Heterogeneous ferroelectricity and conductivity of oxidized BaTiO$_3$ crystals: the role of nanoscale phase segregation in the surface region

Abstract: We investigate the effect of thermal oxidation on BaTiO$_3$ single crystals. Our results reveal that, even at moderate temperatures of up to 1000 °C, complex segregation mechanisms occur involving the movement of Ba-rich compounds to the upper surface, where they form inhomogeneously distributed BaO nanocrystals. As a result, deeper regions of the surface layer become depleted in Ba and become TiO$_2$-rich. A sandwich-like structure evolves in the surface layer, exhibiting a measurable electromotive force and self-polarization. This, in turn, screens the polarization and diminishes the global ferroelectric response. The conductivity is also strongly influenced by the irreversible segregation effects in the surface region. An as-received crystal can be transformed into a metallic state, while oxidation induces semiconducting properties and prevents a return to the metallic state upon subsequent reduction. Nanoscale analysis demonstrates that the conductivity is channeled to filaments forming along dislocations, whose local chemical composition changes upon reduction and oxidation even at moderate temperatures due to preferential Ba and O pipe diffusion thus determining the electric behavior of the whole sample.