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.
Drift velocity:
In the presence of an electric field, the conduction electron acquires a constant
velocity called the drift velocity in the steady state.
eE
vd  
m
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

n.e 2 .

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
Also,

Effect of temperature and impurity on electrical resistivity of metals:

The main factors affecting the resistivity of metals are
a. Temperature
b. Impurities and defects.
The resistivity is generally given by Matthiessen’s rule which states that the total
resistivity of a metal is the sum of the resistivity due to phonon scattering which is
temperature dependent, and the resistivity due to scattering by impurities which is
temperature independent.
ρtotal = ρph + ρi (1)
ρph  Resistivity due to scattering of electrons by lattice vibrations quantized in
terms of phonons which increases with temperature and is therefore temperature
dependent. It is the resistivity exhibited by a pure specimen which is free of all defects
and is called ideal resistivity or pure resistivity.
ρi  Resistivity due to scattering of electrons by the presence of impurities and by
imperfections. It is independent of temperature and contributes to resistivity even at
temperature T = 0 K. It is therefore called residual resistivity.
At lower temperatures, the amplitude of vibrations become small and leads to less
scattering of electrons by the lattice ions. Thus for lower temperatures
 Tn
n  3 to 5
But, at high temperatures, the amplitude of vibrations increases proportionately and
results in large scale scattering of the electrons. Thus, the resistivity becomes linearly
dependent on temperature.
 T


Resistivity

 T

 T5
i
0 5 10 15 20
Temperature T (K)

n.e 2 .
We have   .
m
1 m
Thus,    (2)
 n.e 2 .
Equation (1) can be written as
 m m
 total   (3)
n.e . ph n.e 2 . i
2

where,
τph  Mean collision time assuming that there is no scattering by impurities
τi  Mean collision time assuming that there is no scattering by lattice vibrations.

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 Zinc and Cadmium are 13.10 x 1028 /m3 and
9.28 x 1028 /m3 which are much higher than that of copper and silver which are 8.45 x
1028 /m3 and 5.85 x 1028 /m3 respectively. The electrical conductivities of Zinc and
cadmium which are 1.09 x 107 /Ω.m and 0.15 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 si 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.

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

Therefore
 3
 1
 8 2m 2  2
g ( E )dE   3  E dE
 h 
 
represents the number of states in an energy range E and E+dE for electrons in a three-
dimensional solid of unit volume. From the above equation we also observe that the
number of energy levels in an energy interval dE is proportional to E1/2. Thus, a plot of
g(E) versus E will be as shown in the figure below.
g(E)

Fermi Energy
The Energy corresponding to the highest occupied level at zero degree absolute is called
Fermi Energy and the energy level is referred to as Fermi level. It is denoted by EF.
Fermi Energy at T = 0 K
2
2
h 2  3n  3
EF     Bn 3
8m   
Here, B = 5.85x10-38 J.
Fermi Energy at T >0K
The Fermi energy at any temperature in general is given by
   2  kT  2 
E F  E F 0 1    
 12  E F 0  

Except at extremely high temperatures, the second term in the bracket is very small
compared to unity. So EF=EF0

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 probablility 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.

Effective mass
When a metal is subjected to the influence of an electric field, a free electron in the
metal moves under the combined influence of the applied electric field and that of a
periodic potential due to lattice ions. Because of such a super-imposed effect, the electron
responds as if it possesses a mass called the effective mass which is different from its true
mass with which it is accounted if it were to be under the influence of external field
alone. It is denoted by m*.
2
 h 
 
 2 
m 
*

d 2E
dK 2
where, E is energy, K is the propagation constant.

Lattice defects and resistivity

 Sommerfeld brought the wave nature of electrons and considered the movement of
electrons in metals as passage of matter waves in a periodic lattice.
For a perfectly periodic lattice with stationary lattice ions, the waves pass through the
arrays without being scattered at all. Their mean free path would then be infinite. Btu due
to lattice defects, scattering of waves or in other words, the scattering of electrons takes
place and hence lattice defects become a cause of resistivity. Thus, the mean free path is
decided by how the waves get scattered and not be the scattering of electrons. In addition,
only those electrons which occupy energy states near to EF can participate in conduction
and their drift velocity is equal to the Fermi velocity.


Therefore,  
vF

ne 2 
The electrical conductivity,  
m*v F

m*v F
1
Electrical Resistivity    2
 ne 
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

ne 2 
As per quantum free electron theory   , thus conductivity depends both on n and
m*v F
(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. Further, the value of m* for Al
is1.08 times than that of Cu. Because of the inverse dependence of  on m*, this also
serves as contributing factor for the high values of  for copper.