Module 4

Electrical Conductivity in Metals

All matals are good conductors of electricity. They have loosely bound electrons in their
outermost orbits which are called free electrons. These free electrons can move freely inside
the metals under the action of an external electric field.
Resistivity and Mobility
Conductivity of a material is a measure of the material’s ability to allow charge carriers to
flow through it. The inverse of conductivity is resistivity. The conductivity of metal is given
by ,
𝑛𝑒 2 𝜏
𝜎= 𝑚

The resistivity is
𝑚
ρ = 𝑛𝑒 2 𝜏

Drift velocity: If a constant electric field is applied, the electrons will experience a force, eE
,and gets accelerated. The electrons acquire a constant average velocity opposite to the field.
This velocity is called drift velocity.
The average velocity with which free electrons move in a steady state opposite to the
direction of the electric field is called drift velocity.
Mobility : The magnitude of the drift velocity acquired by the electrons in unit electric field
is called the mobility of the electrons.
If E is the electric field and vd is the drift velocity of the electrons, then the mobility of the
electrons is
𝑣𝑑
𝜇= 𝐸

Phonons: All metals and alloys are crystalline in nature. Hence the atoms or ions are
situated in a in a specific repeating three-dimensional spatial pattern called a lattice. The
atoms act like they are connected with a spring. Because of thermal energy these atoms are
vibrated in all directions from the mean positions. These vibrations of atoms in crystal lattice
are quantised. The quantised lattice vibrations are called phonons. The amplitude of
vibrations is proportional to the temperature.
In other words, a phonon is the quantum energy of the lattice vibration, just like photons are
the quantum energy of electromagnetic radiations. The energy of each phonon is given by:

⇒ E = hv

⇒E = ħ(2π)v

⇒ E = ħω……. (1)
Where,

1
 ω -The angular frequency
ħ - The reduced Planck’s constant
Phonons play an important role in many of the physical properties of solid states, such as they
play a key role in thermal conductivity and electrical conductivity.
Variation of resistivity with temperature and impurity: The electrical resistance of all
metals increases with increase in temperature. This is because as the amplitude of vibrations
of the positive ions increases the temperature increases causing Joule heating of the material.
As a result the resistance of the material increases.
Matthiessen’s rule.
The presence of impurities in the metal and imperfections in the crystal lattice also contribute
to the resistance. The resistance offered by impurities is called residual resistance and is
independent of temperature. Hence the total resistance of a metal at a particular temperature
is sum of the resistance due to scattering and the resistance due to impurities.
For metals containing small amounts of impurities, the electrical resistivity (ρ) may be
written as
ρ = ρ0 +ρp (T)
where ρ0 is constant that increases with increasing impurity content and ρ p (T) is the
temperature dependent part of the resistivity. This is known as Matthiessen’s rule.
If a metal contains impurities, the electrons are scattered by impurity atoms. This scattering is
in addition to that caused by the lattice vibrations. The reason for this scattering is that the
field in the vicinity of the impurities is different from that near the host atoms and deviations
from the periodicity of the potential thus produced, act as scattering centres for electrons. The
variation of resistivity with temperature and defects is as shown in the fig.

Classical free electron theory:

Failure of Classical (Drude-Lorentz) theory
1) Temperature dependence of electrical conductivity

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WKT the conductivity of a metal is inversely proportional to temperature
1
𝜎 proportional
𝑇
electrical conductivity is given by,
𝑛𝑒 2 𝜏
𝜎=
𝑚
𝜆
𝜏=𝑣 b’coz velocity (v) = s/t

𝑛𝑒 2 𝜆
𝜎= 𝑚 𝑣
1 3
But from Kinetic theory m 𝑣 2 = 2kT
2

m 𝑣 2 = 3kT
3𝑘𝑇
𝑣2 = 𝑚

3𝑘𝑇
𝑣=√ 𝑚

𝑛𝑒 2 𝜆
𝑣 ∝ √𝑇 so, 𝜎= 𝑚 √𝑇

1
proportional
√𝑇

ie 𝜎 ∝ 1/ √𝑇
which is not correct
2) Electrical conductivity and electron concentration
𝑛𝑒 2 𝜏
electrical conductivity is given by, 𝜎 = 𝑚

ie 𝜎 directly is proportional to ‘n’

The values of ‘n’ for zinc and aluminium are 13.10 x 1028 /m3 and 18.06 x 1028 / m3 resply.
These are less conducting when compared to copper and silver which have 8.45 x 1028 /m3
and 5.85 x 1028 / m3 resply. for ‘n’. Which is failure.
3) Specific heat :The molar specific heat of a gas at constant volume is given by
3
Cv = 2 𝑅

According to free electron theory, free electrons are treated as gas molecules. Hence the
above equation must be applicable to free electrons. but experimentally it was observed that
the specific heat of a metal is Cv = 10-4 RT. This is far lower than the expected value.

Quantum free electron theory

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Sommerfeld succeeded in overcoming the drawbacks of Drude-Lorentz theory by using
quantization conditions. Sommerfeld developed quantum free electron theory by using
following assumptions,
The assumptions of quantum free electron theory
1. The energy values are quantized. The allowed energy values are realized in terms of
set of energy levels
2. The distribution of electrons in the various energy levels are given by Pauli exclusion
principle
3. The free electrons travel in a constant potential inside the metal but stay confined
within the boundaries.
4. The attraction between the free electrons and the lattice ions, and the repulsion
between the electrons themselves are ignored.

Density of states:
The permitted energy levels for electrons in a solid are in terms of bands
Each band is spread over an energy range. The number of energy levels in each band is
extremely large. The distribution of energy levels in the band is realized by density of states
The density of energy levels in a band is the number of energy levels per unit range in the
band.
Each energy level corresponds to one energy value and each value is applicable to two energy
states, one for an electron with spin up and the other one for an electron with spin down.
The density of states can be defined as the number of available states per unit energy range
centred at a given energy E in the valence band of a material of unit volume. It is a
mathematically continuous function and the product of g(E)dE gives the number of states in
the energy interval dE.
It can be shown on the basis of quantum mechanical calculations that density of states g(E)dE
is given by,
3⁄
8√2 𝜋𝑚 2 1⁄
g (E) dE = 𝐸 2 dE
ℎ3
1
The number of energy states in an energy interval dE is proportional to 𝐸 ⁄2
The number of filled electronic levels at a particular temperature is given by ,
N(E) = g(E) f(E)
3⁄
8√2 𝜋𝑚 2 1⁄
Where f(E) is the Fermi Dirac distribution function and g(E) = = 𝐸 2
ℎ3

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Fermi energy
We know that for a metal with N atoms there will be N allowed energy levels in each band.
As per Pauli exclusion principle each level can accommodate two electrons one with spin up
and other with spin down.
It is defined as the energy of top most filled level in the ground state at 0 degree Kelvin.
At zero temperature the electron states are occupied from the lowest energy state to
a state of maximum energy, known as Fermi energy.
The highest energy corresponding to the highest occupied level at 0 degree Kelvin ” is called
Fermi energy and the energy level is called Fermi level. The Fermi energy is denoted by EF.

The expression for Fermi energy is given by

ℎ2 3𝑛 2/3
𝐸𝐹 = ( )
8𝑚 𝜋
Where ,m, is mass of electron
‘ n’ is concentration of electrons
‘h’ is Planck’s constant.

At 0 K, when the metal is not under the influence of an external field, all the levels above the
Fermi level are empty, those lying below Fermi level are completely filled. Fermi energy is
the energy state at which the probability of electron occupation is ½ at any temperature above
0 k. It is denoted by EF

Fermi Dirac statistics

Under thermal equilibrium the free electrons acquire energy obeying Fermi Dirac statistics.
Fermi Dirac statistics is applicable to the particles that obey Pauli exclusion principle or the
particles of spin of half (1/2)
Fermi Dirac statistics permits the evaluation of probability of finding electrons occupying
energy levels in a certain energy range. The evaluation is done through a function called
Fermi factor f(E).

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The probability f (E)that a given energy state with energy E occupied at a temperature ‘T’ is
given by,
1
f(E) = 𝐸−𝐸
exp( 𝑘𝑇 𝐹 )+1

f (E) is called Fermi factor

It is the probability of occupation of a given energy state for a material in thermal equilibrium
Dependence of Fermi factor on the Temperature and effect on occupancy of energy
levels

The variation of Fermi factor with temperature and the effect on occupancy of energy level is
as shown in fig.

Let us consider the 3 different cases of distribution as explained below.

Case 1) Probability of occupation for E < 𝐸𝐹 at T = 0
1
f(E) = 𝐸−𝐸𝐹
1+exp( )
𝑘𝑇

when E < 𝐸𝐹 , 𝐸 − 𝐸𝐹 is negative

1 1
f (E) = 𝑒 −∞+1 = 0+1 =1 𝑒 −∞ = 0

f (E) =1 for E < 𝐸𝐹

At T = 0 all the energy levels below the Fermi level are occupied.
Case2) Probability of occupation for E > 𝐸𝐹 at T = 0
1 1
f (E) = 𝑒 ∞ +1 = =0
∞

f (E) = 0, for E > 𝐸𝐹

So at T = 0, all the energy levels above the Fermi level are unoccupied.
Case 3) Probability of occupation at ordinary temperatures.

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At ordinary temperatures, the value of f(E) starts decreasing from 1 as the values of E
become closer to 𝐸𝐹 .
E = 𝐸𝐹
1
f(E)= 𝐸−𝐸𝐹
1+exp( )
𝑘𝑇

1 1
f (E ) = =2 𝑒 0 =1
𝑒 0 +1

Further for E > 𝐸𝐹 , the probability value falls off to zero rapidly.
From the above discussion we can conclude that the Fermi energy is the most probable, or the
average energy of the electrons which undergo transitions across the Fermi level at
temperatures above zero degree absolute.

Superconductivity
Introduction to Super Conductors
The electrical conductivity of all metals and alloys decreases when they are cooled. When
the temperature is lowered, the thermal vibrations of the atoms decrease and the conduction
electrons are less frequently scattered. Certain materials however show a very remarkable
behaviour , when they are cooled, their electrical resistance decreases in the usual way but on
reaching a temperature a few degree above absolute zero they suddenly lose all their
resistance. They are said to have passed into the superconducting state.
Superconductivity is the phenomenon observed in certain materials where electrical
resistance disappears completely and the materials conduct electric current with practically
zero resistance when they are cooled below a characteristic temperature.
The phenomenon of superconductivity was discovered by Kammerling Onne’s in 1911. He
observed that when mercury was cooled to the temperature of liquid helium ie 4.2 K, its
resistance suddenly disappeared.
Superconductors are materials that conduct electricity with no resistance. A superconductor
can carry a current indefinitely without losing any energy unlike the familiar conductors like
copper and steel.
Temperature dependence of resistivity

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The variation of resistance of a superconductor with temperature is as shown in fig. It is
observed that the resistance of superconductor decreases with temperature and at a particular
temperature the resistance drops suddenly to zero. The temperature at which a material
undergoes transition from normal state to superconducting state is called critical temperature
Tc
Meissner effect

The Meissner effect is the expulsion of a magnetic field from a superconductor during its
transition to the superconducting state when it is cooled below the critical temperature.
When a superconducting material is in the normal state at T > Tc is placed in a magnetic
field, lines of magnetic induction pass through the body, but when it is cooled below the
critical temperature T<Tc these lines of induction are pushed out of the body so inside the
superconducting material B = 0, This phenomenon is known as Meissner effect. It is the
characteristic property of a superconductor. A super conducting material exhibits perfect
diamagnetism.
The experiments of Meissner effect established that as the temperature is lowered, the
specimen enters superconducting state t T= Tc, and magnetic flux is pushed out from the
materials for all the temperatures T<Tc, This effect is reversible. When the temperature is

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increased from below Tc the magnetic field starts penetrating the specimen at T = Tc, as a
result of which the material returns to the normal state.
The magnetic induction inside the material at T>Tc is given by
B = μ0 (M+H) normal state,
Where H is the external field applied and M is the magnetisation produced within the
specimen.
At T < Tc, B =0,
0 = μ0 (M+H)
M+H=0
M=-H
Dividing by H
𝑀
= −1
𝐻
𝑀
But =𝜒
𝐻

𝜒 = −1
So Susceptibility of a superconducting material is negative and hence it exhibits perfect
diamagnetism
Critical Current
The magnetic field which causes a superconductor to become normal from a superconducting
state need not necessarily by an external applied field, it may arise as a result of electric
current flow in the conductor. The minimum current that can be passed in the sample without
destroying its superconducting properties is called critical current ‘I c’
If a wire of radius ‘r’ of a superconductor carries a current I, there is surface magnetic field
HI =Ic /(2πr) associated with the current, if HI exceeds Hc, the material will go to normal. If
in addition, a transverse magnetic field ‘H’ is applied to the wire, the condition for the
transition to the normal state is that the sum of the applied field and the field due to current
should be equal to the critical field. Thus, we have,
Hc = HI + 2H
HI = Hc – 2H
But HI =Ic/(2πr)
Ic/(2πr) = Hc – 2H
Ic = 2πr (Hc – 2H)
This is called Silsbee’s rule. The critical current Ic will decrease linearly with increase of
applied field until it reaches zero at H = Hc/2. If the applied field is zero, Ic = 2πr Hc
Temperature dependence of Critical field

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Superconducting state of material exists only in a particular range of temperature and field
strength. The superconducting state cannot exist in the presence of a magnetic field greater
than a critical value. Superconductivity vanishes if the temperature is raised above its critical
temperature Tc or if a sufficiently strong magnetic field is applied. when the magnetic field
exceeds the critical value Hc, the superconducting state is destroyed and the material goes to
normal state. Obviously, the value of H varies with temperature, as shown in the fig.
Critical field is defined as the maximum magnetic field strength below which a material
remains superconducting at a given temperature.
The relation between Hc and T is given by ,
𝑇2
Hc = H0 (1 − )
𝑇𝑐2

Where H0 is the magnetic field at 0 K`

Types of Super Conductors

Depending upon their behaviour in an external magnetic field Superconductors are classified
into two categories namely a) Type-I (soft)superconductors and b)Type-II (hard)
superconductors.

Type-I (soft)superconductors

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For a Type I superconductor, only one critical magnetic field, Bc value, separates between the
superconducting state and the normal state. They exhibit complete Meissner effect or perfect
diamagnetism. In type-I superconductors the transition from superconducting state to normal
state occurs sharply at the critical field Hc as shown in the fig. and completely expel the
magnetic field from the interior of the superconducting phase. They have only one critical
field Hc. Mercury, Aluminium, lead, zinc and indium are examples of type -I
superconductors.

Type II (hard) superconductors.

Type II superconductors are hard conductors. They do not show complete Meissner effect.
They are characterized by two critical fields. Type II superconductors are those
superconductors that lose their superconductivity gradually but not easily or abruptly when
placed in the external magnetic field. Type II superconductors start to lose their
superconductivity at the lower critical magnetic field (Hc1) and completely lose their
superconductivity at the upper critical magnetic field (H c2). The state between the lower
critical magnetic field (H c1) and upper critical magnetic field (Hc2) is known as vortex state or
intermediate state. It is the condition in which superconductor partially allows magnetic flux
lines to pass through it. The critical field of type-II superconductors is much greater than that
of type-I, hence they have large applications. Type II superconductors are used for strong

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field superconducting magnets. Transition metals and their alloys and ceramics are examples
of type-II superconductors.

Type-I Superconductor Type-II Superconductor

They exhibit complete Meissner effect They exhibit Partial Meissner effect

They have one critical field They have two critical field

Critical fields are low Critical fields are high

They are soft superconductors They are hard superconductors

They are generally low temperature They are generally high temperature
superconductors superconductors

Current flows through surfaces only Current flows throughout the material

They are generally pure materials They are oxides and ceramics

Applications are limited They have large applications

BCS theory

BCS theory was developed in 1957 by the American physicists John Bardeen, Leon N.
Cooper, and John R. Schrieffer to explain the behaviour of superconducting materials.

This theory involves the electron interactions through phonons as mediators.

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.

BCS showed that the basic interaction responsible for the superconductivity is between the
pair electrons by means of exchange of virtual phonons. This theory makes an important
assumption that there exists an attractive force between the electrons in typical type-I
superconductors,

Suppose an electron approaches a positive ion core. It suffers attractive coulomb interaction,
due to this attraction, ion core is set in motion and consequently distorts the lattice. Suppose
towards that side another electron comes and sees this distorted lattice. Then the interaction
between the two, the electron and distorted lattice occurs which in effect lowers the energy of
the second electron. Thus the two electrons interact via lattice distortion or phonon field
resulting in the lowering of energy for electrons. Due to lowering of energy the force between
the two electron become attractive. This type of interaction is called electron-lattice-electron
interaction. Since the oscillatory distortion of lattice is quantised in terms of phonons, the
interaction between electron and electron van be interpreted as electron-electron interaction
through the phonons as mediators.

Let an electron of wave vector k1 emits a virtual phonon q which is absorbed by an electron
k2. k1 is thus scattered as k1-q and k2 as k2+q.Thus the two electrons are attracted via
phonons. Superconductivity occurs when such an attractive interaction dominates the usual
repulsive interaction. Two such electrons which interact attractively in phonon field are
known as a Cooper Pair. At temperature less than the critical temperature, electron-lattice-
electron interaction is stronger than the electron-electron coulomb interaction, and so the
electrons tend to pair up at a temperature less than critical temperature. T < Tc

High temperature superconductors

Superconductivity was first observed by Kammerling Onnes at temperature of 4.2k. High-

temperature superconductors (abbreviated high-Tc or HTS) are defined as materials that
behave as superconductors at temperatures above 77 K (−196.2 °C). If the transition
temperature is high, then the superconductors are known as high temperature superconductors
(HTS).

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The first high-temperature superconductor was discovered in 1986, by Bednorz and Müller in
ceramic materials" lanthanum-barium-copper oxide ceramic at a critical temperature 30k.
Copper oxide based high superconductors were discovered in 1987. Superconductivity at
about 92k was observed in yttrium, barium and copper oxides (YBa2Cu3O7). Later
superconductivity was found in an oxide of bismuth, strontium, calcium and copper at a
temperature of 105k.

All high temperature superconductors are different types of oxides of copper and exhibit
particular type of crystal structure known as perovskite crystal structure. It is interesting to
note that critical temperature is high for those with a greater number of copper oxygen layers
in the structured unit.
The formation of supercurrents in HTS is direction dependent. The supercurrents are strong
in the copper oxygen planes and weak in a direction perpendicular to the plane. Since they
are ceramics, the flow of supercurrents have a restriction due to grain boundary effects. As a
result the critical current value is pushed down . Flux quantisation experiments have proved
that not exactly the cooper pairs, but the pair of charge carriers resembling cooper pairs
constitute current in these superconductors.
Most high-Tc materials are type-II superconductors and some have high Hc values.

As of 2021, the superconductor with the highest transition temperature at ambient pressure is
the cuprate of mercury, barium, and calcium, at around 133 K

Quantum tunnelling

Quantum tunnelling is defined as a quantum mechanical process where wavefunctions can

penetrate through a potential barrier. Quantum tunnelling is a phenomenon where a
subatomic particle or atom can be present on the opposite side of the physical obstacle that is
normally impossible for the particle to infiltrate.

In superconductors quantum tunnelling is observed when two superconductors separated by a

very thin layer of insulating material. Current passes through the junction via the process
of quantum tunnelling.

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Josephson junctions.

A Josephson junction is made by sandwiching a thin layer of insulating material between

two layers of superconducting material (known as a superconductor–insulator–
superconductor junction, or ( S-I-S),

The Josephson effect is a phenomenon that occurs when two superconductors are placed in
proximity, with some barrier between them.

In 1962 Josephson predicted that a supercurrent can be made to flow across an insulating gap
between two superconductors provided the gap is small enough.

10-9m

Two superconductors are separated by an insulating barrier as shown in the fig. A current is
made to flow in a bar of superconductor. A voltmeter is connected across the superconductor
bar. If the distance between the two superconductors (thickness of insulating barrier) is 1nm a
current flows across the gap. This is known as Josephson effect. Electronic circuits can be
built from Josephson junctions, especially digital logic circuitry.

DC Josephson Effect

DC Josephson effect is actually a direct current that crosses the insulator when any kind of
external electromagnetic field is not present due to tunneling . The DC Josephson current is
equivalent to sine of the Josephson phase which is a phase difference across the insulator that
is constant over time.

Josephson showed that the supercurrent through the junction is given by

I = Ic sin (∅0 )

Where φ0 is the phase difference between wave functions describing cooper pairs on both
sides of the barrier and Ic is the critical current at zero voltage condition which depends on
the thickness and width of the barrier.

AC Josephson Effect

When a dc applied across the junction, it causes radio frequency oscillations across the
junction, this effect is known as AC Josephson effect. The dc voltage generates an
alternating current given by

I = Ic sin (∅0 +∆∅)

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Because of the applied voltage across the junction, the energies of cooper pairs on both sides
of the barrier differs in energy by 2eV. Using quantum mechanical calculations it can be
shown that

2𝑒𝑣
∆∅ =2πt( )
ℏ

2𝑒𝑣
I = Ic sin (∅0 +2πt( )
ℏ

The current in the above equation is known as alternating current of frequency

2𝑒𝑣
ν= ℏ

It shows that a photon of frequency ν is emitted or absorbed when a cooper pair crosses the
junction, thus when a dc voltage is applied an ac current is produced by the junction. A d.c
voltage of 1μV produces a frequency of 483.6MHz.

SQUIDS (Superconducting Quantum Interference devices)

They are Superconducting quantum interference devices formed from two Josephson
junctions. A SQUID is a very sensitive magnetometer used to measure extremely small
magnetic fields, based on superconducting loops containing Josephson junctions. SQUIDs are
sensitive enough to measure fields as low as 5×10⁻¹⁴ T.

The main part (heart) of the Squid is a superconducting ring which contains one or more
Josephson junctions. There are mainly two types of squids DC SQUID and AC/ RF SQUID.

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DC SQUID:

When two Josephson junctions are sandwiched between two insulating layers in the form of a
ring forms DC SQUID as shown in the fig.

It consists of two Josephson junctions arranged in parallel in a superconducting loop so that

electrons tunnelling through the junctions demonstrate quantum interference.

It is based on the DC Josephson effect. In the absence of any external magnetic field, the
input current I splits into the two branches equally. If a small external magnetic field is
applied to the superconducting loop, a screening current, is begins to circulate the loop that
generates the magnetic field canceling the applied external flux, and creates an
additional Josephson phase which is proportional to this external magnetic flux. The induced
current is in the same direction as in one of the branches of the superconducting. The total
current through the two parallel Josephson junction is given by

𝑒𝜙
IT = 2 (I0 sin(∅0 ) cos ( ℎ𝑐 )

The above equation indicates that a progressive increase or decrease of the magnetic flux
causes the current to oscillate between minima and maxima values and the period of
oscillations is one flux quantum ∅0 given by

ℎ
∅0 = = 2.06 x 10-15 webers
2𝑒

RF SQUID

It is based on the AC Josephson effect and uses only one Josephson junction and an RF coil.
It is less sensitive compared to DC SQUID but is cheaper and easier to manufacture in
smaller quantities. Most fundamental measurements in biomagnetism, even of extremely
small signals, have been made using RF SQUIDS

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Suppose one junction superconducting loop is put in an external flux ϕ ex as shown in fig. In
RF Squid the one junction superconducting loop is coupled to a circuit driven by a constant
RF source, ie the loop would experience the flux produced by current. An oscillating current
is applied to an external circuit, whose voltage changes as an effect of the interaction between
it and the ring. The magnetic flux is then measured.

SQUIDs are used in cardiology for magnetic field imaging (MFI), which detects the magnetic
field of the heart for diagnosis and risk stratification. SQUIDs are being used as detectors to
perform magnetic resonance imaging (MRI). While high-field MRI uses precession fields of
one to several teslas, SQUID-detected MRI uses measurement fields that lie in the microtesla
range.

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