Growth of pure and tin-doped indium oxide crystals and their electrical properties

Indium oxide, In/sub 2/O/sub 3/, is an n-type semiconductor with the C-type oxide structure. Its electrical resistivity is greatly decreased by doping with Sn, so that Sn-doped In/sub 2/O/sub 3/(ITO) thin films are widely used as transparent conductive coating and as heat reflection filters. Single crystals of In/sub 2/O/sub 3/ have been grown by vapor phase, flux, chemical transport or hydrothermal method, but only one growth experiment by a vapor phase method has been reported and no growth experiment of Sn-doped In/sub 2/O/sub 3/ crystals from the vapor phase has been carried out. The authors have brown the In/sub 2/O/sub 3/ crystals by the vapor method, one of which utilized air-oxidation of indium or In/sub 2/O vapors which are produced by reduction of In/sub 2/O/sub 3/ with carbon in a closed crucible. With this growth experiment it was, however, difficult to control the crystallization of In/sub 2/O/sub 3/ since the generation of In/sub 2/O or In vapors and oxidation of their vapors by air spontaneously occur in the crucible. The successful growth experiments for ZnP, GeO/sub 2/ and CdO crystals have been performed using the sophisticated method of controlling air-oxidation of Zn, GeO, and Cd vapors, respectively, which are generated by reduction of the oxides with carbon. The purpose of the present paper is to perform the prolonged growth of pure and Sn-doped In/sub 2/O/sub 3/ crystals by utilizing such a controlled reduction-oxidation process and investigating their electrical properties