Crystallization and grain growth characteristics of yttria-stabilized zirconia thin films grown by pulsed laser deposition

Knowledge about the crystallization and grain growth characteristics of metal oxide thin films is essential for effective microstructural engineering by thermal post-annealing and the integration to Si-based miniaturized electroceramic devices. Finite size and interface effects may cause fundamentally different behavior compared to three dimensional macroscopic systems. This work presents a comprehensive investigation of the crystallization kinetics and microstructural evolution upon thermal post-annealing of amorphous 200 nm and 1.2 μm thin films of 8 mol% yttria-stabilized zirconia grown by pulsed laser deposition (PLD) using ex- and in-situ X-ray diffraction, Raman spectroscopy, and electron microscopy techniques. The layers exhibit a remarkably low crystallization temperature of 200–250 °C while exposure to energetic electrons induces the formation of randomly dispersed ~ 20 nm sized crystallites already at ambient temperature. The isothermal amorphous to crystalline phase transformation kinetics can be described quantitatively by the Johnson–Mehl–Avrami–Kolmogorov model. They reveal characteristics of a three dimensional growth under cation bulk diffusion control with heterogeneous nucleation that changes from continuous to instantaneous initial seeding at temperatures above 300 °C. Large (> 100 nm) equiaxed grains are formed rapidly without a stabilization of transient nanocrystals during the thermally induced phase transformation. A stagnation of normal grain growth resulting in a logarithmic normal size distribution is observed once the average grain dimensions approach the film thickness. The results on the crystallization and grain growth of the PLD-grown YSZ films are evaluated with regards to the fabrication of YSZ solid electrolyte membranes for Si-supported micro solid oxide fuel cells and gas sensors.

Research highlights► Quantitative isothermal crystallization kinetics of PLD-grown YSZ thin films. ► 3D grain growth under bulk diffusion control with temperature dependent nucleation. ► Thermal versus electron-beam induced crystallization of PLD-grown YSZ thin films. ► Unusually low crystallization temperature enabling soft processing of YSZ-membranes.