 The goal of electronic materials is to

generate and control the flow of an

electrical current.
Electronic materials include:
1. Conductors: have low resistance which
allows electrical current flow
2. Insulators: have high resistance which
suppresses electrical current flow
3. Semiconductors: can allow or suppress
electrical current flow
 Conductors – classical free electron theory
of metals – Electrical and thermal
conductivity – Wiedemann – Franz law –
Lorentz number – Draw backs of classical
theory – Quantum theory – Fermi
distribution function – Effect of
temperature on Fermi Function – Density of
energy states – carrier concentration in
J
metals
 Conductors or conducting materials are the
materials having high thermal and
electrical conductivities.

 Low resistive materials are also generally

called as conducting materials.
 Zero resistivity materials

 Low resistivity materials

 High resistivity materials.

 Superconductors like alloys of aluminum, zinc,
gallium, nichrome, niobium, etc., are a special
class of materials that conduct electricity almost
with zero resistance below transition
temperature. These materials are known as zero
resistivity materials
 They are used for saving energy in the
power systems, super conducting
magnetism memory storage elements etc.,
 The metals like silver, aluminum and alloys
have very high electrical conductivity. These
materials are known as low resistivity
materials
 They are used as conductors, electrical
contact, etc., in electrical devices and in
electrical power transmission and
distribution, winding wires in motors and
transformers.
 The materials like tungsten, platinum,
nichrome etc., have high resistivity and low
temperature co-efficient of resistance. These
materials are known as high resistivity
materials
 Such metals and alloys are used in the
manufacturing of resistors, heating
elements, resistance thermometers etc.
 The electrons in the outermost orbital of
the atoms, will constitute the solid
determine its electrical properties

 The electron theory of solids aims to

explain the structure and properties of
solids through their electronic structure.
 The electron theory is applicable to all
solids both metals and non –metals

 It explains the behavior of conductor ,

semiconductors and insulators, electrical ,
thermal and magnetic properties of solids

 The theory has been developed in three

main stages.
 The Classical free electron theory

Drude and Lorentz developed this theory

in 1900. According to this theory the metals
containing free electrons obey the laws of
classical mechanics.
 The Quantum free electron theory

Sommerfeld developed this theory during

1928. According to this theory, free
electrons obey quantum laws
 The Zone theory

Bloch stated this theory in 1928. According

to this theory, the free electrons move in a
periodic field provided by the lattice. This
theory is also called Band theory of solids.
 Postulates of classical free electron
 The electron revolving around the nucleus
constitute an atom and a metal is composed of
such atoms
 The valence electrons of atoms are free to move
about the whole volume of the metals like the
molecules of a perfect gas in a container. So in
classical free electron theory one can visualizes
the collection of valence electron from all the
atoms in a given piece of metal as forming an
electron gas which is free to move throughout the
volume of the metal.
 These free electrons move in random
direction and collide with either positive
ions fixed to the lattice or other free
electrons. All the collisions are elastic i.e.
there is no loss of energy.

 The movements of free electrons obey the

laws of the classical kinetic theory of gases.
 The electron velocities in a metal obey the
classical Maxwell – Boltzmann distribution
of velocities.
 The free electrons move in a completely
uniform potential field due to ions fixed in
the lattice
 When an electric field is applied to the
metal the free electrons are accelerated in
the direction opposite to the direction of
applied field.
 Drift velocity(vd)

 It is defined as the average velocity

acquired by the free electrons of a metal in
a particular direction by the application of
an electrical field.
 The average distance traveled by a free
electron between any two successive
collisions in the presence of an applied
electrical field is known as mean free path.
 is the product of drift velocity of free
electrons (vd) and collision time(C).

 = vd x  C
 The average time taken by a free electorn
between any two successive collisions is
known as collision time.
It is expressed mathematically as
C = /vd
Where,  - mean free path
vd - drift velocity
Relaxation time ()

 The average time taken by a free electron

to reach its equilibrium position from its
disturbed position due to the application of
an external field is called relaxation time.

 It other words, it’s the measure of time that

the electrons can relax when the electrical
field is removed. It is approximately equal
to 10 -14 second.
 The amount of electrical charges conducted
(Q) per unit time across unit area (A) of a
solid per unit applied electrical field (E) is
called the electrical conductivity.

Q J
= =
tAE E
 ( Based on Drude and Lorentz classical free
electron theory)

When an electrical field (E) is applied on an

electron of charge e of a rod, the electron
moves in opposite to the applied field with a
velocity vd (fig. 1.). This velocity is known as
drift velocity.
 =Q

If t = 1 second E = 1 volt A= 1 metre2

Where J is the current density and it is
given by
Q
 
 tA 
Also, J =  E (according to Ohm’s law).
Lorentz force acting on the electron is

FL = - eE ….(1)

This is known as the driving

force of the electron. Due to
the applied electrical field, the
electron gains some
acceleration ‘a’,
 Drift velocity(vd ) =
vd
i.e., Acceleration (a) = …………..(2)
Re laxation time( ) 

From the Newton’s second law of

motion, the frictional force or opposing
force on the electron is
Fr = mass of the electron (m) x acceleration (a)

i.e., Fr = ma …………..(3)

Substituting, equation (2) in equation (3), we have

Fr =
mv d

…………..(4)
When the system is in steady state, the Lorentz force
is equal and opposite to the frictional force i.e.,

Fr = -FL
From equations (1) and (4),

mvd
= −(−eE ) = eE

 e 
vd =   eE
m
 According to Ohm’s law, current density(J) is expressed as

J
J=E (or) = …………..(6)
E
Where  is the electrical conductivity of the electron.

But, the current density in terms of drift velocity is given as

J = n e d ... (7)
Substituting equation (5) in equation (7), we have
  e  J ne  2
J = ne   E (or ) =
m E m
Comparing the equations (6) and (8), we have

ne  2
=
m
Electrical Conductivity Animation
Consider two cross-sections A and B, where A
at a high temperature (T) and B at low
temperature (T – dT ) in a uniform metallic rod
AB (fig. 2). These two cross-sections are
separated by a distance . The heat conduction
takes place from A to B through the electrons
Thermal Conductivity -Animation
 T T - dT

A B

Fig. 2 Heat conduction in a metallic rod

Let the density of conduction electron be n and

velocity of electrons be v.

During the collision, electrons near A lose their

kinetic energy while electrons near B gain kinetic
energy.
At A, average kinetic energy of an electron = (3/2)kT …..(1)

1 3
( K.E. = 2
mv = kT)
2 2

where k is Boltzmann’s constant and

T is temperature at A.
At B, average kinetic energy of the electron

3
= k (T – dT) …………..(2)
2
The excess of kinetic energy carried by the electron from A to B

3 3
= kT - k (T – dT)
2 2
3 3 3 3
= kT - kT+ kdT = kdT …………..(3)
2 2 2 2

Number of electrons crossing unit area per unit

1
Time from A to B = nv.
6

The excess of energy carried left to right (A to B) for unit area in unit time

1 3 1
= nv  kdT = nvkdT …………..(4)
6 2 4
Similarly, the deficient of energy carried right to left from B to A in unit area in unit time

1
= - nvkdT …………..(5)
4

Hence, the net amount of energy transferred from A to B per unit area per unit time

1  1 
Q = nvkdT -  − nvkdT 
4  4 
1 1
Q= nvkdT + nvkdT
4 4
1
Q= nvkdT …………..(6)
2
But from the basic definition of thermal conductivity, the amount of heat conducted per
unit area per unit time,
dT  dT 
Q=K
 Q = K ; here = dx 
 dx

1 dT
ie., nvkdT = K
2 
1
 K= nvk …………..(7)
2

We know that for the metals

relaxation time ( )= collision time ( c)


i.e. = c =
v
v =  …………..(8)
Substituting equation (8) in equation (7), we have

1
K= nvkv
2
1 2
= nv k …………..(9)
2
Equation (9) is the classical expression for the thermal conductivity of a metal.
It states that for metals, the ratio of thermal conductivity to electrical
conductivity is directly proportional to the absolute temperature. This ratio is a
constant for all metals at a given temperature.

K
i.e.,  T or K
= LT
 
where L is a proportionality constant. It is known as Lorentz number. Its value is
2.44  10-8 W  K-2 (quantum mechanical value ) at T = 293K.
Widemann - Franz law is derived from the expressions of thermal conductivity and
electrical conductivity of a metal.
We know that
ne 2
Electrical conductivity of a metal = …………..(1)
m
1 2
Thermal conductivity of a metal K= nv k …………..(2)
2
Thermal conductivity K 12 nv 2 k
= =
Electrical conductivity  ne 2
m
K 1 mv 2 k
= …………..(3)
 2 e2

We know that the kinetic energy of an electron is

1 3
mv 2 = kT …………..(4)
2 2
Substituting equation (4) in equation (3), we have

K 3 kT  k 3 k 2T
= =
 2 e 2
2 e2
2
K 3k 
(or) =   T
 2 e
K
or = LT …………..(5)


2
Where L = 3  k  is a constant and it is known as Lorentz number.
 
2 e
K
or T …………..(6)

Thus, it is proved that the ratio of thermal conductivity
to electrical conductivity of a metal is directly
proportional to the absolute temperature of the metal.

This law is verified experimentally and it is found

to hold good at normal temperatures. But, this law is
not obeyed at very low temperatures.

Conclusion
Wiedemann- Franz law clearly shows that if a
metal has high thermal conductivity, it will also have
high electrical conductivity.
Among the metals, the best electrical conductors
(silver, copper, aluminum) are also the best conductors
of heat.
 The ratio of thermal conductivity (K) of a metal to the product of electrical conductivity
() of the metal is a constant. It is known as Lorentz number and it is given by

K
L=
T
2
Consider the expression L = 3  k  .
 
2 e
Substituting the values of Boltzmann’s constant k=1.3810-23JK-1 and the charge of an
electron e=1.60210-19coulomb, we get Lorentz number as L=1.1210-8WΩK-2
1. It verify ohms law

2.It explain the electrical and thermal

conductivity of metals

3.It derives Wiedemann –Franz law

4. It explain optical properties of metal

 The phenomena such as photo
electric effect, Compton effect
and the black body radiation
couldn’t explained classical free
electron theory
According to classical free electron
theory the value of specific heat of
metals is given by 4Ra Where Ra is the
universal gas constant whereas the
experimental value is nearly equal to
3Ra. Also according to this theory the
value of electronic specific heat is
equal to (3/2)Ra while the actual value
is about 0.01Ra only
 Electrical conductivity of semi-
conductor or insulator couldn’t be
explained using this model.
 Though (K/σT) is a constant
according to the classical free
electron theory, it is not a constant
at low temp
 Ferromagnetism couldn’t be
explained by this theory. The
theoretical value of paramagnetic
susceptibility is greater than the
experimental value
 In solids the carrier of electric current are
electrons.
 We known that the allowed energy levels of
an electron belongs to an isolated atom are
quantized.
 Likewise what are the permissible energy
levels for an electron free to move within a
crystal of specific dimension?
 Since the free electron is bound to move
within the crystal only, it is assumed that
free electron travels in constant potential
inside the crystal and is prevented from
leaving the crystal by very high energy
barriers at the crystal surface.
 In other words, the electron is trapped in a
constant potential well
 What are the permissible energy
states for an electron inside a
constant potential well box?
 How are large numbers of free
electron available, distributed
among various permissible energy
states?
 The suitable solutions to the above problems are

 Schrödinger’s wave equation

 Fermi –Dirac distribution function

giving rise to density of states
concepts
Energy distribution of electron in a matels -Animation
 Now Let us consider how the electron
in real material distributes among the
different possible energy states.
 The assembly of electrons may be
considered as ‘electron gas’ behaving
like a system of Fermi particles
obeying Fermi – Dirac statistics.
 Accordingly, the probability F (E) of an electron
occupying an energy level E is given by
1
F (E) = 2.1
 E − EF 
1 + exp 
 kT 
Where EF is called Fermi energy and is a constant for a given system F(E) is called Fermi
function .

At T = 0 K for E < EF, F (E) = 1

E > EF F (E) = 0

At any temp other than OK if E = EF

F (E) = (1/2)
Fermi energy: Fermi level is that
state at which the probability of
electron occupation, is (1/2) at
any temp above O K and also it is
the level of maximum energy of
the filed states at O K.
FERMI ENERGY
  The dependence of Fermi distribution function on temperature and its
effect on the occupancy of energy level is shown in fig.

T3 > T2> T1>0K

F(E) F(E) T3 T 2 T1
1 T=0K 1 T=0K

0.5

E
o (a) EF o (b) EF
When T = 0 K and E < EF , We have
1
F (E) =
1 + e ( −VE / 0 )
1 1 1
F (E) = = = [e-=0]
1+ e −
1+ 0 1
 F(E) =1

Thus at T = 0, there is 100% chance for the electrons to occupy the energy levels below
the Fermi level ie., below the Fermi energy level, all the levels are occupied with the
electrons.
 (ii) Probability of occupation for E > EF at T = 0

When T = 0 K and E > EF

1
F (E) =
1 + e ( −VE / 0 )
1 1 1
= = = =0
1+ e 
1+  
 F(E) = 0

Thus there is 0% chance for the electrons to occupy energy level above Fermi
energy level. Ie, all energy levels above Fermi energy level are unoccupied.

From the Above two cases, at T= 0K the variation of F(E) for different energy values
becomes a step function, as shown in fig. 3 (a).
At ordinary temperature, the value of probability starts, reducing from 1 for values of E
slightly less than EF

With the increase of temperature, i.e., T > 0 K, Fermi function F(E) varies with E as
shown in fig. 1.7(b).
At any temperature other than 0K and E = EF,
1
F (E) =
1 + e0
1 1
F (E) = = = 0.5 [ e 0 = 1]
1+1 2
Hence, there is 50% chance for the electron to occupy Fermi energy level. ie., the
value of F (E) becomes ½ at E = EF

The above result is used to define the Fermi energy level.

Further, for E > EF, the probability value falls off rapidly to zero (fig 3(b).
 When T >> EF or T = , the
electrons lose their quantum
mechanical character and Fermi
distribution function reduces to
classical Boltzmann distribution.
 It gives the probability of an electron
occupying a given energy level at a given
temperature.
 It is very useful in the calculation of
number of free electrons per unit volume at
a given temperature.
 Further, it is very useful in the
calculation of Fermi energy of a metal.
 To calculate the carrier concentration (i.e.)
the number of electrons per unit volume in
a given energy range of interest. This is
given by summing the product of the
density of states Z (E) and the occupancy
probability F(E), that is

nc = 
energy band
Z(E)F(E)dE
We know that the number of energy
states with a particular value of E
depends on how many combination of
quantum numbers result in the same
value of n (degeneracy). To calculate
the number of energy states with all
possible energies with n as radius
(where

(n = n + n + n )
2 2
x
2
y
2
z

sphere is constructed in three –dimensional space

as shown in Fig 4 and every point (n1,n2 and n3)
within this space represent an energy state
DENSITY OF STATE
 nz
E
E+dE

dn

nx

Fig. 4 Calculation of Density of states

 Every integer represents one energy
state.
 (i.e.) unit volume of this space contain
exactly one state.
 Hence the number of state in any volume
is equal to the volume expressed in units
of cubes of lattice parameters
 The number of energy state within a
sphere of radius.
 4  3
 3  n
 Since n1, n2 and n3 can have only positive
integer values.
 We have to consider only one octant of the
sphere
 Hence available energy states
1  4  3
  n
8 3 
In order to calculate the number of states
within a small energy interval E and E + dE we
have to construct two spheres with radii n and
(n+dn) and calculate the space occupied
within these two spheres

Thus the number of energy states having

energy values between E and E + dE

1  4  1  4  3
Z ( E )dE =   ( n + dn ) −   n
3

8 3  8 3 
 
Z ( E )dE = 2
n dn ..(2.3)
2
(Neglecting higher power of dn as it is very small)

The energy eigen values are given by

equation
2 2
h n
E = 2
... (2.4)
8mL
 2
8mL E
n =
2
2
... (2.5)
h

2
8mL E
n= 2
...(2.6)
h
Differentiating n2 in equation
2
8mL
2ndn = 2 dE...(2.7)
h

 1  8mL
2
dn =   2 dE
 2n  h
 1
 8mL
2
  1   h  dE
2 2
dn =  2   2   8mL2  12
 h    E

 1   8mL  dE
2 2
dn =    2  1 ...(2.8)
 
2 h  E 2
 
Z ( E )dE = 2
n dn ..(2.3)
2
Substituting the values of n2 and dn from equation (2.5)
and 2.8 in equation 2.3

1
  8mL2  1  8mL2  dE 2
Z ( E )dE =   2 E   2  1
2  h  2  h  E2

3
  8mL  2 2 1
Z ( E )dE =  2  E dE
2
...(2.9)
4 h 
 According to Pauli’s exclusion
principle two electrons of opposite
spin can occupy each state and hence
the number of energy states available
for electron occupancy is given by
3
  8mL2  2 1
Z ( E )dE = 2   2 
E dE...(2.10)
2

4 h 
 4
Z ( E )dE = 3 ( 2m ) L E dE....(2.11)
3
2 3 12

h
Density of energy states is given by
number of energy states per unit
volume

Density of states
4
Z(E)dE = 3 ( 2m ) E 2 dE...(2.12)
3 1
2

h
 Substituting the values F(E) and Z(E) from
equation (2.1) and 2.12 in equation 2.2 for
calculation of carrier concentration.

nc = 
energy band
Z(E)F(E)dE

4 1

3 1
nc = 3 (2m) 2
E 2
dE..(2.13)
h  E − EF 
energy band
1 + exp  
 B 
k T
 The above equation can be used to calculate the
carrier concentration in metals and
semiconductors

Fermi energy of electrons at 0 K

 In the case of a material at absolute zero, the
upper occupied level is EF and for all the level
below EF , F (E) = 1

4
EF

 ( )
3 1
nc = 3
2 m 2
E 2
dE
0
h
 8 3
nc = 3 (2mEF ) ..(2.14)
2

3h
2
 h   3nc 
2
3
EF =     ....(2.15)
 2m   8 
 Mean energy of electron at 0 K

To estimate the mean electronic

energy at 0 K. Let us first calculate
the total energy Uo at 0 K

EF

Uo = 
0
Z ( E ) F ( E )dEE
F (E) =1 since the temperature at 0 K
Substituting from equation 2.12 for Z(E) dE

4
Z(E)dE = 3 ( 2m ) E 2 dE...(2.12)
3 1
2

4
EF


3 3
U o = 3 (2m) 2
E dE
2

h 0
 2 4 3 5
U o =  3 (2m) 2 ( EF ) 2
5 h
Mean energy at O K is

Uo
Eo =
nc
 2 4 3 5 3h 3
E o =  3 (2m) 2 ( EF ) 2 
8 (2mEF ) 2
3
5 h

3
Eo = EF
5
 The Electrical, Mechanical , thermal and
optical properties of a conductor,
semiconductor and insulator are explained
based on the electron theory of metal

 The concepts such as density of states,

Carrier concentration and band theory are
very useful in theoretical evaluating the
behaviour of solids
 For use as conductors in application such as
transmission and distribution lines , low I2R
loss is the primary consideration.
 Good electrical conductor should have low
resistivity, low temp coefficient of
resistant, enough ductility enabling one to
draw in the form of wires and enough
corrosion resistance.
 They should be free from oxidation
 Copper and Aluminium are the most likely
choices for the above purpose, satisfying
almost all the desired properties.
1. Evaluate the Fermi function for an energy kT
above the Fermi energy

2.At what temp we can expect a 10 % probability

that electron in silver have an energy which is 1%
above the Fermi energy? The Fermi energy of silver
is 5.5 eV