SURFACE CHEMICAL-STATES OF BARIUM-TITANATE - INFLUENCE OF SAMPLE PROCESSING

The composition and chemistry of the near-surface region of BaTiO3 have been studied using x-ray photoelectron spectroscopy (XPS). It is found that the Ba3d photoelectron peak shows two chemical states, one of which is attributed to the bulk perovskite and the other to a special surface state unrelated to contamination. The bulk component is reduced and the surface component increases when the material is annealed at high temperatures (either in reducing or oxidizing atmosphere). Both the components are unaltered if the sample is exposed to air, solvents, or water: processes that lead to adsorption of impurities. The surface peak, therefore, attributed to a relaxation related and not contamination-related state, has been compared with those in other Ba-containing oxides. The oxygen photoelectron peak consists of a normal perovskite peak typical of most titanates and a higher energy component clearly related to surface contamination. Annealing in reducing atmosphere results in drastically different optical and electrical properties, and in chemical reduction of some Ti4+ ions to Ti3+. The overall stoichiometry, however, does not change with annealing atmosphere. These results have been discussed in light of our current understanding of this and other related oxides.