Module 4

Electrical Conductivity in metals

Resistivity ( )
For a material of uniform cross-section, the resistance (R) is directly proportional to its length
(L) and inversely proportional to area of cross-section (A)
i.e.

Therefore ( ) or ( )

where is is a constant of proportionality called resistivity and is defined as the property of a

material that gives the measure of opposition offered during the flow of current.
Mobility ( ):
The mobility of electrons is defined as the magnitude of drift velocity ( ) acquired by
electrons in a unit electric field (E).

Concept of Phonon:
When a metal is at a temperature well above 10 K, the positive ions, which are arranged in a
periodic array start vibrating like harmonic oscillators. Since, the ions are bound to each other
through elastic and electric forces, they vibrate similar to standing waves with fixed energies.
The ions may vibrate either due to their own thermal energy or outside forces may make them
vibrate. This kind of vibration generates mechanical waves that carry heat and sound through
the material. A packet of these waves can travel throughout the material. So, in quantum
mechanical terms the waves can be treated as a particle, called a phonon. A phonon is a
definite discrete unit or quantum of vibrational mechanical energy, just as a photon is
a quantum of electromagnetic or light energy. The phonon concentration is strongly
dependent on temperature. At low temperature, phonon number is considerably low and is
proportional to , whereas at higher temperature the phonon number is proportional to ,
where T is absolute temperature.
Matthiessen’s rule:
According to Matthiessen’s rule the total resistivity ( ) of a metal at any given temperature is
a sum of resistivity due to impurity scattering ( ) and phonon scattering ( ) is given by
The resistivity due to impurity scattering is also called residual resistivity and arises due to
scattering of electrons by lattice imperfections and impurities present in a metal. The phonon
scattering is due to lattice vibration at a temperature well above 10 K.

Classical free electron theory:

This theory was proposed by Paul Drude and later improved by Lorentz, to explain electrical
conductivity in metals. According to this theory metals consist of free electrons and the
expression for electrical conductivity is given by

where n is the free electron concentration

e is the charge on electron
the relaxation time of free electrons
and m is the mass of free electrons
Failures of classical free electron theory:
Classical free electron theory has successfully explained electrical and thermal conductivities
in metals but failed to account for specific heat and, dependence of electrical conductivity on
temperature and electron concentration.
1. Specific heat: The molar specific heat of a gas at constant volume is

Since free electrons are expected to behave like gas molecules as per classical free
electron theory, the above formula is applicable for free electrons as well. However,
 the contribution of free electrons to the specific heat of a metal has been
experimentally found to be

Thus it is experimentally found that specific heat depends on temperature and is far
lower than the expected value.
2. Temperature dependence of electrical conductivity: It has been experimentally
observed that electrical conductivity of a metal is inversely proportional to its
temperature.
i.e

But according to the assumptions of classical theory, electrical conductivity of a metal

is inversely proportional to square root of its temperature.
i.e
√

Thus the prediction of classical free electron theory doesn’t agree with experimental
observations.
3. Dependence of electrical conductivity on electron concentration: As per classical
free electron theory, the electrical conductivity is given by

which implies

where n is the electron concentration

Therefore, as per the above relation, those metals which have high electron concentration
must have high electrical conductivity ( . But, in reality it is not so as per the experimental
data given in the table. In other words, Zinc and Cadmium must be good conductors on
account of their high value of ‘n’ when compared to Copper and Silver. But Copper and
Silver are found to be better conductors compared to Zinc and Cadmium.
Metal Valency ( n
Cu 1
Ag 1
Zn 2
Cd 2
Quantum Free Electron Theory:
Quantum Free Electron Theory was proposed by Arnold Sommerfeld in 1928, in which he
retained the vital features of classical free electron theory, and included Pauli’s exclusion
principle and Fermi-Dirac statistics. It is successful in explaining the low specific heat value
of conduction electrons, the correct dependence of on T and correct expression for
electrical conductivity in terms of Fermi velocity,
Assumptions of Quantum Free Electron Theory:
1. The energy values of conduction electrons are quantized. The allowed energy values
are realized in terms of a set of energy levels.
2. The distribution of electrons in various allowed energy levels occurs as per Pauli’s
exclusion principle.
3. Free electrons in a metal travel at constant potential but stay confined within its
boundaries.
4. The attraction between free electrons and lattice ions, and the repulsion between the
electrons themselves are ignored.

Density of States:
The permitted energy levels for electrons in a solid material will be in terms of bands. Each
band comprises of a huge number of permitted energy levels which are not evenly
distributed. Each energy level corresponds to one energy value and each energy value is
applicable to two electron energy states, one for an electron with spin-up, and the other one
for an electron with spin-down. Thus, we a find a large number of electron energy states even
in a small energy range. The number of available energy states per unit volume per unit
energy range at a certain energy level is called density of states and is represented by g(E).
√
( [ ]

where dE is an infinitesimally small increment at an arbitrary energy value E in a band

m is mass of electrons
and h is Planck’s constant
Fermi Energy:
Consider a conductor containing N free electrons, at absolute zero temperature. These
electrons fill the available energy states starting from lowest energy level i.e from the bottom
of the band and follow Pauli’s exclusion principle. So, below a particular energy level all the
energy levels are completely filled and the ones above it will remain completely vacant. The
energy corresponding to the highest occupied energy level at absolute zero temperature is
called Fermi energy, and the highest occupied energy level is called Fermi level.
Fermi energy at 0 kelvin is denoted by and is written as

( )( )

where m is mass of electrons

n is free electron concentration
and h is Planck’s constant
For all practical purposes Fermi energy ( ) at any temperature T is taken as Fermi energy
at 0 kelvin ( ) itself except at extremely high temperature.
Fermi Factor:
When a metal reaches an ordinary temperature starting from absolute zero temperature,
electrons near Fermi level can take up the thermal energy and reach unoccupied levels. This
kind of distribution of electrons in various energy levels is systematic in nature and is
governed by a statistical function once the system is in thermal equilibrium (steady
temperature state). The probability that a given energy with energy E is occupied at a steady
temperature T is represented by ( and is called Fermi factor. Thus Fermi factor is defined
as the probability of occupation of a given energy state for a material in thermal equilibrium.
It is given by

( (

Variation of Fermi Factor with Temperature and Energy:

Variation of Fermi Factor with Temperature and Energy can be understood by considering
three different cases of probability of occupation as follows:
(i) At T = 0 kelvin and
When T = 0 kelvin and , the Fermi factor can written as follows:

Which means all the energy levels below Fermi level are completely occupied at
T = 0 kelvin.
(ii) At T = 0 kelvin and

Which means all the energy levels above Fermi level are unoccupied at T = 0 kelvin.
(iii) At T kelvin (ordinary temperature) and

( (

Which means the probability of occupation of Fermi level at ordinary temperature is 50 %. It

is also clear from the below diagram that the value of probability remains 1 for at
ordinary temperatures and starts decreasing from 1 as the values of E become closer to .
Further, the probability value falls off to zero rapidly when .

Quantum Free Electron Theory is successful in explaining the low specific heat
value of conduction electrons and the correct dependence of electrical conductivity ( ) on
temperature (T). Also, it gave the correct expression for electrical conductivity in terms of
free electron concentration ( ), Fermi velocity ( ), mean free path ( ) and effective mass
( ) as given below.

( )