MODULE -4

ELECTRICAL CONDUCTIVITY OF METALS

Most of the properties of metal can be explained by assigning a free electron model to them.
A classical model of electrical conduction in a metal was first proposed by Paul Drude.

Drude –Lorentz theory (Classical free electron theory) :

Free-electron and phonon concept:

All metal atom consists of valance electrons. These valance electrons are responsible for
electrical conduction in a metal. Consider copper as an example for metals. A copper atom
consists of 29 electrons, out of which 28 electrons are filled in the first 3 shells. And forms
the core part. The remaining one electron will be present
in the 4th shell and is the valance electron of the copper
atom. It is very loosely bound in the atom.

When large number of copper atoms join to form a

metal, the boundaries of the neighbouring atoms slightly
overlap on each other. Due to this the valance electron
find continuity from atom to atom. Thus, it can move
easily throughout the body of the metal. The free
movement of electrons means none of them belongs to any
atom, but each of them belongs to the metal to which they are confined to. Thus, such
electrons are named free electrons. These free electrons are responsible for physical property
of metal such as electrical and thermal conductivities, electron emission etc. Since free
electrons are responsible for electrical conduction in a solid, they are also called conduction
electrons.

However, the loss of electrons makes the atom to loose their electrical neutrality. They
become positive ions fixed about in their mean position. The structure formation due to the
array of such ions in 3 dimension is called lattice. Thermal vibrations of ions at lattice points
cause elastic waves in crystal. The energy of these lattice vibrations is quantised and quantum
of this energy is phonon.

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 Phonon: it is particle like entity which carries the unit energy of elastic field in a particular
mode is called phonon. The energy of the phonon is given by hν.

The free electrons collide with ion core at lattice point. The
collision results in a change in the direction of velocity of
the electrons. In absence of electric field, the velocities of
electrons are in random directions as in fig.2 due to which
there is no net transfer of charge.

According to Drude –Lorentz theory all metals contain free electrons move through the
positive ionic core of the metals. The metal is then pictured to be held together by
electrostatic forces of attraction between the positively charged ions and negatively charged
electron gas. Mutual repulsion between negative electrons is ignored in this theory.

Failures of classical free electron theory:

Classical free electron theory failed to account for many experimental facts among which
the notable once are specific heat, temperature dependence of electric conductivity (𝜎), and
the dependence of electrical conductivity on electron concentration.

1) Temperature dependence of electrical conductivity:

It has been experimentally observed that for metals, the electrical conductivity 𝜎 is inversely
proportional to temperature T,
1
 exp  .............1
T
1
 CFT  .............2
T

From (1) and (2) it is clear that the prediction of classical free electron theory is not agreeingwith
experimental observation.

2) Dependence of 𝜎 on electron concentration:

𝑛𝑒2𝑐
According to classical free electron theory, the electrical conductivity 𝜎 is given by 𝜎 =
𝑚
where n is the electron concentration.

i.e. free electron theory suggest that 𝜎 is proportional to electron concentration n.

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 Experimental conductivity values for different metals are as follow

Metal Electron concentration(n) Conductivity (𝜎)

per m3 Siemens per meter
Ag 5.85*1028 6.30*107
Cu 8.45*1028 5.88*107
Cd 9.28*1028 0.15*107
Zn 13.10*1028 1.09*107
Ga 15.30*1028 0.67*107
Al 18.06*1028 3.65*107

Practically it is observed from above table that 𝜎 is not strictly proportional to electron
concentration.

2) Dependence of 𝜎 on specific heat:

3
According to the Molar specific heat of metals = 𝐶𝑣 = 𝑅 -------------(1 )
2

According to experiments, Specific heat of metal𝐶𝑣 = 10−4𝑅𝑇 ----------- (2 )

From (1) and (2) it is clear that the prediction of classical free electron theory is not agreeing
with experimental observation.

Drift velocity (Vd):

In the absence of applied field, the free electrons move rapidly in all direction. i,e the net
current moving across any given plane at any instant is zero. If a constant electric field is
applied, the electron will experience a force eE and get accelerated.

“The average velocity with which free electrons move in a steady state opposite to the
direction of the electric field in a metal is called drift velocity”.

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Resistivity and mobility:

Electrons tend to accelerate in the direction of the field, they are deflected in random
directions by vibrating lattice points, which is scattering. The overall effect of scattering of
electrons by vibrating lattice manifests as resistance to electric current.

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

For a material of uniform cross section, the resistance R is directly proportional to length of
wire (L) and inversely proportional to cross sectional area (A)

𝐿
𝑅=𝜌 𝜌 𝑖𝑠 𝑐𝑎𝑙𝑙𝑒𝑑 𝑟𝑒𝑠𝑖𝑠𝑡𝑖𝑣𝑖𝑡𝑦
𝐴

It is the property of the material measuring opposition offered by material to flow of current

1 1
𝑐𝑜𝑛𝑑𝑢𝑐𝑡𝑖𝑣𝑖𝑡𝑦 = i.e 𝜎 =
𝑟𝑒𝑠𝑖𝑠𝑡𝑖𝑣𝑖𝑡𝑦 𝜌

Mobility of electrons: The mobility of electrons is defined as the magnitude of drift velocity
acquired by the electrons in unit electric field
𝑣𝑑
Mobility of electrons 𝜇 =
𝐸

vd is drift velocity, E is electric field applied

EFFECT OF TEMPERATURE AND IMPURITY ON ELECTRICAL RESISTIVITY OF

METALS:

The variation of electrical resistivity 𝜌 with

temperature T in the low temperature region
for sodium is shown in the figure.

Except for some metals that are super

conducting, this variation in general applies to
all the metals. It may be noticed that 𝜌

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 does not become zero even at T = 00 K , but has a small constant value. From this value, 𝜌 increases
with T slowly in beginning, latter it assumes linear but faster variation . The linearity in variation is
continued throughout till the metal melts.

From our earlier discussion we understand that resistivity of metals is attributed to the scattering of
conduction electrons. In metals the scattering takes place basically under two mechanisms which give
rise to two components of resistivity which are described below.

1. Resistivity 𝜌𝑃ℎ due to scattering of electrons by lattice vibrations (phonons) which increases with
temperature. 𝜌𝑃ℎ is therefore temperature dependent. It is the resistivity exhibited by pure
specimen that is free of all defects, and hence called the Ideal resistivity
2. Resistivity 𝜌𝑖 due to scattering of conduction electrons by the presence of impurities, and
imperfections such as dislocation vacancies, and grain boundaries. This type of scattering is
independent of temperature and contributes to resistivity even at the temperature T= 0 0K. 𝜌𝑖 is
therefore called residual resistivity.

Since the two scattering mechanisms mentioned above act independently , the two resistivities are
additive. If 𝜌 is the total resistivity of the metal, then 𝜌 is given by ,

𝜌 = 𝜌𝑃ℎ + 𝜌𝑖 ................................................................. (1)

The above equation is called Matthiessen’s rule. Matthiessen’s rule 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 .

Quantum free electron theory

After the development of quantum mechanics, a new free electron theory was proposed by
Sommerfeld in 1928.He succeeded in overcoming many of the drawbacks of classical free
electron theory while retaining all its essential features. He treated electrons quantum
mechanically and included the effects of Pauli’s exclusion principle. This new theory
proposed by Sommerfeld is known as Quantum free electron theory.

Assumptions of Quantum free electron theory:

1) The energy values of the conduction electrons are quantized. The allowed energy
values are realized in terms of a set of energy levels.
2) The distribution of electrons in the various allowed energy levels occurs as per Pauli’s
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 exclusion principle.
3) The free electrons travel in a constant potential inside the metal but stay confined
within its boundaries.
4) The attraction between the free electrons and the lattice ions, and the repulsion
between the electrons themselves are ignored.

Density of states:

We know that the permitted energy levels for electrons in a solid material will be in terms of
bands. Each band is spread over an energy range of few electron volts. The number of energy
levels in each band will be extremely large. Therefore, in a small energy range, the energy
values appear to be virtually continuous over the band spread. However, number of energy
levels per unit energy range varies with energy in band. This variation is realized through a
function g(E), which is known as density of states function. Density of states g (E) can be
defined as it is the number of available energy states per unit volume per unit energy centred
at E. It is mathematically continuous function and the product g(E) dE gives the number of
states per unit volume in an energy interval dE at E.

Let us consider the case of free electrons in

a material. The possible energy values for the free
electrons corresponds to only the set of energy
levels available vacant but adjacent to the filled
energy levels in the band. Consider such a band as
shown in fig below. Let the energy band be spread
in an energy interval between E1 and E2.

Consider an infinitesimally small increment dE at arbitrary energy value E in the

band. Since dE is an infinitesimally small increment in E, we can assume that g(E) remains
constant between E and E+dE. Then the number of energy levels in the range E and (E+dE)
is obtained by evaluating the product of g(E) and dE

 8 2m 3 2  1
g E dE    E 2 dE
 
3
h

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As per this equation, the number of energy levels in an energy interval dE is proportional to √𝐸 .A plot
of g(E) verses E is shown in fig below.

Fermi energy:

The energy corresponding to the highest

occupied levels at zero degree absolute is called the
Fermi energy, and the energy levels is referred to as
Fermi level. The Fermi energy is denoted as 𝐸𝐹.

Thus at T=O⁰K all the energy levels lying above the

Fermi level are empty and those lying below are
completely filled as shown in fig below.

Fermi factor and its temperature dependence:

Fermi factor is the probability of occupation of a given energy state for a

material in thermal equilibrium. The probability f(E) that a given energy state with energy
E is occupied at a steady temperature T, is given by

1
f (E) = (𝐸−𝐸𝑓)
𝑒 𝐾𝑇 +1

Where EF is the Fermi energy and K is the Boltzmann constant.

The dependence of Fermi factor on temperature, and the effect on occupancy of

energy level is as shown in fig below. Let us consider different cases of distribution as
follows.

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

When T= O and E < EF, we have for the probability, f E  

1 1

 1
e 1 0 1

Therefore f (E) =1, for E < EF Here f(E ) = 1 means the energy level is certainly
occupied, and E < EF applies to all the energy levels below EF.

Therefore, at T=O, all the energy levels above Fermi level are occupied.

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

When T= O and E > EF, we have for the probability, f E  

1 1

 0
e 1 

Therefore f (E) = 0, for E >EF. i.e at T=O, all the energy levels above Fermilevels
are unoccupied.
(iii) Probability of occupation at ordinary temperature:

At ordinary temperature the value of probability remains 1 for E<< EF. But it startsdecreasing
from 1 as E reaches closer to EF.
The value of f(E) becomes ½ at E=E FThis is
because, for E = EF,

f E  
1 1 1
 
e 1 11 2
0

Further, for E> EF the probability value falls off to zero rapidly.

From the discussion we may say that the Fermi energy is the
most probable or the average energy of the electrons across
which the energy transition occurs at temperature above zero
degree absolute. This may be considered as the physical basis
for the concept of Fermi energy.