β-Ga₂O₃, In₂O₃, and SnO₂ are attractive transparent semiconducting oxides (TSOs) with wide bandgaps of 4.8, 2.8, and 3.6 eV, respectively. They are however, chemically unstable at elevated temperatures and tend to decompose, therefore growing such single crystals from the melt is a very challenging task. Bulk β-Ga₂O₃ (MP=1820°C) single crystals were grown by the Czochralski method using a self-adjusting dynamic growth atmosphere. The crystal appearance and electrical / optical properties are strongly dependent on applied growth conditions. In₂O₃ (MP=1950°C) is much more unstable than Ga₂O₃ and ZnO, and for the purpose of growing bulk In₂O₃ single crystals from the melt we have developed a novel crystal growth method (PCT patent application, 2012), which will be disclosed for the first time at this conference. SnO₂ is the most chemically unstable compound at high temperatures (MP>2100°C) among other TSOs so that single crystals of SnO₂ cannot be grown from the melt. Therefore, bulk SnO₂ single crystals were obtained by the physical vapor transport (PVT). All these bulk TSO single crystals showed n-type conductivity with free electron concentrations in the range of 5x10¹⁶–5x10¹⁸ cm^–3 and electron mobilities between 120–220 cm²/(V s). A systematic annealing study of the bulk TSOs at different atmospheres, temperatures, and times revealed that all the crystals are thermo-chemically stable up to 1200°C in non-reducing and up to 600–700°C in highly reducing conditions. Moreover, in terms of electrical properties, bulk TSO single crystals are sensitive to annealing conditions: the free electron concentration of bulk In₂O₃ crystals could be modified by more than 2 orders of magnitude, while bulk β-Ga₂O₃ and SnO₂ crystals could be even switched interchangeably between semiconductor and electrical insulator just by suitable annealing. Availability of truly bulk TSO single crystals combined with their unique electrical and optical properties opens the door to new applications, such as high power electronics, transparent electronics, and light detectors.

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