Stability of Solid-Solution Phase and the Nature of Phase Separation in Ru–Zr–O Ternary Oxide

Abstract

Equilibrium phase diagram of ruthenium–zirconium oxide (Ru–Zr–O) was calculated by a combination of ab initio density functional theory and thermodynamic calculations. The phase diagrams suggest that the solubility between ruthenium oxide and zirconium oxide is very low under normal experimental conditions, in good agreement with the prior reports in literature. Also provided is the theoretical support for the reported phenomenon that doping or amorphization of Ru–Zr–O might suppress phase separation of the oxide. To study the spinodal decomposition of Ru–Zr–O, we successfully prepared an amorphous Ru0.48Zr0.52O2 film of a solid solution phase by a thermal decomposition at a low temperature (563 K). In situ transmission electron microscopy was utilized to witness the spinodal decomposition of the amorphous Ru0.48Zr0.52O2 solid solution by electron–beam annealing. The present fundamental study of the phase behavior of Ru–Zr–O provides a guideline for the phase and microstructure design of Ru-based mixed ox...