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MODULE - 4 ELECTRICAL PROPERTIES OF SOLIDS

4.1 ELECTRICAL CONDUCTIVITY OF METALS

CLASSICAL FREE ELECTRON THEORY (CFET) OF METALS

ASSUMPITONS OF CLASSICAL FREE ELECTRON THEORY

[Postulates of Drude-Lorentz Theory, 1900]

1. A metal is a 3-dimensional regular arrangement of atoms or positive ions. Between

these atoms, there are randomly moving free (valence) electrons. Free electrons
remain within the body of the metal.
2. The free electrons are equivalent to the molecules of a gas and hence they obey the
laws of kinetic theory of gases. Then, the kinetic energy of an electron is
1 mv th2  3 kT . Here k is Boltzmann constant, T is the temperature of the metal, m
2 2
is the mass of electron and vth is the thermal velocity or the root mean square
velocity of the electron.
3. The ion field inside the metal is constant. Electron-ion attraction & electron-
electron repulsion are negligible.
4. The electric current in a metal is due to the drift motion of electrons, under the
application of an electric field.

EXPRESSION FOR CONDUCTIVITY ON THE BASIS OF CFET

ne 2
Conductivity σ = where n is the electron density, τ is the mean collision time, m is
m
the mass and e is the charge of electron.
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FAILURE OF CLASSICAL FREE ELECTRON THEORY

Classical free electron theory successfully explains electrical and thermal conductivities
of metals.
But, it fails to account for specific heat, relation between temperature and conductivity,
and dependence of conductivity on electron density.

1. Specific heat:

According to classical free electron theory, the molar specific heat at constant volume, of
the free electron gas of a metal is Cv = 3/2 R where R is gas constant. This is very large
and is independent of temperature.
But, it is experimentally found that Cv = 10-4 RT, which is small and which depends on
temperature. So, CFET fails to explain the specific heat of metals.

2. Conductivity and temperature:

1 2 3
According classical free electron theory, the kinetic energy of an electron is mv th  kT
2 2
where k is Boltzmann constant, m is mass of the electron, vth is its thermal velocity and T
is the temperature of the metal.

From the above equation, vth α T

1 1
The mean collision time τ α . Therefore τ α
v th T

ne 2 1
The conductivity σ = . Or σατ  σα
m T

1
But, experiments show that σ α .
T
Thus, CFET fails to explain the relation between conductivity and temperature.
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3. Conductivity and electron density:

From classical free electron theory, conductivity σ α n.

It essentially means that the conductivity is always larger with larger electron density. But
experiments reveal that there is no systematic relation between σ & n. In the case of Al
and Cu, Al has larger electron density, but its conductivity is smaller than that of copper.
Hence, CFET fails to explain the relation between conductivity and electron density.

QUANTUM FREE ELECTRON THEORY (QFET) OF METALS

ASSUMPTIONS OF QUANTUM FREE ELECTRON THEORY

[Postulates of Sommerfeld’s theory, 1928]

1. Energy values of the conduction electrons are quantized.

2. Distribution of electrons in various allowed levels takes place according to Pauli’s

exclusion principle.

3. Conduction electrons move in a constant potential due to the positive ions.

4. The repulsion between electrons is ignored.

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FERMI ENERGY

A metal with N atoms has N discrete levels in its valence band.

Each level can accommodate two electrons of opposite spins, according to
Pauli’s exclusion principle.
Further, the tendency of the valence electrons is to fill from the bottom of the band.
As a result, the lower levels will be completely filled and the higher levels will be
completely vacant, at absolute zero.
The highest occupied level at absolute zero is called the Fermi level and the
corresponding energy is called the Fermi energy.
Energy of the highest occupied level at absolute zero is called the Fermi energy (or
Fermi energy at absolute zero). Or
Maximum energy of the conduction electrons at absolute zero is called the Fermi energy.
Fermi energy of different metals varies from 1eV to 15 eV.
[Cs – 1.6; Au – 5.5; Cu – 7; Fe – 11.1; Al – 11.8; Be – 14.3: in eV]
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FERMI-FACTOR
At a given temperature, the probability of filling of electrons at a given energy level (in
the valence band) is called the Fermi-factor or Fermi function. Or
Under thermal equilibrium, the probability of occupancy of electrons at a given energy
level is called the Fermi-factor.

1
Fermi-factor f(E) = E  EF

e kT
1

where E is the energy of the given level, EF is the Fermi energy of the metal, k is
Boltzmann constant and T is the absolute temperature of the metal.

VARIATION OF FERMI-FACTOR

1. T = 0K:

(i) E < EF.

E  EF 1 1
In this case, =-∞  f(E) = 
or f(E) = =1
kT e 1 0 1
It simply means that all the energy levels below Fermi level are occupied at 0 K.

(ii) E > EF.

E  EF 1 1 1
In this case, = ∞  f(E) = or f(E) = = =0
kT e 1
 1 

That is, all the energy levels above Fermi level are empty at 0 K.
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2. T > 0 K:

i. E << EF, f(E) = 1

ii. E >> EF , f(E) = 0 and

1 1
iii. E = EF , f(E) = = = 0.5
e 1
0
11
At ordinary temperatures (like the room temperature), electrons get a small energy of the
order of 0.025eV.
Only those electrons which lie near the Fermi level can absorb this energy. Hence at
ordinary temperatures, the distribution alters only near the Fermi level.

DENSITY OF STATES

The number of electronic energy states available to the electrons per unit volume of the
solid (metal) in a given energy range (in the valence band) is called the density of states.

The density of states in the energy range between E and E + dE is given by

3
  8m  2 1
g(E) dE = E 2 dE where m is mass of electron and h is Planck’s constant.
2  h 2 

3
½   8m  2
Further, g(E)dE = C E dE where C = = 1056 SIU
2  h 2 
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EFFECTIVE MASS OF ELECTRON, m*.

According to modified quantum free electron, a conduction electron moves in a periodic

potential of positive ions. Hence mass of the electron effectively changes. The apparent
mass of an electron inside a metal is called the effective mass of electron m*. Effective
mass of electron is different for different metals.

EXPRESSION FOR CONDUCTIVITY ON THE BASIS OF QFET

ne 2 
According to quantum free electron theory, electrical conductivity σ = where n is
m*v F

the electron concentration, λ is the mean free path, m* is the effective mass electron and
vF is the Fermi velocity (maximum velocity).

SUCCESS OF QUANTUM FREE ELECTRON THEORY

1. Specific heat:

From the CFET, it can be shown that the molar specific heat of the electron gas at
constant volume is Cv = 3/2 R where R is gas constant. This is large and is independent of
temperature.
But, the experiments show that the specific heat is small and it depends on temperature.
QFET explains specific heat of metals.

2k 
From QFET, it can be shown that Cv =   RT
 EF 

k – Boltzmann constant. R - gas constant. T – Temperature of the metal.

Using EF = 5eV, we get Cv = 10-4 RT.

This agrees with the experimental result.
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2. Conductivity and temperature:

1
According to classical free electron theory, conductivity σ α
T .

But, experimental results show that σ α 1/T, which can be explained on the basis of
QPET as follows.

As the conduction electrons travel in a metal, they are subjected to scattering by vibrating
ions.
If r is the amplitude of vibration, then the ion can be present effectively anywhere in a
circular area πr2.
If the area is increases, the mean free path decreases. That is λ α 1/(πr2).

But, r2 α T.  λ α 1/T
Further, σ α λ. Hence σ α 1/T

3. Conductivity and electron density:

ne 2
From CFET, conductivity σ = . ⸫ σ α n.
m
So, conductivity should be larger if electron density is larger.
But, experimental results say that there is no systematic relation between conductivity
and electron density.
QFET explains the experimental result.

ne 2 
According to quantum free electron theory, σ = where n is the electron
m*v F

concentration near Fermi level, λ is the mean free path, m* is the effective mass electron
and vF is the Fermi velocity.

According to QFET, σ depends on both n and (λ/vF).

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In the case of aluminum and copper, n of Al is 2.3 times greater than that of Cu. But,
(λ/vF) of Cu is 3.7 times greater than that of Al. Hence conductivity of copper is more.

CONCEPT OF PHONON
The atoms (positive ions) in a metal vibrate about their mean positions and these
vibrations are called lattice vibrations.
Lattice vibrations generate mechanical waves that carry heat energy throughout the metal.
These mechanical waves consist of packets of energy.
Each packet of energy travels with definite momentum and is treated as a particle called phonon.
A phonon is a packet of energy or a quasi- particle, associated lattice vibrations. Or
A phonon is the quantum (smallest unit) of lattice vibrational energy.
It is considered as a boson.
Absorption or emission of phonons is responsible for non-radiative transitions of atoms.

VARIATION OF RESISTIVITY WITH TEMPERATRUE IN METALS

The variation of resistivity ρ with temperature for all the metals, except superconducting
metals is as shown in the figure. It is clear from the graph that ρ is not zero even at
absolute zero. It has a small value ρi. From this value, ρ increases gradually (almost
independent of temperature) in the low temperature region. The variation becomes linear
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(depending on temperature) at higher temperatures. Careful observation of the curve

shows that there must be two types of resistivities - the temperature dependent resistivity
called the ideal resistivity and the temperature independent resistivity called the residual
resistivity.

Ideal resistivity (ρph) arises due to scattering of electrons by vibrating ions. It increases
with increase in temperature. It is exhibited by a pure specimen which is free from
defects.
Residual resistivity (ρi) arises due scattering of electrons by impurities.
It is independent of temperature and it exists even at 0 K.

Since the two mechanisms of electron scattering are independent of each other, the total
resistivity is ρ = ρph + ρi . This equation is known as Matthiessen’s rule.

Matthiessen’s rule states that the total resistivity of a metal is the sum of the resistivity
due to phonon scattering (scattering by vibrating ions) which is temperature dependent
and the resistivity due to scattering by impurities which is temperature independent.

At low temperatures, ion vibrations are minimum and hence the ideal resistivity becomes
negligible. So, ρ = ρi. At high temperatures ion vibrations are considerable and hence ρ =
ρph + ρi.
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4.1 EQUATIONS

ne 2
1. 1 mv th2  3 kT
2 2
2. σ =
m

ne 2 
3. Cv = 3/2 R 4. σ =
m*v F

3
1   8m  2 1
f(E) = g(E) dE = E 2 dE
5.
E  EF
6. 2  h 2 
e kT
1


2k 
7. Cv =   RT 8. Cv = 10-4 RT
 EF 

9. ρ = ρph + ρi
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Questions from VTU Question Papers

4.1 Quantum Free Electron Theory of Metals

1. Enumerate the failures of classical free electron theory [CFET] and mention the
assumptions of quantum free electron theory [QFET]. (7)

2. Enumerate the failures of classical free electron theory and discuss the success of
quantum free electron theory of metals. (8)

3. What is Femi level? Describe the variation of Fermi factor with temperature and
energy. (6)

4. Explain Fermi energy and Fermi factor. Discuss the probability of occupation of
various energy states by electron at T = 0K & T > 0K on the basis of Fermi- factor. (6)

5. Explain Fermi-energy & Fermi factor. (6)

6. Define Fermi energy. Discuss Fermi factor f(E) for the cases of E < Ef , E > Ef

and E = Ef at T = 0. (6)

7. Define Fermi factor. Discuss the variation of Fermi factor with temperature and
energy. (7)

8. With a graph, explain the variation of resistivity with temperature and impurity in
metals. State Matthiessen’s rule (8).

9. State Matthiessen’s rule. Discuss the variation of resistivity in low temperature and
high temperature regions. (5)

10. Explain the effect of temperature and impurity on the of electrical resistivity of a
metal. (5)

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