PREPARED BY

Mr. A.CHARIS ISRAEL. M.Sc., B.Ed., (Ph.D.)

Asst. Professor of PHYSICS
Mobile No: +91-9866934653

SECUNDERABAD
 UNIT – III(PART-A) ELECTRON THEORY OF METALS 2008-2009

UNIT –III(A)

ELECTRON THEORY OF METALS

Basic Definitions:
(i) Random Velocity (Vran)
(ii) Drift Velocity (Vd)
(iii) Mean free path (λ)
(iv) Relaxation time (τ)
(v) Mobility (µ)
(vi) Current density (j)

Classical free electron theory:

Postulates, Electrical conductivity – Ohm’s law (jαE), Electrical conductivity ‘σ’ in terms of
mobility ‘µ', temperature dependence of Electrical Conductivity ‘σ’, Merits and Demerits,
problems.

Quantum free electron theory:

Postulates, Electrical conductivity

Fermi-Dirac distribution function:

Properties, Fermi energy, Graphical representation of Fermi-Dirac distribution function, problems

Density of Energy states and Carrier Concentration

Electron Scattering and resistance

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 UNIT – III(PART-A) ELECTRON THEORY OF METALS 2008-2009

BASIC DEFINITIONS RELATING TO THE MOTION OF FREE ELECTRONS IN A METAL:

i) Random Velocity (Vran):

In the absence of external Electric field E, the free electrons in a conductor (metal) move
randomly in all possible directions undergoing scattering at the ionic sites. The velocity of these
randomly moving electrons in the absence of applied electric field is called Random Velocity
‘Vran’.
The current due to the random motions of these free electrons is Zero.
ii) Drift Velocity (Vd):
In the presence of external Electric field E, the average velocity acquired by free
electrons between two successive collisions and has acquired a steady state in a direction opposite
to the direction of applied field is called Drift Velocity ‘Vd’.
iii) Mean free path (λ λ ):
In the presence of external Electric field E, the average distance travelled by a free
electron between two successive collisions is called Mean free path ‘λ’.
iv) Relaxation time (ττ):
In the presence of external Electric field E, the time taken by an electron to reach its
equilibrium state from its disturbed state is called Relaxation time ‘τ’.
(Or)
In the absence of external electric field, after an electron reaches the stead state velocity,
the time taken for the drift velocity to decay to 1/e times of its initial value is called the relaxation
time ‘τ’.
v) Mobility (µ µ):
In the presence of external Electric field, the magnitude of drift velocity |Vd | per unit
Electric field E is defined as Mobility of electrons ‘µ’.
vi) Current Density (j):
It is defined as the ratio of the current ‘i’ to the cross-sectional area ‘A’ of the given
conductor.
(Or)
It is the amount of charge ‘-ne’ crossing a unit area ‘A’ per unit time‘t’.

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 UNIT – III(PART-A) ELECTRON THEORY OF METALS 2008-2009

CLASSICAL FREE ELECTRON THEORY OR DRUDE-LORENTZ THEORY OF METALS:

This theory is proposed by Lorentz and Drude in 1900. The conducting properties of a solid are
not a function of the total number of electrons in the solid. This is because; only the outermost electrons
of the atoms take part in conduction.
Postulates of Classical Free Electron theory:
1) The outermost electrons of an atom are not bound to that atom, but are free to move through the
whole solid like the molecules of a perfect gas in a container. These electrons are also called as
the free electron gas or free electron cloud.
2) Collisions made by these electrons either with positive ions or with other electrons are of elastic
in nature. That is, no loss of energy during collisions.
3) The movements of these electrons obey the laws of Classical Kinetic Theory of Gases.
4) The velocities of these electrons obey the Classical Maxwell-Boltzmann Distribution of
velocities.
5) These electrons move in Uniform potential field due to the positive ions fixed in the lattice.
6) In presence of external electric field, these electrons move in a direction opposite to the direction
of the field.
Merits of Classical free electron theory:
1) It successfully verifies Ohm’s Law.
2) It explains the electrical and thermal conductivities of metals.
3) It derives Wiedemann-Franz Law (the ratio of Thermal conductivity to the Electrical conductivity
is a constant i.e. K/σ = Constant).
Expression for electrical conductivity in terms of number of free electrons ‘n’ and their mobility ‘µ’
(Verification of Ohm’s Law):
In the absence of applied electric field, the net current due to the movement of electrons is Zero
since they move randomly in all directions. The current in a conductor is due to the motion of free
electrons under the influence of the external electric field ‘E’.
Now, this field ‘E’ exerts a force ‘F’ on the electrons given by F = − eE .  (1)1
mv
The frictional force arising due to the collisions is given by F frictional = −  (2)
τ
Using Newton’s law, the motion of these free electrons is governed by
dv mv
m = −eE −  (3)
dt τ

Under steady-state, the acceleration is zero i.e. dv = 0

dt
−eτ
Hence eq. (3) can be written as, v= E  (4)
m
In steady-state, the velocity acquired by free electrons in presence of electric field is a Drift velocity ' vd ' .

Hence eq.(4) can be written as, −eτ  (5)

vd = E
m

1
The negative sign indicates that the direction of force is opposite to the direction of the applied electric field.

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 UNIT – III(PART-A) ELECTRON THEORY OF METALS 2008-2009

If ' n ' is the number of conduction electrons per unit volume, then the charge per unit volume is
given by '− ne ' . Now current density ' J ' in terms of charge density and drift velocity is given
by J = −nevd
 −eτ 
J = −ne  E
 m 
 ne 2τ 
J = E
 m 
The above equation is of the form, J = σ E (Ohm’s Law)  (6)
where 'σ ' is called electrical conductivity.
ne 2τ
Hence, σ=  (7)
m
Equation (7) shows the electrical conductivity in terms of number of free electrons ' n ' which
explains that with the increase in electron concentration ' n ' the conductivity 'σ ' increases.
v
We know that mobility ' µ ' is given by µ = d i.e. µ = eτ
E m

Rearranging Eq.(7) as  eτ 
σ = ne  
m

We have σ = neµ  (8)2

Eq.(8) shows the electrical conductivity in terms of mobility.

Demerits of Classical free electron theory3:

In spite of the above successful explanation of the electrical conductivity, Classical theory has the
following drawbacks.
1) It failed to explain the phenomena such as Photoelectric effect, Compton effect and the Black
body radiation.
2) Electrical conductivity of semiconductors couldn’t be explained using this model.
3) Ferromagnetism couldn’t be explained by this theory.
4) According to this theory, K/σT=constant (Wiedemann-Franz law) but it is not a constant at low
temperatures.

2
It is clear that the electrical conductivity depends on two factors, the charge density ‘ne’ and the mobility‘µ’. These two quantities depends on
temperature. In metals, ‘n’ is constant and ‘µ’ decreases slightly with temperature and hence with increase in temperature, the conductivity
decreases. In semiconductors, the exponential increase in ‘n’ with temperature is responsible for increase of conductivity with temperature. In
insulators ‘n’ remains constant and above certain temperature ‘µ’ increases exponentially resulting in dielectric break down. Resistivity of the
material of the conductor is given by, 1 1 m
ρ = = =
σ neµ n e 2τ
3
Acccording to this model, the specific heat of metals is given by 4.5R whereas the experimental value is nearly equal to 3R. Also according to
this theory the value of electronic specific heat is equal to 3/2R while the actual value is about 0.01R only, where R is Universal gas constant.

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 UNIT – III(PART-A) ELECTRON THEORY OF METALS 2008-2009

Solved problems:

1) Calculate the mobility and the relaxation time of the electron in copper obeying classical laws.
Given data
Density of copper = 8.92 x 103 kg / m3
Resistivity of copper = 1.73 x 10−8 ohm − m
Atomic weight = 63.5
Avogadro’s number = 6.02 x 1026 per k − mol

Solution: We know that σ = neµ ,

σ 1
µ= µ=
ne ρ ne
3density x Avogadro number
i) Number of copper atoms/m = n =
Atomic weight
8.92 x 103 x 6.02 x 1026
= = 8.456 x 10 28
63.5
Hence 1 1
µ= =
ρ ne 1.73 x 10−8 x 8.456 x 1028 x 1.6 x 10−19
µ = 0.427 x 10−2 mV −1 s −1
ii) Relaxation time,τ = m 9.1 x 10−31
= = 2.43 x 10-14 s
2
ne ρ 8.456 x 1028 x 1.6 x 10−19 x 1.73 x 10-8

QUANTUM FREE ELECTRON THEORY OR SOMMERFELD’S THEORY OF METALS:

Sommerfeld in 1928 investigated the behavior of a free electron gas taking into account the
Quantum theory and the Pauli’s exclusion principle.

Postulates of Quantum free electron theory:

1) Electrons are considered to be subjected to a constant potential ‘V’.

2) The collisions of these electrons with the other electrons and with the positive ions are negligible
i.e. they are free from frictional forces.
3) Electrons can only take discrete energy values but not continuous and follow Pauli’s exclusion
principle.
4) Electrons in a metal follow the Fermi-Dirac statistics and hence they are treated as Fermi gas.

Expression for the electrical conductivity by applying Quantum laws:

When an external electric field ‘E’ is applied, the force ‘F’ exerted on the electron is given by
F = − eE  (1)
According to Newton, force is also rate of change of momentum given by
dp
F=  (2)
dt
Hence the equation governing the motion of an electron is given by
dp
−eE =  (3)
dt

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 UNIT – III(PART-A) ELECTRON THEORY OF METALS 2008-2009

But according to de Broglie, every material particle is associated with a wave whose wave length is given
h h
by λ= or p =
p λ
h 2π
p= x
2π λ
p = hK  (4)
Where ' K ' is a wave vector of magnitude 2π .
λ
d hK dK −eE
Substituting eq(4) in eq(3) we have −eE = =h ⇒ dK = dt  (5)
dt dt h
The above equation represents that the origin of a K space moves through a distance dK on time dt on
application of external field.
In steady state dK = ∆K and dt = τ the average collision time.

Hence −eE  (6)

∆K = τ
h

We know that p = mv = hK , then incremental velocity ∆ v is given by

h
∆v = ∆K
m

 h   eEτ 
= −  
 m  h 

eEτ  (7)
∆v = −
m

If represents ' n ' the electron density then current density J in terms of electron density is given by

J = n ( −e ) ∆v
ne2 Eτ
=
m
 ne2τ 
= E
 m 
J =σE ( Ohm ' s Law)
where 'σ ' is called the electrical conductivity given by

ne 2τ  (8)
σ=
m

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 UNIT – III(PART-A) ELECTRON THEORY OF METALS 2008-2009

FERMI-DIRAC DISTRIBUTION FUNCTION F(E):

Fermi-Dirac Distribution function gives the distribution of electrons in real material among the
different possible energy states. We know that an assembly of electrons may be considered as Fermi gas
which obey Fermi-Dirac statistics.
The probability F(E) of an electron occupying an energy level E is given by
1
F (E) =
 E − EF   (1)
1 + exp  
 kT 
Where EF is called Fermi Energy, which is a constant for a given system.

Case (i): At absolute temperature i.e. T = 0K and for energies below the Fermi energy level i.e. E < EF,
the above equation(1) results as shown below
1 1  (2)
F ( E) = = =1
1 + exp ( −∞ ) 1 + 0
Equation(2) says that, the probability of finding an electron in the energy level below the Fermi level is
maximum.

Case(ii): At absolute temperature i.e. T = 0K and for energies above the Fermi energy level i.e. E > EF,
equation(1) results as below
1 1  (3)
F (E ) = = =0
1 + exp ( ∞ ) ∞
Equation(3) says that the probability of finding an electron in the energy level above the Fermi level is
Zero. From this we conclude that “the Fermi energy level is the maximum possible energy level that an
electron can occupy at absolute temperature”. In other words, at absolute temperature, all energy levels
below the Fermi energy level are completely filled whereas all energy levels above the Fermi level are
completely vacant.
General case: At temperatures other than absolute zero i.e. T > 0K, and in the energy level equal to
Fermi level i.e. E = EF, equation(1) results as below

1 1  (4)
F ( EF ) = = = 0.5
1 + exp ( 0 ) 2

From equation(3) Fermi energy level may be defined as “ it is the energy level for which the probability
of finding an electron is half at temperatures greater than absolute zero”.

Graphical representation of Fermi distribution function:

F(E) F(E)

1 T = 0K T = 0K

0.5 T > 0K

0 EF E 0 EF E

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 UNIT – III(PART-A) ELECTRON THEORY OF METALS 2008-2009

Solved Problems:

1) Find the temperature for which there exists 1% probability of an electron occupying an energy
level at 0.5eV above the Fermi level.

Soln: We know that the probability function is given by

1
F ( E) =
 E − EF 
1 + exp  
 kT 
Given F(E) = 1%
E = (EF + 0.5) eV = (EF + 0.5) x 1.6 x 10-19 J.
k = 1.38 x 10-23

Substituting the above data in the equation we have,

1 1
=
100  ( E + 0.5 − EF ) x 1.6 x 10−19 
1 + exp  F 
 1.38 x 10−23T 
 ( E + 0.5 − EF ) x 1.6 x 10−19 
1 + exp  F  = 100
 1.38 x 10 −23 T 
0.5 x 1.6 x 10−19
= ln 99
1.38 x 10−23 T
0.5797 x 104
T= = 1261.6K
ln 99

2) At what temperature we can expect a 10% probability that electrons in silver have an energy
which is 1% above the Fermi energy? The Fermi energy of Silver is 5.5eV.

Soln: We know that the probability function is given by

1
F ( E) =
 E − EF 
1 + exp  
 kT 
Given F(E) = 10% = 0.1
EF = 5.5eV
E = (EF+1%EF) eV = (5.5+0.055) eV = 5.555 eV
K = 1.38x10-23

Substituting the above data in the equation we have,

10 1
=
100  ( 5.555 − 5.5) x 1.6 x 10−19 
1 + exp  
 1.38 x 10−23T 
 0.055 x 1.6 x 10−19 
1 + exp  −23  = 10
 1.38 x 10 T 
637.68 637.68
= ln 9 ⇒ T= ⇒ T = 290.2 K
T ln 9

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 UNIT – III(PART-A) ELECTRON THEORY OF METALS 2008-2009

DENSITY OF ENERGY STATES AND CARRIER CONCENTRATION:

The number of electrons per unit volume in a given range (between E and E + dE) of energy or
Carrier concentration is given by summing the product of the density of energy states Z(E) and the
probability of occupancy F(E), i.e.
nC = ∫ Z ( E ) F ( E ) dE
energy band  (1)
The number of energy states having energy values between E and E + dE is given by
π
Z ( E ) dE = n2 dn  (2)
2
n2 h2
We know that En =  (3)
8ma 2
Rearranging the above equation, we have
8ma 2
n2 = En  (4)
h2
1/ 2
 8ma 2 
n= 2  E 1/ 2  (5)
 h 
Differentiating the equation(4),
8ma 2
2 n dn = dE  (6)
h2
1 8ma 2
dn = dE  (7)
2n h 2
Substituting the value of ‘n’ from eq(5) in the above equation, we have
1/ 2
1  8ma 2  h 2  1
dn =  2   dE
2  h  8ma 2  E1/ 2
1/ 2
1   8ma 2  h 2 
2
1
=  2   dE
2   h  8ma 2  E 1/ 2
 
1/ 2
1  8ma 2  1
dn =  2  dE
2 h  E 1/ 2
 (8)
Now substituting the values of ‘n’ & ‘dn’ from equations (5) & (8) in eqn(2), we have
π  8ma 2   1  8ma 2  1 
1/ 2

Z ( E ) dE =  2 E    2   dE
  2  h  E 
1/ 2
2 h
3/ 2
π  8ma 2 
=  2  E 1/ 2 dE
4 h 
3/ 2
π  8m 
3 1/ 2
Z ( E ) dE =
 2  a E dE  (9)
4 h 
But according to Pauli’s Exclusion principle two electrons of opposite spin can occupy each state
and hence the number of energy states available for the electron occupancy is given by
3/ 2
π  8m 
Z ( E ) dE = 2 x   a 3 E1/ 2 dE
4  h2 

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 UNIT – III(PART-A) ELECTRON THEORY OF METALS 2008-2009

4π 3/2
 (10)
Z ( E ) dE = ( 2m ) a3 E1/ 2dE
h3
Eqn(10) represents the Density of energy states in a given volume a3. Therefore the density of energy
states per unit volume is given by
4π 3/2
i.e., Density of states Z ( E ) dE = 3 ( 2m ) E1/ 2 dE  (11)
h
We know that the probability of occupancy of an electron in the given energy state is given by
1  (12)
F (E) =
 E − EF 
1 + exp  
 kT 
Substituting the values of Z(E) & F(E) from equations (11) & (12) in Eqn (1), we have
4π 1
∫
3/2
3 (
nC = 2 m ) E 1/ 2 dE
h  E − EF 
Energy band 1 + exp  
 kT 
4π 1
∫
3/2
3 (
nC = 2m ) E 1/ 2 dE  (13)
h  E − EF 
Energy band 1 + exp  
 kT 

Equation(13) is the expression for Density of charge carriers or carrier concentration in a given metal
at any temperature.

ELECTRON SCATTERING AND RESISTANCE OR SOURCES OF ELECTRICAL RESISTANCE:

The main factors affecting the electrical resistance in solids are temperature and defects or
impurities present in the solid.
According to Matthiessen’s rule, the total resistivity of the material is given by
ρTotal = ρ pure + ρimpurity
where ρ pure is temperature dependent resistivity which is due to the thermal vibrations of the
lattice while ρimpurity is due to the scattering of electrons caused by the impure atoms present in the
material.

Temperature dependence of resistivity, ρ pure :

We know that as the temperature ' T ' of the material increases

the amplitude ' A ' of the lattice vibrations increases, according to
Ni
A2 α kT . Hence these lattice vibrations cause the scattering effect on the ρ
electrons. This scattering is the cause of electrical resistance in metals. Cu
Also, the mean free path ' λ ' of the electrons decreases with the increase
in amplitude ' A ' of the lattice vibrations according to the relation,
1 . Hence, at room temperature 1 but at low Temp
λα 2
ραTα
A λ
temperatures ρ α T where n 3 to 5 which implies that as T → 0, ρ → 0 where the material behaves
n

as a superconductor.

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 UNIT – III(PART-A) ELECTRON THEORY OF METALS 2008-2009

Defects dependence of resistivity, ρimpurity :

The scattering effect on the electrons can also be due to the As

Ge
presence of impurity atoms in dilute alloys. For small
concentrations, the resistivity of an alloy consisting of a dilute
Sn
solution of metal B in metal A is given by ρ Ga

ρ α x (1 − x )
where x is the concentration of metal A atoms and Zn

(1 − x ) is the concentration of B atoms.

The adjacent figure shows the variation of resistivity of Atomic per cent
binary alloys of copper as a function of concentrations of the second
component.

QUESTIONS:

1) Explain the terms

a) Mean free path
b) Relaxation time
c) Drift velocity and
d) Mobility of an electron in a metal.
2) Assuming the electron-lattice interaction is responsible for scattering of conduction electrons in a
metal, obtain an expression for conductivity in terms of relaxation time and explain any three
drawbacks of classical theory of free electrons.
3) What are the salient features of the ‘free electron gas’ model? Obtain the Ohm’s law based on it.
4) Derive the expression for the electrical conductivity on the basis of classical free electron theory.
Explain the temperature dependence of electrical conductivity.
5) Explain Lorentz-Drude theory of metals.
6) Explain briefly the Sommerfeld’s theory of metals.
7) Distinguish between Classical and Quantum free electron theories.
8) Explain Fermi-Dirac distribution function for electrons in a metal. Discuss its variation with the
temperature. Explain Fermi Energy.
9) Explain the main sources of electrical resistance in metals.

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