INTRODUCTION

Low resistive materials are generally called conducting materials. These materials
have high electrical and thermal conductivity. The conducting property of a solid is
not a function of total number of electrons in the metal, but it is due to the number
of valence electrons so called free electrons or conduction electrons. Thus, the
electrical conductivity depends on the number of free electrons available.

BASIC TERMINOLOGIES

Experimental measurements showed that the metals and their alloys exhibit large
electrical conductivity in the order of 10 Ω m . Hence they are known as
conductors Conducting materials are the materials having high electrical and
thermal conductivities.

CLASSIFICATION OF CONDCUTING MATERIALS

Conducting materials are classified in to three major categories based on the

conductivity. They are (i). Zero resistive materials (ii). Low resistive materials (iii).
High resistive materials.

ZERO RESISTIVE MATERIALS

Super conductors like alloys of aluminium, zinc, gallium, niobium, etc., are a
special classof materials. These materials conduct electricity almost with zero
resistance with low transition temperature. Thus, they are called zero resistive
materials.These materials are used for saving energy in the power systems, super
conducting magnets, memory storage elements etc.,

LOW RESISTIVE MATERIALS

Metals like silver, aluminium and alloys have high electrical conductivity. These
materials are called low resistive materials.They are used as conductors, electrical
conduct etc., in electrical devices and electrical power transmission and
distribution, winding wires in motors and transformers.

HIGH RESISTIVE MATERIALS

Materials like tungsten, platinum, nichrome etc., have high resistive and low
temperature co-efficient of resistance. These materials are called high resistive
materials.Such metals and alloys are used in the manufacturing of resistors, heating
elements, resistance thermometers.

ELECTRON THEORY OF METALS

Electrons have similar behaviour in conductors, semiconductors, dielectric,

magnetic and super conducting materials. They also have same behaviour in all
applications such as computer, television, radiography; electrical conduction etc.,
The electron theory of metals explains the following concepts

(i) Structural, electrical and thermal properties of materials.

(ii) Elasticity, cohesive force and binding solids.

(iii) Behaviour of conductors, semiconductors, insulators etc.

CLASSICAL FREE ELECTRON THEORY

This theory was developed by Drude and Lorentz in 1900. It is a macrosocpic

theory. According to this theory, a metal consists of electrons which are free to
move. The mutual repulsion between electrons is ignored. Thus potential energy is
taken as zero. The total energy of the electron is equal to its kinetic energy.

POSTULATES OF CLASSICAL FREE ELECTRON THEORY

1. A solid metal has nucleus with revolving electrons. The electrons move freely
like molecules in a gas.
2. The free electrons move in a uniform potential field due to the ions fixed in the
lattice.
3. In the absence of electric field (E=0), the free electrons move in random
directions and collide with each other. During this collision no loss of energy is
observed since the collisions are elastic as shown in figure 1.
4. When the presence of electric field (E≠0) the free electrons are accelerated in the
direction opposite to the direction of applied electric field, as shown in figure. 2.
5. They obey classical theory of gases.
6. Classical free electron theory obey Maxwell – Boltzmann statistics.
Fig: 1. In absence of Electric field Fig: 2. In presence of Electric field

BASIC TERMS IN FREE ELECTRON THEORY

1. Drift velocity (Vd)

The drift velocity is defined as the average velocity acquired by the free electron in
particular direction,due to the applied electric field.

ms-1

2. Mobility (μ)

The mobility is defined as the drift velocity (Vd) acquired by the electron per unit
electric field (E).

m2V-1s-1

3. Mean free path (λ)

The average distance travelled by an electron between two successive collisions.

4. Mean collision time (τc) or Collision time

It is the time taken by the free electron between two successive collisions.

sec

5. Relaxation time (τ)

It is the time taken by the electron to reach equilibrium position from disturbed
position in the presence of electric field.
 sec

where l is the distance travelled by the electron. The value of the relaxation time is
in the order of 10-14 sec.

6. Band gap (Eg )

It is the energy difference between the minimum energy of conduction band and
the maximum energy of valence band.

7. Current density (J)

It is defined as the current per unit area of cross section of a plane normal to the
direction of flow of current in a current carrying conductor.

EXPRESSION FOR ELECTRICAL CONDUCTIVITY

The electrical conductivity is defined as the quantity of electricity flowing per unit
area per unit time at a constant potential gradient.

Ohm-1 m-1

Fig:3- Moment of electron

When an electric field (E) is applied to a conductor, the free electrons are
accelerated and give rise to current (I) which flows in the direction of electric field.

Let ‘n’ be the number of electrons per unit volume and ‘e’ be the charge of the
electrons.
The current flowing through a conductor per unit area in unit time is given by

J = nvd(-e)

J= - nvd(e) -------------(1)

The negative sign indicates the direction of current is in the opposite direction to
the movement of electron.

Due to the applied electric field, the electron acquire acceleration ‘a’ can be given
by

vd= aτ -------------(2)

The force experienced by the electron due to the electric field strength (E) is given
by

F= -eE -------------(3)

From Newton’s second law of motion, the force acquired by electrons can be
written as

F= ma -------------(4)

Comparing eqn (3) and (4) -eE = ma

-------------(5)

Substituing the value of a in eqn (2), we get

 -------------(6)

Substituing eqn (6) in eqn 1 we get

-------------(7)

The electrical conductivity , so Ω-1m-1 . Thus the

electrical conductivity of a material is directly proportional to the free electron
concentration in the material.

THERMAL CONDUCTIVITY

The thermal conductivity is defined as the amount of heat flowing through an unit
area per unit temperature gradient.

Consider a metal bar with two planes A and B separated by a distance ‘λ’ from C.
T1 is hot end and T2 is cold end. T1>T2.

Fig :4- Thermal conductivity

Let ‘n’be the number of conduction electrons and ‘v’ be the velocity of the
electrons. KB is the Boltzmann constant.
From kinetic theory of gases

Energy of an electron at mv2

= ---------(1)

The Kinetic energy of an electron at B is given by

mv2

= ---------(2)

The net energy transferred from A to B = ---------(3)

Fig:5- moment of electron field

Let usassume that there is equal probability for the electrons to move in all the six
directions. Each electrons travels with thermal velocity ‘V’ and ‘n’ is the free

electron then on average of nv electron will travel in any one direction

No. of electrons crossing per unit area in unit time at C = nv-----(4)

Q is the energy carried by the electrons from A to B which is given by

Q = Average energy transfer from A to B x No of electron crossing per unit area

Q = =

-----(5)

We know that the thermal conductivity, K =

The heat energy transferred per unit sec per unit area Q=K [A = 1 unit
area]

Q= ) -------(6) (dT = T1 – T2, dx =2λ)

Comparing equations (5) & (6)

)=

Thermal Condutivity K =

WIEDEMANN-FRANZ LAW

The ratio between the thermal conductivity (K) and electrical conductivity (σ) of a
metal is directly proportional to the absolute temperature of the metal.

or where L is called Lorentz number, The value of

L is 2.44 x 10-8 WΩK-2.
DERIVATION

The expression for thermal conductivity K=

The expression for electrical conductivity

since

We know that kinetic energy of an electron, mv2 =

. L is Lorentz number. Thus, it is proved that the ratio of thermal

conductivity and electrical conductivity of a metal is directly proportional to the
absolute temperature of the metal.
L= L= 1.12x 10-8 WΩK-2

SUCCESS OR USES OF CLASSICAL FREE ELECTRON THEORY

1. It is used to verify Ohm’s law.

2. It is used to explain electrical conductivity (σ) and thermal conductivity (K) of

metals.

3. It is used to derive Widemann-Franz law.

4.It is used to explain the optical properties of metal.

DRAWBACKS OF CLASSICAL FREE ELECTRON THEORY

1. This theory cannot explain compton effect, photoelectric effect, paramagnetism

and ferromagnetism.

2. This theory cannot explain electrical conductivity of semicondcutors and

insulators.

3. Dual nature of light radiation cannot be explained.

4. The theoretical and experimental values of specific heat and electronic specific
heat are not matched.

5. By classical theory, = T is constant for all temperature. But by quantum

theory, it is not constant.
6. The Lorentz number obtained by classical theory does not have good agreement
with experimental value and theoretical value. It is rectified by quantum theory.

QUANTUM FREE ELECTRON THEORY

Somerfield developed a new theory in which he included some of the features of

classical free electron theory along with quantum mechanical concepts and fermi
dirac statistics. It is a microscopic theory.

POSTULATES OF QUANTUM FREE ELECTRON THEORY

1. The available free electrons are fully responsible for electrical conduction in
metal.
2. The electrons move in a constant potential inside metal. They cannot come out
from the metal surface.
3. The electrons have wave nature.
4. Quantum free electron theory obey Fermi-Dirac statistics
5. The velocity and energy distribution of the electron is given by Fermi-Dirac
distribution function
6. The loss of energy occurs due to interaction of free electron with the other free
electron.
7. Electrons are distributed in various energy levels according to Pauli’s Exclusion
principle.

ADVANTAGES OFQUANTUM FREE ELECTRON THEORY

1. This theory explains the specific heat capacity of materials.

2. This theory explains photoelectric effect, compton effect and black body
radiation.
3. This theory gives correct mathematical expression for the thermal conductivity
of metals.

DRAWBACKS OFQUANTUM FREE ELECTRON THEORY

1. This theory fails to distinguish between metal, semiconductor and insulator.

2. It also fails to explain the positive value of Hall coefficient.

3. As per this theory, only two electrons are present in the fermi level. These two
electrons are responsible for conduction which is not true.

THERMAL CONDUCTIVITY BY QUANTUM FREE ELECTRON

THEORY

In quantum theory, the mass ‘m’ is replaced by ‘m*’ which is effective mass.

So the electrical conductivity

The expression for thermal conductivity is modified considering electronic specific

heat as

K=

or .

On substituting the values for Boltzmann constant (KB) and the charge of an
electron, we get Lorentz number L = 2.44 x 10-8 WΩK-2 . Thus, quantum theory
verifies Wiedeman-Franz law and has good agreement with experimental value of
Lorentz number.

FERMI DIRAC STATISTICS

(i) The particles are indistinguishable.

(ii) Electrons which obey fermi dirac statistics are called as fermions.

(iii) Each energy state can have only one particle with one spin.

(iv) The number of energy state should be greater than or equal to no. of particles.

(v) The total energy of system is the sum of all energies of particles.

FERMI ENERGY AND ITS IMPORTANCE

Fermi energy level is the maximum energy level up to which the electrons can be
filled at 0K.

IMPORTANCE

1. It acts as a reference level which separates the vacant and filled states at 0K.
2. It gives the information about the filled electrons states and empty states.
3. At OK, electrons are filled below fermi energy level and above fermi energy
level it will be empty.
4. When temperature is increased, few electrons gains the thermal energy and it
goes to higher energy levels.
 Fig:6- Energy band diagram of semiconductor

FERMI DISTRIBUTION FUNCTION

Fermi function F (E) represents the probability of an electron occupying a given

energy state. To find out the energy states actually occupied by the free electron at
any temperature (T), we can apply Fermi-Dirac statistics. The Fermi-Dirac
statistics deals with the particles (electrons) having half integral spin, named
Fermions.

Thus F(E) = -------(1)

EF-Fermi energy, KB – Boltzmann constant, T- absolute temperature

EFFECT OF TEMPERATURE ON FERMI FUNCTION

At 0K and E<EF At 0K and E>EF At 0K and E=EF

1. F(E)= 1. F(E)=
1. F(E)=

=0
=1 = 0.5
2. F(E) = 0%
2. F(E) = 100% 2. F(E) = 50%
3. It means that 0%
3. It means that 100% probability for the 3. It means that 50%
probability for the electrons not to be filled chance for an electron
electron to be filled within the fermi energy to be filled and not to be
within the fermi energy level. filled within the Fermi
level energy level
This clearly shows that at 0 Kelvin all the energy states below EF0 are filled and all
those above it are empty.

When the temperature is raised slowly from absolute zero, the fermi distribution
function smoothly decreases to zero as shown in Figure. This is due to the supply
of thermal energy within the range of KBT. The electrons below the fermi level take
the energy and goes to higher energy state. Hence at any temperature (T), empty
states will also be available below EF0.

Fig:7- Fermi-Dirac distribution function

DENSITY OF STATES

The fermi function gives only the probability of filling up of electrons on a given
energy state. It does not give the information about the number of electrons that
can be filled in a given energy state. To know that we should know the number of
available energy states so called density of states.

A parameter of interest in the study of conductivity of metals and semiconductors

is the density of states.
It is defined as the number of available electron states per unit volume in an energy
interval (dE). It is used to calculate the number of charge carriers per unit volume
of any solid.

Z(E)dE =

Fig:8-Positive octant of sphere

To fill the electrons in an energy state, we have to first find the number of
available energy states within a given energy interval. Let us construct a three
dimensional space of points which represents the quantum numbers nx, ny and nz as
shown in fig.8. Let us consider a cubical sample with side ‘a’. Let us construct a
sphere of radius ‘n’ in the space.

The sphere is further divided into many shells and each of this shell represents a
particular combination of quantum numbers (nx, ny and nz) and therefore represents
a particular energy value
n2 = nx2+ny2+nz2

A radius ‘n’ is drawn from the origin ‘O’ to a point nx, ny and nz in space. All
points on the surface of the sphere will have same energy E. Any change in nx, ny
and nz will change ‘E’.

The number of energy states with in a sphere of radius ‘n’

n -------------(1)

Since the quantum numbers nx, ny and nz can have only positive integer value, we
have to take only 1/8 th of the spherical volume. The number of energy states with
in a sphere of radius n corresponding to E is

n -------------(2)

Similarly the number of energy states between the spheres of radius n+dn
corresponding to energy E+dE is

-------(3)

Subtracting equation (2) from equation (3)

Z(E)dE =

Z(E)dE =

--------(4)
Since dn is very small, the higher powers dn2 and dn3 terms are neglected. Equation
(4) becomes

Z(E)dE = -------(5)

Number of available energy states between interval E and E+dE is given by

Z(E)dE =

Z(E)dE = -------(6)

From the application of schrodinger wave equation, the energy of an electron in a

cubical metal piece of side ‘l’ is given by

-----------(7)

Taking square root of above equation, we get

--------(8)

Differentiating equation (7) we get dE

dE-------(9)

substitute eqn (8) and (9) in eqn (6) we have

Z(E)dE = dE

Z(E)dE = dE ----------(10)

l3 – Volume of metal piece. If l3=1, then we can write

Z(E)dE = dE

According to Pauli’s exclusion principle, each energy level consists of 2 electrons

withdifferent spins.

Z(E)dE = dE

Z(E)dE = dE--------(11)