Change in cation nonstoichiometry at interfaces during crystal growth in polycrystalline BaTiO₃

Using an embedded single crystal in a polycrystalline matrix and quantitative electron energy loss spectroscopy, we have demonstrated that Ti-excess grain boundary nonstoichiometry can vary with the extent of boundary migration. While a slight excess in Ti was detected at the boundaries between small matrix grains, a large increase in Ti/Ba ratio, to as much as ∼1.50 compared to the stoichiometric value, was present at the interface between a growing single crystal and the matrix grains when the embedded crystal grew up to a few hundred micrometers. This change in nonstoichiometry was attributed to a continuous accumulation of excessive Ti at the moving boundary during crystal growth. The present result indicates that growth kinetics can critically affect the interface chemistry in polycrystals.