Chapter 3

ELECTRICAL PROPERTIES
Introduction
The objective of this chapter is to explore the electrical properties of materials, i.e. their responses to an
applied electric field. We begin with the phenomenon of electrical conduction: the parameters by which
it is expressed, the mechanism of conduction by electrons, and how the electron energy band structure
of a material influences its ability to conduct. These principles are extended to metals, semiconductors
and insulators. Particular attention is given to the dielectric characteristics of insulating materials. The
final sections are devoted to the peculiar phenomena of Ferro electricity and piezoelectricity.

The electrical conductivity is one of the properties of materials that vary most widely and the best
conductors such as copper and silver have values of about 10 8-1m-1 and a good insulator such as
polystyrene has conductivity 10-15-1m-1. In a metal, the current is carried by conduction electrons, and
hence the name electronic conduction.

In an isolated atom, the electrons are tightly bound to the nucleus. These electrons are known as core
electrons. But there are a few electrons which are loosely bound to the nucleus and are called as
valance or conduction electrons which are responsible to the properties of the materials. When the
crystal is formed, the valence electrons are treated as electrons of the crystal and do not belong to the
individual atom in that crystal. In a crystal, the valence electrons experience an effective potential of all
the positive ion cores and is less than that when it experience an effective potential of all positive ion
cores and is less than that when it experiences in an isolated atom.
A useful assumption can be made here that the effective potential inside the metal is constant and can
be considered as zero as a first assumption. This is the fact that at the surface of a metal, the atoms are
not completely bonded and there appears the so called surface potential which is much higher than the
effective potential. Thus the valance electrons are freely moving in a metal, and it requires certain
amount of energy which is more than the surface energy to leave the metal. Thus, the electrons are in
potential energy well of finite depth as shown in figure 3.1. Remember that we have studied infinite
potential well or particle in a rigid box problem in quantum mechanics. The free electron theory of
metals is a fundamental theory for understanding the electrical properties.

1
 Figure 1: Free electrons in a potential well of finite depth

Here are some important characteristics of metals and these will be discussed in detailed in the classical
free electron theory of metals proposed by Drude and Lorentz
Main characteristics of metals:
(1) Metals exhibit an excellent electrical and thermal conductivity.
(2) Metals obey Ohm`s law. In the steady state condition, the current density j is proportional to the
applied electric potential.
J E or J = E
(3) Where, is electrical conductivity, which is about 107mhos m-1.
(4) At low temperatures, the resistivity is proportional to the fifth power of absolute temperature.
T5
(5) Above Debye temperature, the resistivity of metals is proportional to the absolute temperature.
Thus metals have positive temperature coefficient of resistivity.
(6) In the case if the metal contains small impurity, the resistivity can be written as
= i +ph (T)
Where i is constant which increases with impurity content and ph (T) is the temperature dependent

2
 part, and this equation is known as Matthiessen`s rule.

(7) The ratio of thermal and electrical conductivity is a constant at constant temperature.
K/ = LT.
(8) This is known as Wiedemann-Franz Law. The constant L is called Lorentz number
(10) Metals exhibit the phenomenon of superconductivity, its resistivity disappears in temperature
range 0 < T < Tc. The temperature Tc is called critical temperature and above this temperature the
resistivity is finite.
(11) For most metals, the electrical resistivity decreases with increase of pressure.
(12) Metal alloys exhibit order-disorder transitions and the resistivity shows pronounced minimum
corresponding to the ordered phase.

Session-9: Classical free electron theory and Free electron model:

Successes & Failures.
30 Minutes
Classical free electron theory: Success and Failure (Board Teaching)

The discovery of the electron by J. J. Thomson in 1897 enbaled P. Drude to produce a very satisfactory
theory of the electrical and thermal conductivities of metals in 1900. In 1904-1905, H. A. Lorentz gave
an improved mathematical formulation of Drude theory without essentially adding anything to its
physical content. These two independent models are now combined and called it as Drude-Lorentz
classical free electron theory of metals.

In order to understand this model, consider a sodium crystal. Each sodium atom contains 11 electrons
and its electronic configuration is 1s22s22p63s1. The inner shells are completely filled and the outer shell
is unfilled and contains only one electron. The inner 10 of the electrons are in filled shells which are
tightly bound to the nucleus to form a net positive charge. These electrons can be treated as core
electrons. The remaining 11th electron in the outer shell is loosely bound to the nucleus and moves
around the positive ion core. This electron is called as valence electron or conduction electron. In this
sodium crystal the atoms are close enough to form metallic bonds between them and the valence
electrons are not associated with the parent atom as illustrated in the figure 3.2. These electrons may be
considered as moving freely in between positive ions or the crystal hence they constitute a free electron

3
gas similar to the molecules in a gas container. The theory connected to these electrons is known as free
electron theory or free electron gas theory of metals.

Figure 3.2: Valence electrons in sodium metal (left) and the free electron approximation (right).

This model has been developed by the application of Kinetic theory of gases, Maxwell-Boltzmann
statistics and Equilibrium Theorem to the electrons in the metal. For the purpose of understanding
the electrical and thermal properties of metals, the following basic assumptions have been made in
the theory.
Basic Assumptions:
A metal consists of positive ion cores surrounded by delocalized electrons called valence
electrons which are freely moving between charged ions similar to the molecules in a gas
container. Hence they constitute a free electron gas.
The mutual repulsion between the electrons is neglected and this approximation is called
independent electron approximation (true).
Forces between conduction electrons and ion cores should be neglected and this
approximation is called free electro approximation (not true).
All collisions are assumed to be elastic in nature i.e., no energy is lost in the interaction
process.
The potential experienced by the electrons due to the positive ions is completely uniform
and without loss if generality, this potential can be considered as zero. As a result, there is no
change in the energy of the electron when it is moving inside the metal or it strikes the surfaces.
The total energy of conduction electrons in a metal is all kinetic energy.

4
 At room temperature, the conduction electrons cannot escape from the surface of the
metal because of the surface potential. Thus the electrons are confined within volume of the
metal. This means that the potential energy of the electron inside the metal must be lower than
that at the surface of the metal. Therefore, we assume that the edges of the metal surfaces are
the sites of sharp potential barrier and crystal acts as potential energy box. In this energy box,
the conduction electrons move freely like molecules in a gas container.
Since the electron gas in a metal having properties similar to those of an ordinary
molecular gas, so one can approximate that the free electron gas also obeys the same laws of
Kinetic theory of gases.
The free electron gas is now treated as a perfect gas and at thermal equilibrium; the
electrons obey the Maxwell-Boltzmann statistics.
According to the equipartition theorem, in the absence of electric field, the energy
associated with each electron at a temperature T is 3/2KBT, where KB is the Boltzmann constant.
Based on the above assumptions, a simple physical model has been developed to understand the
electrical conductivity in metals. According to the free electron theory, the free electrons in a metal
move randomly with an average speed ~ 10 5 m/s. Consider a metal consists of valence electrons. These
electrons are freely moving in all possible directions in the absence of an electric field as shown in the
figure 3.3. Hence, their average velocity becomes zero. Let n be number of free electrons per cubic
meter in the conductor and vibe the velocity of the ith electron, then the average velocity va of free
electrons can be expressed as
n
1
Va = vi = 0
n i=1
At thermal equilibrium, there is an equal probability for number of electrons moving in one direction to
those moving in the opposite direction. Therefore the free electrons follow Maxwell-Boltzmann
distribution function. This fact explains that in the absence of an external electric field, the contribution
of electrons to electric current in a conductor is zero.

5
 Figure 3.3:Random motion of electrons in the absence of electric potential.

SUCCESSESOF THE CLASSICAL FREE ELECTRON THEORY

This theory has been given an idea about the electrical conductivity which depends on
temperature.
This theory successfully explained the Ohms law.
This theory successfully explained the conductivity of monovalent metals.
This theory successfully explained the skin depth.
This theory is used to verify the Wiedmann-Franz law, which relates the electric conductivity
and thermal conductivity K in metals.
K
=L
T
Where, L is called the Lorentz number and it is a constant value.
FAILURES OF CLASSICAL FREE ELECTRON THEORY

This theory fails to explain the temperature variation of electrical conductivity in metals.
Experimentally the conductivity T-1.
According to the free electron theory, the conductivity is proportional to the electron
concentration. It is supersizing that the divalent metals and even trivalent metals exhibit less
conductivity than monovalent metals despite the fact that the former have higher electron
concentration compared to the later one.
Wiedmann-Franz law is constant for all the temperatures in the free electron theory. But this is
not true at low temperatures is ten times larger than the value at room temperature.
This theory is unable to explain the negative and positive hall coefficients in semiconductor.
This theory could not predict the different colors of metals.

6
10 Minutes
Verify
1. Define free electron.
2. Write assumptions of classical free electron theory.
3. Explain reasons for failure of classical free electron theory.

30 Minutes
QUANTUM FREE ELECTRON THEORY OF METALS: SOMMMERFELD THEORY ( Board
Teaching)

The study of metallic properties in terms of the motion of free electrons has been started before the
invention of quantum mechanics. Drude and Lorentz made first attempts to understand the properties of
metals using the laws of classical mechanics. This classical theory has several remarkable successes
like the verification of ohms law and the Wiedmann-Franz law but it could not reconcile with all the
experimental observations. The failures of classical free electron theory leads to the invention of
quantum free electron theory which was introduced by sommerfeld. In this theory, he applied quantum
laws to the electrons in a metal in addition to the Fermi-Dirac statistics and Pauli Exclusion Principle.
He developed a model based on the assumptions which are discussed as below.

Basic assumptions of the theory:

Sommerfeld free electron theory of metals is simple theory in which the electron can be treated
as a quantum particle.
The classical free electron model is modified by taking into account quantum mechanics and the
Pauli Exclusion Principle.
Free electrons are valence electrons of the atoms just like in the classical theory.
A valence electron in a metal finds itself in the field of all ions and that of the other electrons.
The mutual repulsion between the electrons is neglected and the potential representing the attractive
interaction of ions is assumed to be completely uniform everywhere inside the solid.
The independent electron approximation and the free electron approximations are retained in the
sommerfeld theory also.

7
 Distribution of electrons in the energy states in an electron gas obeys the Fermi-Dirac quantum
statistics.
Only electrons close to the Fermi energy are scattered that is only a fraction of valence electrons
contribute to the electrical conductivity and such a fraction of electrons is called effective number
of electrons or conduction electrons.
Each energy level corresponding to the principal quantum number splits up into two very close
energy levels representing the electron spin-up and spin-down states. According to Pauli Exclusion
Principle only one electron can occupy one energy level. Thus an energy level in this model can
accommodate at the most two electrons.
The potential energy of the electrons within the metal is constant and might be taken as zero
everywhere except at the ends of the box. Hence, the electrons are moving freely in the metal and
can be treated as free electron gas in a potential energy box. Thus it is called sommerfeld quantum
free electron theory of metals.
Sommerfeld applied these assumptions and the first to find the possible energy levels of electrons in the
potential energy box by solving the solution of the wave equation. Then he applied the Pauli Exclusion
Principle for the distribution of a large number of electrons among these energy levels in the metal. The
expression for the energy of a free electron in a potential energy box and is given by,
2 2 2
E= n
2m L2
n=1,2,3
From the above equation it is clear that the energy eigen values depend on the values of n, the principal
quantum number. For a given value of n, there must be one energy level. So we have a set of energy
levels constituting a discrete energy spectrum.

10 Minutes
Verify
1. State the quantum concept incorporated in quantum free electron theory.
2. State the approximation in quantum free electron theory.
3. Explain the property that could not be explained by the quantum free electron theory.

8
Session 10: Kronig - Penny Model; Energy band theory:
Classification of materials into conductors,
semiconductors and insulators
30 Minutes
PARTICLE IN A PERIODIC POTENTIAL (Board Teaching)
BLOCH THEOREM
One of the first great successes of quantum theory in applied physics is band theory, which eventually
resolved the puzzle of electrical transport in metals, semiconductors, and insulators. The core of
modern understanding of electronic and optical properties of solid-state materials is based on the band
theory, which describes the properties of electrons in a periodic potential. The periodic potential is due
to the periodic arrangement of atoms in a crystal.
The description of the electron in the periodic material has to be via the Schrodinger equation

[ 2 2
2m 0 ]
+U ( r ) ( r ) =E ( r )

where U(r) is the background potential seen by the electrons. Due to the crystalline nature of the
material, the potential U(r) has the same periodicity, R, as the lattice U(r) = U ( r + R)
If the background potential is zero, the electronic function in a volume V is
eik .r
(r)=
V
and the electron momentum and energy are
p= k
2 2
k
E=
2m 0
The wave function is spread in the entire sample and has equal probability (*) at every point in
space. Let us examine the periodic crystal. We expect the electron probability to be same in all unit
cells ofthe crystal because each cell is identical. If the potential was random, this would not be the case,
as shown schematically in Fig. 3.7a. This expectation is, indeed, correct and is put in a mathematical
form by Blochs theorem. Blochs theorem states that the eigen functions of the Schrodinger equation
for a periodic potential are the product of a plane wave eik.r and a function Uk(r), which has the same
periodicity as the periodic potential.
ik . r
Thus k ( r ) =e U k (r )

9
Figure 3.7: (a) Potential and electron probability value of a typical electronic wave-function in a
random material. (b) The effect of a periodic background potential on an electronic wave-function.
In the case of the periodic potential, 2 has the same spatial periodicity as the potential. This puts a
special constraint on (r) according to Bloch's theorem is the form of the electronic function. The
periodic part Uk(r) has the same periodicity as the crystal; i.e.,
U k (r)= U k (r+R)

10
The wave-function has the property
k ( r+R ) =e ik . ( r+R ) U k ( r+R ) =eik . ( r ) U k ( r ) eik . R =e ik . R k ( r )
The wave-function is illustrated in Fig. 3.7b. Before discussing the solutions of the periodic potential
problem, let us take a look at some of the important properties of crystalline materials.
KRONIG-PENNEY MODEL
The Kronig-Penney model is represented by the one-dimensional periodic potential shown in figure
3.8.
Even though the model is one-dimensional, it is the periodicity of the potential that is the crucial
property that yields electronic band structure. The mathematical form of the repeating unit of the
potential is

Figure 3.8: Kronig-penney potential.

V(x)=Vo -b<x<0
=0 0<x<a
As shown in the above figure the potential has a period of c=a+b. The schrodinger equation for the
model is,

The coefficients in both of these equations are constants, so the solutions are similar to that of a particle
in a box. The solutions to Equations 2 are

11
 The Schrodinger equations will have non-zero solution if the following condition is satisfied, i. e.,

sin a
P + cos a=cos Ka
a

where P=
4 2 mV 0 ab
h
2
, =
8 2 m E
h
2
,K=
2

and a is width of potential well.

The two variables in the above equation are and K. The right hand side of the above equation s
bounded between +1 and -1. Thus, left hand side of the above equation also should be in between +1
and -1. So only those values of (related to energy), which will permit the left hand side of the
equation to take values between + 1 and 1 are allowed. The range of such values can be found from
the following plot.

12
Conclusions drawn from the plot:

1. Motion of electrons is a periodic lattice is characterised by the band of allowed energy separated
by forbidden regions.
2. As the values of a increases, the width of allowed band also increases and width of forbidden
band decreases.
3. Effect of P: P is measure of potential barrier strength. If V0b is large, then P will be large. Then
the allowed bands are narrower and forbidden bands are wider. On the other hand if P = 0, then
all energies are allowed for electron.
Energy band structure for three cases: 1. P= 0 (free electron), 2. P = intermedeate values, 3. P=
(tight binding) are in the following figure.

13
Figure 3.9:A plot of energy E against wave number k showing the band gaps that appear when k
A(1+R)= N. The dashed line is the parabolic result for free electrons.
BRILLOUIN ZONES:
The Brillouin zones highly depend on momentum of electrons (k-space). The energy spectrum of an
electron moving in the presence of periodic potential field is divided into allowed and forbidden zones.
When a parabola representing the energy of a free electron is compared with the energy of an electron
in a periodic field, it is clear that the discontinuities in the parabola occur at values of k given by,
K = n/a
where n = 1, 2, 3. since k is the wave vector.
k = 2/ = n /a
2a = n
From the parabola it can be observed that the electron has allowed energy values in the region (zone)
extending from k = -/a to +/a. This zone is called first Brillouin zone. After the forbidden gap,
where there is a discontinuity in energy. Another zone of energy extending fromk = -/a to -2/a and k
= /a to 2/a. This zone is known as second Brillouin zone. Similarly, other higher order Brillouin
zones can be defined.
Importance of Brillouin zone:
The Brillouin zones are used to describe and analyze the electron energy in the band energy structure of
crystals.

10 Minutes

14
Verify
1. Draw the potential well for a one dimensional lattice as proposed by Kronig - Penny (Let a is the
inter atomic spacing).
2. Explain variation of energy gap with increase of energy level.
3. Explain the conclusions of Kronig - Penny model.

30 Minutes

ENERGY BAND STRUCTURES IN SOLIDS (Board Teaching & PPT)

In an isolated atom electron occupy well defined energy states, when atoms come together to form a
solid, their valence electrons interact with each other and with nuclei due to Coulomb forces. Inter
atomic spacing is small in solids compared with liquids and gases. Due to this closeness of atoms,
energy levels of the atoms are disturbed. Energy levels of the valence electrons are most affected. Each
energy level splits up into a number of closely spaced levels. These split energy levels form a
continuous band called energy band as shown in fig 3.13.
Energy level is the discrete energy of an electron in an atom. But energy band is the energy of the same
electron when it is in a solid. At large separation distances, each atom is independent of all the others,
so they have energy levels. But the atoms come close to each other, electrons respond to the influence
of other nuclei and electrons. So each atomic level splits into N levels each of which may be occupied
by pairs of electrons of opposite spins. The extent of splitting depends on inter atomic separation.
Firstly outer most electron shells are disturbed.
In each energy band, energy levels are discrete; the difference between adjacent states is infinitesimally
small. At the equilibrium spacing, band formation may not occur for electron sub shells nearestthe
nucleus as shown in fig 3.13. Further gaps exist between adjacent bands. The electron does not have
any energy with in energy gap.

15
 Figure 3.13: Electron energy versus inter atomic separation for an aggregate of atoms

ENERGY BAND STRUCTURES AND CONDUCTIVITY

There are four types of band structures which are possible at 0 K. The highest filled state at 0 K is
called Fermi Energy (EF). The two important energy bands are:
Valence band: Valence band is the wide range of energies possessed by the valence electrons.The
highest filled energy band where the electrons are present at 0 K.
Conduction band: Conduction band is the wide range of energies possessed by the conduction
electrons. A partially filled or empty energy band where the electrons can increase their energies by
going to higher energy levels within the band when an electric field is applied.

Energy Band Structures and Conductivity for metals

In metals (conductors), highest occupied band is partially filled or bands overlap. Conduction occurs by
promoting electrons into conducting states that starts right above the Fermi level. The conducting states
are separated from the valence band by an infinitesimal amount. Energy provided by an electric field is
sufficient to excite many electrons into conducting states.
Ex: Copper atomic number is 29, its electronic configuration is - 1s 22s22p63s23p63d104s1. Each copper
atom has one 4s electron. For a solid consisting of N atoms, the 4s band can accommodate 2N
electrons. Thus only half of the 4s band states are filled. This is shown in fig 3.14(a).
For the second band structure, there is an overlap of filled band (valence band) and empty band
(conduction band). Ex: Magnesium atomic number is 12, its electronic configuration is 1s 22s22p63s2.

16
Each magnesium atom has two 3s electrons. In a solid of magnesium, the 3s and 3p bands are
overlapped. This is shown in fig 3.14(b).

Figure 3.14: The various possible electron band structures in solids at 0 K. (a) The electron band
structure found in metals such as copper, in which there are available electron states above and adjacent
to filled states, in the same band. (b) The electron band structure of metals such as magnesium, wherein
there is an overlap of filled and empty outer bands. (c) The band structures of insulators. (d) The band
structure of semiconductors.

Energy Band Structures and Conductivity for Semiconductors and insulators:

As shown in fig 3.14, (c) and (d) band structures are similar. The valence band is completely filled with
electrons. There is large energy gap between filled valence band and empty conduction band. Ex:
Insulators. If the energy gap between valence and conduction band is small than i.e. semiconductor.
Electrical conduction requires that electrons be able to gain energy in an electric field. To become free,
electrons must be promoted (excited) across the band gap. The excitation energy can be provided by
heat or light. In semiconductors and insulators, electrons have to jump across the band gap into
conduction band to find conducting states above Ef.The energy needed for the jump may come from
heat or from irradiation at sufficiently small wavelength (photo excitation).
The difference between semiconductors and insulators is that in semiconductors electrons can reach the
conduction band at ordinary temperatures, where in insulators they cannot. An electron promoted into
the conduction band leaves a hole(positive charge) in the valence band, that can also participate in
conduction. Holes exist in metals as well, but are more important in semiconductors and insulators.
10 Minutes
Verify
1. In terms of electron energy band structure, discuss reasons for the difference in electrical

17
 conductivity between metals, semiconductors, and insulators.
2. Explain formation of energy band structure considering decrease in inter atomic spacing in to
account.
3. Define equilibrium spacing.

Session 11
Process of electrical conduction in metals, conductivity,
mobility and Matthiessen's rule
30 Minutes
Process of electrical conductivity in metals (Board Teaching)

It is defined as the voltage apply to a conductor which is equal to the product of current passing
through the conductor times its resistance. This law is independent of size and shape of the conductor
under consideration. However, it can alsobe expressed in terms of current density J and electric field E.
The current density in the direction of electric field is defined as the amount of charge flowing across a
unit area of cross section per unit time in a conductor. If n is a number of electrons crossing a unit area
in unit time then the amount of charge is equal to ne. Average velocity of electrons is the drift
velocity. The flow of charge per unit time through unit area of the conductor is equal to the product of
electon charge times the drift velocity of the electrons which is current density
J = -nevd.

ne 2
J= m E
Or
J=E
It follows that the electric current density is proportional to the applied electric field. This equation is
known as Ohms law and proportionality constant is called electrical conductivity .

(iv) Electrical conductivity

In general the electrical conductivity is a property of a conducting material which allows the flow of
current.

18
 ne 2
= m
This is one of the central results of the classical free electron theory of metals. This formula is not
useful for calculating the conductivity of a given metal, since it contains an unknown term called
relaxation time. The theory itself has important implications. This picture of electron gas undergoing
constant scattering and is still used. For a particular metal n, e and m are constants. Therefore, the
electrical conductivity depends on the relaxation time . Thus in the absence of collision process the
relaxation time is infinite and hence the conductivity becomes infinite. The electrical conductivity can
also be expresses in terms of mobility.
= ne
Thus in general the electrical conductivity of a metal depends on two factors. They are n and .

(v) Electrical Resistivity ()

Electrical resistivity is a measure of how strongly a materialopposes the flow of electric current. A low
resistivity indicates a material that readily allows the movement of electric charge. The S.I. unit of
electrical resistivity is -m. It is commonly represented by a Greek letter .
(vi) Electrical conductivity ()
It is the ability of a substance to conduct an electric current. It is the inverse of the resistivity.

Figure 3.6:Schematic representation of the apparatus used to measure electrical resistivity.

Ohm's law can be rewritten in terms of the current density J = I/A as: J = E. Ohms law can be
expressed in both microscopic and macroscopic forms.

19
 (Macroscopic form)
(Microscopic form)
Electrical conductivity varies between different materials by over 27 orders of magnitude.
Metals: > 105 (.m)-1
Semiconductors: 10-6< < 105 (.m)-1

Insulators: 10-6 (.m)-1<<10-20(.m)-1

One of the best materials for electrical conduction (low resistivity) is silver, but its use is restricted due
to the high cost. Most widely used conductor is copper: inexpensive, abundant, high , but rather soft
cannot be used in applications where mechanical strength is important.

Table 3.1: Room temperature electrical conductivities for eight common metals and alloys

Solid solution alloying and cold working improve strength but decrease conductivity. If hardeningis
preferred, Cu-Be alloy is used. When weight is important one uses aluminum, which is half as good as
Cu and more resistant to corrosion. Heating elements require low (high R), and resistance to high
temperature oxidation: nickel chromium alloy.

Drift velocity of electrons :

When an electric field E is applied to a conductor, the electrons modify their random motion and move
with an average drift velocity vd in a direction opposite to that of the electric field and an electric
current is established in the conductor. The flow of current in a conductor is an indication that the
electron in it moves in a specific direction. As a result, Maxwell-Boltzmann distribution function of the
electrons in the conductor undergoes a change. The directional motion of the electrons is due to the

20
applied electric field. The group of electrons within the conductor drifts in the direction opposite to the
applied electric field. This motion is called a drift motion and the associated velocity of the electron is
called drift velocity.
Due to the electric field E an electron inside the metal experiences a force and this force F is equal to
the product of electric charge and electric field.
F=-e * E
wheree is the charge of the electron. As a result, the electron acquires acceleration. According to
newtons second law of motion, the force experienced by the electron is given by
F=m * a
wherea is the acceleration of the electron and m is the mass of the electron. Eliminating F from the
above equations gives the acceleration of the electron under the influence of electric field eE=ma.
eE
a=
m
It is clear from the above equation that the electrons are accelerated indefinitely because of growth of
their velocity due to electric field i.e. its drift velocity vd increases with time. However the electrons
are not accelerated indefinitely because during their motion the electrons collide with impurities and
lattice imperfections in the crystal. Here Drude assumed that the conduction electron acquires random
motion after collision with impurities and lattice imperfections. In the collision process the electron
loses the energy and after collision it again gains energy from the electric field. The velocity of the
electrons after collision does not depend upon its velocity before collision. When the electron collides
with the lattice imperfection it stops momentarily and moves in another direction with a new velocity.
Thus electrons acquire random motion even in the presence of electric field. This problem can be
solved by considering these collisions are similar to the collision process of an ideal gas in a container.
The collision process introduces the concept of relaxation time, which influences the conductivity in
the metals. The average time between successive collisions of electron with the lattice imperfection is
called relaxation time and is denoted by .

The acceleration of the electron due to collision with impurities is given by vd/ (negative sign is due
to the acceleration is opposite to the direction of electric field). Now, the acceleration is equal to sum
of the acceleration due to electric field and acceleration due to collision with impurities.
eE vd
a=
m

21
After sometime the acceleration of the electrons due to the electric field and acceleration due to
collision should compensate with each other but leads to steady state condition of the electron gas. As
a result the acceleration of electron becomes zero
eE vd
=0
m
The drift velocity of the electron is then obtained by arranging the above equation.
eE
vd=
m
Thus the electrons in a conductor attain a constant drift velocity under the application of the electric
field. The drift velocity is proportional to applied electric field and the proportionality constant is
called the electron mobility .
(ii) Electron Mobility () :
The electron mobility is defined as the drift velocity vdper unit applied electric field E.
vd
=
E
Substituting the value of dirft velocity in the above equation we get
e
=
m
The above equation shows that mobility of an electron depends on the relaxation time and hence it
depends on temperature.

10 Minutes
Verify
1. Draw energy band structure for Copper and Magnesium.
2. Write microscopic and macroscopic forms of Ohm's law
3. Define drift velocity and mobility of electron and write the expression of electrical conductivity in
metals.
30 Minutes
ELECTRICAL RESISTIVITY OF METALS :
The resistivity is defined by scattering events due to the imperfections and thermal vibrations. Total
resistivity tot can be described by the Matthiessens rule:
total = thermal + impurity + deformation , Wherethermal - from thermal vibrations, impurity - from impurities,

22
deformation - from deformation-induced defects resistivity increases with temperature, with deformation,
and with alloying.
Graphical explanation to electrical resistivity in metals:

APPLICATIONS OF ELECTRICAL CONDUCTING MATERIALS

One of the best materials for electrical conduction (low resistivity) is silver, but its use is restricted due
to the high cost. Most widely used conductor is copper: inexpensive, abundant, high , but rather soft
cannot be used in applications where mechanical strength is important.

Table 3.1: Room temperature electrical conductivities for eight common metals and alloys

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Solid solution alloying and cold working improve strength but decrease conductivity. If hardeningis
preferred, Cu-Be alloy is used. When weight is important one uses aluminum, which is half as good as
Cu and more resistant to corrosion. Heating elements require low (high R), and resistance to high
temperature oxidation: nickel chromium alloy.

10 Minutes
Verify
1) Discuss the origin of electrical resistance in metals.
2) Explain variation of electrical resistance of a metal with change of temperature?
3) Compare the influence of temperature, impurity concentration and deformation on electrical
resistance of metals.

Session 12 : Semiconductors and conductivity

30 Minutes
Classification - conductivity (Board Teaching)
SEMI CONDUCTORS
INTRODUCTION (10 min)
The electrical conductivity of the semiconducting materials is not as high as that of the metals.
Nevertheless they have some unique electrical characteristics that render them especially useful. The
electrical properties of these materials are extremely sensitive to the presence of even minute
concentrations of impurities.
Intrinsic Semiconductors (20 min):
Intrinsic semiconductors - electrical conductivity is defined by the electronic structure of pure
material.
Extrinsic semiconductors - electrical conductivity is defined by impurity atoms.
Intrinsic semiconductors
Highly pure semiconductors with no impurities are called intrinsic semiconductors. In such a material
there are no charge carriers at 0K. Since the valence band is filled and the conduction band is empty. At
higher temperatures, the electrons reaching the conduction band due to thermal excitation leave equal
number of holes in valence band. In intrinsic semiconductor, the number of free electrons is equal to
the number of holes. The bond structure and band structures of intrinsic semiconductors are shown in

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below fig 3.15.
Examples: Si, Ge, GaP, GaAs, InSb, CdS, ZnTe

(a) (b)
Figure 3.15: (a) For a semiconductor, occupancy of electron states after an electron excitation from the
valence band into the conduction band in which both a free electron and a hole are generated. (b)
Electron bonding model of electrical conduction in intrinsic silicon after excitation.

Number of electrons in the conduction band increases exponentially with temperature.E g is the band-
gap width. In an electric field, electrons and holes move in opposite direction and participate in
conduction.Since both electrons and holes are charge carriers in an intrinsic semiconductor, the
conductivity is
=ne e +peh
where p is the hole concentration and h the hole mobility.
Electrons are more mobile than holes, e>hIn an intrinsic semiconductor, a hole is produced by
thepromotion of each electron to the conduction band. Therefore, n = pand (only for intrinsic
semiconductors)
=ne( e +h ) =pe( e +h )

n (and p) increase exponentially with temperature, whereas e and h decrease (about linearly) with
temperature.The conductivity of intrinsic semiconductors is increasing with temperature (different from
metals)
=ne( e +h )

Extrinsic semiconductors
The application of intrinsic semiconductors is restricted due to its low conductivity. In electronic
devices, high conducting semiconductors are more essential. The concentration of either electrons or

25
holes in a semiconductor should be increased depending upon the requirements in the electronic
devices.
This can be carried out simply by adding impurities (one atom in 10 7 host atoms) to the intrinsic
semiconductors. The process of adding impurity to the intrinsic semiconductors is called doping. The
doped semiconductor is called as extrinsic semiconductor. The concentration of electrons and holes are
not equal in an extrinsic semiconductor.
Usually the doping material is either penta-valent atoms (P, AS, Sb, Bi) or trivalent atoms (B, Al, Ga,
In). The penta-valent atom is called donor atom because it donates one electron to the conduction band
of pure semiconductor. The trivalent doping atom is called acceptor atom because it accepts one
electron from semiconductor atom. The added impurity is called dopant.
In Extrinsic semiconductors, electrical conductivity is defined by impurity atoms.
Example: Si is considered to be extrinsic at room T if impurity concentration is one impurity per 10 12
lattice sites (remember our estimation of the number of electrons promoted to the conduction band by
thermal fluctuations at 300 K) unlike intrinsic semiconductors, an extrinsic semiconductor may have
different concentrations of holes and electrons. It is called p-type if p > n and n-type if n > p.
Thus there are two types of extrinsic semiconductors depending on the type of impurity added (10
min).
1. N-type extrinsic semiconductors
2. P-type extrinsic semiconductors
N-type extrinsic semiconductors:
Excess electron carriers are produced by substituting impurities that have more valence electron per
atom than the semiconductor matrix.
Example: phosphorus (or As, Sb) with 5 valence electrons, is an electron donor in Si since only 4
electrons are used to bond to the Si lattice when it substitutes for a Si atom. Fifth outer electron of P
atom is weakly bound in a donor state(~ 0.01 eV) and can be easily promoted to the conduction
band.Impurities which produce extra conduction electrons are called donors,Elements in columns V
and VI of the periodic table are donors for semiconductors in the IV column, Si and Ge.
The hole created in donor state is far from the valence band and is immobile. Conduction occurs mainly
by the donated electrons thus n-type.

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Figure 3.16: Extrinsic n-type semi conduction model (electron bonding). An impurity atom such as
phosphorus, having five valence electrons, may substitute for a silicon atom.

(a) (b)
Figure 3.17: (a) Electron energy band scheme for a donor impurity level located within the band gap
and just below the bottom of the conduction band. (b) Excitation from a donor state in which a free
electron is generated in the conduction band.

P-type extrinsic semiconductors:

Excess holes are produced by substituting impurities that have fewer valence electrons per atom than
the matrix. A bond with the neighbors is incomplete and can be viewed as a holeweakly bound to the
impurity atom. Elements in columns III of the periodic table (B, Al, Ga) are donors for semiconductors
in the IV column, Si and Ge. Impurities of this type are called acceptors.

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 (a) (b)
Figure 3.18: (a) Energy band scheme for an acceptor impurity level located within the band gap and
just above the top of the valence band. (b) Excitation of an electron into the acceptor level leaving
behind a hole in the valence band.

Figure 3.19: Extrinsic p-type semi conduction model (electron bonding). An impurity atom such as
boron having three valence electrons, may substitute for a silicon atom.

The energy state that corresponds to the hole (acceptor state) is close to the top of the valence band. An
electronmay easily jump from the valence band to complete the bondleaving a hole behind. Conduction
occurs mainly by theholes (thus p-type). For extrinsic p-type semiconductors
=pe p

10 Minutes
Verify
1) Explain the conductivity and resistivity of different types of semiconductors.

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 2) Compare the temperature dependence of the conductivity for metals and intrinsic
semiconductors. Briefly explain the difference in behavior.
3) Draw energy band stucture of n-type and p-type semiconductors.
4) Compare the temperature dependence of the conductivity for metals and intrinsic
semiconductors. Briefly explain the difference in behavior.

30 Minutes
Factors effecting conductivity of semiconductors
1) Temperature effect on concentration of charge carrier in intrinsic and extrinsic semiconductors.
2) Effect of concentration of charge carriers on mobility of charge carriers.
3) Effect of temperature on mobility of charge carriers
(Please refer Callister's Materials science and engineering - An Introduction)

10 Minutes
Verify
1. State the reason for increase of electrical conductivity with increase of temeperature in intrinsic
semiconductor.
2. State the reason for decrease of mobility with increase of concentration of charge carriers and
temperature.
3. Explain the resons for no change in carrier concentration with increase of temperature in extrinsic
region.

Session 13: Basic definitions in Dielectrics, relations and

Polarization
30 Minutes
DIELECTRICS ( Board Teaching)

All dielectric materials are electrical insulators. But all electric insulators need not be dielectrics. Ex:
Vacuum is an insulator but it is not dielectric.The distinction between a dielectric material and an
insulator lies in the application. The insulating materials are used to resist the flow of current through

29
it, when a potential difference is applied across its ends. On the other hand the dielectric materials are
used to store electric energy.
Dielectrics are the materials having electric dipole moment permanently or temporarily by applying the
electric field. In dielectrics all the electrons are bound to their parent molecules and there are no free
charges. Further at the ordinary temperatures, the electrons cannot be dislocated either by thermal
vibrations or by ordinary applied voltages. Generally the dielectrics are non-metallic materials of high
resistivity and have negative temperature coefficient of resistance.
A dielectric material is an insulator in which electric dipoles can be induced by the electric field (or
permanentdipoles can exist even without electric field), that is wherepositive and negative charge are
separated on an atomic ormolecular levelwith r = 81 for water, 20 for acetone,12 for silicon, 3 for ice,
etc.
FUNDAMENTAL DEFINITIONS :
Dielectric constant (r)
The dielectric characteristic of a material are determined by the dielectric constant or relative
permittivity r of that material. The dielectric constant determines the share of the electric stress
which is absorbed by the material. It is the ratio between the permittivity of the medium and the
permittivity of free space.

r =
free
The dielectric constant r has no unit and it is a measure of the electric polarization in the dielectric
material.
Electric polarization
When an electric field is applied to a crystal or a glass containing positive and negative charges, the
positive charges are displayed in the direction of field, while the negative charges are displaced in the
opposite direction. This displacement produces local dipoles throughout the solid. Thus the process of
producing dipoles by an electric field is called polarization in dielectrics.
Polarization vector (P)
It is found that the strength of the induced electric dipole moment is proportional to the applied electric
field.
=E
Where is the constant of proportionality, called the polarizability. If -is the average dipole moment

30
per molecule and N is the number of molecules per unit volume then the polarization the solid is given
by the polarization vector P and it can be written as
P=N
So the polarization vector P is the dipole moment per unit volume of the dielectric material.
Electric displacement vector D:
The electric displacement vector (or) electric induction D is a quantity which is a very convenient
function for analyzing the electrostatic fields in the dielectric and is given by
D= E=o E+P
From this one can get
P
= o = o ( r 1 )
E
This quantity D is similarly to the magnetic inductionB in the magnetism. Further the electric
displacement vector D has the remarkable property that its sources are only the free electric charges.
The dielectric constant of vacuum is 1 and is close to 1 for air and many other gases. But when a piece
of a dielectric material is placed between the two plates in capacitor the capacitance can increase
significantly.
A
C=r o
L
Magnitude of electric dipole moment is = q d
DIELECTRIC MATERIALS IN CAPACITORS :
Dipole formation and/or orientation along the external electric field in the capacitor causes a charge
redistribution so that the surface nearest to the positive capacitor plate is negatively charged and vice
versa. The process of dipole formation/alignment in electric field is calledpolarizationand is described
by P = Q1/A. Dipole formation induces additional charge Q1 on plates: total plate charge Qt = |Q+ Q1|.
Qt
Therefore, C= has increased and dielectric constant of the material r = C / Cvac> 1.
V
In the capacitor surface charge density (also called dielectric displacement) is
D = Q/A = roE = oE +P
Polarization is responsible for the increase in charge density above that for vacuum.
10 Minutes
Verify
1) Define and explain (i) dielectric constant (ii) electric susceptibility (iii) electric polarization and

31
 (iv) polarizability.
2) What is meant by local field in a dielectric material? Explain how the local field could be
calculated for a cubic dielectric crystal.
3) Explain the polarization mechanism in dielectric materials.
4) Establish a relation between the electronic polarizability ( e) and relative permittivity (r) using
the concept of internal field.
5) With usual notations show that P = O (r - 1) E.
6) Obtain an expression for the internal field seen by an atom in an infinite array of atoms
subjected to an external field.

30 Minutes
TYPES OF POLARIZATION :
Polarization is the alignment of permanent or induced atomic or molecular dipole moments with an
external applied electric field. There are three types of polarization (fig. 3.21).
1. Electronic polarization
2. Ionic polarization
3. Molecular (orientation) polarization

(c)
Figure 3.21: (a) Electronic polarization that results from the distortion of an atomic electron cloud by
an electric field.(b) Ionic polarization that results from the relative displacements of electrically
charged ions in response to an electric field. (c) Response of permanent electric dipoles (arrows) to an
applied electric field, producing orientation polarization.

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Electronic (induced) polarization: Applied electric field displaces negative electron clouds with
respect to positive nucleus. It occurs in all materials.
Ionic (induced) polarization: In ionic materials, applied electric field displaces cations and anions in
opposite directions
Molecular (orientation) polarization: Some materials possess permanent electric dipoles (e.g. H2O).
In absence of electric field, dipoles are randomly oriented. Applying electric field aligns these dipoles,
causing net (large) dipole moment.

Ptotal = Pe + Pi + Po

Session 14: Frequency dependence of polarization,

piezoelectricity and Ferroelecity

FREQUENCY DEPENDENCE OF POLARIZATION:

For alternating currents, an applied voltage or electric field changes direction with time. Now, consider
a dielectric material which is connected to ac supply. With each direction reversal, the dipoles attempt
to reorient with the field as shown in below fig 3.22.

33
 Figure 3.22: Dipole orientations for (a) one polarity of an alternating electric field and (b) for the
reversed polarity.

As shown in above fig.in a process requires some finite time. For each type of polarization some
minimum reorientation time exists, which depends on the ease with which the particular dipoles are
capable of realignment. A relaxation frequency is taken as a reciprocal of this minimum reorientation
time.
Electrons have much smaller mass than ions, so they respond more rapidly to a changing electric field.
For electric field that oscillates at very high frequencies (10 15Hz) only electronic polarization can occur.
Compared with electrons, ions have large mass so ionic polarization cant occur at optical frequencies.
It requires large time to displace ions. At smaller frequencies (10 13 Hz) ionic polarization also occur in
addition to electronic polarization.

Figure 3.23: Variation of dielectric constant with frequency of an alternating electric field. Electronic,
ionic and orientation polarization contributions to the dielectric constant are indicated.

Now third type is orientation polarization. Orientation of permanent dipoles which require the rotation
of a molecule can occur only if the oscillation is relatively slow. So at low frequencies (10 6 1010 Hz)
the orientation polarization occurs in addition to electronic and ionic polarization. Space charge
polarization is the slowest process and occurs only at power frequencies (102 Hz).
Thus at low frequencies the value of total polarization is very high and at high frequencies the value of
total polarization is very small. If polarization is large, dielectric constant is also large from formulae
D=0E+P and D=E. Dielectric constant versus frequency graph is as shown in fig 3.23.
TEMPERATURE DEPENDENCE OF POLARIZATION

34
Electronic and ionic polarizations are practically temperature independent at normal temperatures. But
orientation polarization and space charge polarization are affected by temperature.In orientation
polarization, the sum of dipoles in presence of electric field is opposed by thermal vibrations of atoms.
So polarization decreases with increasing temperature. In contrast to this in some polar substances,
normal temperatures will oppose the permanent dipoles to align in the field direction. But higher
temperatures facilitate the movement of dipoles. So polarization increases with increasing temperature.
For example:
1. Dielectric constant of solid HCl decreases from 19 to14 when temperature is increased from 100 to
160 K. This shows that the number of molecules per unit volume decreases due to the expansion on
melting.
2. Solid nitrobenzene is a polar molecule, but it does not exhibit orientation polarization in its solid
state because the rotation of molecules is prevented under an applied field. But in liquid state, the
molecules have sufficient energy to reorient themselves in the applied field. The relative dielectric
constant increases from 3 to 37 on melting. This is in contrast with the results obtained for solid HCl.
DIELECTRIC STRENGTH (OR) DIELECTRIC BREAKDOWN
Very high electric fields (>108 V/m) can excite electrons to the conduction band and accelerate them to
such high energies that they can, in turn, free other electrons, in an avalanche process (or electrical
discharge). The field necessary to start the avalanche process is called dielectricstrength or breakdown
strength.
DIELECTRIC LOSS
When an ac electric field is applied to a dielectric material, some amount of electrical energy is
absorbed by the dielectric material and is wasted in the form of heat. This loss of energy is called
dielectric loss. This loss is at the electric field frequencies in the vicinity of the relaxation frequency for
each of the operative dipole types for a specific material. A low dielectric loss is desired at the
frequency of utilization.

10 Minutes
Verify
1. Explain relatin between dielectric constant and polarization.
2. Explain the reasons decay fo dielectric constant with incrase in frequency of applied field.
3. Define dielectric loss.

35
30 Minutes
FERRO ELECTRICITY :
Ferro electricity is defined as the spontaneous alignment of electric dipoles by the mutual interaction in
the absence of an applied electric field. It arises from the fact that the local field increases in proportion
to the polarization. Thus, ferro-electric materials must possess permanent dipoles.Ex.:BaTiO 3, Rochelle
salt(NaKC4H4O6.4H2O), potassium di hydrogen phosphate(KH2PO4),Potassium niobate (KNbO3).These
materials have extremely high dielectric constants at relatively low applied field frequencies. Thus,
capacitors made from ferro electric materials are smaller than capacitors made of other dielectric
materials.
Properties of Ferro electric Materials:
1. Ferro electric materials can be easily polarized even by very weak electric fields.
2. They exhibit dielectric hysteresis. Lagging of polarization behind the applied electric field is
called dielectric hysteresis. Ferro electricity is a result of dielectric hysteresis.
3. Ferro electric materials possess spontaneous polarization, which is a polarization that persists
when the applied field is zero.
4. Ferro electric materials exhibit ferro-electricity when the temperature T<T c where Tc is
ferroelectric curie temperature when T>Tc, they are converted into para electric materials.
5. They exhibit domain structures as in the case of ferromagnetic materials.
6. Ferro electric materials exhibit piezo electricity and pyro electricity. Piezo electricity means the
creation of electric polarization by mechanical stress. Pyro electricity means the creation of electric
polarization by thermal stress.
Spontaneous polarization and domains in BaTiO3:
The structural changes in BaTiO 3 crystal due to lattice variation give rise to ferro electricity. Above
1200C BaTiO3 has a cubic crystal structure with the titanium ions exactly at the body centre, Barium
ions are at the body corners and oxygen ions are at the face centers as shown in fig 3.25. At those
temperatures, there is no spontaneous dipole moment.
If the crystal is cooled below 1200C the titanium ions shift to one side of the body centre. This
displaces the neighboring ions along one of the crystal directions which become elongated. This gives
the tetragonal structure due to the shifting of the titanium ion. This displacement of the titanium ion
creates electric dipoles and all the dipoles of the adjacent unit cells get aligned in

36
Figure 3.25: A barium titanate unit cell in an isometric projection which shows the displacements of
Ti4+ and O2- ions from the center of the face.

one direction. Below 1200C temperatures there is an enormous value for dielectric constant. The
dielectric constants of these materials are some three orders of magnitude larger than that in ordinary
dielectrics. Since ferro electric materials are similar to ferromagnetic materials. They exhibit domain
structure.
Applications of Ferro electric Materials:
1. In optical communication, the ferro electric crystals are used for optical modulation.
2. The high dielectric constant of ferro electric crystals is also useful for storing energy in
small sized capacitors in electrical circuits.
3. These are used in electro acoustic transducers such as microphone.
PIEZO ELECTRICITY (10 min):
In some ceramic materials, application of external forces produces an electric (polarization) field and
vice-versa. Applications of piezoelectricmaterials is based on conversion of mechanical strain into
electricity (microphones, strain gauges, sonar detectors) stress-free with applied stress
Examples: barium titanate BaTiO3 leadzirconate PbZrO3 quartz.

37
Figure 3.24: (a) Dipoles within a piezoelectric material. (b) A voltage is generated when the material is
subjected to a compressive stress.

10 Minutes
Verify
1. Define piezoelectricity and ferroelectrity
2. Write important characteristics of ferro electric materials?
3. Discuss some of the important applications of the piezoelectrics.

38