Covalent superconductors are superconducting materials where the atoms are linked by covalent bonds. The first such material was boron-doped synthetic diamond grown by the high-pressure high-temperature (HPHT) method. [1] The discovery had no practical importance, but surprised most scientists as superconductivity had not been observed in covalent semiconductors, including diamond and silicon.
The priority of many discoveries in science is vigorously disputed (see, e.g., Nobel Prize controversies). Another example, after Sumio Iijima has "discovered" carbon nanotubes in 1991, many scientists have pointed out that carbon nanofibers were actually observed decades earlier. The same could be said about superconductivity in covalent semiconductors. Superconductivity in germanium and silicon-germanium was predicted theoretically as early as in the 1960s. [2] [3] Shortly after, superconductivity was experimentally detected in germanium telluride. [4] [5] In 1976, superconductivity with Tc = 3.5 K was observed experimentally in germanium implanted with copper ions; [6] it was experimentally demonstrated that amorphization was essential for the superconductivity (in Ge), and the superconductivity was assigned to Ge itself, not copper.
Superconductivity in diamond was achieved through heavy p-type doping by boron such that the individual doping atoms started interacting and formed an "impurity band". The superconductivity was of type-II with the critical temperature Tc = 4 K and critical magnetic field Bc = 4 T. Later, Tc ≈ 11 K has been achieved in homoepitaxial CVD films. [7] [8]
Regarding the origin of superconductivity in diamond, three alternative theories were suggested: conventional BCS theory based on phonon-mediated pairing, correlated impurity band theory [9] and spin-flip-driven pairing of holes weakly localized in the vicinity of the Fermi level. [10] Experiments on diamonds enriched with 12C, 13C, 10B or 11B isotopes revealed a clear Tc shift, and its magnitude confirms the BCS mechanism of superconductivity in bulk polycrystalline diamond. [11]
While there have been reports of intrinsic superconductivity in carbon nanotubes, [12] [13] many other experiments found no evidence of superconductivity, and the validity of these results remains a subject of debate. [14] Note, however, a crucial difference between nanotubes and diamond: Although nanotubes contain covalently bonded carbon atoms, they are closer in properties to graphite than diamond, and can be metallic without doping. Meanwhile, undoped diamond is an insulator.
When metal atoms are inserted (intercalated) between the graphite planes, several superconductors are created with the following transition temperatures: [15] [16]
| Material | CaC6 | Li3Ca2C6 | YbC6 | SrC6 | KC8 | RbC8 | NaC3 | KC3 | LiC3 | NaC2 | LiC2 |
|---|---|---|---|---|---|---|---|---|---|---|---|
| Tc (K) | 11.5 | 11.15 | 6.5 | 1.65 | 0.14 | 0.025 | 2.3–3.8 | 3.0 | <0.35 | 5.0 | 1.9 |
It was suggested [1] that "Si and Ge, which also form in the diamond structure, may similarly exhibit superconductivity under the appropriate conditions", and indeed, discoveries of superconductivity in heavily boron doped Si (Si:B) [17] and SiC:B [18] have quickly followed. Similar to diamond, Si:B is type-II superconductor, but it has much smaller values of Tc = 0.4 K and Bc = 0.4 T. Superconductivity in Si:B was achieved by heavy doping (above 8 at.%), realized through a special non-equilibrium technique of gas immersion laser doping.
Superconductivity in SiC was achieved by heavy doping with boron [19] or aluminum. [20] Both the cubic (3C-SiC) and hexagonal (6H-SiC) phases are superconducting and show a very similar Tc of 1.5 K. A crucial difference is however observed for the magnetic field behavior between aluminum and boron doping: SiC:Al is type-II, same as Si:B. On the contrary, SiC:B is type-I. In attempt to explain this difference, it was noted that Si sites are more important than carbon sites for superconductivity in SiC. Whereas boron substitutes carbon in SiC, Al substitutes Si sites. Therefore, Al and B "see" different environment that might explain different properties of SiC:Al and SiC:B. [21]
At pressures above 90 GPa (gigapascal), hydrogen sulfide becomes a metallic conductor of electricity. When cooled below a critical temperature its high-pressure phase exhibits superconductivity. The critical temperature increases with pressure, ranging from 23 K at 100 GPa to 150 K at 200 GPa. [22] 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. By substituting a small part of sulfur with phosphorus and using even higher pressures, it has been predicted that it may be possible to raise the critical temperature to above 0 °C (273 K) and achieve room-temperature superconductivity. [23]
Boron nitride is a thermally and chemically resistant refractory compound of boron and nitrogen with the chemical formula BN. It exists in various crystalline forms that are isoelectronic to a similarly structured carbon lattice. The hexagonal form corresponding to graphite is the most stable and soft among BN polymorphs, and is therefore used as a lubricant and an additive to cosmetic products. The cubic variety analogous to diamond is called c-BN; it is softer than diamond, but its thermal and chemical stability is superior. The rare wurtzite BN modification is similar to lonsdaleite but slightly softer than the cubic form.
High-temperature superconductors are defined as materials with critical temperature above 77 K, the boiling point of liquid nitrogen. They are only "high-temperature" relative to previously known superconductors, which function at even colder temperatures, close to absolute zero. The "high temperatures" are still far below ambient, and therefore require cooling. The first break through of high-temperature superconductor was discovered in 1986 by IBM researchers Georg Bednorz and K. Alex Müller. Although the critical temperature is around 35.1 K, this new type of superconductor was readily modified by Ching-Wu Chu to make the first high-temperature superconductor with critical temperature 93 K. Bednorz and Müller were awarded the Nobel Prize in Physics in 1987 "for their important break-through in the discovery of superconductivity in ceramic materials". Most high-Tc materials are type-II superconductors.
Silicon carbide (SiC), also known as carborundum, is a hard chemical compound containing silicon and carbon. A semiconductor, it occurs in nature as the extremely rare mineral moissanite, but has been mass-produced as a powder and crystal since 1893 for use as an abrasive. Grains of silicon carbide can be bonded together by sintering to form very hard ceramics that are widely used in applications requiring high endurance, such as car brakes, car clutches and ceramic plates in bulletproof vests. Large single crystals of silicon carbide can be grown by the Lely method and they can be cut into gems known as synthetic moissanite.
Magnesium diboride is the inorganic compound with the formula MgB2. It is a dark gray, water-insoluble solid. The compound has attracted attention because it becomes superconducting at 39 K (−234 °C). In terms of its composition, MgB2 differs strikingly from most low-temperature superconductors, which feature mainly transition metals. Its superconducting mechanism is primarily described by BCS theory.
Diamond is the allotrope of carbon in which the carbon atoms are arranged in the specific type of cubic lattice called diamond cubic. It is a crystal that is transparent to opaque and which is generally isotropic. Diamond is the hardest naturally occurring material known. Yet, due to important structural brittleness, bulk diamond's toughness is only fair to good. The precise tensile strength of bulk diamond is little known; however, compressive strength up to 60 GPa has been observed, and it could be as high as 90–100 GPa in the form of micro/nanometer-sized wires or needles, with a corresponding maximum tensile elastic strain in excess of 9%. The anisotropy of diamond hardness is carefully considered during diamond cutting. Diamond has a high refractive index (2.417) and moderate dispersion (0.044) properties that give cut diamonds their brilliance. Scientists classify diamonds into four main types according to the nature of crystallographic defects present. Trace impurities substitutionally replacing carbon atoms in a diamond's crystal structure, and in some cases structural defects, are responsible for the wide range of colors seen in diamond. Most diamonds are electrical insulators and extremely efficient thermal conductors. Unlike many other minerals, the specific gravity of diamond crystals (3.52) has rather small variation from diamond to diamond.
Imperfections in the crystal lattice of diamond are common. Such defects may be the result of lattice irregularities or extrinsic substitutional or interstitial impurities, introduced during or after the diamond growth. The defects affect the material properties of diamond and determine to which type a diamond is assigned; the most dramatic effects are on the diamond color and electrical conductivity, as explained by the electronic band structure.
In the area of solid state chemistry. graphite intercalation compounds are materials prepared by intercalation of diverse guests into graphite. The materials have the formula (guest)Cn where n can range from 8 to 40's. The distance between the carbon layers increases significantly upon insertion of the guests. Common guests are reducing agents such as alkali metals. Strong oxidants, such as arsenic pentafluoride also intercalate into graphite. Intercalation involves electron transfer into or out of the host. The properties of these materials differ from those of the parent graphite.
Tungsten disulfide is an inorganic chemical compound composed of tungsten and sulfur with the chemical formula WS2. This compound is part of the group of materials called the transition metal dichalcogenides. It occurs naturally as the rare mineral tungstenite. This material is a component of certain catalysts used for hydrodesulfurization and hydrodenitrification.
Indium(III) oxide (In2O3) is a chemical compound, an amphoteric oxide of indium.
The interior of a bulk superconductor cannot be penetrated by a weak magnetic field, a phenomenon known as the Meissner effect. When the applied magnetic field becomes too large, superconductivity breaks down. Superconductors can be divided into two types according to how this breakdown occurs. In type-I superconductors, superconductivity is abruptly destroyed via a first order phase transition when the strength of the applied field rises above a critical value Hc. This type of superconductivity is normally exhibited by pure metals, e.g. aluminium, lead, and mercury. The only alloy known up to now which exhibits type I superconductivity is tantalum silicide (TaSi2). The covalent superconductor SiC:B, silicon carbide heavily doped with boron, is also type-I.
Electron-beam-induced deposition (EBID) is a process of decomposing gaseous molecules by an electron beam leading to deposition of non-volatile fragments onto a nearby substrate. The electron beam is usually provided by a scanning electron microscope, which results in high spatial accuracy and the possibility to produce free-standing, three-dimensional structures.
Superconductors can be classified in accordance with several criteria that depend on physical properties, current understanding, and the expense of cooling them or their material.
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.
National Institute for Materials Science is an Independent Administrative Institution and one of the largest scientific research centers in Japan.
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.
Phenacenes are a class of organic compounds consisting of fused aromatic rings. They are polycyclic aromatic hydrocarbons, related to acenes and helicenes from which they differ by the arrangement of the fused rings.
Carbon peapod is a hybrid nanomaterial consisting of spheroidal fullerenes encapsulated within a carbon nanotube. It is named due to their resemblance to the seedpod of the pea plant. Since the properties of carbon peapods differ from those of nanotubes and fullerenes, the carbon peapod can be recognized as a new type of a self-assembled graphitic structure. Possible applications of nano-peapods include nanoscale lasers, single electron transistors, spin-qubit arrays for quantum computing, nanopipettes, and data storage devices thanks to the memory effects and superconductivity of nano-peapods.
Boron nitride nanotubes (BNNTs) are a polymorph of boron nitride. They were predicted in 1994 and experimentally discovered in 1995. Structurally they are similar to carbon nanotubes, which are cylinders with sub-micrometer diameters and micrometer lengths, except that carbon atoms are alternately substituted by nitrogen and boron atoms. However, the properties of BN nanotubes are very different: whereas carbon nanotubes can be metallic or semiconducting depending on the rolling direction and radius, a BN nanotube is an electrical insulator with a bandgap of ~5.5 eV, basically independent of tube chirality and morphology. In addition, a layered BN structure is much more thermally and chemically stable than a graphitic carbon structure. BNNTs have unique physical and chemical properties, when compared to Carbon Nanotubes (CNTs) providing a very wide range of commercial and scientific applications. Although BNNTs and CNTs share similar tensile strength properties of circa 100 times stronger than steel and 50 times stronger than industrial-grade carbon fibre, BNNTs can withstand high temperatures of up to 900 °C. as opposed to CNTs which remain stable up to temperatures of 400 °C, and are also capable of absorbing radiation. BNNTS are packed with physicochemical features including high hydrophobicity and considerable hydrogen storage capacity and they are being investigated for possible medical and biomedical applications, including gene delivery, drug delivery, neutron capture therapy, and more generally as biomaterials BNNTs are also superior to CNTs in the way they bond to polymers giving rise to many new applications and composite materials.