High-temperature superconductivity

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A small sample of the high-temperature superconductor BSCCO-2223. BI2223-piece3 001.jpg
A small sample of the high-temperature superconductor BSCCO-2223.

High-temperature superconductors (abbreviated high-Tc or HTS) are materials that behave as superconductors at unusually high temperatures. [1] The first high-Tc superconductor was discovered in 1986 by IBM researchers Georg Bednorz and K. Alex Müller, [2] [3] who were awarded the 1987 Nobel Prize in Physics "for their important break-through in the discovery of superconductivity in ceramic materials". [4]

Nobel Prize in Physics One of the five Nobel Prizes established in 1895 by Alfred Nobel

The Nobel Prize in Physics is a yearly award given by the Royal Swedish Academy of Sciences for those who have made the most outstanding contributions for mankind in the field of physics. It is one of the five Nobel Prizes established by the will of Alfred Nobel in 1895 and awarded since 1901; the others being the Nobel Prize in Chemistry, Nobel Prize in Literature, Nobel Peace Prize, and Nobel Prize in Physiology or Medicine.

Contents

Whereas "ordinary" or metallic superconductors usually have transition temperatures (temperatures below which they are superconductive) below 30 K (−243.2 °C) and must be cooled using liquid helium in order to achieve superconductivity, HTS have been observed with transition temperatures as high as 138 K (−135 °C), and can be cooled to superconductivity using liquid nitrogen. [2] Until 2008, only certain compounds of copper and oxygen (so-called "cuprates") were known to have HTS properties, and the term high-temperature superconductor was used interchangeably with cuprate superconductor for compounds such as bismuth strontium calcium copper oxide (BSCCO) and yttrium barium copper oxide (YBCO). Several iron-based compounds (the iron pnictides) are now known to be superconducting at high temperatures. [5] [6] [7]

Liquid helium Liquid state of the element helium

At standard pressure, the chemical element helium exists in a liquid form only at the extremely low temperature of −269 °C. Its boiling point and critical point depend on which isotope of helium is present: the common isotope helium-4 or the rare isotope helium-3. These are the only two stable isotopes of helium. See the table below for the values of these physical quantities. The density of liquid helium-4 at its boiling point and a pressure of one atmosphere is about 0.125 grams per cm3, or about 1/8th the density of liquid water.

Liquid nitrogen Liquid state of nitrogen

Liquid nitrogenLN2—is nitrogen in a liquid state at an extremely low temperature (−195.79 °C (77 K; −320 °F) boiling point at sea level).

Cuprate superconductors are high temperature superconductors made of cuprates. They are layered materials, consisting of superconducting CuO2 layers separated by spacer layers.

However, HTS materials still have many manufacturing issues: one of them is that ususally they are brittle ceramics, which is very inconveninet for fabricating wires [8]

In 2015, hydrogen sulfide (H2S) under extremely high pressure (around 150 gigapascals) was found to undergo a superconducting transition near 203 K (70 °C), due the formation of H3S, a new record high temperature superconductor. [9] [10] [11]

Hydrogen sulfide Poisonous, corrosive and flammable gas

Hydrogen sulfide is the chemical compound with the formula H
2
S
. It is a colorless chalcogen hydride gas with the characteristic foul odor of rotten eggs. It is very poisonous, corrosive, and flammable.

Pascal (unit) SI unit of pressure

The pascal is the SI derived unit of pressure used to quantify internal pressure, stress, Young's modulus and ultimate tensile strength. The unit, named after Blaise Pascal, is defined as one newton per square metre.

For an explanation about Tc (the critical temperature for superconductivity), see Superconductivity § Superconducting phase transition and the second bullet item of BCS theory § Successes of the BCS theory.

History

The phenomenon of superconductivity was discovered by Kamerlingh Onnes in 1911, in metallic mercury below 4 K (−269.15 °C). Ever since, researchers have attempted to observe superconductivity at increasing temperatures [12] with the goal of finding a room-temperature superconductor. [13] By the late 1970s, superconductivity was observed in several metallic compounds (in particular Nb-based, such as NbTi, Nb3Sn, and Nb3Ge) at temperatures that were much higher than those for elemental metals and which could even exceed 20 K (−253.2 °C). In 1986, J. Georg Bednorz and K. Alex Müller, working at the IBM research lab near Zurich, Switzerland were exploring a new class of ceramics for superconductivity. Bednorz encountered a barium-doped compound of lanthanum and copper oxide whose resistance dropped to zero at a temperature around 35 K (−238.2 °C). [12] Their results were soon confirmed [14] by many groups, notably Paul Chu at the University of Houston and Shoji Tanaka at the University of Tokyo. [15]

Heike Kamerlingh Onnes Dutch physicist, Nobel prize winner

Professor Heike Kamerlingh Onnes FRSFor HFRSE FCS was a Dutch physicist and Nobel laureate. He exploited the Hampson–Linde cycle to investigate how materials behave when cooled to nearly absolute zero and later to liquefy helium for the first time, in 1908. He was also the discoverer of superconductivity in 1911.

A room-temperature superconductor is a material that is capable of exhibiting superconductivity at operating temperatures above 0 °C (273.15 K). While this is not strictly "room temperature", which would be approximately 20–25 °C, it is the temperature at which ice forms, and can be reached and easily maintained in an everyday environment. As of 2019 the material with the highest accepted superconducting temperature is highly pressurized lanthanum decahydride (LaH10), whose transition temperature is 250 K (−23 °C). Previously the record was held by hydrogen sulfide, which has demonstrated superconductivity under high pressure at temperatures as high as 203 K (−70 °C). By substituting a small part of sulfur in the latter with phosphorus and using even higher pressures, it has been predicted that it might be possible to raise the critical temperature to above 0 °C and achieve room-temperature superconductivity. At atmospheric pressure the record is still held by the cuprates, which have demonstrated superconductivity at temperatures as high as 138 K (−135 °C).

Niobium-titanium (Nb-Ti) is an alloy of niobium and titanium, used industrially as a type II superconductor wire for superconducting magnets, normally as Nb-Ti fibres in an aluminium or copper matrix.

Shortly after, P. W. Anderson, at Princeton University came up with the first theoretical description of these materials, using the resonating valence bond theory, [16] but a full understanding of these materials is still developing today. These superconductors are now known to possess a d-wave[ clarification needed ] pair symmetry. The first proposal that high-temperature cuprate superconductivity involves d-wave pairing was made in 1987 by Bickers, Scalapino and Scalettar, [17] followed by three subsequent theories in 1988 by Inui, Doniach, Hirschfeld and Ruckenstein, [18] using spin-fluctuation theory, and by Gros, Poilblanc, Rice and Zhang, [19] and by Kotliar and Liu identifying d-wave pairing as a natural consequence of the RVB theory. [20] The confirmation of the d-wave nature of the cuprate superconductors was made by a variety of experiments, including the direct observation of the d-wave nodes in the excitation spectrum through Angle Resolved Photoemission Spectroscopy, the observation of a half-integer flux in tunneling experiments, and indirectly from the temperature dependence of the penetration depth, specific heat and thermal conductivity.

Until 2015 the superconductor with the highest transition temperature that had been confirmed by multiple independent research groups (a prerequisite to being called a discovery, verified by peer review) was mercury barium calcium copper oxide (HgBa2Ca2Cu3O8) at around 133 K. [21]

After more than twenty years of intensive research, the origin of high-temperature superconductivity is still not clear, but it seems that instead of electron-phonon attraction mechanisms, as in conventional superconductivity, one is dealing with genuine electronic mechanisms (e.g. by antiferromagnetic correlations), and instead of conventional, purely s-wave pairing, more exotic pairing symmetries are thought to be involved (d-wave in the case of the cuprates; primarily extended s-wave, but occasionally d-wave, in the case of the iron-based superconductors). In 2014, evidence showing that fractional particles can happen in quasi two-dimensional magnetic materials, was found by EPFL scientists [22] lending support for Anderson's theory of high-temperature superconductivity. [23]

Crystal structures of high-temperature ceramic superconductors

The structure of high-Tc copper oxide or cuprate superconductors are often closely related to perovskite structure, and the structure of these compounds has been described as a distorted, oxygen deficient multi-layered perovskite structure. One of the properties of the crystal structure of oxide superconductors is an alternating multi-layer of CuO2 planes with superconductivity taking place between these layers. The more layers of CuO2, the higher Tc. This structure causes a large anisotropy in normal conducting and superconducting properties, since electrical currents are carried by holes induced in the oxygen sites of the CuO2 sheets. The electrical conduction is highly anisotropic, with a much higher conductivity parallel to the CuO2 plane than in the perpendicular direction. Generally, critical temperatures depend on the chemical compositions, cations substitutions and oxygen content. They can be classified as superstripes; i.e., particular realizations of superlattices at atomic limit made of superconducting atomic layers, wires, dots separated by spacer layers, that gives multiband and multigap superconductivity.

YBaCuO superconductors

YBCO unit cell Ybco.jpg
YBCO unit cell

The first superconductor found with Tc > 77 K (liquid nitrogen boiling point) is yttrium barium copper oxide (YBa2Cu3O7−x); the proportions of the three different metals in the YBa2Cu3O7 superconductor are in the mole ratio of 1 to 2 to 3 for yttrium to barium to copper, respectively. Thus, this particular superconductor is often referred to as the 123 superconductor.

The unit cell of YBa2Cu3O7 consists of three pseudocubic elementary perovskite unit cells. Each perovskite unit cell contains a Y or Ba atom at the center: Ba in the bottom unit cell, Y in the middle one, and Ba in the top unit cell. Thus, Y and Ba are stacked in the sequence [Ba–Y–Ba] along the c-axis. All corner sites of the unit cell are occupied by Cu, which has two different coordinations, Cu(1) and Cu(2), with respect to oxygen. There are four possible crystallographic sites for oxygen: O(1), O(2), O(3) and O(4). [24] The coordination polyhedra of Y and Ba with respect to oxygen are different. The tripling of the perovskite unit cell leads to nine oxygen atoms, whereas YBa2Cu3O7 has seven oxygen atoms and, therefore, is referred to as an oxygen-deficient perovskite structure. The structure has a stacking of different layers: (CuO)(BaO)(CuO2)(Y)(CuO2)(BaO)(CuO). One of the key feature of the unit cell of YBa2Cu3O7−x (YBCO) is the presence of two layers of CuO2. The role of the Y plane is to serve as a spacer between two CuO2 planes. In YBCO, the Cu–O chains are known to play an important role for superconductivity. Tc is maximal near 92 K when x ≈ 0.15 and the structure is orthorhombic. Superconductivity disappears at x ≈ 0.6, where the structural transformation of YBCO occurs from orthorhombic to tetragonal. [25]

Bi-, Tl- and Hg-based high-Tc superconductors

BSCCO lattice Bscco lattice.png
BSCCO lattice

The crystal structure of Bi-, Tl- and Hg-based high-Tc superconductors are very similar. [26] Like YBCO, the perovskite-type feature and the presence of CuO2 layers also exist in these superconductors. However, unlike YBCO, Cu–O chains are not present in these superconductors. The YBCO superconductor has an orthorhombic structure, whereas the other high-Tc superconductors have a tetragonal structure.

The Bi–Sr–Ca–Cu–O system has three superconducting phases forming a homologous series as Bi2Sr2Can−1CunO4+2n+x (n=1, 2 and 3). These three phases are Bi-2201, Bi-2212 and Bi-2223, having transition temperatures of 20, 85 and 110 K, respectively, where the numbering system represent number of atoms for Bi, Sr, Ca and Cu respectively. [27] The two phases have a tetragonal structure which consists of two sheared crystallographic unit cells. The unit cell of these phases has double Bi–O planes which are stacked in a way that the Bi atom of one plane sits below the oxygen atom of the next consecutive plane. The Ca atom forms a layer within the interior of the CuO2 layers in both Bi-2212 and Bi-2223; there is no Ca layer in the Bi-2201 phase. The three phases differ with each other in the number of CuO2 planes; Bi-2201, Bi-2212 and Bi-2223 phases have one, two and three CuO2 planes, respectively. The c axis lattice constants of these phases increases with the number of CuO2 planes (see table below). The coordination of the Cu atom is different in the three phases. The Cu atom forms an octahedral coordination with respect to oxygen atoms in the 2201 phase, whereas in 2212, the Cu atom is surrounded by five oxygen atoms in a pyramidal arrangement. In the 2223 structure, Cu has two coordinations with respect to oxygen: one Cu atom is bonded with four oxygen atoms in square planar configuration and another Cu atom is coordinated with five oxygen atoms in a pyramidal arrangement. [28]

Tl–Ba–Ca–Cu–O superconductor: The first series of the Tl-based superconductor containing one Tl–O layer has the general formula TlBa2Can-1CunO2n+3, [29] whereas the second series containing two Tl–O layers has a formula of Tl2Ba2Can-1CunO2n+4 with n =1, 2 and 3. In the structure of Tl2Ba2CuO6 (Tl-2201), there is one CuO2 layer with the stacking sequence (Tl–O) (Tl–O) (Ba–O) (Cu–O) (Ba–O) (Tl–O) (Tl–O). In Tl2Ba2CaCu2O8 (Tl-2212), there are two Cu–O layers with a Ca layer in between. Similar to the Tl2Ba2CuO6 structure, Tl–O layers are present outside the Ba–O layers. In Tl2Ba2Ca2Cu3O10 (Tl-2223), there are three CuO2 layers enclosing Ca layers between each of these. In Tl-based superconductors, Tc is found to increase with the increase in CuO2 layers. However, the value of Tc decreases after four CuO2 layers in TlBa2Can-1CunO2n+3, and in the Tl2Ba2Can-1CunO2n+4 compound, it decreases after three CuO2 layers. [30]

Hg–Ba–Ca–Cu–O superconductor: The crystal structure of HgBa2CuO4 (Hg-1201), [31] HgBa2CaCu2O6 (Hg-1212) and HgBa2Ca2Cu3O8 (Hg-1223) is similar to that of Tl-1201, Tl-1212 and Tl-1223, with Hg in place of Tl. It is noteworthy that the Tc of the Hg compound (Hg-1201) containing one CuO2 layer is much larger as compared to the one-CuO2-layer compound of thallium (Tl-1201). In the Hg-based superconductor, Tc is also found to increase as the CuO2 layer increases. For Hg-1201, Hg-1212 and Hg-1223, the values of Tc are 94, 128 and the record value at ambient pressure 134 K, [32] respectively, as shown in table below. The observation that the Tc of Hg-1223 increases to 153 K under high pressure indicates that the Tc of this compound is very sensitive to the structure of the compound. [33]

Critical temperature (Tc), crystal structure and lattice constants of some high-Tc superconductors
FormulaNotationTc (K)No. of Cu-O planes
in unit cell
Crystal structure
YBa2Cu3O7123922 Orthorhombic
Bi2Sr2CuO6Bi-2201201 Tetragonal
Bi2Sr2CaCu2O8Bi-2212852Tetragonal
Bi2Sr2Ca2Cu3O10Bi-22231103Tetragonal
Tl2Ba2CuO6Tl-2201801Tetragonal
Tl2Ba2CaCu2O8Tl-22121082Tetragonal
Tl2Ba2Ca2Cu3O10Tl-22231253Tetragonal
TlBa2Ca3Cu4O11Tl-12341224Tetragonal
HgBa2CuO4Hg-1201941Tetragonal
HgBa2CaCu2O6Hg-12121282Tetragonal
HgBa2Ca2Cu3O8Hg-12231343Tetragonal

Preparation of high-Tc superconductors

The simplest method for preparing high-Tc superconductors is a solid-state thermochemical reaction involving mixing, calcination and sintering. The appropriate amounts of precursor powders, usually oxides and carbonates, are mixed thoroughly using a Ball mill. Solution chemistry processes such as coprecipitation, freeze-drying and sol-gel methods are alternative ways for preparing a homogeneous mixture. These powders are calcined in the temperature range from 800 °C to 950 °C for several hours. The powders are cooled, reground and calcined again. This process is repeated several times to get homogeneous material. The powders are subsequently compacted to pellets and sintered. The sintering environment such as temperature, annealing time, atmosphere and cooling rate play a very important role in getting good high-Tc superconducting materials. The YBa2Cu3O7−x compound is prepared by calcination and sintering of a homogeneous mixture of Y2O3, BaCO3 and CuO in the appropriate atomic ratio. Calcination is done at 900–950 °C, whereas sintering is done at 950 °C in an oxygen atmosphere. The oxygen stoichiometry in this material is very crucial for obtaining a superconducting YBa2Cu3O7−x compound. At the time of sintering, the semiconducting tetragonal YBa2Cu3O6 compound is formed, which, on slow cooling in oxygen atmosphere, turns into superconducting YBa2Cu3O7−x. The uptake and loss of oxygen are reversible in YBa2Cu3O7−x. A fully oxygenated orthorhombic YBa2Cu3O7−x sample can be transformed into tetragonal YBa2Cu3O6 by heating in a vacuum at temperature above 700 °C. [25]

The preparation of Bi-, Tl- and Hg-based high-Tc superconductors is difficult compared to YBCO. Problems in these superconductors arise because of the existence of three or more phases having a similar layered structure. Thus, syntactic intergrowth and defects such as stacking faults occur during synthesis and it becomes difficult to isolate a single superconducting phase. For Bi–Sr–Ca–Cu–O, it is relatively simple to prepare the Bi-2212 (Tc ≈ 85 K) phase, whereas it is very difficult to prepare a single phase of Bi-2223 (Tc ≈ 110 K). The Bi-2212 phase appears only after few hours of sintering at 860–870 °C, but the larger fraction of the Bi-2223 phase is formed after a long reaction time of more than a week at 870 °C. [28] Although the substitution of Pb in the Bi–Sr–Ca–Cu–O compound has been found to promote the growth of the high-Tc phase, [34] a long sintering time is still required.

Properties

"High-temperature" has two common definitions in the context of superconductivity:

  1. Above the temperature of 30 K that had historically been taken as the upper limit allowed by BCS theory (1957).[ citation needed ] This is also above the 1973 record of 23 K that had lasted until copper-oxide materials were discovered in 1986.
  2. Having a transition temperature that is a larger fraction of the Fermi temperature than for conventional superconductors such as elemental mercury or lead.[ citation needed ] This definition encompasses a wider variety of unconventional superconductors and is used in the context of theoretical models.

The label high-Tc may be reserved by some authors[ citation needed ] for materials with critical temperature greater than the boiling point of liquid nitrogen (77 K or −196  °C). However, a number of materials – including the original discovery and recently discovered pnictide superconductors – had critical temperatures below 77 K but are commonly referred to in publication as being in the high-Tc class. [35] [36]

Technological applications could benefit from both the higher critical temperature being above the boiling point of liquid nitrogen and also the higher critical magnetic field (and critical current density) at which superconductivity is destroyed. In magnet applications, the high critical magnetic field may prove more valuable than the high Tc itself. Some cuprates have an upper critical field of about 100 tesla. However, cuprate materials are brittle ceramics which are expensive to manufacture and not easily turned into wires or other useful shapes. Also, high-temperature superconductors do not form large, continuous superconducting domains, but only clusters of microdomains within which superconductivity occurs. They are therefore unsuitable for applications requiring actual superconducted currents, such as magnets for magnetic resonance spectrometers. [37] . For a solution to this (powders), see HTS_wire.

After two decades of intense experimental and theoretical research, with over 100,000 published papers on the subject, [38] several common features in the properties of high-temperature superconductors have been identified. [5] As of 2011, no widely accepted theory explains their properties. Relative to conventional superconductors, such as elemental mercury or lead that are adequately explained by the BCS theory, cuprate superconductors (and other unconventional superconductors) remain distinctive. There also has been much debate as to high-temperature superconductivity coexisting with magnetic ordering in YBCO, [39] iron-based superconductors, several ruthenocuprates and other exotic superconductors, and the search continues for other families of materials. HTS are Type-II superconductors, which allow magnetic fields to penetrate their interior in quantized units of flux, meaning that much higher magnetic fields are required to suppress superconductivity. The layered structure also gives a directional dependence to the magnetic field response.

Cuprates

Simplified doping dependent phase diagram of cuprate superconductors for both electron (n) and hole (p) doping. The phases shown are the antiferromagnetic (AF) phase close to zero doping, the superconducting phase around optimal doping, and the pseudogap phase. Doping ranges possible for some common compounds are also shown. After. Cuphasediag.png
Simplified doping dependent phase diagram of cuprate superconductors for both electron (n) and hole (p) doping. The phases shown are the antiferromagnetic (AF) phase close to zero doping, the superconducting phase around optimal doping, and the pseudogap phase. Doping ranges possible for some common compounds are also shown. After.

Cuprate superconductors are generally considered to be quasi-two-dimensional materials with their superconducting properties determined by electrons moving within weakly coupled copper-oxide (CuO2) layers. Neighbouring layers containing ions such as lanthanum, barium, strontium, or other atoms act to stabilize the structure and dope electrons or holes onto the copper-oxide layers. The undoped "parent" or "mother" compounds are Mott insulators with long-range antiferromagnetic order at low enough temperature. Single band models are generally considered to be sufficient to describe the electronic properties.

The cuprate superconductors adopt a perovskite structure. The copper-oxide planes are checkerboard lattices with squares of O2− ions with a Cu2+ ion at the centre of each square. The unit cell is rotated by 45° from these squares. Chemical formulae of superconducting materials generally contain fractional numbers to describe the doping required for superconductivity. There are several families of cuprate superconductors and they can be categorized by the elements they contain and the number of adjacent copper-oxide layers in each superconducting block. For example, YBCO and BSCCO can alternatively be referred to as Y123 and Bi2201/Bi2212/Bi2223 depending on the number of layers in each superconducting block (n). The superconducting transition temperature has been found to peak at an optimal doping value (p=0.16) and an optimal number of layers in each superconducting block, typically n=3.

Possible mechanisms for superconductivity in the cuprates are still the subject of considerable debate and further research. Certain aspects common to all materials have been identified. [5] Similarities between the antiferromagnetic low-temperature state of the undoped materials and the superconducting state that emerges upon doping, primarily the dx2-y2 orbital state of the Cu2+ ions, suggest that electron-electron interactions are more significant than electron-phonon interactions in cuprates – making the superconductivity unconventional. Recent work on the Fermi surface has shown that nesting occurs at four points in the antiferromagnetic Brillouin zone where spin waves exist and that the superconducting energy gap is larger at these points. The weak isotope effects observed for most cuprates contrast with conventional superconductors that are well described by BCS theory.

Similarities and differences in the properties of hole-doped and electron doped cuprates:

Fig. 1. The Fermi surface of bi-layer BSCCO, calculated (left) and measured by ARPES (right). The dashed rectangle represents the first Brillouin zone. Fermi surface of BSCCO.jpg
Fig. 1. The Fermi surface of bi-layer BSCCO, calculated (left) and measured by ARPES (right). The dashed rectangle represents the first Brillouin zone.

The electronic structure of superconducting cuprates is highly anisotropic (see the crystal structure of YBCO or BSCCO). Therefore, the Fermi surface of HTSC is very close to the Fermi surface of the doped CuO2 plane (or multi-planes, in case of multi-layer cuprates) and can be presented on the 2D reciprocal space (or momentum space) of the CuO2 lattice. The typical Fermi surface within the first CuO2 Brillouin zone is sketched in Fig. 1 (left). It can be derived from the band structure calculations or measured by angle resolved photoemission spectroscopy (ARPES). Fig. 1 (right) shows the Fermi surface of BSCCO measured by ARPES. In a wide range of charge carrier concentration (doping level), in which the hole-doped HTSC are superconducting, the Fermi surface is hole-like (i.e. open, as shown in Fig. 1). This results in an inherent in-plane anisotropy of the electronic properties of HTSC.

Iron-based superconductors

Simplified doping dependent phase diagrams of iron-based superconductors for both Ln-1111 and Ba-122 materials. The phases shown are the antiferromagnetic/spin density wave (AF/SDW) phase close to zero doping and the superconducting phase around optimal doping. The Ln-1111 phase diagrams for La and Sm were determined using muon spin spectroscopy, the phase diagram for Ce was determined using neutron diffraction. The Ba-122 phase diagram is based on. Fephasediag.png
Simplified doping dependent phase diagrams of iron-based superconductors for both Ln-1111 and Ba-122 materials. The phases shown are the antiferromagnetic/spin density wave (AF/SDW) phase close to zero doping and the superconducting phase around optimal doping. The Ln-1111 phase diagrams for La and Sm were determined using muon spin spectroscopy, the phase diagram for Ce was determined using neutron diffraction. The Ba-122 phase diagram is based on.

Iron-based superconductors contain layers of iron and a pnictogen—such as arsenic or phosphorus—or a chalcogen. This is currently the family with the second highest critical temperature, behind the cuprates. Interest in their superconducting properties began in 2006 with the discovery of superconductivity in LaFePO at 4 K [46] and gained much greater attention in 2008 after the analogous material LaFeAs(O,F) [47] was found to superconduct at up to 43 K under pressure. [48] The highest critical temperatures in the iron-based superconductor family exist in thin films of FeSe, [49] [50] [51] where a critical temperature in excess of 100 K was reported in 2014. [52]

Since the original discoveries several families of iron-based superconductors have emerged:

Most undoped iron-based superconductors show a tetragonal-orthorhombic structural phase transition followed at lower temperature by magnetic ordering, similar to the cuprate superconductors. [44] However, they are poor metals rather than Mott insulators and have five bands at the Fermi surface rather than one. [60] The phase diagram emerging as the iron-arsenide layers are doped is remarkably similar, with the superconducting phase close to or overlapping the magnetic phase. Strong evidence that the Tc value varies with the As-Fe-As bond angles has already emerged and shows that the optimal Tc value is obtained with undistorted FeAs4 tetrahedra. [61] The symmetry of the pairing wavefunction is still widely debated, but an extended s-wave scenario is currently favoured.

Hydrogen sulfide

At pressures above 90 GPa (Gigapascals), hydrogen sulfide becomes a metallic conductor of electricity. When cooled below a critical temperature this high-pressure phase exhibits superconductivity. The critical temperature increases with pressure, ranging from 23 K at 100 GPa to 150 K at 200 GPa. [62] If hydrogen sulfide is pressurized at higher temperatures, then cooled, the critical temperature reaches 203 K (−70 °C), the highest accepted superconducting critical temperature as of 2015. [10] It has been predicted that by substituting a small part of sulfur with phosphorus and using even higher pressures it may be possible to raise the critical temperature to above 273 K (0 °C) and achieve room-temperature superconductivity. [10] [63]

Other materials sometimes referred to as high-temperature superconductors

Magnesium diboride is occasionally referred to as a high-temperature superconductor [64] because its Tc value of 39 K is above that historically expected for BCS superconductors. However, it is more generally regarded as the highest-Tc conventional superconductor, the increased Tc resulting from two separate bands being present at the Fermi level.

Fulleride superconductors [65] where alkali-metal atoms are intercalated into C60 molecules show superconductivity at temperatures of up to 38 K for Cs3C60. [66]

Some organic superconductors and heavy fermion compounds are considered to be high-temperature superconductors because of their high Tc values relative to their Fermi energy, despite the Tc values being lower than for many conventional superconductors.[ citation needed ] This description may relate better to common aspects of the superconducting mechanism than the superconducting properties.

Metallic hydrogen

Theoretical work by Neil Ashcroft in 1968 predicted that solid metallic hydrogen at extremely high pressure should become superconducting at approximately room-temperature because of its extremely high speed of sound and expected strong coupling between the conduction electrons and the lattice vibrations. [67] As of 2016 this prediction is yet to be experimentally verified.

Magnetic properties

All known high-Tc superconductors are Type-II superconductors. In contrast to Type-I superconductors, which expel all magnetic fields due to the Meissner effect, Type-II superconductors allow magnetic fields to penetrate their interior in quantized units of flux, creating "holes" or "tubes" of normal metallic regions in the superconducting bulk called vortices. Consequently, high-Tc superconductors can sustain much higher magnetic fields.

Ongoing research

Superconductor timeline. BCS superconductors are displayed as green circles, cuprates as blue diamonds, and iron-based superconductors as yellow squares. (YBaCuO should be at 93K according to table below.) Timeline of Superconductivity from 1900 to 2015.svg
Superconductor timeline. BCS superconductors are displayed as green circles, cuprates as blue diamonds, and iron-based superconductors as yellow squares. (YBaCuO should be at 93K according to table below.)

The question of how superconductivity arises in high-temperature superconductors is one of the major unsolved problems of theoretical condensed matter physics. The mechanism that causes the electrons in these crystals to form pairs is not known. [5] Despite intensive research and many promising leads, an explanation has so far eluded scientists. One reason for this is that the materials in question are generally very complex, multi-layered crystals (for example, BSCCO), making theoretical modelling difficult.

Improving the quality and variety of samples also gives rise to considerable research, both with the aim of improved characterisation of the physical properties of existing compounds, and synthesizing new materials, often with the hope of increasing Tc. Technological research focuses on making HTS materials in sufficient quantities to make their use economically viable and optimizing their properties in relation to applications.

Possible mechanism

There have been two representative theories for high-temperature or unconventional superconductivity. Firstly, weak coupling theory suggests superconductivity emerges from antiferromagnetic spin fluctuations in a doped system. [68] According to this theory, the pairing wave function of the cuprate HTS should have a dx2-y2 symmetry. Thus, determining whether the pairing wave function has d-wave symmetry is essential to test the spin fluctuation mechanism. That is, if the HTS order parameter (pairing wave function) does not have d-wave symmetry, then a pairing mechanism related to spin fluctuations can be ruled out. (Similar arguments can be made for iron-based superconductors but the different material properties allow a different pairing symmetry.) Secondly, there was the interlayer coupling model, according to which a layered structure consisting of BCS-type (s-wave symmetry) superconductors can enhance the superconductivity by itself. [69] By introducing an additional tunnelling interaction between each layer, this model successfully explained the anisotropic symmetry of the order parameter as well as the emergence of the HTS. Thus, in order to solve this unsettled problem, there have been numerous experiments such as photoemission spectroscopy, NMR, specific heat measurements, etc. Up to date the results were ambiguous, some reports supported the d symmetry for the HTS whereas others supported the s symmetry. This muddy situation possibly originated from the indirect nature of the experimental evidence, as well as experimental issues such as sample quality, impurity scattering, twinning, etc.

This summary makes an implicit assumption: superconductive properties can be treated by mean field theory. It also fails to mention that in addition to the superconductive gap, there is a second gap, the pseudogap. The cuprate layers are insulating, and the superconductors are doped with interlayer impurities to make them metallic. The superconductive transition temperature can be maximized by varying the dopant concentration. The simplest example is La2CuO4, which consist of alternating CuO2 and LaO layers which are insulating when pure. When 8% of the La is replaced by Sr, the latter act as dopants, contributing holes to the CuO2 layers, and making the sample metallic. The Sr impurities also act as electronic bridges, enabling interlayer coupling. Proceeding from this picture, some theories argue that the basic pairing interaction is still interaction with phonons, as in the conventional superconductors with Cooper pairs. While the undoped materials are antiferromagnetic, even a few percent of impurity dopants introduce a smaller pseudogap in the CuO2 planes which is also caused by phonons. The gap decreases with increasing charge carriers, and as it nears the superconductive gap, the latter reaches its maximum. The reason for the high transition temperature is then argued to be due to the percollating behaviour of the carriers - the carriers follow zig-zag percolative paths, largely in metallic domains in the CuO2 planes, until blocked by charge density wave domain walls, where they use dopant bridges to cross over to a metallic domain of an adjacent CuO2 plane. The transition temperature maxima are reached when the host lattice has weak bond-bending forces, which produce strong electron-phonon interactions at the interlayer dopants. [70]

Junction experiment supporting the d symmetry

The Meissner effect or a magnet levitating above a superconductor (cooled by liquid nitrogen) Meissner effect p1390048.jpg
The Meissner effect or a magnet levitating above a superconductor (cooled by liquid nitrogen)

An experiment based on flux quantization of a three-grain ring of YBa2Cu3O7 (YBCO) was proposed to test the symmetry of the order parameter in the HTS. The symmetry of the order parameter could best be probed at the junction interface as the Cooper pairs tunnel across a Josephson junction or weak link. [71] It was expected that a half-integer flux, that is, a spontaneous magnetization could only occur for a junction of d symmetry superconductors. But, even if the junction experiment is the strongest method to determine the symmetry of the HTS order parameter, the results have been ambiguous. J. R. Kirtley and C. C. Tsuei thought that the ambiguous results came from the defects inside the HTS, so that they designed an experiment where both clean limit (no defects) and dirty limit (maximal defects) were considered simultaneously. [72] In the experiment, the spontaneous magnetization was clearly observed in YBCO, which supported the d symmetry of the order parameter in YBCO. But, since YBCO is orthorhombic, it might inherently have an admixture of s symmetry. So, by tuning their technique further, they found that there was an admixture of s symmetry in YBCO within about 3%. [73] Also, they found that there was a pure dx2-y2 order parameter symmetry in the tetragonal Tl2Ba2CuO6. [74]

Qualitative explanation of the spin-fluctuation mechanism

Despite all these years, the mechanism of high-Tc superconductivity is still highly controversial, mostly due to the lack of exact theoretical computations on such strongly interacting electron systems. However, most rigorous theoretical calculations, including phenomenological and diagrammatic approaches, converge on magnetic fluctuations as the pairing mechanism for these systems. The qualitative explanation is as follows:

In a superconductor, the flow of electrons cannot be resolved into individual electrons, but instead consists of many pairs of bound electrons, called Cooper pairs. In conventional superconductors, these pairs are formed when an electron moving through the material distorts the surrounding crystal lattice, which in turn attracts another electron and forms a bound pair. This is sometimes called the "water bed" effect. Each Cooper pair requires a certain minimum energy to be displaced, and if the thermal fluctuations in the crystal lattice are smaller than this energy the pair can flow without dissipating energy. This ability of the electrons to flow without resistance leads to superconductivity.

In a high-Tc superconductor, the mechanism is extremely similar to a conventional superconductor, except, in this case, phonons virtually play no role and their role is replaced by spin-density waves. Just as all known conventional superconductors are strong phonon systems, all known high-Tc superconductors are strong spin-density wave systems, within close vicinity of a magnetic transition to, for example, an antiferromagnet. When an electron moves in a high-Tc superconductor, its spin creates a spin-density wave around it. This spin-density wave in turn causes a nearby electron to fall into the spin depression created by the first electron (water-bed effect again). Hence, again, a Cooper pair is formed. When the system temperature is lowered, more spin density waves and Cooper pairs are created, eventually leading to superconductivity. Note that in high-Tc systems, as these systems are magnetic systems due to the Coulomb interaction, there is a strong Coulomb repulsion between electrons. This Coulomb repulsion prevents pairing of the Cooper pairs on the same lattice site. The pairing of the electrons occur at near-neighbor lattice sites as a result. This is the so-called d-wave pairing, where the pairing state has a node (zero) at the origin.

Examples

Examples of high-Tc cuprate superconductors include La1.85Ba0.15CuO4, and YBCO (yttrium-barium-copper oxide), which is famous as the first material discovered to achieve superconductivity above the boiling point of liquid nitrogen.

Transition temperatures of well-known superconductors (Boiling point of liquid nitrogen for comparison)
Transition temperature
(in kelvins)
Transition temperature
(in degrees Celsius)
MaterialClass
203−70 H2S (at 150 GPa pressure) [10] Hydrogen-based superconductor
195−78 Sublimation point of dry ice
184−89.2 Lowest temperature recorded on Earth
145−128Boiling point of tetrafluoromethane
133−140 HgBa2Ca2Cu3Ox(HBCCO) Copper-oxide superconductors
110−163 Bi2Sr2Ca2Cu3O10(BSCCO)
93−180 YBa2Cu3O7 (YBCO)
90−183Boiling point of liquid oxygen
77−196Boiling point of liquid nitrogen
55−218SmFeAs(O,F) Iron-based superconductors
41−232CeFeAs(O,F)
26−247LaFeAs(O,F)
20−253Boiling point of liquid hydrogen
18−255 Nb3Sn Metallic low-temperature superconductors
10−263 NbTi
9.2−263.8 Nb
4.2−268.8Boiling point of liquid helium
4.2−268.8Hg (mercury)Metallic low-temperature superconductors

See also

Related Research Articles

Superconductivity Electrical conductivity with almost zero resistance.

Superconductivity is the set of physical properties observed in certain materials, wherein electrical resistance vanishes and from which magnetic flux fields are expelled. Any material exhibiting these properties is a superconductor. Unlike an ordinary metallic conductor, whose resistance decreases gradually as its temperature is lowered even down to near absolute zero, a superconductor has a characteristic critical temperature below which the resistance drops abruptly to zero. An electric current through a loop of superconducting wire can persist indefinitely with no power source.

Unconventional superconductors are materials that display superconductivity which does not conform to either the conventional BCS theory or Nikolay Bogolyubov's theory or its extensions.

Yttrium barium copper oxide chemical compound

Yttrium barium copper oxide (YBCO) is a family of crystalline chemical compounds, famous for displaying high-temperature superconductivity. It includes the first material ever discovered to become superconducting above the boiling point of liquid nitrogen (77 K) at about 92 K. Many YBCO compounds have the general formula YBa2Cu3O7−x (also known as Y123), although materials with other Y:Ba:Cu ratios exist, such as YBa2Cu4Oy (Y124) or Y2Ba4Cu7Oy (Y247). They are GL-superconductors (their superconduction is explainable with the Ginzburg–Landau theory).

Superconductivity is the phenomenon of certain materials exhibiting zero electrical resistance and the expulsion of magnetic fields below a characteristic temperature. The history of superconductivity began with Dutch physicist Heike Kamerlingh Onnes's discovery of superconductivity in mercury in 1911. Since then, many other superconducting materials have been discovered and the theory of superconductivity has been developed. These subjects remain active areas of study in the field of condensed matter physics.

Bismuth strontium calcium copper oxide, or BSCCO (pronounced "bisko"), is a family of high-temperature superconductors having the generalized chemical formula Bi2Sr2Can−1CunO2n+4+x, with n = 2 being the most commonly studied compound (though n = 1 and n = 3 have also received significant attention). Discovered as a general class in 1988, BSCCO was the first high-temperature superconductor which did not contain a rare-earth element. It is a cuprate superconductor, an important category of high-temperature superconductors sharing a two-dimensional layered (perovskite) structure (see figure at right) with superconductivity taking place in a copper-oxide plane. BSCCO and YBCO are the most studied cuprate superconductors.

Pseudogap State at which a Fermi surface has a partial energy gap in condensed matter physics

In condensed matter physics, a pseudogap describes a state where the Fermi surface of a material possesses a partial energy gap, for example, a band structure state where the Fermi surface is gapped only at certain points. The term pseudogap was coined by Nevill Mott in 1968 to indicate a minimum in the density of states at the Fermi level, N(EF), resulting from Coulomb repulsion between electrons in the same atom, a band gap in a disordered material or a combination of these. In the modern context pseudogap is a term from the field of high-temperature superconductivity which refers to an energy range which has very few states associated with it. This is very similar to a true 'gap', which is an energy range that contains no allowed states. Such gaps open up, for example, when electrons interact with the lattice. The pseudogap phenomenon is observed in a region of the phase diagram generic to cuprate high-temperature superconductors, existing in underdoped specimens at temperatures above the superconducting transition temperature.

A charge density wave (CDW) is an ordered quantum fluid of electrons in a linear chain compound or layered crystal. The electrons within a CDW form a standing wave pattern and sometimes collectively carry an electric current. The electrons in such a CDW, like those in a superconductor, can flow through a linear chain compound en masse, in a highly correlated fashion. Unlike a superconductor, however, the electric CDW current often flows in a jerky fashion, much like water dripping from a faucet due to its electrostatic properties. In a CDW, the combined effects of pinning and electrostatic interactions likely play critical roles in the CDW current's jerky behavior, as discussed in sections 4 & 5 below.

Superconductors can be classified in accordance with several criteria that depend on physical properties, current understanding, how expensive is cooling them or their material.

Iron-based superconductor iron- and pnictide-containing chemical compounds showing superconductivity

Iron-based superconductors (FeSC) are iron-containing chemical compounds whose superconducting properties were discovered in 2006. In 2008, led by recently discovered iron pnictide compounds, they were in the first stages of experimentation and implementation..

In chemistry, oxypnictides are a class of materials composed of oxygen, a pnictogen and one or more other elements. Although this group of compounds has been recognized since 1995, interest in these compounds increased dramatically after the publication of the superconducting properties of LaOFeP and LaOFeAs which were discovered in 2006 and 2008. In these experiments the oxide was partly replaced by fluoride.

Scanning SQUID microscopy

Scanning SQUID microscopy is a technique where a superconducting quantum interference device (SQUID) is used to image surface magnetic field strength with micrometre scale resolution. A tiny SQUID is mounted onto a tip which is then rastered near the surface of the sample to be measured. As the SQUID is the most sensitive detector of magnetic fields available and can be constructed at submicrometre widths via lithography, the scanning SQUID microscope allows magnetic fields to be measured with unparalleled resolution and sensitivity. The first scanning SQUID microscope was built in 1992 by Black et al. Since then the technique has been used to confirm unconventional superconductity in several high-temperature superconductors including YBCO and BSCCO compounds.

122 iron arsenide

The 122 iron arsenide unconventional superconductors are part of a new class of iron-based superconductors. They form in the tetragonal I4/mmm, ThCr2Si2 type, crystal structure. The shorthand name "122" comes from their stoichiometry; the 122s have the chemical formula AEFe2Pn2, where AE stands for alkaline earth metal (Ca, Ba, Sr or Eu) and Pn is pnictide (As, P, etc.). These materials become superconducting under pressure and also upon doping. The maximum superconducting transition temperature found to date is 38 K in the Ba0.6K0.4Fe2As2. The microscopic description of superconductivity in the 122s is yet unclear.

Superconducting wire Wires exhibiting zero resistance

Superconducting wires are wires made of superconductors. When cooled below their transition temperatures, they have zero electrical resistance. Most commonly, conventional superconductors such as niobium-titanium are used, but high-temperature superconductors such as YBCO are entering the market. Superconducting wire's advantages over copper or aluminum include higher maximum current densities and zero power dissipation. Its disadvantages include the cost of refrigeration of the wires to superconducting temperatures, the danger of the wire quenching, the inferior mechanical properties of some superconductors, and the cost of wire materials and construction. Its main application is in superconducting magnets, which are used in scientific and medical equipment where high magnetic fields are necessary.

Superstripes is a generic name for a phase with spatial broken symmetry that favors the onset of superconducting or superfluid quantum order. This scenario emerged in the 1990s when no-homogeneous metallic heterostructures at the atomic limit with a broken spatial symmetry have been found to favor superconductivity. Before a broken spatial symmetry was expected to compete and suppress the superconducting order. The driving mechanism for the amplification of the superconductivity critical temperature in superstripes matter has been proposed to be the shape resonance in the energy gap parameters ∆n that is a type of Fano resonance for coexisting condensates.

Strontium ruthenate chemical compound

Strontium ruthenate (SRO) is an oxide of strontium and ruthenium with the chemical formula Sr2RuO4. It was the first reported perovskite superconductor that did not contain copper. Strontium ruthenate is structurally very similar to the high-temperature cuprate superconductors, and in particular, is almost identical to the lanthanum doped superconductor (La, Sr)2CuO4. However, the transition temperature for the superconducting phase transition is 0.93 K, which is much lower than the corresponding value for cuprates.

Iron(II) selenide refers to a number of inorganic compounds of ferrous iron and selenide (Se2−). The phase diagram of the system Fe–Se reveals the existence of several non-stoichiometric phases between ~49 at. % Se and ~53 at. % Fe, and temperatures up to ~450 °C. The low temperature stable phases are the tetragonal PbO-structure (P4/nmm) β-Fe1−xSe and α-Fe7Se8. The high temperature phase is the hexagonal, NiAs structure (P63/mmc) δ-Fe1−xSe. Iron (II) selenide occurs naturally as the NiAs-structure mineral achavalite.

Kathryn Ann Moler is an American physicist, and current Dean of Research at Stanford University. She received her BSc (1988) and Ph.D. (1995) from Stanford University. After working as a visiting scientist at IBM T.J. Watson Research Center in 1995, she held a postdoctoral position at Princeton University from 1995-1998. She joined the faculty of Stanford University in 1998, and became an Associate in CIFAR's Superconductivity Program in 2000. She became an Associate Professor at Stanford in 2002 and is currently a Professor of Applied Physics and of Physics at Stanford. She currently works in the Geballe Laboratory for Advanced Materials (GLAM), and is the Director of the Center for Probing the Nanoscale (CPN), a National Science Foundation-funded center where Stanford and IBM scientists continue to improve scanning probe methods for measuring, imaging, and controlling nanoscale phenomena. She lists her scientific interests and main areas of research and experimentation as:

A polar metal, metallic ferroeletric, or ferroelectric metal is a metal that contains an electric dipole moment. Its components have an ordered electric dipole. Such metals should be unexpected, because the charge should conduct by way of the free electrons in the metal and neutralize the polarized charge. However they do exist. Probably the first report of a polar metal was in single crystals of the cuprate superconductors YBa2Cu3O7-δ,. A polarization was observed along one (001) axis by pyroelectric effect measurements, and the sign of the polarization was shown to be reversible, while its magnitude could be increased by poling by an electric field. The polarization was found to disappear in the superconducting state.. The lattice distortions responsible were considered to be a result of oxygen ion displacements induced by doped charges that break inversion symmetry. The effect was utilized for fabrication of pyroelectric detectors for space applications, having the advantage of large pyroelectric coefficient and low intrinsic resistance. Another substance family that can produce a polar metal is the nickelate perovskites. One example interpreted to show polar metallic behavior is lanthanum nickelate, LaNiO3. A thin film of LaNiO3 grown on the (111) crystal face of lanthanum aluminate, (LaAlO3) was interpreted to be both conductor and a polar material at room temperature. The resistivity of this system, however, shows an upturn with decreasing temperature, hence does not strictly adhere to the definition of a metal. Also, when grown 3 or 4 unit cells thick (1-2 nm) on the (100) crystal face of LaAlO3, the LaNiO3 can be a polar insulator or polar metal depending on the atomic termination of the surface. Lithium osmate, LiOsO3 also undergoes a ferrorelectric transition when it is cooled below 140K. The point group changes from R3c to R3c losing its centrosymmetry. At room temperature and below, lithium osmate is an electric conductor, in single crystal, polycrystalline or powder forms, and the ferroelectric form only appears below 140K. Above 140K the material behaves like a normal metal.

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