Epitaxial polymorphism of La2O3 on Si(111) studied by in situ x-ray diffraction

The phase formation of La2O3 epitaxial films during growth on Si(111) is investigated by synchrotron-based in situ grazing incidence x-ray diffraction and high resolution transmission electron microscopy. We find that first a 2–4 nm thick cubic bixbyite La2O3 layer grows at the interface to Si(111) substrate, followed by a hexagonal La2O3 film. Hence, to keep a cubic on cubic heteroepitaxy and to achieve high quality epitaxial nanostructures or multi-layers, the thickness of the interfacial La2O3 layer has to be restricted to 2 nm. The larger formation energy of the cubic phase can only partially be compensated by the biaxial strain in the epitaxial film based on density functional perturbation theory. Hence, the stabilization of the cubic phase is not due to bulk strain but could be related to a lower surface or interface free energy, or to kinetic effects.