Electron Microscopy of Ion Deposited Thin Films of the Oxides of Titanium

ABSTRACTThe reactive ion beam deposition of ceramic films onto unheated substrates can produce amorphous films with essentially molecular mixing. The annealing and hot isotatic pressing (hipping) of these films to produce crystalline phases have reproducable effects which are sensitive to the temperature and the density of the film. Experiments with titanium oxides indicate that it is principally the equilibrium phases that are formed and that hipping can be used to encourage the same transformations at lower temperatures.Thin films of titanium oxide close to the stoichiometry of TiO2 were deposited onto unheated substrates of sodium chloride. Some of the films were removed from the substrate by floating them off in water and the remainder were either annealed or hipped to induce crystallization. The anneals were performed either in air or argon and the hipping was done under an argon pressure of about twenty thousand pounds per square inch. Several of the free standing films were annealed in the same atmospheres on nickel grids. All the specimens were prepared for transmission electron microscopy by the same floating technique and were examined in a Philips 400 T.E.M. at 125 keV. The as deposited films were amorphous and showed no visible texture other than that derived from a small amount of porosity. The films were sufficiently conductive that they could be examined directly in the T.E.M. without carbon coating provided they were supported on a grid of fairly fine mesh. One specimen was also examined in the Kratos 1.5 MeV high voltage electron microscope at the National Center for Electron Microscopy. The specimen was annealed in vacuum using an in-situ hot stage to directly observe the behavior of the film.The post deposition annealing and hipping of these films reproducibly induced the crystallization of anatase below 800°C. This is the equilibrium phase [1] and the extent to which the films transformed and the morphology of the growing crystallites were determined principally by the film thickness. There was little difference between the responses of free standing films and films left on the salt substrate. They tended to transform at about the same temperature, which was reproduced in the in-situ hot stage experiment and the microsructures which formed were very similar. The dependence upon thickness was also reflected in all the microstructures of the different post deposition treatments and it was possible to complete the transformations that were very sluggish in some of the films by hipping them at the same temperatures.