Module-2: Electrical properties of materials
Terminologies of free electron theory of metals:
(d) Mobility of electrons: The mobility of electrons is defined as the magnitude of drift velocity acquired
by the free electrons in a unit field.
Or, the mobility is defined as the drift velocity gained by the free electrons per unit rise of an electric
field. If E is the applied field, vd is the drift velocity, then mobility of the electrons,
vd eE e
µ
E Em m
Expression for Electrical conductivity in a metal or conductor:
According to the classical free electron theory of metals the expression for electrical conductivity is
given by.
ne2
m
Assumptions of quantum free electron theory.
1. The energy values of the conduction electrons are quantized. The allowed energy values are
realized in terms of a set of energy levels.
2. The distribution of electrons among the various allowed energy levels follows the Pauli’s
Exclusion Principle.
3. The electric potential due to the ionic cores is taken to be essentially constant throughout the
dimension of the metal.
4. The attraction between the free electrons and the lattice ions and the repulsion between the
electrons themselves are considered insignificant.
Differences between Classical free electron theory and Quantum free electron theory.
Classical free electron theory Quantum free electron theory
1) The energy levels of the free 1) The energy levels of the free electron
electron are continuous. are discontinuous.
2) Free electrons may possess same 2) Free electrons obeys Pauli’s Exclusion
energy. Principle so no two electrons can
possess same energy
3)The distribution of energy among 3)The distribution of energy among the
the free electrons obeys Maxwell- free electrons obeys Fermi-Dirac
Boltzmann statistics statistics
Success of Quantum free electron theory.
Specific Heat
According to classical free electron theory, all the free electrons in a metal absorb the heat energy,
when the metal is heated. It results in a large value of the specific heat as predicted. But as per quantum
free electron theory, only few electrons occupying energy levels close to Fermi level Ef absorbs the heat
energy and get excited to the higher energy level. Hence the value of specific heat is very small.
According to Quantum free electron theory
2k
CV RT
E
f
Since the order of magnitude of the Fermi energy for metals is about 5eV, we get
2k
0.345 104 104
Ef
CV 10 4 RT
The above equation agrees with experimental value.
Temperature Dependence on Electrical Conductivity
1
We know that
T
From the Quantum free electron theory
ne2
-----------------> (1)
mv f vf
v f is independent of temperature , but is dependent on temperature. As the electrons get scattered
by lattice ions, which is vibrating in such a way that displacement of ions takes place in all direction.
Hence ions are assumed to have circular cross section of area r 2 which blocks the path of electron.
Here ‘r’ is the amplitude of vibration, as the temperature increases energy of the vibrating ions
increasing the amplitude of vibration, decreasing the mean free path.
1
Tr 2 and r 2
1
T --------------- (2)
From (1) we know that
1
From (1) and (2) which holds good with the experimental result.
T
Dependent of electrical conductivity and electron concentration
According to Quantum free electron theory,
ne2
mv f
n and also
vf
n Al
18.66 1028 / m3 nCu 8.45 1028 / m3
Though electron concentration of Aluminium is 2.137 times higher than Copper.
The value of of Cupper is 3.73 times more than that of Aluminium.
vf
Hence, the Conductivity of Copper exceeds that of Aluminium.
Module-3, Superconductivity
The resistance offered by certain materials to the flow of electric current abruptly drops to zero below a
threshold temperature. This phenomenon is called ‘Superconductivity’ and the threshold temperature
is called ‘Critical temperature, Tc’. The materials that exhibit superconductivity and which are in the
superconducting state are called ‘Superconductors’. Superconductivity was discovered by Kamarlingh
Onnes in the year 1911.
Temperature dependence of resistivity in superconducting materials:
Up to a particular temperature Tc, the critical temperature, resistance of the superconductor in the non
superconducting state decreases with decrease in temperature as in the case of normal metal. At Tc, the
resistance abruptly drops to zero as shown in Figure 2. At critical temperature, the normal state
transforms into the superconducting state. Different superconducting materials have different critical
temperatures. For example, critical temperature of pure mercury is 4.2 K.
Resistivity (m)
Tc
0 Temperature T (K)
Figure 2: Dependence of resistivity of a
superconductor on temperature
Effect of magnetic field — Meissner effect:
Consider a superconductor in its normal state. Suppose the magnetic field is applied to it, then the
magnetic field lines pass through the material when the temperature is above critical temperature Tc
(Figure 3a). As the temperature of the material is cooled below Tc, all the magnetic field lines are
suddenly expelled out of the material (Figure 3b) for all temperatures T < Tc. The material becomes a
perfect diamagnetic [Meissner and Ochensfeld (1933)].
“The expulsion of magnetic flux from the interior of the superconductor when it is cooled
below the critical temperature is called Meissner effect”. [Or “The expulsion of magnetic
flux during the transition from normal to the superconducting state is called Meissner
effect”.]
Hext Hext
Cooling
(a) T > Tc (b) T Tc
Figure 3(a): A superconductor at T >Tc held in a Figure 3(b): The superconductor
magnetic field. The magnetic flux penetrates the expelling the field lines from its body
body in normal state.
interior for T T
This effect is reversible. When the temperature is raised above Tc, cthe flux suddenly starts
penetrating the specimen as a result of which the material returns to normal state.
The magnetic induction inside the specimen is given by
B = o ( H + M ) … Normal state
where H is the external applied field and M is the magnetization produced within the
specimen.
At T < Tc, B = 0 and o ( H + M ) = 0 … Superconducting state
Or M = H
Hence the susceptibility of the material,
M
1 ….. Perfect diamagnetism
H
Thus, superconducting state is characterized by perfect diamagnetism. This conclusion
cannot be derived from the simple definition of superconductivity as a state of zero
resistivity. Two mutually independent properties, viz. Zero resistivity ( = 0) and Perfect
diamagnetism (B=0; = 1) are the essential properties that characterize the
superconducting state.
Critical field Hc : Temperature dependence of Critical field
It is observed that the superconductivity vanishes if a sufficiently strong magnetic field is applied
[Kammerlingh Onnes, 1913]. The strength of magnetic field required to just switch a material from
superconducting state to normal state is called ‘Critical field’. It is denoted by ‘Hc’ and found to be a
function of temperature. Figure 4 shows the dependence of Hc on temperature.
If T is the temperature of the superconducting
material, Tc is the critical temperature and Hc,
H0 the critical field, and then the dependence of
Normal phase critical field on temperature is given by the
relation,
Hc Superconducting T2
H c H 0 1 2
phase Tc
where H0 is critical magnetic field at 0 K
T Tc
(absolute zero).
Figure 4: Dependence of critical field Hc
on temperature T
Types of Superconductors:
Based on the magnetic behavior, superconductors are classified into two categories, viz. (a)
Type I superconductors and (b) Type II superconductors.
Type I superconductors or Soft superconductors – Type I superconductors, also known as soft
superconductors, exhibit complete Meissner effect. In this type of materials, the transition from
superconducting state to normal state in the presence of magnetic field occurs sharply at the critical
value Hc.
The magnetic curve for type I superconductor is as
shown in Figure 5. In the presence of an external
magnetic field H < Hc, the material in superconducting
state is a perfect diamagnet. As soon as the applied
–M
Normal field H exceeds Hc, the entire material becomes normal
Super by losing its diamagnetic property completely and the
state
magnetic flux penetrates throughout the body. Since
conducting superconductors are perfect diamagnet, it possesses a
H Hc negative magnetic moment (M).
state
Figure 5: Variation of magnetic moment
with magnetic field
Aluminum, Lead, Indium, Tin and Mercury are the
examples for type I superconductors. The critical field
Hc is relatively low for soft superconductors (0 – 1T). As such they are not of much use for production
of high magnetic fields.
Type II Superconductors Or Hard superconductors: Type II (Hard) superconductors are
characterized by 2 critical magnetic fields – Hc1 (lower critical field) and Hc2 (upper critical field).
Normal state
No flux
Magnetization –M
penetration
Partial flux
penetration
Vortex
state
Hc1 Hc Hc2
External field H
Figure 6: Variation of magnetization with external field
in Type II superconductors
For applied field (H) below Hc1, the material expels magnetic flux completely and behaves as a perfect
diamagnet, as shown in Figure 6. When H exceeds Hc1, the flux begins to penetrate and the penetration
of flux increases until Hc2 is reached. At Hc2, the superconductivity vanishes and the specimen returns to
normal state.
Type II superconductors are inhomogeneous. When the applied field strength is between Hc1
and Hc2, the material is in a mixed state called ‘Vortex state’, and in this state, the flux penetration
occurs through channelized parts of the body called filaments. In this state, though there is no flux
penetration, the material retains its zero resistance property and hence it is still a superconductor in this
magnetic field interval. The flux penetration occurs through small channelized parts of the body, called
filaments.
The most distinguishing characteristic of type II superconductors is that the value of upper
critical field is very high. Thus they are very useful in the buildup of devices which work in high magnetic
fields such as superconducting magnets. Transition metals and alloys consisting of niobium, aluminum,
silicon and vanadium exhibit type II superconductivity. Ceramic superconductors also belong to this
category.
BCS Theory:
A fundamental understanding of electronic structure of the superconductor was given in 1957 by the
American physicists, John Bardeen, Leon N. Cooper and Robert Schrieffer. The theory is based on the
purely quantum mechanical concept of ‘Cooper pairs’.
According to BCS theory, during the flow of current in the superconductor, when an electron
approaches a positive ion in the lattice, there is a coulomb attraction between the electron and the
lattice ion. This produces a distortion in the lattice. This interaction causes an increase in the density of
ions in the region of distortion. The higher density of ions in the distorted region attracts, in turn,
another electron. Thus, a free electron exerts a small attractive force on another electron through
phonons which are quanta of lattice vibrations. This process is called electron - electron interaction via
phonon field.
At lower temperature i.e., below the critical temperature, the attraction force reaches a
maximum value for any two electrons of equal and opposite spin and opposite momentum. This force
of attraction exceeds the force of repulsion between two electrons and thus a pair of free electrons
couple through a phonon, called cooper pair. Cooper pair is a bound pair of electrons formed by the
interaction between the electrons with opposite spin and momenta in a phonon field.
At normal temperatures, the attractive force is too small and pairing of electrons does not take
place. At lower temperatures (T < Tc), the attractive electron-electron interaction exceeds coulomb
repulsion. According to quantum mechanics, a wave function could be associated with a cooper pair.
But the wave function is spread over a space. As a result, the wave function of one cooper pair overlaps
with that of other cooper pairs. For a given cooper pair, the overlapping may extend over 10 6 other
pairs and hence almost the entire volume of the superconductor. Therefore, the entire cooper pairs
move as a single unit. Thus, the superconducting state is an ordered state of electrons. Since the density
of Cooper pairs is quite high, even large currents require only a small velocity. As a result, the extremely
rare collision of Cooper pairs with the lattice combined with precise ordering leads to vanishing
resistivity. Therefore, the conductivity becomes infinite.
***