134Ba diffusion in polycrystalline BaMO3 (M = Ti, Zr, Ce)

Cation diffusion in functional oxide materials is of fundamental interest, particularly in relation to interdiffusion of cations in thin film heterostructures and chemical stability of materials in high temperature electrochemical devices. Here we report on 134Ba tracer diffusion in polycrystalline BaMO3 (M = Ti, Zr, Ce) materials. The dense BaMO3 ceramics were prepared by solid state sintering, and thin films of 134BaO were deposited on the polished pellets by drop casting of an aqueous solution containing the Ba-tracer. The samples were subjected to thermal annealing and the resulting isotope distribution profiles were recorded by secondary ion mass spectrometry. The depth profiles exhibited two distinct regions reflecting lattice and grain boundary diffusion. The grain boundary diffusion was found to be 4-5 orders of magnitude faster than the lattice diffusion for all three materials. The temperature dependence of the lattice and grain boundary diffusion coefficients followed an Arrhenius type behaviour, and the activation energy and pre-exponential factor demonstrated a clear correlation with the size of the primitive unit cell of the three perovskites. Diffusion of Ba via Ba-vacancies was proposed as the most likely diffusion mechanism.