Superconductivity is a phenomenon occurring in certain materials generally at very low temperatures, characterized by exactly zero electrical resistance and the exclusion of the interior magnetic field (the Meissner effect).
The electrical resistivity of a metallic conductor decreases gradually as the temperature is lowered. However, in ordinary conductors such as copper and silver, impurities and other defects impose a lower limit. Even near absolute zero a real sample of copper shows a non-zero resistance. The resistance of a superconductor, on the other hand, 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. Like ferromagnetism and atomic spectral lines, superconductivity is a quantum mechanical phenomenon. It cannot be understood simply as the idealization of " perfect conductivity" in classical physics.
Superconductivity occurs in a wide variety of materials, including simple elements like tin and aluminium, various metallic alloys and some heavily- doped semiconductors. Superconductivity does not occur in noble metals like gold and silver, nor in pure samples of ferromagnetic metals.
In 1986 the discovery of a family of cuprate- perovskite ceramic materials known as high-temperature superconductors, with critical temperatures in excess of 90 Kelvin, spurred renewed interest and research in superconductivity for several reasons. As a topic of pure research, these materials represented a new phenomenon not explained by the current theory. And, because the superconducting state persists up to more manageable temperatures, past the economically-important boiling point of liquid nitrogen (77 Kelvin), more commercial applications are feasible, especially if materials with even higher critical temperatures could be discovered.
For history of superconductivity see here.
Elementary properties of superconductors
Most of the physical properties of superconductors vary from material to material, such as the heat capacity and the critical temperature, critical field, and critical current density at which superconductivity is destroyed.
On the other hand, there is a class of properties that are independent of the underlying material. For instance, all superconductors have exactly zero resistivity to low applied currents when there is no magnetic field present. The existence of these "universal" properties implies that superconductivity is a thermodynamic phase, and thus possess certain distinguishing properties which are largely independent of microscopic details.
Zero electrical "dc" resistance
The simplest method to measure the electrical resistance of a sample of some material is to place it in an electrical circuit in series with a current source I and measure the resulting voltage V across the sample. The resistance of the sample is given by Ohm's law as . If the voltage is zero, this means that the resistance is zero and that the sample is in the superconducting state.
Superconductors are also able to maintain a current with no applied voltage whatsoever, a property exploited in superconducting electromagnets such as those found in MRI machines. Experiments have demonstrated that currents in superconducting coils can persist for years without any measurable degradation. Experimental evidence points to a current lifetime of at least 100,000 years, and theoretical estimates for the lifetime of a persistent current exceed the estimated lifetime of the universe.
In a normal conductor, an electrical current may be visualized as a fluid of electrons moving across a heavy ionic lattice. The electrons are constantly colliding with the ions in the lattice, and during each collision some of the energy carried by the current is absorbed by the lattice and converted into heat, which is essentially the vibrational kinetic energy of the lattice ions. As a result, the energy carried by the current is constantly being dissipated. This is the phenomenon of electrical resistance.
The situation is different in a superconductor. In a conventional superconductor, the electronic fluid cannot be resolved into individual electrons. Instead, it consists of bound pairs of electrons known as Cooper pairs. This pairing is caused by an attractive force between electrons from the exchange of phonons. Due to quantum mechanics, the energy spectrum of this Cooper pair fluid possesses an energy gap, meaning there is a minimum amount of energy ΔE that must be supplied in order to excite the fluid. Therefore, if ΔE is larger than the thermal energy of the lattice, given by kT, where k is Boltzmann's constant and T is the temperature, the fluid will not be scattered by the lattice. The Cooper pair fluid is thus a superfluid, meaning it can flow without energy dissipation.
In a class of superconductors known as Type II superconductors, including all known high-temperature superconductors, an extremely small amount of resistivity appears at temperatures not too far below the nominal superconducting transition when an electrical current is applied in conjunction with a strong magnetic field, which may be caused by the electrical current. This is due to the motion of vortices in the electronic superfluid, which dissipates some of the energy carried by the current. If the current is sufficiently small, the vortices are stationary, and the resistivity vanishes. The resistance due to this effect is tiny compared with that of non-superconducting materials, but must be taken into account in sensitive experiments. However, as the temperature decreases far enough below the nominal superconducting transition, these vortices can become frozen into a disordered but stationary phase known as a "vortex glass". Below this vortex glass transition temperature, the resistance of the material becomes truly zero.
Superconducting phase transition
In superconducting materials, the characteristics of superconductivity appear when the temperature T is lowered below a critical temperature Tc. The value of this critical temperature varies from material to material. Conventional superconductors usually have critical temperatures ranging from around 20 K (Kelvin) to less than 1 K. Solid mercury, for example, has a critical temperature of 4.2 K. As of 2001, the highest critical temperature found for a conventional superconductor is 39 K for magnesium diboride (MgB2), although this material displays enough exotic properties that there is doubt about classifying it as a "conventional" superconductor. Cuprate superconductors can have much higher critical temperatures: YBa2Cu3O7, one of the first cuprate superconductors to be discovered, has a critical temperature of 92 K, and mercury-based cuprates have been found with critical temperatures in excess of 130 K. The explanation for these high critical temperatures remains unknown. Electron pairing due to phonon exchanges explains superconductivity in conventional superconductors, but it does not explain superconductivity in the newer superconductors that have a very high critical temperature.
The onset of superconductivity is accompanied by abrupt changes in various physical properties, which is the hallmark of a phase transition. For example, the electronic heat capacity is proportional to the temperature in the normal (non-superconducting) regime. At the superconducting transition, it suffers a discontinuous jump and thereafter ceases to be linear. At low temperatures, it varies instead as e−α /T for some constant α. This exponential behaviour is one of the pieces of evidence for the existence of the energy gap.
The order of the superconducting phase transition was long a matter of debate. Experiments indicate that the transition is second-order, meaning there is no latent heat. Calculations in the 1970s suggested that it may actually be weakly first-order due to the effect of long-range fluctuations in the electromagnetic field. Only recently it was shown theoretically with the help of a disorder field theory, in which the vortex lines of the superconductor play a major role, that the transition is of second order within the type II regime and of first order (i.e., latent heat) within the type I regime, and that the two regions are separated by a tricritical point.
When a superconductor is placed in a weak external magnetic field H, the field penetrates the superconductor for only a short distance λ, called the London penetration depth, after which it decays rapidly to zero. This is called the Meissner effect, and is a defining characteristic of superconductivity. For most superconductors, the London penetration depth is on the order of 100 nm.
The Meissner effect is sometimes confused with the kind of diamagnetism one would expect in a perfect electrical conductor: according to Lenz's law, when a changing magnetic field is applied to a conductor, it will induce an electrical current in the conductor that creates an opposing magnetic field. In a perfect conductor, an arbitrarily large current can be induced, and the resulting magnetic field exactly cancels the applied field.
The Meissner effect is distinct from this because a superconductor expels all magnetic fields, not just those that are changing. Suppose we have a material in its normal state, containing a constant internal magnetic field. When the material is cooled below the critical temperature, we would observe the abrupt expulsion of the internal magnetic field, which we would not expect based on Lenz's law.
The Meissner effect was explained by the brothers Fritz and Heinz London, who showed that the electromagnetic free energy in a superconductor is minimized provided
where H is the magnetic field and λ is the London penetration depth.
This equation, which is known as the London equation, predicts that the magnetic field in a superconductor decays exponentially from whatever value it possesses at the surface.
The Meissner effect breaks down when the applied magnetic field is too large. Superconductors can be divided into two classes according to how this breakdown occurs. In Type I superconductors, superconductivity is abruptly destroyed when the strength of the applied field rises above a critical value Hc. Depending on the geometry of the sample, one may obtain an intermediate state consisting of regions of normal material carrying a magnetic field mixed with regions of superconducting material containing no field. In Type II superconductors, raising the applied field past a critical value Hc1 leads to a mixed state in which an increasing amount of magnetic flux penetrates the material, but there remains no resistance to the flow of electrical current as long as the current is not too large. At a second critical field strength Hc2, superconductivity is destroyed. The mixed state is actually caused by vortices in the electronic superfluid, sometimes called fluxons because the flux carried by these vortices is quantized. Most pure elemental superconductors, except niobium, technetium, vanadium and carbon nanotubes, are Type I, while almost all impure and compound superconductors are Type II.
Conversely, a spinning superconductor generates a magnetic field, precisely aligned with the spin axis. The effect, the London moment, was put to good use in Gravity Probe B. This experiment measured the magnetic fields of four superconducting gyroscopes to determine their spin axes. This was critical to the experiment since it is one of the few ways to accurately determine the spin axis of an otherwise featureless sphere.
Theories of superconductivity
Since the discovery of superconductivity, great efforts have been devoted to finding out how and why it works. During the 1950s, theoretical condensed matter physicists arrived at a solid understanding of "conventional" superconductivity, through a pair of remarkable and important theories: the phenomenological Ginzburg-Landau theory (1950) and the microscopic BCS theory (1957). Generalizations of these theories form the basis for understanding the closely related phenomenon of superfluidity, because they fall into the Lambda transition universality class, but the extent to which similar generalizations can be applied to unconventional superconductors as well is still controversial. The four-dimensional extension of the Ginzburg-Landau theory, the Coleman-Weinberg model, is important in quantum field theory and cosmology.
History of superconductivity
Superconductivity was discovered in 1911 by Heike Kamerlingh Onnes, who was studying the resistance of solid mercury at cryogenic temperatures using the recently-discovered liquid helium as a refrigerant. At the temperature of 4.2 K, he observed that the resistance abruptly disappeared. In subsequent decades, superconductivity was found in several other materials. In 1913, lead was found to superconduct at 7 K, and in 1941 niobium nitride was found to superconduct at 16 K.
The next important step in understanding superconductivity occurred in 1933, when Meissner and Ochsenfeld discovered that superconductors expelled applied magnetic fields, a phenomenon which has come to be known as the Meissner effect. In 1935, F. and H. London showed that the Meissner effect was a consequence of the minimization of the electromagnetic free energy carried by superconducting current.
In 1950, the phenomenological Ginzburg-Landau theory of superconductivity was devised by Landau and Ginzburg.This theory, which combined Landau's theory of second-order phase transitions with a Schrödinger-like wave equation, had great success in explaining the macroscopic properties of superconductors. In particular, Abrikosov showed that Ginzburg-Landau theory predicts the division of superconductors into the two categories now referred to as Type I and Type II. Abrikosov and Ginzburg were awarded the 2003 Nobel Prize for their work (Landau having died in 1968).
Also in 1950, Maxwell and Reynolds et al. found that the critical temperature of a superconductor depends on the isotopic mass of the constituent element. This important discovery pointed to the electron- phonon interaction as the microscopic mechanism responsible for superconductivity.
The complete microscopic theory of superconductivity was finally proposed in 1957 by Bardeen, Cooper, and Schrieffer. Independently, the superconductivity phenomenon was explained by Nikolay Bogolyubov. This BCS theory explained the superconducting current as a superfluid of Cooper pairs, pairs of electrons interacting through the exchange of phonons. For this work, the authors were awarded the Nobel Prize in 1972.
The BCS theory was set on a firmer footing in 1958, when Bogoliubov showed that the BCS wavefunction, which had originally been derived from a variational argument, could be obtained using a canonical transformation of the electronic Hamiltonian. In 1959, Lev Gor'kov showed that the BCS theory reduced to the Ginzburg-Landau theory close to the critical temperature.
In 1962, the first commercial superconducting wire, a niobium-titanium alloy, was developed by researchers at Westinghouse. In the same year, Josephson made the important theoretical prediction that a supercurrent can flow between two pieces of superconductor separated by a thin layer of insulator. This phenomenon, now called the Josephson effect, is exploited by superconducting devices such as SQUIDs. It is used in the most accurate available measurements of the magnetic flux quantum , and thus (coupled with the quantum Hall resistivity) for Planck's constant h. Josephson was awarded the Nobel Prize for this work in 1973.
High Temperature superconductivity
Until 1986, physicists had believed that BCS theory forbade superconductivity at temperatures above about 30 K. In that year, Bednorz and Müller discovered superconductivity in a lanthanum-based cuprate perovskite material, which had a transition temperature of 35 K (Nobel Prize in Physics, 1987). It was shortly found by M.K. Wu et al. that replacing the lanthanum with yttrium, i.e. making YBCO, raised the critical temperature to 92 K, which was important because liquid nitrogen could then be used as a refrigerant (at atmospheric pressure, the boiling point of nitrogen is 77 K). This is important commercially because liquid nitrogen can be produced cheaply on-site with no raw materials, and is not prone to some of the problems (solid air plugs, et cetera) of helium in piping. Many other cuprate superconductors have since been discovered, and the theory of superconductivity in these materials is one of the major outstanding challenges of theoretical condensed matter physics.
From about 1993 the highest temperature superconductor was a ceramic material consisting of thallium, mercury, copper, barium, calcium, and oxygen, with Tc=138 K.
In February 2008 an iron-based family of high temperature superconductors was discovered. Hideo Hosono of the Tokyo Institute of Technology and colleagues found that lanthanum oxygen fluorine iron arsenide (LaO1-xFxFeAs) a oxypnictide becomes a superconductor at 26 Kelvin. Subsequent research from other groups suggests that replacing the lanthanum in LaO1-xFxFeAs with other rare earth elements such as cerium, samarium, neodymium and praseodymium leads to superconductors that work at 52 K. Experts hope that having another family to study will simplify the task of explaining how these materials work.
There is not just one criterion to classify superconductors. The most common are:
- By their physical properties: they can be Type I (if their phase transition is of first order) or Type II (if their phase transition is of second order).
- By the theory to explain them: they can be conventional (if they are explained by the BCS theory or its derivates) or unconventional (if not).
- By their critical temperature: they can be high temperature (generally considered if they reach the superconducting state just cooling them with liquid nitrogen, that is, if Tc > 77K), or low temperature (generally if they need other techniques to be cooled under their critical temperature).
- By material: they can be chemical elements (as mercury or lead), alloys (as niobium-titanium or germanium-niobium), ceramics (as YBCO or the magnesium diboride), or organic superconductors (as fullerens or carbon nanotubes, which technically might be included between the chemical elements as they are made of carbon).
Superconducting magnets are some of the most powerful electromagnets known. They are used in maglev trains, MRI and NMR machines and the beam-steering magnets used in particle accelerators. They can also be used for magnetic separation, where weakly magnetic particles are extracted from a background of less or non-magnetic particles, as in the pigment industries.
Superconductors have also been used to make digital circuits (e.g. based on the Rapid Single Flux Quantum technology) and RF and microwave filters for mobile phone base stations.
Superconductors are used to build Josephson junctions which are the building blocks of SQUIDs (superconducting quantum interference devices), the most sensitive magnetometers known. Series of Josephson devices are used to define the SI volt. Depending on the particular mode of operation, a Josephson junction can be used as photon detector or as mixer. The large resistance change at the transition from the normal- to the superconducting state is used to build thermometers in cryogenic micro-calorimeter photon detectors.
Other early markets are arising where the relative efficiency, size and weight advantages of devices based on HTS outweigh the additional costs involved.
Promising future applications include high-performance transformers, power storage devices, electric power transmission, electric motors (e.g. for vehicle propulsion, as in vactrains or maglev trains), magnetic levitation devices, and Fault Current Limiters. However superconductivity is sensitive to moving magnetic fields so applications that use alternating current (e.g. transformers) will be more difficult to develop than those that rely upon direct current.