Solid State Physics-2

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Solid State
Physics
Written by Professor Mr. Iftikhar Ali

Lecturer in Govt. Post Graduate Collage Mardan
Composed By His Student Muhammad Darwish
Contact No: 0346 198 36 30
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Name:________________
Class No:_____________
Subject:______________
Semester:_____________
Department:___________
Contact No____________
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Table of Contents
Topic Name Page No.
Crystal Defects (C-D)……………………………………………………………….……….9
Introduction……………………………………………………………………………………………………9
Phonons…………………………………………………………………………………………………….12
Point Defects OR Point Imperfection ………………………………………………………….13
Vacancy Defect…………………………………………………….……………………………..13
Self-Interstitial Defect………………………………….………………………………………14
Impurity Interstitial Defect……………………………………………………………………14
Substitutional Impurity Defect…………………………………..…………………………14
Schottky Defect……………………………..…………………………………………………….15
Frenkel Defect………………………………………………………………………………………15
Color Center…………………………………………………………….……………………………15
Schottky Defect………………………………………………………………………………………….16
Frenkel Defect……………………………………………………………………………………………24
Color Center………………………………………………………………………………………………30
Types of Color Center………………………………………………………………………………..32
F-Color Center…………………………………………………….………………………..……32
M-Color Center……………………………………………………………..……………………33
R-Color Center……………………………………..…………………………………………….33
-Color Center………………………………………………….……………………………..34
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H-Color Center…………………………………..………………………………………………..34
-Color Center…………………………………………………..………………………..34
Band Theory of Solid (BTS)…………………………………………………………….35

Review of Free Electrons Gas Model…………………………………………………………35
Bloch Theorem……………………………………………………………………….……………37
Band Theory of Solid………………………………………………….………………………..40
Energy Verses Wave Vector Graph E-K Graph…………………………………..……….53
Motion (Velocity) of Electrons in Band (Crystals)……………………………….…..…58
Effective Mass of Electrons in crystal ( )…………………………………………….....60
Density of States & Fermi Surface (DSF)………………………..……………………….…63
Density of States…………………………………………………………………………………….…66
Free Electrons Theory of Metals (Solids) (FETM)……………………………………….71
Drude Model & Lorentz………………………………………………………………………….…75
Dielectric Properties of Solid (DPS)………………………………………………..80

Dielectric Properties of Solid is the Response of Solid (Insulators) to the
Applied Electric Field “E” ………………………………………………..……………………....80
Maxwell’s Equation in Dielectric Medium………………………………………………...88
Solved Problem………………………………………………………………………………………..90
Dielectric Constant…………………………………………………………………………………..90
Clausius Mossotti Relation (CMR)……………………………………………………………92
Electric Polerizability……………………………………………………………………………….97
Origin OR Sources of Polerizability…………………………………………………………..98

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Electronic Polerizability ( )……………………………………………………………..……..99
Ionic Polerizability ( )…………………………………………………………………………….102
Orientation OR Dipoler Polerizability ( )……………………………………………..103
Ferroelectric Properties of Dielectrics (FEPD)…………………………………………107
Ferroelectric Hysteresis………………………………………………………………………....109
Temperature Dependence of polarization of Ferroelectric Materials And
Currie Wien’s Law *Thermo-dynamics Theory of Ferroelectric materials…110
Piezo-Electric Effect (PEF)………………………………………………………………………..114
Applications of Piezo-Electric Effect……………………………………………………......117
Other Applications……………………………………………………………………………………117
Sensor…………………………………………………………………………………….………..117
Actuators………………………………………………………………………………..………...117
High Voltage and Power Source ……………………………………..…….………….118
Piezoelectric motors……………………………………………………….…………………118
MAGNETISM…………………………………………………………………………………119
Magnetization (M)………………………………………………………………………………….…120
Diamagnetism……………………………………………………………………………………….….121
Langevin Theory of Diamagnetism……………………………………………………….……122
Para Magnetism (PM) (Langevin Theory of Para Magnetism)……………....…126
Ferromagnetism……………………………………………………………………………………..….132
Weiss Theory of Ferromagnetism 1907……………………………………………………...133

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Semi-Conductors & Super Conductivity……………………………………..…138

Semi-Conductors…………………………………………………………………………………..…138
Intrinsic Semi-Conductors (Pure Semi-Conductors)……………………………..…..139
Intrinsic Carriers Charge Concentration……………………………………………………140
Conductivity ( ) in Intrinsic Semi-Conductors………………………………………..…142
Fermi Energy Level of intrinsic Semi-conductors………………………………….…..143
Extrinsic Semi-Conductors (Ex-Sc)……………………………………………………….……153
Definition of Extrinsic Semi-Conductors……………………………….……154
N-Type Doping (Donor)………………………………………………………………………….…154
P-Type Doping (Acceptors)………………………………………………………………….……157
Conductivity and Concentration in Extrinsic Semi-Conductors…………………159
Conductivity and Concentration in N-type Extrinsic
Semi-Conductors…………………………………………………………………………...159
Conductivity and Concentration in P-type Extrinsic
Semi-Conductors……………………………………………………………………..…....160
Super-Conductivity (S-C)………………………………………………………………………….162
Meissner Effects……………………………………………………………………………………...165
Type-I Super-Conductors…………………………………………………………………………167
Type-II Super-Conductors……………………………………………………………………....168
London’s Equation (L-E), The Electromagnetic Behavior of

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Super-Conductivity…………………………………………………………………………….….169
Statement of London’s Equation OR London’s Law…………………………….....169
BCS Theory of Super-Conductors (B-C-S)……………………………………………..…175
Cooper Pair in Super-Conductors………………………………………………...175

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C-D-1
 Crystal Defects:
 Introduction:
We are given some of daily life questions and we have to
answer these questions.
1. Why we add cow dung in mud plastering?
Ans: We add the cow dung in mud plastering in order to
make it strength. The cow dung introduces the rate of
shrinkage and stop to dislocation motion, or slow it, when
the dislocation motion is stopped then the materials becomes
strengthen.
2. Why we add Hay straw in mud plastering?
Ans: As when the Hay straws are uniformly distribution
throughout the mud and it is plastered then it becomes
strengthen. The reason of it is that the function of hay
straw is to remove the chance of propagation of crack.
Actually the Hay straw stops the dislocation motion and
materials become strengthen.
3. Why a blacksmith put iron agricultural utensil in cold water
after putting them in shape?
Ans: The blacksmith put the iron utensil in cold water
because first of all it produces defects in the crystal and
then make it suddenly cool in order to make it defect and
hence materials become strengthen. Actually the atoms
when the materials is heated they are randomly distributed
and then they are left at their places by cooling it
suddenly.
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4. Why a carefully prepare crystal is mechanically weak but

roughly prepare crystal is strong.
Ans: The roughly prepare crystal have large number of
dislocation and the atoms are displaced and defects are
present in it but in case of carefully prepared crystal it
have all the atoms nearly at the same position because it
is slowly cooled upon the equilibrium and therefore no
dislocation and as a result it is weaker than the roughly
prepared crystal.
5. Why we keep the surface of car wind screen polished?
Ans: We make the surface of car wind screen polished in
order to stop the crack propagation and make the
materials mechanically harden.
6. Why a copper wire breaks after a few twists?
Ans: As we know that in the twists to the copper wire.
The dislocations are produced. These dislocation moves the
twists point. When the other twists is given to it, then
the other dislocations are also produced in it which moves
toward the twist point. When the other dislocations are
produced then the already existing dislocation resists and
stops the motion of these dislocations and as a result the
copper wire breaks into two pieces.
7. Why ceramics are hard and brittle?
Ans: The ceramics materials are hard and brittle because
they have large number of grains boundaries and therefore
the dislocation motion is stopped and a result the materials
are hard and brittle.
8. Why steel is hard while iron is soft?
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Ans: The steel is hard because in steel the carbon atoms

are placed as a impurity atoms. These atoms make the
steel harder but we know that every element in pure
form is soft. Therefore the iron is soft which is pure
form and steel is harder in which impurity is added.
9. Why some salt (NaCl) crystal are pink color and others
salts of other colors?
Ans: If we consider a natural salt (NaCl) crystal and if
we create a negative ion vacancy in it and for the
charge balance we place an electron in that vacancy
position then as a whole the crystal will becomes neutral.
The electron in this position in now a bound particle and
it can be excited as well de-excited. When the light
suitable wavelength falls upon it then it is excited and
then a de-excitation it gives us the color. Thus we say
the due to this factor some salt (NaCl) crystal have pink
color while other salts are different colors.
Written By: Professor Mr. Iftekhar Ali

Edit & Composed By his Student: Muhammad Darwish.
Contact No: 0346 198 36 30
Email: muhdarwish835@gmail.com
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Ph
 Phonons:
If the crystals have no other types of defects but this defect
is always present in almost all crystals.
As we know that the atoms if solid are vibrating at their
means position or their actual lattice site, so the motion of
atoms will gives us phonons. The vibration of the atoms
increases with increase the temperature. Many properties of the
materials can be easily explained on the basis of spring model
in which atoms are vibrating.
This defect is present almost in all types of crystals.

Contact No: 0346 198 36 30
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P-D
 Point Defects OR Point
Imperfections:
Point defects are zero dimensional defects. Point defects are
the simplest defects which consist of single atom or two
atoms. These defects are present in metallic crystals and ionic
crystals.
The point defects may be of the following types.
 Vacancy Defects
 Self-Interstitial Defects
 Impurity interstitial Defects
 Substitutional Impurity Defects
 Schottky Defects
 Frenkel Defects
 Color Center
Vacancy Defect:
The vacancy is that type of defect
in which we have a neutral atom
missing from a regular lattice site,
such type of point defect is called
“Vacancy Defect”.
Show in the given diagram
is a neutral crystal and missing one negative ion from the
regular lattice site.
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Self-Interstitial
Defect:
If the atoms from the regular
lattice site go and place itself on
the irregular lattice site then this
type of point defect is called
“Self-Interstitial Defect”.
Show in the given diagram the negative ion place itself on the
irregular lattice site (Position).
Impurity Interstitial Defect:
If the impurity atom comes and places
itself on the irregular position of the
lattice site then it is called “impurity
Interstitial Defect”.
Show in the figure.
Substitutional Impurity Defect:
If we have a neutral crystal in
which present a vacancy and a
neutral impurity atom comes to fill
up this vacancy then it is called
“Substitutional Defect”. Show in
figure.
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Schottky Defects:
The combination of an-ions and
cat-ions vacancies (in pair) is called
“Schottky Defect”.
Show in figure.
Frenkel Defects:
The combination of vacancy and
interstitial is called “Frenkel Defect”.
Show in figure.
Color Center:
Sometime we have a neutral ionic crystal from which a
negative ion is removed and for the charge neutrality an
electron is placed on this vacancy then as a whole the charge
on the crystal will be neutral and the electron will acts as a
bound electron which can be excited and de-excited to give a
particular color is called “Color Center”.
Now we will discuss the main two types of point defects
in detail which are Schottky and Frenkel defects.
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S-D
 SCHOTTKY DEFECT:
In any there will be equilibrium number of defects in a
crystal. The schottky defects are mostly present in ionic
crystals.
Let us consider a neutral ionic crystal such as
which have equal numbers of positive and negative ions. The
crystal as whole is neutral. We know that there is always
site for atoms at the grain boundaries. For a certain
vacancy to occur a positive ion must migrate to the surface
of the crystal or grain boundary. If the other positive ion
goes there to accommodate itself on the surface of the
crystal then it will be repelled by the positive ion which is
already existence on the surface crystal. As the negative
charge will be produce inside the crystal. For the charge
neutrality the negative ion will goes to the surface of the
crystal. Such a negative ion vacancy will be produce. Thus
for any number of positive ion vacancies there will be
always equal number of negative ion vacancies. Thus in the
absence of any external force the number of positive and
negative vacancies are equal. So this defect in a crystal is
called “Schottky Defects”.
In other words we can say that, The combination of an-ions
(positive ions) and cat-ions (negative ions) vacancies (in pair) is
called “Schottky Defect”.
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Show in figure.
Let there will be “ ”
number of atoms in a
crystal and let us
consider “ ” be the
number of schottky
defects which are
produced due to the
removal of an-ions and
cat-ions from the crystal
interior. The number of ways in which each kind of ion can
be removed to the surface is given by;
( )( )( ) ( )
( )
( )
Different ways in which “ ” schottky defects can be produced

is obtained by squaring equation ( ) because equation ( ) gives
the number of ways in one ion is removed but in case of
schottky defects we have pair ions (positive ions and negative
ions) which are removed and we say that in case of schottky
defects the positive and negative ions must be equal therefore
we taken the square of equation ( ).
Thus the number of ways in which “ ” number of schottky
defects can be produced is given by;
6 7
( )
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The production of the defects in a crystal increases the

entropy of the crystal. The increase in entropy is given by
the Boltzmann relation;
Putting the value of “ ” in above equation then we will get;
0( )
1 ( )
Where “ ” is the Boltzmann constant.

Its value is
The change in entropy produces the change in the Helmholtz
free energy and is given by;
Putting the value of “ ” in above equation;
0( )
1 ( )
Where “ ” is the energy required to produce a

Sterling
positive and negative ion vacancies and “ ” is the approximation
number of schottky defects and “ ” is the total

energy of the crystal.
0( )
1 0( )
1
0( 1 , * ( ) +-
)
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0( 1 , ( ) -
)
0( )
1 ,
*( ) ( ) ( )+ ( )-
0( )
1 ,
*( ) ( ) + -
0( 1 , ( ) ( )
)
0( 1 , ( ) ( )
)
-
Putting this value in equation ( ) then;
0( )
1 ( )
, ( ) ( ) -
, ( ) ( ) - ( )
At equilibrium position the Helmholtz free energy will be
constant and the derivative of the constant term is equal to
zero and is given by;
. /
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Differentiating equation ( ) and applying above condition then

we will get;
. / . / , ( ) ( ) -
0 ( ) ( ) 1 ( )
Taking first part in the bracket of the equation ( );
( )
Because “ ” does not depend on “ ”.

Taking second part in the bracket of the equation ( );
And applying product rule of derivative;
( ) ( ) ( ) ( ) ( ) ( )
( ) ( ) ( )( ( ) ( )( )
)
( ) ( ) ( )( ) ( )( )
( ) ( ) ( ) ( )
( ) ( ) ( ) ( )
Taking third part in the bracket of the equation ( );

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( )
( )
Putting equations ( ), ( ) and ( ) in equation ( ) we have;
( )
( ) ( ) ( ) ( )
( )
0 ( ) ( ) 1 ( )
, * ( )+ * +-
, ( ) -
, ( ) -
( )
0 1
( )
0 1
( )
Taking anti log on both sides we have;

( )
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At any temperature “ ” as “ ” is so much small as compare

to “ ” then “ ” putting in above equation we will
get;
This is the most important relation which gives us the number

of schottky defects at any particular temperature “ ”.

Contact No: 0346 198 36 30
Think before, you speak or

write.
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 Example:
If we have then calculate the number of schottky
defects in crystal per cubic centimeter at room
temperature ( ).
 Solution:
Given data;
( )
We know that;
putting the above values then;
( )( )
( )
This is the required number of defects in the given crystal.

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F-D
 FRENKEL DEFECT:
This type of defects is produced in a crystal when we
displaced the ions from
the lattice site to the
interstitial position.
This type of defects will
be occur in ,
etc.
When we move the ion
from the own lattice site
to the interstitial position, then in this case a vacancy and
interstitial will be produced in the crystal such type of
defect is called “Frenkel Defect”. Show in the figure.
Let us consider that “ ” be the number of frenkel defects
“ ” be the number of lattice site, and “ ” is the number
of interstitial site in a crystal, then the number of ways in
which “ ” frenkel defects can be produced are given by;
( ) ( )
( )
By Boltzmann we know that entropy is given by;

( )
Putting the value of equation ( ) in equation ( ) we have;
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0( ) ( )
1 ( )
The change in entropy will increase the Helomholtz free energy

and is given by; Sterling
approximation
( )
Putting equation ( ) in equation ( );
0( ) ( )
1
0 ( ) ( )
1
, ( ) ( ) -
, ( ) -
( ) -
, ( ) ( ) ( )
( ) ( ) ( )
-
, ( ) ( )
( ) ( )
-
, ( ) ( )
( ) ( ) -
, ( ) ( )
~ 26 ~
( ) ( ) -
, ( ) ( )
( ) ( ) - ( )
We know that the crystal free energy at equilibrium is given
by;
. /
Now differentiate equation ( );
( ) , ( ) ( )
( ) ( ) -
, ( ) ( )
( ) ( ) - ( )
Taking first and second parts in the bracket of the equation

( );
and ( )
Because “ ” does not depend on “ ” and “ ”.

Taking third part in the bracket of the equation ( );
( ) ( ) ( ) ( ) ( ) ( )
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( ) ( ) ( )( ( ) ( )( )
)
( ) ( ) ( )( ) ( )( )
( ) ( ) ( ) ( )
( ) ( ) ( ) ( )
Taking fourth part in the bracket of the equation ( );

( ) ( ) ( ) ( )
( ) ( )
( ) ( ) ( )( ( )
)
( )( )
( ) ( ) ( )( ) ( )( )
( ) ( ) ( ) ( )
( ) ( ) ( ) ( )
Taking fifth part in the bracket of the equation ( );

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0 1
0 ( )1
, -
, -
, - ( )
Putting equations ( ), ( ), ( ) and ( ) in equation ( ) we

have;
and ( )
( ) ( ) ( ) ( )
( ) ( ) ( ) ( )
, - ( )
, ( ) ( )
( ) ( ) - ( )
, * ( )+ * ( )+
* +-
, ( ) ( ) -
, ( ) ( ) -
~ 29 ~
, ( ) ( ) -
( )( )
0 1
( )( )
( )( )
Taking antilog on both side we have;

( )( )
We know that “ ” and also “ ”, then we have

“ ” and “ ”. Putting these values in above
equation we have;
( )
This equation gives us the number of Frenkel defcets at a
particular temperature “ ”.
At a particular temperature both the Schottky and Frenkel
defects are present in a crystal.
As we know that the Frenkel defects produce greater change
in crystal free enrgy as compare to Schottky defects.
The number of frenkel defects will be always smaller than
that of the number of Schottky defects.
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C-C
 COLOR CENTER:
Most insulator crystals and pure alkali halide crystals are
transparent to visible light. However when irradiated these
crystals appear to be colored due to selective absorption of
some component of visible spectrum by certain imperfection
(defect) which are usually present in the crystal. Thus a color
center is a lattice imperfection which absorbs visible light. The
transmitted beam receive by our eyes contain only the
complimentary colors.
Let us consider a crystal, if there are vacancies of
one constituent of a diatomic crystal, the charge balance occur
either by equal number of
interstitials of the same
constituent (Frenkel) or by equal
number of vacancies of other
constituent (Schottky).
It is also possible that the
missing charging of the negative
ions vacancy is balanced by
electrons located in the vacancy
of point defects.
Such an electron can regarded as bound to an effectively
positive charge center and have a spectrum of energy level.
~ 31 ~
Excitation between these lines produces a series of absorption

lines analogous to those of single isolated atom. They stand
out of a quite string peak in the optical absorption spectrum,
these and such others defects
of electrons structure are
known as “Color Center”.
Now let us consider a
crystal. Consider that there is
a vacancy is produced of that
of the ion. For the
charge neutrality the electron
comes and fills this vacancy
to make the crystal electrically neutral. This electron is
strapped between the positive charges and hence it is bound
particle. This electron act as neutral atom and can be excited
as well as de-excited in the given energy levels. When
radiation of suitable range fall on it then it is excited and
then on de-excitation it gives us the light in the visible range.
There are different methods by which the color center are
produced in a crystal.
In one method such type of crystal can be produced by
exposing these crystals to the X-ray or gamma ray. Similar
type defects in a crystal can also be produced by heating
alkali halides crystals in presence of alkali metals. The alkali
metals are incorporated the crystal but the mass density is
reduced. This shows that the atoms are not absorbed
interstitially. The alkali metals are ionized and taken position in
~ 32 ~
the site of the perfect positively

charge sub lattice. The excess
electrons are bound to an equal
number of negative ion vacancies.
If we consider a neutral crystal in
which every atoms is in its
respective site. If we heat this crystal in vapors then it
will be color center because the color centered will be produced
in it.
If we heat this system in vapors then there will be more
ions than the positive ions and
as a result a positive ions vacancy
will be produced and that positive
ion vacancy will act as a hole. This
trapped hole just like the trapped
electron and it can have discrete
values of energies.
 TYPES OF COLOR CENTER:

There are the following types of color centers.
 F-Color Center:
If the electron takes place of a negative ion in the crystal,
the crystal is colored. This is because the electron which is
bound to the positive center has various energies levels.
~ 33 ~
These levels can be determined by plotting the absorption

spectrum. In this case the light is produced by excitation and
de-excitation of electron and such centers are called “F-Color
Center”.
 M-Color Center:
The presence of a single
electron at the site of the
negative ion is not the only
way to color the crystal but it
is possible in alkali halide the
two negative ions vacancies are
produced in a particle plane such
( ) plane, then the incoming
electron will fill these vacancies and the two electrons will be
bound together. Such types of color center are called “M-Color
Center”.
 R-Color Center:
In this case three electrons are
trapped in ( ) plane and as
a result the “R-Color Center” is
produced.
~ 34 ~
 -Color Center:
If holes are trapped by the negative ions then as a result
the color center which is formed is called “ -Color Center”.
 H-Color Center:
H-Color Center is formed when a single ionized molecule
occupied a negative ion site.
 -Color Center:
The -Color Center in alkali halide is the negative ion
vacancy (which acts as an effective positive charge) which one
excess electron trapped in it. The orbital motion of the trapped
electron is quantized and therefore has a series of discrete
permitted energy levels.
Similarly if we heat up the following crystals in the following
metals vapors. Then before heating they are transparent but
after heating they take a particular color.
( )
is a transparent, heated up in the vapor of .
( )
( )
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BTS-1
 Band Theory Of Solid:
Review of Free Electrons Gas Model:
For metals (solid) we know about the free electrons theory,
according to this theory solids are divided into two categories:
1) Conductors 2) Insulators
The free electrons gas theory was explained by:
1) Maxwell Boltzmann distribution of electrons in the
metals, the distribution is governed by factor ( )
i.e. The distribution is
“ ” is the number of electrons in energy Electrons are consider to
be Classical
level “ ” Particle.
“ ” is the total number of electrons

“ ” is the Boltzmann Constant
“ ” is the Temperature
2) Quantum Mechanics aspect of Electrons are consider to be
Quantum Mechanical
electrons distribution in metals was Fermions. Spin = 1/2
given by
( ) ( ) called Fermi Dirac distribution.
Now some of the phenomena could not be explained by using

free electrons model (theory). Therefore solids are subdivided
into three categories;
~ 36 ~
1) Metals (conductors) 2) Semiconductors 3) insulators

So another theory came into existence which is called “Band
Theory of Solids”.
According to this theory the crystals (solids) can be described
by nearly free electrons model. Where the electrons are
treated as perturbed by the periodic potential of the positive
ions in the solids and these are not distributed continuously in
the solids (from to ).
Study of group 1, 2, 3, & 4 of the periodic table revealed
that the conduction electrons can be observed to move in a
constant potential.
The electrons are actually move freely under these weak
periodic potential, ( ) ( )
“ ( )” is the potential energy and “ ” is the lattice constant.

Now let consider the picture of electrons and positive ions in
crystals (solids) as shown below a more realistic approached.
The electrons are moving in the

positive ions such that there is a
potential “ ( ) ” between two
consecutive lattice points.
Hence there is a periodicity of potential among the ions in
given figure.
~ 37 ~
There is a barrier (potential) between two consecutive ions

(V0) and the potential is zero at
the ions location.
Here
( ) 0 1
The above square well potential idea is known as “Kronig-

Penney Model”.
Now a wave function “ ( ) ” is the helpful to explain

the periodic potential among the positive ions (lattice). In free
electrons model, no potential involve.
 Bloch Theorem:
It is known that in free electrons model, the potential of
electrons in a crystal is zero. The wave function for this is;
⃗ ⃗
( ) (3D)
Where “A” is the amplitude of the periodic potential which is
constant.
~ 38 ~
On the other hand in nearly free electrons theory, the

electrons are moving under the periodic potential and the these
wave function have no constant amplitude, and the total
potential “ ( ) ” has two parts.
1. The electrostatic potential due to array of atomic cores
for a perfect lattice (no phonons). This ensure the
translation periodicity of the lattice.
2. The potential due to all other outer electrons the charge
density from this source have the same average in every
point cell, and is also periodic.
Thus we have consider the potential due to atomic cores. The
Schrödinger equation for this is;
( ) ( )
Bloch argued that the wave function which obey or satisfy the
above equation “( )”, subject to atomic core potential is of the
form;
⃗ ⃗
( ) ( ) ( ) ( )
Where “ ( ) ” is not a constant amplitude but a function of

“ ” which has a complete periodic of the lattice. In 0ne
dimension equation “( )” become;
⃗ ⃗
( ) ( ) ( ) ( )
Thus the Bloch theorem state that; “The Eigen function
“ ( ) ” of the wave equation for a periodic potential is the
~ 39 ~
⃗
product of a plane wave “ ⃗ ” and a function a periodic
potential “ ( ) ” of the periodicity of the crystal lattices.
If “ ” is the lattice constant then;
( ) ( ) ( )
Now if the potential periodic then probability distribution of the

electrons must show the same periodicity i.e. the probability of
finding an electrons will be the same at “ ” and “ ”.
| ( )| | ( )| ( )
( ) ( ) ( )
| ( ) | | ( )| | |
The quantity “ ” can also be express as;

and
| |
So equation “( )” ( ) ( ) ( )
( ) ( )
( ) ( ) ( )
Multiplying by “ ” both side of the equation “6”;
( ) ( )
~ 40 ~
( )
( ) ( ) --->7
From Bloch Theorem,
( ) ( ) ( ) ( ) ---> 8
Similarly;
( )
( ) ( ) ---->9
Put equation “8” and equation “9” in equation “7”;
( )
( ) ( ) --->7
( ) ( )
( ) ( )
Both “ ” and “ ” are periodic of lattice “ ”.
Band Theory of Solids:

Now in order to explain this theory we
consider atoms in the crystal with their
nearly free electrons in the crystal
order in one dimension.
As shown in the diagram.
The electrons with in the lattice site are under the periodic
potential.
( ) ( )
For simplicity we consider the square well potential. This

square well potential idea is called “Kronig-Penney Model”.
~ 41 ~
Here “ ( )” is define as;
( ) 0 1 -->A
Now the wave function for the electrons is;
( ) ( ) -->1 “Bloch equation”

“ ( )” is a variable function (Amplitude) and is a periodic i.e.
( ) ( )
The Schrödinger equation for this is;
( ) ( ) ( ) ( )
Time independent Schrödinger equation.
( ) ( ) ( ) ( )
( ) ( ) ( ) ( )
( ) [ ( ) ] ( )
We apply this equation on the basis of equation “A”;
( ) ( ) ( )
[ ]>2
( ) , - ( ) ( )
( )
Let
Now equation “2” becomes;
~ 42 ~
( ) ( ) ---- > 3
( ) ( ) ------- > 4
In order to solve the equations “3” and “4”. We let the
Kronig-Penny wave function;
( ) ( ) --------- > 5
Taking derivative of the above equation with respect to “ ”;
( ) [ ( ) ] applying product rules
( ) ( ) ( )
( ) ( )
Taking again derivative of the above equation with respect to

“ ”;
( ) 0 ( ) 1 applying product rule
( ) ( )
( ) ( )
( ) ( ) [ ]
Re-arranging of the equation then;
( ) ( )
~ 43 ~
Taking “ ” as a common of the above equation then;
( ) 0 ( )1 --->6
( ) ( ) --->5
Put equations “5” and “6” in equation “3” and replace
“ () ”
( ) ( ) ---- >3
20 1 3
Taking “ ” as a common of the above equation then;
20 13
Dividing both side by “ ” we get;
0 1
( ) ---> 7
Similarly equation “4” and replace “ ( ) ”
( ) ( ) ------- > 4
( ) -->8
Now general solution of equation “7”;
( ) ( )
-->9
~ 44 ~
And general solution of equation “8”;

( ) ( )
->10
Where “ ”, “ ”, “ ” and “ ” are constant and can be
evaluated by boundary condition.
Boundary Condition
Put “ ” in equations “9”;
( ) ( ) --- > a
( ) ( )
| | -- > b
Also due to periodicity
( ) ( ) ---- > c
| | ---> d
( ) ( )
Now applying boundary condition “a” in the given box;
( ) ( ) put the values of “ ” and “ ” then;
---->11
Differentiate equation “9” with respect to “ ”
( ) ( )
( ) ( )
( ) ( )
Now put “ ” then

( ) ( )
( ) ( )
~ 45 ~
( ) ( )
Now Differentiate equation “10” with respect to “ ”

( ) ( )
( ) ( )
( ) ( )

( ) ( )
( ) ( )
( ) ( )
Now applying boundary condition “b” in given box;
| | Now put the values of “ ” and “ ”

then;
( ) ( ) ( ) ( )
( ) ( ) ( ) ( ) -->12
( ) ( )

( )( ) ( )( )
( ) ( )
Now applying boundary condition “c” in given box;

~ 46 ~
( ) ( )
( ) ( ) ( ) ( )
( ) ( ) ( ) ( )
--->13
Differentiate equation “9” with respect to “ ”
( ) ( )
( ) ( )
( ) ( )

( ) ( )
( ) ( )
Now Differentiate equation “10” with respect to “ ”

( ) ( )
( ) ( )
( ) ( )

( )( ) ( )( )
( ) ( )
( ) ( )
( ) ( )
Now applying boundary condition “d” in given box;
| |
~ 47 ~
( ) ( ) ( )
( ) ( ) ( )
( )
( )
( ) ( ) ( )
( ) ( ) ( )
( )
( ) -- > 14
------- > 11
( ) ( ) ( ) ( ) ->12
( ) ( ) ( ) ( )
-->13
( ) ( ) ( )
( ) ( ) ( )
( )
( ) -- > 14
In order to solve equations “11, 12, 13 and 14” we apply

determinant method in math as i.e. the determinant of co-
efficient of “A, B, C and D” in above box;
1 1 1 1
i(  k )  i(  k )  i(   ik ) i(   k )
i (  k ) a
e e i (  k ) a  e i (  ik )b  e i (  ik )b
i(  k )e i ( k ) a  i(  k )e i (  k ) a  i(   ik )e i (  ik )b i(   ik )e i (  ik )b
Now solving “4x4” determinant we get;
( )---->15
~ 48 ~
So the above equations satisfy the square wave pattern of

periodic potential.
In order to simplify equation “15” Kronig-Penny assumed that
if but and
( )
from equation “2”
( )
, -
, -
, -
If “ ” is
very very
small then;
from equation “15”
, , and
Put above values in equation “15”
( )---->15
( ) ( )
Multiplying & Dividing “ ” with first term in the above

equation;
~ 49 ~
{let an important
parameter} then;
------>Sixteen “16”
Equation “Sixteen 16” is very

important equation to describe the
Band structure of the electrons in the
crystal.
is called “Scattering
Power Strength”.
is called “Potential Barrier Strength”.
= The energy variable.
Let plot R.H.S against “ ” of equation “16” and L.H.S is
“ ”,
So it is clear from the given figure, that the electrons are
allowed to stay in energy band between “ ” and “ ” and
so electrons bound between energy bands and are not exist in
forbidden gap.
~ 50 ~
Case No: 01
For
The energy band is very narrow and
potential barrier strength ( ) is
very high and electrons cannot cross
the barrier also called “tight binding”.
 Proof Mathematically
if [“ ”] then;
, shows
that;
Factor
n = ±1, ±2, ±3.…….
0 1 ------ > a
Also we know that from equation “2”;
----- > b
Compare equation “a” and “b” then
0 1
~ 51 ~
This equation is similar to the energy in potential well and

electrons cannot move out of the well. 0 1
Case NO: 02
For
( ) will be weak energy band will
be wide enough to touch together i.e.
free electrons will be allowed
everywhere and energy will be
continuously distribution.
Energy gap (forbidden energy gap) 0
and energy band is very wide and over
lapping each other shown in figure.
 Proof Mathematically
If then;A
(0)
------ > a
Also we know that from equation “2”;
------- > b
Compare equation “a” and “b” then
~ 52 ~
0 1 here
0 1 0 1 here
here
( )
here
This is the kinetic energy of free particle (electrons). Hence

free electrons are allowed everywhere and energy is
continuously distribution.

Contact No: 0346 198 36 30
~ 53 ~
E-K-1
 Energy Verses Wave Vector Graph
Graph:
It is known that energy of electrons in crystal depends on
the ionic potential. In this case “ ” relation is very
important.
The electrons in the crystal are not free and are under the
periodic potential, what then will be the concept of mass of
electrons, velocity, momentum etc. whether these are constant
are not.
The mass is not constant and called effective mass “ ” and
it may negative. Now for free
electron.
Now for free electrons where

Here mass of
electrons is
constant in
the plotting is as under; equation;
In the graph seen that the energy of electrons

will be continuously increases with no gaps. Hence
energy “ ” continuously distributed and all
values of wave vector “ ” are allowed.
But in contradiction with free electrons.
The value of “ ” does not take all possible
value but some discrete allowed values under
equation;
~ 54 ~
----------- > 1
The allowed value of “ ” are

As for
Now “ ” vs “ ” relation is plotted shown in
figure;
The graph shows that the energy “ ” is allowed allowed
in some value of “ ” i.e.

gap 0 1 and then
energy “ ” not allowed
for some value of “ ” on
vertical axis and then again
allowed energy “ ” on
positive “ ” 0 1.
Similarly on negative allowed “ ” 0 1.
The gap between 0 1 is called “First Brillion Zone”.

That is this allowed area is a chemical unit cell (the Winger-
Sietz Unit Cell).
Also the gap between 0 1 is “Second Brillion Zone.”
The figure is the extended zone which consist of all zones of

allowed “ ” levels.
0 1 1stzone. And 0 1 2nd zone and so on.

~ 55 ~
But the picture may be

reconstructed to form reduce
zone, as shown in the figure.
Now for a finite size of a
crystal; let length of crystal
along one dimension is “ ”.
So number of lattice points then;
Then or
So the number of value of “ ” with in first zone where
So there are “ ” of “ ” i.e. there is a “ ” number of

wave function (E- state).
Hence the number of wave function or number of energy state
represents the number of unit cell and so there will be much
number of free electrons available’
So real crystal the size is finite and “ ” have specific value;
specific energy “ ” and wave function “ ” it form allowed
bands.
~ 56 ~
And some values of energy “ ” are missing in “ ” vs “ ”

graph. So no wave function, no lattice points and no free
electrons (it form forbidden energy bands).
For free electrons the energy is . The mas,

velocity and momentum are classical.
While in band theory the electrons move under periodic
potential due to which the velocity,
momentum and even mass of the electrons ( ) ( ) Periodic plot
Bloch theorem:
in crystal is effect.
( )
( ) ( )
Now the number of wave functions in a ( ) ( )
band of a finite crystal of length “ ” is;
( )
== >
And “ ”
== >
But in 1st Brillion zone
Maximum values.
So the number of wave function
Number of unit cell in the
finite crystal
one primitive cell
two primitive cell
two primitive cell
~ 57 ~
.
.
filled.
Now if the “N” primitive cell consist one atom has one
electron ( ̅ )
and each energy level has two electrons ̅ ̅ .
So the first Brillion zone is half filled.
If the “ ” primitive cell consist of one atom has two
electrons ( ̅ ) i.e. the Brillion zone the energy level will be
fulfilled.
Also if the primitive cell consist of two atoms having one
electron ( ̅ ) the energy level in the band is also fulfilled.
Therefore the half-filled are called metals conductor, which
fulfilled are insulators but if we apply
(Temperature) and then fulfilled becomes
semiconductors.
~ 58 ~
 Motion (Velocity) of Electrons in Band

(Crystal):
We know that the electrons are free to move inside
conductors under classical free electrons theory. This energy is
.
But in case of band theory (under the influence
Classically:
of periodic potential) the electrons are moving ( ) ( )
here
in groups and is called “Group Velocity” and is amplitude is fixed and
“ ” is called
given by; phase and it is constant.
= constant
----- > 1 called phase

velocity;
In the case of band;
both “ ” and “ω” are not constant.
Such that
Graphically group velocity is given in following figure.
Now as
~ 59 ~
From equation “1”; ----- > 2
Now looking into “ ” and “ ” relation;

Nothing the change in “ ” ( ) verses in “ ” ( ) we can
guess about “ ”.
Classically free electrons;
Consider first Brillion zone “ ” from
== > a
equation “1” shows that “ ” is the
== >
slop of “ ” curve. So in a band
at the bottom ( ) the velocity is put this in equation “a”
zero (slop=0) == >
In the mid of the band velocity is where “ ” and “m” are constant then;
maximum (slop=maximum) and at the top . shown the given figure.
again (slop=0) as shown in the given

figure.
~ 60 ~
 Effective Mass of Electrons in Crystal

( ):
We know that the velocity of electrons when it is in band is
given by;
--- > a
When a force is applied from the electric field it accelerate
the electrons;
----- > b where “ ” is the electric field intensity.
Taking derivative of equation “a” with respect to “t”;
0 1
R.H.S multiplying and dividing by “dk”
and then;
---- > c
( )( )
and , distance then;
( )( )
Now put “ ” in above equation;
Divided by “ ” of the above equation;
Now multiplying both side by “ ” then;

~ 61 ~
Classically free model:

== >
== > –
1
0 1
Now multiplying both side by “ ” then; Put the value of equation
“1” in above equation;
0 1
0 1
put this value in
equation “C” So mass is constant.
---- > c
---- > d
Now --> e
Comparing equation “d” and “e” then;
0 1
This is called effective mass of electrons
in a band.
Classically the mass electrons in crystal is constant which is
equal to ( ).
~ 62 ~
But in band theory mass of electrons is not constant but a

variable one and it may be negative as well.
0 1 give us curvature or concavity of “ ” graph.
The mass “ ” is positive before the inflection the curvature

is positive.
While after inflection the mass of electron is negative.
It means that electrons are when at the top of band its
mass of electrons “ ” is negative. Actually when electric
field “ ” is applied to electrons in the band its velocity “⃗ ”
increases until inflection point. But then start decreases here
some deceleration appear and so some retarding force is in
action and the electrons becoming positive starting moving back.
Their velocity becomes zero at the top of band at this stage
the positive behavior of electrons is known as “Hole”.
And electrons with the positive and “ ” becomes negative
and decelerated toward point of inflection.
shown the given previous figure (C);
Conclusion:
At the top of the band the retarding
electron means negative mass “ ” and
negative charge and the same absent
electrons is called “Hole”(positive mass
and positive charge).This gives the concept of semiconductor with
“Electrons” and “Hole”. (Pentavelant and trivalent respectively).
~ 63 ~
DSF-1
 Density of State & Fermi Surface:
Let have a three dimension box of solid
has length “ ” and volume
“ ” and we have “ ” number of
electrons in the box;
̅
Hence the wave function describing the
system will be;
⃗ ⃗
( ) --------- > 1
( ) | |
Schrödinger’s equation for this is;
( )
0 1 ( ) ( ) ---->2
[ ( ) ]
[ ( ) ]
( ) ----- > 3
[ ]
( ) --------- > 4
Also ( ) ( ) [condition of periodicity]
[ ( ) ] [ ]
, ( )-
, ( )-
~ 64 ~
Similarly ,
, and ⃗ ⃗ ⃗ ⃗
Now equation “4”;

[ ]
( ) ------>4
Taking double derivative of equation “4” with respect to “ ”,
“ ” and “ ” and then add we get;
[ ]
0 1 ( ) , - ->5
Put equation “4” and “5” in equation “2”;
0 1 ( ) ( ) ---- > 2
[ ] [ ]
2 , - 3
[ ] [ ]
, -
[ ]
[ ]
Similarly ,
Put these values in above equation;
~ 65 ~
[. / . / . / ]
. / [ ]--->6
Now;
Here we have a -Space (sphere) having
radius “ ”.
So for a particular set;
Similarly ,
We have allowed sphere of volume; 0 1
While the volume of K-Space is;
So number of orbitals
0 1 Each orbitals
have two
electrons as;
And the number of electrons in such orbitals
[ ] [ ] [ ]
0 1
6 7 as , -
[ ] 0 1
0 . /1 ---->AB
~ 66 ~
So the Fermi Energy will be; put the value of

“ ” in this equation
0 . /1 ----- > 7
0 . /1 ---->AB
Hence both Fermi sphere “ ” and Fermi “ ” depend on 0 1

i.e. electrons density (concentration).
⃗⃗ ⃗⃗ ⃗⃗ ( )
⃗⃗ ( )
⃗ ( )
⃗⃗ ⃗
 Density of State:
The density of state is the number of orbitals (electrons) per
unit energy range at the Fermi level (Fremi sphere)
represented by;
( ) ---- > 1
Where “ ” is the number of orbitals consist twice electrons
( ).
As at the Fermi Level; [ ]

0 1
Now from equation “7”; 0 . /1 ----- > 7
0 1
~ 67 ~
0 1
0 1
0 1 [ ] ----- > 2
Now taking derivative of the above equation with respect “ ”;
8 0 19
0 1 [ ]
0 1 [ ]
0 1 [ ]
Now From equation “1”;
( )
( ) 0 1 [ ]
( ) [ ] where 6 0 1 7 is constant.
~ 68 ~
( ) √
From the graph all orbitals with in the
Fermi level are filled.
Now from equation “2”;
0 1 [ ] ---- > 2
Taking “ ” of the above equation.
{ 0 1 [ ]}
0 1 [ ]
[ ] 8 0 1 9 is constant.
Now taking derivative of the above equation with respect “ ”;
0 1
Dividing both side by “ ” and multiplying “ ” then;
and from equation “1” 0 ( ) 1 now;

~ 69 ~
( ) ----- > 3
Here we are dealing with low temperature “ ” the levels

are gradually filled to Fermi level. It is called “the down
state distribution.”
Now let temperature increases from “ ” to “ ”.
The levels are set to fill according to Fermi Dirac distribution
which is given by;
( ) ( ) -----> A
The probabilities to stay the electron in a particular level

(state).
Here “ ” is variable called energy level and “ ” is Fermi
energy level.
 Case No:1
Now at low temperature “ ” then;
If “ ” then
Now equation “A” ( ) ----- A
( ) ( )
So level is filled.
~ 70 ~
 Case No:2
Now at low temperature “ ” then;
If “ ” then
Now equation “A” ( ) ----- A
( ) ( )
So level is filled.
 Case No:3
If “ ” then the “ ( )” is undefined, so there is
discontinuity. Shown in figure.
Do Good And Forget It.

~ 71 ~
FET-1
 Free Electrons Theory Of
Metals (Solids):
 Introduction:
The thermal and electrical powers of solids (metals) are
determined by conduction electrons gas
with in the ionic.
Conduction electrons gas is subjected to
Pauli-Exclusion Principle.
So satisfy Fermi Dirac distribution and
Boltzmann distribution.
Electrons gas in metals are such that if there is energy level
occupied by electrons then there is no other electrons to occupy
this level that is called the Pauli-Exclusion Principle.
Electrons gas satisfy Fermi Dirac distribution.
At Fermi level the thermal excitation of free electrons can
contributed to specific heat
and
Total contribution of electrons in specific heat ;
So Conduction (electrons)
~ 72 ~
This imply that electronic specific heat =
“ ” = electronic heat capacity co-efficient.

and
Total specific heat =
------------------ -------------- ---------
----------- ----.
Now metals are very good
conductors of current ( ). If there is no field then electrons are in
random motion and not form current(I)
because they cancel the effect of each
Hence let conduction electrons gas in other. As the average distance to a
the metals and apply an electric field particular velocity is zero.
no current density.
“ ”.
________________________________________
The electron of mass “m” and If electric (E) is apply it exert force on
charge“e”. electrons to move and covering net distance
and with same velocity called “Drift
Velocity” ( ).
Apply electric field “ ”.
“ ” is the charge of electron.

----- > 1
And --- >2

Compare equations “1” and “2” then;
----- > 3
~ 73 ~
This theory was 1st proposed by “DRUDE”.
Now from equation “3”
Taking integration of the above equation;
∫ ∫ ------ > 4
So put the value of “ ”
0 1 ----- > 5
Now where electrons gas move under electric field “ ”

scattering and retarded by ions. As the ions are vibrating they
act as a scattering center for moving electrons gas.
The vibrating positive ions are generated energy called
“Phonons”.
Now the scattering of electrons gas from phonons must be
take into account where we calculate ( ).
Here the entire moment of electrons gas is relaxed back due
to reflection (scattering). So there is net drift velocity “ ”.
The relaxation is done in the time “ ” is called “Relaxation
Time” and it is represented by “ ” and is given by;
relaxation time .
~ 74 ~
On the basis of free electrons theory there are some

assumptions which are given the following;
 Electrons in metals make collisions with each other as a
result they scatters in a straight line(in the absence of
electric field “E” and magnetic field “B”)
 During collisions they interaction with other electrons and
ions(positive medium) are neglected.
 The mean free time between collisions is “ ” and is
independent of the position and velocity of the
electrons.(and the probability of collision per unit time is
0 1).
 Electrons achieved thermal equilibrium in collisions with
lattice atoms. They emerge after collisions at random
directions with speed appropriate to the temperature of the
region where collisions occur. High the temperature high will
be the speed of emergence.
Soon after J.J Thomson discovered 0 1 ratio 1898, DRUDE in
1900 assumptions above proposed a model of electrons gas.
Which was further worked out by LORENTZ, it shows how
electrical conductivity occur in metals (solids).
~ 75 ~
 DRUDE MODEL & LORENTZ:

According to Drude and Lorentz metals contain free electrons
in the form of gas wandering around.
Let for simplicity a rod of a metal has electric charge “ ”
and electric field intensity “ ”. The force applied on the
charge “ ” is given by ⃗⃗
Therefore ⃗⃗ ---- > A
That is electrons “ ” will be accelerated by the applied of

electric filed “ ”. Shown in figure.
Equation “A” indicates that by applying “ ” which is constant

and charge of electrons , - and mass of electrons
, - are also constant.
Then there will be change in velocity “⃗ ” as the time goes

on.
But actually it not happened , actually electrons “ ” gain
velocity “⃗ ” and is control by positive ions and electron gas
so there as a resistive medium then equation “A” becomes;
⃗⃗
⃗ ---- > A ⃗ ---- > *
⃗ ---- > B
~ 76 ~
In equation “B” “ ⃗⃗ ” is constant force. So in the quantity

“ ”, the velocity is controlled by “ ” which is the resistive
factor of electron collisions.
Now let the net force ( ) on the electrons is zero then

the velocity will be constant then equation “B” becomes;
⃗ ⃗⃗
So like terminal velocity will be constant
and gain maximum value which is called final
put this in equation “B”; velocity.
⃗ ---- > B
⃗ ( )
( ) ( )
By separable variable;
4 5
Now taking integration both side and limit ( ) and

( );
∫ ∫
4 5
( )
∫ ∫ ∫
4 5
~ 77 ~
4 5
( )
( ) ( ) ----- > D
Now from first equation of motion;

⃗⃗
and {⃗ }
( )
( )
where “ ” is a relaxation time the mean free time between

collisions.
Now equation “D” is;
( ) ( ) ----- > D
( ) . / [ ]
( ) ./
Now taking anti log;

~ 78 ~
( )
( ) 0 1 ------ > E
This equation shows that “ ( ) ” is a function of time at

“ ” “ ” (initially the electrons are at rest)
{ ( ) , -} ( )
And “ ” (longer time) [ ] Linear velocity. Practically

, -
Now the current density is “ ” and
the charge carriers are electrons “ ̅ ”.
So the number of free electrons per
unit volume;
̅
The velocity with which charges are transported =

So current density “J” is given by;
̅
put in above equation;
. /̅ ( )
~ 79 ~
( ) ----- > F = >
Where ( ) is electrical conductivity.
Now “ ” (electron gas).

= >
put in above
These free electrons are contributed one atom i.e. equation.
atoms each contributions one electron. ⃗ = >

⃗⃗⃗
(While ideal gas ).
⃗⃗⃗
Also ̅ , , i.e. current density=
Electric field
Conductivity.
putting these values to find

“ ”
( )
( ) 4 5
( )
Hence metals (solids) are conductors on the basic having free
electrons gas.

Contact No: 0346 198 36 30
~ 80 ~
DPS-1
 Dielectric Properties of Solids:
Dielectric Property of Solid is the Response of
Solids (insulators) to the Applied Electric Field “E”.
It is known that insulators have no free electrons and so
when external electric field is applied, it dominates the internal
electric field of the solids (insulators) and distort the internal
energy (Nucleus and Electrons). The give rise to dipoles and
hence the materials are polarized. The material is electrically
neutral but produced electric field both outside and inside.
Dielectric Materials:
1. In solid the dielectric (insulator) the electrons are tightly
bound to their parent atoms.
2. Charge separation takes place, in the presence of electric
field.
3. These are neutral but produce electric field both inside and
outside the sample.
 Some materials have naturally occurring in the shape that
there is little separation between the positive and negative
center. There are called “Permanently Dipoles Materials”.
~ 81 ~
 And there are some materials, where positive and negative

center coincides. However if the electric field is applied; the
change occur and the positive and negative charge
separated called “Induced Dipoles Materials”. So charge
separation happen only in the presence of electric field.
Any way both types are electrically neutrals and produce their
own electric field outside and inside.
The materials become of the “Dipole” nature.
Let consider a sample of solid state in which there is a small

spherical charge distribution due to dipole.
Let calculate the electric field “E” and electric potential “V”
due to polarization at point “P” where is at “ ” from the
arbitrary origin and charged body is at “⃗⃗⃗ ” from the origin.
Shown in given the figure.
Now we know that the potential at
point “P” the distance “⃗ ” is given by;
( )
And volume charge density is;

~ 82 ~
∫ put in above equation then;

( ) ∫
Now from the figure;
(⃗⃗⃗ )
∫ ( ) ------ > A
|⃗ ⃗⃗⃗ |
Now we know that; Law of Cosine;
⃗⃗⃗
| ⃗⃗⃗ | ( )
⃗⃗⃗
| ⃗⃗⃗ |
. /
Taking “ ” as a common from denominator

in R.H.S
⃗⃗⃗
| ⃗⃗⃗ |
( ) 4 5
Higher term will be neglected i.e.
⃗⃗⃗
| ⃗⃗⃗ |
4 ( ) 5
⃗⃗⃗ |
[ . / ] Now from Binomial Series;
|⃗⃗⃗
( ) ( )( )
( )
~ 83 ~
⃗⃗⃗ ⃗⃗⃗ |
8[ ( . / )] [ . / ] 9
|
Higher term “. / ” will be neglected then we get;
⃗⃗⃗ ⃗⃗⃗ |
[ ( )]
|
⃗⃗⃗ ⃗⃗⃗ |
( )
|
⃗⃗ ⃗⃗
Also we now that; ⃗⃗ ⃗⃗
⃗ ⃗⃗⃗
Now from the figure; [ ] put this in above equation;
⃗ ⃗⃗⃗ ⃗ ⃗⃗⃗
⃗⃗⃗ ⃗⃗⃗ |
( ) 4 ( ) 5 ⃗ ⃗⃗⃗
|
⃗ ( ) and
⃗⃗⃗
.⃗ ⃗⃗⃗ /
( )
⃗ ⃗⃗⃗
⃗⃗⃗ |
( )
|⃗⃗⃗
Taking LCM “ ”, R.H.S then;
⃗ ⃗⃗⃗ .⃗ ⃗⃗⃗ /
⃗⃗⃗ ⃗⃗⃗ |
[ ]
|
⃗ ⃗⃗⃗
⃗⃗⃗ ⃗⃗⃗ |
0 (⃗ ⃗⃗⃗ ) 1--->B
|
Where (⃗ ⃗⃗⃗ ) ( )
~ 84 ~
⃗ ⃗⃗⃗ ∑
Similarly ; ∑ ∑
Where 4 5
Now equation “B” becomes;

⃗ ⃗⃗⃗
⃗⃗⃗ ⃗⃗⃗ |
0 (⃗ ⃗⃗⃗ ) 1----> B
|
⃗ ⃗⃗⃗
⃗⃗⃗ ⃗⃗⃗ |
∑ ∑ ∫( ) ( )
|
Put above value in equation “A”;
(⃗⃗⃗ )
∫ ( ) ⃗ ⃗⃗⃗ ------ > A
| |
(⃗⃗⃗ )
⃗ ⃗⃗⃗
∫ ( )[ ∑ ∑ ∫( ) ( )]
⃗
(⃗⃗⃗ )
, ∫ ( ) ∫ ⃗⃗⃗ ( )
∑ ∑ ∫( ) ( ) -
 1st Term;
(⃗⃗⃗ )
0 ∫ ( ) 1 1st term
~ 85 ~
If “r” is very, very large then point “P” is far away and
the sphere body is act as point charge.
 2nd Term;
⃗
(⃗⃗⃗ )
0 ∫ ⃗⃗⃗ ( ) 1 2nd term
This term contain “ ” etc. called dipole moment and we are

interest in this term which explain in detail.
 3rd Term;
(⃗⃗⃗ )
0∑ ∑ ∫( ) ( ) 1 3rd term
This term is called “Quadruple”.

Dipole
 2nd Term;
⃗
(⃗⃗⃗ )
0 ∫ ⃗⃗⃗ ( ) 1 2nd term
And
⃗
(⃗⃗⃗ )
0 ∫ ⃗⃗⃗ ( )1
Dipole
moment
⃗
⃗
(⃗⃗⃗ )
0 ⃗1
Where “⃗ ⃗ ” dipole moment.

Potential due to dipole.
Now as our discussion is on “Dielectric
Property”. So neglect 1st and 3rd terms and
consider only 2nd term i.e.;
~ 86 ~
⃗ ⃗
(⃗⃗⃗ )
0 1---->C
So we have a small volume element due to charge separation.

Small volume has net dipole moment and so have a polarization
vector.
⃗⃗ ∑⃗
Where “⃗⃗ ” Polarization vector and is define as the total dipole

moment per unit volume.
So the potential due to dipole is;
⃗⃗ .⃗ ⃗⃗⃗ /
(⃗⃗⃗ )
∫ ⃗⃗⃗ ⃗⃗⃗⃗⃗|
|
⃗⃗ .⃗ ⃗⃗⃗ /
(⃗⃗⃗ )
∫ ⃗⃗⃗ ⃗⃗⃗⃗⃗| ⃗⃗⃗ ⃗⃗⃗⃗⃗| ̂
⃗
unit vector.
| | | |
⃗
⃗⃗ ⃗⃗⃗
( ⃗⃗⃗ )
(⃗⃗⃗ )
∫ ⃗⃗⃗ ⃗⃗⃗⃗⃗| | |
| =
̂ ̂
⃗⃗ And
(⃗⃗⃗ )
∫ ⃗⃗⃗ ⃗⃗⃗⃗⃗|
(̂) ⃗⃗ (
| ( )⃗ ) (⃗⃗ ( )) ⃗ ( ) (⃗⃗ ⃗)
Commutative property
(̂)
(⃗⃗⃗ )
∫ ⃗⃗ ⃗⃗ ( ⃗ (⃗⃗ ( ) (⃗⃗
|⃗⃗⃗ ⃗⃗⃗⃗⃗| ( )⃗ ) ( )) ⃗)
⃗⃗ ( ( )⃗ ) ( ) (⃗⃗ ⃗) ⃗ (⃗⃗ ( ))
(⃗⃗⃗ )
∫ ⃗⃗ ⃗⃗⃗⃗⃗|
--->D
|⃗⃗⃗ ⃗ (⃗⃗ ( ))
⃗⃗ ( ( )⃗ ) ( ) (⃗⃗ ⃗)
⃗⃗
(⃗⃗⃗ )
[∫ ⃗⃗⃗⃗ ⃗⃗⃗ ⃗⃗⃗⃗⃗|
|
∫ ⃗⃗⃗ ⃗⃗⃗⃗⃗|
(⃗⃗⃗⃗ ⃗⃗ ]
|
~ 87 ~
From divergence theorem;
∫⃗ ̂ ∫ ⃗⃗ ⃗⃗ then;
⃗⃗ ̂
(⃗⃗⃗ )
[∫ ] [∫ ⃗⃗⃗ ( ⃗⃗⃗⃗ ⃗⃗ ) ]
| ⃗⃗⃗⃗⃗|
⃗⃗⃗ | ⃗⃗⃗⃗⃗|
[ ⃗⃗ ̂ ] and [ ⃗⃗⃗⃗ ⃗⃗ ] now above equation

becomes;
(⃗⃗⃗ )
[∫ ⃗⃗⃗ ⃗⃗⃗⃗⃗|
] [ ⃗⃗⃗ ⃗⃗⃗⃗⃗|
]
| |
Where “, ⃗⃗ ̂ - ” surface charge density due to dipole

moment called bound surface charge density and is equal to
normal component of polarization vector “⃗⃗ ” and;
“[ ⃗⃗⃗⃗ ⃗⃗ ]” volume charge density due to dipole called

bound volume charge density and is equal to the divergence of
polarization vector “⃗⃗ ”.
⃗⃗ ̂
So 6 7------- > A-1
⃗⃗⃗⃗ ⃗⃗
The given figure shows the divergence of

polarization “ ” and is volume charge
density.
⃗⃗⃗⃗ ⃗⃗
The given shows the surface charge
density and
~ 88 ~
⃗⃗ ̂
So equation “A-1” shows that the effect of Maxwell’s Equations:
⃗⃗ ⃗⃗ -->1st
dielectric is essentially given by a collection of ⃗⃗ ⃗⃗ --->2nd
volume charge density “ ” and surface charge ⃗⃗ ⃗
⃗⃗
-> 3rd
⃗⃗
⃗⃗ ⃗⃗⃗
density “ ”. ->4th
Maxwell’s Equations in Dielectric

⃗⃗ ⃗
Medium:
-- > D
And;
The Maxwell’s Equation for electric field “E” is;
⃗⃗ ⃗⃗
⃗⃗ ⃗⃗ ⃗⃗ ⃗⃗ --> A-1
For dielectric medium;

⃗⃗ ⃗⃗
⃗⃗ ⃗⃗ ----->E
Where “ ” is replaced by two surface densities.

1. “ ” is the surface charge density due to free
charges.
2. “ ” is the surface charge density due to bound
charges i.e. due to dipole charges.
Now we taken an auxiliary vector “⃗⃗ ” which is called
“Displacement vector” and define as;
⃗⃗ ⃗⃗ ⃗⃗ { ⃗⃗ and ⃗ are different }
~ 89 ~
Taking divergence of the above equation then;

⃗⃗ ⃗⃗ ⃗⃗ ⃗⃗ ⃗⃗ ⃗⃗
Put equation “E” in above equation then; ⃗⃗⃗⃗ ⃗⃗
⃗⃗ ⃗⃗ [ ] , -
⃗⃗ ⃗⃗
⃗⃗ ⃗⃗ ------->F
So the Maxwell’s equation for “⃗⃗ ” is such that the divergence

of “⃗⃗ ” is equal to the free charge density with in dielectric.
Consider the integral form of Maxwell’s equation
is; ∫
∫ ⃗⃗ ⃗⃗ ∫
{Divergence theorem}
∮ ⃗⃗ ̂
Note that the vector “⃗⃗ ” is attached with free charge density
{⃗⃗ ⃗⃗ } while “⃗ ” is attached with bound charge density
and free charge density
2⃗⃗ ⃗⃗ 3.
~ 90 ~
 Solved Problem:
The total charge in the dielectric is always zero i.e.
Solution;
∫ ∮
Divergence theorem;
∫( ⃗⃗ ⃗⃗ ) ∮ ⃗⃗⃗ ̂ ∫ ⃗⃗ ⃗ ∮⃗ ̂
∮ ⃗⃗ ̂ ∮ ⃗⃗⃗ ̂
And;
⃗⃗ ⃗⃗
⃗⃗⃗ ̂
Hence there is no net charge inside the dielectric

materials.
Dielectric Constant:
There are a clause of materials called “Linear dielectric
materials” in which the polarization vector “⃗⃗ ”
∑⃗
0⃗⃗ 1 is directly proportional to the
electric field “⃗ ” i.e.;
⃗⃗ ⃗⃗ or ⃗⃗ ⃗⃗
~ 91 ~
⃗⃗ ⃗⃗
= Dielectric Susceptibility and is
Also ⃗⃗ ⃗⃗ ⃗⃗ given by;
⃗⃗ ⃗
put the value of “⃗⃗ ” then; ⃗⃗
= ⃗⃗
⃗⃗ ⃗⃗ ⃗⃗
⃗⃗ ⃗⃗ ( )
⃗⃗ ( )⃗
⃗⃗ ⃗⃗ where ( )
⃗⃗ ⃗ where
The term “( ) ” is called “Dielectric Constant” pronouns

“kappa” and “ ” is called “Permittivity of medium”.
Dielectric constant is also called relative permittivity “ ”;
So
Where “ ” is the permittivity of medium as compare with

vacuum.
~ 92 ~
CMR-1 [Dielectric-1]
 Clausius Mossotti Relation:
Let us consider a dielectric material
placed between into two oppositely
charge plates as shown in figure.
The applied electric field “ ” then the
material will get polarized (converts into
dipoles) such that “ ” is the electric
field due to dipole at the surface of
the material.
Now let consider a small volume (sphere) of radius “r” inside
the material which experience an electric field “ ” due to
polarization at its surface. The magnitude of the resultant
electric field is less than the applied electric field i.e. .
Then the resultant electric field due to applied electric field and
polarized material is “ ” called macroscopic field.
---- > A
“ ” is the applied electric field.
“ ” is the electric field due to polarization of the material
at the surface.
“ ” is the electric field due to outer charges of the sphere
inside the material. “ ” is the electric field due to the
interior of the small sphere usually “ ” (due to symmetry
of the sphere).
~ 93 ~
[Dielectric-2]
So the local electric field will have four (4) component the
last to “ ” is known as “Lorentz Force (Field)”.
So equation “A” is ---- > A
0 1
---- > B {from the given box}

Now we have to calculate the interior electric field “ ”. It
is clear that; ⃗⃗⃗ ̂ And surface charge density
is;
Now from the solid geometry (sphere).

put this value in
above equation is;
( )
( )
= ( ( ))
Now the electric field due to spherical = ( ) ( )
interior has two components “ || ” and =
“ ”. So “ || ” is inside the direction of :.
“ || ” which is calculated now. So And
So || ||
~ 94 ~
[Dielectric-3]
Put the value of “dq” in above equation;
. ( )/
||
|| ( )
|| ( ) integrating both side;
∫ || ∫ ∫
0 ∫ 1
|| , -
∫
∵
{ ∫ }
( ) ∫
0 1 Compare with above equation;
== >
2 3 solved in the box == >
∫ ( )
put this in equation “B”
∫ ( )
---- > B Also we known that;
---- > C ( )
( )
( )
== > ( )
(
) ( )
∫
[Dielectric-4]
~ 95 ~
[Dielectric-4]
Now as displacement “⃗⃗ ” vector is given by;
⃗⃗ ⃗⃗ and ⃗⃗ then;
⃗⃗
⃗⃗ , -
⃗⃗
⃗⃗
( ) ⃗⃗ put this in equation “C”.
( )
---- > C
( )
0( )
1
0( )
1
0 1 ---- > D
“ ” is the electric field due to polarization in the interior

of the material, it will also polarize the material i.e. give rise
to polarizability.
The dipole moment due to “ ” is directly proportional to
“ ” i.e.;
~ 96 ~
[Dielectric-5]
“ ” is constant of proportionality and called “Polerizability of
the atom of material”.
Now as;
{P=Polerizability Vector. N=Number of molecules per unit volume}
Put the value of “ ” then;
and 0 1
2 0 13
invert the equation
This relation is called “Clausius Mossotti Relation.”

For various types of atoms in the sample materials “ ” is
replaced by;
∑
Therefore;
~ 97 ~
[Dielectric-6]
∑
Is a general form of Clausius Mossotti Relation.
It express the dielectric constant “ ” of the materials

in term of the atomic polerizability “ ” of the constituent
atoms or molecules of the materials.
It is named after “Hoviano-Fabrizo Mossotti And Rodulf
Clausius.
Now if “ ” is the refractive index of the material and “ ”
is the relative permittivity. Then √ or
Hence Clausius Mossotti Relation becomes;
∑ ∑
or
This expression is called “Lorentz Equation”. It relates the

refractive index to the atoms or molecules polerizability.
 Electric Polerizability:
It is the ability of dielectric materials to form instantaneous as
a result of applied or local electric field.
Polerizability determined the quick response of a bound system
(interior of insulator) to external electric field.
~ 98 ~
[Dielectric-7]
In solid it gives the measure of dipole moments.
Now there is local electric field “ ” due to the
polarization of interior cavity (sphere) of molecules in the
dielectric.
This “ ” also gives rise to dipole moment such that;
or
The constant “ ” is called the electric polerizability of the
material.
OSP-1
Origin OR Sources of Polerizability:
The dipole formation per unit electric field is called
“Polrizability”. It is denoted by “ ” and is given by;
Polerizability have three (3) sources.

1. Electronic Polerizability
2. Ionic polerizability
3. Orientation / Dipolar Polerizability
~ 99 ~
[Dielectric-8]
It is known that the formation of dipoles depends on the
nature of dielectric materials and the frequency of applied
electric field.
Now we discuss one by one in detail.
1. Electronic Polerizability ( );
The atoms of the dielectric materials are neutral, if we apply
the electric field the electrons cloud around the nucleus shifted
to one side and so form a dipole which is given by;
where “ ” represent dipole.
That is the center of two (2) charges one is negative charge

“ ” and the other is positive charge “ ” are separated by a
small displacement “ ”.
Here OR
Where “ ” is called “Electric Polerizability”.
Classical aspect of “ ” the electrons are bound to nucleus
with harmonic frequency “ ”
, -
--->1
~ 100 ~
[Dielectric-9]
Now if “ ” is the displacement of electron by net field force
“⃗ ” then;
---->2
Compare equation “1” and “2” then;
dividing both side by “ ”
---->3
Now as;
Put and equation “3” in this equation;
To treat “ ” as frequency dependent polerizability. We

consider it as “Simple Harmonic Oscillator.”
If “ ” is the frequency of the local field then the field is
at time “ ” is given by; “ ”
So
Let be the solution

~ 101 ~
[Dielectric-11]
Thus ( )( )
( )
( )
Multiplying both side by “ ” then;
( )
( )
Also we know that electric polarization is then
above equation becomes;
( )
And put the value of “ ” then
. /
( )
Hence the electronic polerizability is;
( )
While quantum mechanics ∑

. /
Where “ ” is the Oscillator strength between “ ” and “ ”

states.
~ 102 ~
[Dielectric-11]
2.Ionic Polerizability ( )
Some materials are exist in the form of ions like ,
etc. if electric field is applied the ions centers are
displaced a little and form dipoles.
Let the ions are displaced by “ ” at the application of
electric field then;
0 1
and by comparing then;

multiplying both side by “ ” them;
where
And put the value of “ ” then;
This is the “Ionic Polerizability”.

~ 103 ~
[Dielectric-12]
3. Orientation OR Dipolar Polerizability ( )
Some molecules are exist permanent
dipoles like or .
These dipoles are randomly oriented
inside the molecules and there is no
net polarization but if external electric
field “ ” is applied then all these permanent dipoles oriented
their self along the applied electric field “ ” and so produced
“Orientation Polerization “( )”.
Letus consider a dipole with charges “ ”, “ ” in the
presence of electric field “ ”, then the molecules with start
orientation along the applied electric field “ ”. In this case the
thermal agitation of molecules also disturbs the ordering
molecules, but there is equilibrium state of ordering (Orientation)
of molecules between ( ) along the applied electric field
“ ”. Shown in figure:
Now the dipole ( ⃗⃗ ⃗ ) during

orientation is given by;
⃗⃗ ⃗
Now according to statistical mechanics the number of dipoles
having orientation between ( ) ie. Which lie with in
the solid angle ( ) is proportional to . /.
~ 104 ~
[Dielectric-13]
( ) where “ ” is constant.
But the dipole moment along the applied

Solid angle;
electric field “ ” is given by;
Now the average contribution to the polarization

from “ ” to “ ” is;
∫
̅ Let
∫
∫
̅ put the “ ”
∫
∫
̅
∫
∫
̅ ---->1
∫
Let
then
and
if then and
~ 105 ~
[Dielectric-14]
if then Put these value in
equation “1” then; ∫
Integration by part;
∫
̅ ---->1 ∫ ∫ ∫ -
∫
, -| ∫ ( )
̅ ∫ ( ) ( ) ( )
8( )6 79 8( ) 9 [ ]|
∫ ( )
̅ ( ) [ ]|
∫
∫ ( ) ( )
̅ . / . / ( ) ( )
. / And;
∫
̅ . / . /
6 7 6 7
. / . / [ ]|
̅ ( ) [ ( ) ( )
]
0 1 , -
( )
( )
̅ ( )
0( )
1
;
and
̅
, - , - then
̅
( ) And;
̅ ( )
~ 106 ~
[Dielectric-15]
put the value of “ ”
( ) . / is also called “Lager in’s

. /
Function”. i.e.
( )
( ) 0 1
For small value of “ ” i.e. then;

⃗⃗ ⃗⃗
( ) ( ) . / ( )
So ̅ ̅ put “ ̅ ( )” then;
⃗⃗ ⃗⃗
( ) put “ ( ) ” then;
⃗⃗ ⃗⃗ ( )
Therefore;
( )
put “ ”
( )
Known as “Orientation Polerizability.”

~ 107 ~
FEPD-1
 Ferroelectric Properties of
Dielectrics:
The Ferro electricity of dielectric materials are characterized by
the spontaneous dielectric polarization i.e. the formation of
dipoles in the absence of electric field.
These pre-existing dipoles in the materials as a result of minor
deviation from crystallographic symmetry in the crystal structure
of these materials.
The property seems to be analogues to ferromagnetic behavior
of materials.
History:
These materials was first in the shape of “Rochelle Salt”
{Sodium Potassium Titrate ( ) in 1920.
In 1930 similar properties were found in KDP: Potassium
Dihydrogen Phosphate ( ).
Most important ferroelectric material (Ceramic) (Barium
Titanate) were found in 1940.
Now-a-days hundred compound exhibits of such properties.
In ferroelectric materials the origin of polarization is dominantly
orientational polarization . /. The internal picture is like
as shown the figure;
~ 108 ~
Here it seems that there are domains in Ferro-electric

materials with in which dipole are aligned. But not all domain
are aligned at “ ”.
That is there is no net polarization due to random domains.
In the presence of electric
field “⃗⃗ ”, these materials are
non-linear dielectrics, so if we
plot the graph between
polarization “⃗⃗ ” and electric
field “⃗⃗ ”. The graph is a curve, not a straight, the
polarization is maximum where all domain become aligned along
the applied electric field “⃗ ”. As shown in above figure.
See the next structure exhibits Ferroelectric shape structure is
called “Perovskite Structure of ”.
~ 109 ~
It is clear from the structure that all Oxygen (O) atoms

located a little lower than the Titanium (Ti) and Barium (Ba)
by some smaller displacement shown “d” and its form a dipole.
Ferroelectric
Hysteresis:
If we apply the external
Electric Field “⃗⃗ ” to the
sample of this type of
material, the domains start
aligned in one particular
direction and continuous until
all the domains becomes parallel to the applied electric field
“ ⃗ ”, that point is also called “Saturation Point”. Where further
formation stops if we reverse the external electric field “⃗ ”
the domains recycles not follow the same path, as shown the
given figure.
 At point “E” there is maximum alignment called “Saturated
Point”.
~ 110 ~
 At point “B” the polarization decreased at point have

some value called “Remanance Point”.
 At point “A” there is random orientation of domains.
 At point “F” the electric field “⃗⃗ ” has been completely
reversed then this is called “Saturation of alignment in
opposite direction.”
Temperature Dependence of Polerization of

Ferroelectric Materials and Currie Wien’s
Law [Thermodynamic Theory of
Ferroelectric Materials]:
It is known that the polarization of ferroelectric materials
dominantly due to orientation of the dipoles. So the relation is;
is valid. Where
Where “ ” is orientation polerizability, “P” is polarization

vector, “C” is constant, “ ” is Boltzmann constant, “E” is
electric field and “T” is the temperature.
It has been found that at very high temperature condition the
electric dipoles dispersion and the domains are randomly oriented,
and the ferroelectric materials behave like a paraelectric
materials where there are no dipoles.
The dipole moment due to “ ” is directly proportional to
“ ” i.e.;
~ 111 ~
“ ” is constant of proportionality and called “Polerizability of

the atom of material”.
Now as;
{P=Polerizability Vector. N=Number of molecules per unit volume}
Put the value of “ ” in above equation then;
⃗⃗ ----- > 1
Also ------ > 2
Put equation “2” in equation “1”

⃗⃗ 0 1 ⃗⃗
⃗⃗ 0 1
----- > 3
[ ]
Also electric susceptibility;

∑⃗
The polarization vector “⃗⃗ ” 0⃗⃗ 1 is
directly proportional to the electric field “⃗⃗ ” i.e.;
⃗⃗ ⃗⃗ or ⃗⃗ ⃗⃗
⃗⃗ ⃗⃗ ---->4
Compare equation “3” and “4” then;
~ 112 ~
⃗
[ ]
Dividing both side by “ ⃗⃗ ” then:
⃗⃗ [ ]
[ ]
[ ] ------ >5
[ ]
As “ ” now there must be a value of temperature

where “ ” where 0 1 means both “ ” and “ ”
are maximum and after that the temperature, there will be no
polarization. This critical temperature is called “Currie
Temperature ( )”.
But at
0 1
0 1 ---> 6
Now put in equation “5”;
[ ]
[ ]
~ 113 ~
{ }
[ ]
[ { }]
2 3
[ ] --- >7
[ { }]
Put equation “6” in equation “5”;

2 3
6 7
0 * +1
6 7
0 1 0 1
---- >8 where “ ”
Equation “8” is called “Currie Wien’s Law”.

Contact No: 0346 198 36 30
~ 114 ~
PEF-1
 Piezo-Electric Effects:
The word Piezo stand for Pressure.
So the effect in which an Electric field (Electricity) is
generated from a crystal by the application of external
pressure on the crystal is called “Piezoelectric Effect”.
There are some crystal which generates piezoelectricity, for
example Quartz ( ), Wurtzite ( ), Tourmalline etc.
Here the Mechanical Energy (Applied pressure) is converting into
Electrical Energy (Voltage).
Similarly if an A.C electricity is applied across the crystal
(Piezoelectric Materials) it produce strain in the materials and it
gets vibrates (Mechanical energy) and so generates sound
energy (Ultrasound) it is called “Reverse Piezoelectric effect”.
Hence the materials that generates electricity by the external
pressure also exhibits the reverse
effect (Mechanical Vibration).
The piezoelectric effect was 1st
discovered by Currie brothers “Perry”
and “Jacque” in 1880.
In order to explain the piezoelectric
effect let’s take the example of
“Quartz”. A very simple structure of
quartz as shown in figure:
~ 115 ~
It is clear that when pressure is applied on the crystal

(Quartz) the ions are squeezed and there is a net positive
charges at the top and negative charges at the bottom end of
each ions ( ). As shown in figure (b), which behave like a
small voltage.
Similarly in figure (c) when the pressure is relaxed the
structure of ions distorts in such a way that there is net
negative charge at the top and net positive charge at the
bottom end this behave like a small battery (Source of
Electricity).
As a whole by applied pressure through
push and pull an A.C signal of electricity is
generated. Show in figure.
Likewise if A.C voltage is applied across
the crystal it will start vibrating with
~ 116 ~
frequency (f) then producing sound

signal (ultrasound). Show in figure.
It can also be noted that potential
difference “ ” generated is directly
proportional to the change in pressure
change i.e.
2 3
* +
( )
As usually “ ”, “ ” and “ ” are

And
constant. So potential difference “ ”
Where “ ” is Piezoelectric constant and
is given by; “ ” is the thickness of materials.
That is the potential difference is

directly proportional to the stress
acceleration.
(Quartz)
(Rochelle Salt)
(Tourmaline Crystal)
~ 117 ~
Applications of Piezo-Electric Effects:

1. Sonar accelerometer sends ultrasound in water
(H2O) by generating through piezoelectric
effect, on return back of these waves, these
allowed to hit the piezo materials to create
electrical signals and these locating the objects
in the way of submarine etc.
2. Electric signaler is based on piezoelectric
effect. On triggering the button an electrical
signal is generated that produce light spark.
3. In ultrasound machine a materials is used
called “Transducer” that propagates ultrasound
waves which reflect back from the patient
and create reverse voltage and gives the
image of interior.
4. A piezoelectric materials is mounted below a
walking track to produce electrical signals also
the materials is adjusted in the pads of shoes
and mobile and keyboard to generate electric
voltage.
 Others Applications:
 Sensor
-Microphones, Pick-ups
-Pressure sensor
-Force sensor
-Strain gauge
 Actuators
-Loudspeaker
-Piezoelectric motors
~ 118 ~
-Nano positioning in AFM, STM

-Acosta optic modulators
-Valves
 High voltage and power source
-Cigarette lighter
-Energy harvesting
-AC voltage multiplies
 Piezoelectric motors
-Traveling wave motor
-Inchworm motor
-Piezo ratchet motor
-Stepping sot or using slip-stick motion
~ 119 ~
MAGNETISM
T he response of a material to external magnetic field is
known as magnetism .magnetism was observed very early

around 1800 BC in the shape of a load stone. In fact
magnetism is originated form the moving charges whether the
charges move in conductors or charges (electrons) move round
the nucleus in orbitals or spinning motions.
Materials are made up of molecules and atoms, they have
moving charges in the orbitals and also a spin motion. Thereby
having magnetic moments, a group of atoms or molecules have
the same magnetic directions is called magnetic domain with
specific domain boundaries, in each domain
there are tiny magnets aligned in particular
direction even in the absence of external
magnetic field and give rise to magnetism.
Now in order to discuss a few terms
relating to magnetism we consider a material
inside an external magnetic field of a
solenoid with field strength “ ”.
If at first there is no material in the coil
then
where is the permeability of

free space 0 1 is the magnetic induction and “ ” is the
~ 120 ~
field strength that is .

now in the Presence of material where is called
the permeability of the material .
The permeability of material relative to vacuum is known as
Relative Permeability given by or
The material inside the field either assist the magnetic field or
oppose it
Magnetization (M):
It is defined as the total magnetic dipole moments inside the
material per unit volume as a result of the response of the
material to external magnetic field where is called
the susceptibility
Now the equation comprising of two parts
1. Magnetic field strength due to vacuum
2. Magnetic field strength due to material in the solenoid
That is B
( )
( ( )
( ( )
( ( )
~ 121 ~
Where ( ) the relative permeability and is unitless

Now the material present in the field consists of electrons
moving in orbitals and also spins around themselves forms tiny
magnets due to their rotations such that if there are two
pairs of electrons one spins up another spins down cancelled
the magnetic effect of each other, for example completely filled
atoms or molecules like inert gases have zero magnetic
moments . Therefore only those materials having odd number of
electrons in their outer most shells will produce net magnetic
moments having bohar magneton
similarly the orbital magnetic moment is where “ ” is an
integer (Quantum Number).
The materials are divided according to their response to
magnetic field
1. Diamagnetism
In these material there is no magnetization in the absence of
magnetic field that is there is no net magnetic moment and
weakly opposes the external magnetic fields so try to reduce
H. Actually these materials repel and are repelled by the
external magnetic field the electrons in these materials
rearranged their orbits slightly, creating a current which
opposes the external magnetic field.
As we know that . For diamagnetic materials
therefore
So magnetic susceptibility is ( ) and is
negative on the average
Example of such materials are Bismuth graphite gold
~ 122 ~
antimony water Quartz alcohol etc .
Langevin Theory of Diamagnetism

It is clear that diamagnetism arises when the orbital condition
is changed by the external magnetic field. Consider the electron
is revolving round the nucleus in an orbit of the outer most
shell of the atom it constitute an electric current in the loop.
When an external
field is applied it
induces an emf in
the loop the emf
will decelerate the
electron in the loop due to lens law.
the deceleration of the electron due to induced emf ( ) is
given by
Also where
Where is the circumference of the circular loop.
( )
--->2
According to Faraday law, change the flux
produce emf (Voltage).
put in equation “2”
then;
( )---->3
~ 123 ~
We know that; and “ ” is the area of the

loop which is given by then:
put in equation “3”
. / ( )
. / ( )
∫ ∫
----> 4
this change in the velocity results in angular momentum and so
an induced magnetic moment is produced given by
where “ ” is the area of the loop and “ ” is
current due to moving electron;
---->5
and put in equation “5”
Put equation “4” in above equation then

( )
4 5
~ 124 ~
( )
4 5
But the magnetic susceptibility therefore

( )
. / this expression the magnetic susceptibility for a
single electron .
But in atom of atomic number Z there are Z electrons
( )
therefor z orbits should be consider so . /.
Now if the atom is consider to be spherical and not all orbits
are in the same plane so we take the average of squared
radius that is 〈 〉 〈 〉 〈 〉
also
〈 〉 〈 〉 〈 〉 〈 〉
and 〈 〉 〈 〉 〈 〉
〈 〉 〈 〉
that is 〈 〉 〈 〉
Hence 〈 〉 〈 〉 〈 〉
( )
So 〈 〉 〈 〉 put this value in . / we get
( )〈 〉
4 5
this implies that
Conclusions:
1. Magnetic susceptibility is proportional to the atomic number of the
material. The bigger the atom larger will be the magnetization
and strongly will oppose the external field.
~ 125 ~
2. Negative sign indicates that the diamagnetism is an induced

opposing effect it reduces the external magnetic field and it
disappears as the external field is switched off.
( )〈 〉
3. The . / is found to be independent of temperature.
~ 126 ~
P.M-1
 Para magnetism (Langevin Theory of
Para magnetism):
Para magnetism are those materials in which outer most shell
contain odd number of electrons, each electron move around the
nucleus in an orbits (loops) just is like a current caring ring,
such that one face is north pole (N) and the other is south
pole (S). So have magnetic moment from south pole (S) to
north pole (N). Example of such materials are Aluminum, Gold,
Copper etc.
Let us consider number of dipoles “n” present randomly in the
material. Therefore we can apply Maxwell’s distribution to this
problem i.e.
------->(1)
Where “ ” is the energy of dipole, “ ” is the number of
dipoles at temperature, “ ” is the Boltzmann constant and “ ”
is the temperature.
Now when we apply external magnetic
force which is strength “ ”, then
magnetic moment of the orbitals starting
aligning in the direction of magnetic force
“ ”.
During the orientation of dipoles there is
~ 127 ~
a torque applied on “ ” to rotate it in the direction of

magnetic force “ ”.i.e.
⃗ ⃗ ⃗⃗⃗
Energy is acquired by dipoles during torque “⃗ ” is given by;
∫ put the value of “⃗ ”
∫
∫ ∫
Put this value in equation “1”;
-------> (1)
( )
( )
-----> (2)
Now the average dipoles moment is;
∫
∫
∫
--- >(3)
∫
Now differentiate equation “2” with

~ 128 ~
respect to “ ”;
( )
----->(2)
( ) ( )
( ) [ ] . /
( )
[ ]. / ( )
( )
( )
[ ]. /( )
( )
0 . /1 ( )
( )
( ) -->(4)
Where . /
Put equation “4” in “3”;

∫
--- >(3)
∫
( )
∫ 8 ( ) 9
( )
∫ 8 ( ) 9
( )
∫ 8 ( ) 9
( )
∫ 8 ( ) 9
~ 129 ~
( )
∫
( ) ---->(5)
∫ 8 9
Now Let then ∫
and Integration by part;
∫ ∫ ∫ -
if then
, -| ∫ ( )
and
( ) ( )
8( )6 79 8( ) 9 [ ]|
if then
Put these value in equation “1” then; ( ) [ ]|
( ) ( )
∫ ( ) ( ) ( )
∫ ( )
And;
∫ ∫
∫ [ ]|
0. / . /1 [ ( ) ( )
]
0. /1
( )
. / . /
6 7 6 7 ;
. / . /
and
( )
0 1 , - then
( )
( )
0( )
1
And;
~ 130 ~
, - , -
0 1
( ) where ( )
If the number of dipoles is;

then; ( )
0 1
0 1
0 1 --->(6)
We know that; if “ ” then “ ” is very very

small and higher term will be neglegted. So equation “6”
becomes;
0 1 0 1
also we know that;
. / . / where
~ 131 ~
So Para Magnetism depend on temperature

“ ”.
 Graph:
It is clear that at low
temperature there is a high
magnetization but a high
temperature the
magnetization becomes low.

Contact No: 0346 198 36 30
~ 132 ~
FM-1
 Ferromagnetism:
Like paramagnetic materials, ferromagnetic materials also shows
magnetism in the absence of external magnetic field but the
difference between them is that the paramagnetic materials
there are individual electrons magnetic dipoles moment while
ferromagnetic materials there are group of atoms having net
dipoles moment.
Ferromagnetic materials has a spontaneous magnetization.
That is it has magnetic domain in the absence of external
magnetic field “ ”. These domain exist below certain
temperature which is called Currie temperature denoted by “ ”
and is due to exchange magnetic field interaction between
magnetic ions.
Above Currie temperature “ ” the ferromagnetic materials
become paramagnetic (Having random orientation of individual
magnetic moment).
The ferromagnetic materials have very high magnetization “ ”
even at small external magnetic field “ ” is applied.
It has much greater and positive magnetic susceptibility i.e.
( )
It exhibits the variation of magnetization “ ” versus external

magnetic field “ ” called Hysteresis curve.
~ 133 ~
Example of such materials are , , , and some alloys

, etc.
 Weiss Theory of Ferromagnetism 1907:
This theory is based on assumption that;
1. The ferromagnetic materials have small regions of order
magnetic moment called domains and there is a net
magnetization “ ” inside the domains boundary.
2. The magnetization “ ” of domain is due to exchange
magnetic field “ ” which tent to align the individual
magnetic moment inside the domain in the absence of
external magnetic field “ ”.
That is;
Where lambda “ ” is constant called “Weiss field constant.
“ ” is magnetization and “ ” is the exchange mahnetic field
arises due to interaction between adjacent molecules, also called
molecular field.
Now there are two magnetic field strength For ferromagnetic
materials;
one is applied magnetic field strength “ ”and when small
the other is magnetization field strength external magnetic field
“ ” is applied.
“ ” in the materials.
Usually
Now the net magnetic field strength is given
by;
put
~ 134 ~
---- (1)
where “ ” is total magnetic field strength inside the
ferromagnetic materials, “ ” is applied magnetic field strength
and “ ” is exchange magnetic field strength with no
external magnetic field.
Now we know that for a paramagnetic materials, Generally;
---- (2)
But for ferromagnetic materials put in (2)
So ( )
~ 135 ~
Taking “ ” as a common from R.H.S then;
. /
Dividing both side by “ ” then;
. /
( ) ∵
Subtract 0 1 from both side then we get;
Taking “ ” as a common then;
0 1
Taking “ ” as a common from L.H.S then;
0 1
0 1
Dividing both side by 0 1 then we get;

~ 136 ~
[ ]
Currie Constant And

, -
Currie
Temperature
This is Weiss law of
ferromagnetism.
Conclusion:
 Case No.1
If temperature “ ” is greater than Currie temperature “ ”
then the magnetic susceptibility “ ” is greater than zero i.e.
then .
In this case the materials will become paramagnetism because
if the temperature “ ” is higher than the Currie temperature
“ ” of the ferromagnetic materials then the domain structure is
random that it shifts to paramagnetic materials. (See previous
figures).
 Mathematically Proof:
If then .
We know that; , -
0 1
~ 137 ~
is very small approximate equal to zero i.e. then

above equation becomes;
0 1 , -
, -
This is the magnetic susceptibility of paramagnetic materials

which is already discussed.
 Case No.2
If temperature “ ” is smaller than Currie temperature “ ”
then the magnetic susceptibility “ ” is smaller than zero i.e.
then .
In this case the materials will have group of same
magnetizing position that is the domain will be retain even at
external magnetic field “ ” is zero and it will be due to
“ ” is the exchange field arises due to interaction between
adjacent molecules, also called molecular field.
Explained by Weiss in 1907 (Spontaneous magnetization).
~ 138 ~
Semi-Conductor-1
Semi-Conductors:
Those materials which has the conductivity in between
conductors and insulators or the resistivity in between the
conductors and insulators is called semi-conductor.
The semi-conductors can also define as the materials which
have the negative temperature coefficient of resistance, and is
given by:
The resistivity of the conductors is to ,

The resistivity of the semiconductors is to ,
The resistivity of the insulators is to .
Famous semi-conductors in element form are germanium ( )
and silicon ( ) of resistivity ( ) and .
And some compound semi-conductors are gallium arsenide ( )
and indium phosphate ( ) cadmium sulphide ( ) etc.
Another important aspect of semi-conductors is that the band
energy gap ( ) is smaller as compere to insulators.
It ranges from to while that of insulators
e.g. diamond (same 4th group) is .
~ 139 ~
S.No. Elements Eg Types

1 Carbon ( ) Almost insulator
2 Silicon ( ) Semi-conductor
3 Germanium ( ) Semi-conductor
4 Stannum, tin ( ) Conductor (Metal)
5 Plumbum, lead ( ) Conductor (Metal)
The energy “ ” may be given for

excitation to conduction band in the form
of “ ” where .
Where “ ( )”
Intrinsic Semi-Conductors (Pure Semi-

Conductors):
The intrinsic semiconductors are pure semiconductors in which no
impurities are added. The electric conductivity of this types of
semiconductors is purely due to thermally generated carriers
electrons (negative charge) and holes (positive charge).
So at zero kelvin temperature there is no charge carriers to
conduct electricity means no current ( ) because each electrons
( ̅ ) are tightly bounded to its own atom. Shown in the figure:
~ 140 ~
Actually the electrons ( ̅ ) at temperature jumps from

valence to the conduction band, as thermal energy crush the
energy gap ( ) and so a holes is created in valence position
(band), this holes is also act as a charge carriers.
Intrinsic semiconductors have no larger use still have some
application as optical sensors, sensor for X-ray or electron
microscope, have silicon ( ) and germanium ( ) is used to
cool temperature of .
 Intrinsic Carriers Charge Concentration:

It is known that at temperature high temperature, the
electrons in the conduction band have equal number of holes in
the valence band.
Here
~ 141 ~
Such that
But beside that the
electrons generation there
may be a recombination of
electrons from conduction
band into the holes in
valence band, then it will
emit energy ( ) in the
form of “ ” as shown
in the figure.
At last the rate of generation ( ) of the electrons depends

on the temperature ( ) and nature of semiconductors.
The rate of recombination ( ) depends on the number of
electrons in the conduction band and the number of holes
present in valence band at that temperature ( ).
So
Where “ ” is constant depends on nature of materials.
But in case of intrinsic materials at high temperature ( ).
So
~ 142 ~
Conductivity ( ) in Sntrinsic semi-

Conductors:
It is known that at temperature some electrons ( ̅ )
and holes ( ) are present for constituent in semiconductors but
in the absence of external electric field ( ) the net current
( ) is zero as electrons ( ̅ ) and holes ( ) move in random
directions.
The conductivity ( ) of intrinsic of semiconductors depends on;
1. Concentration of electrons ( ̅ ) and holes ( ), high
concentration of electrons ( ̅ ) and holes ( ) then the
conductivity ( ) will be high and vice versa.
2. As electrons ( ̅ ) and holes ( ) are moving in the
semiconducting materials collide with the ions and so
scatters, hence conductivity ( ) also depends on how far
the electrons ( ̅ ) and holes ( ) travel before scattering.
Therefore the drift velocity ( ) is given by;
Where “ ” is the constant of mobility of charge carriers.

---- (1)
So current density is = for electrons ( ̅ )
concentration in conduction band.
Put the value of “ ” in above equation then;
~ 143 ~
( )
∵
Where “ ” is the electronic conductivity in semiconductors.
Similarly for holes ( ) concentration;
Where “ ” and “ ” are the concentration and mobility of the

holes ( ) respectively.
Such that total conductivity in intrinsic semiconductors is;
Put the values of “ ” and “ ” in above equation then;
as
( )
So ( )
Hence this is the total conductivity in intrinsic semiconductors.
~ 144 ~
 FERMI ENERGY LEVEL OF

INTRINSIC SEMICONDUCTORS:
We are going to discuss the Fermi energy level in case of
intrinsic semi-conductors. As we know that in case of
intrinsic semi-conductors at temperature of the valance
band is completely filled and the conduction band is
completely emplty. In case of intrinsic semi-conductors the
Fermi level of enrgy must be greater than the energy of
valance band and smaller than the enrgy of conduction band
i.e. . So the
Fermi level of energy
“ ” will lies somewhere
above the valance band
and below the conduction
band.
The probability of
occupation of states at
any temperature is given
by;
( ) ( ) ( )
As we have discussed above that at temperature of the

valance band is completely filled and the conduction band is
completely emplty for intrinsic semi-conductors. In the
language of mathematics it will be given as at temperature
“ ” then;
~ 145 ~
Fermi energy level is;
( ) in valance band---- A
( ) in conduction band--- B
Now let us consider that maximum value of energy in the
valance band is given by “ ” and maximum value of energy
in the conduction band is given by “ ”.
Then we know that in case of semi-conductors at
temperature, the probability state will be maximum;
( ) ( ) ( )
The above equation is only possible if we have;

then
Which is means that “ ” will have negative value when
“ ( )”
Putting this value in equation ( );
( ) ( ) ( ) at
( ) ( ) ( )
( ) ( )
Where “ ” we consider the Fermi level of energy.

~ 146 ~
So we have verified equation “A”.

In order to verified equation “B”, we know that the
conduction band is completely empty at temperature
( ) ( ) ( )
The above equation is only possible if we have;

then
Which is means that “ ” will have positive value when
“ ( )”
Putting this value in equation ( );
( ) ( ) ( ) at
( ) ( ) ( )
( ) ( )
So we have verified equation “B” also, the equations ( )

and ( ) are given as
( )
( )
Which mean that the Fermi energy level lies above the top of
the valance band and below the lowest value of the conduction
~ 147 ~
band. The Fermi energy level will lies in the forbidden region
between the valance band and conduction band.
Now let us suppose the electron can only goes from the top
of the valance band to the bottom of the conduction band. If
we consider that there are “ ” number of states involved
then the probability of occupation of states in the conduction
band will be given as at any temperature “ ”.
( ) ( ) ( )
In case of intrinsic semi-conductors we know that there is a

one to one correspondence which means that electrons holes
pairs are produced. If one electron goes from the valance band
to the conduction band then one hole will be produced in the
valance band.
The probability of occupation of states in the valance band will
be given as at any temperature “ ”.
( ) ( )
The probability of non-occupation of states in the valance band

will be given as;
( ) ( )
According to one to one correspondence we know that the

electrons holes pairs are produced the electron goes to the
conduction band and holes present to the valance band. Then
~ 148 ~
the number of occupied states in the conduction band will be

equal to the number of non-occupied states in the valance band
i.e.
Number of occupied states in C.B=Number of non-occupied states
in V.B
Then comparing equations ( ) and ( );
( ) ( ) ( )
( ) ( )
( ) . /
( ) [ . /
]
( ) [ . /
] taking L.C.M
. /
( ) [ . /
]
~ 149 ~
. /
( ) [ . /
]
By cross multiplication we have;

. / . / . /
( )
. / . / . /
. / . / . /
. /
Subtract from both sides we have;

. /
. /
Taking log on both sides;

. /
( )
( )
( )
~ 150 ~
( )
( )
Which mean that the Fermi level

of energy lies in the mid-way
between the top of the valance
band and the bottom of the conduction band.
The result is obtained is only for the intrinsic semi-conductors.
This result does not hold for the extrinsic semi-conductors.
As we have consider that the electrons only go from the top
of the valance band to the bottom of the conduction band but
it is also possible that the electron from the middle of the
valance band to the middle of the conduction band OR it goes
from the top of the valance band to the bottom of the
conduction band. In all these cases the Fermi energy level will
be the mid-way between the valance band energy from where
it is gone and the conduction band energy to which it is gone.
As we know that the energy of the electron in the material
change with that of the K-values.
~ 151 ~
Now we consider the case when

the K-value of both valance band
and conduction band is zero and
their peaks are at the same
level.
The case when the peaks values
of both are at opposite case then
these materials are called “Direct
Semi-Conductors”. Show in the
figure.
But if the maximum value of the
valance band is not at the same
line with that of the maximum
value of the conduction band then
these materials are called “Indirect
semi-Conductors”. Show in figure.
In the case of transition of the electrons from the valance
band ton the conduction band is required as compare to the
first case.
We know that the large energy is required for the same
energy gap transition of electron from the valance band to the
conduction band in case of intrinsic semi-conductor and small
energy is required for the transition of the electron from the
valance band to the conduction band in case of extrinsic semi-
conductor.
~ 152 ~
For the same energy gap in case of direct semi-conductors

because in the direct lattice the “K” has same value and the
phonons also convert energy in this case.
But in the first case k-value is zero.

Contact No: 0346 198 36 30
Think before, you speak or

write.
~ 153 ~
Ex-Sc
 EXTRINSIC SEMI-CONDUCTORS:
It is known that at room temperature ( ) the pure
semiconductors have no number of charge carriers of the order
of . So consequently the conductivity is
also .
Now the only way to increase the charge carrier concentration
at room temperature is to create “Extrinsic Semiconductors” by
the process of doping.
Also by law of mass action . So we
can increases only one type of charge carrier at same time
and the other charge carrier decreases.
 Definition of Extrinsic Semi-Conductors:
A small amount of impurities is added in pure semiconductors
( ) to increases the charge carrier electrons (Add
Pentavalent Impurities), or holes (Add Trivalent Impurities),
polarity ( ) is called “Extrinsic Semi-Conductors”.
The first type of extrinsic semiconductors in which the charge
carrier is electrons called “N-Type Semi-Conductors”.
It is also called “Donor”, because they give the electrons for
conduction (electricity).
The second type of extrinsic semiconductors in which the charge
carrier is holes called “P-Type Semi-Conductors”.
~ 154 ~
It is also called “Acceptor”, because they accept the

electrons for conduction (electricity).
 N-Type Doping (Donors):

In N-Type extrinsic semiconductors we add the
impurities from the fifth group of the periodic
table of the element which consist of Nitrogen
( ), Phosphorus ( ), Arsenic ( ), Arsenic ( ),
Stibium or antimony ( ) and Bismuth ( ). These
elements have five valence electrons. Shown in the
figure;
Here the number of negative charge ( ̅ ) carrier
are greater than the number of positive charge
(holes), i.e. .
Now we know that the structure
of semiconductors (silicon)
hybrid orbital, so we have
four electrons ( ̅ ) in the outer
region in covalent bond. (in given
fig)
Let we add dopant from the 5th
group (N, P, As, Sb, Bi) of the
periodic table, such that the silicon lattice not to disturbed,
Phosphorus has five valence electrons in which four electrons
bonds with four silicones and one electron remain in excess.
~ 155 ~
Now we consider the phosphorus atom in silicones as the free

electron behave just like a Hydrogen atom which has one
electron in it, but mass is effective because in N-Type
Semiconductors the electrons move forward and backward
(acceleration & retardation) between lattice.
So we replace Hydrogen ( ) atom on the place of Phosphorus
( ) atom.
In quantum
and mechanics;
Binding energy of electrons in silicones ( ) due

to phosphorus ( ) atoms; Where
---- (1)
Now for silicon ( ),

, ,
, and
Put these values in equation (1);
( )( )
( ) ( ) ( )
Calculate this we get;

~ 156 ~
This is the amount of energy ( ) in order to ionized extra

electron from valence band into conduction band.
The actual ionized energy ( ) of phosphorus ( ) atom
.
While thermal energy of silicon at room temperature
.
So ionization energy for extra electron in silicones ( )
structure is approximately equal to the actual ionization energy
of phosphorus ( ).
Ionization energy extra electron in silicones ( ) structure is
approximately equal to the thermal energy at room temperature.
Therefore at room temperature the electrons can easily be
shifted into conduction band for flow of current in extrinsic
semiconductors.
Similarly for
and
So all Nitrogen ( ),
Phosphorus ( ),
Arsenic ( ) and
Stibium or antimony ( ) can be add as a dopant N-Type
extrinsic semiconductors. Now let the pentavalent atom (5
valence electrons As) impurities have ( ) concentration of
~ 157 ~
impurities i.e. atoms of dopants contribute into conduction,

i.e.
( )
Where “ ” indicate for Donor.
According to law of mass action;
Put the value of “ ”;
That as the number of free electrons for conduction
And the number of holes for conduction
The impurities from the fifth group of the periodic table are
called “Donors”.
 P-Type Doping (Acceptors):
In P-Type extrinsic semiconductors we add the
impurities from the third group of the periodic table
of the element which consist of Boron ( ),
Aluminum ( ), Gallium ( ), Indium ( ) and
Thallium ( ). These elements have three valence
electrons. Shown in the figure.
~ 158 ~
The ionization energy of Boron

( ) is , Aluminum ( ) is
and Gallium ( ) is
. Since again these energy
are of the order of thermal
energy at room temperature. So
all number of Boron ( ) atoms
have one hole, shown in the
figure.
The Band gap of P-Type of extrinsic semiconductors as shown

in figure.
The impurities from the third group
of the periodic table are called
“Accepter”, such that concentration
is and and
From the law of mass action;
Put the value of “ ”.

~ 159 ~
 Conductivityand Concentration in Extrinsic

Semi-Conductors:
 Conductivity and Concentration In N-Tpye

Extrinsic Semi-Conductors:
Let calculate electrons and holes concentration and conductivity.
The reason of doping into semiconductors is to increase the
concentration of charge carrier for conduction.
For intrinsic semiconductors i.e. silicon ( ) at room temperature;
And conductivity of intrinsic semiconductors is;
Let add group five atoms i.e. Arsenic ( ) with
Therefore
( )
So there majority electrons times more than the intrinsic

semi-conductors, we know that;
As “ ” is very large as compare to “ ”, so we neglected
“ ” then above equation become;
~ 160 ~
, and
put these value in above equation then;
Concentration of Arsenic (As) doping
This calculation means that right doping will be

( ) ( )
 Conductivity and Concentration In P-Tpye

Extrinsic Semi-Conductors:
For intrinsic semiconductors i.e. silicones (Si);
Accepter concentration of Boron (B)

Boron (B) is the third group atom of the periodic table.
So
Now law of mass action;
( )
Put “ ”
~ 161 ~
And conductivity is;

As “ ” is very large as compare to “ ”, so we neglected
“ ” then above equation become;
Here also there majority of holes are time greater than

the intrinsic semiconductors.

Contact No: 0346 198 36 30
~ 162 ~
S-C
 Super-Conductivity:
Super conductivity is define as; the property of some materials
which has zero resistivity “ ” at some temperature which is
called “critical temperature” and denoted by “ ” ( ).
The graph of temperature ( ) and resistivity ( ) as shown in
figure.
We know that;
( )
Where “ ” is a constant and is known as temperature
coefficient of resistivity. Its value is different for different
materials.
From the above equation it is clear that the resistivity “ ” is
directly proportional to the temperature “ ”.
It can be seen that the resistivity ( ) of normal conductors
approaches to some value even at zero (low) temperature, but
the resistivity ( ) of superconductors does not appear some
~ 163 ~
value at some nonzero value of the temperature, even has

zero value at critical temperature ( ).
This effect was first discovered by “Dutch Physicist Heike
Kamarkingh Onnes in 1911”.
Similarly superconductors are materials which losses its resistivity
below magnetic field strength which is called called critical
magnetic field strength and denoted by ( ).
For Mercury ( );
given the table.

Liquid Helium temperature.
The superconductors have some
other factors, for its
superconductivity behavior like;
(Critical Magnetic Field)
Meissner idea.
(Critical Temperature)
Kamarkingh idea
(Critical Current density)
~ 164 ~
Superconductor materials exhibits perfect conductor no power

losses (Zero resistance) and perfect diamagnetism (Repulsion of
external magnetic fields) means a strong force against gravity
(Lavitation problem).
Some compound exhibits superconductors even at high temperature
for example; Niobium tin ( ),
Niobium Germinate ( ), Niobium Titanium (alloy)
( ) etc.
But the drawback is that these materials doesn’t exist super-
conductors at high (Room) temperature and efforts are being
made to discovered them at normal life temperature in 1980 at
compound like found to have superconductivity at
.
It is also discussed above that the superconductors exist not
only at the critical temperature ( ) but also exist at critical
magnetic field strength ( ). The very high magnetic field also
turns the superconductors to normal conductors.
Also it has been found that magnetic field ( ) is a function
of temperature given by the empirical formula;
( ) ( )[ . / ]
Where ( ) is the critical magnetic field at and is

the constant for a materials.
~ 165 ~
Some values are listed in the table if

( ) ( ) each materials in list losses
superconductivity.
Meissner Effects:
In 1933 Meissner and oschsenfeld discovered
that when a materials (Superconductors) is
placed in a weak magnetic field strength
(below ). The magnetic field lines force
passes through the materials if temperature is greater than the
critical temperature i.e. but the lines are completely
repelled if the temperature is smaller than the critical
temperature i.e. .
The 2nd diagram, the superconductors shows the diamagnetic

behavior.
Here ⃗⃗ ⃗⃗ ⃗⃗⃗
~ 166 ~
“⃗⃗ ” is the magnetic field which is repelled by the

superconductor and so inside superconductivity “ ”,
“⃗⃗ ” is the applied magnetic field,
“⃗⃗⃗ ” is the magnetization and “ ” is the permeability of free

space.
Here above equation becomes;
⃗⃗ ⃗⃗⃗
⃗⃗⃗ ⃗⃗
⃗⃗
⃗⃗⃗
So negative sign indicate that the materials opposes the applied

field (⃗⃗ ), likewise; ⃗⃗
⃗⃗
⃗⃗⃗ ⃗⃗⃗
⃗⃗⃗
Dividing by “ ” both side we get:

⃗⃗⃗
Hence superconductors shows diamagnetism behavior i.e. not only

superconductors are perfect conductors but perfect diamagnetic
also.
~ 167 ~
Type-I Super-Conductors:
There are about twenty eight
(28) pure materials which exhibits
zero resistivity at low
temperature and have
property of repelled the external
magnetic field (Meissner Effect)
i.e. showing perfect diamagnetic
property, that are called “Type-I
super Conductors”. These have
zero magnetic field internally.
Model of these types of
materials is explained by BCS
theory. Their magnetic susceptibility “ ” is given by;
⃗⃗
(⃗⃗⃗ )
So the graph of magnetization “⃗⃗⃗ ”

versus applied magnetic field “⃗⃗ ” is
given by.
That as at low magnetic field (
) these materials are good
superconductors but at high magnetic field
then superconductivity vanish.
Further these materials are of very limited applications.
These are also some time called soft superconductor.
~ 168 ~
Type-II Super-Conductors:
 Fortunately there are some compounds made from alloys,
which show superconductivity at much higher temperature
(Even greater than critical temperature ) and higher
magnetic field (greater than critical magnetic field ).
 These are also called hard superconductors.
 These materials also have greater critical temperature ( )
and critical magnetic field ( ), and mechanically harder
than type-I.
 For example ( ), are used in the construction of high
field superconductivity magnets (So used in MRI).
 These materials exist in the mixed state of normal and
superconducting regions called “Vortex State”.
The critical temperature ( ) and magnetic field ( ) and
graph is given below.
This graph shows that the type-II superconductors exist at

low and high magnetic field until ( ), above “ ” the
materials will become normal conductors. These materials carry
high current, so having high current density ( ).
~ 169 ~
L-E
 LONDON’S EQUATION: [The
Electromagnetic Behavior of Super-
Conductivity]:
The electromagnetic behavior of superconductors was first given
by two brothers Heinz London and Fritz London.
This equation shows that how much external magnetic field is
penetrated into superconductors. It is known that for normal
materials the ordinary third (3rd) equation of Maxwell is;
⃗⃗
⃗ ⃗⃗
For superconductors (perfect conductors) the magnetic field ( )

inside the superconductors is zero.
⃗⃗
So that the magnetic induction ( ) is constant in
time (because the derivative of constant is zero).
Also by Miessner effect for perfect diamagnetic materials the
magnetic field ( ) inside the superconductors is zero.
Statement of London’s Equation OR

London’s Law:
London’s equation proposed that, “the current density of
superconductors OR super current density ( ) is directly
proportional to a vector potential (⃗⃗ ) of magnetic field, such
that ⃗⃗ ⃗ ⃗ ”.
~ 170 ~
Mathematically it is given by;

⃗⃗ ⃗⃗
This is the London’s Equation OR London’s Law which we
proof the following.
We know that generally; ⃗
Since over all charge carrier, Where “ ” is the concentration

of charge carrier, “ ” is the charge on each carrier and
“⃗ ” is the velocity of the charge carrier.
Above can be written as;
∑ ⃗
Taking derivative on both side w.r.to “ ”
,∑ ⃗ -
⃗
∑ ---- (1)
Now from Newton’s 2nd law;
⃗ ⃗
⃗ ⃗ ⃗ ∵⃗ ⃗⃗ ⃗
⃗⃗ ⃗
put this in equation (1)
⃗
∑
⃗⃗
∑ . /
~ 171 ~
⃗⃗
∑
Taking curl both side;

⃗⃗
⃗ ⃗ ∑
(⃗ ) ∑ (⃗ ⃗⃗ )
⃗⃗
(⃗ ) ∑ . / Maxwell’s 3rd
equation;
⃗⃗⃗
Multiplying by “ ” both side we get; ⃗⃗ ⃗⃗
(⃗ ) ∑ ( ⃗⃗ )
Now taking integration on both side,
∫ (⃗ ) ∑ ∫ ⃗⃗
⃗ ∑ ⃗⃗
For a single carrier (the charge become identical)
⃗ ⃗⃗ Vector potential;
⃗⃗ ⃗⃗ ⃗⃗⃗
⃗ (⃗ ⃗)
⃗⃗ ⃗
⃗ London’s Equation. proved

~ 172 ~
Also by electrodynamics;
⃗ ⃗⃗ Maxwell’s 4th equation;
⃗⃗
⃗⃗ ⃗⃗⃗
Taking curl on both side then;
For superconductivity 2nd term is
⃗ (⃗ ⃗⃗ ) ⃗ zero;
⃗⃗ ⃗⃗⃗
⃗ (⃗ ⃗⃗ ) ⃗
And vector triple product;
⃗ (⃗ ⃗⃗ ) ⃗⃗ (⃗ ⃗ ) ⃗ ⃗⃗ .⃗⃗⃗ ⃗⃗ / ⃗⃗⃗ .⃗⃗ ⃗⃗ / ⃗⃗ (⃗⃗ ⃗⃗⃗ )
And from Maxwell’s 2nd

⃗( ) ⃗⃗ ( ) ⃗ equation
⃗⃗ (⃗ ) ---- (2) ⃗⃗ ⃗⃗⃗
We know that;
⃗ ⃗⃗ put in (2)
⃗⃗ [ ⃗⃗ ]
⃗⃗ [ ⃗⃗ ]
⃗⃗ [ ] ⃗⃗
⃗⃗ ⃗⃗ ----- (3)
Where [ ]
is known as London’s Penetration Depth.

~ 173 ~
Let us consider one dimensional superconductors, the equation (3)

becomes;
⃗⃗
⃗⃗
The solution of this equation is;

( )
( )
This shows that the field of penetration into superconductors

exponentially decreases and it penetrated to the extent of ( ).
( )
At then ( )
( )
( ) ( )
That is the magnetic field ( ) will penetrate into

superconductors from (edge of the superconductors) to
( ).
~ 174 ~
Also the typical value of [ ] i.e. the

London penetration depth is of the order of fraction of micron.
The London’s equation ⃗
Shows that macroscopic quantum state such that;

| |
Which is the assumption of London.

Contact No: 0346 198 36 30
~ 175 ~
B-C-S
 BCS Theory of Super-Conductors:
(Bardeen, Cooper & Schrieffer)
Cooper Pair in Super-Conductors:

Cooper pair (2) of electrons (one spin up and other spin down)
was explained in BCS theory of superconductors.
According to this theory when electrons move in the positive
ions of superconductors then the positive ions come closer
together and then far, so ions vibrating and generating energy
called “Phonons”.
The closer ions (distorted ions) look like strong positive region.
this region fastly attract another electrons and the first and
second electrons makes pair under the influence of phonons. So
by this process there are many electrons are developed inside
the superconductors (metal) and the positive ions are vibrating.
The formation of electrons pair is called “Cooper pair”.
~ 176 ~
As shown in figure.
The first electrons bring the two positive ions close together
producing phonons and the second electrons absorbed this phonons
and pair together with the first electrons. So it seem that
there is an interaction of electrons and phonons. The electrons
become close enough to bound together in a pair and move
inside Superconductors materials with no resistance.
~ 177 ~
Now consider a sea of electrons in the Fermi Sphere inside

the super-conductors materials.
Such that the Fermi Energy is;
Let’s an electrons be just out of the

field of Fermi sphere in order to
interacted with another electrons to
form pair.
Now let us consider two electrons in
⃗ ⃗
the pair with the wave function .
One have wave vector (⃗⃗⃗ ) and other

wave vector ( ⃗⃗⃗ ) both have energy;
The Hamiltonian of these two electrons (Pair Electrons) is;

∑ --- (1)
Where “ ” Kinetic energy and “∑ ” interaction
potential between electrons in pair.
In equation (1) if the electrons are not interacting then;
∑
Now the Schrodinger’s equation for this is;
---- (2)
~ 178 ~
(Zero order Schrodinger equation)

⃗ ⃗ ⃗ ⃗
The wave function is a linear combination of and .
The general Schrodinger’s equation is’
---- (3)
Where ∑ ---- (4) (Linear combined function)
∑ --- (1)
Put equations (1) and (4) in equation (3);
---- (3)
( ∑ ) (∑ ) (∑
∑ ∑ ∑ ∑
∑ ∑ ∑
[∑ ∑ ] ,∑ -
∑ ∑ ∑
∑ ∑
~ 179 ~
subtract ∑ from both side we get;
∑ ∑
∑ [ ∑ ]
[ ∑ ] ∑
So
∑
, ∑ -
Sum over all “ ” take;
∑
∑
, ∑ -
---- (5)
Here
[ ]
Equation (5) become;
∫ ( )
~ 180 ~
Where ( ) is the density of electrons a slowly varying

function.
( ) ∫
Multiplying and dividing be “2” with R.H.S;
[ ( ) ∫ ]
[ ( ) ∫ ]
( )
∫
[ ( ) , -| ]
( ) [{ [ ( )]} * [ ( )]+ ]
( ) [{ [ ]} * [ ]+ ]
( ) 4 5
( ) 4 5
( ) 4 5
~ 181 ~
Multiplying by “ ” and dividing by “ ( ) ” both side we get;
4 5
( )
Taking anti natural log;
4 5 ( )
4 5
[ ] ∵
4 5
4 5
Subtract and add with both side we get;
4 5
Invert the equation;
( )
[ ]
Multiplying both side by we get;

~ 182 ~
( )
[ ]
4 5
Taking as a common from the denominator of the R.H.S
of the above equation we get;
---- (6)
( ) ( )
[ ]
Where “ ” difference in energy (Energy Gap) take the

approximation . This also called weak coupling limit.
4 5
So . Equation (6) become;
( )
, -
( )
( )
( )
( )
( )
( )
~ 183 ~
i.e. ( )
So if “ ” is attractive potential energy ( ), then “ ”

shows that cooper pair is a bound state under the mediation
of phonons.

Contact No: 0346 198 36 30
WEAK PEOPLE REVANGE.

STRONG PEOPLE FORGIVE.
INTELLIGENCE PEOPLE IGNORE.

Solid State Physics-2

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~1~

Written by Professor Mr. Iftikhar Ali

Impurity Interstitial Defect……………………………………………………………………14

Substitutional Impurity Defect…………………………………..…………………………14

Types of Color Center………………………………………………………………………………..32

Band Theory of Solid (BTS)…………………………………………………………….35

Energy Verses Wave Vector Graph E-K Graph…………………………………..……….53

Motion (Velocity) of Electrons in Band (Crystals)……………………………….…..…58

Effective Mass of Electrons in crystal ( )…………………………………………….....60

Density of States & Fermi Surface (DSF)………………………..……………………….…63

Free Electrons Theory of Metals (Solids) (FETM)……………………………………….71

Drude Model & Lorentz………………………………………………………………………….…75

Dielectric Properties of Solid (DPS)………………………………………………..80

Applied Electric Field “E” ………………………………………………..……………………....80

Maxwell’s Equation in Dielectric Medium………………………………………………...88

Clausius Mossotti Relation (CMR)……………………………………………………………92

Origin OR Sources of Polerizability…………………………………………………………..98

Electronic Polerizability ( )……………………………………………………………..……..99

Ionic Polerizability ( )…………………………………………………………………………….102

Orientation OR Dipoler Polerizability ( )……………………………………………..103

Ferroelectric Properties of Dielectrics (FEPD)…………………………………………107

Temperature Dependence of polarization of Ferroelectric Materials And

Currie Wien’s Law *Thermo-dynamics Theory of Ferroelectric materials…110

Piezo-Electric Effect (PEF)………………………………………………………………………..114

Applications of Piezo-Electric Effect……………………………………………………......117

High Voltage and Power Source ……………………………………..…….………….118

Langevin Theory of Diamagnetism……………………………………………………….……122

Para Magnetism (PM) (Langevin Theory of Para Magnetism)……………....…126

Weiss Theory of Ferromagnetism 1907……………………………………………………...133

Semi-Conductors & Super Conductivity……………………………………..…138

Intrinsic Semi-Conductors (Pure Semi-Conductors)……………………………..…..139

Intrinsic Carriers Charge Concentration……………………………………………………140

Conductivity ( ) in Intrinsic Semi-Conductors………………………………………..…142

Fermi Energy Level of intrinsic Semi-conductors………………………………….…..143

Extrinsic Semi-Conductors (Ex-Sc)……………………………………………………….……153

Definition of Extrinsic Semi-Conductors……………………………….……154

N-Type Doping (Donor)………………………………………………………………………….…154

P-Type Doping (Acceptors)………………………………………………………………….……157

Conductivity and Concentration in Extrinsic Semi-Conductors…………………159

Conductivity and Concentration in N-type Extrinsic

Conductivity and Concentration in P-type Extrinsic

London’s Equation (L-E), The Electromagnetic Behavior of

Statement of London’s Equation OR London’s Law…………………………….....169

BCS Theory of Super-Conductors (B-C-S)……………………………………………..…175

Cooper Pair in Super-Conductors………………………………………………...175

4. Why a carefully prepare crystal is mechanically weak but

Ans: The steel is hard because in steel the carbon atoms

Written By: Professor Mr. Iftekhar Ali

Written By: Professor Mr. Iftekhar Ali

Different ways in which “ ” schottky defects can be produced

The production of the defects in a crystal increases the

Putting the value of “ ” in above equation then we will get;

Where “ ” is the Boltzmann constant.

Putting the value of “ ” in above equation;

Where “ ” is the energy required to produce a

number of schottky defects and “ ” is the total

Differentiating equation ( ) and applying above condition then

Taking first part in the bracket of the equation ( );

Because “ ” does not depend on “ ”.

Taking third part in the bracket of the equation ( );

Putting equations ( ), ( ) and ( ) in equation ( ) we have;

Taking anti log on both sides we have;

At any temperature “ ” as “ ” is so much small as compare

This is the most important relation which gives us the number