Journal
PHYSICAL REVIEW MATERIALS
Volume 4, Issue 2, Pages -Publisher
AMER PHYSICAL SOC
DOI: 10.1103/PhysRevMaterials.4.025801
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Funding
- DoE-BES, Division of Chemical Sciences, Geosciences and Biosciences [DE-SC0007347]
- National Natural Science Foundation of China [51602092]
- Science and Technology Innovation Project Foundation of Hunan Province [2018RS3103]
- Slovenian Research Agency [P2-0393]
- U.S. Department of Energy (DOE) [DE-SC0007347] Funding Source: U.S. Department of Energy (DOE)
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Two-dimensional (2D) metallic states induced by oxygen vacancies (V(O)s) at oxide surfaces and interfaces provide opportunities for the development of advanced applications, but the ability to control the behavior of these states is still limited. We used angle resolved photoelectron spectroscopy combined with density-functional theory (DFT) to study the reactivity of V-O-induced states at the (001) surface of anatase TiO2, where both 2D metallic and deeper lying in-gap states (IGs) are observed. The 2D and IG states exhibit remarkably different evolutions when the surface is exposed to molecular O-2: while IGs are almost completely quenched, the metallic states are only weakly affected. DFT calculations indeed show that the IGs originate from surface V(O)s and remain localized at the surface, where they can promptly react with O-2. In contrast, the metallic states originate from subsurface vacancies whose migration to the surface for recombination with O-2 is kinetically hindered on anatase TiO2 (001), thus making them much less sensitive to oxygen dosing.
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