Titanium di- and sesquioxide films were epitaxially grown on the (001) surface of sapphire single-crystalline substrates by an activated reactive evaporation method. Formation range for each titanium oxide was determined as a function of oxygen pressure (Po2) by means of x-ray diffraction, transmission electron microscopy, and Raman spectroscopy. Films prepared at Po2 ≥ 2.0 × 10−4 Torr were stoichiometric (100)-oriented rutile of TiO2, and with decreasing Po2 they would accommodate more and more Ti3+ ions in the rutile structure. At Po2 = 0.6 × 10−4 Torr, on the other hand, (001)-oriented Ti2O3 was formed and an electrical transition was clearly detected at about 400 K. However, the large lattice mismatch between the substrate and these films leads to a periodic introduction of misfit dislocations in the case of the TiO2 films and a mixing of stacking sequences for the Ti2O3 films.

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