Electronic Conduction in Solids 21

ELECTRONIC CONDUCTION IN SOLIDS

Classical free electron theory of metals: In order to explain electrical

conductivity in metals, Lorentz and Drude put forward a theory called free
electron theory of metals. It is based on the following assumptions.

1. Free electrons in a metal resemble molecules of a gas. Therefore, Laws

of kinetic theory of gasses are applicable to free electrons also. Thus free
electrons can be assigned with “ average velocity c”, ‘Mean free path λ”
and “mean collision time ”. τ
2. The motion of an electron is completely random. In the absence of electric
field, number of electrons crossing any cross section of a conductor in one
direction is equal to number of electrons crossing the same cross section
in opposite direction. Therefore net electric current is Zero.
3. The random motion of the electron is due to thermal energy. Average
kinetic energy of the electron is given by
3 1
KT = mc −2
2 2
3KT
or C =
m
c=Average Velocity, k=Boltzman Constant, T=Absolute Temperature,
m=mass of the electron.

4. Electric current in the conductor is due to the drift velocity acquired by the
electrons in the presence of the applied electric field.
5. Electric field produced by lattice ions is assumed to be uniform throughout
the solid.
6. The force of repulsion between the electrons and force of attraction
between electrons and lattice ions is neglected.

The Drift Velocity :

In the absence of the applied electric field, motion of free electron is

completely random. During their motion electrons undergo collisions with the
residual ions and during each collision direction and magnitude of their
velocity changes in general. When electric field is applied, electrons
experiences force in the direction opposite to the applied field. Therefore in
addition to their random velocity, electron acquires velocity in the direction of
the force. Since electrons continue to move in their random direction, with
only a drift motion due to applied field, velocity acquired by the electrons in
the direction opposite to the applied field is called Drift velocity and is
denoted by vd. Note the vd is very small compared to c, the average thermal
velocity. Electric current in a conductor is primarily due to the drift velocity of
the electrons.

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Electronic Conduction in Solids 22

Relaxation Time, Mean collision time and Mean free path:

Mean free path (λ): The average distance traveled by electrons between two
successive collisions during their random motion is called mean free path, it
denoted by λ.
τ
Mean collision Time : The average time taken by an electrons between
two successive collisions during their random motion is called mean collision
time, it is denoted by τ. The relationship between λ and τ is given by λ=cτ.
τ
Relaxation Time r: In the presence of an applied electric field, electrons
acquire drift velocity vd in addition to the thermal velocity c. if electric field is
switched off, vd reduces and becomes zero after some time. Let electric field
is switched off at the instant t = 0, when drift velocity vd=v0. The drift velocity
of the electron after the lapse of ‘t’ seconds is given by
−t
τr
v = v0 e
τ τ
Where r is called relaxation time. Suppose t= r,then vd=v0e-1=1/ev0
Thus the relaxation time is defined as the time during which drift velocity reduces
to 1/e times its maximum value after the electric filed is switched off.
The relationship between relaxation time and mean collision time is given
by
τ
τr =
1 − cosθ
Where θ is scattering angle, cosθ is average value of cosθ taken over
very large number of collision made by electrons.
It can be shown that, τ=τr for metals.
Ohm’s Law :

Consider a conductor of length “l” and area of cross section ‘A’. Let “σ” is the
electrical conductivity of the conductor, then resistance of the conductor is given
by
 1 
R= ρ = .
A σ A

Let a potential difference of “V” volts is applied between two ends of the
conductor, which causes current I to flow through the conductor. Then, according
to Ohm’s Law.

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Electronic Conduction in Solids 23

V = IR
Il jl
V = =
σA σ
where j = I is called current density
A
V
= j
l σ
If " E" is the electric field established inside the conductor ,
then, E = V
l
∴E = j
σ
or J = σE
The above equation also represents Ohm’s law.

Expression for electrical conductivity:

Consider a conductor of length ‘l’, area of cross section “A”, having “n”
number of free electron per unit volume. Let a Pd of ‘V’ volts is applied between
two ends of the conductor and ‘E’ is the electric field established inside the
conductor. Then according to Ohm’s law
J=σE
Where σ is the electrical conductivity of the conductor and j is a current density
given by
J=I/A

σ=j/E -1
Consider a cross section “X” of the conductor. Let I is the current flowing through
the conductor. Then according to the definition, current I is given by the quantity
of charge flowing across the cross section “X” per second.
I=Ne
Where N is the number of electrons crossing the cross section X in one second.
We know that, if vd is drift velocity of the electrons. Electrons travel a distance
equal to “vd” in one second. Therefore number of electrons crossing the cross
section “X” in one second is equal to number of electrons occupying the space
between two cross sections “X’ and “Y” separated by the distance vd.

X Y

vd
E
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Electronic Conduction in Solids 24

N = n( Avd )
I = nAvd e
But j=I
= nevd
A
nevd
∴σ = j =
E E
nevd
σ= −2
E
We know that free electrons undergo collisions with positive ions during their
random motion. Let the drift velocity acquired by the electron becomes Zero
during each collision and let vd is the drift velocity acquired by the electron just
before next collision then
vd =0+a . τ
Where ‘a’ is the acceleration acquired by the electron in the presence of electric
τ
field ‘E’ and ‘ ’ is the average time taken by the electron between two successive
collisions. Force acting on the electron in the presence of electric field is given by
F = eE = ma
eE
∴a = .
m
eE
∴ vd = τ.
m
∴ equation 2 becomes
ne nEτ
σ = X
E m
ne τ
2
σ = − 3
m
λ
but τ = (λ = mean free path)
c
ne 2 λ 3kT
∴σ = from free electron theory c=
mc m
ne 2 λ
∴σ =
3kT
m
m
ne λ2
σ = −4
3mkT

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Electronic Conduction in Solids 25

Equation 4 gives expression for electrical conductivity.

Note that, electrical conductivity of a conductor d is proportional to

1. No. of electrons per unit volume and
2. Mean free path for free electrons and inversely proportional to
3. Square root of the absolute temperature.

Mobility of Electrons:

The easiness with which electrons get drifted in the presence of applied electric
field is called “Mobility”. It is defined as the drift velocity acquired by the electron
per unit electric field. It is denoted by µ
vd
Mobility µ =
E
nevd
we have σ = = neµ
E
σ = neµ
σ
µ=
ne
ne 2τ
Also σ = = µne
m
e
∴ µ =  τ
m

Effect of temperature and impurity on electrical resistivity of metals.

Resistance of a conductor can be mainly attributed to two reasons, namely

1. Scattering of electrons with the vibrating lattice ions and

2. Scattering of electrons by the presence of impurities present in the metal.

1. During their random motion electrons undergo scattering from ions, which
are in the continuous state of vibrations. This scattering is called phonon
scattering and gives rise to resistance of metals. The resistance depends
on the number of scattering that electrons undergo. As the temperature of
the metal increases amplitude of vibrations of the ions increases, therefore
number of collision also increases. This leads to increase in resistance.
This resistivity is called ideal resistivity denoted by ρph and is given by
m
ρ ph = -1
ne 2τ ph

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Electronic Conduction in Solids 26

τph = mean collision time assuming that there are no impurities.

2. Scattering of electrons from the sites of Impurities presents in the metals such
as dislocation joints, Grain Boundaries, Impurity atom, etc gives rise to resistivity
called residual resistivity. It exists even at absolute zero temperature. It is
temperature independent and denoted by ρi . It is given by

m
ρ i=
ne 2τ i
Where τi is mean collision time assuming that temp phonon scattering is
absent.

Thus net resistivity of the conductor is given by

ρ = ρ i + ρ ph
m m
ρ= +
ne 2τ i ne 2τ ph
The above equation is called Matthiessen’s Rule, Which states that the
net resistivity of conductor is equal to the sum of the resistivity due to the phonon
scattering which is temperature dependent and resistivity due to the presence of
impurity which is temperature independent.
A graph of ρ against T is as shown in the fig.

At absolute zero temperature ρ= ρI .

As the temperature increases ρ(T)
increases gradually for lower
temperatures. At higher temperatures,
ρ(T) increases rapidly overtaking the
effect of ρI and becomes linearly ρ Impure metal
dependent on temperature. Thus at
higher temperatures the effect of ρ(T)
impurity on resistivity becomes
negligible and resistivity mainly ρI Pure metal
depends on temperature. ρ(T)

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Electronic Conduction in Solids 27

Failure of classical free electron theory.

Though classical free electron theory successfully explained electrical

conductivity of metals, thermal conductivity and other phenomenon, it could not
explain number of other experimentally observed facts. This led to the failure of
classical free electron theory of metals. Some of the important reasons, which led
to the failure of the theory, are,

1.The specific heat of the Solids: When heat is supplied to solids free
electrons also absorb energy. Thus free electrons also contribute to the Specific
heat of solids. This is called electronic specific heat.
According to the free electron theory of metals energy of all the electrons
in one-kilo mole of solid is given by
3
E= N A kT
2
Where NA =Avagadro number, k = Boltzman constant T=Absolute temperature.

Therefore the electronic specific heat is given by

dE 3
CV = = N Ak
dT 2
3
= × 6.023 × 10 26 × 1.38 × 10 − 23
2
= 12.5kJ / kmole / K
But experimentally determined value of CV is 100 times less than the
above value. Thus contribution to specific heat from electrons is negligibly small.

2.Teperature dependence of conductivity: According to free electron

theory of metals, electrical conductivity of a conductor is given by
ne 2 λ
σ =
3mkT
It is clear from the above equation that σ αℓ 1/√T
But experimentally it was found that σ αℓ 1/T

3.Dependence of conductivity on Electron concentration: According

to free electron theory of metals, electrical conductivity of conductor is given by

ne 2 λ
σ =
3mkT
It is clear from the above equation that σ αℓ n
The value of electron concentration and conductivity for some of the
metals are given below.

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Electronic Conduction in Solids 28

Metals Electron concentration Conductivity

In 1028 / m3 In 107 / Ωm
Ag 5.85 6.30
Cu 8.45 5.88
Cd 9.28 0.15
Zn 13.10 1.09
Ga 15.30 0.67
Al 18.06 3.65

It is clear from the above table that there is no direct relationship between
electron concentration and electrical conductivity.

From the above discussion it is clear that there exists discrepancy

between theoretical predictions and experimental observation. This led to the
failure of classical free electron theory of metals.

Quantum free electron theory of metal

Since classical free electron theory failed to account for the number of
experimentally observed facts, Sommerfeld put forward a new theory, called
quantum free electron theory, in the year 1928. The quantum free electron theory
is based on following assumptions:

1. Though free electrons are free to move anywhere in the solid, they are
bound within the boundary of the solid. Therefore, their energies are
quantised according to quantum mechanics. Thus free electrons can have
only discrete values of energy.
2. There exists large number of closely spaced energies for the electrons.
Electrons are distributed among these energy levels according to Pauli’s
exclusion principle, which states that there cannot be more than two
electrons in any energy level.
3. The potential energy of the electrons remains uniform throughout the
solid.
4. The force of repulsion between the electrons and force of attraction
between electrons and lattice ions is neglected.

Fermi Energy

According to quantum free electron theory, free electron energies are

quantised. Thus if there are N free electron there exists N closely spaced energy
levels. Electrons are distributed among these energy levels according to Pauli’s
exclusion principle. At absolute zero temperature, two electrons with least energy
having opposite spins occupy lowest available energy level. The next two
electrons with opposite spins occupy next energy level. And so on. In this way
N/2 energy levels are occupied, and remaining N/2 energy levels are vacant. The
top most energy level occupied at absolute zero temperature is called Fermi

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Electronic Conduction in Solids 29

Energy level. The energy corresponding to that energy level is called Fermi
Energy.
Fermi Energy can be defined as energy of that energy level below which
all energy levels are completely occupied and above which all energy levels
completely empty. It is denoted by EF

Thus Fermi energy represents maximum energy that electrons can have
at absolute zero temperature.

Fermi factor Vacant energy levels

We know that at T=0 K, all energy
levels below EF are completely filled and
above EF are completely empty. As the
temperature is increased, some of the

Energy
electrons absorb energy and start
migrating to energy level above EF. As a
result there exists some vacant energy
levels below EF and filled energy levels EF N/2
above EF. Now it becomes difficult to say
whether a particular energy level is
occupied or vacant. The probability of
occupation of any energy level is given by
a mathematical function

Filled energy levels

1
f (E) = ( E − EF )

e kT
+1
f(E) is called Fermi factor. It is defined as follows.

Fermi factor is a function, which gives the probability of occupation of an

energy level E at the given temperature T for a material in thermal equilibrium.

The dependence of Fermi factor on Energy & Temperature

The variation of Fermi factor with Energy for various temperatures can be
discussed as follows
(i) At absolute zero temperature (T=0):
(a) When energy E< EF

When T=0 & E< EF

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Electronic Conduction in Solids 30

1 1
f (E) = −∞
= =1
e +1 0 +1
∴ f ( E ) =1, for E < EF
∴ Since f(E)=1, at T=0, all energy levels below Fermi level are occupied.

(b) When energy E > EF

When T=0 & E > EF

1 1
f (E) = = =0
e∞ + 1 ∞ + 1
∴ f ( E ) = 0, for E > E F
∴ At T=0, all the energy levels above Fermi energy level are vacant.

The graph of f(E) Against E at T=0 is as shown in the fig.

T=0o K
1.0

f(E)

T=0o K
0
E EF

(ii) For temperatures T >0:

(a) When energy E< EF
E − EF
is > 0 But <1
e kT

∴ f(E) is less than 1 but greater than 1/2

(b) When energy E > EF
E − EF
is > 1
e kT

∴ f(E) is greater than 0 but less than 1/2

(c) When energy E = EF

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Electronic Conduction in Solids 31

E − EF
=0
e kT

∴ f(E) = ½

The curve obtained is as shown in the Fig.

It is clear from the above discussion that irrespective of the temperature the
probability of occupation of the Fermi energy is always ½.
Therefore Fermi energy is considered as the most probable energy that
electron posses in the solid.

Density of States

The density of states is defined as the number of energy levels available

per unit volume per unit energy centered at E. It is denoted by g(E). The product
g(E)dE gives the number of states per unit volume between the energy levels E
and E+dE.

Then the number of electrons per unit volume having energies between E
and E+dE is given by

N(E)dE = g(E)dE×f(E)

Where f(E) is Fermi factor.

Expression for density of States

Let a free electron is bound within a cube of side ‘a’.

According to quantum mechanics, the energy of an electron confined within a

one-dimensional potential well is given by

n2h2
E=
8ma 2
Where n=1,2,3.h=Plank’s constant, m=mass of the electron, a=width of the
potential well.

For 3 dimension the above equation becomes

h2
E= 2
(nx2 + n y2 + nz2 ) -1
8ma
Where nx, ny, nz are positive integers greater than zero.

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Electronic Conduction in Solids 32

Equation 1 can be written as

E = E0R2 -2

h2 R 2 = nx2 + n y2 + nz2
Where E0 = and -3
8ma 2
The number of Energy states with a particular value of E can be obtained
by constructing a space in which each point is represented by nx, ny, and nz .
Then all allowed energy states are within a sphere of radius R bound by three
mutually perpendicular axes nx, ny, and nz . Since nx, ny, and nz can take only
integer values, we can consider only an octant as shown in the Fig.

ny

dR

nx

nz

Therefore number of energy states within an octant of radius R is given by

1 4 3
 πR 
8 3 
Again the number of energy states within a sphere of radius R+dR is given by

1 4 3
 π ( R + dR ) 
8 3 
Thus number of energy states having energy values between E
and E+dE is given by

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Electronic Conduction in Solids 33

1 4 3 1 4 3
g(E)dE =  π ( R + dR )  ―  πR 
8 3  8 3 

g(E)dE =
π
6
{ }
( R + dR ) 3 − R 3 = π { R 3 + dR 3 + 3R 2 dR + 3dR 2 R −R 3 }
6
π π π
g(E)dE ≅
6
( 3R 2 dR ) = R 2 dR = R ( RdR
2 2
) -4

E E
From equation 2 R2 = ∴ R=
E0 E0

dE
Differentiating 2 RdR =
E0

π E dE π E
Therefore g(E)dE = × × = × 3 dE
2 E0 2 E0 4 E 2
0

Substituting for E0 from equation 3 we get

π E
= × dE
g(E)dE 4  h 2  32
 
2 
 8ma 

3
π  8ma 2  2
g(E)dE =   E dE
4  h2 

Since Pauli’s exclusion principle allow two electrons in each state

3
π  8ma 2  2
g(E)dE = 2  2  E dE
4 h 

3
π  8ma 2  2
g(E)dE =   E dE
2  h2 

Dividing the above equation by a3 gives the number of electrons per unit
volume having energies between E and E+dE.

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Electronic Conduction in Solids 34

3
π  8m  2
Therefore g(E)dE = E dE
2  h 2 

The above equation is called density of energy states. The graph of g(E)
against E is as shown in the fig.

g(E
)

dE E

Expression for Fermi Energy at T=0 K

Number of electrons per unit volume having energies between E and

E+dE is given by

N(E)dE = g(E)dE×f(E)

At T=0, only energy levels up to EF are filled. Therefore f(E)=1 for E < EF
3
π  8m  2
N(E)dE = g(E)dE = E dE
2  h 2 

Therefore the number of electrons per unit volume is given by

EF 3
π  8m  2
n = ∫ N ( E ) dE = ∫ E dE
0
2  h 2 

3
π  8m  2 EF
 E 3 2   2 
n =
2  h 2    0  3 

3
π  8m  2 3
n =  2  EF 2
3 h 

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Electronic Conduction in Solids 35

3
 3n   h 
2 2
3
EF 2 =   
 π   8m 

2 2
 h 2   3n  3  h 2   3n  3
EF =     =    
 8m   π   2m   8π 

( in electron volt )
3
E F = 3.65 ×10 −19 n 2

Fermi energy at T > 0 K

The Fermi energy at any temperature in general is given by

 π 2  kT  2 
E F = E F0 1 −   
 12  E F0  
 

Where E F0 represents Fermi energy at T=0

Except at very high temperature it can be shown that

E F = E F0

Fermi temperature, (TF)

The temperature at which the average thermal energy of the free electron
in a solid becomes equal to the Fermi energy at T=0 K is called Fermi
temperature. Since thermal energy of an electron is given by kT

When T= TF

E F = kTF
EF
∴ TF =
k

Fermi Velocity, (vF)

The velocity of the electrons whose energy is equal to Fermi energy

is called Fermi velocity

1 2
∴ EF = mv F
2
1
 2E  2
Or v F =  F 
 m 

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Electronic Conduction in Solids 36

The Fermi-Dirac Distribution

The Fermi-Dirac Distribution gives the distribution of electrons among the

permitted energy levels in a given solid.

We know that number of electrons occupying the energy levels between

the energies E and E+dE is given by

N(E)dE = g(E)dE×f(E)

Where g(E)dE is called density of states given by

3
π  8m  2
g(E)dE = E dE
2  h 2 

and f(E) is called Fermi factor given by

1
f (E) = ( E − EF )

e kT
+1
The graph of N(E)dE against E gives the distribution of electrons among the
available energy levels in the solid at the given temperature. The distribution is
known as Fermi-Dirac Distribution. The graph representing the distribution is
shown below.

N(E)

T=0 K T>0K

T >> 0 K

EF E

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Electronic Conduction in Solids 37

It is clear from the graph that N(E) increase with the temperature
becomes maximum for E=EF and then decreases to zero for the energies E>EF,
at the temperature T=O K. At higher temperatures some of the electrons
occupying energy levels below Fermi energy absorb energy and move to higher
energy levels above EF . It is clear from the graph that even at very high
temperature only few electrons occupying energy levels closer to Fermi energy
absorb energy and move to higher energy levels above Fermi energy. Electrons
at lower energy levels are not at all disturbed.

Thermionic Emission

The emission of electrons by the surface of

the metals on heating is called Thermionic
Emission. This phenomenon is employed in Highest
number of electronic devises such as TV Emitted
Energy level electrons
Tubes, X-Ray Tubes, and Electronic Emax
Valves.
We know that free electrons are Thermally
distributed among various closely spaced excited
energy levels available in the solid. At Φ electrons
absolute zero temperature all energy levels bound inside
up to the Fermi energy EF are filled while the solid
energy levels above EF are empty.
Energy

Therefore minimum energy required for the

electrons to come out the solid is equal to
the difference between the maximum EF
energy Emax and EF . This minimum energy is
called work function of the metal and is
denoted by Φ. The work function Φ is
different for different metals.

Therefore work function Φ = ( Emax - EF )

When solid is heated electrons absorb energy and move to higher energy levels
above Fermi energy. If total energy of the electrons exceed Emax , electrons find
themselves out side the surface of the solid. This leads to Thermionic emission.

A plate kept at positive potential with respect to the surface can collect the
electrons emitted by the surface. Electrons collected by the plate gives rise to
current called saturation current when potential is sufficiently high. The saturation
current density J is given by

− φ 
J = AT e 2  kT 

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Electronic Conduction in Solids 38

Where A is Constant, k is Boltzman constant, and T is absolute temperature.

The above equation is called Richardson – Dushman equation.

Success of Quantum free electron theory

The drawbacks of classical free electron theory were removed by

Quantum theory. Some examples are given below.

1.Specific Heat: According to classical theory electrons gives significant

contribution to specific heat of solids. But experimentally it was found that
contribution to specific heat from electrons is negligibly small.
According to quantum theory, When heat energy is supplied to solid, only
those electron occupying energy levels closer to Fermi level absorb energy and
get exited to higher energy levels. Thus only small percentage of electrons is
capable of contributing to specific heat of the solid.
It can be shown that only the fraction (kT/ EF) of electrons contribute to
specific heat of solid.
Thus according to the quantum free electron theory of metals energy of all
the electrons in one-kilo mole of solid is given by
3  kT 
E= N A kT  
2  EF 
3
= NA
( kT ) 2

2 EF
Where NA =Avagadro number, k = Boltzman constant T=Absolute temperature.

Therefore the electronic specific heat is given by

dE 3 T
CV = = N A 2k 2
dT 2 EF
at roomTemp. and for E F = 5 eV
3 300
= × 6.023 ×10 26 × 2 × (1.38 ×10 −23 ) 2 ×
2 5 ×1.6 ×10 −19
= 0.129 kJ / kmole / K
Which is in agreement with the experimental result.

2.Temperature dependence of electrical conductivity:

According to classical theory σ αℓ 1/√T
But experimentally it is found that σ αℓ 1/T
Expression for electrical conductivity can be written as

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Electronic Conduction in Solids 39

ne 2τ F λ
σ = with τ F = F
m vF
Since EF is independent of temperature, vF is also independent of
temperature. Then only λF is dependent on temperature. We know that even at
very high temperature only electrons closer to Fermi energy get exited. Thus only
small percentage of electrons contributes to the electrical conductivity. It can
shown that at very temperatures λF is inversely proportional to the temperature.
Therefore it follows that
σ αℓ 1/T.
Which is agreement with the experimental results.

3.Dependence of electrical conductivity on electron concentration.

According to quantum free electron theory expression for electrical

conductivity is given by

ne 2 λ F
σ =
mv F
Note that σ depends on n , but n depends on EF , also vF depends on EF.
Thus there is no direct relationship between σ and n.

Expression for electron concentration from molecular data.

Let MA= Atomic weight, N=number of free electrons contributed by each atom to
solid, D = is the density of the solid and NA = Avagadro number.
MA kg of solid contains NA atoms
1 kg of solid contains NA / MA atoms

Unit volume of a solid weighs D kgs

Therefore unit volume of solid contains D (NA / MA ) atoms
Therefore number of electrons per unit volume is given by
NN A D
n=
MA

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