Revisit to the Origin of Grain Growth Anomaly in Yttria-Doped Barium Titanate

Abstract

In this study, the effect of atmosphere during calcining and sintering of Y2O3-doped BaTiO3 was investigated to reveal the origin of the anomaly of grain growth and conductivity as a function of Y2O3 content. Samples with various atmospheric histories were prepared. Microstructural and electrical variations were observed using SEM, dielectric (ɛr vs T) and thermopower measuring techniques, and impedance spectroscopy. An abrupt decrease in grain growth and a transition from semiconducting to insulating behavior were observed when the Y2O3 concentration exceeded 0.3 mol% and the samples were heat-treated in an O2 atmosphere. In contrast, the samples treated under N2+ 5% H2 atmosphere revealed neither grain growth anomaly nor conductivity anomaly even though the Y2O3 concentration was much greater than 3 mol%. The undoped BaTiO3 samples also demonstrated increased average grain size with increased oxygen partial pressure. Therefore, it was suggested that the grain growth anomaly did not result from the formation of cation vacancies V″Ba or V″″Ti. To investigate the origin of the grain growth anomaly, the Curie temperature, concentration of free electrons, and impedance spectra were measured. The grain growth anomaly and conductivity anomaly were associated with abrupt changes in all the measurements. These abrupt changes could be explained by the partial incorporation of donor dopants. Consequently, the origin of the anomaly in the microstructure and electrical properties are discussed in terms of grain-boundary segregation of the donor dopant.