Interdiffusion-driven synthesis of tetragonal chromium (III) oxide on BaTiO3

Interfaces play a crucial role in the study of novel phenomena emerging at heterostructures comprising metals and functional oxides. For this reason, attention should be paid to the interface chemistry, which can favor the interdiffusion of atomic species and, under certain conditions, lead to the formation of radically different compounds with respect to the original constituents. In this work, we consider Cr/BaTiO3 heterostructures grown on SrTiO3 (100) substrates. Chromium thin films (1-2 nm thickness) are deposited by molecular beam epitaxy on the BaTiO3 layer, and subsequently annealed in vacuum at temperatures ranging from 473 to 773 K. A disordered metallic layer is detected for annealing temperatures up to 573 K, whereas, at higher temperatures, we observe a progressive oxidation of chromium, which we relate to the thermally activated migration of oxygen from the substrate. The chromium oxidation state is + 3 and the film shows a defective rocksalt structure, which grows lattice matched on the underlying BaTiO3 layer. One out of every three atoms of chromium is missing, producing an uncommon tetragonal phase with Cr2O3 stoichiometry. Despite the structural difference with respect to the ordinary corundum alpha-Cr2O3 phase, we demonstrate both experimentally and theoretically that the electronic properties of the two phases are, to a large extent, equivalent.