Chapter - 3
3. Superconductors
3.1. Basic theory of superconductivity
A state of material in which it has zero resistivity is called Superconductivity. When cooled
to sufficiently low temperatures, a large number of metals and alloys can conduct electric
current without resistance. Obviously, these specific materials undergo a phase transition to a
new superconducting state characterized by the complete loss of d.c. resistance below a well
defined critical temperature, TC. Thus zero resistivity (ρ = 0), i.e. infinite conductivity is
observed in a superconductor at all temperatures below a critical temperature (ρ = 0 for all T
< TC). The most sensitive measurements have shown that the resistance of these materials in
the superconducting state is at least 1016 times smaller than their room temperature values.
However, if we pass a current higher than the critical current density Jc, superconductivity
disappears. This limits the maximum current that the
material can sustain and is an important problem for
applications of superconducting material.
For elements, the transition temperature, TC lies
generally below 10oK. Figure.1 shows resistance versus
temperature for a low-temperature superconductor. At the
transition temperature TC the resistance drops abruptly to
an un measurably small value. The transition from normal Figure.1
to the superconducting phase is often sharp and occurs within 10–2 to 10–4 oK. In pure metals
the zero resistance state can be reached within a temperature range of 1moK. In the case of
impure metals the transition to the superconducting state may be considerably broadened. A
transition width of 0.05oK was observed for impure tin. The resistivity of a superconductor
to direct current is zero as far as it can be measured.
The estimates of the resistivity in superconducting phase are less than 4x10–25Ω-m,
which is essentially zero for all practical purposes. A striking way to demonstrate zero
resistivity is to induce a current around a close ring of a superconducting metal. Experiments
have been performed in which a persistent current has run for over two and a half year
without any measurable decay. The critical temperature, TC varies from superconductor to
superconductor but lies between less than 1oK and approximately 20 oK for metals and metal
alloys. Until 1986 the maximum TC was observed in an alloy of niobium, aluminium and
germanium. Recently it has been demonstrated that some complex cuprate oxide ceramics
have critical temperatures in excess of 100oK. Today, the highest known TC is 133oK for
mercury based cuprate oxide.
The superconductors with TC < 25oK are called conventional or low TC
superconductors (LTSC), Where as cuprate oxides and some other recently discovered
superconductors with TC>25 K are termed as high temperature superconductors (HTSC).
In addition no resistance to less current transport, the superconducting state is
characterized by perfect diamagnetism, i.e. B = 0 inside the superconductor. The magnetic
inductance becomes zero inside the superconductor when it is cooled below TC in a weak
external magnetic field: the magnetic flux is expelled from the interior of the superconductor
Figure.2
Figure.2 Expulsion of weak magnetic field from the interior of superconducting material
This effect is called the Meissner-Ochsenfeld effect after its discoverers and it is the
ultimate practical test in any new material. We must note that there always exists some
critical field Hc, above which superconductivity disappears. Superconductivity disappears
and the material returns to the normal state if one applies an external magnetic field of
strength greater than Hc.
3.2. Classification of Superconductors
On the basis of magnetic response, superconducting materials may be divided into
two classes designated as type-I and type-II.
Type-I materials, while in the superconducting state, are completely diamagnetic; i.e.,
all of an applied magnetic field will be excluded from the body of material (Meissner effect).
Several metallic elements including aluminium, lead, tin, and mercury belong to type-I group.
Type-II superconductors are completely diamagnetic at low applied fields, and field
exclusion is total. However the transition from the superconducting state to the normal state
is gradual and occurs between lower critical and upper critical fields, designated Hc1 & H c2
respectively, Figure.3.
Type -II
Type -I
Figure.3 Resistivity of Type-I and Type-II superconductors
The magnetic flux lines begin to penetrate into the body of the material at Hc1, and
with increasing applied magnetic field, this penetration continues; at Hc2, field penetration is
complete. For fields between Hc1 & H c2, the material exists in what is termed a mixed state
or vortex state both normal and superconducting regions are present. Type-II
superconductors are preferred over type-I for most practical applications by virtue of their
higher critical temperatures and critical magnetic fields.
The three material parameters, TC, Hc and Jc
are of extreme importance in the practical
applications of superconductivity. Figure. 4
shows schematically the boundary in
temperature magnetic field-current density
space separating normal and superconducting
states. The position of this boundary will, of
course, depend on the material. For
temperature, magnetic field, and current
density values lying between the origin
and this boundary, the material will be Figure.4 Tc,Hc,Jc separating superconducting &
superconductive; outside the boundary, normal conducting states
conduction is normal.
3.3. Characteristic properties of Superconductors
(i) Zero Resistivity, i.e. Infinite Conductivity ( ρ = 0 for all T < TC):
The d.c. (zero frequency) electrical resistance of a
superconductor at all temperatures below a critical
temperature TC is practically zero (Fig.1). In the
first approximation, the transition is not
accompanied by any change in structure of
property of the crystal lattice and has been
interpreted as an electronic phase transition. The
transition from the normal to the superconducting
state occurs sharply in pure metals but not so in
some impure, deformed and HTSC oxides. Figure.5 ρ vs T for single & multiphase HTSC
A two-step transition reflects the presence of atleast two superconducting phases. Figure.5
shows resistance versus temperature for a single and multi-phase high temperature
superconductor.
(ii) Meissner-Ochsenfeld Effect (B = O inside the superconductor):
The magnetic inductance becomes zero inside the superconductor when it is cooled in a weak
external field (Fig.2). The effect is called the Meissner-Ochsenfeld effect. The
superconducting state of a metal exists only in a particular range of temperature and field
strength. The condition for the superconducting state to exist in the metal is that some
combination of temperature and field strength should be less than a critical value.
Superconductivity of the metal will disappear if the temperature of the specimen is raised
above its Tc, or if a sufficiently strong magnetic field is employed. There always exists some
critical field Hc, above which superconductivity disappears. This field is temperature
dependent and the empirical relation which describes well this dependence is given as
where Ho is the value of Hc at 0oK.
The superconducting materials that completely expel magnetic flux until they become
completely normal are called type-I superconductors. For a type-II superconductor there are
two critical fields: the lower Hc1 and the upper Hc2 (Fig.3 ). So if applied field smaller than
Hc1, the type-II superconductor behaves just like a type-I superconductor below HC.
Above Hc1 the flux partially penetrates into the material until the upper critical field
Hc2 is reached. Above Hc2 the material returns to the normal state. Between Hc1 and Hc2 the
superconductor is said to be in a mixed state. For all applied fields Hc1 < H < Hc2 , magnetic
flux partially penetrates the superconducting specimen in the form of tiny microscope
filaments called vortices. Hence it is also said to be in vortex state. Since the super current
can flow in the mixed state through the superconducting regions between vortices, type-II
superconductors allow one to construct wires needed for high field magnets.
iii) Persistent currents lead to constant magnetic flux
An important consequence of the persistent currents that flow in materials with zero
resistance is that the magnetic flux that passes through a continuous loop of such a material
remains constant.
(iv) Perfect diamagnetism
Diamagnetism is due to currents induced in atomic orbital by an applied magnetic field.
In diamagnetic material, B = μrμ0H, with the relative permeability μ slightly less than unity.
Superconductors take the diamagnetic effect to the extreme, since in a superconductor the
field B is zero – the field is completely screened from the interior of the material. Thus the
relative permeability of a superconductor is zero.
(v) Critical magnetic field
An important characteristic of a superconductor is that its normal resistance is
restored if a sufficiently large magnetic field is applied. The nature of this transition to the
normal state depends on the shape of the superconductor and the orientation of the magnetic
field, and it is also different for pure elements and for alloys. If a sufficiently strong magnetic
field is applied to a superconductor at any temperature below Tc, it will return to the normal
state. The field at which superconductivity is destroyed is called critical magnetic field
strength (Bc). In some materials if the field is reduced keeping the temperature constant, it
returns to superconducting state. Example; Tin.
(vi) Critical current
The current density for a steady current flowing along a wire in its normal state is
essentially uniform over its cross-section. A consequence of this is that the magnetic field
strength B within a wire of radius a, carrying current I, increases linearly with distance from
the centre of the wire, and reaches a maximum value of μ0I / 2Пa at the surface of the wire.
The magnetic field strength B just outside the surface of the wire is μ0I / 2Пa. It
follows that, if the current flowing in a superconducting wire is increased, eventually the field
strength at the surface of the wire will exceed Bc and the sample will revert to its normal
state. The maximum current that a wire can carry with zero resistance is known as its critical
current.
(vii)Entropy
Entropy of all superconductors decreases considerably upon cooling below TC. The
entropy is a measure of the degree of disorder of a given system and hence this decrease in a
superconductor signifies that the superconducting state is more ordered than the normal state.
The fraction of electrons that is thermally excited in the normal state becomes ordered in the
superconducting state.
(viii)Thermal Conductivity:
The thermal conductivity of superconductors undergoes a continuous change between the two
phases and usually lowers in a superconducting phase and at very low temperatures approaches zero.
This suggests that the electronic contribution drops, the superconducting electrons possibly plays no
part in heat transfer. The thermal conductivity of tin (Tc = 3.73oK) at 2oK is 16 Wcm–1K–1 for the
superconducting phase and 34 Wcm–1K–1 for the normal phase.
(ix)Flux Quantization:
The magnetic flux threading a superconducting loop cannot have an arbitrary value; it
has to be a multiple of Φ0 = h/2e. The flux quantum is defined as
Superconducting devices can measure this tiny variation of magnetic flux which is
exceedingly important in metrology and advanced instrumentation.
Examples of superconducting materials:
s.no Material Tc (oK) Bc (Tesla)
1. Aluminium 1.18 0.0105
2 Tin 3.72 0.0305
3 Mercury 4.15 0.0411
4 Lead 7.19 0.0803
5 Niobium 9.5 0.2
6 Tungsten 0.02 0.0001
7 Titanium 0.40 0.0056
HTSC materials: Yttrium barium copper oxide, YBa2Cu3O7 (TC = 92 K) ; Bismuth (Bi) based
cuprates, Bi2Sr2Ca2Cu3O10 (TC = 110 K) and Thallium (Tl) based cuprate Tl2Ba2Ca2Cu3O10 (TC = 125
K); mercury based cuprate, HgBa2CA2O8(TC = 133 K)
3.4. Basic theories regarding superconductivity
BCS Theory
The microscopic theory of superconductivity was formulated by Bardeen, Cooper and
Schrieffer (BCS theory) in 1957. It is an elegant but mathematically complex theory,
therefore a brief discussion of the results of this theory are dealt. BCS theory is capable of
explaining the properties of conventional superconductors reasonably well.
The first clue to the basic interaction between electrons which gives rise to superconductivity
was provided by the isotope effect. Two different isotopes of the same metal exhibit different
Tc’s. Why is the mass of an atom involved in a purely electronic property? Obviously, the
motion of ions has something to do with superconductivity.
The second clue was found by Leon Cooper. He showed that a normal metal (with standard
metallic properties) could not be formed if there was a small attraction between electrons. In
such a case, two electrons would form pairs however small the attractive interaction.
One key to the understanding of the BCS theory is accepting the existence of a pair of
electrons (Cooper pair) that has a lower energy than two individual electrons. Imagine an
electron in a metal at T = 0 K (no lattice vibrations). This electron perturbs the lattice slightly
in its neighbourhood. When such an electron drifts through a crystal the perturbation is only
momentary and after passing, a displaced ion reverts back into its original position. One can
consider this ion to be held by springs in its lattice position, so that after the electron has
passed by the ion does not simply return to its original site,
but overshoots and eventually oscillates around its rest
position.
A phonon is created this phonon in turn interacts quickly
with a second electron, which takes advantage of the
deformation and lowers its energy.
Electron 2 finally emits a phonon by itself, which interacts
with the first electron and so on.
It is this passing back and forth of phonons which couples Fig.6 Cooper pair
the two electrons together and brings them into a lower energy state.
One can visualize that all electrons on the Fermi surface having opposite momentum
and opposite spin (i.e., k+ve and k -ve) form those Cooper pairs, so that these electrons form
a cloud of Cooper pairs which drift cooperatively through the crystal.
Thus, the superconducting state is an ordered state of the conduction electrons. The
scattering on the lattice atoms is eliminated, thus causing a zero resistance, as ordering of the
atoms in a crystal lattice reduces the resistivity.
The main assumptions of BCS theory are
(i) The superconducting ground state can be expressed in terms of Cooper pairs so that the
states (K+ve and K-ve) are simultaneously occupied or empty.
(ii) Various interactions in the normal and superconducting states are identical and only the
effective screened Coulomb interaction has to be considered.
(iii) The effective interaction is zero, except when two electrons of wave vectors K+ve and
K-ve have energies close to the Fermi energy.
The critical temperature (TC) of simple conventional superconductors is given by the well-
known BCS formula
Where
λep is the dimensionless electron-phonon coupling parameter. Its value for conventional
superconductors is very close to ~ 0.3.
ωD is Debye or characteristic frequency, varies from one metal to another but only over
a small range of value.
London Theory
The brothers Heinz and Fritz London (London and London, 1935) gave a phenomenological
description of the basic facts of superconductivity
Phenomena
(a) Zero resistance: No resistance is detectable even for high scattering rates of conduction
electrons.(decay time is as large as 1010years.
(b) Absence of thermoelectric effects: No See beck voltage, no Peltier heat, no Thomson
heat is detectable.
(c) Ideal diamagnetism: Weak magnetic fields are completely screened away from the bulk
of a superconductor.
(d) 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.
(e) Flux quantization: The magnetic flux through a superconducting ring is quantized and
constant in time. This phenomenon was theoretically predicted by F. London in 1950 and
experimentally verified 1961.
A simple but useful description of the electrodynamics of superconductivity was put
forward by the brothers Fritz and Heinz London in 1935. It is one of modeling of the
properties of superconductors. (Other modeling – the two fluid model, the magnetic field
model, the penetration depth model,…).
The proposed equations are consistent with the Meissner effect and can be used to
predict how the magnetic field and surface current vary with distance from the surface of a
superconductor.
London brothers proposed the following equation which relates current and magnetic field in
a superconductor.
They were introduced as a restriction on Maxwell's equations so that the behavior of
superconductors deduced from the equations was consistent with experimental observations
and in particular with the Meissner effect. The London equations lead to the prediction of an
exponential decay of the magnetic field within the superconductor.
Penetration depth
The characteristic length, λ, associated with the decay of the magnetic field at the
surface of a superconductor is known as the penetration depth, and it depends on the number
density ns of superconducting electrons.
We can estimate a value for λ by assuming that all of the free electrons are
superconducting. If we set ns = 1029 m−3, a typical free electron density in a metal, then we
find that
The small size of λ indicates that the magnetic field is effectively excluded from the
interior of macroscopic specimens of superconductors, in agreement with the experimentally
observed Meissner effect.
3.5. Applications of Superconductors
Superconducting magnets of every desired size and geometry have now been planned and
already manufactured. For equal power and uppermost field, the superconducting magnet is
much smaller than its normal counterpart made out of copper wires. Superconducting
magnets are employed not just in scientific research, in high energy and solid state physics, as
was the case in 1960’s. They are already in planning for controlled thermonuclear fusion, for
superconducting motors with output of several kilowatts, for energy storage facilities and for
the magnetic suspension of trains (Levitation trains).
Powerful magnets, super magnets, are also used in medicine for diagnostics, for e.g.
in nuclear spin tomographs. Superconducting magnets generate homogeneous, low noise and
extremely high magnetic fields. A number of manufacturers now sell 20-T superconducting
magnets with bore size in the range of 50 nm. Efforts are in process to design construct
solenoidal magnets having fields approaching 25 T using new superconducting materials,
including HTSC oxides.
Superconducting magnets seem more complicated than electromagnetic, especially
because of their requirement of low temperature to keep the magnetic solenoid in its
superconducting state. Superconducting magnet technology allows users to produce
extremely high magnetic fields without the kilowatt or megawatt power supplies needed for
electromagnets. Once superconducting magnets are energized, users can easily disconnect
them from their power source and they will remain energized which significantly reduces
electricity costs.
However, the consideration of superconductivity for large scale applications is not
limited to superconducting magnets. A great deal of effort is going into using
superconductivity for the generation and transmission of electric power. Superconducting
cables and storage elements will offer crucial advantages.
Most of these applications are based on Josephson Effect that enables the construction
of the fastest nanoscopic switches, Josephson junctions, and related device structures,
SQUIDs (Superconducting Quantum interference devices). SQUIDs explore subtle quantum
interference effects: an analysis of superconducting loop shows that the magnetic flux that
can thread the loop is quantized in quantum units of flux which have a value of 2x10–15
Weber. SQUIDs are suitably processed superconducting loops which detect minute changes
in magnetic flux, i.e. they are high sensitivity magnetic flux detectors that can be used in the
finest precision instruments at the forefront of metrology.
