Films of various iron oxides including FeO, Fe3 O4 , and α-Fe2 O3 were formed on the α-Al2 O3 (0001) surface by a reactive vapor deposition method and characterized by x-ray diffraction and conversion electron Mössbauer spectroscopy (CEMS). The formation range for each phase was determined as a function of the substrate temperature (Ts ) and oxygen partial pressure (PO2 ). Typically, the deposition of (111)-oriented epitaxial magnetite films could be performed at low temperatures of Ts =523∼623 K and PO2 =1.0–5.0×10−4 Torr. Good stoichiometry of the as-grown films were confirmed by CEMS, and the Verwey transition was clearly detected by measurements of resistivity and CEMS down to 77 K. However, the large lattice mismatch between the substrate and Fe3 O4 resulted in a columnar particle growth. The initially grown phase on such a mismatched substrate was specifically characterized by depositing the Mössbauer active isotope, 57 Fe, only at the deepest layers. On the other hand, by depositing 57 Fe only in the topmost layers, surface layers of well-crystallized films have been found to be rather stable against oxidation.

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