The growth and characterization of epitaxial Co3O4(111) films grown by oxygen plasma-assisted molecular beam epitaxy on single crystalline a-Al2O3(0001) is reported. The Co3O4(111) grows single crystalline with the epitaxial relation Co3O4(111)[-12-1]||a-Al2O3(0001)[10-10], as determined from in situ electron diffraction. Film stoichiometry is confirmed by x-ray photoelectron spectroscopy, while ex situ x-ray diffraction measurements show that the Co3O4 films are fully relaxed. Post-growth annealing induces significant modifications in the film morphology, including a sharper Co3O4/a-Al2O3 interface and improved surface crystallinity, as shown by x-ray reflectometry, atomic force microscopy and electron diffraction measurements. Despite being polar, the surface of both as-grown and annealed Co3O4(111) films are (1 * 1), which can be explained in terms of inversion in the surface spinel structure.
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