Indian Institute of Science Education & Research, Kolkata 14th December 2010

John Bardeen, Leon N. Copper & John R. Schrieffer’s

Theory of Superconductivity
Harsh Purwar (07MS – 76)
4th Year, Integrated M.S. (Physics)
Indian Institute of Science Education and Research, Kolkata

Seminar Course (SM – 411) Submitted on: December 14, 2010

Abstract

This report discusses some of the main features of the so called BCS Theory proposed John
Bardeen, Leon N. Cooper and John R. Schrieffer in 1957. Some of the phenomenological theories
proposed by Ginzburg and Landau and London Brothers to explain the experimental facts are also
briefly discussed. Finally some of the major predictions of the BCS theory are highlighted.

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Indian Institute of Science Education & Research, Kolkata 14th December 2010
Contents
Abstract .............................................................................................................................................................. 1
Superconductivity – General Discussion ............................................................................................................ 3

FEW CHARACTERISTIC PROPERTIES OF SUPERCONDUCTORS ......................................................................................... 3

CLASSIFICATION OF SUPERCONDUCTORS .................................................................................................................. 4
CRITICAL TEMPERATURE ....................................................................................................................................... 5

London Equations .............................................................................................................................................. 5

Ginzburg – Landau Theory ................................................................................................................................. 6
Cooper Pairs ....................................................................................................................................................... 7
BCS Ground State ............................................................................................................................................... 8
Quantitative Predictions of the Elementary Microscopic Theory ..................................................................... 8

CRITICAL TEMPERATURE ....................................................................................................................................... 8

ENERGY GAP ...................................................................................................................................................... 9
CRITICAL FIELD ................................................................................................................................................... 9
SPECIFIC HEAT .................................................................................................................................................... 9

Works Cited ...................................................................................................................................................... 10

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Superconductivity – General Discussion

Superconductivity is an electrical resistance of exactly zero which occurs in certain materials below a
characteristic temperature ( ). It was discovered by Heike Kamerlingh Onnes in 1911. It is also
characterized by a phenomenon called the Meissner effect (Figure 1), the ejection of any sufficiently weak
magnetic field from the interior of the superconductor as it transitions into the superconducting state. The
occurrence of the Meissner effect indicates that superconductivity cannot be understood simply as the
idealization of "perfect conductivity" in classical physics.

Figure 1: A magnet levitating above a high-temperature superconductor,

cooled with liquid nitrogen. Persistent electric current flows on the surface
of the superconductor, acting to exclude the magnetic field of the magnet
(the Faraday's law of induction). This current effectively forms an
electromagnet that repels the magnet.

The electrical resistivity of a metallic conductor decreases gradually as the temperature is lowered.
However, in ordinary conductors such as copper and silver, this decrease is limited by impurities and other
defects. Even near absolute zero, a real sample of copper shows some resistance. Despite these
imperfections, in a superconductor the resistance drops abruptly to zero when the material is cooled
below its critical temperature. An electric current flowing in a loop of superconducting wire can persist
indefinitely with no power source.
Superconductivity occurs in many materials: simple elements like tin and aluminum, various
metallic alloys and some heavily-doped semiconductors. Superconductivity does not occur in noble metals
like gold and silver, or in pure samples of ferromagnetic metals.
In 1986, it was discovered that some cuprate-perovskite ceramic materials have critical
temperatures above 90 K (−183.15 °C). These high-temperature superconductors renewed interest in the
topic because of the prospects for improvement and potential room-temperature superconductivity. From
a practical perspective, even 90 K is relatively easy to reach with the readily available liquid nitrogen
(boiling point 77 K), resulting in more experiments and applications.

FEW CHARACTERISTIC PROPERTIES OF SUPERCONDUCTORS

The characteristic properties of metals in the superconducting state appear highly anomalous when
regarded from the point of view of the independent electron approximation. The most striking features (1)
of a superconductor are:

 A superconductor can behave as if it had no measurable DC electrical resistivity. Currents have

been established in superconductors which, in the absence of any driving field, have nevertheless
shown no discernible decay for as long as people have had the patience to watch.
 A superconductor can behave as a perfect diamagnet. A sample in thermal equilibrium in an applied
magnetic field, provided the field is not too strong, carries electrical surface currents. These

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currents give rise to an additional magnetic field that precisely cancels the applied magnetic field in
the interior of the superconductor.
 A superconductor usually behaves as if there were a gap in energy of width centered about the
Fermi energy, in the set of allowed one-electron levels. Thus an electron of energy can be
accommodated by (or extracted from) a superconductor only if | | exceeds . The energy gap
increases in size as the temperature drops, leveling off to a maximum value ( ) at very low
temperatures.

CLASSIFICATION OF SUPERCONDUCTORS
Superconductors can be classified in accordance with several criteria that depend on our interest in their
physical properties, on the understanding we have about them, on how expensive is cooling them or on
the material they are made of.

Based on their physical properties:

 Type I superconductors: Those having just one critical field, , and changing abruptly from one
state to the other when it is reached.
 Type II superconductors: Having two critical fields, and , being a perfect superconductor
under the lower critical field ( ) and leaving completely the superconducting state above the
upper critical field ( ), being in a mixed state when between the critical fields.

Based on the understanding we have about them:

 Conventional superconductors: Those that can be fully explained with the BCS theory or related
theories.
 Unconventional superconductors: Those that failed to be explained using such theories like iron
based superconductors.
This criterion is important, as the BCS theory is explaining the properties of conventional superconductors
since 1957, but on the other hand there have been no satisfactory theory to explain fully unconventional
superconductors. In most of cases type I superconductors are conventional, but there are several
exceptions as Niobium, which is both conventional and type II.

Based on their critical temperatures:

 Low-temperature superconductors or LTS: Those whose critical temperature is below 77K.

 High-temperature superconductors or HTS: Those whose critical temperature is above 77K.
This criterion is used when we want to emphasize whether or not we can cool the sample with liquid
nitrogen (whose boiling point is 77K), which is much more feasible than liquid helium (the alternative to
achieve the temperatures needed to get low-temperature superconductors).

Based on the Material:

 Some Pure elements, such as lead or mercury (but not all pure elements, as some never reach the
superconducting phase).
 Some allotropes of carbon, such as fullerenes, nanotubes, diamond or intercalated graphite.
Most superconductors made of pure elements are type I (except niobium, technetium, vanadium, silicon
and the above mentioned carbons).

 Alloys, such as Niobium-titanium (NbTi), whose superconducting properties where discovered in

1962.
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Ceramics, which include the YBCO family, which are several yttrium-barium-copper oxides, especially
YBa2Cu3O7. They are the most famous high-temperature superconductors. Magnesium di-boride (MgB2),
whose critical temperature is 39 K (2), being the conventional superconductor with the highest known .

CRITICAL TEMPERATURE
The transition to the superconducting state is a sharp one in bulk specimens. Above a critical temperature
the properties of the metal are completely normal; below , superconducting properties are displayed,
the most dramatic of which is the absence of any measurable DC electrical resistance. Measured critical
temperatures range from a few milli-degrees Kelvin up to a little over 50 K. The corresponding thermal
energy , varies from about – eV up to a few thousandths of an electron volt.

London Equations

Fritz London & Heinz London first examined in a quantitative way that a metal in the superconducting state
permits no magnetic field in its interior. Their analysis starts with the two-fluid model of Gorter and Casimir
with the assumption that in a superconductor at temperature , only a fraction ( ) of the total
number of conduction electrons are capable of participating in a super-current, where the quantity ( )
is the density of superconducting electrons. It approaches the full electron density as falls well below
, but drops to zero as rises to . The remaining fraction of electrons are assumed to constitute a
‘normal fluid’ of density , that cannot carry an electric current without normal dissipation. The
normal current and the super-current are assumed to flow in parallel; since the later flows with no
resistance whatever, it will carry the entire current induced by any small transitory electric field, and the
normal electrons will remain quite inert and are therefore ignored in the discussion that follows.
A momentary electric field ( ) arising within a superconductor will accelerate the superconducting
electrons freely without any dissipation and their mean velocity will satisfy,
⃗⃗⃗
⃗ ( )
The current density carried by these electrons is given by,
⃗⃗⃗
⃗⃗⃗ ( )
Substituting it back in equation ( ) we get,
⃗ ( )

⃗ ( )
Equation ( ) is known as the 1st London equation. Substituting ( ) into the Faraday’s law of induction
or one of the Maxwell’s equations given by,
⃗
⃗ ⃗
we get,
⃗
⃗

(⃗ ⃗) ( )
Above relation together with the following Maxwell’s equation,
⃗ ⃗ ( )
determines the magnetic fields and current densities that can exist within a perfect conductor.
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Now note that any static field ⃗ determines a static current density through equation ( ). Since any time-
independent ⃗ and are trivial solutions of equation ( ), the two equations are consistent with an
arbitrary static magnetic field. This is incompatible with the observed behavior of superconductors, which
permit no fields in their interior. London brothers discovered that this characteristic behavior of
superconductors could be obtained by restricting the full set of solutions of equation ( ) to those that
obey,
⃗ ⃗ ( )
Equation ( ) is known as the 2nd London equation. This equation characterizes superconductors and
distinguishes them from mere “perfect conductors”.
The reason for replacing ( ) by more restrictive London equation ( ) is that the latter leads directly to the
Meissner effect. From equation ( ) we have,
⃗ (⃗ ⃗) (⃗ ⃗ )⃗ ⃗ ⃗
Divergence of magnetic field is zero (from Maxwell’s equation) implies,
⃗ ⃗
Using ( ) this becomes,
⃗ ⃗ ( )
Following similar manipulation starting from ( ) this time,
⃗ (⃗ ) (⃗ )⃗ ⃗ ⃗
Again ⃗ and using ( ) then this becomes,
( )
Equation ( ) and ( ) predict that currents and magnetic fields in superconductors can exist only within a
layer of thickness of the surface, where is known as the London penetration depth and is given by,

√( )

Thus the London equation implies the Meissner effect, along with a specific picture of the surface currents
that screen out the applied field. These currents occur within a surface layer of thickness
well below .
Note: The thickness can be much greater near where approaches to zero.

Ginzburg – Landau Theory

Landau and Ginzburg asserted that the superconducting state could be characterized by a complex “order
parameter” ( ), which vanishes above and whose magnitude measures the degree of superconducting
order at position below . From the perspective of the BCS theory order parameter can be viewed as a
one particle wave function describing the position of the center of mass of a Cooper pair. Since all Cooper
pairs are in the same two-electron state a single function suffices.
In the ground state of the superconductor each pair is in a translationally invariant state that does not
depend on the center of mass coordinate; i.e. the order parameter is a constant. The order parameter
develops interesting structure when current flows, or when an applied field appears. A fundamental
assumption of this theory is that the current flowing in a superconductor is characterized by the order
parameter ( ) in the presence of a magnetic field given by the vector potential ( ) is given by the

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ordinary quantum mechanical formula for the current due to a particle of charge and mass (that is
Cooper pair itself) described by a wave function ( ), namely,

* {( ⃗ ) } {( ⃗ ) } + ( )
The London equation ( ) follows from ( ) provided it is assumed that the significant spatial variation of
the order parameter | | is through the phase and not the magnitude | |. Since the magnitude
of the order parameter measures the degree of the superconducting ordering, this assumption restricts
consideration to disturbances in which the density of Cooper pairs is not appreciably altered from its
uniform thermal equilibrium value. This is the case where the pairs are allowed to flow but not accumulate
or be destroyed.

Cooper Pairs

The microscopic theory of superconductivity proposed by BCS requires a net attractive interaction
between the electrons in the neighborhood of the Fermi surface. Although the direct electrostatic
interaction is repulsive, it is possible for the ionic motion to over screen the Coulomb interaction to a net
attraction. This idea was presented by Leon N. Cooper in 1956. He showed that the Fermi sea of electrons
is unstable against the formation of at least one bound pair regardless of how weak the interaction is, as
long as it is attractive. This is a consequence of the Fermi statistics and of the existence of the Fermi sea
background.
Consider a simple model of two electrons added to a Fermi sea at , with the stipulation at the extra
electrons interact with each other but not with those in the sea, except via the exclusion principle. Now
since the lowest energy state must have zero total angular momentum, the two electron will have equal
and opposite momenta. This suggests building up of an orbital wave function of the form,
⃗ ⃗⃗⃗⃗ ⃗ ⃗⃗⃗⃗
(⃗⃗⃗ ⃗⃗⃗ ) ∑

Taking into account the anti-symmetry of the total wave function with respect to the exchange of the two
electrons, is converted either to the sum of products of ⃗ (⃗⃗⃗ ⃗⃗⃗ ) with the anti-symmetric singlet
spin function ( ) or to a sum of products of ⃗ (⃗⃗⃗ ⃗⃗⃗ ) with one of the symmetric triplet
spin functions ( ). (Note in these expressions refers to the up spin state of the
particle and to its down spin state.) Anticipating an attractive interaction, singlet state is preferred as
cosinusoidal dependence of its orbital wave function on ⃗⃗⃗ ⃗⃗⃗ gives larger probability amplitude for the
electrons to be near each other. Thus we have,

(⃗⃗⃗ ⃗⃗⃗ ) [∑ ⃗ (⃗⃗⃗ ⃗⃗⃗ )] ( ) ( )

Inserting ( ) in the Schrodinger equation,

(⃗ ⃗ ) ( ) ( ) ( )
where is the eigenvalue of the pair, gives,
∑

( ) ∑ ( )

In the expression are the unperturbed plane wave energies and are the matrix elements of the
interaction potential,
( )
∫ ( )

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where is the distance between the two electrons and is the normalization volume.
characterizes the strength of the potential for scattering a pair of electrons with momenta ( ) to
momenta ( ).
Since it is hard to analyze this situation for general Cooper introduced the very serviceable
approximation that all for states out to a cutoff energy away from and that
beyond . Then the right hand side of ( ) is a constant and we get,
∑
( )
Summing both sides and cancelling ∑ we get,
∑ ( )

Now replacing the summation by integration with ( ) representing the density of states at the Fermi
level for electrons of one spin orientation, we get,
( )∫
( )
( ) ( )
In most classic superconductors it is found that ( ) . This allows use of the so called weak
coupling approximation, valid for ( ) , in which the solution to the preceding equation can be
written as,
( )
⏟ ( )

Clearly, , remember is the energy eigenvalue of the Cooper pair each of whose electrons have
energy . So indeed there is a bound state with negative energy with respect to the Fermi surface. The
contribution to the energy of the attractive potential outweighs this access kinetic energy, leading to
binding regardless of how small is. Note that the form of the binding energy is not analytic at ; i.e.
it cannot be expanded in the powers of . As a result it cannot be obtained by the perturbation theory.

BCS Ground State

The BCS approximation to the electronic ground state wave function can be described as follows: Group
the electrons into pairs and let each pair be described by a bound state wave function ( ),
where is the electronic position and is the spin quantum number. Then consider the electron wave
function that is just the product of identical such two-electron wave functions:
( ) ( ) ( ) ( )
This describes a state in which all electrons are bound, in pairs, into identical two electron states. However
it lacks symmetry required by the Pauli’s principle. To construct a state that changes sign whenever the
space and spin coordinates of any two electrons are interchanged, we must anti-symmetrize the state. This
leads to the BCS ground state,

Quantitative Predictions of the Elementary Microscopic Theory

CRITICAL TEMPERATURE
In zero magnetic field, superconducting ordering sets in at a critical temperature given by,
( )

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where is the density of the electronic levels for a single spin population in the normal metal.
Because of the exponential dependence the effective coupling cannot be determined precisely enough
to permit very accurate computations of the . However this exponential dependence accounts for the
very low critical temperatures.

ENERGY GAP
Zero temperature energy gap is predicted using the following formula,
( ) ( )
This result appears to hold for a large number of superconductors to within about 10 percent. Those for
which it fails tend systematically to deviate from the other predictions of the simple theory as well, and can
be brought closer into line with theoretical predictions by using the more elaborate analysis of the strong
coupling theory.
The elementary theory also predicts that near the critical temperature the energy gap vanishes according
to the universal law,
( )
( )
( )

CRITICAL FIELD
The elementary BCS prediction for ( ) is often expressed in terms of the deviation from the empirical
law,
( )
( )
( )
The quantity [ ( )⁄ ( )] [ ( ⁄ ) ] is shown for several superconductors in Figure below along
with the BCS prediction. The departure is small in all cases, but note that the strong-coupling
superconductors lead and mercury are more out of line than the others.

SPECIFIC HEAT
At the critical temperature (in zero magnetic field) BCS theory predicts a discontinuity in the specific heat,
| |

The aggrement of this prediction is again good to about 10 pecent except the strong-coupling supCs.
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The low-temperature electronic specific heat can be written as,
( ) ( )
( ) ( )
where is the coefficient of the linear term in the specific heat of metal in the normal state.

Works Cited

1. Ashcroft, Neil W. and Mermin, N. David. Solid State Physics. [ed.] Dorothy Garbose Crane. College
Edition. s.l. : Harcourt College Publisher, 1976. pp. 725-755. ISBN: 0030839939.
2. Superconductivity at 39 K in magnesium diboride. Nagamatsu, Jun, et al., et al. s.l. : Nature, February 5,
2001, Nature, Vol. 410, pp. 63-64. doi:10.1038/35065039.
3. London Equation. Wikipedia.org. [Online] Wikipedia.org. http://en.wikipedia.org/London_Equation.
4. Theory of Superconductivity. Bardeen, John, Cooper, L. N. and Schrieffer, J. R. 5, Illinois : s.n., December
1, 1957, Physical Review, Vol. 108, pp. 1175-1204.
5. Microscopic Theory of Suoerconductivity. Bardeen, J., Cooper, L. N. and Schrieffer, J. R. Illinois : s.n.,
Feburary 18, 1957, Letters to the Editor, pp. 162-164.
6. Electron - Phonon Interaction in Metals. Bardeen, John and Pines, David. 4, Illinois : s.n., August 15,
1955, Physical Review, Vol. 99, pp. 1140-1150.
7. Bound Electron Pairs in a Degenerate Fermi Gas. Cooper, Leon N. 4, Illinois : s.n., November 15, 1956,
Physical Review, Vol. 104, pp. 1189-1190.
8. Tinkham, Michael. Introduction to Superconductivity. 2nd. s.l. : McGraw Hill, 1996. pp. 43-71.
0070648786.
9. Kittel, C. Introduction to Solid State Physics. 8th. s.l. : John Wiley & Sons, 2005. 047141256X.

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