Covalent superconductors are superconducting materials where the atoms are linked by covalent bonds. The first such material was synthetic diamond grown by the high-pressure high-temperature (HPHT) method. The discovery had no practical importance, but surprised most scientists as superconductivity had not been observed in covalent semiconductors, including diamond and silicon.
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 Hc = 4 T. Later, Tc ~ 11K has been achieved in homoepitaxial CVD films.
Regarding the origin of superconductivity in diamond, three alternative theories exist at the moment: conventional BCS theory based on phonon-mediated pairing, correlated impurity band theory and spin-flip-driven pairing of holes weakly localized in the vicinity of the Fermi level. Whereas there is no solid experimental support for either model, recent accurate measurements of isotopic shift of the transition temperature Tc upon boron and carbon isotopic substitutions favor the BCS theory.
It was suggested 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) and SiC:B have quickly followed. Similar to diamond, Si:B is type-II superconductor, but it has much smaller values of Tc = 0.4 K and Hc = 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 or aluminum. 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.
While there have been reports of intrinsic superconductivity in carbon nanotubes, many other experiments found no evidence of superconductivity, and the validity of these results remains a subject of debate. 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.
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. Shortly after, superconductivity was experimentally detected in germanium telluride. In 1976, superconductivity with Tc = 3.5 K was observed experimentally in germanium implanted with copper ions; it was experimentally demonstrated that amorphization was essential for the superconductivity (in Ge), and the superconductivity was assigned to Ge itself, not copper.
- Conventional superconductor
- List of superconductors
- High-temperature superconductivity
- Room temperature superconductor
- Superconductor classification
- Technological applications of superconductivity
- Timeline of low-temperature technology
- Type-I superconductor
- Type-II superconductor
- Unconventional superconductor
- Silicon carbide
- Synthetic diamond
- Ekimov, E. A.; Sidorov, V. A.; Bauer, E. D.; Mel'Nik, N. N.; Curro, N. J.; Thompson, J. D.; Stishov, S. M. (2004). "Superconductivity in diamond". Nature 428 (6982): 542–545. doi:10.1038/nature02449. PMID 15057827.
L. Boeri, J. Kortus and O. K. Andersen "Three-Dimensional MgB2-Type Superconductivity in Hole-Doped Diamond",
K.-W. Lee and W. E. Pickett "Superconductivity in Boron-Doped Diamond",
X. Blase, Ch. Adessi and D. Connetable "Role of the Dopant in the Superconductivity of Diamond",
E. Bustarret et al. "Dependence of the Superconducting Transition Temperature on the Doping Level in Single-Crystalline Diamond Films" - free download
- Y. Takano et al. (2007). "Superconducting properties of homoepitaxial CVD diamond". Diam. Relat. Mater. 16: 911. Bibcode:2007DRM....16..911T. doi:10.1016/j.diamond.2007.01.027.
- Y. Takano (2006). "Overview". Sci. Technol. Adv. Mater. 7: S1. Bibcode:2006STAdM...7S...1T. doi:10.1016/j.stam.2006.06.003.
- G. Baskaran (2008). "Impurity band Mott insulators: a new route to high Tc superconductivity". Sci. Technol. Adv. Mater. 9 (4): 044104. Bibcode:2008STAdM...9d4104B. doi:10.1088/1468-6996/9/4/044104.
- J. Mares et al. (2008). "Selected topics related to the transport and superconductivity in boron-doped diamond". Sci. Technol. Adv. Mater. 9 (4): 044101. Bibcode:2008STAdM...9d4101M. doi:10.1088/1468-6996/9/4/044101.
- E. A. Ekimov et al. (2008). "Structure and superconductivity of isotope-enriched boron-doped diamond". Sci. Technol. Adv. Mater. 9 (4): 044210. Bibcode:2008STAdM...9d4210E. doi:10.1088/1468-6996/9/4/044210.
- E. Bustarret et al. (2006). "Superconductivity in doped cubic silicon". Nature 444 (7118): 465. Bibcode:2006Natur.444..465B. doi:10.1038/nature05340. PMID 17122852.
- Zhi-An Ren et al. (2007). "Superconductivity in Boron-doped SiC". J. Phys. Soc. Japan 76: 103710. Bibcode:2007JPSJ...76b3710M. doi:10.1143/JPSJ.76.023710.
- M. Kriener et al. (2008). "Superconductivity in heavily boron-doped silicon carbide". Sci. Technol. Adv. Mater. 9 (4): 044205. arXiv:0810.0056. Bibcode:2008STAdM...9d4205K. doi:10.1088/1468-6996/9/4/044205.
- T. Muranaka et al. (2008). "Superconductivity in carrier-doped silicon carbide". Sci. Technol. Adv. Mater. 9 (4): 044204. Bibcode:2008STAdM...9d4204M. doi:10.1088/1468-6996/9/4/044204.
- Y. Yanase and N. Yorozu (2008). "Superconductivity in compensated and uncompensated semiconductors". Sci. Technol. Adv. Mater. 9 (4): 044201. Bibcode:2008STAdM...9d4201Y. doi:10.1088/1468-6996/9/4/044201.
- Z.K. Tang et al. (2001). "Superconductivity in 4 Angstrom Single-Walled Carbon Nanotubes". Science 292 (5526): 2462. Bibcode:2001Sci...292.2462T. doi:10.1126/science.1060470. PMID 11431560.
- M. Kociak et al. (2001). "Superconductivity in Ropes of Single-Walled Carbon Nanotubes". Physical Review Letters 86: 2416. arXiv:cond-mat/0010220. Bibcode:2001PhRvL..86.2416K. doi:10.1103/PhysRevLett.86.2416.
- M. Bockrath (2006). "Carbon nanotubes: The weakest link". Nature Physics 2: 155. Bibcode:2006NatPh...2..155B. doi:10.1038/nphys252.
- N. Emery et al. (2008). "Review: Synthesis and superconducting properties of CaC6". Sci. Technol. Adv. Mater. 9 (4): 044102. Bibcode:2008STAdM...9d4102E. doi:10.1088/1468-6996/9/4/044102.
- I.T Belash et al. (1990). "Superconductivity of GIC with Li, Na and K". Synthetic Metals 34: 455. doi:10.1016/0379-6779(89)90424-4.
- Gurevich V L, Larkin A I and Firsov Yu A (1962). Sov. Phys. Solid State 4: 185.
- M. L. Cohen (1964). "The Existence of a Superconducting State in Semiconductors". Rev. Mod. Phys. 36: 240. Bibcode:1964RvMP...36..240C. doi:10.1103/RevModPhys.36.240.
- R.A. Hein et al. (1964). "Superconductivity in Germanium Telluride". Phys. Rev. Lett. 12: 320. Bibcode:1964PhRvL..12..320H. doi:10.1103/PhysRevLett.12.320.
- L. Finegold (1964). "Germanium Telluride: Specific Heat and Superconductivity". Phys. Rev. Lett. 13: 233. Bibcode:1964PhRvL..13..233F. doi:10.1103/PhysRevLett.13.233.
- B. Stritzker and H. Wuhl (1976). "Superconductivity of amorphous Germanium produced by ion implantation". Zeitschrift für Physik B 24: 367. Bibcode:1976ZPhyB..24..367S. doi:10.1007/BF01351526.
- International Workshop on superconductivity in Diamond and Related Materials 2005
- International Workshop on Superconductivity in Diamond and Related Materials 2008
- New Diamond and Frontier Carbon Technology Volume 17, No.1 Special Issue on Superconductivity in CVD Diamond
- Some papers on superconducting diamond