SUPERCONDUCTIVITY

In 1986, George Bednorz and Alex Müller

found superconductivity in (La,Sr)2CuO4
with Tc = 36K. Within months Tc values
in cuprates shooted up to 135K.

Variation of resistance of
Hg in Ohms with
temperature. This is the plot
by Kammerling Onnes
marked the discovery of
superconductivity (1911).
Evolution of Tc with time
287 K: H2S + CH4 at 267 GPa (2021)
250 K: LaH10 under 170 GPa (2019)
203 K: H3S under 155 Gpa (2015)
Phenomena:

Zero resistance:
No resistance is detectable even for high scattering rates of conduction electrons.

Absence of Thermoelectric Effects:

No Seebeck voltage, no Peltier heat, no Thomson heat is detectable.

Ideal Diamagnetism:
χm = -1. Weak magnetic fields are completely screened away from the bulk of a
superconductor.

Meissner Effect:
If a superconductor is cooled down in the presence of a weak magnetic field, below Tc the
field is completely expelled from the bulk of the superconductor.

Flux Quantization:
The magnetic flux through a superconducting ring is quantized and constant in time. This
phenomenon was theoretically predicted in 1950 by F. London and experimentally verified in
1961.
Magnetic Field Dependence
 Meissner Effect
Meissener and Oschenfeld found
that if a superconductor placed in a
magnetic field is cooled below the
transition temperature Tc, then the
lines of induction B originally
present in the specimen is suddenly
pushed out. This phenomenon is
called Meissner effect.
Thus, a bulk superconductor behaves in an applied external field H as
if inside the specimen

Thus, a superconductor exhibits diamagnetism.

From Ohm's law,

If the resistivity goes to zero while

By Maxwell's equation,

So, for zero resistivity

This eqn. predicts that the flux through the metal cannot change on cooling
through the transition temperature, a result in contradiction to Meissner
effect.
Thus, perfect diamagnetism and zero resistivity are two independent and
essential properties of superconductors.

Therefore, the two conditions defining the superconducting state are

London Equations: Electrodynamics
The Meissner effect shows that the magnetic flux is pushed out
of the body of the superconductor at the transition temperature.

This, however, is not exactly true. Observation shows that the

magnetic flux decays from a constant value at the surface of the
superconductor to zero value in the interior somewhat gradually
rather than abruptly.
The depth of penetration is, however, small. This indicates that
there is no Meissner effect in thin films.
 To account for these two contradictory observations, one
should modify the electrodynamic equation to obtain the
Meissner effect.
The assumption of zero resistivity in case of superconductors leads
to the acceleration equation

The current density

This is the first London equation which describes the absence of

resistance.
It shows that it is possible to have steady current in the absence
of electric field which is the phenomenon of superconductivity.

Integrating with respect to time
Ho is the magnetic field at time t = 0.
This result admits the particular solution
H = H0, where H0 is an arbitrary magnetic
field existing at t = 0.
But, the Meissener effect does not allow
any "frozen in" fields.
F. London and H. London suggested that the acceleration equation be
abandoned and one should take instead as the fundamental equation

Taking the curl of both sides

penetration depth
 A andThis
B areequation
constants, accounts
x represents
forthethe
distance into the metal
Meissener effect from
whichtheshows
surface.
that a
uniform magnetic field cannot exist in
Drawbacks:
The first factor predicts that Haincreases with x which is contrary to
superconductor
Although London's
the fact. Thus, theory
we should explains
take only the two
the second conditions:
factor which leads to
Ethe= appropriate
0 and H =solution.
0
characterizing the superconducting state, it does not give
any insight into underlying electronic process in
superconductors.
The penetration depth can,
therefore, be defined as the
distance into the superconductor at
which the field value falls to 1/e
times its value at the surface.
 Thermodynamics of Superconducting Transition
Van Laer and Keesom demonstrated experimentally that the transition between the
superconducting and the normal states is thermodynamically reversible, just as the
transition between liquid and vapor phases of a substance is reversible under the condition of
slow evaporation.
 Since the transition is reversible, one can apply the laws of thermodynamics and obtain an
expression for the entropy difference between the normal and superconducting states in terms
of the critical field Hc.
 We treat only type I superconductor with a complete Meissener effect so that B = 0 inside the
superconductor.
 We shall show that the critical field is a measure of the energy difference between the
superconducting and the normal states at absolute zero.
 Consider a superconducting specimen in the form of a very long cylinder placed inside a
solenoidal winding.
 When an electric current is passed through the winding, a magnetic field acts on it and
magnetization is induced in the specimen.
 We shall calculate the energy of induced magnetization by considering the work done by the
external power supply in building up the field inside the solenoid carrying the specimen.
 Note that work is done by the power supply in building up the magnetic field, because the
changing flux through the solenoid induces a back emf.
From the theory of magnetism, the work done per unit volume in magnetizing the specimen
is

The first term on the RHS denotes the magnetic energy

of the solenoid, whereas the second term denotes the
energy of induced magnetization.

Thus, we have
 From the first law of thermodynamics,

dW is the amount of work done by the specimen in the process

of magnetization. It is equal to -HadM.
Note that the work done (dW) on the body is equivalent to (-
dW) done by the body.

We are assuming that the magnetization is induced at a constant volume and pressure.
If dS be the change in the entropy of the system, then from the 2nd law of thermodynamics
 Compare this eqn. with the expression for a gaseous system.

Ha plays the role of p and, M plays the role of V.

The expression for Gibb’s free energy for a gaseous system is

Since Ha plays the role of p and, M plays the role of -V, Gibbs' free energy per unit volume in a
magnetic field can be written as

Differentiating, the above equation gives

 as

At a constant temperature,

and at a constant field,

We solve the above equation for the normal and superconducting states of the specimen.
Let the normal state of the metal is non-magnetic with zero magnetic susceptibility.
Then, M is zero and the Gibb’s free energy GN of a unit volume of the metal in the normal state N is
not changed by the application of the external field.
Next, consider the specimen in the superconducting state S under the same condition.
In this case, the Meissner effect takes place (i.e., B = 0 or M = - Ha/4π as B = Ha + 4πM)

Integrating,

When Ha = 0,

This relation shows that the Gibb’s free energy of the superconductor is increased when it is placed in a
magnetic field.
At the critical field HC, the energies of the specimen in normal and superconducting states must be equal,
as the two states are in equilibrium at the critical field HC and temperature T.
 This shows that the superconducting and
normal states of a specimen are in
equilibrium along the critical field curve.

This eqn is an important result. It shows that is a direct measure of the stabilization energy density of
the superconductors.
 Differentiating this eqn. with respect to T, one gets

Using the above equation becomes

At T = Tc, Hc = 0. So, the above equation yields

Thus, the entropies of the normal and superconducting phases are equal at the critical temperature.
Since is always found to be negative, the entropy is always greater in the normal state than the
superconducting state.
As entropy is a measure of the disorder of the system, it also follows that the superconducting state is more
ordered than the normal state because is never zero, except at T = 0 and at TC.

Thus, there is a finite entropy change when a transition takes place between the normal and
superconducting states and this finite entropy change implies that there is a latent heat.
 The specific heat is given by

At T = Tc, HC = 0.

This is known as Rutger's formula. This shows that if the metal is cooled or warmed in the absence of
magnetic field, there will be a discontinuity in specific heat in passing through the transition temperature.

This equation also shows that when Hc = 0, Cs > CN.

The discontinuity in specific heat at Tc has been experimentally verified.

It is found that in the superconducting state the electronic specific heat rises exponentially with
temperature, unlike that of normal metals for which the electronic specific heat varies linearly with
temperature.
 BCS Theory (Qualitative Discussion)

 Modern theory of superconductivity was developed by Bardeen, Cooper, and Schrieffer in 1957.
Their BCS theory has received universal acceptance because it has proved capable of explaining all
observed phenomena relating to superconductivity.

 Employing a completely quantum treatment, their theory explains the various observed effects, like
zero resistance, the Meissner effect, etc. As this theory is based on quantum mechanics, one can not
discuss it meaningfully without using advanced quantum concepts and mathematical techniques.

 Here, in the interest of simplicity, let us get a brief, qualitative, concept on the BCS theory.
 Consider a metal in which the conduction electrons lie inside the Fermi
sphere.
 Suppose that two electrons lie just inside the Fermi surface, and repel
each other due to coulomb interaction.
 But this Coulomb force is reduced substantially on account of the
screening due to the presence of other electrons in the Fermi sphere.
 After the screening is taken into account, the interaction between the
two electrons mostly disappears, although a small repulsion remains.
Suppose that, for some reason the two electrons attract each other.
 Cooper showed that the two electrons would then form a bound state (provided they are very close
to the Fermi surface).
 In a bound state, the electrons are paired to form a single system and their motions are correlated.
These two electrons are called a Cooper pair.
 The pairing can be broken if an energy equal to the binding energy is supplied to the system.
 The binding energy is strong when the electrons forming the pair have opposite moments and
opposite spins.
 If there is any attraction between the electrons established, then all the electrons in the
neighborhood of the Fermi surface will condense into a system of Cooper pairs.
(These pairs are also the superelectrons.)
What is the source of attraction between the electrons?
In superconductors, it is electron-phonon interaction.

 Suppose that the two electrons, 1 and 2 pass each other.

 As electron 1is negatively charged, it attracts positive ions towards itself
(electron-phonon interaction).
 Thus, electron 2 can not see bare electron 1 as electron 1 is screened by
positive ions.
 The screening may greatly reduce the effective charge of this electron. In
fact, the ions may overrespond and produce a net positive charge.
 If this happens, then electron 2 will be attracted towards the electron 1.
 This leads to a net attractive interaction, required for the formation of the
Cooper pair.
The ions' overresponse may be understood qualitatively.
 Since electron 1 is near the Fermi surface, its speed is very large.
 At the same time, the ions, because of their heavy mass, respond rather
slowly. By the time they have felt and completely responded to electron
l, electron 1 has left its initial region, at least partially.
 This will be more effective when electron 1 and electron 2 move in
opposite directions.

One can say that each electron is surrounded by a "phonon cloud," and that
the two electrons establish an attractive interaction by exchanging phonons.
Electron 1 emits phonons which are quickly absorbed by electron 2.
Phonon is involved twice - once in emission and once in absorption.
 As a result of the binding between electron 1 and 2, an energy gap appears in the spectrum of the
electron. This gap spans over the Fermi energy level.

 Some states in the energy range are now forbidden.

 These states have been "pulled" both down and up,
resulting in a peaking of the density of states just
below and just above the gap.
 Far from the Fermi energy, the density of states for the
The density of states g(E) versus E
plot for a superconductor, illustrating superconductor is the same as in the normal metal.
the energy gap. The cross-hatched
region is fully occupied at T = 0 K.
The theory shows that the energy gap at zero temperature is given by

ɷD = the Debye frequency,

g(EF) = the density of states for the normal metal at the Fermi level,
V’ = the strength of the electron-lattice interaction.
Several interesting results follow from the expression.
a) ħɷD = the energy of a typical phonon ≈ l0-2 eV.

When the exponential factor of is included, Δo = ~ l0-4eV, in agreement with observation.

b) Since ɷD ∞ 1/√M, (M = the mass of the vibrating ion), it follows that Δo ∞ 1/√M.
According to BCS theory
Thus, the gap and hence TC decrease as M increases.
This is experimentally found by varying the isotope ratio of the metal, and is called the isotope effect.
c. The gap increases, and so does TC, as the electron-lattice interaction V’ increases.
 In other words, a strong V’ favors superconductivity.
 This is reasonable because the ions are then attracted more strongly to the electron,
increasing the chance of overcompensation occurring.
 This result is curious, because V’ is also responsible for the resistivity in the normal state, in
which the larger the V’, the higher the resistivity.

 Thus, we therefore reach the seemingly contradictory conclusion that poor normal conductors
make good superconductors, while good normal conductors are poor superconductors!
 This is, however, in agreement with experiment: the poor normal conductors include, for
instance, Pb and Nb, and the good normal conductors include the alkali and noble metals, which
exhibit no superconductivity, even at the lowest attainable temperatures.
 Tunneling & Josephson Effect

Consider two metals separated by an

insulator. (Giaever, 1960)
The insulator normally acts as a
barrier to the flow of conduction
electrons from one metal to the other.
 If the barrier is sufficiently thin (less
than l0 or 20 A) there is a significant
probability that an electron which
impinges on the barrier will pass from
one metal to the other.
 This is called tunneling.
 Josephson Tunnelling
Under suitable conditions we observe
remarkable effects associated with the
tunnelling of superconducting electron pairs
from a superconductor through a layer of an
insulator into another superconductor. Such a
junction is called a weak link.
The effects of pair tunnelling include:
Dc Josephson effect: A direct current flows
across the junction in the absence of any
electric or magnetic field.
Ac Josephson effect: A dc voltage applied
across the junction causes rf current
oscillations across the junction.
Dc Josephson Effect
 Let ψ1 be the probability amplitude of electron pairs on one
side of a junction, and let ψ2 be the amplitude on the other side.
For simplicity, let both superconductors be identical.
We suppose that they are both at zero potential.
We use the time-dependent Schrödinger equation.

 represents the effect of the electron-pair

coupling or transfer interaction across the insulator;
It is a measure of the leakage of ψ1 into the region
2, and of ψ2 into region 1.
If the insulator is very thick, T is zero and there is
no pair tunneling.
 (1)

(2)

multiply (1) by

(3)

multiply (2) by

(4)
Now equate the real and imaginary parts of (3) and of (4):

(5)

(6)

For identical superconductors n1 = n2. From (6) we have,

(7)

From (5) we have, (8)

The current flow from (1) to (2) is proportional to or .

We therefore conclude from (5) that the current J of superconductor pairs across the junction
depends on the phase difference

J0 is proportional to the transfer interaction T.

The current J0 is the maximum zero-voltage current that can be passed by the
junction.

With no applied voltage a direct current (Dc) will flow across the junction
with a value between J0 and - J0 according to the value of the phase difference
θ2 – θ1. This is the Dc Josephson effect.
Ac Josephson Effect
Let a dc voltage V be applied
across the junction.
We can do this because the
junction is an insulator.
An electron pair experiences a
potential energy difference qV on
passing across the junction, where q
= -2e.
We can say that a pair on one side
is at potential energy - eV and a pair
on the other side is at eV.
The equations of motion become
(9)

(3)

(10)

This equation breaks up into the real part

(11) (without the voltage V)

The imaginary part

(12)
 (4)

(13)

where
(14)

(15)

From (12) and (15) with n1 = n2, we have

(16)

On integration of (16) we get a dc voltage across the junction whose

relative phase of the probablity amplitudes vary as
The superconducting current is given by

The current oscillates with frequency

 A dc voltage of 1μV produces a frequency of 483.6 MHz.

By measuring the voltage and the frequency it is possible to
obtain a very precise values of e.
Josephson effect