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MODULE-2
ELECRICAL CONDUCTIVITY IN MATERIALS
DRUDE-LORENTZ THEORY OF FREE ELECTRON
Paul Drude, a German Physicist gave a generally accepted theory on electrical
conductivity in metals and Lorentz, a Holland Physicst improved it.
Hence this theory is named DRUDE- LORENTZ THEORY. (Only for
information)

Every metal atom consists of valence electrons and these are responsible for
electrical conduction . In a metal, the atoms are tightly packed. Each atom consists
of valence electrons. These valence electrons are out of the atom and free to move
within the metal. There is continuity in movement of these electrons from atom to
atom.

Hence, valence electrons belong to any atom. These electrons are named as free
electrons. These are responsible for conduction and hence also called as conduction
electrons.

ASSUMPTIONS OF CLASSICAL FREE ELECTRON THEORY

1. In a metal there are freely moving valence electrons called free electrons
confined to its body. The electric current in a metal due to an applied field is a
consequence of the drift velocity of the free electrons in a direction opposite to
the direction of the field.

2. The free electrons are treated equivalent to gas molecules and thus assumed to
obey the law of kinetic theory of gases. Given by,
𝟑𝟐 𝑲𝑻 = 𝟏𝟐 𝒎𝑽𝟐𝒕𝒉
Where, K →Boltzmann constant
Vth→ Thermal velocity.

3. The electrical potential due to cores (Lattice point) is taken to be throughout the
metal.

4. The attraction between the free electrons and the ions and the repulsion between
the electrons themselves are considered insignificant (ignored)

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MEAN FREE PATH

Mean free path is the average distance travelled by the free electrons two
successive collisions. It is denoted by ” λ”.

MEAN COLLISION TIME

Mean collision time is the average time elapsed between two successive collision.
It is denoted by “τ”.
RELATION BETWEEN λ AND τ
τ =𝝀
𝑽
V→ Total velocity of electrons which is the sum of drift velocity(V d) and thermal
velocity(Vth).
RELAXATION TIME
In the absence of electric field, the average velocity of the electrons in any given
direction is zero,
i.e., Vaverage or Vav=0 (Absence of electric field)
But in the presence of electric field, the average velocity is not zero, i.e.,
𝑽𝒂𝒗 = 𝑽′𝒂𝒗(Presence of electric field)
Now, once we turn off the field, 𝑉𝑎𝑣 starts reducing exponentially from the value
𝑉𝑎𝑣′ as shown in the graph below
The decay process is given by
𝑽𝒂𝒗 = 𝟏 𝒆 𝑽′𝒂𝒗
“Relaxation time is the time required for the average velocity of the free electrons to
reduce to 1 times its everage velocity that existed when the field is just turned
𝑒
off”

LATTICE
The periodic arrangement of fixed ions in 3 dimensions is called lattice.

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DRIFT VELOCITY
When an electric field is applied, the free electrons will have net displacement in
one single direction and displaces with respect to time in a direction opposite to the
direction of the field.
The displacement of free electrons per unit time is called drift velocity. It is called
drift velocity. It is denoted by Vd. Given by Vd=𝒆𝑬 𝛕
𝒎
Where, e→ charge of electron=1.6x10-19C
E→ Electric field τ
→mean collision time m→mass
ofelectron=9.1x10-31Kg EXPRESSION
FOR ELECTRICAL CONDUCTIVITY
AS PER CLASSICAL
FREE ELECTRON THEORY
𝛕𝒆𝟐
σ=𝒏
𝒎
where, σ →Electrical conductivity
e →charge of electron τ
→Relaxation time m
→mass of electron.

FAILURES OF CLASSICAL FREE ELECTRON THEORY.

1.Specific heat: The theory compares free electron to the gas molecules, same
specific heat should be applicable for both. The Specific heat should be applicable
for both. The specific heat of a gas at constant volume is given by,
CV=𝟑 𝑹 .............(1)
𝟐
But experimentally it was found that, CV=10-4RT ............(2)
From (1) & (2), we see that ,CV for a metal is not only far smaller than CV for gas
molecule but also its dependent on temperature.
2.Temperature dependence of electrical conductivity(σ)
Experimentally observed value of σ for metals is inversely proportional to
temperature T.
i.e., σexp α 𝟏...........(1)

𝑻 𝑚𝑉𝑡2ℎ
Now from classical assumption we have,
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Vth
𝑚

Vth
We know that , Ƭ α
Vth

(or) Ƭ α ......... (3) [from eqn 2]

Also we have,
𝑛Ƭ𝑒2 σ=

𝑚
σ α Ƭ
(or)σ α
From (1) & (4) it is clear that the prediction of classical free electron theory is not
agreeing with the experimental observation.
3. Dependence of electrical conductivity on electron concentration ‘ n’
Conductivity ‘σ’ is given by,
σ=𝑛 𝛕𝑒2 where ‘n’ is electron concentration .
𝑚

Metal Valency σ (Ωm) n

Cu 1 5.88*107 8.45*1028
Zn 2 1.09*107 13.10*1028

According to classical free electron theory, n α σ, which means higher the number
of free electrons higher is its conductivity.
From the above table we observe that Zn has more free electrons than Cu, but
conductivity of Cu is higher than that of Zn. Hence the prediction , n α σ does not
always hold good.

ASSUMPTIONS MADE IN QUANTUM FREE ELECTRON THEORY.

One of the important realization was, the role played by Pauli’s exclusion principle.
The assumptions of Quantum free electron theory are,
1. The free electrons possess energy and these energy values are quantised. The
allowed energy levels are realized in terms of a set of energy levels.

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2. The distribution of electrons in various energy levels occurs as per Pauli’s
exclusion principle...i.e., single energy level can be occupied by only 2 electrons
with opposite spin.
3. The electric potential throughout the lattice is taken to be constant.
4. The attraction and the repulsion between the lattice points and electrons (or) lattice
points themselves (or) electrons themselves are ignored.

DENSITY OF STATES
Energy levels of electrons in a solid will look like bands. On a closer look we see
that the energy levels in the band are not uniformly distributed. The number of
energy levels/unit energy range is explained by density of states.
“Density of states is the number of allowed energy levels in infinitesimally small
energy increment dE in the valence band of the material.
𝟖√𝟐𝜫𝒎𝟑 𝟏𝒉

Given by, g(E)dE= 𝟑 𝑬𝟐 dE

𝟏
g(E)α 𝑬𝟐
FERMI ENERGY
Consider a metal of N atoms and hence there will be N allowed energy levels in
each band. The electrons will occupy energy levels according to Pauli’s exclusion
principle. When no external energy is supplied for the electrons, such as thermal
energy i.e., at t=0K, we see that levels above valence band will be vacant.
“Fermi energy is the energy corresponding to the highest occupied level at zero
degree absolute temperature and the energy level is referred to as the FERMI
LEVEL (EF)”
At T=0K, energy levels lying above the Fermi level are empty and those lying below
are completely filled.

FERMI FACTOR AND DEPENDANCE OF FERMI FACTOR

ON TEMPERATURE AND ENERGY (PROBABILITY OF OCCUPATION OF
VARIOUS ENERGY STATES BY ELCTRONS AT T=0K AND T>0K, ON THE
BASIS OF FERMI FACTOR)
Fermi-Dirac Statistics permits the evaluation of probability of finding electrons
occupying energy levels in a certain energy range. This is done through a function
called Fermi Factor f(E).It is given by, f(E)= 𝑬−𝑬𝑭𝟏
𝒆 𝑲𝑻 + 𝟏
“Fermi factor is the probability of occupation of a given energy state for a material
in thermal equilibrium”
Probability of occupation is considered for following cases,

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

We have, F(E)= 𝐸−𝐸𝐹1
𝑒 𝐾𝑇 + 1
If E<EF , E-EF will be negative and T=0,

f(E)= 𝑒 −∞
1 +1

f(E) =
f(E)=1
• f(E)=1 means, the energy level is certainly occupied.i.e,there is 100%
probability that the electrons occupy the energy level below Fermi energy
• All the energy levels below Fermi level are occupied
• E<EF applies to all the energy levels below EF
ii) Probability of accupation for E>EF at T=0K
If E>EF , E-EF will be positive and for T=0,
1 1
f(E)= ∞ +
=
1
𝑒 ∞
f(E)=0
All the energy levels above Fermi level are unoccupied.i.e, 0% probability for
the electrons to occupy the energy level above the Fermi level
iii) Probability of occupation at ordinary temperature.
At ordinary temperature, though value of probability remains 1 for E<<EF ,it
starts decreasing from 1 as the value of E become closer to EF For E=EF ,
f(E)= 0
1+ = 1= 1
𝑒 1 1+1 2

f(E)= 𝟏
𝟐
There is 50% probability for the electrons to occupy the Fermi energy level
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EXPRESSION FOR ELECTRICAL CONDUCTIVITY AS PER QUANTUM
FREE ELECTRON THEORY
𝒏𝒆𝟐𝝀

𝒎 𝑽𝑭
where,
m*→ effective mass of the
electron VF→ Fermi velocity
λ →Mean free path e →charge of
the electron
n →electron concentration

MERITS OF QUANTUM FREE ELECTRON THEORY (SUCCESS

OFQUANTUM FREE ELECTRON THEORY IN OVERCOMING THE
FAILURES OF CLASSICAL FREE ELECTRON THEORY)

1.Specific heat(CV)- The small value of specific heat (CV) for the conduction
electrons can be explained as follows.
According to quantum theory, only those electrons that occupy energy levels
close to EF can absorb the energy and move to the higher energy states. Number
of such electrons absorbing the energy is small and hence CV is small, It is given
by,
CV RT
𝐸𝐹
Ex., For EF=5eV

𝐸𝐹
CV=10-4RT.
This confirms with the experimentally observed values.

2.Temperature dependence of electrical conductivity.

The experimental fact that the electrical conductivity σ has a dependence on

1 and not on is explained
here,
𝑇
𝑛𝑒2𝜆

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We have, σ=𝑚 ∗𝑉𝐹 ........(1)
The dependence of σ on T is analysed as follows,
The free electrons are subjected to scattering due to vibration of ion in the
lattice.If ‘r’ is the amplitude of vibration ,it is same in all the directions then the
ions can be considered to be present effectively in a circular cross-section of area
Πr2.The value of mean free path λ decreases when Πr2 increases.i.e,
1
λα𝛱𝑟2.........(2)
Now consider the facts,
• Energy of ion α square of the amplitude
i.e, E α r2........(3)
• Energy of ion α Temperature
i.e, E α T..........(4) from eqn (3) & (4)
→r2 α T............(5)
1 from eqn
(2) → λ α 𝑟 2..........(6)
1 from eqn
(5) & (6)→ λ α .............(7)
𝑇
1
from (1) & (7)→ σ α
𝑇
3.Electrical conductivity and electron concentration.
It was not possible to understand why metals such as Aluminium and gallium which
have 3 free electrons/atom have lower electrical conductivity than metals such as
copper and silver which possess only 1 free electron/atom. Quantum free electron
theory could explain why,
𝑛𝑒2𝜆
We know that , σ=𝑚 ∗𝑉𝐹 ...............(1)
𝜆
From(1),it is clear that ‘σ’ depends on both ‘n’ and also on ⌊ ⌋ ratio
𝑉𝐹

The value of ‘n’ for aluminium is 2.13 times higher than that of copper. But the
values of ⌊ 𝜆 ⌋for copper is about 3.73 times higher than that of aluminium.
𝑉𝐹
Therefore, conductivity of copper exceeds that of aluminium.

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SUPERCONDUCTORS

TEMPERATURE DEPENDENCE OF RESISTIVITY OF A METAL.

Metals have loosely bound electrons in their outermost shell or valence shell which
is responsible for conduction. These electrons are called free electrons/conduction
electrons.
The dependence of resistivity (𝜌) on temperature is as shown below.

The total resistivity of a metal is the sum of the resisitivity due to impurities(𝜌o) at
T=0K and the resistivity due to phonon scattering which is temperature dependent 𝜌
(T). We can see that the resistance decreases with temperature and reaches minimum
at T=0K
The Variation is expressed by the Matthiessen’s rule
𝜌 = 𝜌o +𝜌 (T)
Where, 𝜌 →is the resistivity of the given metal
𝜌o → is the residual resistivity
𝜌 (T)→ is the temperature dependent of resistivity
( Note: Lattice vibrations are called phonons)

TEMPERATURE DEPENDENCE OF RESISTIVITY OF

A SUPERCONDUCTOR:

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Resisitivity (𝜌) is the non superconducting state decreases with decrease in

temperature upto a particular temperature Tc. At Tc, 𝜌 abruptly drops to zero. Tc is
called the critical temperature and signifies the transition from normal state to the
superconducting state of the material under study.

“The resistance offered by certain materials to the flow of electric current

abruptly drops to zero below a certain temperature. This phenomenon is
called Superconductivity”
➢ Materials exhibiting this property are called superconductors.
➢ The temperature at which the resistance becomes zero is called the critical
temperature.
➢ Critical temperature is different for different materials . The critical
temperature is different for different superconductors.

Superconductors symbol Tc(K)

elements
Mercury Hg 4.2
Gallium Ga 1.15
Aluminium Al 1.20
Indium In 3.40
Ti n Sn 3.72
Tantaum Ta 4.48
Vanadium V 5.38
Lead Pb 7.19
Lanthanum La 6.00
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Niobium Nb 9.50

BCS THEORY
BCS theory-(Bardeen,Cooper and Schrieffer theory)
• This theory explains the phenomenon of Superconductivity. This
theory is based upon the formation of cooper pairs, which is a
quantum mechanical concept.

• When the free electron leaves the atom, the atom becomes positively
charged. When electron comes near a positive ion core of the
lattice,it experiences an attractive force because of the opposite
polarity between electron and ion.
• Due to this attraction ,the ion is displaced from its position, leading
to lattice distortion.At the same time,if other electron which comes
near that place will also interact with the distorted lattice. This
process is looked upon as equivalent to interaction between the two
electrons through the lattice .The process is called ”electronlattice-
electron interaction through the phonon field”
• The attractive force between two electrons will be maximum if they
have equal and opposite spin and momenta.This force will even
exceed the coulomb repulsive force between electrons. “Hence
,cooper pair is a bound pair of electrons formed by the interaction
between the electron with opposite spin and momenta in a phonon
field”

• Each cooper pair is associated with a wavefuction. The wavefuction

with similar cooper pairs start overlapping which may extend over
106 other pairs. This leads to a union of vast number of cooper pairs.
• When the electron flow in the form of cooper pairs,they do not
encounter any scattering and the resistance factor vanishes or in
other words conductivity becomes infinite hence a material becomes
superconductor.

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MEISSNER EFFECT.
When a superconducting material is cooled in a magnetic field below the critical
temperature, the flux lines are expelled from the body of the material .i.e. the
material behaves like a perfect Diamagnetic. This effect is known as Meissner
effect.

CRITICAL FIELD
The strength of minimum magnetic field required to just switch a material from
Superconducting state to normal state is called Critical field.

➢ If “T” is the temperature of the superconducting material(T<TC)

“Hc” is the critical field and
“H0” is the field required to turn the superconductor to normal conductor at
0 K.

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Then the relation for critical field (Hc) is given by
Hc=H0 [1-T2/T2c]

TYPES OF SUPERCONDUCTORS:
Superconductors are classified into two types they are,
1. Type -I Superconductors(soft)
2. Type-II superconductors(hard)
Type -I Superconductors (soft)

• When magnetic field H<Hc ,they exhibit complete Meissner effect.

In the presence of external magnetic field the material is in the
superconducting state and behaves as a perfect diamagnet.
• When H> 𝐻c the magnetic flux enters the material and it loses its
diamagnetic property and the material comes to normal state.
• It is found that for type I superconductors the critical field values
are low.

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Type –II Superconductors (hard)

Where-H is the External magnetic field and M is the -ve magnetic moment.
Hc1 and Hc2 are the lower & higher critical fields.
• They are characterized by two critical fields Hc1 and Hc2 when
H<Hc1 the Material is in the superconducting state and it behaves
as a perfect Diamagnet.
• When H>Hc1 the flux penetrates the body and fills partially with
further increase in H, the flux filling also increases thereby
decreasing the diamagnetic part of the material and covers the
entire body when H becomes equal or greater than a second
critical value Hc2 .the material then turns into a normal
conductor.Hc1and Hc2 are called lower critical field and upper
critical field respectively.
• When H lies between Hc1and Hc2 the material loses some of its
diamagnetic properties and enters into a mixed state called vortex
state.
• When H>Hc2 the material enters into the normal state .it is found
that for type –II superconductor’s critical field values are high.
Note: The number of magnetic lines flowing per unit area is called flux. High
temperature superconductivity:
“Superconductors having higher critical temperatures are called high temperature
superconductors”.

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All high temperature superconductors are not pure metals, but they are different
types of oxides of copper. And bear a particular type of crystal structure called
Pervoskite crystal structure. It is found that, the critical temperature is higher for
those materials having more number of copper oxygen layers. It is found that the
formations of super currents in high temperature superconductors are directional
dependent.
The super currents are strong in copper oxygen planes and weak in a direction
perpendicular to the copper oxygen planes. Applications
superconductors:
Maglev vehicles:

Magnetically levitated vehicles are called maglev vehicles.The vehicle is levitated

above the tracks hence friction is eliminated.
• Maglev vehicles do not slide over the tracks.
• The maglev vehicles work on the principle of Meissner effect.
• Superconducting magnets are built onto the base of the vehicle, and
current is passed through the guide way.
• Magnetic field is produced by the superconducting magnet and
current in the guideway.
• Now, enormous repulsion happens between these two magnetic
fields as the result vehicle will be set a float.
• The vehicle is levitated to about 10 to 15cm above the guideway.
• When the vehicles runs on the guideway, the wheels are retraced
into its body, while stopping the wheels are drawn out and the
vehicle slowly settles on the guideway.

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SEMICONDUCTORS
Semiconductors have conductivity in the range intermediate between those of
conductors and insulators.
The resistivity of semiconductors lie in the range 10-6 to 10+8Ωm.
Elements such as Silicon(Si), Germanium (Ge) , Selenium (Se) and compounds
such as Gallium Arsenide (GaAs), Gallium Phosphide (GaP) are some examples of
semiconductors.

Conductivity of Semiconducting Materials:

Carrier concentration in an intrinsic semiconductor:
The number of electrons in the conduction band per unit volume of the
material is called electron concentration (Ne) given as,
(𝐸𝐹−𝐸𝑔)

Ne (𝜋KT 𝑚𝑒∗)3/2 𝑒 𝑘𝑇 ………….. (1)

Where 𝑚𝑒 is the effective mass of

∗

electron EF is the Fermi Energy and Eg is

the energy gap.
Similarly, the number of holes in the valence band per unit volume of the material is
called hole concentration. (Nh)
(𝐸𝐹−𝐸𝑔)

Nh (𝜋KT 𝑚 3/2 𝑒 𝑘𝑇 …………… (2)

Where 𝑚ℎ∗ is the effective mass of

holes EF is the Fermi Energy and Eg is
the energy gap.
T is the absolute temperature and h
is the Planck’s constant.
In general, the number of charge carriers per unit volume of the material is called
carrier concentration.
The charge carriers, both electrons and holes contribute to the conductivity of the
semiconductor.
The conductivity of a semiconductor is given by the expression σ = e [ (Neµe) +
(Nhµh) ] where Ne and Nh are the carrier concentrations of electrons and holes
respectively.

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µe and µh are mobility of electrons and holes respectively and ‘e’ is the magnitude
of charge of the electron.
Law of Mass Action for Semiconductors:
Law of mass action says that, for a given semiconductors material either
intrinsic or extrinsic, the product of the charge carrier concentration remains a
constant at any given temperature, even if the doping is varied. We have the
equations for Ne and Nh as
(𝐸𝐹−𝐸𝑔)

Ne (𝜋KT 𝑚 3/2
𝑒 𝑘𝑇 ………….. (1) and
(𝐸𝐹−𝐸𝑔)

Nh (𝜋KT 𝑚ℎ∗ )3/2 𝑒 𝑘𝑇 …………… (2)

In the above expressions, we see that Ne and Nh depends on EF .

Consider the product of Ne and Nh,

Ne . Nh = 32ℎ 6 . (𝜋KT)3.(𝑚𝑒𝑚ℎ)3⁄2 .𝑒−𝐸𝑔⁄𝐾𝑇

The above equation shows that Ne and Nh do not sepend on EF, but remains a constant.
Ne . Nh = constant Therefore,

This condition is applicable to both intrinsic and extrinsic semiconductors.

In the case of an intrinsic semiconductor,
Ne = Nh = ni
Where ni is the intrinsic charge carrier concentration. Therefore,
Ne . Nh = ni2 = constant.

QUESTION BANK

1) Describe Type I and Type II superconductors

2) Explain the terms a) relaxation time, b) mean collision time, c) mean free
path, and drift velocity
3) Discuss in brief BCS theory of superconductivity
4) Write a note on maglev vehicles
5) Describe how quantum free electron theory has been successful in
overcoming the failure of classical free electron theory.

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

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