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Contributions of oxygen vacancies and titanium interstitials to band-gap states of reduced titania

Abstract : The spectroscopic fingerprints of the point defects of titanium dioxide remain highly controversial. Seemingly indisputable experiments lead to conflicting conclusions in which oxygen vacancies and titanium interstitials are alternately referred to as the primary origin of the Ti 3d band-gap states. We report on experiments performed by electron energy loss spectroscopy whose key is the direct annealing of only the very surface of rutile TiO2(110) crystals and the simultaneous measurement of its temperature via the Bose-Einstein loss/gain ratio. By surface preparations involving reactions with oxygen and water vapor, in particular, under electron irradiation, vacancy- and interstitial-related band-gap states are singled out. Off-specular measurements reveal that both types of defects contribute to a unique charge distribution that peaks in subsurface layers with a common dispersive behavior.
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Jingfeng Li, Rémi Lazzari, Stéphane Chenot, Jacques Jupille. Contributions of oxygen vacancies and titanium interstitials to band-gap states of reduced titania. Physical Review B: Condensed Matter and Materials Physics (1998-2015), American Physical Society, 2018, 97 (4), pp.041403. ⟨10.1103/PhysRevB.97.041403⟩. ⟨hal-01700847⟩

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