous emission and induced
emission coefficients and show that probability of spontaneous emission increases rapidly
with the energy difference between the two states.

106
POPULATION IN VERSION AND PUMPING
Usually the number of particles N2 i.e., population of higher energy level is less
than the population N1 of lower energy level which is essentially possible by supplying
energy from outside the system. Otherwise, atoms would eventually radiate, fall to the
lowest energy state, and stop emitting altogether. Therefore, as required by conservation
of energy, all laser systems must be connected to external energy sources to maintain this
non-thermal equilibrium situation. Making N2> N1 i.e., the number of particles N2 in ore
in higher energy level than the number of particles N1 in lower energy level is called
population inversion or inverted population. The states of system, in which the population
of higher energy state is more in comparison to the population of lower energy state are
called negative temperature states. Here it should be clearly understood that the negative
temperature is not a physical quantity but it is a convenient mathematical expression,
signifying the equilibrium state of the system. When the system has a number of states,
then one of them may have negative temperature with respect to other states.
A system in which population inversion is achieved is called an active system.
The method of raising a particle from lower energy state to higher energy state is called
pumping. This can be done by a number of ways:

For example; atoms can be energized by electron impact in sufficiently intense gaseous
discharges, known as ‘electrical pumping’. The electrical pumping is suited to gas and
semiconductor lasers.
We can also supply energy by powerful lamps or a laser beam whose light
populates excited states by photon absorption, known as optical pumping. This method is
particularly suited to solid state or liquid lasers (dye-lasers). The availability of efficient
and powerful laser sources at many wavelengths has made laser pumping both attractive
and practical.
A form of pumping somewhat similar to optical pumping involves a medium
excited by an x-ray beam, known as x-ray pumping.
A conceptually different and interesting type of pumping occurs when the
required population inversion is produced directly from an exothermic chemical reaction,
known as chemical pumping. Chemical pumping usually applies to materials in the gas
phase and it generally requires highly reactive and often explosive gas mixtures.

NEED OF THREE LEVELS

Suppose there are only two energy levels, a metatab1e state hv above the ground
state. The more photons of frequency v we pump into the assembly of atoms, the more
upward transitions there will be from the ground state to the metastable state. However, at
the same time the pumping rill induce (stimulate) downward transition from the
metastable state to the ground state. When half the atoms are in each state, the rate of
stimulated emissions will equal the rate of induced absorptions, so the assembly cannot
even have more than half its atoms in the metastable state. Hence a condition of
population inversion will not achieve because (N1= N2) and therefore in this situation
stimulated emission will not take place and laser amplification will not occur.

107
CHARACTERISTICS OF A LASER BEAM
The laser beam has certain remarkable properties which are as follows:

Fig. 4

The laser beam is coherent, with the waves all exactly in phase with one another [Fig.
4(c)1. 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 term coherence basically refers to the degree of correlation between phases at
different points in a beam of light. It is of two types
(i) temporal or time coherence (ii) spatial coherence.

(i) Temporal or time Coherence. If the phase difference of waves crossing two points
lying along the direction of propagation of the beam is time independent, then a beam of

108
light is said to possess temporal or time coherence. This coherence is also known as
longitudinal coherence. It refers to spectral purity or the degree of two waves of laser
light remains in phase over many wavelengths. Fig.5 shows a beam of light traveling
along the axis X’X. P and Q are the two points lying on this line. The beam is said to
possess temporal coherence if the phase difference of the waves crossing P and Q at any
instant is always constant.
Accordingly, the light wave train emitted from each source can be characterized
by an average time T0. It is called coherent time. Also the band width of the spectral
distribution is inversely proportional to T0.

Fig.5

(i)
The average length of the wave trains is called coherent length. If the velocity of light is c
then coherent length Lc is given by
Lc = cT0 (ii)
Since ∆ω = 2π∆ν
Where ∆ν is the frequency in Hz

(iii)

|∆ν|| = -(c/λ2) ∆λ (iv)

From eqs. (ii) and (iii), we get

(v)

109
ss

Here is called the natural line width.

Hence temporal coherence depends upon the value of coherent length and coherent time.

(ii) Spatial Coherence. A laser beam is said to possess spatial coherence, if the phase
difference of the waves crossing the two points lying on a plane perpendicular to the
direction of propagation of the beam is time-independent. This coherence is also termed
as transverse or lateral coherence. It is a measure of the minimum separation across the
wave from where two waves remain coherent. Fig.6 shows a beam of light travelings
along the line X’X. Here abed is a plane perpendicular to X’X. The beam is said to
possess spatial coherence if the phase difference of the waves crossing P and P’ at any
instant is always constant.

Fig.6
In Fig.7, S is a source and S1, S2, are two slits of separation l. If interference occurs for
lmax = lw then this dimension is called the spatial coherence length of the source.
From Fig7 (i) the source S is at a distance D from slits S1 and S2. The condition for
coherence of S1 and S2 is

Fig.7 (1) & (2)

110
Since a/D = θ, angle subtended by width of slit S. Thus, we get
lω = λ/θ
1. In this case interference fringes have not been observed for separation S1S2 as small as
1O-3 cm. Thus no constant phase relation exists between S1 and S2.
2. The laser light is almost perfect1y monochromatic i.e., highly temporarily coherent and
spatially coherent. This means that they have exactly mw frequency, direction and
polarization as the primary photon (spatial coherence) exactly the same phase and speed
(temporal coherence).
3. The laser beam does not diverge. Hence a laser beam is very narrow and can travel to
long distances without spreading.
The angular spread is given by
∆θ = 1.22λ/d
where d is the diameter of the front mirror.
4. The laser beam is extremely intense. To achieve an energy density equal to that in
some laser beams, a hot object would have to be at a temperature of 1O30 K. It is
estimated that light from a typical 1-mW laser is 10,000 times brighter than the light from
the sun at the earth’s surface

SEMICONDUCTOR LASER: Ga As LASER

Light emitting diodes are basically semiconductor lasers. A widely used
semiconductor laser is Ga As laser. The Fig.8 gives a schematic diagram of p-n junction
laser. The shaded layer is the deplation layer. The thickness of depletion layer is usually
very small (0. 1µm). To obtain laser action end faces are polished flat and parallel. The
other two faces are left unfinished to suppress the oscillations. The active layer consists
of a layer of thickness of the order 1µm, a lattice wider than the depletion region. The
transverse dimension of the beam is much greater ( 40µm). The laser beam, therefore
extends well into the p and n regions.

111
 Fig. 8
Operation: Population inversion in semiconductor is achieved by using heavily doped
(106 atoms/m3 donor or acceptor atoms) crystal. We know that n—type semiconductor
has many highly mobile electrons whereas p-type has the less mobile positive holes.
When two types of structures are joined then the type of structure shown in Fig.9 results
As the material is heavily doped, the Fermi level of p-type falls within the valence
band while that of n—type falls within the conduction band. When no voltage is applied
the two Fermi levels lie in the some horizontal line. The two bands are separated by an
energy gap. E known as forbidden—hand. Due to this gap conduction electrons can not
occupy the holes in n—type material. If an external voltage V is applied, the conduction
electrons can he made to be attracted p—type up is made positive (i.e. junction is forward
biased). Thus, iicJ we can say that condition of population inversion is achieved. If this
condition is satisfied, electrons jump across the forbidden gap to combine with a hole,
giving rise to the emission of light.
Thus. LED is basically a junction between heavily doped p-type and n-type
semiconductor such as Ga As. LEDs are commonly available in near infra-red and red
regions of the spectrum. They have been made with a wavelength as short as the
wavelength of green light..

112
 Fig.9

He-Ne Laser
The main drawback of ruby laser is that the output beam is not continuous though
very intense. For continuous laser beam, gas lasers are used. One such type of laser is He-
Ne laser. As the name implies, the laser medium is a mixture of Helium and Neon in the
ratio 10 : 1. It is encapsulated in a long narrow discharge tube as shown in Fig10 . The
pressure inside the tube is about 1 mm of mercury. The plane or concave mirrors M1 and
M2 are placed on the two sides of the tube to obtain a resonator system. One of the mirror
say M1 is highly reflecting whereas M2 is partially reflecting and partially transparent.
Laser beam comes out through the mirror M2.

Fig. 10 Schematic Diagram of He-Ne Laser

113
 The first few energy levels of He and Ne are shown in Fig11. The levels E2 and E3
of helium have nearly the same energy as the levels E’4 and E’6of neon. However, the
levels E2 and E3 are metastable. When discharge is passed through the mixture of gas, the
electrons collide with helium atoms and excite them to the metastable states E2 and E3.
This may be termed as pumping. The He atoms continue in these states for long time.
These helium atoms collide with unexcited neon atoms raising them (Ne atoms) to te
levels E’4 and E’3 . This results in a large number of neon atoms in the energy states E’6
and E’4 and this population inversion occurs with respect to the levels E’3 and E’5.
Therefore, the following three transitions occur:
1. E’6! E’5 producing laser of 3.39 µm
2. E’6 ! E’3 producing laser of 632.8 µm
3. E’4 ! E’3 producing laser of 1.15 µm

Fig.11 Energy Level Diagram for He-Ne Laser

To eliminate the photons of wavelengths 1.15 µm. and 3.3 µm., mirrors are atoms
drop to level E’2 through spontaneous emission and then de-excited to ground level
through, collisions. Thus, they are again ready to go through the cycle. This is achieved
by making the tube narrow (—0.6 cm), so that the neon atoms are de-excited by collision
with the walls of the tube.
The power output from He-Ne is rather small (—100 mW maximum), however,
the radiation is extremely useful in a wide range of applications because, it is highly
collimated, coherent and has extremely narrow bandwidth.

114
APPLICATION
The lasers are profitably used in almost every field including fundamental
research. The common applications of lasers are as follows:
1. Metallic rods can be melted and joined by means of a laser beam (laser welding),
2. The laser beam is used to vaporize unwanted material during the manufacture of
electronic circuits on semiconductor chips.
3. CO2 gas lasers of about 100W output are helpful in surgery because they seal small
blood vessels while cutting through tissue by vaporizing water in the path of their IR
beams.
4. Lasers are used to detect and destroy enemy missiles during warfare.
5. Low power semiconductor lasers are used in CD (compact disc) players, laser printers,
laser copiers, facsimile machine etc.
6. Semi-conductor lasers are ideal for fibre-optic transmission lines in which the electric
signals that would normally be sent along copper wires are first converted into a series of
pulses according to a standard code. Lasers then turn the pulses into flashes of IR light
that travel along thin glass fibres and at the other end are changed back into electric
signals.
7. High power lasers are used to bring about thermonuclear reactions which would
become the ultimate inexhaustible power source for human civilization,
8. Lasers are also being employed for separating the various isotopes of an element.
9. Lasers are used in the production of three-dimensional images of an object in
holography.
10. Laser beams have also been used in the “inertial confinement” of plasma.
11. The narrow red laser beam is used in supermarkets to read the bar codes.

EXERCISE
1. Calculate the coherence length for laser whose line width is 1 X 10-5 nm at
IR emission wavelength of 10.6 µm.
(ans. ∆l = 11.2km)
2. Imagine that we chop a continuous laser beam ( assumed to be perfectly
monochromatic λ0 = 623.8 nm ) into ns pulses using some sort of shutter .
Compute the resultant line width, band width and coherence lengths. (ans. ∆l =
3cm. ∆ν = 1010 Hz. ∆λ = 0.013nm )

115
 CHAPTER 9

FIBRE OPTICS
Fibre Optics
In case of electronic communication, the information is normally carried over in
the form of radio waves and microwaves, through copper wires and co-axial cables.
However, the information carrying capacity of these wires is restricted, due to their
limited band-width and is not efficient, as per the needs of the modern communication
techniques.
If light waves are used instead of radio waves, or microwaves, the number of
signals transmitted can be increased enormously. Technically, Grahm Bell in 1880
invented Photophone. which transmitted speech on a beam of light. By 1960, it was
established that light could t guided by glass fiber. However, the glass available at that
time heavily attenuated light propagating through them.
It was due to the invention of solid state lasers in 1970 and fabrication of low Ioss
glass fibres, that made the optical communication practical. With this the era of
photonics-started.
In addition to the use of optical fibre in communication, these have been extensively used
as sensors to detect electrical, mechanical and thermal energies. Also they are bung used
in copying machines and in medical diagnostics (Endoscopy).

Fig.1
Optical fibres
These are made up of glass or plastic conduicts as thin as a human hair which is designed
to guide light waves along the length of the fibre with the help of successive total internal
reflections from side walls of the fibre. The movement of light is in a zig-zag path and
some fraction of light may escape through side walls hut major fraction comes out from
the other end of the fibre. Fig.1

Construction
An optical fibre consists, in general, the following three regions:

116
(i) Inner-most region, which is the light guiding region is called core.
(ii) Core region is surrounded by a middle region, called cladding. The refractive index
of cladding is always lower than that of the core..
iii) The outermost region is called sheath. The sheath protects the core and cladding from
moisture, abrasion contamination and to give mechanical strength to fibre.
Optical fibres are either made as a single fibre or a flexible bundle of cable. A bundle
fibre is a number of fibres in a single jacket.

Fig.2
Basic propose of cladding is to confine the light to the core as the light falling on core
and striking core cladding interface at angle greater than the critical angle will be
reflected back to the core.
Propagation of Light Through Fibre
Main function of the optical fibre is to accept maximum light and transmit the same with
minimum attenuation.
Light gathering ability of a fibre depends on two factors:
(i) Core size
(ii) Numerical aperture
Numerical aperture of fibre is determined by acceptance angle and fractional refraction
index change.

Acceptance Angle and Acceptance Cone

Consider an optical fibre through which light is being sent. The end at which light
enters is called launching end. Let the refractive indices of the core and cladding be n1
and n2 respectively; n2 <n1. Let the refractive index of the medium k through which light
is launched be n0.
Let the light beam enter at an angle i to the axis of the fibre. The ray gets refracted
at an angle r and strikes the core cladding interface at an angle Φ. For angle Φ more than
the critical angle C, light will undergo total internal reflection. The ray will also undergo
total internal reflection at interface as n1 > n2. It means that so long as Φ is greater than
critical angle C, ‘light will stay within the fibre.

117
 Fig. 3

Let us now compute the incident angle i for which Φ ≤ C such that light rebounds within
the fibre.
Applying Snell’s law to the launching face of the fibre, we get

` (1)
If i is increased beyond a light, Φ will drop below the critical value C and the ray
escapes from the side walls of the fibre. The largest value of i occurs when Φ = C.
For the ∆ABC, we have

(2)
Putting sin i from equation (I) into equation (2), we get

(3)
But

(4)
Putting the expression (4) into (3), we get

(5)
When incident ray is launched from air medium, we have n0 = 1 Designing i (max) =θ0,
equation (5) may be simplified to

(6)

118
 (7)
The angle θ0 is called the acceptance angle of the fibre. Acceptance angle may be
defined as the maximum angle that a light ray can have relative to the axis of the fibre
and propagate down the fibre.

Fig.4
The light rays contained within the cone having a full angle 2θ0 are accepted and
transmitted’ along the fibre. The cone is called the acceptance cone. (Fig. 4)
Light incident at an angle beyond θ0 refracts through the cladding and the corresponding
optical energy is lost. It is clear that the greater the diameter of the core, the larger the
acceptance angle.

Fractional Refractive Index Change

The fractional difference between the refractive indices of the core and the cladding is
called fractional refractive index change. It may be expressed as

(8)
This parameter is always positive as n1 n2 for the total internal reflection
conduction condition. In order to guide light rays effectively through a fibre, ∆ < 1.
Typically, ∆ is of the order of 0.01.

Numerical Aperture
The numerical aperture (NA) is defined as the sine of the acceptance angle. So we
may write NA = sinθ0

(9)

Approximating , we can express the above may be

written as.

(10)

119
Numerical aperture accounts for the light gathering ability of the fibre and it measures the
amount of light accepted by the fibre. As is clear from eq. (9) numerical aperture depends
only on the refractive indices of the core and cladding materials.
Numerical aperture ranges between 0.13 to 0.50 and a larger value of numerical aperture
will mean that the fibre can accept more light from the source.

Modes of Propagation

120
In an optical fibre light travels as an e.m. wave and all the waves moving in directions
above the critical angle will be trapped in the fibre due to total internal reflections.
However, all such waves do not propagate through the fibre, and only certain ray
directions are allowed for propagations. These allowed directions corresponds to modes
of the fibre.

Fig.5
In simple form, we can understand the modes as the number of paths of light an
an optical fibre The paths are all zig-zag with the exception of light moving along axial
directions So the light rays moving through a fibre may be classified as (i) axial rays (ii)
zig-zag rays.
Since the rays get repeatedly reflected at the walls of the fibre, there occurs a
phase shift. So wave along certain zig-zag path be in phase and get intensified while
some other waves moving in other paths will be out of phase and may fade out due to
destructive interference.
The light ray paths along which the waves are in phase inside the fibre are called
modes.
Number of modes, a fibre can support depends on the ratio d/λ where ,d is the diameter of
the core and λ is the wavelength of the wave transmitted.
In general, modes are represented by an order number m. In a fibre of fixed
thickness, the higher order propagates at smaller angles than the lower order modes.
Axial ray that travels along the axis of the fibre is called zero order ray.
Types of Optical Fibre
Optical fibres are in general of two types:
(i) Single Mode fibre (SMF)
(ii) Multimode Fibre (MMF)
A single fibre has a smaller core diameter and can support only one mode of
propagation while a multimode fibre has a large core diameter and can support a large
number of modes.
Multimode fibres are further classified on the basis of index profie. An index
profile is graph of refractive index (along X-axis) and distance from the core (along Y-
axis). Index profit of a MMF can be either step index (SI) type or graded index (GRIN)
type. Index profile of SMF is usually a step index (SI) type.

Single Mode Step Index Fibre

A single mode step index fibre consists of a very fine thin core of uniform
refractive index surrounded by a cladding of refractive index lower than that of the core.
Since the refractive index abruptly changes at the core cladding boundary, it is known as
step index fibre. A typical SMF has a core diameters of 4µm which corresponds to some
of the wavelengths of light waves. Light travels along a single path, i.e., along the axis

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only and so zero order mode is supported by SMF. Usually SMF is characterised by a
very small value of ∆(~ O.002).
The fibre is surrounded by some opaque protective sheath

Fig. 5

Multimode Step Index Fibre

It is similar to the single mode step index fibre with the exception that it has a
large diameter (~100 µm). Core diameter is very large as compared to the wavelength of
transmitted light. Light moves along zig-zag paths along MME A typical structure along
with profile of step lfldex MMF are shown in Fig.6
NA in case of a MMF is quite large as core diameter is larger and is ~ 0.3.

Fig.6
Grain Index Fibre (GRIN)
A GRIN is a multimode fibre which has concentric layers of refractive indices
which means that the refractive index of the core varies with distance from the fibres
axis, i.e., it has high value at the centre and falls of rapidly as the radial distance increases
from the axis.
As is shown in profile (Fig.7) such a profile causes typical periodic focussing of
the light moving through the fibre.
It is important to note that in case of GRIN fibres, acceptance angle and numerical
aperture diminish with increase of radial distance from the axis. In the case of fibres of
parabolic profile, numerical aperture is given by:

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 The convention of writing the size of optical fibre is to given the core/cladding
diameter.
Sizes of SI fibre are 50/125, 10/140, 200/230 etc.
Size of GRIN fibres are 50/125, 62.5/125, 85/125, etc. For example, a fibre has 50
µm core and 125 µm cladding.

Fig.7

Fig.8

Normalized Frequency (V-number) of a fibre

An optical fibre may be characterized by one more or parameter called V-number
or the normalized frequency of the fibre.
V-number is denoted by the relation

(1)
where a ! Radius of the core
and λ! Free space wavelength.
Also we have Numerical Aperture given as:
Maximum number of modes Nm supported by an SI fibre may be got using the relation

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 In case V < 2.405, fibre can support only one mode and is called SMF.
For V> 2.405, ii is classified as MMF and it can support number of modes
simultaneously.
Wavelengths corresponding to value of V = 2.405 is called the cut off wavelength
of the fibre and is given as
Cut off wavelength λC = λV/2.405
In the case of GRIN fibres, for large values of V. we have

Applications of Optical Fibers

1. Military Applications. Optical fibers are finding lot of applications in various war
fares and military operations.
If conventional copper cables are to be transported by an aircraft, a ship or a tank for
control mechanisms or communication, then lot of weight has to be carried. However,
with fiber optics, the weight is enormously reduced and also communication network is
greatly improved, as with fiber optics; secrecy is also maintained.
During recent wars, fiber guided missiles have been extensively used. Sensors are
mounted on missiles to collect the video information. This information is passed on to the
ground control van which sends further commands t the missile through sensors. Control
van constantly monitors the course of missiles and corrects the direction of the missile to
hit the target precisely.

2. Optical fiber Sensors. In this case the basic characteristics of the optical fiber are
used, viz, the variation of refractive index of the fiber under the external forces may be
utilized for using the optical fiber as transducer.
In case the fiber is subjected to heat, the refractive index changes because of
temperature. As temperature increases, the difference of refractive index between the
core and cladding is reduced, thereby some light leaks into cladding. This characteristic
can be used for measurement of temperature using a LED as light source.
Fiber optics may also be used to measure pollution and foreign suspended particles
in the air. A beam of light is sent from one end of fiber and in case foreign particles are
present, they scatter the light and measurement of variation of intensity of light will
account of the extent of the presence of foreign particles.
Fiber optics may also be used to measure the level of a liquid in a container. A part
of fiber is suspended in the liquid and light is directed to pass through it and its intensity
is measured. A bare core loses more light when it is immersed in liquid than when it is
placed in air. A sudden change in intensity of light will indicate the liquid level. A LED
source, a photodector and a MMF is used to monitor the liquid level and is finding many
applications in the filling of petroleum tanks.

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3. Entertainment applications. A coherent optical fiber bundle can greatly enhance the
size of the image on a TV screen. In case we have to use the conventional method of
getting larger images than the projection system because quick bulky and unmanageable.

4. Medical Applications. Fiber optics are finding large number of applications in

medical fields. Many parts of human body which are otherwise inaccessible can be
studied by illumination with fiber optics. A bundle of MMF (multi mode fibers) is used to
illuminate a part of human organ and the other part to collect the reflected light. This
fiberscopic technique is employed for endoscopic applications. Fiber optics can be
employed to attach a detached retina or rectify other eye defects using lasers.
In heart problems also laser angioplasty is replaced by balloon angioplasty and bypass
surgery. A special catheter is used which consists of three channels, viz. (1) to visualize
the various veins (2) to supply power for lasers (3) an open tube to collect and suck the
debris and other blocking materials.

(Endoscopy)

5. In Communications. A fiber communication system is similar to the traditional

communication system with the exception that this highly efficient.
A block diagram of the typical communication system is shown in fig . A
transducer changes a non- electric message to electrical signals in case of fiber
communication. Light waves act as carrier waves. Light waves are generally generated by
a laser diode or a LED (light emitting diode) and the intensity of light given by these
sources is proportional to the current passing through them.

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 As a message in the form of an electric signal is received by the optical source,
light output will follow the path of variation of signal with the massage digital
modulation is preferred in optical communication over the analogue modulation as it
can pass through a larger distance with the same power.
However, one basic difficulty arises due to the attenuation of optical signal
overlarge distance because of various losses and dispersion in the optical fiber. So to
overcome it various repeaters are used in the transmission line to amplify and reshape the
signal.
At the receiver end an optical coupler is used to direct the light coming from the
fiber into a photo detector or, which converts light into electric current, which will
contain the message fed into the optical fiber. In the next step, the message is extracted
from this current and is amplified if the nearby. Then this message is put into a transducer
to get it either in video or radio form depending upon the nature of the original message.

Advantages

1. Cheaper. The main ingredient in glass is sand (SiO2), and there is an almost
unlimited supply of sand in the world compared to the supply of copper or
aluminum.
2. Safety. Through optical fibres, photons of light moves instead of an electrical
current. Therefore there is no chance of a spark flash, which could be dangerous.
3. Radio frequency interference (RFI). Since the fibre system carries no electrical
current. The energy transmitted through the fibre cannot radiate RF interference ,
nor can it be contaminated by any external noise or RF fields
4. Security. Because of the absence of the flow of current through the fibre, criminal
intrusion into th e system is also prevented. Confidential information cannot be
routed to unwanted receivers, nor can false information be fed into data stream,
5. Low losses. The transmission loss per unit length of an optical fibre is about 4
dB/km. Therefore, longer cables run between repeaters are feasible.
6. Wider bandwidth. Within a totally closed system, the number of signals that can
be modulated on a fibre optic light beam exceeds the number that can be
modulated on a very high frequency RF carrier by a factor of about 1000.
7. Deterioration. Glass is immune to corrosive and oxide degradation and will stand
up well in harsh environments. Moisture, toxic vapours and acids will not degrade
the glass fibres.
8. Small size and light weight. The size of the core and clad of a single fibre
conductor is much smaller than the diameter of a common copper wire conductor;

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 however, when the insulation is included, the sizes are similar. Bundles of optical
fibre cables are smaller by a factor of 10 and weight less by a factor of 14 than an
equal number of copper wire conductors.
9. Temperature. Excluding the protective insulation, the melting point of glass is
much higher than copper.
10. Long life. The life expectancy of glass fibres is predicted to exceed 100 years.

Disadvantages

1. Limited applications. All fibre optics system is limited to fixed point – to- point
ground installation. They cannot leave the ground nor be associated with a mobile
communication system.
2. Nuclear radiation. Glass, when exposed to neutron bombardment, will darken.
The harder the glass. The more quickly it will discolor.
3. Low power. Popular light –emitting sources are restricted to very low power
devices. Though, higher power devices are available but they are costly.
4. Distance. Because of the low power sources, the distance between repeater
amplifiers must be relatively short for the high date rates demanded in some
systems.
5. Modulation. There are limited ways in which the light source can be modulated
6. Fragility. The optical fibres are easily broken or damaged due to age and
vibrations

EXERCISE
1. Calculate the fractional index change for a given optical fiber if the refractive indices
of the core and cladding are 1.563 and 1.498, respectively. (ans. ∆ = 0.0415)
2. Calculate the numerical aperture and hence the acceptance angle for an optical fiber
given that refractive indices of the core and the cladding are 1.45 and 1.40
respectively. (ans. NA = 0.3775, θm = 22.180 )
3. A glass clad fiber is made with core glass of refractive index 1.5 and the cladding is
doped to give a refractive index difference of 0.0005, Find (a) the cladding index
(b) the critical internal reflection angle. (c) the external critical acceptance angle. (d)
the numerical aperture. ( ans. n2 = 1.49925, Φc = 88.20 ,θm = 2.720 , NA = 0.15)
4. An optical fiber has a NA of 0.20 and a cladding refractive index of 1.59. Determine
the acceptance angle for the fiber in water which has a refractive index of 1.33. ( ans.
θm = 8.60 )

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Bibliography
1. Charles Kittel : Introduction to Solid State Physics
2. B.S. Sexena, R. C. Gupta & P.N. Sexena: Solid State Physics
3. A.J. Dekkar: Introduction to solid state physics
4. Arthur Beiser: Concept of modern physics
5. Nandita & Amitava Das Gupta: Semiconductor devices
6. Ashok Sharma: Solid State Physics & Electronics
7. Ben C. Streetman & Sanjay Banerjee: Solid State Electronics Devices
8. S.O. Pillai: Solid State physics.
9. Rakesh Dogra: Essentials of physics.
10. S. K. Hajra Chaudhary: Material Sci. & Progress.
11. Navneet Gupta & A. K. Tayagi: Fundamentals of Engg. Physics

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