Time-Temperature-Transformation (TTT) Diagrams for Crystallization of Metal Oxide Thin Films

Time-temperature-transformation (TTT) diagrams are proposed for the crystallization of amorphous metal oxide thin films and their specific characteristics are discussed in comparison to glass-based materials, such as glass-ceramics and metallic glasses. The films crystallize from amorphous to full crystallinity in the solid state. As an example the crystallization kinetics for a single-phase metal oxide, ceria, and its gadolinia solid solutions are reported made by the precipitation thin-film method spray pyrolysis. The crystallization of an amorphous metal oxide thin film generally follows the Lijschitz-Sletow-Wagner (LSW) Ostwald ripening theory: Below the percolation threshold of 20 vol% single grains crystallize in the amorphous phase and low crystallization rates are measured. In this state no impact of solute on crystallization is measurable. Once the grains form primary clusters above the threshold the solute slows down crystallization (and grain growth) thus shifting the TTT curves of the doped ceria films to longer times and higher temperatures in comparison to undoped ceria. Current views on crystallization of metal oxide thin films, the impact of solute dragging, and primary TTT diagrams are discussed. Finally, examples on how to use these TTT diagrams for better thermokinetic engineering of metal oxide thin films for MEMS are given, for example, for micro-Solid Oxide Fuel Cells and resistive sensors. In these examples the electrical properties depend on the degree of crystallinity and, thereby, on the TTT conditions.