O 18 tracer diffusion in Pb(Zr,Ti)O3 thin films: A probe of local oxygen vacancy concentration

A series of O18 tracer in-diffusion experiments have been conducted on state-of-the-art metal organic chemical vapor deposition–grown Pb(Zr,Ti)O3 (PZT) films. Prior to O18 incorporation, samples were preequilibrated in O216 at the same temperature and total pressure used for the following O218 isotope exchange anneal. The final O18 depth profiles were obtained using secondary ion mass spectroscopy (SIMS), which provides a depth resolution of 3–5Å. The SIMS results indicate that the O18 tracer diffusivity varies as a function of depth from the PZT film surface in a way that is inconsistent with a combined grain boundary and lattice diffusion mechanism. Based on a previously-developed model for point defect equilibrium in metal titanate thin films, simulations of O18 tracer diffusion into PZT thin films that are consistent with the experimental results are described.