Formation of charged (neutral) vacancies of bulk (surface) cubic-ZrO2 was calculated from density functional theory, and compared with available experiments. Relationships among vacancy formation energy, electron and element chemical potentials were established within a wide range of oxygen chemical potentials. The +2 (−2) oxygen (zirconium) vacancy was predicted stable near the valence (conduction) band edge of the bulk, and the neutral oxygen vacancy had the lowest formation energy on (100) O-terminated surface without exhibiting a defect state within the band gap. Therefore, manipulation of oxygen vacancy concentration became possible by optimizing growth surface and oxygen chemical potentials.

Intrinsic Vacancies in Cubic-Zirconia Bulk and Surface. P.J.Shen, S.P.Jiang, K.P.Ong, W.Z.Ding, P.L.Mao, X.G.Lu, C.H.Li, P.Wu: Journal of Alloys and Compounds, 2010, 506[2], 898-901