CHAPTER 4

FREE ELECTRON
THEORY
Classification of Solids
Electrical Properties
 Some solids conduct current at all temperatures and,
generally, the resistivity of such solids increases with
temperature. These are METALS

 Other solids stop conducting at low temperatures and their

resistivity falls with increasing temperature. These
INSULATORS and SEMICONDUCTORS
 Free Electron Theory
Many solids conduct electricity.

There are electrons that are not bound to atoms but are able to move through the
whole crystal.

Conducting solids fall into two main classes; metals and semiconductors.

 ( RT ) metals ;10 6  108   m and increases by the addition of small

amounts of impurity. The resistivity normally decreases monotonically with

decreasing temperature.

 ( RT ) pure  semiconductor  ( RT ) metal and can be reduced by the addition of

small amounts of impurity.

Semiconductors tend to become insulators at low T.

 Free Electron Theory

The common physical properties of metals;

• Great physical strength
• High density
• Good electrical and thermal conductivity, etc.

This chapter will calculate these common properties of metals

using the assumption that conduction electrons exist and consist
of all valence electrons from all the metals; thus metallic Na, Mg
and Al will be assumed to have 1, 2 and 3 mobile electrons per
atom respectively.
A simple theory of ‘ free electron model’ which works
remarkably well will be described to explain these properties of
metals.
Free Electron Theory
 According to free electron model (FEM), the
valance electrons are responsible for the
conduction of electricity, and for this reason these
electrons are termed conduction electrons.

 Na11 ￫ 1s2 2s2 2p6 3s1 Valance electron (loosely bound)

Core electrons

 This valance electron, which occupies the third atomic shell,

is the electron which is responsible chemical properties of
Na.
 When we bring Na atoms together to form a Na
metal,

Na metal

 Na has a BCC structure and the distance between

nearest neighbours is 3.7 A˚
 The radius of the third shell in Na is 1.9 A˚

 Solid state of Na atoms overlap slightly. From this

observation it follows that a valance electron is no
longer attached to a particular ion, but belongs to
both neighbouring ions at the same time.
 A valance electron really belongs to the whole
crystal, since it can move readily from one ion to
its neighbour, and then the neighbour’s
neighbour, and so on.
 This mobile electron becomes a conduction
electron in a solid.
 The removal of the valance electrons
+ + + leaves a positively charged ion.
+ + +
 Free Electron Theory

 Classicaland Quantum Free Electron

Models of Electrical Conductivity
 Electron Theory of
Metals(Drunde-
Lorentz)
Postulates of CFEM

** In an atom electrons revolue around the nucleus and a metal is

composed Of such atoms
 A valance electron really belongs to the whole
crystal, since it can move readily from one ion to
its neighbour, and then the neighbour’s
neighbour, and so on.
 This mobile electron becomes a conduction
electron in a solid.

+ + +

+ + +
CFEM

 These free electrons move in random

directions and collide with either positive
ions fixed to the lattice or other free
electrons. All the collision are elastic. i.e.
there is no loss of energy.

 The movements of free electrons obey the

classical free electron theory of gases
CFEM

 The electron velocities in a metal obey the

Classical Statistics. i.e Maxwell-Boltzmann
Distribution of velocities .

 When an electric field is applied to the

metal ,the free electrons are accelerated
in the direction opposite to the direction of
applied electric field.
Electrical Conductivity
 In metals free electrons roam freely
through the crystal lattice .

 In the absence of applied external field the

net current due to the movement of
electrons is zero since they are randomly
in all directions .

 In between two collisions the electron

move with uniform velocity.
Electrical Conductivity

During every collision both the direction

+ + +
And the magnitude of velocity change.

+ + +
Electrical Conductivity
 According to the Ohm’s Law
I=V/R
R resistance of the wire

** The current is due to the motion of the

conduction electrons under the influence
of the electric field.
** The field E exerts a force –eE on the
electron
  When an external field applied the electrons
accelerated. Here we consider the frictional force
acting on the electron due to the collision.
 If is the velocity of the electron and  is the time
between two consective collisions The frictional force
can be written as F  m


useNewton ' sLaw
d 
m  eE  m
dt 
underSteadyStateCondition
d
0
dt
This is the steady-state velocity
 e
 E
m
Drift Velocity And Mean Free Path
In the absence of the field the electrons
have random motion ,just as gas
molecules move randomly in a gas
container ,the randomly moving electrons
undergo scattering and the change the
direction. This random motion contributes
zero current and the corresponding
velocity is called the random velocity
Drift Velocity And Mean Free Path
 In the presence of a field, in addition to
random velocity ,there is an additional net
velocity associated with electrons called
drift velocity due to applied electric field .
 Due to drift velocity (vd )electrons with
negative charge move opposite to the field
direction
Drift Velocity And Mean Free Path
 If n is the number of conduction per unit volume
,then the charge per unit volume is (–ne).The
amount of charge crossing a unit area per unit time
is given by the current density J

  e
J  ( ne) d   ne( E)
m
ne 2
 E
m
J  E
ne 2

m
Drift Velocity And Mean Free Path
 Mean Free Path:

 The average distance traveled by an

electron between two successive collision
in the presence of applied field is known
as Mean Free Path
Relaxation Time

 Relaxation Time can be defined as the

time taken for the drift velocity to decay
to 1/e of its initial value.
 Let assume that the applied field is cut off after
the drift velocity of the electron has reached its
steady value.Drift velocity after this instant is
governed by
d d 
m  m
dt 
d d dt

d 
 d (t )   d (0) exp(t /  )

Vd(0)is the stedy state drift velocity

Relaxation Time

Vd(0)

Let t=T
vd
Vd(t)=vd(0)/e

t
Mobility
 Mobility of the electron μ is defined as the steady
state drift velocity<vd> per unit electric field.

d e
 
E m
ne 2 e
  ne.
m m
  ne
1 m m
   2
 ne ne 
Where (  )resistivit y
 The electrical conductivity σ depends on
two factors ,the charge density n and their
mobility . These two quantities depend on
temperature.
 In metals n is constant and μ decreases
slightly with temperature and hence with
increase of temperature ,the conductivity
decreases.
 In semiconductors the exponential
increase of n with temperature is
responsible for increase of conductivity
with temperature
 In insulator n remains constant and above
certain temperature μ increase
exponentially resulting in dielectric
breakdown
Success of classical free electron
theory
** It verifies Ohm’s Law

** It explains the electrical and thermal

conductivities of metals

** It derives Wiedemann-Franz Law

** It explains Optical Properties of metals.
Drawbacks of Classical Free Electron
Theory
 The phenomena such as photoelectric
Effect, Compton Effect and the Black Body
Radiation couldn’t be explained by free
electron theory.
 According to CFET the value of specific
heat of metals is given by 4.5Ru.Where as
the experimental value nearly equal to
3Ru.
 Electrical conductivity of Semiconductor or
Insulators Couldn’t be explained using this
model
Quantum Theory of Free Electrons
 This theory is proposed by Sommerfeld in
1928,with help of quantum of statistics (Fermi-
Dirac) explained QFET.

 The difficulty of classical FET arises M-B it permits

all the free electrons to gain energy.

 But in Quantum Statistics turn out that only about

one percent of the free electron to gain a energy
 Free electron moving in uniform potential
within in a metal .potential field inside the
metal not uniform.
 But instead ,the field experienced by a
moving free electrons varies periodically
with the periodicity of the crystal.
 To determine the restriction imposed by
quantum mechanics the energies that free
electron can have inside the metal
 It is assumed that valence electrons are traped in
constant potential well
∞ ∞

V(x)
 2k 2 n2h2
E ( n)   2
2m 8mL

X=0 X=L
Quantum Theory of Free Electrons
 When an external
electric field E is
applied the force dp
exerted on the  eE 
dt
electron is –eE. h h 2
p    k
 Since force is also rate  2 
of change of d dk
 eE  (k )   ( )
momentum dt dt
eE
dk   dt

Quantum Theory of Free Electrons
 This Means that origin of the k space
moves through a distance dk in time dt on
application of external field. Because of
collision with imperfection, displacement
of k space becomes steady Δk and dt is
then the average collision time
Quantum Theory of Free Electrons
eE
k  

p  m  k , incrementa lVelocity 
  eE
  k  ( )( )
m m 
eE
  
m
No.of e-s per unit volume is n,then J is
J  n(e)
ne 2 E
J
m
J  E
ne 2

m

This treatment tell us that current carried out by very few electrons
Free Electron Models
 Classical Model:  Quantum Model:
 Metal is an array of positive  Electrons are in a potential
ions with electrons that are well with infinite barriers:
free to roam through the They do not leave metal,
ionic array but free to roam inside
 Electrons are treated as an ideal  Electron energy levels are
neutral gas, and their total discrete (quantized) and
energy depends on the well defined, so average
temperature and applied field energy of electron is not
 In the absence of an electrical equal to (3/2)kBT
field, electrons move with  Electrons occupy energy
randomly distributed thermal levels according to Pauli’s
velocities exclusion principle
 When an electric field is  Electrons acquire additional
applied, electrons acquire a net energy when electric field is
drift velocity in the direction applied
opposite to the field
Fermi-Dirac distribution
. The Fermi function f(E) specifies how many of the existing states
at the energy E will be filled with electrons. The function f(E)
specifies, under equilibrium conditions, the probability that an
available state at an energy E will be occupied by an electron. It is
a probability distribution function.

EF = Fermi energy or Fermi level

k = Boltzmann constant = 1.38 1023 J/K
= 8.6  105 eV/K
T = absolute temperature in K
Fermi-Dirac distribution function
 At a temperature T the probability of occupation
of an electron state of energy E is given by the
Fermi distribution function

1
f FD  ( E  EF ) / k BT
1 e
 Fermi distribution function determines the
probability of finding an electron at the energy E.
 Fermi-Dirac distribution: Consider T  0 K

1
For E > EF : f ( E  EF )   0
1  exp ()

1
For E < EF : f ( E  EF )   1
1  exp ()

EF

0 1 f(E)
Temperature dependence of Fermi-
Dirac distribution
 Fermi Function at T=0
and at a finite temperature
1  fFD=? At 0°K
f FD  ( E  EF ) / k B T
1 e
fFD(E,T)
i. E<EF
1
f FD  ( E  EF ) / k B T
1
1 e

0.5 ii. E>EF 1

f FD  ( E  EF ) / k B T
0
1 e

E
E<EF EF E>EF
Fermi-Dirac distribution function at
various temperatures,
Fermi-Dirac distribution function
 At any temperature other than 0k,if E=Ef
F(E)=1/2
Fermi level is that state at which the
probability of electron occupation is
½ at any temperature above 0k and
also it is the highest level of the filled
energy state at 0k
Fermi-Dirac distribution function
 Fermi energy is the energy of the state at
which the probability of electron occupation
is ½ at any temperature above 0k
 Electrons with Fermi energy move with Fermi
velocity and the same is related to the Fermi
temperature by the relation

1
m F  kT
2

2
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