Prepared By Dr.A.Rajalakshmi, Dept.

of Physics, SSNCE

UNIT - I
CONDUCTING MATERIALS
Part - 1
 Prepared By Dr.A.Rajalakshmi, Dept. of Physics, SSNCE

Lecture #1

Learning Objectives

➢ Introduction to Electron Theory of solids

➢ Classical free Electron Theory of Metals-

Derivation of expression for Electrical
Conductivity and dependence of Resistivity on
Temperature.
 Prepared By Dr.A.Rajalakshmi, Dept. of Physics, SSNCE

Introduction
The field of materials science plays an important role in the
understanding of various properties of materials like physical, chemical,
electrical, mechanical, magnetic etc. All these have a wide range of
applications in the field of engineering, medicine and day to day life. Of these,
many materials, by virtue of their electrical properties, find applications in
electrical appliances, solar cells, capacitors, transformers, microwave oven
etc.

Various theories were developed by scientists to correlate with the

experimentally observed values. This, in fact, has led to the improvement of
material quality and also invention of new materials. Hence, the electrical
properties of materials with theories are explained in a chronological manner
in this chapter.
 Prepared By Dr.A.Rajalakshmi, Dept. of Physics, SSNCE

The characteristic of conducting materials is high electrical conductivity due to the

presence of free electrons. Hence, good conducting materials are used for the conduct of
electricity.

Most metals and some non-metals are electrical conductors and their conducting
properties vary widely depending on the free electrons. In this context, we may define
conductance as the property of the material by which it allows flow of electric current.
Conductance is the reciprocal of resistance and its unit is mho (℧).

Based on electrical conductivity, materials can be broadly classified as

(i). Good conductors (Resistivity 10–9 - 10–6 Ωm)

(ii). Semi conductors (Resistivity 102 - 109 Ωm)

(iii). Non conductors (Resistivity 1011 - 1012 Ωm)

The electron theory of solids was discussed to explain the properties of the above
mentioned materials.
 Prepared By Dr.A.Rajalakshmi, Dept. of Physics, SSNCE
ELECTRON THEORY OF SOLIDS
The scientists have developed numerous theories like classical free electron theory,
quantum free electron theory, band theory etc., to correlate the theory and experimental
values to explain the structure and properties of solids as follows:
Classical Free Electron Theory
Drude and Lorentz developed the classical free electron theory in 1900. This
assumes that the metals contain free electrons which behave like the molecules of a perfect
gas. They obey the Maxwell-Boltzmann statistics and laws of classical mechanics. They are
also assumed to move in a constant potential.
Based on classical free electron theory, Ohm’s law, Wiedemann-Franz law (i.e
ratio of electrical conductivity to the thermal conductivity) etc. can be explained
satisfactorily. It fails to explain many experimental observed facts. For example, the
variation of electrical conductivity of a metal with temperature cannot be explained.
Experimentally, it is known that specific heat of all solids including metal is same where as
on the basis of free electron theory, there should be a difference between the specific heat of
metal and non-metal at room temperature.
 Prepared By Dr.A.Rajalakshmi, Dept. of Physics, SSNCE

Quantum Free Electron Theory

To remove the shortcomings of the free electron theory, it was modified
by Pauli and Sommerfeld in 1928. They suggested that Fermi Dirac statistical law
should be applied to the electron gas rather than the Maxwell-Boltzmann
statistical law. The free electrons obey quantum laws and the wave nature of
electrons is taken into account. The free electrons are assumed to move in a
constant potential and the Fermi level electrons are responsible for determining
the properties of materials. With this modification, the theory could able to
explain all these phenomena which were not explained earlier. But this theory
could still not explain semiconductors and insulators, the positive value of Hall
coefficient etc.
 Prepared By Dr.A.Rajalakshmi, Dept. of Physics, SSNCE
Band Theory
This was developed by Bloch in 1928 and in 1931 Kronig and Penny used a
simplified model to solve Schrödinger’s equation for particle in a box. Here, the
electrons are assumed to move in a periodic potential. The Quantum free electron
theory was modified by taking into consideration the interaction of free electrons with
the residual positive ions in the metal. Due to this interaction, the electrons in metals
as well as in non-metals can occupy only discrete set of energy levels which are
grouped into separate energy bands. The electrons in metals can possess only those
energies which lie in one of the allowed energy bands. Introducing this idea, the
variation of electrical conductivity with temperature, superconductivity and many
other experimental observations like classification of materials into conductors,
semiconductors and insulators could be explained. The origin of band gap, concept of
hole and the effective mass of electrons are the special features of this theory.
Before proceeding to classical free electron theory, the knowledge of some
basic definitions and microscopic form of Ohm’s law are to be explained.
 Prepared By Dr.A.Rajalakshmi, Dept. of Physics, SSNCE

Microscopic form of Ohm’s law

The electrical conductivity of the material is defined as the ratio of current
density ' J ' in (A/m 2 ) to the applied field intensity ' E ' in (V/m).
J
i.e., = (1.1)
E
where  is the electrical conductivity in mhos/m or Siemens/m.
i.e., J = E (1.2)
The above equation is the microscopic form of Ohm’s law.
The conductivity  depends on the nature of the material and not on its
dimensions. It also depends on temperature and impurity concentrations in the
material. The electrical conductivity of the material is given by
1
 = (1.3)


where  is the resistivity in   m .

l
Also, = (1.4)
RA
 Prepared By Dr.A.Rajalakshmi, Dept. of Physics, SSNCE

where l is the length of the conductor in metre (m), R is the resistance of the
conductor in Ohm (Ω) and
1
A is the area of cross section of the conductor in m 2 . The unit of  is or (  m) -1
m

It is also known that

I
J= (1.5)
A
V
and E= (1.6)
l
where I is the current passing through the conductor in ampere and V is the voltage
applied across the length of the conductor in volts.
Hence, from Eqn. 1.4, 1.5 and 1.6 , we have
l J I/A
= = =
RA E V / l
l I/A
=
RA V / l
i.e., V = RI (1.7)
The above equation is the well known macroscopic form of Ohm’s law.
 Prepared By Dr.A.Rajalakshmi, Dept. of Physics, SSNCE

CLASSICAL FREE ELECTRON THEORY OF METALS

POSTULATES / ASSUMPTIONS
1. The valence electrons of the atoms in a metal free to move across its
entire volume. This can be treated like an array of fixed positive ion cores in
a sea of free electron gas (fig 1.1). The mutual repulsion between the
electrons can be neglected.

Fig 1.1 Free electron gas in positive ion cores

 Prepared By Dr.A.Rajalakshmi, Dept. of Physics, SSNCE

2. When no field is applied, the electrons move randomly colliding with the ion
cores and other electrons. Hence the resultant velocity in any direction becomes
zero (Fig 1.2).

Fig. 1.2 Random motion of electrons

3. Maxwell Boltzmann statistics can be applied to the velocity distribution of

electrons.

4. Also kinetic theory of gases is obeyed by the free electron gas.

 Prepared By Dr.A.Rajalakshmi, Dept. of Physics, SSNCE

5.On application of a field É’’across the metal, there will be a drift of

electrons opposite to the field as they gain energy from the field. But they
will still collide with the fixed ion cores and among themselves and hence
also loose energy. Finally, when these balances each other, the electrons

reach an average drift velocity vd which is a constant and opposite to the

field as shown in Fig 1.3.

Fig. 1.3 Drift velocity

 Prepared By Dr.A.Rajalakshmi, Dept. of Physics, SSNCE

6.But once the field is removed, the electrons will go back to their
equilibrium position of random motion. The time taken for this is called
the relaxation time τ

7.The average time taken by the free electron between two successive
collisions is called the collision time  c .  =  c for metals.

Using the above postulates, the expression for electrical

conductivity  of a metal can be derived as given below.
 Prepared By Dr.A.Rajalakshmi, Dept. of Physics, SSNCE
ELECTRICAL CONDUCTIVITY

To calculate the electrical conductivity, let us first calculate the drift

velocity of an electron in an electric field ' E' .

The force on the electron is

F = eE (1.8)
where e is charge of the electron.
This accelerates the electron according to the Newton’s second law.
If a is the acceleration of the electron in and m is the mass of the electron,
F = ma (1.9)

or ma = eE (1.10)
eE
i.e., a= (1.11)
m
 Prepared By Dr.A.Rajalakshmi, Dept. of Physics, SSNCE

As per the above equation, the electrons should be the accelerated

continuously as a result of the electric field. But this is not the actual case.
The electrons collide with lattice vibrations called phonons,
impurities, lattice imperfections and with the positive ion cores. This
causes a loss of kinetic energy thereby reducing their velocity gained in
the field. Hence, the electrons experience an opposing force ‘Fr’ which
will be proportional to the drift velocity and directed opposite to it.
mvd (t )
Thus, Fr = −
 (1.12)
where ′τ′ is the relaxation time in seconds.
Hence, the equation for motion of the electron in presence of field may be
written as

dvd (t ) mv (t )
m = eE − d
dt  (1.13)
 Prepared By Dr.A.Rajalakshmi, Dept. of Physics, SSNCE

The drift velocity of the electrons will increase till the two forces on
the right-hand side of Eqn. (1.13) become equal. The drift velocity is now
said to have attained its maximum value. The net force acting on the
electron and hence its acceleration become zero.

dvd (t ) dvd (t )
Therefore, m =0 or =0 (1.14)
dt dt

i.e., vd (t ) = a constant = vd (1.15)

where vd is the average drift velocity.
mvd
or , eE = (1.16)

eE
i.e., vd = (1.17)
m

Now, the current density (i.e., the number of charges flowing per unit area
per sec) can be written as
J = ( ne)vd (1.18)
Number of free electrons
where n=
m3
 Prepared By Dr.A.Rajalakshmi, Dept. of Physics, SSNCE

Substituting for vd from Eqn. (1.17), we get

 neeE 
J = 
 m 

 ne2 
i.e., J =   E (1.19)
 m 

The above equation is exactly similar to the equation 1.18 J = E. for
metals.
Comparing Eqn. (1.2) and Eqn.(1.19),
 ne2 
 =   (1.20)
 m 

We can also express  in terms of the mobility of the electron . It is defined

as the drift velocity per unit field.
 vd 
i.e.,  =  (1.21)
E

or vd = E (1.22)
Since J = nevd , we may write
J = (ne ) E (1.23)
 = ne (since J = E ) (1.24)
 Prepared By Dr.A.Rajalakshmi, Dept. of Physics, SSNCE
Comparing Eqn (1.20) and (1.24), we have
e
= (1.25)
m

Hence, the equations for conductivity  and restivity  are summarized as

 ne2 
 = ne =  
 m  (1.26)
1 1  m 
and = = = 2 
 ne  ne   (1.27)
On reaching a constant drift velocity, if the field É’ ís cut off ‘, the
electrons soon relax back to their random motion (equilibrium state) due
to collisions with lattice, impurities etc.
When the field is cutoff, E = 0 and Eqn.(1.13) becomes
dvd (t ) v (t )
=− d (1.28)
dt 
dvd (t ) dt
=−
vd (t ) 

dvd (t ) dt
 vd (t )
=−

 Prepared By Dr.A.Rajalakshmi, Dept. of Physics, SSNCE

Integrating , we obtain

ln vd (t ) = − + ln vd (0)

t
(1.29)

Taking exponential on both the sides, we have
 t 
 − +ln vd (0 )
e ln vd (t ) = e  

Therefore,
vd (t ) = vd (0) e(−t / ) as e ( a +b )
= e ( a ) . e(b ) (1.30)

Here, vd (0) = vd is the the steady state drift velocity of an electron at
the instant ' E' is at cut-off. Since ' ' is very small i.e., 10 −14 s, vd (t ) relaxes
to zero very rapidly. A graph of vd (t ) versus t is shown in Fig. 1.4.

Fig. 1.4 Graph of drift velocity vs time after field is cut off
 Prepared By Dr.A.Rajalakshmi, Dept. of Physics, SSNCE
Substituting t =  in Eqn. (1.30) results in

vd (t ) =
vd
(1.31)
e

Hence, the relaxation time  is the time taken for the drift velocity to decay
to 1/e times its initial value.
For metals, the relaxation time  = collision time  c
From kinetic energy of gases ,
1 3
mv 2 = kT (1.32)
2 2

Here, v is the average velocity of random motion or r.m.s velocity of

electrons, k is the Boltzmann constant in JK −1 and T is the absolute
temperture in K.

The average time between two collisions is given by


c = (1.33)
v

where '  ' is the mean free path of the electrons in m which is the mean
distance travelled by the electron in between two successive collisions.
 Prepared By Dr.A.Rajalakshmi, Dept. of Physics, SSNCE


Hence, v= (since  =  c ) (1.34)
c

From Eqn. (1.32), we have

3kT
v = (1.35)
m

3kT   (as  =  c for metals)

= = =
m c 

Therefore, m (1.36)
τ =λ
3kT

ne2
Applying Eqn. (1.36) in = , we obtain
m

ne2 m
= 
m 3kT

ne2 
i.e., = (1.37)
3mkT

which gives the expression for electrical conductivity in terms of '  ' &
‘T’
 Prepared By Dr.A.Rajalakshmi, Dept. of Physics, SSNCE

1 3mkT
Hence = =
 ne2 

3mkT
i.e., = (1.38)
ne2 

n is a constant for metals and  varies slowly except for very low
temperatures. In the normal temperature range,  can be assumed to be a
constant. Thus,   T according to the above theory. But the experimental
evidence shows that resistivity is proportional to T . n again varies from
metal to metal. A metal with a larger value of n should exhibit higher
conductivity which is not the actual case. Hence, the asumptions of
classical theory are at fault. In spite of this, there are some successes of
this theory.
Prepared By Dr.A.Rajalakshmi, Dept. of Physics, SSNCE

IMPORTANT FORMULAE

1. J = E A/m2

 ne2 
2.  = ne =   (  m) -1
 m 

1 1  m 
3. = = = 2 
 ne  ne  

3mkT
4. =
ne2 
 Prepared By Dr.A.Rajalakshmi, Dept. of Physics, SSNCE

CHECK YOUR UNDERSTANDING

1. What are the 3 theories proposed to explain the electrical
properties of solids?
2. What is the microscopic form of Ohm’s Law?
3. What are the main postulates of Classical free electron theory?
4. Differentiate between drift velocity and random/thermal
velocity.
5. Define the terms Current density, relaxation time, mean free
path, mobility, and electrical resistivity with their units.
6. Write down the formula for electrical conductivity in terms of
relaxation time and mobility.
7. How does electrical conductivity vary with temperature
according to classical theory?