A Stabilization Mechanism of Zirconia Based on Oxygen Vacancies Only

Abstract

The microscopic mechanism leading to stabilization of cubic and tetragonal forms of zirconia (ZrO$_2$) is analyzed by means of a self-consistent tight-binding model. Using this model, energies and structures of zirconia containing different vacancy concentrations are calculated, equivalent in concentration to the charge compensating vacancies associated with dissolved yttria (Y$_2$O$_3$) in the tetragonal and cubic phase fields (3.2 and 14.4% mol respectively). The model is shown to predict the large relaxations around an oxygen vacancy, and the clustering of vacancies along the $$ directions, in good agreement with experiments and first principles calculations. The vacancies alone are shown to explain the stabilization of cubic zirconia, and the mechanism is analyzed.Comment: 19 pages, 6 figures. To be published in J. Am. Ceram. So