Luca Varani - University Montpellier 2 - Physics of Semiconductor Devices - Part II Material Physics

The Crystal Structure of Solids
Amorphous Solids
Insulators and dielectrics
Energy Bands
Electrical Conduction in Solids
Density of States
Statistical Mechanics
Physics of Semiconductors Devices

Part II - Material Physics
Luca Varani
University Montpellier 2
September 27, 2011
L. Varani Physics of Semiconductors Devices

The Crystal Structure of Solids Semiconductor Materials
Amorphous Solids Types of solids
Insulators and dielectrics Space lattices
Energy Bands Crystal Planes and Miller Indices
Electrical Conduction in Solids Atomic bonding
Density of States Imperfections and Impurities in Solids
Statistical Mechanics Growth of Semiconductor Materials
Outline
1 The Crystal Structure of Solids

Semiconductor Materials
Types of solids
Space lattices
Primitive and Unit Cell
Basic Crystal Structures
Crystal Planes and Miller Indices
The Diamond Structure
Atomic bonding
Imperfections and Impurities in Solids
Imperfections in Solids
Impurities in Solids
This lectures deal with the electrical properties and characteristics

of semiconductor materials and devices.
The semiconductor is in general a single crystal.
The electrical properties of a single-crystal material are determined
not only by the chemical composition but also by the arrangement
of atoms in the solid.

The formation or growth of the single-crystal material is an

important part of semiconductor technology.
This introductory chapter provides the necessary background in
single-crystal materials for the basic understanding of the electrical
properties of semiconductor materials and devices.

Semiconductors are a group of materials having conductivities

between those of metals and insulators.
Two general classifications of semiconductors are the elemental
semiconductor materials found in group IV of the periodic table
(see Fig. 1) and the compound semiconductor materials, most of
which are formed from special combinations of group III and
group V elements.

1
1
GROUP
IA
1.0079
PERIODIC TABLE OF THE ELEMENTS http://www.ktf-split.hr/periodni/en/
18 VIIIA
2 4.0026
PERIOD
1 H GROUP NUMBERS
IUPAC RECOMMENDATION
GROUP NUMBERS
CHEMICAL ABSTRACT SERVICE
He
HYDROGEN 2 IIA (1985) (1986) 13 IIIA 14 IVA 15 VA 16 VIA 17 VIIA HELIUM
3 6.941 4 9.0122 13 IIIA 5 10.8116 12.0117 14.0078 9

15.999 18.998 10 20.180
ATOMIC NUMBER 5 RELATIVE ATOMIC MASS (1)
2 Li Be 10.811
B C N O F Ne
LITHIUM BERYLLIUM SYMBOL
B BORON CARBON NITROGEN OXYGEN FLUORINE NEON
11 22.990 12 24.305 BORON ELEMENT NAME 13 26.982 14 28.086 15 30.974 16 32.065 17 35.453 18 39.948
3 Na Mg Al Si P S Cl Ar
VIIIB
SODIUM MAGNESIUM 3 IIIB 4 IVB 5 VB 6 VIB 7 VIIB 8 9 10 11 IB 12 IIB ALUMINIUM SILICON PHOSPHORUS SULPHUR CHLORINE ARGON
19 39.098 20 40.078 21 44.956 22 47.86723 50.94224 25 54.938 26

51.996 55.845 27 58.933 28 58.693 29 63.546 30 65.39 31 69.723 32 72.64 33 74.922 34 78.96 35 79.904 36 83.80
4 K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
POTASSIUM CALCIUM SCANDIUM TITANIUM VANADIUM CHROMIUM MANGANESE IRON COBALT NICKEL COPPER ZINC GALLIUM GERMANIUM ARSENIC SELENIUM BROMINE KRYPTON
37 85.468 38 87.62 39 88.906 40 91.224 41 92.906 42 95.94 43 (98) 44 101.07 45 102.91 46 106.42 47 107.87 48 112.41 49 114.82 50 118.71 51 121.76 52 127.60 53 126.90 54 131.29
5 Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
RUBIDIUM STRONTIUM YTTRIUM ZIRCONIUM NIOBIUM MOLYBDENUM TECHNETIUM RUTHENIUM RHODIUM PALLADIUM SILVER CADMIUM INDIUM TIN ANTIMONY TELLURIUM IODINE XENON
55 132.91 56 137.33 57-71 72 178.49 73 180.95 74 183.84 75 186.21 76 190.23 77 192.22 78 195.08 79 196.97 80 200.59 81 204.38 82 207.2 83 208.98 84 (209) 85 (210) 86 (222)
6 Cs Ba La-Lu Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
Lanthanide
CAESIUM BARIUM HAFNIUM TANTALUM TUNGSTEN RHENIUM OSMIUM IRIDIUM PLATINUM GOLD MERCURY THALLIUM LEAD BISMUTH POLONIUM ASTATINE RADON
87 (223) 88 (226) 89-103 104 (261) 105 (262) 106 (266) 107 (264) 108 (277) 109 (268) 110 (281) 111 (272) 112 (285) 114 (289)
7 Fr Ra Ac-Lr Rf Db Sg Bh Hs Mt Uun Uuu Uub Uuq

FRANCIUM RADIUM
Actinide RUTHERFORDIUM DUBNIUM SEABORGIUM BOHRIUM HASSIUM MEITNERIUM UNUNNILIUM UNUNUNIUM UNUNBIUM UNUNQUADIUM
LANTHANIDE Copyright 1998-2002 EniG. (eni@ktf-split.hr)
57 138.91 58 140.12 59 140.91 60 144.24 61 (145) 62 150.36 63 151.96 64 157.25 65 158.93 66 162.50 67 164.93 68 167.26 69 168.93 70 173.04 71 174.97
(1) Pure Appl. Chem., 73, No. 4, 667-683 (2001)
Relative atomic mass is shown with five
significant figures. For elements have no stable
nuclides, the value enclosed in brackets
6 La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
indicates the mass number of the longest-lived LANTHANUM CERIUM PRASEODYMIUM NEODYMIUM PROMETHIUM SAMARIUM EUROPIUM GADOLINIUM TERBIUM DYSPROSIUM HOLMIUM ERBIUM THULIUM YTTERBIUM LUTETIUM
isotope of the element.
However three such elements (Th, Pa, and U) ACTINIDE
do have a characteristic terrestrial isotopic
composition, and for these an atomic weight is 89 (227) 90 232.04 91 231.04 92 238.03 93 (237) 94 (244) 95 (243) 96 (247) 97 (247) 98 (251) 99 (252) 100 (257) 101 (258) 102 (259) 103 (262)
tabulated.
7 Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
Editor: Aditya Vardhan (adivar@nettlinx.com) ACTINIUM THORIUM PROTACTINIUM URANIUM NEPTUNIUM PLUTONIUM AMERICIUM CURIUM BERKELIUM CALIFORNIUM EINSTEINIUM FERMIUM MENDELEVIUM NOBELIUM LAWRENCIUM
Figure 1: Periodic Tables of the Elements

Table 1 shows a portion of the periodic table in which the more

common semiconductors are found.
III IV V
B C N
Al Si P
Ga Ge As
In Sn Sb
Table 1: A portion of the periodic table

Table 2 lists a few of the semiconductor materials.
Elemental semiconductors
Si Silicon
Ge Germanium
Elemental semiconductors
AlP Aluminium phosphide
AlAs Aluminium arsenide
GaP Gallium phosphide
GaAs Gallum Arsenide
InP Indium Phosphide
Table 2: A list of some semiconductor materials

Semiconductors can also be formed from combinations of group II

and group VI elements.
The elemental materials, those that are composed of single species
of atoms, are silicon and germanium.
Silicon is by far the most common semiconductor used in
integrated circuits.

The two-element, or binary compounds such as gallium arsenide or

gallium phosphide, are formed by combining one group III and one
group V element.
Gallium arsenide is one of the more common of the compound
semiconductors.
His good optical properties make it usefull in optical devices.
GaAs is also used in specialized applications in which, for example,
high speed is required.

We can also fom a three-element, or ternary compound

semiconductors
An example is Alx Ga1x As in which the subscript x indicates the
fraction of the lower atomic number element component.
More complex semiconductors can also be formed that provide
flexibility when choosing material properties.

Types of solids
Amorphous, polycrystalline, and single crystal are the three

general types of solids.
Each type is characterized by the size of an ordered region within
the material.
An ordered region is a spatial volume in which atoms or molecules
have a regular geometric arrangement or periodicity.
Amorphous materials have order only within a few atomic or
molecular dimensions, while polycrystalline materials have a high
degree of order over many atomic or molecular dimensions.

These ordered regions, or single-crystal regions, vary in size and

orientation with respect to one another.
The single-crystal regions are called grains and are separated from
one another by grain boundaries.
Single-crystal materials, ideally, have a high degree of order, a
regular geometric periodicity throughout the entire volume of the
material.

The advantage of a single-crystal material is that, in general, its

electrical properties are superior to those of a nonsingle-crystal
material, since grain boundaries tend to degrade the electrical
characteristics.
Two-dimensional representations of amorphous, polycrystalline,
and single-crystal materials are shown in Fig. 2.

Figure 2: Schematic, of three general types of crystals: (a) amorphous.

(b) polycrystalline. (c) single crystal.

Space lattices
Our primary concern will be the single crystal with it regular

geometric periodicity in the atomic arrangement.
A representative unit, or group of atoms, is repeated at regular
intervals in each of the three dimensions to form the single crystal.
The periodic arrangement of atoms in the crystal is called the
lattice.

Primitive and Unit Cell
We can represent a particular atomic array by a dot that is called a

lattice point. Figure 3 shows an infinite two-dimensional array of
lattice points.
The simplest means of repeating an atomic array is by translation.
Each lattice point in Figure 3 can be translated a distance a1 in
one direction and a distance b1 in a second noncolinear direction
to generate the two-dimensional lattice.
A third noncolinear translation will produce the three-dimensional
lattice.
The translation directions need not be perpendicular.

Figure 3: Two-dimensional representation of a single-crystal lattice.

Since the three-dimensional lattice is a periodic repetition of a

group of atoms. we do not need to consider the entire lattice, but
only a fundamental unit that is being repeated.
A unit cell is a small volume of the crystal that can be used
to reproduce the entire crystal.
A unit cell is not a unique entity.
Figure 4 shows several possible unit cells in a two-dimensional
lattice.

io nal lauice is a periodiC repetition Amorphous
of a group of atoms.
Solids Types of solids
he entire lattice. but only n fundamentalEnergy unit Bands
that is being
all volume of the crystal that can be used Density toofreprod
States uce Imperfections
the and Impurities in Solids
not a Uni4uc emily. Figure 1.3 shows several
Statistical possible unil
Mechanics Growth of Semiconductor Materials
attice.
---- - n; . . ------ -- --- I't I
- . ,,'" - - - - - ' B
,,t' -
- - - - - - ., . -
- _. J;L..!.:'
,. _- _ : _- _- _- _-
'"
Figure 1.31 Two-dimensional l'ellresent<ltion of a single-crystnl
tallauice.
Figure 4: Two-dimensional representation of a single-crystal lattice
lallic.:e .showing various plll,sible unit cells.
showing various possible unit cells.

The unit cell A can be translated in directions a2 and b1 , the unit

cell B can be translated in directions a3 and b3 , and the entire
two-dimensional lattice can be constructed by the translations of
either of these unit cells.
The unit cells C and D in Figure 4 can also be used to construct
the entire lattice by using the appropriate translations.
This discussion of two-dimensional unit cells can easily be extended
to three dimensions to describe a real single-crystal material.

A primitive cell is the smallest unit cell that can be repeated to to

form the lattice.
In many cases, it is more convenient to use a unit cell that is not a
primitive cell.
Unit cells may be chosen that have orthogonal sides whereas the
sides of a primitive cell may be nonorthogonal.
A generalized three-dimensional unit cell is shown in Figure 5.

T.R 1 The Crystal Stn,JCiure of So::ds
,,
,,,
,,,
,,
"
Figure
Figure 5: A 1.4 rA gener:lIized
generalized primitive unit cell.
primifi ve unit cell .
The relationship between this cell and the lattice is characterized

by three vectors: a, b and c, which need not be perpendicular and
which may or may not be equal in length.
Every equivalent lattice point in the three-dimensional crystal can
be found using the vector
r = pa + qb + sc (1)
where p, q and s are integers.

Since the location of the origin is arbitrary, we will let p, q and s
be positive integers for simplicity.

Basic Crystal Structures

Before we discuss the semiconductor crystal, let us consider three
crystal structures and determine some of the basic characteristics
of these crystals.
Figure 6 shows the simple cubic (sc), body-centered cubic (bcc)
and face-centered cubic (fcc) structures.
1 . 3 Space lattioes II
\
I \
,
I \ I
I
I \ I
I \ I
I
I
I
I
I
,.-----
I
I
I
(a) (b) (e)
Figure 1.5 1Three laltice Iypes: (a) simple cubic. (b) bodycenlcred cubic. (c) Faccccmcrcd cubic.
Figure 6: Three lattice Iypes: (a) simple cubic. (b) body-centered cubic.
Objective EXAMPLE 1.1
(c) Face-centered cubic.
To find the volume of atoms in a crystal.
Consider a singlc-crY5131 material that
L. isVarani
a body-centered Physics
cubic with aoflattice Constant
Semiconductors Devices
For these simple structures, we may choose unit cells such that the
general vectors a, b and c are perpendicular to each other and the
lengths are equal.
The simple cubic (sc) structure has an atom located at each
corner: the body-centered cubic (bcc) structure has an additional
atom at the center of the cube; and the face-centered cubic (fcc)
structure has additional atoms on each face plane.

By knowing the crystal structure of a material and its lattice

dimensions, we can determine several characteristics of the crystal.
For example, we can determine the volume density of atoms.

To find the volume density of atoms in a crystal

Consider a single-crystal material that is a body-centered cubic
with a lattice constant a = 5 A = 5 108 cm. A corner atom is
shared by eight unit cells which meet at each corner so that each
comer atom effectively contributes one-eighth of its volume to each
unit cell. The eight comer atoms then contribute an equivalent of
one atom to the unit cell. If we add the body-centered atom to the
comer atoms, each unit cell contains an equivalent of two atoms.
Solution
The volume density of atoms is then found as
2 atoms
n= = 1.6 1022 cm3
(5 108 )3

The volume density of atoms just calculated represents the order of

magnitude of density for most materials,
The actual density is a function of the crystal type and crystal
structure since the packing density-number of atoms per unit-cell
depends on the crystal structure.

Since real crystals are not infinitely large, they eventually terminate
at a surface.
Semiconductor devices are fabricated at or near a surface, so the
surface properties may influence the device characteristics.
We would like to be able to describe these surfaces in terms of the
lattice.
Surfaces, or planes through the crystal, can be described by first
considering the intercepts of the plane along the a, b and c axes
used to describe the lattice.

The Crystal
surfaces in terms of th eStructure
lattice. of Solids
Surfaces. Or Semiconductor
planes through Materials
the crystal, can be de
scribed by first considering
Amorphous Solids
the dielectrics
Insulators and
Types of solids
intercepts of the plane
Space lattices c
along the ii , b, and axes used
(0 describe the laILicc. Energy Bands Crystal Planes and Miller Indices
LE 1.2 Objective
To describe Iht JJ1 anc shown in Figure 1.6. (The lanice points in Figure 1.6 are shown
To describe the planes shown in Figure 7
the ii. b. and caxes only.)
Ie
Figure 1.61 A representati ve crystal-

Figure 7: AJanice
representative
plane. crystal lattice plane.
Solution
From Equati(.\11 (1 .1). (he intercepts of the plane correspond to I' = 3. q = 2. and $" == I. Now
wrice Ihe of Ihe inlcrcepcs. which gives
From Equation 1 the intercepts of the plane correspond to p = 3,

q = 2 and s = 1. Now write the reciprocals of the intercepts,
which gives
111
321
Multiply by the lowest common denominator, which in this case is

6, to obtain (236).
The plane in Figure 7 is then referred to as the (236) plane.
Multiply by Ihe lowest common denominator, which in this case is
6, to obtain (236).
The plane in Figure 7 is then referred to as the (236) plane.

The integers are referred to as the Miller indices.

We will refer to a general plane as the (hkl) plane.
Three planes that are commonly considered in a cubic crystal are
shown in Figure 8

1. 3 S;>ace Lattices 7
I
,I I
...
I I
... .------- ,
(
....
I I I
(
, ---- -
I I I
----
,, ,,
(
- ---,:
;; b (
jj
- --
(
/
'- -
/ / ",,.-
/
ii Ii
(a) (h) (e)
Figure 1.71 Three lauiee planes: (.)( 100) plane. (b) (110) plane. Ie) (I II ) plane.
Figure 8: Three lattiee planes: (a) (100) plane. (b) (110) plane. (c)
(111) plane.
number of lattice constants is equivalent and is refe rred to as the (100) plane. One ad-
vancage to taking the reciprocal oftlte intercepts I() obtain the Miller indices is that the
use of infinity is avoided when describing. plane that is paraUel to an axis. If we were
to describe a plane passing through the origin of our system. we would obtai n infin-
ity as one or nlore of the Miller indices after taking the reciprocal of the intercepts.
However. the location of the origin of our system is entirely arbitmry and so, by trans-
lating the origin to anoth er equivalent lattice poinl , wecan avoid the use of infinity in
the set of Miller indices.
For the simple cubic structure. the body-centered cubic. and the face-centered
cubic. there is a high degree of symmetry.L. TheVarani
axes can be r(ltated
Physicsby 90
of in each of the
The plane in Figure 8a is parallel to the b and c axes so the

intercepts are given as p = 1, q = , and s = .
Taking the reciprocal, we obtain the Miller indices as (1, 0, 0), so
the plane shown in Figure 8a is referred to as the (100) plane.
Again, any plane parallel to the one shown in Figure 8a and
separated by an integral number of lattice constants is equivalent
and is referred to as the (100) plane.

One advantage to taking the reciprocal of the intercepts to obtain

the Miller indices is that the use of infinity is avoided when
describing a plane that is parallel to an axis.
If we were to describe a plane passing through the origin of our
system. we would obtain infinity as one or more of the Miller
indices after taking the reciprocal of the intercepts.
However, the location of the origin of our system is entirely
arbitrary and so, by translating the origin to another equivalent
lattice point, we can avoid the use of infinity in the set of Miller
indices.

For the simple cubic structure, the body-centered cubic, and the
face-centered cubic, there is a high degree of symmetry.
The axes can be rotated by 90 in each of the three dimensions
and each lattice point can again be described by Equation 1.
Each face plane of the cubic structure shown in Figure 8a is
entirely equivalent.
These planes are grouped together and are referred to as the
[100] set of planes.

One characteristic of a crystal that can be determined is the

distance between nearest equivalent parallel planes.
Another characteristic is the surface concentration of atoms,
number per square centimeter, that are cut by a particular plane.
Again, a single-crystal semiconductor is not infinitely large and
must terminate at some surface.
The surface density of atoms may be important, for example, in
determining how another material, such as an insulator, will fit
on the surface of a semiconductor material.

To calculate the surface density of atoms on a particular plane in a

crystal.
Consider the body-centered cubic structure and the (110) plane
shown in Figure 9a. Assume the atoms can be represented as hard
spheres with the closest atoms touching each other. Assume the
lattice constant is a1 = 5
A. Figure 9b shows how the atoms are
cut by the (110) plane.

(110) plane.
The ulom 31each C,)rner j s shitrx:d
Amorphous by four similar
Solids Typesequivalent
of solids I:ltlice pl anes. so each Comer
atom effecti vely contributes one-four1h of its areaSpace
Insulators and dielectrics lattices
to this lanice plane as indicated in the
ure. The four corner alUms then effecti vely contribute
one atom (0 this lattice plane. The atorn
Atomic bonding
in the center is comp letelyDensity
enclosed of in the Jauice plane.
States There is and
Imperfections no other equivalent
Impurities plane thai
in Solids
Statistical
eul S the ccolcr illom and Mechanics
the COMler aloms. so lhe Growth of Semiconductor
entire center almll included Materials
in the number
of ,HOrns in (he crystal plane. The Jaui<..'C 1>lanc in Fjgurc ).8b. then. contains two atoms.
II- !" ...

I
I
(a) Ibl
Figure 1.SI <a) The ( ltO) plane in a body-centered cubic and <b) the alom, cui by Ihe
Figure 110) plane
9: ( (a) Theill a(110)
body-centered
plane cubic
in. a body-centered cubic and (b) the
atoms cut by the (110) plane in a body-centered cubic .
Solution
We find the surface ltellSicy by dividing the number of lattice atoms by the surface area. Of in
Ihis case
2
L.yVarani
Sunace de nsil = Physics
= of Semiconductors Devices
We find the surface density by dividing the number of lattice

atoms by the surface area, or in this case
2 atoms 2
Surface density = = =
(a1 )(a1 2) (5 108 )2 2
= 5.66 1014 cm2

In addition to describing crystal planes in a lattice, we may want to

describe a particular direction in the crystal.
The direction can be expressed as a set of three integers which are
the componems of a vector in that direction.
For example, the body diagonal in a simple cubic lattice is
composed of vector components 1, 1 and 1.
The body diagonal is then described as the [111] direction.
The brackets are used to designate direction as distinct from the
parentheses used for the crystal planes.

The three basic directions and the associated crystal planes for the
simple cubic structure are shown in Figure 10.
Note that in the simple cubic Iattices, the [hkl] direction is
perpendicular to the (hkl) plane.
This perpendicularity may not be true in noncubic lattices.

1.3.4 The Diamond Structure
As already stated. silicon Insulators
is the mostandcommon semiconductor
dielectrics Spacematerial.
latticesSilicon is reo
ferred to as a group IV clement and has a diamond
Energy Bands crystalCrystal
structure. Germanium
Planes is Indices
and Miller
also a group IV and
Electrical the same diamond stl'llct1.1re. A utlit
Conduction in Solids Atomic cell of the dia
bonding
mond structure, shown in FigureDensity 1.10. is of States
more Imperfections
complicated and Impurities
than the simple cubic in Solids
Statistical
struclUres that we have considered up to Mechanics
this paint. Growth of Semiconductor Materials
We may begin to understand the diamond latrice by conSidering the tetrahedral
structure sholVn ill Figure 1.11. This structu re is basically" bOOy-centered cubic with
, .. .- - --::j;
l'tOI
(al \b) (el
Figure 1.9 1Three lallice direeti<>ns and plan",,, (a) (100) ptane and ll 00j direction, (b) ( I to) plane and II tOI direCli()n.
IC) 1I1 1)pl,ne and \ 1111 dircc.ion.
Figure 10: Three lallice direetions and planes: (a) (100) plane and (100)
direction, (b) (100) plane and (100) direction, (c) (111) plane and (111)
direction.

The Diamond Structure
Silicon is the most common semiconductor material.

Silicon is referred to as a group IV element and has a diamond
crystal structure.
Germanium is also a group IV eIement and has the same diamond
structure.
A unit cell of the diamond structure, shown in Figure 11 is more
complicated than the simple cubic structures.

10 C HAP
Density n R
of States
1Imperfections
The Crystal SIIUClule
and Impurities of Solids
in Solids
Growth of Semiconductor Materials
Fig
stru
Figure 1.10 IThe diamond structure. in t
Figure 11: The diamond structure.
We may begin to understand the diamond latrice by considering

the tetrahedral structure shown in Figure 12.
This structure is basically a body-centered cubic with four of the
corner atoms missing.
Every atom in the tetrahedral structure has four nearest
neighbors and it is this structure which is the basic building block
of the diamond lattice.

Clule of Solids Amorphous Solids Types of solids
T. 12
1
Figurestructure
Figure 12: The tetrahedral 1.111 The '<l mhed",1
of closest neighbors in the diamond
lattice structure of closest neighbors
in the di:lnlond lattice.
There are several ways to visualize the diamond structure.

One way is by considering Figure 13.
Figure 13a shows two body-centered cubic, or tetrahedral,
structures diagonally adjacent to each other.
The shaded circles represent atoms in the lattice that are
generated when the structure is translated to the right or left one
lattice constant a.

Amorphous Solids
Types of solids
Space lattices
1
Figure 1.111 The '<l mhed",1
structure of closest neighbors
Figure 1.10 IThe diamond structure. in the di:lnlond lattice.
I ;' /"
: / JI . . -
/
, //'
,'
// II
,
___ ___ __ _ . -_
' _ .......Y
L.
t _ _ __ " _ _ _- I
F
(a) (b)
Figure 1.12 1Portions of the diamond lallice: (a) honom half and (b) top half.
Figure 13: Portions of the diamond lattice: (a) bottom half and (b) top
half. four of the corner atoms missing. Every atom in the tetrahedral <tructure has four
nearest neighbor.; and it is this stTUcture whi ch is the basic building bloc k of the dia
mono lattice.
There are several ways to visuali ze the diamond structu re. One wa), to gain a fur
ther under.;tanding of the diamond lattice is by considering Figure I. I 2. Figure 1.1 2a
shows two bodycentcred cubic, or tctrahedral, structures diagonally adj acent to each
other. The shaded ci rcles rcpresem atoms in the lattice that are generated when the
Figure 13b represents the top half of the diamond structure.

The top half again consists of two tetrahedral structures joined
diagonally, but which are at 90 with respect to the bottom half
diagonal.
An important characteristic of the diamond lattice is that any
atom within the diamond structure will have four nearest
neighborig atoms.

The diamond structure refers to the particular lattice in which all

atoms are of the same species, such as silicon or germanium.
The Zincblende structure differs from the diamond structure onIy
in that there are two different types of atoms in the lattice.
Compound semiconductors, such as gallium arsenide, have the
zincblende structure shown in Figure 14

Statistical Mechanics Growth of Semiconductor Materials t .4 Atom'c Son:rlO9
1
.... ... I
' e '/
,, '-..,
__ l
,
/ ,
/
/
Figure 1.J4 I
structure of
f'igure 1.13 IThe zillcblende (sphalerite) lanice or GaA,. ziucblcnd
Figure 14: The zincblende lattice of GaAs
The diamond structure refers to the particular latlice in which all atoms are of the
same species, such as silicon or germanium. The Zincblende (sphalerite) struclure
L. Varani
differs from the diamond structurePhysics
onIy ofin Semiconductors
that there areDevices
two different types of atoms
The important feature of both the diamond and the zincblende

structures is that the atoms are joined together to form a
tetrahedron.
Figure 15 shows the basic tetrahedral structure of GaAs in which
each Ga atom has four nearest As neighbors and each As atom has
four nearest Ga neighbors.
This figure also shows the interpenetration of two sublattices that
can be used to generate the diamond or zincblende lattice.

t .4 Atom'c Son:r
Density of lO9
States
Imperfections and Impurities
tt in Solids
,
",, ,,
1
.... ... I #
' e '/
,, '-.., - -
__ l _
- ---1f-..Y
__ _
, \
, ',
/
/
/
,,
Figure 1.J4 IThe leuahedraJ

Figure 15: The tetrahedral structure
structure of ofneighbors
closets neighbors
ill
in the
zincblendc
nice or GaA,. lattice ziucblcndc latti ce.

Atomic Bonding
The question arises as to why one particular crystal structure is

favored over another for a particular assembly of atoms.
A fundamental law of nature is that the total energy of a system
in thermal equilibrium tends to reach a minimum value.
The interaction that occurs between atoms to form a solid and to
reach the minimum total energy depends on the type of atom or
atoms involved.

The type of bond, or interaction, between atoms. then, depends

on the particular atom or atoms in the crystal.
If there is not a strong bond between atoms, they will not stick
together to create a solid.
The interaction between atoms can be described by quantum
mechanics

We can nevertheless obtain a qualitative understanding of how

various atoms interact by considering the valence electrons of an
atom.
The atoms at the two extremes of the periodic table (excepting the
inert elements) tend to lose or gain valence electrons, thus forming
ions.
These ions then essentially have complete outer energy shells.

The elements in group I of the periodic table tend to lose their one
electron and become positively charged, while the elements in
group VII tend to gain an electron and become negatively charged.
These oppositely charged ions then experience a coulomb
attraction and form a bond referred to as an ionic bond.
If the ions were to get too close a repulsive force would become
dominant, so an equilibrium distance results between these two
ions.

In a crystal, negatively charged ions tend to be surrounded by

positively charged ions and positively charged ions tend to be
surrounded by negatively charged ions.
So a periodic array of the atoms is formed to create the Iattice.
A classic example of ionic bonding is sodium chloride.

Another atomic bond that tends to achieve closed-valence energy

shells is covalent bonding, an example of which is found in the
hydrogen molecule.
A hydrogen atom has one electron and needs one more electron to
complete the lowest energy shell.
A schematic of two noninteracting hydrogen atoms, and the
hydrogen molecule with the covalent bonding, are shown in
Figure 16.

I
-@)
I
@- -@ @ =
(a) (b)
.'igure 1.15
Figure 16: Representation of and (b)
Rcpre. valence electrons
of (a)Jhydrogen
covalent bonding(a)
in ahydrogen ...alence dectrons
hydrogen molecule
ami (b) cov3lenl honding ill ;) Figur
Covalent bondingbydrogen
results inmolecule.
electrons being shared between atoms, clCClr
so that in effect the valence energy shell of each atom is full.

Atoms in group IV of the periodic table, such as silicon and

germanium, also tend to form covalent bonds.
Each of these elements has four valence electrons and needs
four more electrons to complete the valence energy shell.
If a silicon atom has four nearest neighbors, with each neighbor
atom contributing one valence electron to be shared, then the
center atom will in effect have eight electrons in its outer shell.

ing results in ele<o!ronsThe
being shared
Crystal between
Structure of Solidsatoms, so that in Materials
Semiconductor effect the valence
enercAY s.hen of each atom isInsulators
ful1. Amorphous Solids
and dielectrics
Types of solids
Space lattices
Atoms in group IV of the periodic table,
Energy Bandssuch as silicon
Crystal and
Planes andgerrnanium,
Miller Indices also
tend to form covalent bonds. EachDensity
of these elementsAtomic
of States
bonding
has four valence
Imperfections electrons
and Impurities and
in Solids
needs four more eJectrons to complete
Statisticalthe valence energy
Mechanics Growthshell. If a siliconMaterials
of Semiconductor atom. for
example, has four nearest neighbors, with each neighbor atom contributing one va-
lenceFigure
electron 17
to beashared,
schematically
then the center shows fivein noninteracting
atom will siliconin atoms
effect have eight electrons
withshell.
its outer theFigure
four 1.16a
valence electrons
schematically showsaround each atom.
five noninterilC:ting silicon atoms
with the four valence electrons around each atom. A (wo .. dimensional
I
-@)-
I
I
-@)-
I I I I II I
-@)- -@)- - @)- -@)=@)=@)-
I I I I II I
@)
@ @ = I
I
(b) -@)-
I
J Rcpre. of (a) ib)
n ...alence dectrons
lenl honding ill ;) Figure 1.161 Representation of (a) silicon valence
olecule. Figure 17: Representation of covalent
clCClrHns and (b) (a) silicon valence
bOJlding electrons
in the si licon crystal. and (b)
covalent bonding in the silicon crystal.

A two-dimensional representation of the covalent bonding in silicon

is shown in Figure 17b.
The center atom has eight shared valence electrons.
A significant difference between the covalent bonding of hydrogen
and of silicon is that, when the hydrogen molecule is formed, it has
no additional electrons to form additional covalent bonds, while
the outer silicon atoms always have valence electrons available for
additional covalent bonding.

The silicon array may then be formed into an infinite crystal, with
each silicon atom having four nearest neighbors and eight shared
electrons.
The four nearest neighbors in silicon forming the covalent bond
correspond to the tetrahedral structure and the diamond lattice,
which were shown in Figures 12 and 11, respectively.
Atomic bonding and crystal structure are obviously directly related.

The third major atomic bonding scheme is referred to as metallic

bonding.
Group I elements have one valence electron.
If two sodium atoms (Z = 11), for example, are brought into close
proximity, the valence electrons interact in a way similar to that in
covalent bonding.

When a third sodium atom is brought into close proximity with the
first two, the valence electrons can also interact and continue to
form a bond.
Solid sodium has a body-centered cubic structure, so each atom
has eight nearest neighbors with each atom sharing many valence
electrons.
We may think of the positive metallic ions as being surrounded
by a sea of negative electrons, the solid being held together by
the electrostatic forces.

A fourth type of atomic bond, called the Van der Waals bond, is
the weakest of the chemical bonds.
A hydrogen fluoride (HF) molecule, for example, is formed by an
ionic bond.
The effective center of the positive charge of the molecule is not
the same as the effective center of the negative charge.

This nonsymmetry in the charge distribution results in a small

electric dipole that can interact with the dipoles of other HF
molecules.
With these weak interactions, solids formed by the Van der Waals
bonds have a relatively low melting temperature in fact, most of
these materials are in gaseous form at room temperature.

Imperfections and Impurities in Solids
In a real crystal, the lattice is not perfect, but contains

imperfections or defects.
The perfect geometric periodicity is disrupted in some manner.
Imperfections tend to alter the electrical properties of a material
and, in some cases, electrical parameters can be dominated by
these defects or impurities.

Imperfections in Solids
One type of imperfection that all crystals have in common is

atomic thermal vibrations.
A perfect single crystal contains atoms at particular lattice sites,
the atoms separated from each other by a distance we have
assumed to be constant.
The atoms in a crystal, however, have a certain thermal energy,
which is a function of temperature.

The thermal energy causes the atoms to vibrate in a random

manner about an equilibrium lattice point.
The random thermal motion causes the distance between atoms to
randomly fluctuate, slightly disrupting the perfect geometric
arrangement of atoms.
This imperfection, called lattice vibrations or phonons, affects
some electrical parameters, as we will see later in our discussion of
semiconductor material characteristics.

Another type of defect is called a point defect.

There are several of this type that we need to consider. In a real
crystal, an atom may be missing from a particular lattice site.
This defect is referred to as a vacancy; it is schematically shown
in Figure 18a.

t4 1 The Oysta\ Stl\)c'."re 01 So'.i(Js
....
--- - I
..
I
I
..
I
/
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..
- -
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.. - -+ - --'!'-" - -?'
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---- r "..,J - ---t6
- - --
" I I ,/ ,/
.
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/ - - . . . . : _ __ _ ... 0- i -- -I
(3)
...
I
I
I
I
,'"
"I
(b)
I I
I
F1gure 1.17 ITwo-dimensional representation of a single-crystal lattice sho\\ting (a) if vacancy defect
and (b) an interstitial defect.
Figure 18: Two-dimensional representation of a single-crystal lattice
showting (a) a vacancy defect and (b) an interstitial defect.
crystal. however, have a certain thennal energy, whic h is a fu nction of temperature.
The thermal energy causes the alOms to vibrate in a mndom manner abo ut an equi.
librium lattice point. Thb random thermal motion causes the distance between atoms
to randomly fluctuate, slightl y disrupting the perfect geometric arrangement of atoms.
This imperfection, caBed lattice vibratiOIlS, affects some electrical parameters, as we
will see later in our discussion of semiconductor material characteristics.
Another type ofL. defect
Varani is called a poim
Physics defect. There are
of Semiconductors several of this type that
Devices
In another situation, an atom may be located between lattice sites.

This defect is referred to as an interstitial and is schematically
shown in Figure 18b.
In the case of vacancy and interstitial defects, not only is the
perfect geometric arrangement of atoms broken, but also the ideal
chemical bonding between atoms is disrupted, which tends to
change the chemical properties of the material

A vacancy and interstitial may be in close enough proximity to

exhibit an interaction between the two point defects.
This vacancy-interstitial defect, also known as a Frenkel defect,
produces different effects than the simple vacancy or interstitial.

The point defects involve single atoms or single-atom locations.

In forming single-crystal materials, more complex defects may
occur.
A line defect, for example, occurs when an entire row of atoms is
missing.
Thi defect is referred to as a line dislocation and is shown in
Figure 19

Statistical Mechanics 1 .5 Imperieclioos and Impur
or, ...,, or, , ,'" '", ..., ,.

... ..., ..., ...
I I I
I I I I
+.-
I I
+-+-, -+-, .-... .- +

I I I
I I
I I
\ , ,
I I
I
I I
+, , +..., , ...... ... .-, +

\ \ \ I
I
\
, ..., , , ,, ... ,
I I I
I
-
.- .- ... ... ... ...
I I I
Figure 1.18 1representation

Figure 19: A two-dimensional A two of a line dislocation
dimensional representation
of a line L.diVarani
slocation
Physics.of Semiconductors Devices
As with a point defect, a line dislocation disrupts both the normal

geometric periodicity of the lattice and the ideal atomic bonds in
the crystal.
This dislocation can also alter the electrical properties of the
material, usually in a more unpredictable manner than the simple
point defects.

Impurities in Solids
Foreign atoms, or impurity atoms, may be present in a crystal

lattice.
Impurity atoms may be located at normal lattice sites, in which
case they are called substitutional impurities.
Impurity atoms may also be located between normal sites, in which
case they are called interstitial impurities.
Both these impurities are lattice defects and are schematically
shown in Figure 20.

+ +-+-, -+-, .-... + Semiconductor Materials
The Crystal
I
I Structure ofI Solids
I
I
, , Types of solids
I I
Amorphous I Solids
I
+, +... ...... ... .-, + Space

\ \ \ \ I
I
Insulators and dielectrics lattices
\ , I Bands
, , Energy
... ...
I Crystal Planes and Miller Indices
, , , , ,, , Imperfections
I I
-
.- .- ... ... ... ... Growth of Semiconductor
I I I
Density of States and Impurities in Solids
Statistical Mechanics Materials
Figure 1.18 1A two
dimensional representation
of a line di slocation .
... ... ... ...

... ... . , . - tnlpunty ...
---
-
- - - -
(aJ (b)
Figure 1.19 ITwo-dimensional representation of a showing (a) a SubSlittltional impurity

Figureand (b)
20:;\11 intersitilcd impurily.
Two-dimensional representation of a single-crystal lattice
showing (a) a substitutional
\.5.2 Impurities in Solids impurity and (b) interstitial impurity.
Foreign atoms. or impurity atoms. may be present in a crystal lattice. Impurity atoms
may be located at normal lattice sites. in whic h case they are caned ub.\'/i'I4I;ollu/ im
purities. Impurity atoms may also be localed between normal sites, in which case
they are called illlersr;r;al impurities, Both these impurities are lattice defects and arc
schematically shown in Fib"'JTC 1.1 9. Some impurilies, such as oxygen in silicon. tend
to be essentially inert; however, other impurities, such as gold or phosphorus in sili
con, can drastically alter the electrical properties of the material.
Some impurities, such as oxygen in silicon, tend to be essentially

inert; however, other impurities, such as gold or phosphorus in
silicon, can drastically alter the electrical properties of the material.
In the following we will see that, by adding controlled amounts of
particular impurity atoms, the electrical characteristics of a
semiconductor material can be favorably altered.
The technique of adding impurity atoms to a semiconductor
material in order to change its conductivity is called doping.

There are two general methods of doping: impurity diffusion and

ion implantation.
In general, impurity diffusion occurs when a semiconductor crystal
is placed in a high-temperature ( 1000 C) gaseous atmosphere
containing the desired impurity atom.
At this high temperature, many of the crystal atoms can randomly
move in and out of their single-crystal lattice sites.

Vacancies may be created by this random motion so that impurity

atoms can move through the lattice by hopping from one vacancy
to another.
Impurity diffusion is the process by which impurity particles
move from a region of high concentration near the surface,
to a region of lower concentration within the crystal.

When the temperature decreases, the impurity atoms become

permanently frozen into the substitutional lattice sites.
Diffusion of various impurities into selected regions of a
semiconductor allows us to fabricate complex electronic circuits in
a single semiconductor crystal.

Ion implantation generally takes place at a lower temperature than

diffusion.
A beam of impurity ions is accelerated to kinetic energies in the
range of 50 keV or greater and then directed to the surface of the
semiconductor.
The high-energy impurity ions enter the crystal and come to rest
at some average depth from the surface.

One advantage of ion implantation is that controlled numbers of

impurity atoms can be introduced into specific regions of the
crystal.
A disadvantage of this technique is that the incident impurity
atoms collide with the crystal atoms causing lattice displacement
damage.

However, most of the lattice damage can he removed by thermal

annealing, in which the temperature of the crystal is raised for a
short time.
Thermal annealing is a required step after implantation.

The success in fabricating very large scale integrated (VLSI)

circuits is a result of the development of and improvement in the
formation or growth of pure single-crystal semiconductor materials.
Semiconductors are some of the purest materials.
Silicon, for example, has concentrations of most impurities of less
than 1 part in 10 billion.

The high purity requirement means that extreme care is necessary

in the growth and the treatment of the material at each step of the
fabrication process.
The mechanics and kinetics of crystal growth are extremely
complex.
A general knowledge of the growth techniques and terminology is
valuable.

Growth from a Melt
A common technique for growing single-crystal materials is called

the Czochralski method.
In this technique, a small piece of single crystal material, known as
a seed, is brought into contact with the surface of the same
material in liquid phase, and then slowly pulled from the melt.
As the seed is slowly pulled, solidification occurs along the plane
between the solid-liquid interface.

Usually the crystal is also rotated slowly as it is being pulled,

resulting in a more uniform temperature.
Controlled amounts of specific impurity atoms, such as boron or
phosphorus, may be added to the melt so that the grown
semiconductor crystal is intentionally doped with the impurity
atom.
Figure 21 shows a schematic of the Czochralski growth process and
a silicon ingot grown by this process.

1 . 8 Grov/th SemiconduCiOt Malenals
Container
Chuck
Seed
Crystal - Tube
0 0
Heaters 0 Md t
0 0
0
Cmciblc
(0)
Figure 21: Model of a crystal puller

Some impurities may be present in the ingot that are undesirable.

Zone refining is a common technique for purifying material.
A high-temperature coil, or r-f induction coil, is slowly passed
along the length of the ingot.
The temperature induced by the coil is high enough so that a thin
layer of liquid is formed.
At the solid-liquid interface, there is a distribution of impurities
between the two phases.

The parameter that describes this distribution is called the

segregation coefficient: the ratio of the concentration of
impurities in the solid to the concentration in the liquid.
If the segregation coefficient is 0.1, for example, the concentration
of impurities in the liquid is a factor of 10 greater than that in the
solid.

As the liquid zone moves through the material, the impurities are
driven along with the liquid.
After several passes of the r-f coil, most impurities are at the end
of the bar, which can then be cut off.
The zone-refining technique, can result in considerable purification.

After the semiconductor is grown, the ingot is mechanically

trimmed to the proper diameter and a flat is ground over the entire
length of the ingot to denote the crystal orientation.
The flat is perpendicular to the [110] direction or indicates the
(110) plane.
This then allows the individual chips to be fabricated along given
crystal planes so that the chip can be sawed apart more easily.
The ingot is then sliced into wafers.

The wafer must be thick enough to mechanically support itself.

A mechanical two-sided lapping operation produces a flat wafer of
uniform thickness.
Since the lapping procedure can leave a surface damaged and
contaminated by the mechanical operation, the surface must be
removed by chemical etching.
The final step is polishing.

This provides a smooth surface on which devices may be fabricated

or further growth processes may be carried out.
This final semiconductor wafer is called the substrate material.

Epitaxial Growth
A common and versatile growth technique that is used extensively

in device and integrated circuit fabrication is epitaxial growth.
Epitaxial growth is a process whereby a thin, single-crystal layer of
material is grown on the surface of a single-crystal substrate.
In the epitaxial process, the single-crystal substrate acts as the
seed.
When an epitaxial layer is grown on a substrate of the same
material, the process is termed homoepitaxy.
Growing silicon on a silicon substrate is one example of a
homoepitaxy process.

At present, a great deal of work is being done with heteroepitaxy.

In a heteroepitaxy process, although the substrate and epitaxial
materials are not the same, the two crystal structures should be
very similar if single-crystal growth is to be obtained and if a large
number of defects are to be avoided at the epitaxial-substrate
interface.
Growing epitaxial layers of the ternary alloy AIGaAs on a GaAs
substrate is one example of a heteroepitaxy process.

One epitaxial growth technique that has been used extensively is

called chemical vapor-phase deposition (CVD).
Silicon epitaxial layers, for example, are grown on silicon substrates
by the controlled deposition of silicon atoms onto the surface from
a chemical vapor containing silicon.
A sharp demarcation between the impurity doping in the substrate
and in the epitaxial layer can be achieved using the CVD process.

Liquid-phase epitaxy is another epitaxial growth technique.

A compound of the semiconductor with another element may have
a melting temperature lower than that of the semiconductor itself.
The semiconductor substrate is held in the liquid compound and,
since the temperature of the melt is lower than the melting
temperature of the substrate, the substrate does not melt.
As the solution is slowly cooled, a single-crystal semiconductor
layer grows on the seed crystal.

A versatile technique for growing epitaxial layers is the molecular

beam epitaxy (MBE) process.
A substrate is held in vacuum at a temperature normally in the
range of 400 to 800 C, a relatively low temperature compared
with many semiconductor-processing steps.
Semiconductor and dopant atoms are then evaporated onto the
surface of the substrate.
In this technique, the doping can be precisely controlled resulting
in very complex doping profiles.

Complex ternary compounds, such as AIGaAs, can be grown on

substrates, such as GaAs, where abrupt changes in the crystal
composition are desired.
Many layers of various types of epitaxial compositions can be
grown on a substrate in that manner.

Amorphous Solids
Crystalline and amorphous solids
Preparation of amorphous solids
Energy Bands
The radial distribution function
Applications of amorphous solids
Density of States
Outline
2 Amorphous Solids
Transparent glasses
Polymeric structural materials
Amorphous semiconductors in electronics
Magnetic glasses

Amorphous Solids
Energy Bands
Density of States
Amorphous Solids
Amorphous solid ia any noncrystalline solid in which the atoms and

molecules are not organized in a definite lattice pattern.
Such solids include glass, plastic, and gel.
Solids and liquids are both forms of condensed matter; both are
composed of atoms in close proximity to each other. But their
properties are, of course, enormously different.
While a solid material has both a well-defined volume and a
well-defined shape, a liquid has a well-defined volume but a shape
that depends on the shape of the container.

Amorphous Solids
Energy Bands
Density of States
Externally applied forces can twist or bend or distort a solids

shape, but (provided the forces have not exceeded the solids
elastic limit) it springs back to its original shape when the forces
are removed.
A liquid flows under the action of an external force; it does not
hold its shape.
These macroscopic characteristics constitute the essential
distinctions: a liquid flows, lacks a definite shape (though its
volume is definite), and cannot withstand a shear stress; a solid
does not flow, has a definite shape, and exhibits elastic stiffness
against shear stress.

Amorphous Solids
Energy Bands
Density of States
On an atomic level, these macroscopic distinctions arise from a

basic difference in the nature of the atomic motion.
Figure 22 contains schematic representations of atomic movements
in a liquid and a solid.
Atoms in a solid are not mobile. Each atom stays close to one
point in space, although the atom is not stationary but instead
oscillates rapidly about this fixed point (the higher the
temperature, the faster it oscillates).

Amorphous Solids
Energy Bands
Density of States
Figure 22: Representation of the atomic motion in a liquid (left) and in a

solid (right)

Amorphous Solids
Energy Bands
Density of States
The fixed point can be viewed as a time-averaged centre of gravity

of the rapidly jiggling atom.
The spatial arrangement of these fixed points constitutes the
solids durable atomic-scale structure.
In contrast, a liquid possesses no enduring arrangement of atoms.
Atoms in a liquid are mobile and continually wander throughout
the material.

Amorphous Solids
Energy Bands
Density of States
There are two main classes of solids: crystalline and amorphous.

What distinguishes them from one another is the nature of their
atomic-scale structure.
The essential differences are displayed in Figure23.
The salient features of the atomic arrangements in amorphous
solids (also called glasses), as opposed to crystals, are illustrated in
the figure for two-dimensional structures; the key points carry over
to the actual three-dimensional structures of real materials.

Amorphous Solids
Energy Bands
Density of States
Figure 23: The atomic arrangements in (A) a crystalline solid, (B) an

amorphous solid, and (C) a gas

Amorphous Solids
Energy Bands
Density of States
Also included in the figure, as a reference point, is a sketch of the

atomic arrangement in a gas.
For the sketches representing crystal (A) and glass (B) structures,
the solid dots denote the fixed points about which the atoms
oscillate; for the gas (C), the dots denote a snapshot of one
configuration of instantaneous atomic positions.

Amorphous Solids
Energy Bands
Density of States
Atomic positions in a crystal exhibit a property called long-range

order or translational periodicity; positions repeat in space in a
regular array, as in Figure 23A.
In an amorphous solid, translational periodicity is absent.
As indicated in Figure 23B, there is no long-range order.
The atoms are not randomly distributed in space, however, as they
are in the gas in Figure 23C.
In the glass example illustrated in the figure, each atom has three
nearest-neighbour atoms at the same distance (called the chemical
bond length) from it, just as in the corresponding crystal.

Amorphous Solids
Energy Bands
Density of States
All solids, both crystalline and amorphous, exhibit short-range

(atomic-scale) order.
The well-defined short-range order is a consequence of the
chemical bonding between atoms, which is responsible for holding
the solid together.
In addition to the terms amorphous solid and glass, other terms in
use include noncrystalline solid and vitreous solid.
Amorphous solid and noncrystalline solid are more general terms,
while glass and vitreous solid have historically been reserved for an
amorphous solid prepared by rapid cooling (quenching) of a melt
as in scenario 2 of Figure24.

Amorphous Solids
Energy Bands
Density of States
Figure 24: The two general cooling paths by which a group of atoms can
condense. Route 1 is the path to the crystalline state; route 2 is the
rapid-quench path to the amorphous solid state

Amorphous Solids
Energy Bands
Density of States
Figure 24, which should be read from right to left, indicates the
two types of scenarios that can occur when cooling causes a given
number of atoms to condense from the gas phase into the liquid
phase and then into the solid phase. The temperature Tb is the
boiling point, Tf is the freezing (or melting) point, and Tg is the
glass transition temperature.
In scenario 1 the liquid freezes at Tf into a crystalline solid, with
an abrupt discontinuity in volume.
When cooling occurs slowly, this is usually what happens. At
sufficiently high cooling rates, however, most materials display a
different behaviour and follow route 2 to the solid state.

Amorphous Solids
Energy Bands
Density of States
Tf is bypassed, and the liquid state persists until the lower

temperature Tg is reached and the second solidification scenario is
realized.
In a narrow temperature range near Tg , the glass transition occurs:
the liquid freezes into an amorphous solid with no abrupt
discontinuity in volume.

Amorphous Solids
Energy Bands
Density of States
The glass transition temperature Tg is not as sharply defined as

Tf .

Amorphous Solids
Energy Bands
Density of States
It was once thought that relatively few materials could be prepared

as amorphous solids, and such materials (notably, oxide glasses and
organic polymers) were called glass-forming solids.
It is now known that the amorphous solid state is almost a
universal property of condensable matter.
The table 3 of representative amorphous solids presents a list of
amorphous solids in which every class of chemical bonding type is
represented.
The glass transition temperatures span a wide range.

Amorphous Solids
Energy Bands
Density of States
glass bonding transition temperature (K)

silicon dioxide covalent 1430
germanium dioxide covalent 820
silicon, germanium covalent -
beryllium difluoride ionic 570
arsenic trisulfide covalent 470
polystyrene polymeric 370
isopentane van der Waals 65
iron, cobalt, bismuth metallic -
Table 3: Bonding types and glass transition temperatures of

representative amorphous solids

Amorphous Solids
Energy Bands
Density of States
Glass formation is a matter of bypassing crystallization. The

channel to the crystalline state is evaded by quickly crossing the
temperature interval between Tf and Tg .
Nearly all materials can, if cooled quickly enough, be prepared as
amorphous solids.
The definition of quickly enough varies enormously from material
to material.

Amorphous Solids
Energy Bands
Density of States
Four techniques for preparing amorphous solids are illustrated in

Figure 25.
These techniques are not fundamentally different from those used
for preparing crystalline solids; the key is simply to quench the
sample quickly enough to form the glass, rather than slowly
enough to form the crystal.
The quench rate increases greatly from left to right in the figure.

Amorphous Solids
Energy Bands
Density of States
Figure 25: Four methods for preparing amorphous solids. (A) Slow
cooling, (B) moderate quenching, (C) rapid splat quenching, and (D)
condensation from the gas phase.
Amorphous Solids
Energy Bands
Density of States
The absence of long-range order is the defining characteristic of

the atomic arrangement in amorphous solids.
However, because of the absence in glasses of long parallel rows
and flat parallel planes of atoms, it is extremely difficult to
determine details of the atomic arrangement with the
structure-probing techniques (such as X-ray diffraction) that are so
successful for crystals.
For glasses the information obtained from such structure-probing
experiments is contained in a curve called the radial distribution
function (RDF).

Amorphous Solids
Energy Bands
Density of States
Figure 26 shows a comparison of the experimentally determined

RDFs of the crystalline and amorphous forms of germanium, an
elemental semiconductor similar to silicon.
The significance of the RDF is that it gives the probability of
neighbouring atoms being located at various distances from
an average atom.
The horizontal axis in the figure specifies the distance from a given
atom; the vertical axis is proportional to the average number of
atoms found at each distance

Amorphous Solids
Energy Bands
Density of States
Figure 26: Comparison of the atomic radial distribution functions of

crystalline (c-Ge) and amorphous (a-Ge) germanium. The value of the
function at each distance r from a given atom is proportional to the
number of atoms found at that distance.

Amorphous Solids
Energy Bands
Density of States
The curve for crystalline germanium displays sharp peaks over the
full range shown, corresponding to well-defined shells of
neighbouring atoms at specific distances, which arise from the
long-range regularity of the crystals atomic arrangement.
Amorphous germanium exhibits a close-in sharp peak
corresponding to the nearest-neighbour atoms (there are four
nearest neighbours in both c-Ge and a-Ge), but at larger distances
the undulations in the RDF curve become washed out owing to the
absence of long-range order.

Amorphous Solids
Energy Bands
Density of States
The first, sharp, nearest-neighbour peak in a-Ge is identical to the

corresponding peak in c-Ge, showing that the short-range order in
the amorphous form of solid germanium is as well-defined as it is in
the crystalline form.

Amorphous Solids
Energy Bands
Density of States
In this sections we discuss technological applications of amorphous

solids in connection with the properties that make those
applications possible.
Amorphous solids exhibit essentially the full range of properties
and phenomena exhibited by crystalline solids.
There are amorphous-solid metals, semiconductors, and insulators;
there are transparent glasses and opaque glasses; and there are
superconducting amorphous solids and ferromagnetic amorphous
solids.

Amorphous Solids
Energy Bands
Density of States
The atomic-scale disorder present in a metallic glass causes its

electrical conductivity to be lower than the conductivity of the
corresponding crystalline metal, because the structural disorder
impedes the motion of the mobile electrons that make up the
electrical current.
For a similar reason, the thermal conductivity of an insulating glass
is lower than that of the corresponding crystalline insulator; glasses
thus make good thermal insulators.

Amorphous Solids
Energy Bands
Density of States
Crystals and glasses also differ systematically in their optical

spectra, which are the curves that describe the wavelength
dependence of the degree to which the solid absorbs infrared,
visible, or ultraviolet light.
Although the overall spectra are often similar, crystal spectra
typically exhibit sharp peaks and other features that specifically
arise as a consequence of the long-range order of the crystals
atomic-scale structure.
These sharp features are absent in the optical spectra of
amorphous solids.

Amorphous Solids
Energy Bands
Density of States
The continuous liquid-to-solid transition near Tg , the glass

transition, has a profound significance in connection with classical
applications of glasses.
While crystallization abruptly transforms a mobile, low-viscosity
liquid to a crystalline solid at Tf , near Tg the liquid viscosity
increases continuously through a large range in the transformation
to an amorphous solid.
Viscosity, expressed in units of poise, is used in the table of
characteristics of oxide glasses to specify characteristic working
temperatures in the processing of the liquid precursors of various
oxide glasses.

Amorphous Solids
Energy Bands
Density of States
A poise is the centimetre-gram-second (cgs) unit of viscosity.

It expresses the force needed to maintain a unit velocity difference
between parallel plates separated by one centimetre of fluid: one
poise equals one dyne-second per square centimetre.
Molten glass may have a viscosity of 1013 poise (similar to honey
on a cold day), and it quickly gets stiffer when cooled since the
viscosity steeply increases with decreasing temperature.
The ability to tune the viscosity of the melt (by changing
temperature) allows glass to be conveniently processed and worked
into desired shapes.

Amorphous Solids
Energy Bands
Density of States
The table4 below lists some important technological uses of

amorphous solids.
In addition to the application, the general type of amorphous solid
used, and the material properties that make the application
possible, the table also includes information about the chemical
compositions of typical materials employed in these techniques.

Amorphous Solids
Energy Bands
Density of States
type application special property

oxide glass window glass transparency, solidity,
formability as large sheets
oxide glass fibre-optic waveguides ultratransparency, purity,
formability as uniform fibres
organic polymer structural materials, plastics strength, light weight,
ease of processing
chalcogenide glass copiers and laser printers photoconductivity,
formability as large-area films
amorphous semiconductor solar cells, copiers, photovoltaic optical properties,
flat-panel displays arge-area thin films,
semiconducting properties
metallic glass transformer cores ferromagnetism, low power loss,
formability as long ribbons
Table 4: Some technological applications of amorphous solids

Amorphous Solids
Energy Bands
Density of States
A significant theme of the table is the role of amorphous solids in

applications calling for large-area sheets or films.
Amorphous solids often have great advantages over crystalline
solids in such applications, since their use avoids the functional
problems associated with polycrystallinity or the expense of
preparing large single crystals.
Thus, while it would be prohibitively expensive to fabricate large
windows out of crystalline SiO2 (quartz), it is practical to do so
using SiO2 -based silicate glasses.

Amorphous Solids
Energy Bands
Density of States
Transparent glasses
The terms glass and window glass are often used interchangeably
in everyday language, so familiar is this ancient architectural
application of amorphous solids.
Not only are oxide glasses, such as those characterized in the table,
excellent for letting light in, they are also good for keeping cold
out, because (as mentioned above) they are efficient thermal
insulators.
The second application in the table of technological applications of
amorphous solids represents a modern development that carries the
property of optical transparency to a phenomenal level.

Amorphous Solids
Energy Bands
Density of States
The transparency of the extraordinarily pure glasses that have been

developed for fibre-optic telecommunications is so great that, at
certain wavelengths, light can pass through 1 km of glass and still
retain 95% of its original intensity.
Glass fibres (transmitting optical signals) are now doing what
copper wires (transmitting electrical signals) once did and are doing
it more efficiently: carrying telephone messages around the planet.
How this is done is schematically indicated in Figure 27

Amorphous Solids
Energy Bands
Density of States
Figure 27: The use of ultratransparent glass fibres in telecommunications

networks.

Amorphous Solids
Energy Bands
Density of States
Digital electrical pulses produced by encoding of the voice-driven

electrical signal are converted into light pulses by a semiconductor
laser coupled to one end of the optical fibre.
The signal is then transmitted over a long length of fibre as a
stream of light pulses. At the far end it is converted back into
electrical pulses and then into sound.
The glass fibre is somewhat thinner than a human hair.

Amorphous Solids
Energy Bands
Density of States
The simplest type, as sketched in the upper left of the figure, has a
central core of ultratransparent glass surrounded by a coaxial
cladding of a glass having a lower refractive index, n.
This ensures that light rays propagating within the core, at small
angles relative to the fibre axis, do not leak out but instead are
100% reflected at the core-cladding interface by the optical effect
known as total internal reflection.

Amorphous Solids
Energy Bands
Density of States
The great advantage provided by the substitution of

light-transmitting fibres of ultratransparent oxide glass for
electricity-transmitting wires of crystalline copper is that a single
optical fibre can carry many more simultaneous conversations than
can a thick cable packed with copper wires.
This is the case because light waves oscillate at enormously high
frequencies (about 2 1014 cycles per second for the infrared light
generally used for fibre-optic telecommunications).

Amorphous Solids
Energy Bands
Density of States
This allows the light-wave signal carrier to be modulated at very

high frequencies and to transmit a high volume of information
traffic.
Fibre-optic communications have greatly expanded the
information-transmitting capacity of the worlds
telecommunications networks.

Amorphous Solids
Energy Bands
Density of States
Polymeric structural materials
Polystyrene is a prototypical example of a polymeric glass.

These glasses make up a broad class of lightweight structural
materials important in the automotive, aerospace, and construction
industries.

Amorphous Solids
Energy Bands
Density of States
These materials are also ubiquitous in everyday experience as

plastic molded objects.
The quantity of polymer materials produced each year, measured
in terms of volume, exceeds the quantity of steel produced.
Polystyrene is among the most important of the thermoplastic
materials that, when heated (to the vicinity of the glass transition
temperature), soften and flow controllably, enabling them to be
processed at high speeds and on a large scale in the manufacture
of molded products.

Amorphous Solids
Energy Bands
Density of States
Amorphous semiconductors in electronics
Amorphous semiconductors, in the form of thin films prepared by

methods such as that shown in Figure 25D, are important in
applications requiring large areas of electronically active material.
The first electronic application of amorphous semiconductors to
occur on a large scale was in xerography (or electrostatic imaging),
the process that provides the basis of plain-paper copiers.

Amorphous Solids
Energy Bands
Density of States
The photoconductor, which is an electrical insulator in the absence

of light but which conducts electricity when illuminated, is exposed
to an image of the document to be copied.
This process is also widely used in laser printers, in which the
photoconductor is exposed to a digitally controlled on-and-off laser
beam that is raster scanned (like the electron beam in a television
tube) over the photoconductor surface.

Amorphous Solids
Energy Bands
Density of States
Polymeric organic glasses, in the form of thin films, are now used
in multilayer photoconductor configurations in which the light is
absorbed in one layer and electrical charge is transported through
an adjacent layer.
Both layers are formed of amorphous polymer films, and these
photoreceptors can be made in the form of flexible belts.

Amorphous Solids
Energy Bands
Density of States
Amorphous silicon thin films are used in solar cells that power
handheld calculators.
This important amorphous semiconductor is also used as the image
sensor in fax machines, and it serves as the photoreceptor in some
xerographic copiers.
All these applications exploit the ability of amorphous silicon to be
vapour-deposited in the form of large-area thin films.

Amorphous Solids
Energy Bands
Density of States
Hydrogenated amorphous silicon also is used in high-resolution

flat-panel displays for computer monitors and for television screens.
In such applications the large-area amorphous-semiconductor thin
film is etched into an array of many tiny units, each of which forms
the active element of a transistor that electronically turns on or off
a small pixel (picture element) of a liquid-crystal display.

Amorphous Solids
Energy Bands
Density of States
Magnetic glasses
The last entry in the table of technological applications of

amorphous solids is an application of metallic glasses having
magnetic properties.
These are typically iron-rich amorphous solids.
They are readily formed as long metallic glass ribbons by melt
spinning or as wide sheets by planar flow casting

Amorphous Solids
Energy Bands
Density of States
Ferromagnetic glasses are mechanically hard materials, but they

are magnetically soft, meaning that they are easily magnetized by
small magnetic fields.
Also, because of their disordered atomic-scale structure, they have
higher electrical resistance than conventional (crystalline) magnetic
materials.

Amorphous Solids
Energy Bands
Density of States
The three attributes of ease of manufacture, magnetic softness,

and high electrical resistance make magnetic glasses extremely
suitable for use in the magnetic cores of electrical power
transformers.
High electrical resistance (which arises here as a direct
consequence of amorphicity) is a crucial property in this
application, because it minimizes unwanted electrical eddy currents
and cuts down on power losses

Amorphous Solids
Energy Bands
Density of States
For these reasons, sheets of iron-based magnetic glasses are used

as transformer-core laminations in electrical power applications.
Thin films of magnetic glass are finding use in many other
applications.
These include magnetic recording media for audio and video digital
recording, as well as recording heads used with magnetic disks.

Amorphous Solids
Polarization
Macroscopic Electric Field
Energy Bands
Local electric field at an atom
Dielectric constant and polarizability
Density of States
Outline
2 Amorphous Solids
3 Insulators and dielectrics

Polarization
Depolarization field
Lorentz field
Field of dipoles inside cavity
Amorphous Solids
Polarization
Energy Bands
Density of States
First we relate the applied electric field to the internal electric field
in a dielectric crystal. The study of the electric field within
dielectric matter arises when we ask:
What is the relation in the material between the dielectric
polarization P and the macroscopic electric field E in the Maxwell
equations?
What is the relation between the dielectric polarization and the
local electric field which acts at the site of an atom in the lattice?
The local field determines the dipole moment of the atom.

Amorphous Solids
Polarization
Energy Bands
Density of States
Polarization
Let su recall the Maxwell equations (in SI)

Maxwell equations

rotH = j + (0 E + P)
t
B
rotE =
t
div0 E =
divB = 0

Amorphous Solids
Polarization
Energy Bands
Density of States
The polarization P is defined as the dipole moment per unit

volume, averaged over the volume of a cell.
The total dipole moment is defined as
p = qn rn
where rn is the position vector of the charge qn .

Amorphous Solids
Polarization
Energy Bands
Density of States
The value of the sum will be independent of the origin chosen for
the position vectors, provided that the system is neutral.
The dipole moment of a water molecule is shown in Figure 28.

Amorphous Solids
Polarization
Energy Bands
Density of States
F"lgUre 1 T
water hu
rCdoo from
n.:ctlng the
j X 10",)
Figure 28: The permanent dipole moment of a molecule of water is

directed from O ion toward the midpoint of the line connecting the
H+ ions.

Amorphous Solids
Polarization
Energy Bands
Density of States
The electric field at a point r from a dipole moment p is given by a

standard result of elementary electrostatics:
3(p r)r r 2 p
E(r) = (2)
40 r 5
The lines of force of a dipole pointing along the z axis are shown in
Figure29

The Crystal Structure of Solids water hu the nlllnib.lde 1.9 x 10- ' 05U -('m and
Amorphous Solids
rCdoo from 0 -- ion IQo.\wd the midpoint of the li lll:
Polarization
Macroscopic
n.:ctlngElectric
the HField
' kin" [To C'O<!\'ert to 51 units, nluilip
Energy Bands
Electrical Conduction in Solids j X constant
Dielectric 10",) and polarizability
Density of States
Figure 2 Ekctrostlltic pomltial alld lidd cornpo.:IC'I\IS in CCS at po5itloll ,., 11 b' dip
Figure 29: Electrostatic potential
dirttb:d aIaig the axis. and
For 11field components
- 0, we E, - E" - in CGS
0 and E. -at2pI?; lOr 11 .. 'IIf2 ....1
. =aE,,dipole
position (r , ) for " 0 andpE.directed
" -pi? To convert
along the10 51, rcpIaa: P by
z axis. (Alter E M. Puroel\

Amorphous Solids
Polarization
Energy Bands
Density of States
One contribution to the electric field inside a body is that of the

applied electric field, defined as
E0 = field produced by fixed charges external to the body
The other contribution to the electric field is the sum of the fields
of all charges that constitute the body.

Amorphous Solids
Polarization
Energy Bands
Density of States
If the body is neutral, the contribution to the average field may be

expressed in terms of the sum of the fields of atomic dipoles.
We define the average electric field E(r0 ) as the average field over
the volume of the crystal cell that contains the lattice point r0 :
Z
1
E(r0 ) = dV e(r)
Vc
where e(r) is the microscopic electric field at the point r.

Amorphous Solids
Polarization
Energy Bands
Density of States
The field E is a much smoother quantity than the microscopic field

e.
We could well have written the dipole field in eq. (2) as e(r)
because it is a microscopic unsmoothed field.

Amorphous Solids
Polarization
Energy Bands
Density of States
We call E the macroscopic electric field.

It is adequate for all problems in the electrodynamics of crystals
provided that we know the connection between E, the polarization
P, and the current density j, and provided that the wavelengths of
interest are long in comparison with the lattice spacing.

Amorphous Solids
Polarization
Energy Bands
Density of States
To find the contribution of the polarization to the macroscopic

field, we can simplify tihee sum over all the dipoles.
By a famous theorem of electrostatics the macroscopic electric
field caused by a uniform polarization is equal to the electric field
in vacuum of a fictitious surface charge density = n P on the
surface of the body.
Here n is the unit normal to the surface, drawn outward from the
polarized matter.

Amorphous Solids
Polarization
Energy Bands
Density of States
We apply the result to a thin dielectric slab (Fig. 30a) with a

uniform volume polarization P.
Flgun:l
"'
jill A uniformty pobrized
(I.)
with the poIariutlon "cclOl" P nOl"mal to the

plane orFigure
Ihe 30:
(h) A(a)
pair A uniformly
of unilOnnly polarized
cbarged dielectric
po;mIllel ptales wh;..,h slab,
risewith
to Ihethe poIarization
identlclll
electric vector
Beld E, ISPInnormal to the
(a). TIle opper plaleplane
lli15 tIleof the slab. density
(b) Aq pair ofAnd
- +1', uniformly
the lower charged
1,"'le l..u q - - I'.
parallel plates which give rise to the identical electric field E1 , as in (a).
if = Ii, P on the surl:,cc of the body. Here Ii is the unit normal to the surfaCt'.,
drawn outward from the polarized matter.
We apply the result to a thin dielectric slab (Fig.
L. Varani 3a)ofwith
Physics au nironn
Semiconductors volume
Devices
Amorphous Solids
Polarization
Energy Bands
Density of States
The electric field E1 (r) produced by the polarization is equal to the

field produced by the fictitious surface charge density = n P on
the surface of the slab.
is directed upward and on
On the upper boundary the unit vector n
is directed downward.
the lower boundary n

Amorphous Solids
Polarization
Energy Bands
Density of States
P = P per
The upper boundary bear the fictitious charge = n
unit area, and the lower boundary bears P per unit area.
The electric field E1 due to these charges has a simple form at any
point between the plates, but comfortably removed from their
edges.

Amorphous Solids
Polarization
Energy Bands
Density of States
By Gausss law
|| P
E1 = = (3)
0 0
We add E1 to the applied field E0 to obtain the total macroscopic
field inside the slab, with z the unit vector normal to the plane of
the slab:
P
E = E0 + E1 = E0 z
0

Amorphous Solids
Polarization
Energy Bands
Density of States
We define
P on the boundary
E1 = field of the surface charge density n
This field is smoothly varying in space inside and outside the body
and satisfies the Maxwell equations as written for the macroscopic
field E.
The reason E is a smooth function when viewed on an atomic scale
is that we have replaced the discrete lattice or dipoles pj with the
smoothed polarization P.

Amorphous Solids
Polarization
Energy Bands
Density of States
Depolarization field
The geometry in many of our problems is such that the

polarization is uniform within the body, and then the only
contributions to the macroscopic field are from E0 and E1 :
E = E0 + E1 (4)
Here E0 is the applied field and E1 is the field due to the uniform
polarization

Amorphous Solids
Polarization
Energy Bands
Density of States
The field E1 is called the depolarization field, for within the body
it tends to oppose the applied field E0 as in Fig. 31.
Specimens in the shape or ellipsoids, a class that includes spheres,
cylinders, and discs as limiting forms, have an advantageous
property: a uniform polarization produces a uniform depolarization
field inside the body.

Amorphous Solids
Polarization
Energy Bands
Density of States
> :E+
d E, iJ OVI_ite 10 P. TI", foclitioo. surfaa:
Figure
+ +
lin'! Ind ' ted.
31: The depolarization field E1 is opposite to P. ...,.
-
The fictitious
ith'nlhe eHipsoKl. .
surface charge are indicated: the field of these charges is E1 within the
cc,
ellipsoid.
" "
'"
Amorphous Solids
Polarization
Energy Bands
Density of States
If Px , Py and Pz are the components of the polarization P referred

to the principal axes or an ellipsoid, then the components of the
depolarization field are written
Nx P x N y Py Nz Pz
E1x = E1y = E1z =
0 0 0
Here Nx , Ny Nz are the depolarization factors; their values depend

on the ratios of the principal axes of the ellipsoid.
The Ns are positive and satisfy the sum rule Nx + Ny + Nz = 1 in
SI.

Amorphous Solids 3
Polarization
:E+
Energy Bands
>
Density of States
Values of N parallel to the figure axis of ellipsoids of revolution are

+ + -
plotted
Flgure" in Fig.
11M! depolari:r..:lOOn 5.iJ OVI_ite 10 P. TI", foclitioo. surfaa:
flCld E, Ind ' ted. lin'!
the fldd is E, \\ith'nlhe eHipsoKl. ...,. .
cc,
" "
'"
" "
" no
"
< <
" "
" '"
,, , ,'
,',
Figure S . Ot!pol.... ization factor N panlUd to the flgure of ellipsoiIJs of revolution , llj; II fnncliOIl
of the ....ial ratio do .
Figure 32: Depolarization factor N parallel to the flgure axis of ellipsoids
of revolution, as a function of the axial ratio c/a.
A uniform applied field Eo will induce uniform polarization in an ellipsoid.
We introduce the dielectric susceptibility X such that the relations
Amorphous Solids
Polarization
Energy Bands
Density of States
In limiting cases N has the values:
shape axis N (SI)

sphere any 1/3
thin slab normal 1
thin slab in plane 0
long circular cylinder longitudinal 0
long circular cylinder transverse 1/2
Table 5: Values of depolarization factor N.

Amorphous Solids
Polarization
Energy Bands
Density of States
We can reduce the depolarization field to zero in two ways, either

by working with a long flne specimen or by making an electrical
connection between electrodes deposited on the opposite surfaces
of a thin slab.
A uniform applied field E0 will induce uniform polarization in an
ellipsoid.

Amorphous Solids
Polarization
Energy Bands
Density of States
We introduce the dielectric susceptibility
P = 0 E
This quantity connects the macroscopic field E inside the ellipsoid

with the polarization P.
If E0 is uniform and parallel to a principal axis of the ellipsoid, then
NP
E = E0 (5)
0

Amorphous Solids
Polarization
Energy Bands
Density of States
We obtain
Polarization
0
P = (0 E0 NP) P = E0
1 + N
The value of the polarization depends on the depolarization factor

N.

Amorphous Solids
Polarization
Energy Bands
Density of States
The value of the local electric field that acts at the site of an atom
is significantly different from the value of the macroscopic electric
field.
We can convince ourselves of this by consideration of the local
field at a site with a cubic arrangement of neighbors in a crystal of
spherical shape.

Amorphous Solids
Polarization
Energy Bands
Density of States
The macroscopic electric field in a sphere is

1
E = E0 + E1 = E0 P
30
where we have used eq. (5).
But consider the field that acts on the atom at the center of the
sphere.

Amorphous Solids
Polarization
Energy Bands
Density of States
If all dipoles are parallel to the z axis and have magnitude p, the z
component of the field at the center due to all other dipoles is,
from (2),
p X 3zi2 ri2 p X 2zi2 xi2 yi2

Edipole = =
40 ri5 40 ri5
i i

Amorphous Solids
Polarization
Energy Bands
Density of States
The x, y , z directions are equivalent because of the symmetry of

the lattice and of the sphere; thus
X z2 X x2 X y2
i i i
= =
ri5 ri5 ri5
i i i
whence Edipole = 0.

Amorphous Solids
Polarization
Energy Bands
Density of States
The correct local field is just equal to the applied fleld, Elocal = E0 .
for an atom site with a cubic environment in a spherical specimen.
Thus the local field is not the same as the macroscopic average
field E.
We now develop an expression for the local field at a general
lattice site, not necessarily of cubic symmetry.

Amorphous Solids
Polarization
Energy Bands
Density of States
The local field at an atom is the sum of the electric field E0 from
external sources and of the field from the dipoles within the
specimen.
It is convenient to decompose the dipole field so that part of the
summation over dipoles may be replaced by integration.
We write
Elocal = E0 + E1 + E2 + E3

Amorphous Solids
Polarization
Energy Bands
Density of States
Here
E0 : field produced by fixed charges external to the body;
E1 : depolarization field, from a surface charge density n P on the
outer surface of the specimen;
E2 : Lorentz cavity field: field from polarization charges on inside of
a spherical cavity cut (as a mathematical fiction) out of the
specimen with the reference atom as center, as in Fig. 33; E1 + E2
is the field due to uniform polarization of the body in which a hole
has been created;
E3 : field of atoms inside cavity

Amorphous Solids
Polarization
Energy Bands
Density of States
3'"
E, tn."
"".1..
''e illlen,al dl.:Clric f",1d 011 an ....om in a Cl"yslal is Ih., SUm of the co:ten".1 applied Ilekl
Figure 33: The internal electric field
he fleld due to the other .... oms in Ih.,
of an atom
The standard in of
m."lhod a summing
crustal isthethe sum of
the eternalis flnt
oflhe other applied
to lium field E0 andover
individually of the field due
a moderate to the
"limber other atoms in the
of ndghl>oring
crystal.sphere conc.,ntric "'ith the reference atom : Ihis d(..fl"", Ih" Ileld E3-
e an imagInary
hes at a reference site with rubic symmeiry. The atomli outsidto the sphere can be
unifunn l), po1.ari7.cd dielectric. TIleir contribution to Ihe field at II,c refcrence point is
lv.:re E, iii Ihe depoLariz:Jtion field as.sociatcd with the outcr boundary ,"00 E" is Ihe lidtl
with Ihe surface oflhe sfherlcal cavil)'. L. Varani Physics of Semiconductors Devices
Amorphous Solids
Polarization
Energy Bands
Density of States
The contribution E1 + E2 + E3 to the local field is the total field at

one atom caused by the dipole moments of all the other atoms in
the specimen:
1 X 3(pi ri )ri ri2 pi

E1 + E2 + E3 =
40 ri5
i

Amorphous Solids
Polarization
Energy Bands
Density of States
Dipoles at distances greater than perhaps ten lattice constants

from the reference site make a smoothly varying contribution to
this sum, a contribution which may be replaced by two surface
integrals.
One surface integral is taken over the outer surface of the
ellipsoidal specimen and defines E1 .
The second surface integral defines E2 and may be taken over any
interior surface that is a suitable distance (say 50
A) from the
reference site.

Amorphous Solids
Polarization
Energy Bands
Density of States
We count in E3 any dipoles not included in the volume bounded by

the inner and outer surfaces.
It is convenient to let the interior surface be spherical.

Amorphous Solids
Polarization
Energy Bands
Density of States
Lorentz field
The field E2 due to the polarization charges on the surface of the

fictitious cavity was calculated by Lorentz.
If is the polar angle (Fig. 34) referred to the polarization
direction, the surface charge density on the surface of the cavity is
P cos .
The electric field at the center of the spherical cavity of radius a is
(see Fig. 34):
Z
1 1
E2 = (a2 )(2a sin )(ad)(P cos )(cos ) = P
40 0 30

Amorphous Solids
Polarization
Energy Bands
Density of States
."
<.:...".,.. ..
!."-.';wf .tl8 - 1',,,,/I
Figure 34: Calculation of the field in a spherical cavity in a uniformly

9) is related to the dielectric constant by
polarized medium.
1 P
(S I) . (19)
,,EL. Varani Physics of Semiconductors Devices
Amorphous Solids
Polarization
Energy Bands
Density of States
This is the negative of the depolarization field E1 in a polarized

sphere, so that E1 + E2 = 0 for a sphere.

Amorphous Solids
Polarization
Energy Bands
Density of States
Field of dipoles inside cavity
The field E3 due to the dipoles within the spherical cavity is the
only term that depends on the crystal structure.
We showed for a reference site with cubic surroundings in a sphere
that E3 = 0 if all the atoms may be replaced by point dipoles
parallel to each other.

Amorphous Solids
Polarization
Energy Bands
Density of States
The total local field at a cubic site is, from (6) and (12),
Lorentz relation
1 1
Elocal = E0 + E1 + P=E+ P (6)
30 30
This is the Lorentz relation: the field acting at an atom in a cubic

site is the macroscopic field E of Eq. (4) plus P/30 from the
polarization of the other atoms in the specimen.
Experimental data for cubic ionic crystals support the Lorentz
relation.

Amorphous Solids
Polarization
Energy Bands
Density of States
The dielectric constant of an isotropic or cubic medium relative

to vacuum is defined in terms of the macroscopic field E:
Dielectric constant
0 E + P
= =1+
0 E

Amorphous Solids
Polarization
Energy Bands
Density of States
The susceptibility (9) is related to the dielectric constant by

Susceptibility
P
= =1
0 E

Amorphous Solids
Polarization
Energy Bands
Density of States
In a noncubic crystal the dielectric response is described by the

components of the susceptibility tensor or of the dielectric constant
tensor:
P = 0 E = +

Amorphous Solids
Polarization
Energy Bands
Density of States
The polarizability of an atom is defined in terms of the local

electric field at the atom:
p = Elocal
where p is the dipole moment.

The polarizability is an atomic property, but the dielectric constant
will depend on the manner in which the atoms are assembled to
form a crystal.
For a non-spherical atom will be a tensor.

Amorphous Solids
Polarization
Energy Bands
Density of States
The polarization of a crystal may be expressed approximately as

the product of the polarizabilities of the atoms times the local
electric field:
X X
P= N j pj = Nj j Elocal (j)
j j
where Nj is the concentration and j the polarizability of atoms j,

and Elocal (j) is the local field at atom sites j.

Amorphous Solids
Polarization
Energy Bands
Density of States
We want to relate the dielectric constant to the polarizabilities.

The result will depend on the relation that holds between the
macroscopic electric field and the local electric field.
If the local field is given by the Lorentz relation (12), then
X 1

P= N j j E+ P
30

Amorphous Solids
Polarization
Energy Bands
Density of States
We solve for P to find the susceptibility

P
P N j j
= = (7)
E 1 X
1 Nj j
30
By definition = 1 + ; we rearrange (7) to obtain
Clausius-Mossotti relation
1 1 X
= Nj j
+2 30

Amorphous Solids
Polarization
Energy Bands
Density of States
The Clausius-Mossotti relation relates the dielectric constant to

the electronic polarizability, but only for crystal structures for
which the Lorentz local field (6) obtains.

Amorphous Solids
Polarization
Energy Bands
Density of States
Electronic Polarizability
The total polarizability may usually be separated into three parts:

electronic, ionic, and dipolar, as in Fig. 35.
The electronic contribution arises from the displacement of the
electron shell relative to a nucleus.
The ionic contribution comes from the displacement of a charged
ion with respect to other ions.
The dipolar polarizability arises from molecules with a permanent
electric dipole moment that can change orientation in an applied
electric field.

Amorphous Solids
Polarization
Energy Bands
Density of States
Statistical Mechanics 13 Didecfric. and Ferroelectric.
1,.,.,
"''' ''1
Figure 8
fre</ut""cr dt"pcndt"ncc of the 5e'\cral >1ltriLutions to the pobrizabill1r.
Figure 35: Frequency dependence of the several contributions to the
polarizability.
Table 1 Electronic polarizabilities of ions, In 10- em3
I-Ie L.LiVarani
' Physics of Semiconductors Devices
Amorphous Solids
Polarization
Energy Bands
Density of States
In heterogeneous materials there is usually also an interfacial

polarization arising from the accumulation of charge at structural
interface.
This is of little fundamental Interest, but it is of considerable
practical interest because commercial insulating materials are
usually heterogeneous

Amorphous Solids
Polarization
Energy Bands
Density of States
The dielectric constant at optical frequencies arises almost entirely

from the electronic polarizability.
The dipolar and ionic contributions are small at high frequencies
because of the inertia of the molecules and ions.
In the optical range (7) reduces to
n2 1 1 X
= Nj j (electronic)
n2 + 2 30
here we have used the relation n2 = , where n is the refractive

index.

Amorphous Solids
Insulators and dielectrics Formation of energy bands
Energy Bands The Kronig-Penney Model
Electrical Conduction in Solids The k-space diagram
Density of States
Outline
2 Amorphous Solids
4 Energy Bands
Formation of energy bands
The Kronig-Penney Model
The k-space diagram
5 Electrical Conduction in Solids

Amorphous Solids
Density of States
Energy Bands
One of our goals is to determine the electrical properties of a

semiconductor material, which we will use to develop the
current-voltage characteristics of semiconductor devices.
We have two tasks in this chapter: to determine the properties of
electrons in a crystal lattice, and to determine the statistical
characteristics of the very large number of electrons in a crystal.

Amorphous Solids
Density of States
We can extrapolate the single-atom results to a crystal and

qualitatively derive the concepts of allowed and forbidden energy
bands.
We can then apply quantum mechanics and Schrodingers wave
equation to the problem of an electron in a single crystal.
We find that the electronic energy states occur in bands of allowed
states that are separated by forbidden energy bands.

Amorphous Solids
Density of States
Formation of energy bands
Figure 36a shows the radial probability density function for the
lowest electron energy state of the single, noninteracting hydrogen
atom, and Figure 36b shows the same probability curves for two
atoms that are in close proximity to each other.

rive the conceplS of allowed and forbidden energy bands. We can then apply quan-
The Crystal Structure
lum mechanics and Schrodinger's of Solids
wave equation to the problem of an electron in a
Amorphous Solids
single crystal. We find thatInsulators
the electronic energy states occur
and dielectrics ;11 hands
Formation of allowed
of energy bands
<Iales that are separated by forbidden energy
Energy bands.
Bands The Kronig-Penney Model
Density of States
3.1.1 Formation of Energy Bands
Figure 3.la shows the radi,,1 probability density function for Ihe lowest electron
energy stale of the single, nonintcracting hydrogen atom, and Figure 3.tb shows the
same probability curves for two atoms that are in close proximity to each other. The
wave functions of the two atom electrons overlap, which means that the two electrons
ilL _"_= _I_=__ ==_=_ ". I
(a) (b) (e)
Figure 3.11 (a) Probllbility function of an isolated hydrogen alUm . (b) O"erlapping probability density
functions of two adjacent hydrogen alOnis . (c) The splitting of the II = l s lale.
Figure 36: (a) Probability density function of an isolated hydrogen atom.
(b) Overlapping probability density functions of two adjacent hydrogenal
atoms.(c)The splitting of the n = 1 state.

Amorphous Solids
Density of States
The wave functions of the two atom electrons overlap, which

means that the two electrons will interact.
This interaction or perturbation results in the discrete quantized
energy level splitting into two discrete energy levels, schematically
shown in Figure 36c.
The splitting of the discrete stale into two states is consistent with
the Pauli exclusion principle.

Amorphous Solids
Density of States
Now, if we somehow start with a regular periodic arrangement of

hydrogen-type atoms that are initially very far apart, and begin
pushing the atoms together, the initial quantized energy level will
split into a band of discrete energy levels.
This effect is shown schematically in Figure 37 where the parameter
r0 represents the equilibrium interatomic distance in the crystal.

el and, if the discrete energy !'tatC$ are
then the energy le
19
d by 10- eV. This energy Amorphous Solids
Insulators anddifference
dielectrics is extremely
Formation of energy bands small, so that (If
poses. we have a quasi-continuous
Density of States
energy distribution through the
The k-space diagram
t
u
g
L-__ ____ ____
ro Inter-nomic distance -----..
"'igure
Figure 37: The 3.2 of
splitting 1 an energy
splittjng
stateof;m
into aenergy
band of allowed
energies. state into a band of allowed energies.

Amorphous Solids
Density of States
At any energy level, the number of allowed quantum states is

relatively small.
In order to accommodate all of the electrons in a crystal we must
have many energy levels within the allowed band.
As an example, suppose that we have a system with 1019
one-electron atoms and also suppose that, at the equilibrium
interatomic distance, the width of the allowed energy band is 1 eV.

Amorphous Solids
Density of States
For simplicity, we assume that each electron in the system occupies

a different energy level and, if the discrete energy states are
equidistant, then the energy levels are separated by 1019 eV.
This energy difference is extremely small, so that for all practical
purposes, we have a quasi-continuous energy distribution
through the allowed energy band.

Amorphous Solids
Density of States
Consider again a regular periodic arrangement of atoms, in which

each atom now contains more than one electron.
Suppose the atom in this imaginary crystal contains electrons up
through the n = 3 energy level.
If the atoms are initially very far apart the electrons in adjacent
atoms will not interact and will occupy the discrete energy levels.

Amorphous Solids
Density of States
If these atoms are brought closer together, the outermost electrons

in the n = 3 energy shell will begin to interact initially, so that this
discrete energy level will split into a band of allowed energies.
If the atoms continue to move closer together,the electrons in the
n = 2 shell may begin to interact and will also split into a band of
allowed energies.

Amorphous Solids
Density of States
Finally, if the atoms become sufficiently close together, the

innermost electrons in the n = 1 level may interact, so that this
energy level may also split into a band of allowed energies.
The splitting of these discrete energy levels is qualitatively shown
in Figure 38.

Amorphous Solids
Density of States
C HAP T E R 3 Intrcducoon to tl'..e Quantum Theosy of Sdds
t
S<=,.....--------- n 2
.. = I
ro Inlcraf(lmic distauc-e ----..
fijgure 3.31 Schemalic showing the splitting of three energy states

Figure 38: Schemalic showing
into allowed bands the splitting of three energy states into
of energies.
allowed bands of energies.
4N
o
,, , L. Varani Physics of Semiconductors Devices6N $tnte$
Amorphous Solids
Density of States
If the equilibrium interatomic distance is r0 then we have bands of

allowed energies that the electrons may occupy separatd by
bands of forbidden energies.
This energy-band splitting and the formation of allowed and
forbidden bands is the energy-band theory of single-crystal
materials.
The actual band splitting in a crystal is much more complicated
than indicated in Figure38.
A schematic representation of an isolated silicon atom is shown in
Figure 39.

Amorphous Solids
Insulators and dielectrics .. Formation of energy bands = I
Density of States
Statistical Mechanics ro Inlcraf(lmic distauc-e ----..
fijgure 3.31 Schemalic showing the splitting of three energy states

into allowed bands of energies.
4N
o
,, , 6N $tnte$
n =2
S electIOn$:
'"
t ..>-----;::
)p
3,
4N Sl3tCS
S;, allowed le"cI,
4N
\ at .. me energy 2N electron$.
tr Two allowed
;r levels
,--
energy
At $:IMC
, P
1t =1
2 clC(lrQns '1 - 3 I
(aJ (b)
3.4 1(a) Schematic of an jsolated silicon (b) The spliuiJlg of the 35 and 3p SlaleS of silicon into the
Figure 39:and(a)
aHowell Schematic
ft)Tb)dden
( frum SIJ{x:kley 15/.)
e1)ergy bands. of an isolated silicon atom. (b) The splitting of
the 3s and 3p states of silicon into the allowed and forbidden energy
bands. qualitatively shown in Figure 3.3. If the equilibrium interatomic distance is ro othen
we have bands of ,tllowed energies that the electrons may occupy sep",atcd by bands
of forbidden energies. This energyband splitting and the formation of allowed and
forbidden bands is the energy-band theory of single-crystal materials.
The actual band sp1itting in a crystal is much more complicated than indicated
in Figure 3.3. A schematic representation of an isolated silicon 3tOm is shown in Fig-
ure 3.4a. Ten of the fourteen silicon
L. Varani
atom electIons occupy deep-lying energy level,
Amorphous Solids
Density of States
Ten of the fourteen silicon atom electrons occupy deep-lying

energy levels close to the nucleus.
The four remaining valence electrons are weakly bound and are the
electrons involved in chemical reactions.
Figure39b shows the band splitting of silicon. We need only
consider the n = 3 level for the valence electrons, since the first
two energy shells are completely full and are tightly bound to the
nucleus.

Amorphous Solids
Density of States
The 3s state corresponds to n = 3 and l = 0 and contains two

quantum states per atom.
This state will contain two electrons at T = 0 K.
The 3p state corresponds to n = 3 and l = 1 and contains six
quantum states per atom.
This state will contain the remaining two electrons in the individual
silicon atom.

Amorphous Solids
Density of States
As the interatomic distance decreases, the 3s and 3p states

interact and overlap.
At the equilibrium interatomic distance, the bands have again split,
but now four quantum states per atom are in the lower band and
four quantum states per atom are in the upper band.

Amorphous Solids
Density of States
At absolute zero degrees, electrons are in the lowest energy state,

so that all states in the lower band (the valence band) will be full
and all states in the upper band (the conduction band) will be
empty.
The bandgap energy Eg between the top of the valence band and
the bottom of the conduction band is the width of the forbidden
energy band.

Amorphous Solids
Density of States
The Kronig-Penney Model
In the previous section, we discussed qualitatively the spilling of

allowed electron energies as atoms are brought together to form a
crystal.
The concept of allowed and forbidden energy bands can be
developed more rigorously by considering quantum mechanics and
Schrodingers wave equation.

Amorphous Solids
Density of States
The potential function of a single, noninteracting, one-electron

atom is shown in Figure 40a.
Also indicated on the figure are the discrete energy levels allowed
for the electron.
Figure 40b shows the same type of potential function for the case
when several atoms are in close proximity arranged in a
one-dimensional array. The potential functions of adjacent atoms
overlap, and the net potential function for this case is shown in
Figure 40c.

Amorphous Solids
Density of States
82 cHAPT a A 3 Introduction to the Ouantum Tt)ooryol Solids
X
Atom
(a)
v=o
AIOm Alom
(b)
Atom
v
Atom
v=o
I
I
I
Atom
lnlnlr "
Atom
(e )
ACorn Atom
Figure 3.5 1(I ) Potential functiun of a single

alOIn. (b) Overlapping potential fUilCtions of adjacent
Figure 40: (a) Potential atoms.
function offunction
(c) Net pOlemial a ofsingle
single crystal.
isolated atom. (b)
a one-<limensional
Overlapping potential functions of adjacent atoms. (c) Net potential

function of a one-dimensional single crystal.
V{X)

Amorphous Solids
Density of States
It is this potential function we would need to use in Schrodingers

wave equation to model a one-dimensional single-crystal material.
The solution to Schrodingers wave equation, for this
one-dimensional single-crystal Iattice, is made more tractable by
considering a simpler potential function.
Figure 41 is the one-dimensional Kronig-Penney model of the
periodic potential function, which is used to represent a
one-dimensional single-crystal lattice.

singleThe Crystal Structure of Solids
crystal. Amorphous Solids
Density of States
V{X)
II II If II
- (n + h ) -h o a (a + bJ
Figure 3.6 IThe cmedirnensional periodic potential

Figure 41:funct
Theionone-dimensional periodic potential function of the
of the Kronig- Penney model.
Kronig-Penney model.

Amorphous Solids
Density of States
We need to solve Schrodingers wave equation in each region.

As with previous quantum mechanical problems, the more
interesting solution occurs for the case when E < V0 which
corresponds to a particle being bound within the crystal.
The electrons are contained in the potential wells, but we have the
possibility of tunneling between wells.

Amorphous Solids
Density of States
The Kronig-Penney model is an idealized periodic potential

representing a one-dimensional single crystal, but the results will
illustrate many of the important features of the quantum behavior
of electrons in the periodic lattice.
To obtain the solution to Schrodingers wave equation, we make
use of a mathematical theorem by Bloch.

Amorphous Solids
Density of States
The theorem states that all one-electron wave functions for

problems involving periodically varying potential energy functions,
must be of the form :
(x) = u(x)e jkx (8)
The parameter k is called a constant of motion and will be

considered in more detail as we develop the theory.
The function u(x) is a periodic function with period (a + b).

Amorphous Solids
Density of States
The total solution to the wave equation is the product of the

time-independent solution and the time-dependent solution, or
(x, t) = (x)(t) = u(x)e jkx e j(E /~)t = u(x)e j[kx(E /~)t] (9)
This traveling-wave solution represents the motion of an electron

in a single-crystal material. The amplitude of the traveling wave is
a periodic function and the parameter k is also referred to as a
wave number.

Amorphous Solids
Density of States
We can now begin to determine a relation between the parameter

k, the total energy E , and the potential V0 .
If we consider region I in Figure 41 (0 < x < a) in which
V (x) = 0, take the second derivative of Equation (8), and
substitute this result into the time-independent Schrodingers wave
equation we obtain :
d 2 u1 (x) du1 (x)

+ 2jk (k 2 2 )u1 (x) = 0 (10)
dx 2 dx

Amorphous Solids
Density of States
The function u1 (x) is the amplitude of the wave function in region

I and the parameter is defined as
2mE
2 = (11)
~2

Amorphous Solids
Density of States
Consider now a specific region II (b < x < 0) in which

V (x) = V0 , and apply Schrodingers equation. We obtain :
d 2 u2 (x)

du2 (x) 2 2 2mV0
+ 2jk k + u2 (x) = 0 (12)
dx 2 dx ~2
where u2 (x) is the amplitude of the wave function in region II.

Amorphous Solids
Density of States
We may define :
2m 2mV0
2
(E V0 ) = 2 = 2 (13)
~ ~2
so that Equation 12 may be written as
d 2 u2 (x) du2 (x) 2 2

+ 2jk k u2 (x) = 0 (14)
dx 2 dx
Note that from Equation (13), if E > V0 , the parameter is real,
whereas if E < V0 , then is imaginary.

Amorphous Solids
Density of States
The solution to Equation (10), for region I, is of the form
u1 (x) = Ae j(k)x + Be j(+k)x for (0 < x < a) (15)
and the solution Equation (14), for region II, is of the form
u2 (x) = Ce j(k)x + De j(+k)x for (b < x < 0) (16)

Amorphous Solids
Density of States
Since the potential function V (x) is everywhere finite, both the

wave function (x) and its first derivative (x)/x must be
continuous.
This continuity condition implies that the wave amplitude function
u(x) and its first derivative u(x)/x must also be continuous.
If we consider the boundary at x = 0 and apply the continuity
condition to the wave amplitude, we have
u1 (0) = u2 (0) (17)

Amorphous Solids
Density of States
Substituting Equations (15) and (16) into Equation (17), we obtain
A+B C D =0 (18)
Now applying the condition that

du1 du2
= (19)
dx x=0 dx x=0
we obtain
( k)A ( + k)B ( k)C + ( + k)D = 0 (20)

Amorphous Solids
Density of States
We have considered region I as 0 < x < a and region II as

b < x < 0.
The periodicity and the continuity condition mean that the
function u1 , as x a, is equal to the function u2 , as x b.
This condition may be written as
u1 (a) = u2 (b) (21)

Amorphous Solids
Density of States
Applying the solutions for u1 (x) and u2 (x) to the boundary

condition in Equation (21) yields
Ae j(k)a + Be j(+k)a Ce j(k)b De j(+k)b = 0 (22)
The last boundary condition is

du1 du2
= (23)
dx x=a dx x=b

Amorphous Solids
Density of States
which gives
( k)Ae j(k)a ( + k)Be j(+k)a

(24)
( k)Ce j(k)b + ( + k)De j(+k)b = 0

Amorphous Solids
Density of States
We now have four homogeneous equations, Equations (18), (20),

(22), and (24), with four unknowns as a result of applying the four
boundary conditions.
In a set of simultaneous, linear, homogeneous equations, there is a
nontrivial solution if, and only if, the determinant of the
coefficients is zero.
In our case the coefficients in question are the coefficients of the
parameters A, B , C and D.

Amorphous Solids
Density of States
The evaluation of this determinant is extremely laborious and will

not be considered in detail.
The result is
(2 + 2 )
(sin a)(sin b)+(cos a)(cos b) = cos k(a+b) (25)
2

Amorphous Solids
Density of States
Equation (25) relates the parameter k to the total energy E

(through the parameter ) and the potential function V0 (through
the parameter ).
As we mentioned, the more interesting solutions occurs for
E < V0 , which applies to the electron bound within the crystal.
From Equation (13), the parameter is then an imaginary
quantity. We may define
= j (26)
where is a real quantity.

Amorphous Solids
Density of States
Equation (25) can be written in terms of as
2 2
(sin a)(sinh b) + (cos a)(cosh b) = cos k(a + b) (27)
2
Equation (27) does not lend itself to an analytical solution, but

must be solved using numerical or graphical techniques to obtain
the relation between k, E and V0 .
The solution of Schrodingers wave equation for a single bound
particle results in discrete allowed energies.
The solution of Equation (27) will result in a band of allowed
energies.

Amorphous Solids
Density of States
To obtain an equation that is more susceptible to a graphical

solution and thus will illustrate the nature of the results, let the
potential barrier width b 0 and the barrier height V0 , but
such that the product bV0 remains finite.
Equation (27) then reduces to

mV0 ba sin a
+ cos a = cos ka (28)
~2 a

Amorphous Solids
Density of States
We may define a parameter P 0 as

mV0 ba
P0 = (29)
~2
The, finally, we have the relation
sin a
P0 + cos a = cos ka (30)
a
Equation (30) again gives the relation between the

parameter k, total energy E (through the parameter ), and
the potential barrier bV0 .

Amorphous Solids
Density of States
We may note that Equation (30) is not a solution of

Schrodinger wave equation but give the condition for which
Schrodinger wave equation will have a solution.
If we assume the crystal is infinitely large, then k in Equation (30)
can assume a continuum of values and must be real.

Amorphous Solids
Density of States
The k-space diagram
To begin to understand the nature of the solution, initially consider

the special case for which V0 = 0.
In this case P 0 = 0, which corresponds to a free particle since there
are no potential barriers.
From Equation (30), we have that
cos a = cos ka (31)
or
=k (32)

Amorphous Solids
Density of States
Since the potential is equal to zero, the total energy E is equal to

the kinetic energy, so that, from Equation (11), Equation (32) may
be written as
r s
2mE 2m 21 mv 2 p
= 2
= 2
= =k (33)
~ ~ ~
where p is the particle momentum.

Amorphous Solids
Density of States
The constant of the motion parameter k is related to the

particle momentum for the free electron.
The parameter k is also referred to as a wave number.
We can also relate the energy and momentum as
p2 ~2 k 2
E= = (34)
2m 2m
Figure 42 shows the parabolic relation of Equation (34) between
the energy E and momentum p for the free particle.

quation (3.24) to beThea Crystal
fu ncti on f(aa Solids ) . so that
Structure of Solids
Amorphous
f(aa)
Density of States
= P,sinew
- -
exa
The k-space diagram
COs ex(/ (3
I I
I
,,,
I
I I
,,
I
I I
\ I
I
\
,I
,,
\
\
I
'"
-- .'
.-
p=o
Figure 42: Figure 3.7 I The
The parabolic parob")ic
E versus Ii versus
k curve k free electron.
for the
curve for Ute free electron.

Amorphous Solids
Density of States
Since the momentum and wave number are linearly related,

Figure 42 is also the E versus k curve for the free particle.
We now want to consider the relation between E and k from
Equation (30) for the particle in the single-crystal lattice.
As the parameter P 0 increases, the particle becomes more tightly
bound to the potential well or atom.

Amorphous Solids
Density of States
We may define the left side of Equation (30) to be a function

f (a), so that
sin a
f (a) = P 0 + cos a (35)
a
Figure 43a is a plot of the first term of Equation (35) versus a.
Figure 43b shows a plot of the cos a and Figure 43c is the sum of
the two terms, or f (a).

Amorphous Solids
Density of States
3 1 Allowed and Fo.b:dden Energy Bands 67
-41l'
(a)
(b)
j(rtI)
(e)
Figu", 3.81 A plol of <a) Ihe firsl lenn in Equalion (3.29). (h) Ihe second lerm in Equalion
(3.29), and (c) the entire f(fXa) function. The shaded show the allowed va lues of
Figure 43: A plot ofcorresponding
(a) the
(era) first
to real vaJues of k. term in Equation (35), (b) the second
term in Equationfigure
(35), and (c) the entire f (a) function. The shaded
3.8. is. plol of the first term of Equation (3.29) verslls 'f{f. Figure 3.Sb shows
areas show the allowed
a plot of Ihe cosvalues of
aa len" and Figure (a)
3.8e is thecorresponding
Now from Equation (3.24). we also have that
sum of lhe lwo lemlS, or /(auto ). real values of k.

Amorphous Solids
Density of States
Now from Equation (30), we also have that
f (a) = cos ka (36)
For Equation (36) to be valid, the allowed values of the f (a)

function must be bounded between +1 and 1.

Amorphous Solids
Density of States
Figure 43c shows the allowed values of f (a) and the allowed
values of a in the shaded areas.
Also shown on the figure are the values of ka from the right side of
Equation (36) which correspond to the allowed values of f (a).
The parameter is related to the total energy E of the particle
through Equation (11), which is 2 = 2mE /~2 .

Amorphous Solids
Density of States
A plot of the energy E of the particle as a function of the wave

number k can be generated from Figure 43c.
Figure 44 shows this plot and shows the concept of allowed
energy bands for the particle propagating in the crystal lattice.
Since the energy E has discontinuities, we also have the concept of
forbidden energies for the particles in the crystal.

Amorphous Solids
Density of States
Statistical
CHAPT ER 3 Intmcrucfon to theMechanics
OUamum Thecry Of So.XJs
,, ,,, ,,
'i , ,../
,,,
I
,,,
,,
,,
,
'N]
,,
,,,
,
,,
,
energy
band
I
I
,,
I
I
,, I
I I I , ,
,I
I
It:
I
: Forbidden
I lenergy banlt
,
I
-,JlI'
"
-7
>
"
() < Zff
u
) :1'

k -+-
Figure 3.9 1Tht: VCf$\lS k diagram generated from
Figure 44: The E Figure
versus3,8. The allowed energy
k diagram bands and forbidden
generated from Figure 43. The
energy bandgaps 3fe indicated.
allowed energy bands and forbidden energy bandgaps are indicated.
crystal lattice. Since the energy E has discontinuities, we also have the concepl of I
forbidden energies for the panicles in Ihe c rystal.
Amorphous Solids
Density of States
Consider again the right side of Equation (30), which is the

function cos ka.
The cosine function is periodic so that
cos ka = cos(ka + 2n) = cos(ka 2n) (37)
where n is a positive integer. We may consider Figure 44 and

displace portions of the curve by 2.
Mathematically, Equation (30) is still satisfied.
Figure 45 shows how various segments of the curve can be
displaced by the 2 factor.

Therepresentation.
Crystal Structure of Solids
Amorphous Solids
We noted
Insulators indielectrics
and Equation (3.27) that fo of
Formation r aenergy
free electron.
bands the panicle momentum ,mel
<he wave numberEnergykBands p = lik. Give
are relatedThebyKronig-Penney Model
n the Similarity between the free
Density of States
'i
"
1 ,
: .' ,
I
E ,
,
:
,,
:./
,,
N
1
J
I
I
I
I
\
\ I
f' I
I
I
t\
,I
I I
I
I \
\ I
I I I
I I \,
: '1'----:- '--
J I \ I I
, _ , -- -1. ,, --
,, B I
I "
\
Ii':
:, /
m
\
,,
,,
,,
I
-,,. -. o
"
,._.
Fi&ure 3.101The versus k diagram showing 2"
Figure 45: The E versus kofdiagram showing
several sections the
of allOWed displacements of several
energy Figure 3.11 I T
bands.
sections of allowed energy bands. in the reduced-

Amorphous Solids
Density of States
Figure46 shows the case in which the entire E versus k plot is

contained within /a < k < /a.
This plot is referred to as a reduced k-space diagram. Or a
reduced-zero representation.

Amorphous Solids
hat fo r a free electron. the panicleInsulators
momentum ,mel
and dielectrics Formation of energy bands
y p = lik. Give n the Similarity between the Energy Bands
free The Kronig-Penney Model
Density of States
,,
,
I
I
I t\
,,
:./
,, E
'-!
,,
-. ,,'----
m
,
,._.
showing 2"
lOWed energy Figure 3.11 I The versus k diagram
in thekreduced-lone
Figure 46: The E versus diagram represe1uation.
in the reduced-zone representation.
Amorphous Solids
Density of States
We noted in Equation (33) that for a free electron, the particle

momentum and the wave number k are related by p = ~k.
Given the similarity between the free electront solution and the
results of the single crystal shown in Figure 44, the parameter ~k
in a single crystal is referred to as the crystal momentum.
This parameter is not the actual momentum of the electron in the
crystal, but is a constant of the motion that includes the crystal
interaction.

Amorphous Solids
Density of States
We have been considering the Kronig-Penney model, which is a

one-dimensional periodic potential function used to model a
single-crystal lattice.
The principle result of this analysis is that electrons in the
crystal occupy certain allowed energy bands and are excluded
from the forbidden energy bands.
For real three-dimensionl single-crystal materials, a similar
energy-band theory exists.

The Energy Band and the Bond Model
Amorphous Solids
Drift Current
Electron Effective Mass
Energy Bands
Concept of the Hole
Metals, Insulators, and Semiconductors
Density of States
Extension to Three Dimensions
Outline
2 Amorphous Solids
4 Energy Bands

Drift Current
Amorphous Solids
Drift Current
Energy Bands
Concept of the Hole
Density of States
We are interested in determining the current-voltage characteristics

of semiconductor devices.
We will need to consider electrical conduction in solids as it relates
to the band theory we have just developed.
Let us begin by considering the motion of electrons in the various
allowed energy bands.

Amorphous Solids
Drift Current
Energy Bands
Concept of the Hole
Density of States
Figure 47 shows a two-dimensional representation of the covalent

bonding in a single-crystal silicon lattice.
This figure represents silicon at T = 0 K in which each silicon atom
is surrounded by eight valence electrons that are in their lower
energy state and are directly involved in the covalent bonding.

e nergy states into The
bandsCrystalof
Structure
allowedof Solids
Amorphous Solids
e nergies as the
The Energy Bandsilicon crystal
and the Bond Modelis formed. At
Drift Current
T = 0 K, the 4N states in the Energy
Insulators lowerBands
and bane\. the
dielectrics valence
Electron Effectiveband.
Mass are filled with the va-
Concept of the Hole
lence electrons. All Electrical
of the Conduction
valence inelectrons
Solids schematically
Metals, Insulators, ands\town in FiguI"C 3.12 are
Semiconductors
Density of States
in the valence band. TheStatistical
upper Mechanics
energy band, the conducti on band. is completely
empty at T =
0 K.
II II II II
II 11 II
II II II II
===0=0=0=0=='=
II II 11
===0=0=0=0===
II II II I)
===0=0=0=
I II II
0=
II
==
.. II II ..
II II II II
Figure 3.12 I
Figure 47: Two-dimensional representation of the covalent bonding in a
represe nt3(ion of the c()Va lenl bondin g
semiconductor at Tin=a semiconductor
0 K. at T :: 0 K.

Amorphous Solids
Drift Current
Energy Bands
Concept of the Hole
Density of States
Figure 39b represented the splitting of the discrete silicon energy

states into bands of allowed energies as the silicon crystal is
formed.
At T = 0 K, the 4N states in the lower band, the valence band,
are filled with the valence electrons.
All of the valence electrons schematically shown in Figure 47 are in
the valence band.
The upper energy band, the conduction band, is completely empty
at T = 0 K.

Amorphous Solids
Drift Current
Energy Bands
Concept of the Hole
Density of States
As the temperature increases above 0 K, a few valence band

electrons may gain enough thermal energy to break the
covalent bond and jump into the conduction band.
Figure 48a shows a two-dimensional representation of this
bond-breaking effect and Figure 48b, a simple line representation
of the energy-band model, shows the same effect.

ch.rged "empty state" is created
The Crystal inofthe
Structure o riginal covalent honding poSition in the va-
Solids
lence band. As the temperature Amorphous
funhcrSolids
increases.
Drift more
Currentcovalent ho nds are b)'Oken,
more electrons jump to the conduction Energy Bandsband, and more positive "empty states" ore
Concept of the Hole
l.'reatcd in the valence band. Density of States Metals, Insulators, and Semiconductors
We can also relateStatistical
this bond breaking to the E verSuS k e nergy bands.
Mechanics
Figure 3.14a shows lhe E versus k diagram of the conduction and valence bands at
1/ It JI IJ
" II II II
" II II II
='=0=0-0-0===
=
=
=!=!at4"
I C I I
6==
=
"=0-0-0-0==
It
II
= II II
II tI II f'
11 II II II
(a) (b)
Figure 3.131 (a) Two-dimensional representation of the breaking of .tcova lent bond.
Figure 48: (a) Two-dimensional
(b) Corresponding Ii lie fcpreStllla'10n of representation
(he enetgy band and of
the the breaking
generarion of :a of a
covalent
negativebond. (b)
and positi Corresponding
ve charge. lineofrepresentation
wlth the brcflking a covalent bond. of the energy band
and the generation of a negative and positive charge with the breaking of
a covalent I
bond. I

Amorphous Solids
Drift Current
Energy Bands
Concept of the Hole
Density of States
The semiconductor is neutrally charged.

This means that, as the negatively charged electron breaks
away from its covalent bonding position, a positively charged
empty state is created in the original covalent bonding
position in the valence band.
As the temperature further increases, more covalent bonds
are broken, more electrons jump to the conduction band, and
more positive empty states are created in the valence
band.

Amorphous Solids
Drift Current
Energy Bands
Concept of the Hole
Density of States
We can also relate this bond breaking to the E versus k energy

bands.
Figure 49a shows the E versus k diagram of the conduction and
valence bands at T = 0 K.
The energy states in the valence band are completely full
and the states in the conduction band are empty.

The
(a) Crystal Structure of Solids (b) Bond Model
The Energy Band and the
Amorphous Solids
Drift Current
Figure 3.131 (a) Two-dimensional representation
Energy Bands
Electron
of theEffective
breaking
Concept of the Hole
.t
Mass
of cova lent bond.
(b) CorrespondingElectrical Conduction in Solids
Ii lie fcpreStllla'1 0n of (he
Density of States
enetgy band
Metals, and andgenerarion
the
Insulators, of :a
Semiconductors
negative and positi ve charge. wlth the
Statistical brcflking of
Mechanics a covalent bond.
I I
I I
k k
(0) (b)
figure 3.14 i The \'e .. k diagralll Of lhc. conduclion and valence bands of a
Figure 49: The E versus k diagram of the conduction and valence bands
semiconductor at (a) T '" 0 K and (b) T ,. 0 K.
of a semiconductor at (a) T = 0 K and (b) T > 0 K.

Amorphous Solids
Drift Current
Energy Bands
Concept of the Hole
Density of States
Figure 49b shows these same bands for T > 0 K, in which some
electron, have gained enough energy to jump to the conduction
band and have left empty states in the valence band.
We are assuming at this point that no external forces are
applied so the electron and empty state distributions are
symmetrical with k.

Amorphous Solids
Drift Current
Energy Bands
Concept of the Hole
Density of States
Drift Current
Current is due to the net flow of charge.

If we had a collection of positively charged ions with a volume
density N (cm3 ) and an average drift velocity vd (cm/s), then
the drift current density would be
J = qNvd (A/cm2 ) (38)

Amorphous Solids
Drift Current
Energy Bands
Concept of the Hole
Density of States
If, instead of considering the average drift velocity, we considered

the individual ion velocities. then we could write the drift current
density as
XN
J=q vi (39)
i=1
where vi is the velocity of the ith ion.

The summation in Equation (39) is taken over a unit volume so
that the current density J is still in units of A/cm2 .

Amorphous Solids
Drift Current
Energy Bands
Concept of the Hole
Density of States
Since electrons are charged particles, a net drift of electrons in the

conduction band will give rise to a current.
The electron distribution in the conduction band, as shown
in Figure 49b, is an even function of k when no external
force is applied.
Recall that k for a free electron is related to momentum so that,
since there are as many electrons with a +|k| value as there
are with a |k| value, the net drift current density due to
these electrons is zero.
This result is certainly expected since there is no externally applied
force.

Amorphous Solids
Drift Current
Energy Bands
Concept of the Hole
Density of States
If a force is applied to a particle and the particle moves, it must

gain energy.
This effect is expressed as
dE = Fdx = Fvdt (40)

where F is the applied force, dx is the differential distance the
particle moves, v is the velocity, and dE is the increase in energy.
If an external force is applied to the electrons in the conduction
band, there are empty energy states into which the electrons can
move: therefore, because of the external force, electrons can gain
energy and momentum.

Amorphous Solids
Drift Current
Energy Bands
Concept of the Hole
Density of States
The electron distribution in the conduction band may look like that
shown in Figure 50, which implies that the electrons have gained a
net momentum. We may write the drift current density due to the
motion of electrons as
n
X
J = e vi (41)
i=1
where e is the magnitude of the electronic charge and n is the

number of electrons per unit volume in the conduction band.

Amorphous Solids
Drift Current
Energy Bands
Concept of the Hole
Density of States 3.2 8ectrical Ccoduc
Figure
Figure 50: The 3.1S Idistribution
asymmetric The nsymrnclric distribution
of electrons in the E versus k
of eJeclrons in Ihe 1;.' versus k diagram
diagram when an external force is applied.
when :11\ eXlcmal force is applied.
Amorphous Solids
Drift Current
Energy Bands
Concept of the Hole
Density of States
Again, the summation is taken over a unit volume so the current

density is A/cm2 .
We may note from Equation (41) that the current is directly
related to the electron velocity; that is, the current is related
to how well the electron can move in the crystal.

Amorphous Solids
Drift Current
Energy Bands
Concept of the Hole
Density of States
The movement of an electron in a lattice will in general, be

different from that of an electron in free space.
In addition to an externally applied force, there are internal forces
in the crystal due to positively charged ions or protons and
negatively charged electrons, which will influence the motion of
electrons in the lattice.
We can write
Ftotal = Fext + Fint = ma (42)
where Ftotal , Fext and Fint are the total force, the externally
applied forces and the internal forces, respectively, acting on a
particle in a crystal.

Amorphous Solids
Drift Current
Energy Bands
Concept of the Hole
Density of States
Since it is difficult to take into account all of the internal forces,

we will write the equation
Fext = m a (43)
where the acceleration a is now directly related to the external

force.
The parameter m , called the effective mass, takes into
account the particle mass and also takes into account the
effect of the internal forces.

Amorphous Solids
Drift Current
Energy Bands
Concept of the Hole
Density of States
We can also relate the effective mass of an electron in a crystal to

the E versus k curves, such as was shown in Figure 49.
In a semiconductor material, we will be dealing with allowed energy
bands that are almost empty of electrons and other energy bands
that are almost full of electrons.

Amorphous Solids
Drift Current
Energy Bands
Concept of the Hole
Density of States
To begin, consider the case of a free electron whose E versus k

curve was shown in Figure 43.
Recalling Equation (34), the energy and momentum are related by
E = p 2 /2m = ~2 k 2 /2m, where m is the mass of the electron.
The momentum and wave number k are related by p = ~k.

Amorphous Solids
Drift Current
Energy Bands
Concept of the Hole
Density of States
If we take the derivative of Equation (34) with respect to k, we

obtain
dE ~2 k ~p
= = (44)
dk m m
Relating momentum to velocity, Equation (44) can be written as
1 dE p
= =v (45)
~ dk m
where v is the velocity of the particle.
The first derivative of E with respect to k is related to the
velocity of the particle.

Amorphous Solids
Drift Current
Energy Bands
Concept of the Hole
Density of States
If we now take the second derivative of E with respect to k, we

have
d 2E ~2
2
= (46)
dk m
We may rewrite Equation (46) as
1 d 2E 1
2 2
= (47)
~ dk m
The second derivative of E with respect to k is inversely
proportional to the mass of the particle.

Amorphous Solids
Drift Current
Energy Bands
Concept of the Hole
Density of States
For the case of a free electron, the mass is a constant

(nonrelativistic effect), so the second derivative function is a
constant.
We may also note from Figure 42 that d 2 E /dk 2 is a positive
quantity, which implies that the mass of the electron is also a
positive quantity.

Amorphous Solids
Drift Current
Energy Bands
Concept of the Hole
Density of States
If we apply an electric field to the free electron and use Newtons

classical equation of motion, we can write
F = ma = eE (48)
where a is the acceleration, E is the applied electric field, and e is

the magnitude of the electronic charge.
Solving for the acceleration, we have
eE
a= (49)
m

Amorphous Solids
Drift Current
Energy Bands
Concept of the Hole
Density of States
The motion of the free electron is in the opposite direction to the

applied electric field because of the negative charge.
We may now apply the results to the electron in the bottom of an
allowed energy band.
Consider the allowed energy band in Figure 51a.
The energy near the bottom of this energy band may be
approximated by a parabola, just as that of a free particle.
We may write
E Ec = C 1 k 2 (50)

Amorphous Solids
Drift Current
Energy Bands
Concept of the Hole
Density of States
3.2 8ectric Conduction in Solids
P:I.tClbolic
P;'Irabolic
,I
s.pproximation :
k =O k_ k =O k_
(al (hi
Jiigure3.t61 (a) The conduccion band in reduccd Ii sIX,ce. and the parabolic
Figure 51: (a) The
approximnlion. conduction
(b) The band
\'illence billld in reduced
in reduced k space,kand
space, and the
the parabolic
parabolic approximation.
approximation. (b) The valence band in reduced k space, and
the parabolic approximation.
The energy E,. is the energy at the bollom of the band. Since E > Ec. the parameter
C, is a positive quantity.
Taking the second derivative of with respect to k from Equation (3.44), we
Amorphous Solids
Drift Current
Energy Bands
Concept of the Hole
Density of States
The energy Ec is the energy at the bottom of the band.

Since E > Ec , the parameter C1 is a positive quantity.
Taking the second derivative of E with respect to k from
Equation (50), we obtain
d 2E
= 2C1 (51)
dk 2

Amorphous Solids
Drift Current
Energy Bands
Concept of the Hole
Density of States
We may put Equation 51 in the form
1 d 2E 2C1
2 2
= 2 (52)
~ dk ~
Comparing Equation (52) with Equation (47), we may equate
~2 /2C1 to the mass of the particle.
However, the curvature of the curve in Figure 51 will not, in
general, be the same as the curvature of the free-particle curve.

Amorphous Solids
Drift Current
Energy Bands
Concept of the Hole
Density of States
We may write
1 d 2E 2C1 1
= = 2 = (53)
~2 dk 2 ~ m
where m is called the effective mass.
Since C1 > 0, we have that m > 0 also.

Amorphous Solids
Drift Current
Energy Bands
Concept of the Hole
Density of States
The effective mass is a parameter that relates the quantum

mechanical results to the classical force equations.
In most instances, the electron in the bottom of the conduction
band can be thought of as a classical particle whose motion can be
modeled by Newtonian mechanics, provided that the internal forces
and quantum mechanical properties are taken into account through
the effective mass.

Amorphous Solids
Drift Current
Energy Bands
Concept of the Hole
Density of States
If we apply an electric field to the electron in the bottom of the

allowed energy band, we may write the acceleration as
Electron effective mass
eE
a= (54)
mn
where mn is the effective mass of the electron.

The effective mass mn of the electron near the bottom of the
conduction band is constant.

Amorphous Solids
Drift Current
Energy Bands
Concept of the Hole
Density of States
Concept of the Hole
In considering the two-dimensional representation of the covalent

bonding shown in Figure 49a, a positively charged empty state
was created when a valence electron was elevated into the
conduction band.
For T > 0 K, all valence electrons may gain thermal energy; if a
valence electron gains a small amount of thermal energy, it may
hop into the empty state.

Amorphous Solids
Drift Current
Energy Bands
Concept of the Hole
Density of States
The movement of a valence electron into the empty state is

equivalent to the movement of the positively charged empty state
itself
Figure 52 shows the movement of valence electrons in the crystal
alternately filling one empty state and creating a new empty state,
a motion equivalent to a positive charge moving in the valence
band.
The crystal now has a second equally important charge carrier that
can give rise to a current.

If we consider a band that is tOlally full , all available states are occupied by eloc-.
troos. TheAmorphous
individual Solids
electrons can
ThebeEnergy
thought of as
Band andmoving wich
the Bond a ve]ociLy as given;
Model
by Equation Drift Current
Insulators (3.39):
and dielectrics
Energy Bands
Density of States
Concept of the Hole
veE) = (dE)
dk Dimensions
Extension /I.to Three
(3.39)
The band is symmetric in k and each state is occupied so Ihat, for every e1eclron with
a velocily lvi, there is a corresponding eleclron with a velocity -l vi, Since the band is
full, the dislribution of eleclrons wilh respect 10 k cannol be changed wilh an
extemally applied force. The nel drift current densily generdled from a completely full
Ii II II II II II II II II II 'i II I
?=?== ==r=?___ .?=?!==
\I " II II II " II II .. II II II
=
=?=?-?=r==
==9=9=9=9====9=9=9=9==
II II II II II II
(b)
tI II II II
(e)
II It
(a)
Figure 3.17 IVisualization ofrhc IlII1\'t menl of a hole in a semiconductor.

Figure 52: Visualization of the movement of a hole in a semiconductor.

Amorphous Solids
Drift Current
Energy Bands
Concept of the Hole
Density of States
This charge carrier is called a hole and, as we will see, can also be
thought of as a classical particle whose motion can be modeled
using Newtonian mechanics.
The drift current density due to electrons in the valence band, such
as shown in Figure 49b, can be written as
X
J = e vi (55)
i(filled)
where the summation extends over all filled states.

Amorphous Solids
Drift Current
Energy Bands
Concept of the Hole
Density of States
This summation is inconvenient since it extends over a nearly full

valence band and takes into account a very large number of states.
We may rewrite Equation (55) in the form
X X
J = e vi + e vi (56)
i(total) i(empty)

Amorphous Solids
Drift Current
Energy Bands
Concept of the Hole
Density of States
If we consider a band that is totally full, all available states are

occupied by electrons.
The individual electrons can be thought of as moving with a
velocity as given by Equation (45):
1 dE
v (E ) = (57)
~ dk

Amorphous Solids
Drift Current
Energy Bands
Concept of the Hole
Density of States
The band is symmetric in k and each state is occupied so that, for

every eleclron with a velocity |v |, there is a corresponding electron
with a velocity |v |.
Since the band is full, the distribution of electrons with respect to
k cannot be changed with an externally applied force.
The net drift current density generated from a completely full band
is zero or X
e vi = 0 (58)
total

Amorphous Solids
Drift Current
Energy Bands
Concept of the Hole
Density of States
We can now write the drift current density from Equation (56) for
an almost full band as
X
J = +e vi (59)
empty
where the vi in the summation is the

1 dE
v (E ) =
~ dk
associated with the empty state

Amorphous Solids
Drift Current
Energy Bands
Concept of the Hole
Density of States
Equation (59) is entirely equivalent to placing a positively charged

particle in the empty states and assuming all other states in the
band are empty, or neutrally charged.
This concept is shown in Figure 53.
Figure 53a shows the valence band with the conventional
electron-filled states and empty states, while Figure 53b shows the
new concept of positive charges occupying the original empty
states.

Amorphous Solids
The Energy Band and the Bond Model (3.54)
Drift Current
Energy Bands
Concept of the Hole
We may rearmnge this equation so that
Density of States
I d'E - 2C,
(3.55)
Ii' dk? = Ii'
E
I
k I k
I
I
I
00 I
00'
I
(.J (b)
Figure 3.181 (a) Valence bttnd wi th conve ntional electron-filled states and empty
Figure 53: (a) Valence band with conventional electron-filled states and
states. (b) Concept of positive charges OCC\lpyi1l.g the ()tiginal empty states.
empty states. (b) Concept of positive charges occupying the original
empty states.

Amorphous Solids
Drift Current
Energy Bands
Concept of the Hole
Density of States
The vi in the summation of Equation (59) is related to how well

this positively charged particle moves in the semiconductor.
Now consider an electron near the top of the allowed energy band
shown in Figure 51b.
The energy near the top of the allowed energy band may again be
approximated by a parabola so that we may write
(E Ev ) = C2 k 2 (60)

Amorphous Solids
Drift Current
Energy Bands
Concept of the Hole
Density of States
The energy Ev is the energy at the top of the energy band.

Since E < Ev for electrons in this band, then the parameter C2
must be a positive quantity.
Taking the second derivative of E with respect to k from
Equation (60), we obtain
d 2E
= 2C2 (61)
dk 2

Amorphous Solids
Drift Current
Energy Bands
Concept of the Hole
Density of States
We may rearrange this equation so that
1 d 2E 2C2
2 2
= (62)
~ dk ~2
Comparing Equation (61) with Equation (47), we may write
1 d 2E 2C2 1
= = (63)
~2 dk 2 ~2 m
where m is again an effective mass.

Amorphous Solids
Drift Current
Energy Bands
Concept of the Hole
Density of States
We have argued that C2 is a positive quantity which now implies

that m is a negative quantity.
An electron moving near the top of an allowed energy band
behaves as if it has a negative mass.

Amorphous Solids
Drift Current
Energy Bands
Concept of the Hole
Density of States
We must keep in mind that the effective mass parameter is used to

relate quantum mechanics and classical mechanics.
The attempt to relate these two theories leads to this strange
result of a negative effective mass.
However, we must recall that solutions to Schrodingers wave
equation also led to results that contradicted classical mechanics.
The negative effective mass is another such example.

Amorphous Solids
Drift Current
Energy Bands
Concept of the Hole
Density of States
If we again consider an electron near the top of an allowed energy

band and use Newtons force equation for an applied electric field,
we will have
F = m a = eE (64)
However, m is now a negative quantity, so we may write
eE +eE
a=
= (65)
|m | |m |
All electron moving near the top of an allowed energy band moves
in the same direction as the applied electric field.

Amorphous Solids
Drift Current
Energy Bands
Concept of the Hole
Density of States
The net motion of electrons in a nearly full band can be described

by considering just the empty states, provided that a positive
electronic charge is associated with each state and that the
negative of m from Equation (63) is associated with each state.
We now can model this band as having particles with a
positive electronic charge and a positive effective mass.

Amorphous Solids
Drift Current
Energy Bands
Concept of the Hole
Density of States
The density of these particles in the valence band is the

same as the density of empty electronic energy states.
This new particle is the hole.
The hole, then, has a positive effective mass denoted by mp
and a positive electronic charge, so it will move in the same
direction as an applied field.

Amorphous Solids
Drift Current
Energy Bands
Concept of the Hole
Density of States
Each crystal has its own energy-band structure.

We noted that the splitting of the energy states in silicon, for
example, to form the valence and conduction bands, was complex.
Complex band splitting occurs in other crystals, leading to large
variations in band structures between various solids to a wide range
of electrical characteristics observed in these various materials.

Amorphous Solids
Drift Current
Energy Bands
Concept of the Hole
Density of States
We can qualitatively begin to understand some basic differences in

electrical characteristics caused by variations in band structure by
considering some simplified energy bands.
There are several possible energy-band conditions to consider.
Figure 54a shows an allowed energy band that is completely empty
of electrons.
If an electric field is applied, there are no particles to move, so
there will be no current.

The Crystal Structureversely, the C<)nductivity of an insulator is vcry small. There are essentially no charged
of Solids
Theto Energy
panicles Ihat can conlribule BandFigure
a drift current. and 3.19<
the Bond
shows aModel
simplified energy-
Amorphous Solids
band diagram of an in,ulator.
DriftTheCurrent
bandgap energy , of an insulator is usually (In the
Electron
ord"rof 3.5 10 6cY or larger, so Ihat Effective Mass [here are esscnlially no elec-
al room temperature.
Energy Bands
trons in theeonduction band and theofvllienee
Concept band remains completely full. TIlere",e
the Hole
very few thcnnaUy generated and holesand
ill anSemiconductors
insulator.
Metals, Insulators,
efoclrons
Density ofFigure
States3.20a showsExtension
an energy bandto with
Threerelatively few eleelrons near the bottom
Dimensions
Statistical of
Mechanics
the band. Now. if an electric field is applied. the electrons can gain energy. move to
Allowed
J\lIowt.t1 energy
Cnt1gy band
band (almost
(empty) empty)
I") (a)
Allowed
i\l1owcd energy
band
bUild (almost
(full) full)
(b) (b)
- - - - - - - - - - Conduction
Conduction band
band (almost
- - - - r - - - - -- (.mp'Y) empty)
IE, Electrons E, ( Empty

s lates
- - --!..}''''
............... . .,. ... Valencc I Valence
b.md
_ _ __ _ __ _-'-'
: , (full)
Ie)
Figure 3.19 I AllOwed energy blinds Figure 3.20 I Allowed energy bands
'howing (a) an empty band. (b) a showing (a) ft ll almost empty band, (b) an
Figure 54: Allowed energy bands
completely fullshowing (a) an empty
band. and (e) Ihe bandgap band,
oJmOSllulJ b.nd. (b)
and (e) Ihe a
bandgap
energy belween the tWOaUo\\,,<ed bands. energy between the 1wo allowoo bands.
completely full band, and (c) the bandgap energy between the two
allowed bands.

Amorphous Solids
Drift Current
Energy Bands
Concept of the Hole
Density of States
Figure 54b shows another allowed energy band whose energy states
are completely full of electrons.
We argued in the previous section that a completely full energy
band will also not give rise to a current.
A material that has energy bands either completely empty or
completely full is an insulator.
The resistivity of an insulator is very large or, conversely, the
conductivity of an insulator is very small.

Amorphous Solids
Drift Current
Energy Bands
Concept of the Hole
Density of States
There are essentially no charged particles that can contribute to a

drift current.
Figure 54c shows a simplified energy-band diagram of an insulator.
The bandgap energy Eg of an insulator is usually in the order
of 3.5 to 6 eV or larger, so that at room temperature, there
are essentially no electrons in the conduction band and the
valence band remains completely full.
There are very few thermally generated electrons and holes in an
insulator.

Amorphous Solids
Drift Current
Energy Bands
Concept of the Hole
Density of States
Figure 55a shows an energy band with relatively few electrons near
the bottom of the band.
Now, if an electric field is applied, the electrons can gain energy,
move to higher energy states, and move through the crystal.
The net flow of charge is a current.
Figure 55b shows an allowed energy band that is almost full of
electrons, which means that we can consider the holes in this band.

nol give rise 10 a current. A material that has energy bands cithercomplctely empty 0"
complelely full is an insulator. The resistivity of an insulator is veryThe large Energy
or. con- Band and the Bond Model
Amorphous
versely, the C<)nductivity of an insulator is vcry small. Solids
There are essentially no charged
Drift Current
panicles Ihat can conlribuleInsulators andFigure
to a drift current. dielectrics
3.19< shows a simplified energy-
band diagram of an in,ulator. The bandgapEnergy energy ,Bands
of an insulator isConcept
usually (In the
of the Hole
ord"rof 3.5 10 6cYElectrical Conduction
or larger, so Ihat in Solids
al room temperature. [here are esscnlially no elec-
Density
trons in theeonduction band and the vllienee bandofremains
States completely full. TIlere",e
very few thcnnaUy generated efoclrons and holes ill an insulator. Extension to Three Dimensions
Figure 3.20a shows an energy band with relatively few eleelrons near the bottom
of the band. Now. if an electric field is applied. the electrons can gain energy. move to
Allowed
J\lIowt.t1 energy
Cnt1gy band
band (almost
(empty) empty)
I") (a)
Allowed
i\l1owcd energy
band
bUild (almost
(full) full)
(b) (b)
- - - - - - - - - - Conduction
Conduction band
band (almost
- - - - r - - - - -- (.mp'Y) empty)
IE, Electrons E, ( Empty

s lates
- - --!..}''''
............... . .,. ... Valencc I Valence
b.md
_ _ __ _ __ _-'-'
: , (full)
Ie)
Figure 3.19 I AllOwed energy blinds Figure 3.20 I Allowed energy bands
'howing (a) an empty band. (b) a showing (a) ft ll almost empty band, (b) an
Figure 55: Allowed energy bands showing
completely full band. and (e) Ihe bandgap
oJmOSllulJ b.nd. (a) an almost empty band,
and (e) Ihe bandgap
energy belween the tWOaUo\\,,<ed bands.
energy between the 1wo allowoo bands.
(b)an almost full band, and (e) the bandgap energy between the two
allowed bands.

Amorphous Solids
Drift Current
Energy Bands
Concept of the Hole
Density of States
If an electric field is applied, the holes can move and give rise to a
current.
Figure 55c shows the simplified energy-band diagram for this case.
The bandgap energy may be on the order of 1 eV.
This energy-band diagram represents a semiconductor for
T > 0 K.
The resistivity of a semiconductor can be controlled and
varied over many orders of magnitude.

Amorphous Solids
Drift Current
Energy Bands
Concept of the Hole
Density of States
The characteristics of a metal include a very low resistivity.

The energy-band diagram for a metal may be in one of two forms.
Figure 56a shows the case of a partially full band in which there
are many electrons available for conduction, so that the
material can exhibit a large electrical conductivity.
Figure 56b shows another possible energy-band diagram of a metal.

Amorphous Solids
Drift Current
Energy Bands
Concept of the Hole
Density of States
C HAP T. R 3 Introduction to the QuanluO'l TheolY of Solids
Partially
.. .. . ,, _ band
- ) Upper
/ _ .) b3nd
Full
Lower ----------- -
band ' . - ,- EicClfOtlS
band \
(a) (b)
Figure 3.211 Two possible energy bands of. metal showing (a) a panially filled band
Figure 56: Two possible energy bands of a metal showing (a) a partially
and (b) overlapping allowed energy b.,ods.
filled band and (b) overlapping allowed energy bands.
I
higher energy states. and move through the crystal. 'The nct now of churge is a current.
Figure 3.20b shows an allowed energy band that is almost full of electrons. which
means that we can consider the holes in this band. If an electric field is applied. the
holes can mOve and give rise to a CUrrent. Figure 3.2Oc shows the simplified energy
band diagram for this case. The bandgap energy may be on the order of I cV. This
energyband diagram representsL.aVarani
semiconductor forSemiconductors
Physics of T > 0 K. The resistivity of a
Devices
Amorphous Solids
Drift Current
Energy Bands
Concept of the Hole
Density of States
The band splitting into allowed and forbidden energy bands is a

complex phenomenon and Figure 56b shows a case in which the
conduction and valence ban s overlap at the equilibrium
interatomic distance.
As in the case shown in Figure 56a, there are large numbers of
electrons as well as large numbers of empty energy states
into which the electrons can move, so this material can also
exhibit a very high electrical conductivity.

Amorphous Solids
Drift Current
Energy Bands
Concept of the Hole
Density of States
One problem encountered in extending the potential function to a

three-dimensional crystal is that the distance between atoms varies
as the direction through the crystal changes.
Figure 57 shows a face-centered cubic structure with the [100] and
[110] directions indicated.
Electrons traveling in different directions encounter different
potential patterns and therefore different k-space boundaries.
The E versus k diagrams are in general function of the
k-space direction in a crystal.

Amorphous Solids
Drift Current
Energy Bands
Concept of the Hole
Density of States 3 3 and
Metals, Insulators, Extension to Three
Semiconductors CXtnensions
11 101
di rection
-0
,
,,' ,11
, I
, , I
(100)
direction
Figure 3.22 1The (100) plane of a

Figure 57: The (100) plane of acubic
face-ccntcrea face-centered cubic crystal showing the
erystaJshowing
[100] [110] directions.
Ihe 11001nnd 111 01 directions.

Amorphous Solids
Drift Current
Energy Bands
Concept of the Hole
Density of States
Figure 58 shows an E versus k diagram of gallium arsenide and of

sillicon.
These simplified diagrams show the basic properties considered in
this text, but do not show many of the details more appropriate for
advanced-level courses.
Note that in place of the usual positive and negative k axes, we
now show two different crystal directions.

3.3.1 The k-Space Diagrams of 5i and GaAs
Figure 3.23 shows an EAmorphous Solids
versus k diagram of gallium arsenide and of silkon. These
Drift Current
simplified diagrams show Energythe basic propeniesElectron
Bands
Effective
cullsidered Mass
in this text. but do not
show many of the details
Electrical more app
Conduction ropriate for Concept
in Solids
of the Hole
advanced-level courses.
Note that in place ofDensity of States
the usual positive and negativetokThree
axes, Dimensions
we now show two
Extension
different crystal directions. The E versus k diagram for the one-dimensional model
4 4
GaAs Conduction Si
halld band
3 3
2 2
>
, ....
>
[b >-
e!'
.-
c Jl"
w
0 0
"I'
- I - I
Valence V:;i!cnc(!
band ban<.l
-2 -2
(111 1 u 11001 1111] 0 11001
k k
(a) (b)
Figure 3.23 1Energy band SlrUClUres of (a) G.As nnd (0) Si.
(FromS,, /lI ).)
Figure 58: Energy bands structures of (a) GaAs and (b) Si.

Amorphous Solids
Drift Current
Energy Bands
Concept of the Hole
Density of States
The E versus k diagram for the one-dimensional model was

symmetric in k so that no new information is obtained by
displaying the negative axis.
It is normal practice to plot the [100] direction along the normal
+k axis and to plot the [111] portion of the diagram so the +k
points to the left.
In the case of diamond or zincblende lattices, the maxima in the
valence band energy and minima in the conduction band energy
occur at k = 0 or along one of these two directions.

Amorphous Solids
Drift Current
Energy Bands
Concept of the Hole
Density of States
Figure 58a shows the E versus k diagram for GaAs.

The valence band maximum and the conduction band minimum
both occur atk = 0.
The electrons in the conduction band tend to settle at the
minimum conduction band energy which is at k = 0.
Similarly, holes in the valence band tend to congregate at the
uppermost valence band energy.
In GaAs, the minimum conduction band energy and
maximum valence band energy occur at the same k value.

Amorphous Solids
Drift Current
Energy Bands
Concept of the Hole
Density of States
A semiconductor with this property is said to be a direct

bandgap semiconductor; transitions between the two allowed
bands can take place with no change in crystal momentum.
This direct nature has significant effect on the optical
properties of the material, GaAs and other direct bandgap
materials are ideally suited for use in semiconductor lasers
and other optical devices.

Amorphous Solids
Drift Current
Energy Bands
Concept of the Hole
Density of States
The E versus k diagram for silicon is shown in Figure 58b.

The maximum in the valence band energy occurs at k = 0 as
before.
The minimum in the conduction band energy occurs not at k = 0,
but along the [100] direction.
The difference between the minimum of conduction band energy
and the maximum valence band energy is still defined as the
bandgap energy Eg .

Amorphous Solids
Drift Current
Energy Bands
Concept of the Hole
Density of States
A semiconductor whose maximum valence band energy and

minimum conduction band energy do not occur at the same
k value is called an indirect bandgap semiconductor.
When electrons make a transition between the conduction
and valence bands, we must invoke the law of conservation
of momentum.
A transition in an indirect bandgap material must necessarily
include an interaction with the crystal so that crystal
momentum is conserved.

Amorphous Solids
Drift Current
Energy Bands
Concept of the Hole
Density of States
Germanium is also an indirect bandgap material whose valence

band maximum occurs at k = 0 and whose conduction band
minimum occurs along the [111] direction.
GaAs is a direct bandgap semiconductor but other compound
semiconductors such as GaP and AlAs, have indirect bandgaps.

Amorphous Solids
Drift Current
Energy Bands
Concept of the Hole
Density of States
The curvature of the E versus k diagrams near the minimum of

the conduction band energy is related to the effective mass of the
electron.
We may note from Figure 58 that the curvature of the conduction
band at its minimum value for GaAs is larger than that of silicon,
so the effective mass of an electron in the conduction band
GaAs will be smaller than that in silicon.

Amorphous Solids
Drift Current
Energy Bands
Concept of the Hole
Density of States
The curvature of the E versus k diagram at the conduction band

minimum may not be the same in the three k directionq.
We will not consider the details of the various effective mass
parameters here.
In later sections and chapters, the effective mass parameters used
in calculations will be a kind of statistical average that is adequate
for most device calculations.

Amorphous Solids
Mathematical derivation
Energy Bands
Extension to Semiconductors
Density of States
Outline
2 Amorphous Solids
4 Energy Bands
6 Density of States
Amorphous Solids
Energy Bands
Density of States
Density of States
Since current is due to the flow of charge, an important step in the

process is to determine the number of electron, and holes in the
semiconductor that will be available for conduction.
The number of carriers that can contribute to the conduction
process is a function of the number of available energy or quantum
state, since, by the Pauli exclusion principle, only one electron can
occupy a given quantum state.

Amorphous Solids
Energy Bands
Density of States
When we discussed the splitting of energy levels into bands of

allowed and forbidden energies, we indicated that the band of
allowed energies was actually made up of discrete energy levels.
We must determine the density of these allowed energy states as a
function of energy in order to calculate the electron and hole
concentrations.

Amorphous Solids
Energy Bands
Density of States
Electrons are allowed to move relatively freely in the conduction

band of a semiconducto, but are confined to the crystal.
As a first step, we will consider a free electron confined to a
three-dimensional infinite potential well, where the potential well
represents the crystal.

Amorphous Solids
Energy Bands
Density of States
The potential of the infinite potential well is defined as
V (x, y , z) = 0 for 0 < x < a, 0 < y < a, 0 < z < a (66)
and
V (x, y , z) = elsewhere (67)
where the crystal is assumed to be a cube with length a.

Amorphous Solids
Energy Bands
Density of States
Schrodingers wave equation in three dimensions can be solved

using the separation of variables technique.
Extrapolating the result from the one-dimensional infinite potential
well, we can show that
2
2mE 2 2 2 2 2 2 2
2
= k = kx + ky + kz = (nx + ny + nz ) (68)
~ a2
where nx , ny and nz are positive integers.

Negative values of nx , ny and nz yield the same wave function,
except for the sign, as the positive integer values, resulting in the
same probability function and energy, so the negative integers do
not represent a different quantum slate.

Amorphous Solids
Energy Bands
Density of States
We can schematically plot the allowed quantum states in k space.

Figure 59 shows a two-dimensional plot as a function of kx and ky .
Each point represents an allowed quantum state corresponding to
various integral values of nx and ny .
Positive and negative values of kx , ky , or kz have the same energy
and represent the same energy state.

Amorphous Solids
Energy Bands
Density of States
CHAPTER 3 trcdlJction to lhe Ovamum
Statistical MechanicsTt'.eOty ofSctds
t
-c"
k

. -.(: . ,

,
...... .
k

k. .. I
(a) (b)
FigureFigure 3.24AI (a)

59: (a) A two-dimensionalarray of
two-dimensional of allowed
aUO\ved <.)uantum SHUtS in
quantum states in k
k space. (b) The posi ti ve one.eighlh of 1he spheri cal k spate.
space. (b) The positive one-eighlh of the spherical k space.
energy state. Since negmive values of k", ky,Physics

L. Varani
Or k:ofdo nOt repre sent additional quan
Amorphous Solids
Energy Bands
Density of States
Since negativa values of kx , ky , or kz do not represent additional

quantum states, the density of quantum states will be determined
by considering only the positive one-eighth of the spherical k space
as shown in Figure 59b.
The distance between two quantum states in the kx direction, for
example, is given by

kx+1 kx = (nx + 1) nx = (69)
a a a

Amorphous Solids
Energy Bands
Density of States
Generalizing this result to three dimensions, the volume Vk of a

single quantum state is
3
Vk = (70)
a
We can now determine the density of quantum states in k space.

Amorphous Solids
Energy Bands
Density of States
A differential volume in k space is shown in Figure 59b and is

given by 4k 2 dk, so the differential density of quantum states in k
space can be written as
1 4k 2 dk

gT (k)dk = 2 3 (71)
8
a

Amorphous Solids
Energy Bands
Density of States
The first factor, 2, takes into account the two spin states allowed
for each quantum state; the next factor,1/8, takes into account
that we are considering only the quantum states for positive values
of kx , ky , and kz .
The factor 4k 2 dk is again the differential volume and the factor
(/a)3 is the volume of the quantum state.

Amorphous Solids
Energy Bands
Density of States
Equation 71 may be simplified to
2 kdk 3
gT (k)dk = a (72)
3
Equation 72 gives the density of quantum states as a function of
momentum, through the parameter k.

Amorphous Solids
Energy Bands
Density of States
We can now determine the density of quantum states as a function

of energy E .
For a free electron, the parameters E and k are related by
2mE
k2 = (73)
~2
or
1
k= 2mE (74)
~

Amorphous Solids
Energy Bands
Density of States
The differential dk is
r
1 m
dk = dE (75)
~ 2E
Then, substituting the expressions for k 2 and dk into

Equation (72), the number of energy states between E and E + dE
is given by
a3 2mE 1 m
r
gT (E )dE = 3 dE (76)
~2 ~ 2E

Amorphous Solids
Energy Bands
Density of States
Since ~ = h/2, Equation (76) becomes
4a3 3/2

gT (E )dE = (2m) E dE (77)
h3
Equation (77) gives the total number of quantum states between
the energy E and E + dE in the crystal space volume of a3 .

Amorphous Solids
Energy Bands
Density of States
If we divide by the volume a3 then we will obtain the density of

quantum states per unit volume of the crystal.
Equation (77) then becomes
Density of states per unit volume in a three-dimensional infinite
potential well
4(2m)3/2
g (E ) = E (78)
h3

Amorphous Solids
Energy Bands
Density of States
The density of quantum states is a function of energy E .

As the energy of this free electron becomes small, the number of
available states decreases.
This density function is really a double density, in that the units
are given in tems of states per unit energy per unit volume.

Amorphous Solids
Energy Bands
Density of States
In the last section we derived a general expression for the density of

allowed electron quantum states using the model of a free electron.
We can extend this same general model to a semiconductor to
determine the density of quantum states in the conduction band
and the density of quantum states in the valence band.
Electrons and holes are confined within the semiconductor crystal
so we will again use the basic model of the infinite potential well.

Amorphous Solids
Energy Bands
Density of States
The parabolic relationship between energy and momentum of a free

electron was given in Equation (34) as E = p 2 /2m = ~2 k 2 /2m.
Figure 51a showed the conduction energy band in the reduced k
space.
The E versus k curve near k = 0, the bottom of the conduction
band, can be approximated as a parabola, so we may write
~2 k 2
E = Ec + (79)
2mn
where Ec is the bottom edge of the conduction band and mn is the

electron effective mass.

Amorphous Solids
Energy Bands
Density of States
Equation (79) may be rewritten to give
~2 k 2
E Ec = (80)
2mn
The general form of the E versus k relation for an electron in the

bottom of a conduction band is the same as the free electron,
except the mass is replaced by the effective mass.
We can then think of the electron in the bottom of the conduction
band as being a free electron with its own particular mass.

Amorphous Solids
Energy Bands
Density of States
The right hand side of Equation (80) is of the same form as the
right side of Equation (34), which was used in the derivation of the
density of states function.
Because of this similarity, which yields the free conduction
electron model, we may generalize the free electron results of
Equation (78) and write the density of allowed electronic energy
states in the conduction band as
Electrons density of states per unit volume in the conduction band
4(2mn )3/2 p
gc (E ) = E Ec (81)
h3

Amorphous Solids
Energy Bands
Density of States
Equation (81) is valid for E Ec .

As the energy of the electron in the conduction band decreases,
the number of available quantum states also decreases.
The density of quantum states in the valence band can be obtained
by using the same infinite potential well model, since the hole is
also confined in the semiconductor crystal and can be treated as a
free particle.
The effective mass of the hole is mp .

Amorphous Solids
Energy Bands
Density of States
Figure 51b showed the valence energy band in the reduced k

space. We may also approximate the E versus k curve near k = 0
by a parabola for a free hole, so that
~2 k 2
E = Ev (82)
2mp
Equation Equation (82) may be rewritten to give
~2 k 2
Ev E = (83)
2mp

Amorphous Solids
Energy Bands
Density of States
Again, the right side of Equation (83) is of the same form used in
the general derivation of the density of states function.
We may then generalize the density of states function from
Equation (78) to apply to the valence band, so that
Holes density of states per unit volume in the conduction band
4(2mp )3/2 p
gv (E ) = Ev E (84)
h3
Equation (84) is valid for E Ev .

Amorphous Solids
Energy Bands
Density of States
We have argued that quantum states do not exist within the

forbidden energy band, so g (E ) = 0 for Ev < E < Ec .
Figure 60 shows the plot of the density of quantum states as a
function of energy.
If the electron and hole effective masses were equal, then the
functions gc (E ) and gv (E ) would be symmetrical about the energy
midway between Ec and Ev or the midgap energy, Emidgap .

Amorphous Solids
Energy Bands
Density of States
Statistical
CHAPTER 3 Introduction Mechanics
to the Quaflluln Theory 01Solids
I
8v(E}
Figure 3.25 IThe density of energy

Figure 60: The densitystates
of energy statesband in and
thetheconduction band and the
density of energy statesdenl'ic
in the co nduction
in ythel)f energy Slilles in the \'ulence
valence band as a function of energy.
band as a function of energy.
J
L. Varani
TEST YOUR UNDERSTANDING Physics of Semiconductors Devices
Amorphous Solids
Statistical Laws
The Fermi-Dirac Probability Function
Energy Bands
The Distribution function and the Fermi Energy
Plancks law
Density of States
Outline
2 Amorphous Solids
4 Energy Bands
6 Density of States

Amorphous Solids
Statistical Laws
Energy Bands
Plancks law
Density of States
In dealing with large numbers of particles, we are interested only in

the statistical behavior of the group as a whole rather than in the
behavior of each individual particle.
In a crystal, the electrical characteristics will be determined by the
statistical behavior of a large number of electrons.

Amorphous Solids
Statistical Laws
Energy Bands
Plancks law
Density of States
Statistical Laws
In determining the statistical behavior of particles, we must

consider the laws that the particles obey.
There are three distribution laws determining the distribution of
particles among available energy states.

Amorphous Solids
Statistical Laws
Energy Bands
Plancks law
Density of States
One distribution law is the Maxwell-Boltzmann probability

function.
In this case, the particles are considered to be distinguishable by
being numbered, for example, from 1 to N with no limit to the
number of particles allowed in each energy state.
The behavior of gas particles in a container at fairly low pressure is
an example of this distribution distribution.

Amorphous Solids
Statistical Laws
Energy Bands
Plancks law
Density of States
A second distribution law is the Bose-Einstein function.

The particles in this case are indistinguishable and, again, there is
no limit to the number of particles permitted in each quantum
state.
The behavior of photons, or black body radiation, is an example of
this law.

Amorphous Solids
Statistical Laws
Energy Bands
Plancks law
Density of States
The third distribution law is the Fermi-Dirac probability function.

In this case, the particles are again indistinguishable, but now only
one particle is permitted in each quantum state.
Electrons in a crystal obey this law.
In each case, the particles are assumed to be noninteracting.

Amorphous Solids
Statistical Laws
Energy Bands
Plancks law
Density of States
Figure 61 shows the ith energy level with gi quantum states.

A maximum of one particle is allowed in each quantum state by
the Pauli exclusion principle.
There are gi ways of choosing where to place the first particle,
(gi 1) ways of choosing where to place the second particle,
(gi 2) ways of choosing where to place the third particle, and so
on.

Amorphous Solids
Statistical Laws
g,..,
Energy Bands
W-
Density of States
Plancks law
, - N,'(g; - N, ) !
ilhener gy l l2 f 3 I
I<:"el I
------.
QU3.llIum
Figure 3.261
Figure 61: The.
The ith ilh tncrgy
energy level with gi wilh 8,
quantum states.
quantum states.

Amorphous Solids
Statistical Laws
Energy Bands
Plancks law
Density of States
Then the total number of ways of arranging Ni , particles in the ith

energy level (where Ni < gi ) is
gi !
(gi )(gi 1) (gi (Ni 1)) = (85)
(gi Ni )!
This expression includes all permutations of the Ni , particles

among themselves.

Amorphous Solids
Statistical Laws
Energy Bands
Plancks law
Density of States
However,since the particles are indistinguishable, the Ni ! number

of permutations that the particles have among themselves in any
given arrangement do not count as separate arrangements.
The interchange of any two electrons, for example. does not
produce a new arrangement.

Amorphous Solids
Statistical Laws
Energy Bands
Plancks law
Density of States
Therefore, the actual number of independent ways of realizing a

distribution of Ni particles in the ith level is
gi !
Wi = (86)
Ni !(gi Ni )!

Amorphous Solids
Statistical Laws
Energy Bands
Plancks law
Density of States
Example
To determine the possible number of ways of realizing a particular
distribution. Let gi = Ni = 10. Then (gi Ni )! = 1.
gi ! 10!
= =1
Ni !(gi Ni )! 10!

Amorphous Solids
Statistical Laws
Energy Bands
Plancks law
Density of States
Example
To determine the possible number of ways of realizing a particular
distribution. Let gi = 10 and Ni = 9.
gi ! 10!
= = 10
Ni !(gi Ni )! 9!1!

Amorphous Solids
Statistical Laws
Energy Bands
Plancks law
Density of States
Equation (86) gives the number of independent ways of realizing a

distribution of Ni particles in the ith level.
The total number of ways of arranging (N1 , N2 , N3 , Nn )
indistinguishable particles among n energy levels is the product of
all distributions or
n
Y gi !
W = (87)
Ni !(gi Ni )!
i=1
The parameter W is the total number of ways in which

PnN
electrons can be arranged in this system, where N = i=1 Ni is
the total number of electrons in the system.

Amorphous Solids
Statistical Laws
Energy Bands
Plancks law
Density of States
We want to find the most probable distribution, which means that

we want to find the maximum W .
The maximum W is found by varying Ni among the Ei levels,
which varies the distribution, but at the same time, we will keep
the total number of particles and total energy constant.

Amorphous Solids
Statistical Laws
Energy Bands
Plancks law
Density of States
We may write the most probable distribution function as

Fermi-Dirac distribution
N(E ) 1
= fF (E ) = (88)
g (E ) E EF
1 + exp
kT
where EF is called the Fermi energy.

Amorphous Solids
Statistical Laws
Energy Bands
Plancks law
Density of States
The number density N(E ) is the number of particles per unit

volume per unit energy and the function g (E ) is the number of
quantum states per unit volume per unit energy.
The function fF (E ) is tailed the Fermi-Dirac distribution or
probability function and gives the probability that a quantum
state at the energy E will be occupied by an electron.
Another interpretation of the distribution function is that fF (E ) is
the ratio of filled to total quantum states at any energy E .

Amorphous Solids
Statistical Laws
Energy Bands
Plancks law
Density of States
To begin to understand the meaning of the distribution function

and the Fermi energy, we can plot the distribution function versus
energy.
Initially, let T = 0 K and consider the case when E < EF .
The exponential term in Equation (88) becomes
exp[(E EF )/kT ] exp() = 0.
The resulting distribution function is fF (E < EF ) = 1.

Amorphous Solids
Statistical Laws
Energy Bands
Plancks law
Density of States
Again let T = 0 K and consider the case when E > EF .

The exponential term in the distribution function becomes
exp[(E EF )/kT ] exp(+) = +.
The resulting Fermi- Dirac distribution function now becomes
fF (E > EF ) = 0.

Amorphous Solids
Statistical Laws
Energy Bands
Plancks law
Density of States
The Fermi-Dirac distribution function for T = 0 K is plotted in

Figure 62.
This result shows that, for T = 0 K, the electrons are in their
lowest possible energy states.
The probability of a quantum state being occupied is unity
for E < EF and the probability of a state being occupied is
zero for E > EF .
All electrons have energies below the Fermi energy at
T = 0 K.

Figure 3.28 shows discrete energy fevers of a
Amorphous Solids
Statistical Laws
number of avai lable quantum statesand theat
Energy Bands
The Distribution function
Plancks law
each
Fermi Energy energy.
Density of States
G
::!'; LO f - - - - - - - - ,
Fig
Figure 62:rlllure 3.271
The Fermi The Feooi
probability probability
function versus energy for T = 0 K. and
funclion versusenergy for T = 0 K. !:;ys
Amorphous Solids
Statistical Laws
Energy Bands
Plancks law
Density of States
Figure 63 shows discrete energy levels of a particular system as well

as the number of available quantum states at each energy.
If we assume, for this case, that the system contains 13 electrons,
then Figure63 shows how these electrons are distributed among the
various quantum states at T = 0 K.

ed is 2ero for E > ETheF Crystal
AJI Structure
electrons
of Solidshave energies below
Amorphous Solids
Statistical Laws
Energy Bands
rete energy fevers of a parl'icular system as. well as (he
Density of States
Plancks law
m states at each energy. If we assume, for this case. that

--'''-'''-''=<--=-=-='--
"" "" "" 'ai "" "" .,
--"''--
'ft!
'"
Figure 3.28 I Discre(c energy SHIIcs
Figure 63: Discrete energy levels and quantum states for a particular
bility system at T = 0Kand quantum states for a particular
.
0 K. !:;ystm at T == 0 K.

Amorphous Solids
Statistical Laws
Energy Bands
Plancks law
Density of States
The electrons will be in the lowest possible energy state, so the

probability of a quantum state being occupied in energy levels E1
through E4 is unity, and the probability of a quantum state being
occupied in energy level E5 is zero.
The Fermi energy, for this case, must be above E4 but less than E5 .
The Fermi energy determines the statistical distribution of electrons
and does not have to correspond to an allowed energy level.

Amorphous Solids
Statistical Laws
Energy Bands
Plancks law
Density of States
Now consider a case in which the density of quantum states g (E )

is a continuous function of energy as shown in Figure 64.
If we have N0 electrons in this system, then the distribution of
these electrons among the quantum states at T = 0 K is shown by
the dashed line.
The electrons are in the lowest possible energy state so that all
states below EF are filled and all states above EF are empty.
If g (E ) and N0 are known for this particular system, then the
Fermi energy EF can be determined.

i,(E = E,..) = = -
Amorphous Solids
I ,. exp (0) +
I
Statistical Laws
Energy The
Bands probability of a
state being
The Distribution function and the occupied =
Fermi Energy at EF
Density of Fermi-Dirac distribution function ploued for several
Plancks law
States
Fermi e nergy is independent of temperature.
g(E )
HE
Figure 3.30
JI'lgure 3.29 1 of quantum Stales and elccrrons in a quantum st
Figure 64: Density ofenergy
continuous quantum states
system at T = and
0 K.electrons in a continuous shown in F
energy system at T = 0 K.

Amorphous Solids
Statistical Laws
Energy Bands
Plancks law
Density of States
Consider the situation when the temperature increases above

T = 0 K.
Electrons gain a certain amount of thermal energy so that some
electrons can jump to higher energy levels. which means that the
distribution of electrons among the available energy states will
change.
Figure 65 shows the same discrete energy levels and quantum state
as in Figure 63.

nction ploued forTheseveral
Crystal Structure of Solids assuming the'
Amorphous Solids
of temperature. Insulators and dielectrics
Energy Bands
Statistical Laws
Plancks law
Density of States
...
- - " ' ' - - 1-:,
Figure
Figure 65: Discrete 3.30states
energy I Discrete fnergystates
and quantum state.!)for:tnd
the same
na quantum staleS for the snme system
system show in Figure 63 for T > 0 K.
shown in Figure 3.28 for T > 0 K.
Amorphous Solids
Statistical Laws
Energy Bands
Plancks law
Density of States
The distribution of electrons among the quantum states has

changed from the T = 0 K case.
Two electrons from the E4 level have gained enough energy to
jump to E5 and on electron from E3 has jumped to E4 .
As the temperature changes, the distribution of electrons versus
energy changes.

Amorphous Solids
Statistical Laws
Energy Bands
Plancks law
Density of States
The change in the electron distribution among energy levels for

T > 0 K can be seen by plotting the Fermi-Dirac distribution
function.
If we let E = EF , then Equation (88) becomes
1 1 1
fF (E = EF ) = = = (89)
1 + exp(0) 1+1 2

Amorphous Solids
Statistical Laws
Energy Bands
Plancks law
Density of States
The probability of a state being occupied at E = EF is 1/3.

Figure 66 shows the Fermi-Dirac distribution function plotted for
several temperatures, assuming the Fermi energy is independent of
temperature

Amorphous Solids
Statistical Laws
Energy Bands
Plancks law
Density of States
3.5 StatiStical MechaniCS
I
)'0
,I
n
E
Figure 66: Figure

The Fermi3.31 IThe Fermi probability
probability functionfunction
versus versu,
energyenergy
for different
foc differ!!llt temperarures.
temperatures.
We can see that for above absolute Zero. there is a nonz.ero proba-
bility thai SOme energy slates above EF
will be occupied by eleclrOns and some
energy slates below EF will be empty. This
L. Varani
result again that some electrons
Amorphous Solids
Statistical Laws
Energy Bands
Plancks law
Density of States
We can see that for temperatures above absolute zero there is a

nonzero probability that some energy states above EF will be
occupied by electrons and some energy states below EF will be
empty.
This result again means that some electrons have jumped to higher
energy levels with increasing thermal energy.
We can sec from Figure 66 that the probability of an energy above
EF being occupied increases as the temperature increases and the
probability of a state below EF being empty increases as the
temperature increases.

Amorphous Solids
Statistical Laws
Energy Bands
Plancks law
Density of States
Example
To calculate the probability that an energy state above EF is
occupied by an electron. Let T = 300 K. Determine the
probability that an energy level 3kT above the Fermi energy is
occupied by an electron.
1 1
fF (E ) = =
E EF 3kT
1 + exp 1 + exp
kT kT
which becomes
1
fF (E ) = = 0.0474 = 4.74%
1 + 20.09

Amorphous Solids
Statistical Laws
Energy Bands
Plancks law
Density of States
Example
Assume that the Fermi energy level for a particular material is
6.25 eV. Calculate the temperature at which there is a 1 percent
probability that a state 0.30 eV below the Fermi energy level will
not contain an electron.
1
1 fF (E ) = 1
E EF
1 + exp
kT
Then
1
0.01 = 1
5.95 6.25
1 + exp
kT
We find kT = 0.06529 eV, so that the temperature is T = 756 K.
Amorphous Solids
Statistical Laws
Energy Bands
Plancks law
Density of States
We may note that the probability of a state a distance dE above

EF being occupied is the same as the probability of a state a
distance dE below EF being empty.
The function fF (E ) is symmetrical with the function 1 fF (E )
about Fermi energy, EF .
This symmetry effect is shown in Figure 67.

Amorphous Solids
Statistical Laws
Energy Bands
Plancks law
Density of States
3 .5 Statistical Mect'anics
,!
- B,
Figure 3.32 IThe probability of a state being occupied.

Figure 67: The
/F(e).probability of a state being occupied, f (E ), and the
<Uld th e probabilit.y of a Slate being elUJHy, 1-F ,/j<) .
probability of a state being empty, 1 fF (E ).
,,
I
, Fenni-Oirn.: (uncliQlI
1.01-----_...
L. Varani I Physics of Semiconductors Devices
Amorphous Solids
Statistical Laws
Energy Bands
Plancks law
Density of States
Consider the case when E EF kT , where the exponential term

in the denominator of Equation (88) is much greater than unity.
We may neglect the 1 in the denominator, so the Femi-Dirac
distribution function becomes
Maxwell-Boltzmann distribution function

(E EF )
fF (E ) exp (90)
kT
Equation (90) is known as the Maxwell-Boltzmann approximation,

or simply the Boltzmann approximation, to the Fermi-Dirac
distribution function.

Amorphous Solids
Statistical Laws
Energy Bands
Plancks law
Density of States
Figure 68 shows the Fermi-Dirac probability function and the

Boltzmann approximation.
This figure gives an indication of the range of energies over which
the approximation is valid.

Amorphous Solids
Statistical Laws
Energy Bands
- in Solids
Electrical Conduction B, Plancks law
Density of States
Figure 3.32 IThe probability of a state being occupied.
/F(e). <Uld th e probabilit.y of a Slate being elUJHy, 1- ,/j<) .
,,
I
, Fenni-Oirn.: (uncliQlI
1.01-----_... ,
t
I
I
'V BoltzmOlnll 3ppro)(.i matiun
-- - --- -- -- --- -- -- '.,
E E,.
Figure 3.331 The Fenni- Dirat probability fllncfiUll and rhe

Figure 68: Ma.xwell-
The Fermi-Dirac probability function and the
Boltzmann approximation.
Maxwell-Boltzmann approximation.
Consider the case when - CF kT . where the exponential term in the de-
nominator of Equation (3.79) is much greater Ihan Dnily. We may neglect the I in the
denominator, so the Femli-Dirdc distribution function becomes
Amorphous Solids
Statistical Laws
Energy Bands
Plancks law
Density of States
Plancks law
A black body is an idealized physical body that absorbs all

incident electromagnetic radiation.
Because of this perfect absorptivity at all wavelengths, a black
body is also the best possible emitter of thermal radiation, which it
radiates incandescently in a characteristic, continuous spectrum
that depends on the bodys temperature.
At Earth-ambient temperatures this emission is in the infrared
region of the electromagnetic spectrum and is not visible. The
object appears black, since it does not reflect or emit any visible
light.

Amorphous Solids
Statistical Laws
Energy Bands
Plancks law
Density of States
The thermal radiation from a black body is energy converted

electrodynamically from the bodys pool of internal thermal energy
at any temperature greater than absolute zero.
It is called blackbody radiation and has a frequency distribution
with a characteristic frequency of maximum radiative power
that shifts to higher frequencies with increasing temperature.

Amorphous Solids
Statistical Laws
Energy Bands
Plancks law
Density of States
As the temperature increases past a few hundred degrees Celsius,

black bodies start to emit visible wavelengths, appearing red,
orange, yellow, white, and blue with increasing temperature.
When an object is visually white, it is emitting a substantial
fraction as ultraviolet radiation.

Amorphous Solids
Statistical Laws
Energy Bands
Plancks law
Density of States
Figure 69: As the temperature decreases, the peak of the blackbody

radiation curve moves to lower intensities and longer wavelengths. The
blackbody radiation graph is L.also compared
Varani with
Physics of the classical
Semiconductors Devices model of
Amorphous Solids
Statistical Laws
Energy Bands
Plancks law
Density of States
All matter emits electromagnetic radiation when it has a

temperature above absolute zero. The radiation represents a
conversion of a bodys thermal energy into electromagnetic energy,
and is therefore called thermal radiation. It is a spontaneous
process of radiative distribution of entropy.
Conversely all matter absorbs electromagnetic radiation to some
degree.
An object that absorbs all radiation falling on it, at all
wavelengths, is called a black body.
When a black body is at a uniform temperature, its emission has a
characteristic frequency distribution that depends on the
temperature.
Its emission is called blackbody radiation.
Amorphous Solids
Statistical Laws
Energy Bands
Plancks law
Density of States
The concept of the black body is an idealization, as perfect black

bodies do not exist in nature.
Experimentally, blackbody radiation may be established best as the
ultimately stable steady state equilibrium radiation in a cavity in a
rigid body, at a uniform temperature, that is entirely opaque and is
only partly reflective.
A closed box of graphite walls at a constant temperature with a
small hole on one side produces a good approximation to ideal
blackbody radiation emanating from the opening.

Amorphous Solids
Statistical Laws
Energy Bands
Plancks law
Density of States
In the laboratory, blackbody radiation is approximated by the

radiation from a small hole in a large cavity, a hohlraum, in an
entirely opaque body that is only partly reflective, that is
maintained at a constant temperature.
Any light entering the hole would have to reflect off the walls of
the cavity multiple times before it escaped, in which process it is
nearly certain to be absorbed. Absorption occurs regardless of the
wavelength of the radiation entering (as long as it is small
compared to the hole).

Amorphous Solids
Statistical Laws
Energy Bands
Plancks law
Density of States
The hole, then, is a close approximation of a theoretical black body

and, if the cavity is heated, the spectrum of the holes radiation
(i.e., the amount of light emitted from the hole at each
wavelength) will be continuous, and will depend only on the
opacity and partial reflectivity of the walls, but not on the
particular material of which they are built nor on the material in
the cavity (compare with emission spectrum).

Amorphous Solids
Statistical Laws
Energy Bands
Plancks law
Density of States
Calculating the blackbody curve was a major challenge in

theoretical physics during the late nineteenth century.
The problem was solved in 1901 by Max Planck in the formalism
now known as Plancks law of blackbody radiation.
He found a mathematical expression fitting the experimental data
satisfactorily.
Planck had to assume that the energy of the oscillators in the
cavity was quantized, i.e., it existed in integer multiples of some
quantity.

Amorphous Solids
Statistical Laws
Energy Bands
Plancks law
Density of States
Einstein built on this idea and proposed the quantization of

electromagnetic radiation itself in 1905 to explain the photoelectric
effect.
These quanta were called photons and the blackbody cavity was
thought of as containing a gas of photons.
In addition, it led to the development of quantum probability
distributions, called Fermi-Dirac statistics and Bose-Einstein
statistics, each applicable to a different class of particles, fermions
and bosons.

Amorphous Solids
Statistical Laws
Energy Bands
Plancks law
Density of States
Plancks law states that

Plancks law
2h 3 1
I (, T ) = (91)
c2

h
exp 1
kT
where I (, T ) is the energy per unit time (or the power) radiated
per unit area of emitting surface in the normal direction per unit
solid angle per unit frequency by a black body at temperature T

Amorphous Solids
Statistical Laws
Energy Bands
Plancks law
Density of States
Wiens displacement law shows how the spectrum of black body

radiation at any temperature is related to the spectrum at any
other temperature. If we know the shape of the spectrum at one
temperature, we can calculate the shape at any other temperature.
A consequence of Wiens displacement law is that the wavelength
at which the intensity of the radiation produced by a black body is
at a maximum, max , it is a function only of the temperature
b
max = (92)
T
where the constant, b, known as Wiens displacement constant, is
equal to 2.898 103 K m.

Amorphous Solids
Statistical Laws
Energy Bands
Plancks law
Density of States
The Stefan-Boltzmann law states that the power emitted per unit
area of the surface of a black body is directly proportional to the
fourth power of its absolute temperature:
j = T 4 (93)
where j is the total power radiated per unit area, T is the

absolute temperature and = 5.67 108 Wm2 K4 is the
Stefan-Boltzmann constant.

Luca Varani - University Montpellier 2 - Physics of Semiconductor Devices - Part II Material Physics

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Luca Varani - University Montpellier 2 - Physics of Semiconductor Devices - Part II Material Physics

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The Crystal Structure of Solids

Physics of Semiconductors Devices

September 27, 2011

L. Varani Physics of Semiconductors Devices

1 The Crystal Structure of Solids

The Crystal Structure of Solids

This lectures deal with the electrical properties and characteristics

L. Varani Physics of Semiconductors Devices

The formation or growth of the single-crystal material is an

L. Varani Physics of Semiconductors Devices

Semiconductors are a group of materials having conductivities

L. Varani Physics of Semiconductors Devices

3 6.941 4 9.0122 13 IIIA 5 10.8116 12.0117 14.0078 9

19 39.098 20 40.078 21 44.956 22 47.86723 50.94224 25 54.938 26

7 Fr Ra Ac-Lr Rf Db Sg Bh Hs Mt Uun Uuu Uub Uuq

LANTHANIDE Copyright 1998-2002 EniG. (eni@ktf-split.hr)

Figure 1: Periodic Tables of the Elements

Table 1 shows a portion of the periodic table in which the more

L. Varani Physics of Semiconductors Devices

Table 2 lists a few of the semiconductor materials.

L. Varani Physics of Semiconductors Devices

Semiconductors can also be formed from combinations of group II

L. Varani Physics of Semiconductors Devices

The two-element, or binary compounds such as gallium arsenide or

L. Varani Physics of Semiconductors Devices

We can also fom a three-element, or ternary compound

L. Varani Physics of Semiconductors Devices

Amorphous, polycrystalline, and single crystal are the three

L. Varani Physics of Semiconductors Devices

These ordered regions, or single-crystal regions, vary in size and

L. Varani Physics of Semiconductors Devices

The advantage of a single-crystal material is that, in general, its

L. Varani Physics of Semiconductors Devices

Figure 2: Schematic, of three general types of crystals: (a) amorphous.

L. Varani Physics of Semiconductors Devices

Our primary concern will be the single crystal with it regular

L. Varani Physics of Semiconductors Devices

Primitive and Unit Cell

We can represent a particular atomic array by a dot that is called a

L. Varani Physics of Semiconductors Devices

Figure 3: Two-dimensional representation of a single-crystal lattice.

L. Varani Physics of Semiconductors Devices

Since the three-dimensional lattice is a periodic repetition of a

L. Varani Physics of Semiconductors Devices

---- - n; . . ------ -- --- I't I

L. Varani Physics of Semiconductors Devices

The unit cell A can be translated in directions a2 and b1 , the unit

L. Varani Physics of Semiconductors Devices

A primitive cell is the smallest unit cell that can be repeated to to

L. Varani Physics of Semiconductors Devices

The relationship between this cell and the lattice is characterized

where p, q and s are integers.

L. Varani Physics of Semiconductors Devices

Basic Crystal Structures

(a) (b) (e)

L. Varani Physics of Semiconductors Devices

By knowing the crystal structure of a material and its lattice

L. Varani Physics of Semiconductors Devices

To find the volume density of atoms in a crystal

L. Varani Physics of Semiconductors Devices

The volume density of atoms just calculated represents the order of

L. Varani Physics of Semiconductors Devices

Crystal Planes and Miller Indices

L. Varani Physics of Semiconductors Devices