Anion-mediated electronic effects in reducible oxides: Tuning the valence band of ceria via fluorine doping

Kettner, Miroslav; Duchoň, Tomáš; Wolf, Matthew J.; Kullgren, Jolla; Senanayake, Sanjaya D.; Hermansson, Kersti; Veltruská, Kateřina; Nehasil, Václav

doi:10.1063/1.5109955

Title: Anion-mediated electronic effects in reducible oxides: Tuning the valence band of ceria via fluorine doping

Journal Article · 22 July 2019 · Journal of Chemical Physics

DOI: https://doi.org/10.1063/1.5109955 · OSTI ID:1557709

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Charles Univ., Prague (Czech Republic); Friedrich-Alexander-Univ. Erlangen-Nürnberg, Erlangen (Germany)
Charles Univ., Prague (Czech Republic); Forschungszentrum Jülich, Julich (Germany)
Uppsala Univ., Uppsala (Sweden); Univ. of Bath, Bath (United Kingdom)
Uppsala Univ., Uppsala (Sweden)
Brookhaven National Lab. (BNL), Upton, NY (United States)
Charles Univ., Prague (Czech Republic)

Combining experimental spectroscopy and hybrid density functional theory calculations, we show that the incorporation of fluoride ions into a prototypical reducible oxide surface, namely, ceria(111), can induce a variety of nontrivial changes to the local electronic structure, beyond the expected increase in the number of Ce³⁺ ions. Our resonant photoemission spectroscopy results reveal new states above, within, and below the valence band, which are unique to the presence of fluoride ions at the surface. With the help of hybrid density functional calculations, we show that the different states arise from fluoride ions in different atomic layers in the near surface region. In particular, we identify a structure in which a fluoride ion substitutes for an oxygen ion at the surface, with a second fluoride ion on top of a surface Ce⁴⁺ ion giving rise to F 2p states which overlap the top of the O 2p band. The nature of this adsorbate F^––Ce⁴⁺ resonant enhancement feature suggests that this bond is at least partially covalent. Here, our results demonstrate the versatility of anion doping as a potential means of tuning the valence band electronic structure of ceria.

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Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: SC0012704

OSTI ID:: 1557709

Report Number(s):: BNL--211941-2019-JAAM

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 4 Vol. 151; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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