Femtosecond visualization of oxygen vacancies in metal oxides.

Zhang, Xinping; Tang, Fawei; Wang, Meng; Zhan, Wangbin; Hu, Huaxin; Li, Yurong; Friend, Richard H; Song, Xiaoyan · Sci Adv · 2020

basic_science · Level V

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Abstract

Oxygen vacancies often determine the electronic structure of metal oxides, but existing techniques cannot distinguish the oxygen-vacancy sites in the crystal structure. We report here that time-resolved optical spectroscopy can solve this challenge and determine the spatial locations of oxygen vacancies. Using tungsten oxides as examples, we identified the true oxygen-vacancy sites in WO<sub>2.9</sub> and WO<sub>2.72</sub>, typical derivatives of WO<sub>3</sub> and determined their fingerprint optoelectronic features. We find that a metastable band with a three-stage evolution dynamics of the excited states is present in WO<sub>2.9</sub> but is absent in WO<sub>2.72</sub>. By comparison with model bandstructure calculations, this enables determination of the most closely neighbored oxygen-vacancy pairs in the crystal structure of WO<sub>2.72</sub>, for which two oxygen vacancies are ortho-positioned to a single W atom as a sole configuration among all O─W bonds. These findings verify the existence of preference rules of oxygen vacancies in metal oxides.