Electron microscopy studies of zirconia-alumina nanolaminates and nickel oxide surfaces

Understanding the atomic scale properties and behavior of materials systems offers exciting potential for the development of fresh and innovative technological applications to impact the world in which we live. The basic materials physics problem addressed in this dissertation involves separate studies of the effects owing to the existence of surfaces present in two types of oxide systems: that of polycrystalline zirconia in zirconia-alumina multilayer films, and that of single-crystal NiO.;The first surface science problem involved study of nanometer-sized zirconia crystallites. Due to the small crystallite size, energetics occurring at the surface of crystallites affected properties of the bulk material including its crystallographic phase. High resolution transmission electron microscopy was used to characterize zirconia crystallites within sputter-deposited films containing a range of zirconia layer thickness, i.e. zirconia crystallite size, and crystallographic phase identification of individual crystallites was made directly from digital high resolution images. Information about the growth behavior of zirconia crystallites was inferred from the observed phase and morphology of crystallites as a function of zirconia layer thickness, i.e. growth time. The capabilities for rapid phase identification of individual crystallites allowed for in situ experimentation into the crystallographic phase transformation behavior of the zirconia nanocrystallites, and for a comparison of that behavior to be made against reported behavior of systems containing much larger, micron-sized zirconia crystals.;The second surface science problem involved study of surfaces of single-crystal NiO, specifically, the polar-(111) surface. The NiO(111) surface, when the surface atoms are in their bulk-terminated positions, has an infinite surface energy. Studies were carried out to examine by what mechanisms the polar surface of NiO overcomes this large surface energy. Transmission electron microscopy and diffraction techniques were used to characterize surfaces of samples prepared under various annealing conditions. A preferential desorbtion of oxygen occurred under vacuum annealing conditions, while a reconstruction of the NiO(111) surface with either (1 x 1) or (√3 x √3)R30° surface periodicity, depending upon the annealing temperature, was observed under atmospheric conditions. Direct methods for surface structure determination were applied to transmission electron diffraction data from the (√3 x √3)R30° reconstruction in order to propose an atomic model for the observed reconstruction.