Abstract The intrinsic oxygen vacancy (Ov) in TiO2 is a vital topic of semiconductor materials. Here, we use the first-principles calculations to explore the formation and diffusion properties of Ov at anatase (101) slab, combined with the crystal filed theory. The calculated result shows that Ov at subsurface is not only more stable than that at surface, but also prefers to cluster together at subsurface. The stability of Ov at subsurface is mainly attributed to the Ti3d orbitals in different crystal fields occupied by the excess electrons. Further calculation reveals that the Ov diffusion is greatly affected by the excess electrons. These results presented here show the importance of 3d orbitals in different crystal field, which should be helpful to understand the behavior of Ov at other transition metal oxide.

中文翻译：

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晶场对锐钛矿（101）表面和亚表面氧空位形成和扩散的影响

摘要 TiO2 中的固有氧空位（Ov）是半导体材料的一个重要课题。在这里，我们使用第一性原理计算，结合晶体场理论，探索了 Ov 在锐钛矿（101）平板上的形成和扩散特性。计算结果表明，在地下的Ov不仅比在地表更稳定，而且在地下更倾向于聚集在一起。Ov 在亚表面的稳定性主要归因于不同晶场中的 Ti3d 轨道被多余电子占据。进一步的计算表明，Ov 扩散受多余电子的影响很大。这里呈现的这些结果表明 3d 轨道在不同晶体场中的重要性，这应该有助于理解 Ov 在其他过渡金属氧化物中的行为。