Nanoscale formation of new solid-state compounds by topochemical effects: The interfacial reactions ZnO with Al2O3 as a model system

The chemical reactivity of thin layers (ca. 10 nm thick) of ZnO deposited onto differently oriented Al2O3 single crystals has been investigated by means of atomic force microscopy inspections and X-ray absorption spectroscopy at the Zn–K edge. The View the MathML source(0001)ZnO∥(112¯0)sapphire interface yields the ZnAl2O4 spinel and a quite stable film morphology. Instead, the View the MathML source(112¯0)ZnO∥(11¯02)sapphire and (0001)ZnO∥(0001)sapphire interfaces give origin to a new compound (or, possibly, even two new compounds), whose chemical nature is most likely that of a ZnO/Al2O3 phase, with still unknown composition and crystal structure. In addition, in the last two cases, films collapse into prismatic twins of ca. 1 μm in dimension. These experimental findings demonstrate that in a solid-state reaction, the topotactical relationships between the reacting solids are of crucial importance not only in determining the kinetic and mechanisms of the process in its early stages, but even the chemical nature of the product.