Electrical conductivity in Metals

Classical free electron theory (Drude - Lorentz Theory):

The classical free electron theory was proposed in the year 1900 and is based on
the following postulates/assumptions

a. There are freely moving valence electrons called free electrons in a metal and
these are confined to its body.
b. The free electrons are treated equivalent to gas molecules and thus are assumed to
obey classical kinetic theory of gases. In the absence of electric field the kinetic
energy of the electrons is
1 2 3
mvth  kT
2 2

where

vth  Thermal velocity

k  Boltzmann constant
m  Mass of electron
T  Temperature in absolute scale

c. The free electrons move in random directions and collide with either the positive
ions or with other free electrons. All the collisions are elastic in nature.
d. The electric potential due to the ionic cores is taken to be uniform throughout the
metal.
e. The electron energies and velocities in a metal obey the classical Maxwell-
Boltzmann distribution.
f. The electric current in a metal due to an applied field is a consequence of the drift
velocity of the free electrons in direction opposite to the field
 g. The attraction between the free electrons and the lattice ions, and the repulsion
between the electrons themselves are considered insignificant.
Free Electrons:
The valence electrons that can move easily throughout the body of the metal are
referred to as free electrons. Since the free electrons are responsible for the electrical
conduction in a solid they are also called conduction electrons.

Lattice:
The structure formed due to the 3D array of positive fixed ions is called lattice.

Thermal Velocity(Vth)
The thermal velocity is a typical velocity due to thermal motion of particles which make
up a gas, liquid etc. , thus indirectly thermal velocity is a measure of temperature. The
free electrons are treated equivalent to gas molecules and thus are assumed to obey
classical kinetic theory of gases.
Under thermal equilibrium condition, the valence electrons in a solid are in a state
of random motion. In the absence of electric field the kinetic energy of the electrons is
1 2 3
mvth  kT
2 2
where
vth  Thermal velocity is

3kT
vth 
m

Drift Velocity (vd)

It is the average velocity acquired by an electron after steady state is reached, in the
presence of an electric field and is directed opposite to the applied field.
eE
vd  
m
where,
e  Charge of electron
 m  mass of electron
E  Applied electric field strength
τ  Mean collision time

Resistance:
It is the physical effect brought about by the vibrating lattice by virtue of which the
accelerating effect of an applied field on the conduction electrons is annulled so that the
electrons settle into a state of constant velocity proportional to the strength of the applied
field.

Mean free path (λ):

It is the average distance traveled by the conduction electrons between two
successive collisions with the lattice ions.

Mean collision time (τ):

The average time that elapses between two consecutive collisions of an electron
with the lattice point is called mean collision time.

Relaxation time (τr)

The time required for the average velocity of the conduction electrons to
exponentially decay to 1/e times its value just when the electric field is turned off, is
called relaxation time.

Relation between mean collision time and relaxation time:


r 
1 cos 
where θ  Angle of scattering
<cos θ >  Average value of cos θ
If the probability of scattering is same in all directions, then the scattering is called
isotropic and  r  
Expression for drift velocity:
In the presence of an electric field, the conduction electron acquires a constant
velocity called the drift velocity in the steady state.
If m is the mass of the electron, vd the drift velocity, τ the mean collision time, then
the resistive force ‘Fr’ offered for the motion of electrons is
vd
Fr  m

If e is the charge in the electron, E the strength of the applied field, then the driving
force acting on the electron is
F = eE
For steady state, we have
Fr = F
vd
i.e. m  eE

eE
(or) v d  
m

Current Density (J):

It is the current per unit area of cross-section of an imaginary plane held normal to
the direction of current in a current-carrying conductor.
J = I/A
Where
I  current
A  Area of cross-section

Electric Field (E)

The potential drop per unit length of a conductor gives the electric field that exists
across a homogenous conductor of uniform cross sectional area.

E = V/L
 Where
V  Potential difference between the two ends of the conductor
L  Length of the conductor

Resistivity (ρ)
It is the property of the material that gives a measure of the opposition offerec by
the material during a current flow in it.
RA

L

Conductivity (σ)
It is the physical property that characterizes the conducting ability of a material. It is
the inverse of resistivity.
1 L
 
 RA

Expression for electrical conductivity based on classical free electron theory

Consider a conductor of uniform area of cross section ‘A’ carrying current I. Let ‘v ’ be
the velocity of electrons. Now consider an imaginary plane at ‘X’ normal to the currents
direction. The electrons which are at X at a certain instant will travel a distance ‘v’ in unit
time. Thus the electrons are sweeping a volume ‘v.A’ in the conductor in unit time.

I A I

v
Current carrying conductor

If ‘n’ are the number of electrons per unit volume, then the number of electrons in
volume ‘v.A’ = n.(v.A)
 (or)
the number of electrons crossing any cross-section in unit time = n. (v. A)

If ‘e’ is the charge on an electron, then the quantity of charge crossing any section
per second = e.(n.v.A)

The quantity of charge crossing any section per second is the same as the rate of
flow of charge, which is nothing but the current flowing through the section

I = n.e.v.A. (1)

Since the velocity acquired by the electron is due to the applied field, it is the same
as the drift velocity vd.

v = vd
(or)
I = n.e.vd.A (2)

The electrical conductivity σ is given by

J
  (3)
E

Where ‘J’ is the current density given by

J = I/A (4)

I
=>   (5)
AE

Substituting for ‘I’ from (2)

n.e.vd . A n.e.vd
  (6)
AE E
 Substituting for the drift velocity as
eE
vd   (7)
m

we get,
n.e 2 .E. n.e 2 .
  (8)
mE m
Mobility of electrons (μ):
The mobility of electrons is defined as the magnitude of drift velocity acquired by
the electrons in an unit field.
vd e.
 
E m

Failures of classical free electron theory:

1. Specific heat: The molar specific heat of a gas at constant volume us
3
Cv  R
2
As per classical free electron theory, the free electrons are treated as gas molecules.
Thus the above equation must be applicable for free electrons also. But, the experimental
value for specific heat was found to be
C v  10 4 RT

which was far lower than the expected value and also showed a dependence on
temperature which is contrary to the theory.

2. Temperature dependence of electrical conductivity

It was experimentally observed that for metals, the electrical conductivity is
inversely proportional to temperature.
1

T
n.e 2 .
According to classical free electron theory,   .
m
  3kT
But   and v  .
v m
n.e 2 .
Thus,  
3mkT
This equation suggests that the temperature dependence of conductivity is
1
 ;
T
Thus, it is clear that the prediction of classical free electron theory is not agreeing
with the experimental observations.

3. Dependence of electrical conductivity on electron concentration

n.e 2 .
As per classical free electron theory, the electrical conductivity is   ,
m
where n is the electron concentration. From the above equation, we see that
 n .
The electron concentrations for divalent and trivalent metals such as Cadmium
and aluminium are 9.28 x 1028 /m3 and 18.06 x 1028 /m3 which are much higher than
that of copper and silver (monovalent metals) which are 8.45 x 1028 /m3 and 5.85 x
1028 /m3 respectively. The electrical conductivities of cadmium and aluminium which
are and 0.15 x 107 / Ω.m and 3.65 x 107 / Ω.m. respectively are much lesser than that
for copper and silver which are 5.88 x 107 /Ω.m and 6.3 x 107 / Ω.m respectively.
This implies that the prediction of classical electron theory that   n does not hold
well.

Quantum free electron theory:

This theory was developed by Sommerfeld in 1928. The main assumptions of this
theory are
a. The energy values of conduction electrons are quantized and the allowed
energy values are realized in terms of a set of energy levels
b. The distribution of electrons in the various allowed energy levels occurs as per
Pauli’s exclusion principle.
 c. The free electrons travel in a constant potential inside the metal but stay
confined within its boundaries.
d. The attraction between the free electrons and the lattice ions and the repulsion
between the electrons themselves are ignored.
e. The distribution of energy among the free electrons is according to Fermi-
Dirac statistics.

Density of states
It is defined as the number of available states per unit energy range centered at a
given energy E in the valence band of a material of unit volume. It is denoted by g(E). It
is a continuous function and the product g(E)dE gives the number of states in the energy
interval dE at E.
Evaluation of density of states for the electrons in a 3-D solid of unit volume:
The equation for allowed energy for an electron in one-dimensional potential well is
n2h2
E (1)
8ma 2
where
n  1,2.3,…
h  Planck’s constant
m  Mass of electron
a  Length over which electron is free to move in one dimension

The free electrons in a metal are identical to particles in 3-D potential well and the
equation for energy is written as

E
h2
8ma 2

n x2  n y2  n z2  (2)

where, nx, ny and nz are positive integers greater than zero.

h2
Let Eo  2
and R 2  n x2  n y2  n z2 . (3)
8ma
Thus, E = Eo.R2. (4)
 ny
dR

R
nx

nz

For various values of nx, ny and nz, the allowed energy states have a spherical
distribution. Since the values of nx, ny and nz are restricted to be positive, there is only
one octant of the sphere of radius ‘R’ where in each point corresponds to only positive
values of nx, ny and nz.
Hence, we have the number of allowed energy values upto an energy E = number of
points in the octant of sphere radius ‘R.’

If we consider a small energy range between E and E+dE, then

The number of allowed energy values in an energy range E and E+dE
= number of points in the space between the two octants of radii R and R+dR.
= (volume of space between the octants of radii R and [R+dR]) x (Number of points per
unit volume)
1 
=  4R 2 dR   1  R 2 dR
1
8  2

Now each energy value is applicable to two energy states, one for an electron, with spin
up and other for spin down. Thus, the number of allowed energy states in the range E
1
and E+dE = 2. R 2 dR = R 2 dR (5)
2
Let g(E) be the number of states/ unit energy range, then the number of energy states in
the range E & E+ dE is g(E).dE
g ( E )dE  R 2 dR (6)
From (4)
1
 E 2
   R (7)
 Eo 
Differentiating (4), we get
dE  Eo 2 RdR (8)
Multiplying (7) and (8)
1 1
 E 2 E2
  dE  Eo 2 R 2 dR (or) R 2 dR  3
dE (9)
 Eo  2 Eo 2

Substituting (9) in (6), we get

1
E 2
g ( E )dE  3
dE (10)
2 Eo 2

Substituting for Eo
1
 3
 1
E 2  8 2m 2 a 3  2
g ( E )dE  3
dE   3  E dE (11)
 h2  2  h 
2   
2 
 8ma 

If the solid if of unit volume, a3=1,

Therefore
 3
 1
 8 2m 2  2
g ( E )dE   3  E dE (12)
 h 
 
Eq. (12) represents the number of states in an energy range E and E+dE for electrons in a
three-dimensional solid of unit volume.
Thus, a plot of g(E) versus E will be as shown in the figure below.

g(E)
E

Fermi Energy
The Energy corresponding to the highest occupied level at zero degree absolute (i.e. 0 K)
is called Fermi Energy and the energy level is referred to as Fermi level. It is denoted by
E F.

Fermi Temperature
It is the temperature at which the average thermal energy of the free electrons in a solid
becomes equal to the Fermi energy at Zero Kelvin (0 K). It is denoted by TF.
TF = EF/K
K  Boltzmann constant

Fermi Velocity
The velocity of the electrons, which occupy the Fermi level, is called Fermi velocity.
1
 2E  2
vF   F 
 m 

Fermi Factor (or) Fermi-Dirac distribution Function

Fermi Factor is the probability of occupation of a given energy state for a material in
thermal equilibrium. It is denoted by f(E).
 1
f (E)   E  EF 
e KT
1

Dependence of Fermi Factor on Temperature and Effect on occupancy of energy

Levels
The Dependence of Fermi factor on Temperature and effect on occupancy of energy
levels is shown below.

T  0K
1.0
f(E)

0.5 T  0K

0
EF
E
Variation of f(E) with E

(i) Probability of occupation for E < EF at T = 0 K

when T = 0 K, and E < EF , the probability is given by

1
f (E)  
1
e 1
Here f(E) = 1 means that the energy level is certainly occupied and E < EF applies to all
the energy levels below EF. Thus, at T = 0 K, all the energy levels below the Fermi level
are occupied.

(ii) Probability of occupation for E > EF at T = 0 K

When T = 0 and E > EF, the probability is given by
 1
f (E)  
0
e 1
Therefore, at T= 0 K, all the energy levels above the Fermi level are unoccupied.
Thus, the variation of f(E) for different energy values becomes a step function at T =
0 K as shown.

(iii) Probability of occupation at ordinary temperatures

At ordinary temperatures, though the probability remains ‘1’ for E << EF, it starts
decreasing from ‘1’, as the values of E become closer to EF as is evident from the
curve.
At E = EF, and T > 0 K
1
f (E)   0.5
e 1
0

Thus, at E = EF, the probability of occupation is 0.5. Furthermore, for E > EF, the
probability value falls off to ‘0’ rapidly.

The Fermi energy can hence be defined as the most probable or the average value of
energy of the electrons that undergo transitions across the Fermi level at
Temperatures above 0 K.

Fermi Energy at T =0K

Calculation of Fermi Energy at T = 0 K
The Fermi energy at 0 K is denoted by EF0
Let N(E)dE be the number of free electrons per unit volume possessing energy only
in the range E and E+dE. Then, N(E)dE is given by the product of the number of
available states in the energy range E and E+dE, g(E), and the probability of occupation
or the energy states, f(E).
N(E)dE=g(E)dE. f(E) (1)
 The number of free electrons per unit volume of the material, n, is equal to the total
number of electrons that are distribute in various energy levels up to the Fermi level.
Thus, ‘n’ can be evaluated by integrating N(E)dE in the limits E= 0 and E= EF0 .

EF 0 EF 0

n  N ( E).dE   f ( E).g ( E).dE

0 0
(2)

But for all energy levels between E = 0 and E= EF0 , f(E) =1 at T= 0 K.

E F0

n  g ( E ).dE
0
(3)

 3
 1
 8 2m 2  2
But g ( E )dE   3  E dE . Therefore, (3) becomes
 h 
 
3 3
E
8 2m 8 2m 2
2 F0 1 23
n
h3 
0
E dE 
2
h3
E
3 0
F
2 (4)

Simplifying and rearranging the equation,

2
2
h 2  3n  3
E F0     Bn 3 (5)
8m   
Here, B = 5.85x10-38 J.
Equation (5) represents the expression for Fermi energy at 0 K denoted by EF0.
Fermi Energy at T >0K
The Fermi energy at any temperature in general is given by
  2  kT  2 
EF  EF 0 1    
 12  EF 0  

Except at extremely high temperatures, the second term in the bracket is very small
compared to unity. So EF=EF0
Fermi Dirac Distribution
Fermi Dirac distribution is a representation which depicts the details of distribution of
electrons among the various available energy levels of a material under thermal
equilibrium conditions.
It is denoted by N(E)dE and is given by N(E) d(E)=g(E) d(E)x f(E)
At a given temperature T, the values of f(E) & g(E) change only with E. Thus the value
of N(E)dE can change only with E.
Dependence of the distribution on temperature
The plot of N(E) versus E for the conditions T = 0K, T > 0K & T>> 0K are shown
below

T  0K
N(E)

T  0 K

T  0K
EF
E
N(E) versus E

Case (i) T = 0 K
In the plot for T= 0 K, N(E) increases with E up to E=EF. This is basically due to the
increase in g(E) with E. But beyond E=EF we know f(E) =0 for T = 0 K. thus, for all
values of E > EF, irrespective of the value of g(E), N(E) =0. This is shown by the sudden
drop of N(E) to zero at E=EF.

Case (ii) T > 0 K

At ordinary temperatures, the value of f(E) undergoes slight change near the Fermi
energy one either side of it. Hence, there are slight variations in N(E) for energy values
near EF on either side of it. But for energy values away from EF, since the value of F(E) is
essentially the same for both T = 0 K and T > 0 K, N(E) remains indistinguishable for the
two temperature conditions. Thus, the electrons which possess energy quite lower than
EF, are unaffected at ordinary temperatures.

Case (iii) T >> 0 K

At very high temperatures, the value of f(E) changes from what it was at T = 0K even
for energy values which are not quite close to EF. This in turn has effect on N(E) with its
value undergoing reduction and increase respectively over a large range of energy states
below and above EF . But even at a very high temperature, a significant portion of the plot
remins same as that at T = 0K, indicating that electrons at very low energy levels
practically remain undisturbed inspite of a high thermal energy input.

In the light of above discussion, it is that, the distribution of electrons in the various
energy levels is principally controlled by Fermi factor. Hence Fermifactor is also known
as Fermi-Dirac distribution function.
Success of quantum free-electron theory
1. Specific heat
According to quantum free-electron theory, only those electrons occupying energy
levels close the Fermi energy can absorb the heat energy. Such electrons constitute a very
small portion of the total free electrons, thus the specific heat value becomes very small.
Further, it was found that
2k
Cv  RT
EF
Taking typical values of EF=5 eV (for metal EF lies in the range 1 to 10 eV), we get,
2k
 10  4
EF

So C v  10 4 RT
This is in agreement with the experimentally observed values.
 2. Temperature dependence of electrical conductivity
As per quantum free electron theory, the electrical conductivity for a metal is
ne 2 
 . Also, as per the theory, EF and vF are essentially independent of temperature
m*v F
1 1
and λ is inversely proportional to temperature i.e.   . Therefore,   . The nature
T T
of dependence of λ on T can be analyzed as follows.
We know that waves associated with the electrons are subjected to scattering by the
vibrating ions of the lattice. The vibrations occur such that the displacement of ions takes
place equally in all directions. If r is the amplitude of vibration, the ions can be
considered to present effectively in a cross section of area πr2 that blocks the path of
electron irrespective of direction of approach. Since vibrations of larger area of cross
section cause scattering of the waves associated with electrons more effectively.
Increased scattering of waves results in reduction in the mean free path of the electrons.
1
So mean free path  
r 2
Considering the fact that 1) The energy of vibrating body is proportional to square of
amplitude. 2) The energy of ions is due to thermal energy. 3) The thermal energy is
proportional to temperature.
1
We can write, r2  T and  
T
since   
1
So  
T
Thus, dependence of conductivity on temperature is correctly explained.

3. Electrical conductivity and electron concentration

According to quantum free electron theory, only those electrons which occupy
energy states near to EF can participate in conduction and their drift velocity is

equal to the Fermi velocity. So v d  v F . Therefore, mean collision time  c 
vF
 ne 2 
As per quantum free electron theory   , thus conductivity depends both on n and
mvF
(λ/vF). If we compare the case of copper and aluminum, the value of ‘n’ for Al is 2.13
times higher than that of Cu. But the value of (λ/vF) for Cu is 3.73 times higher than that
for Al. Thus the conductivity of Al is less than that of Cu.