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Theory of Superconductivity BCS

18/02/1957

BCS theory, in physics, a comprehensive theory developed in 1957 by the American physicists John Bardeen, Leon N. Cooper, and John R. Schrieffer (their surname initials providing the designation BCS) to explain the behaviour of superconducting materials. Superconductors abruptly lose all resistance to the flow of an electric current when they are cooled to temperatures near absolute zero.

Cooper had discovered that electrons in a superconductor are grouped in pairs, now called Cooper pairs, and that the motions of all of the Cooper pairs within a single superconductor are correlated; they constitute a system that functions as a single entity. Application of an electrical voltage to the superconductor causes all Cooper pairs to move, constituting a current. When the voltage is removed, current continues to flow indefinitely because the pairs encounter no opposition. For the current to stop, all of the Cooper pairs would have to be halted at the same time, a very unlikely occurrence. As a superconductor is warmed, its Cooper pairs separate into individual electrons, and the material becomes normal, or nonsuperconducting. The theory describes superconductivity as a microscopic effect caused by a condensation of Cooper pairs into a boson-like state. The theory is also used in nuclear physics to describe the pairing interaction between nucleons in an atomic nucleus.

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Rapid progress in the understanding of superconductivity gained momentum in the mid-1950s. It began with the 1948 paper, "On the Problem of the Molecular Theory of Superconductivity", where Fritz London proposed that the phenomenological London equations may be consequences of the coherence of a quantum state. In 1953, Brian Pippard, motivated by penetration experiments, proposed that this would modify the London equations via a new scale parameter called the coherence length. John Bardeen then argued in the 1955 paper, "Theory of the Meissner Effect in Superconductors", that such a modification naturally occurs in a theory with an energy gap. The key ingredient was Leon Cooper's calculation of the bound states of electrons subject to an attractive force in his 1956 paper, "Bound Electron Pairs in a Degenerate Fermi Gas".

In 1957 Bardeen and Cooper assembled these ingredients and constructed such a theory, the BCS theory, with Robert Schrieffer. The theory was first published in April 1957 in the letter, "Microscopic theory of superconductivity". The demonstration that the phase transition is second order, that it reproduces the Meissner effect and the calculations of specific heats and penetration depths appeared in the December 1957 article, "Theory of superconductivity".They received the Nobel Prize in Physics in 1972 for this theory.

In 1986, high-temperature superconductivity was discovered in some materials at temperatures up to about 130 K, considerably above the previous limit of about 30 K. It is believed that BCS theory alone cannot explain this phenomenon and that other effects are in play. These effects are still not yet fully understood; it is possible that they even control superconductivity at low temperatures for some materials.

At sufficiently low temperatures, electrons near the Fermi surface become unstable against the formation of Cooper pairs. Cooper showed such binding will occur in the presence of an attractive potential, no matter how weak. In conventional superconductors, an attraction is generally attributed to an electron-lattice interaction. The BCS theory, however, requires only that the potential be attractive, regardless of its origin. In the BCS framework, superconductivity is a macroscopic effect which results from the condensation of Cooper pairs. These have some bosonic properties, and bosons, at sufficiently low temperature, can form a large Bose–Einstein condensate. Superconductivity was simultaneously explained by Nikolay Bogolyubov, by means of the Bogoliubov transformations.

In many superconductors, the attractive interaction between electrons (necessary for pairing) is brought about indirectly by the interaction between the electrons and the vibrating crystal lattice (the phonons). Roughly speaking the picture is the following:

An electron moving through a conductor will attract nearby positive charges in the lattice. This deformation of the lattice causes another electron, with opposite spin, to move into the region of higher positive charge density. The two electrons then become correlated. Because there are a lot of such electron pairs in a superconductor, these pairs overlap very strongly and form a highly collective condensate. In this "condensed" state, the breaking of one pair will change the energy of the entire condensate - not just a single electron, or a single pair. Thus, the energy required to break any single pair is related to the energy required to break all of the pairs (or more than just two electrons). Because the pairing increases this energy barrier, kicks from oscillating atoms in the conductor (which are small at sufficiently low temperatures) are not enough to affect the condensate as a whole, or any individual "member pair" within the condensate. Thus the electrons stay paired together and resist all kicks, and the electron flow as a whole (the current through the superconductor) will not experience resistance. Thus, the collective behavior of the condensate is a crucial ingredient necessary for superconductivity.


Eletron-Phonon interaction.
Phonon interaction.

BCS theory starts from the assumption that there is some attraction between electrons, which can overcome the Coulomb repulsion. In most materials (in low temperature superconductors), this attraction is brought about indirectly by the coupling of electrons to the crystal lattice (as explained above). However, the results of BCS theory do not depend on the origin of the attractive interaction. For instance, Cooper pairs have been observed in ultracold gases of fermions where a homogeneous magnetic field has been tuned to their Feshbach resonance. The original results of BCS (discussed below) described an s-wave superconducting state, which is the rule among low-temperature superconductors but is not realized in many unconventional superconductors such as the d-wave high-temperature superconductors.

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Extensions of BCS theory exist to describe these other cases, although they are insufficient to completely describe the observed features of high-temperature superconductivity.

BCS is able to give an approximation for the quantum-mechanical many-body state of the system of (attractively interacting) electrons inside the metal. This state is now known as the BCS state. In the normal state of a metal, electrons move independently, whereas in the BCS state, they are bound into Cooper pairs by the attractive interaction. The BCS formalism is based on the reduced potential for the electrons' attraction. Within this potential, a variational ansatz for the wave function is proposed. This ansatz was later shown to be exact in the dense limit of pairs. Note that the continuous crossover between the dilute and dense regimes of attracting pairs of fermions is still an open problem, which now attracts a lot of attention within the field of ultracold gases.


Underlying evidence

  • Evidence of a band gap at the Fermi level (described as "a key piece in the puzzle")

The existence of a critical temperature and critical magnetic field implied a band gap, and suggested a phase transition, but single electrons are forbidden from condensing to the same energy level by the Pauli exclusion principle. The site comments that "a drastic change in conductivity demanded a drastic change in electron behavior". Conceivably, pairs of electrons might perhaps act like bosons instead, which are bound by different condensate rules and do not have the same limitation.

  • Isotope effect on the critical temperature, suggesting lattice interactions

The Debye frequency of phonons in a lattice is proportional to the inverse of the square root of the mass of lattice ions. It was shown that the superconducting transition temperature of mercury indeed showed the same dependence, by substituting natural mercury 202Hg with a different isotope 198Hg.

  • An exponential rise in heat capacity near the critical temperature for some superconductors

An exponential increase in heat capacity near the critical temperature also suggests an energy bandgap for the superconducting material. As superconducting vanadium is warmed toward its critical temperature, its heat capacity increases massively in a very few degrees; this suggests an energy gap being bridged by thermal energy.

  • The lessening of the measured energy gap towards the critical temperature

This suggests a type of situation where some kind of binding energy exists but it is gradually weakened as the critical temperature is approached. A binding energy suggests two or more particles or other entities that are bound together in the superconducting state. This helped to support the idea of bound particles - specifically electron pairs - and together with the above helped to paint a general picture of paired electrons and their lattice interactions.


Implications

BCS derived several important theoretical predictions that are independent of the details of the interaction, since the quantitative predictions mentioned below hold for any sufficiently weak attraction between the electrons and this last condition is fulfilled for many low temperature superconductors - the so-called weak-coupling case. These have been confirmed in numerous experiments:

The electrons are bound into Cooper pairs, and these pairs are correlated due to the Pauli exclusion principle for the electrons, from which they are constructed. Therefore, in order to break a pair, one has to change energies of all other pairs. This means there is an energy gap for single-particle excitation, unlike in the normal metal (where the state of an electron can be changed by adding an arbitrarily small amount of energy). This energy gap is highest at low temperatures but vanishes at the transition temperature when superconductivity ceases to exist. The BCS theory gives an expression that shows how the gap grows with the strength of the attractive interaction and the (normal phase) single particle density of states at the Fermi level. Furthermore, it describes how the density of states is changed on entering the superconducting state, where there are no electronic states any more at the Fermi level. The energy gap is most directly observed in tunneling experiments and in reflection of microwaves from superconductors.

BCS theory predicts the dependence of the value of the energy gap Δ at temperature T on the critical temperature Tc. The ratio between the value of the energy gap at zero temperature and the value of the superconducting transition temperature (expressed in energy units) takes the universal value

∆(T = 0) = 1.764KBTc

independent of material. Near the critical temperature the relation asymptotes to

∆(T → Tc) ≈ 3.07KBTc √(1 – T/Tc)

which is of the form suggested the previous year by M. J. Buckingham based on the fact that the superconducting phase transition is second order, that the superconducting phase has a mass gap and on Blevins, Gordy and Fairbank's experimental results the previous year on the absorption of millimeter waves by superconducting tin.

Due to the energy gap, the specific heat of the superconductor is suppressed strongly (exponentially) at low temperatures, there being no thermal excitations left. However, before reaching the transition temperature, the specific heat of the superconductor becomes even higher than that of the normal conductor (measured immediately above the transition) and the ratio of these two values is found to be universally given by 2.5.

BCS theory correctly predicts the Meissner effect, i.e. the expulsion of a magnetic field from the superconductor and the variation of the penetration depth (the extent of the screening currents flowing below the metal's surface) with temperature. This had been demonstrated experimentally by Walther Meissner and Robert Ochsenfeld in their 1933 article Ein neuer Effekt bei Eintritt der Supraleitfähigkeit.

It also describes the variation of the critical magnetic field (above which the superconductor can no longer expel the field but becomes normal conducting) with temperature. BCS theory relates the value of the critical field at zero temperature to the value of the transition temperature and the density of states at the Fermi level.

In its simplest form, BCS gives the superconducting transition temperature Tc in terms of the electron-phonon coupling potential V and the Debye cutoff energy ED:

KBTc = 1.13EDe-1/N(0)V

where N(0) is the electronic density of states at the Fermi level. For more details, see Cooper pairs.

The BCS theory reproduces the isotope effect, which is the experimental observation that for a given superconducting material, the critical temperature is inversely proportional to the mass of the isotope used in the material. The isotope effect was reported by two groups on 24 March 1950, who discovered it independently working with different mercury isotopes, although a few days before publication they learned of each other's results at the ONR conference in Atlanta. The two groups are Emanuel Maxwell, who published his results in Isotope Effect in the Superconductivity of Mercury and C. A. Reynolds, B. Serin, W. H. Wright, and L. B. Nesbitt who published their results 10 pages later in Superconductivity of Isotopes of Mercury. The choice of isotope ordinarily has little effect on the electrical properties of a material, but does affect the frequency of lattice vibrations. This effect suggests that superconductivity is related to vibrations of the lattice. This is incorporated into BCS theory, where lattice vibrations yield the binding energy of electrons in a Cooper pair.

Little-Parks experiment - One of the first indications to the importance of the Cooper-pairing principle.

Many other aspects of the behaviour of superconductors are explained by the BCS theory. The theory supplies a means by which the energy required to separate the Cooper pairs into their individual electrons can be measured experimentally. The BCS theory also explains the isotope effect, in which the temperature at which superconductivity appears is reduced if heavier atoms of the elements making up the material are introduced.

Little-Parks experiment

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REFERENCES

Instituto de Física da Universidade de Campinas. Available in: https://portal.ifi.unicamp.br/images/files/graduacao/aulas-on-line/fen-emerg/lecture_notes_BCS.pdf. Access in: 20/10/2018.

Encyclopaedia Britannica. Available in: https://www.britannica.com/science/BCS-theory. Access in: 20/10/2018.

Wikipedia. Available in: https://en.wikipedia.org/wiki/BCS_theory. Access in: 20/10/2018.

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Published in 21/10/2018

Updated in 19/02/2021

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