Unit 2 Conduction in Metals- Free electron model (12 hrs)

Introduction – conduction electrons-free electron gas-electrical conductivity-electrical resistivity

versus temperature-heat capacity of conduction electrons -Fermi surface –electrical conductivity-
effects of the Fermi surface-thermal conductivity in metals-Hall effect and magneto resistance -A.C
conductivity and optical properties-failure of free electron model. -The Kronig -Penney model-
conductors, semiconductors and insulators.

Conduction Electrons
The outermost electrons in an atom are called valance electrons. In a solid a valance
electron is no longer attached to a particular atom. It belongs to both neighboring ions at the same
time. Since a valance electron can move readily from one ion to its neighbor it really belongs to the
entire crystal. This mobile electron which is called a valance electron in a free atom becomes a
conduction electron in a solid.
These are called conduction electrons since they can carry electric current under the action
of an electric field. The number of conduction electrons in a metal is given by the expression
Z N
N=
M
Where ZV is the atomic valance,  the density, NA the Avogadro number and M is the atomic weight.
Free Electron Gas (Drude’s Theory)
According to Drude’s theory the free electrons in a metal have random motion just like that
of the molecules of a gas in a container.
The metal consists of positive ion cores with the valance electrons moving freely among
these cores. The electrons are bound to move within the metal due to the electrostatic attraction
between the positive ion cores and the electrons. The potential field of these ion cores is assumed
to be constant throughout the metal and the mutual repulsion among the electrons is neglected.
The behavior of free electrons moving inside the metal is considered to be similar to that of atoms or
molecules in perfect gas. These free electrons are therefore referred to as free electron gas.
Since free electrons are called electron gas, the classical kinetic theory of gases can be
applied to electrons. Drude also made the following assumptions
i) The collision among electrons and electron – ion interaction are ignored.
ii) The electrons move along a straight line when there is no external field.
iii) When an electric field is applied, the electrons move opposite to the direction of the
field
iv) In such a motion the electrons collide with the positive ion core
v) The average electron velocity just after such collision is zero
vi) The electrons obey Maxwell – Boltzmann distribution law
Factors Affecting Resistance
The resistance of a resistor is
(i) Directly proportional to the length of the wire
(ii) Inversely proportional to the area of cross section
(iii) Depends on the material of the wire and
(iv) Depends on temperature.
Specific Resistance (Resistivity)
 At constant temperature, the resistance of a wire is directly proportional to its length l and
inversely proportional to its area of cross section A.
ie, R  l /A
or R =  l /A, where  is called resistivity of the material of the
wire
When l = 1 and A = 1, R=
 Resistivity of the material of a conductor may be defined as the resistance of the wire
having unit length and unit area of cross section.
Conductivity (Specific Conductance)
The reciprocal of resistivity is called conductivity.
ie,  = 1/
Current Density
The electric current passing through unit area of cross section of a conductor is called
current density.
ie, current density j = I/A
= nvde
Relation Between E and j
By Ohm’s law
V = RI ……… (1)
where V is the p.d applied, I is the current and R is the resistance of the conductor.
But R =  L /A, where  is the resistivity of the material of the wire, L the length and A the area of
cross section of the wire.
If E is the magnitude of uniform electric field in the conductor, then
V = EL
Hence eqn (1) becomes
E L = I L /A
But I/A = j, the current density
 E=jρ
 j = E/ ρ
But 1/ρ = σ, called the conductivity
 j=σE
Drift Velocity and Relaxation Time
When an electric field is applied to a conductor the free electrons get accelerated in a
direction opposite to the electric field. Due to this acceleration the velocity of the electron
increases. But it happens so only for a short time. This is because after a momentary acceleration a
moving electron collides with one of the fixed particles in the conductor. So it is slowed down or
brought to rest. After this it is again accelerated. Thus the electron moves with a certain average
velocity called drift velocity.
The average time between two successive collisions is called the average relaxation time.
Expression for Drift Velocity
Let an electric field E be applied to a conductor. Then the acceleration produced on an
electron is given by a = -eE/m, where m is the mass and –e the charge of the electron.
Let τ be the average time between successive collisions. Then
[Vi] ave = – (eE/m) τ
This average velocity of electron is called drift velocity.
ie, vd = – (eE/m) τ
Relation between Current and Drift Velocity
Consider a conductor having n free electrons per unit volume. Let e be the magnitude of
charge and vd the drift velocity of electron. Then the number of electrons passing through any
section of area A per second is nAvd.
 The charge passing through the conductor per second = nAvde
ie, The current through the conductor I = nAvde
NOTE
1. Drift velocity of electron is of the order of 10 – 5 m/s
2. The relaxation time is of the order of 10 – 14 second.
Nature of Electrical Resistance
Let I be the current passing though an area of cross section A.
 Current density j=I/A
= nvde
where n is the number of free electrons per unit volume in the conductor vd the drift velocity of
electron and e its charge.
But vd = (eE/m) τ
(numerically) where τ is the average relaxation time.
 j = n (eE/m) τ e
= ne2 E τ /m
But j = σ E , where σ is the conductivity.
 σ = ne2 τ /m
 Resistivity  = m/ne2 τ
Origin of Collision Time
When an electron moves in a free lattice, it collides with ions, which has the effect of
slowing down the electrons momentum. Between two successive collisions the electron travels a
distance of more than 20 times the interatomic distance. This much larger than one would expect.
This paradox can be explained using quantum concept.
According to quantum mechanics an electron has a wave character. The wavelength of the
electron in the lattice is given by  = . When a wave passes through a periodic lattice, it continues
propagating indefinitely without scattering. The atoms in the lattice absorb energy from the wave
and radiate it back. So the net result is the wave continues without modification in both direction
and intensity. But the velocity of propagation is modified. Hence the collision time gets modified.
Electrical resistivity versus temperature
The electrical resistivity of a conductor is given by  = m/ne2 τ. Here 1/ represents the
probability of the electron suffering a scattering of electron per unit time. The electron undergoes a
collision only because the lattice is not perfectly regular. The deviation from a perfect lattice are of
two types
i) Lattice vibrations of the ions due to thermal excitation
ii) Static imperfections such as foreign impurities
So the resistivity can be written as
 = I + ph = 
+ 

This splitting is known as Matthiessan rule. The term I is due to scattering by impurities. It
is independent of temperature. This is called residual resistivity. The term ph is due to scattering by
phonons. It is temperature dependent. It is called ideal resistivity.
At very low temperature the scattering by phonon is negligible. Hence
 = I, a constant
As temperature increases scattering by phonons becomes more effective. So ph and hence 
increases. In the high temperature region scattering by phonons is predominant. So   ph.
Expression for ideal resistivity
If Nion is the concentration of metallic ions and ion is the scattering cross section for ions,
then the mean free path for collision of phonon is
lph = 

If the distance of deviation from equilibrium is x, then ion = x2

Where x2 is the average of x2. Its value can be estimated from the concept of potential energy of
harmonic oscillator. The average potential energy of a harmonic oscillator is equal to half its total
energy.

 x2 = / 

Using these substitutions in the expression ph = 

, we get


ph  ( 
)  
Where M is the mass of the ion.

When temperature T is very large, ph  ( 
) 
Kondo Effect
The deviations from Matthiessan rule is called Kondo effect. For an example when some
impurities of Fe are dissolved in Cu, the resistivity has a minimum value at low temperature. This
anomalous behavior is due to the additional scattering of electrons by the magnetic moments on the
impurity centers. Complications in the band structure is also responsible for deviation from
Matthiessan rule.
Heat Capacity of Conduction Electrons
A free particle in equilibrium at a temperature T has an average energy of kT. Hence
average energy per mole is
 E = NA kT = RT
Where NA is the Avogadro number and R = kNA
Therefore electrons heat capacity is Ce = R  3 cal/mol oK
The total heat capacity in metals including phonons at high temperature is
C = Ce + Cph = R + R = 4.5 R  9 cal/mol oK

But experiments show that at high temperature C  3R, similar to that of insulators. In order to
explain this quantum concept is adopted.
According to quantum mechanics, the energy of electron in a metal is quantized. The
electrons in the metal occupy the energy levels obeying the Pauli Exclusion Principle. The energy of
the4 highest occupied energy level is called the Fermi energy or Fermi level EF.
Even at the lowest possible temperature the electron system has a considerable amount of
energy by virtue of the exclusion principle. The distribution of electrons among the levels is usually
described by the distribution function f(E). This function at T = 0 oK has the form
f(E) = 1 if E  EF
and f(E) = 0 if EF  E
When the system is heated, thermal energy excites the electrons. But this energy is not
shared equally by all the electrons. The electrons close to the Fermi level are excited. Thus only a
small fraction of electrons are thermally excited. This explains the low electronic specific heat.
Fermi Temperature
Fermi temperature is defined as TF = EF/k, where EF is the Fermi energy and k is the
Boltzmann constant.
Fermi Surface
The electrons in a metal are in random motion. Hence these electrons are considered as
free particles. The energy of such an electron is
E = mv2
Where m is the mass and v the velocity of electron
Consider a velocity space whose axes are vx, vy and vz. Consider the conduction electrons in
this space. These electrons have many different velocities. Hence the points representing them in
the velocity space are distributed uniformly. Now consider a sphere outside which the points are
empty. The radius of this sphere is called Fermi speed vF. It is related to the Fermi energy as EF =
mvF2. All the points inside this sphere are completely full. This sphere is known as Fermi sphere. Its
surface is known as Fermi surface.
Note

The value of Fermi energy is given by EF = (32N)2/3

Electrical Conductivity - Effects of the Fermi Surface
In the absence of an external electric field the Fermi sphere is centered at the origin. The
various electrons in this sphere are in random motion. But the total current of the system is zero
because for every electron at velocity v there exists another electron with velocity – v. Thus the
total current vanishes due to pair wise cancellation of the electron current.
 When an external field is applied, each electron acquire a drift velocity. So the Fermi sphere
is displaced from the centre. The displacement is very small. But a some electrons now remain
uncompensated. This produces a small current.
The fraction of electrons which remain uncompensated is nearly vd/vF, where vd is the drift
velocity and vF is the Fermi velocity. So the concentration of uncompensated electrons is N(vd/vF).
Since each electron has a velocity approximately – vF, the current density is given by
J = e N(vd/vF) (vF) = Nevd
 
But vd = – , where F is the collision time of an electron at the Fermi sphere.
  
 J = Ne =

 Electrical conductivity =
Thermal Conductivity in Metals
The amount of thermal energy crossing per unit area per unit time is proportional to the
temperature gradient.

ie, Q=K , where K is the thermal conductivity.

In a metal heat is transported by both electrons and phonons. Hence
K = Ke + Kph
But in most metals Ke is very large due to the high concentration of electrons.
But K = Cv vl, where Cv is the specific heat per unit volume, v the speed and l is the mean free path
of the particles. Since only electrons at the Fermi levels are effective, then K = Cv vFlF

But Cv =

K= vFlF

But EF = mvF2 and lF/vF = F

 
K=
Lorentz Number
The ratio K/T, where K is the thermal conductivity,  the electrical conductivity and T the
temperature is called Lorentz Number L.
On substituting the expressions of K and , it can be shown that

L= ( )
Cyclotron Resonance
When a magnetic field is applied across a metallic slab, the free electrons in the metal begins
to move in a circular fashion in a plane normal to the field. The frequency of this motion is called
cyclotron frequency. It is given by e =
If an electromagnetic signal is passed through the slab in a direction perpendicular to the
magnetic field, the electric field of the signal acts on the electrons. Hence some of the energy of the
signal is absorbed. The rate of absorption is greatest when the frequency of the signal is exactly
equal to the frequency of the cyclotron. This is the condition for cyclotron resonance.
Hall Effect
When a magnetic field is applied at right angles to the direction of current flow in a
conductor, an electric field is developed which is mutually perpendicular to the current and the
magnetic field. This is called Hall effect.

Let a current I be flowing through a flat metal strip in the positive x – direction. Let a
uniform magnetic field B be applied along the z-direction as shown in figure. Under this magnetic
field the charge carriers in the strip experiences the Lorentz force.
Due to this force the free electrons move towards the face efgh. So the side abcd gets
positive charge and efgh gets negative charge. This produces an electric field which is perpendicular
to both the direction of current and the direction of magnetic filed. The potential difference thus
produced is called Hall voltage
Magneto Resistance
The resistance of some of the metal and the semiconductor material varies in
the presence of the magnetic field, this effect is called the magnetoresistance. The element which
has these effects is known as the magnetoresistor.
The resistance of the magneto resistor is directly proportional to the magnetic field, i.e.,
their resistance raises with the increase of the magnetic field.
Types of Magneto resistor

The magnetoresistor is classified into three categories.

1) Giant Magnetoresistance (GMR) – In this effect, the resistance of the magneto resistor
becomes small when their ferromagnetic layers are parallel to each other.

2) Extraordinary Magnetoresistance – In this effect, the resistance of the metal is high in the
absence of magnetic field and low in the presence of a field.

3) Tunnel Magneto Resistor – The current will flow from the one ferromagnetic electrode
through the insulator.

A.C conductivity
Consider an EM wave propagating in the x-direction and polarised along the y-direction
ε =ε e( )

The equation of motion of a conduction electron in the presence of this ac field is

eτ 1
v =− ∗
ε
m 1 − iωτ
and the current density is
J = −Nev
Hence the ac conductivity is given by
σ
σ=
1 − iωτ
where o is the static conductivity
The conductivity is now a complex quantity, given by
 = ’ + i”
Where
σ
σ′ =
1−ω τ
𝜎 𝜔𝜏
𝜎" =
1−𝜔 𝜏
Optical Properties
The complex conductivity of conduction electron is
σ
σ=
1 − iωτ
where o is the static conductivity
The form of  indicates that the electrons have a mixed resistive – inductive character. The
resistive character dominates in the low frequency region and the inductive character dominates in
the high frequency region.
The dielectric constant for the whole crystal including both the lattice and the electron is
𝑖𝜎
𝜀 =𝜀 +
𝜔
If the dielectric constant is known, we can determine the reflective and absorptive
properties of the crystal
In low frequency region, the wave penetrates the metal a short distance, known as skin
depth. The skin depth is given by
/
2𝜀 𝑐
=
𝜎 𝜔
The reflectivity in this frequency range is very close to unity
In the intermediate frequency region, the wave is evanescent and the metal exhibits total
reflection.
In the high frequency region, the metal acts as a regular dielectric through which the wave
propagate without attenuation

The Kronig -Penney model- conductors, semiconductors and insulators.

Advantages of classical free electron theory
1) It explains the electrical conductivity and thermal conductivity of metals.
2) It explains the Wiedemann - Franz law.
3) It verifies Ohm’s law.
4) It is used to explain the optical properties of metals.
Drawbacks of classical free electron theory
1) It fails to explain the electric specific heat and the specific heat capacity of metals.
2) It fails to explain superconducting properties of metals.
3) It fails to explain phenomena like photo-electric effect, Compton effect, Black body radiation, etc.
4) It fails to explain electrical conductivity of semiconductors or insulators.
5) The classical free electron model predicts the incorrect temperature dependence of σ.
6) It fails to give a correct mathematical expression for thermal conductivity.
7) Ferromagnetism could not be explained by this theory.
8) Susceptibility has greater theoretical value than the experimental value