Covalent superconductor

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. 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.

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