Anion-mediated electronic effects in reducible oxides

Tuning the valence band of ceria via fluorine doping

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

Research output: Contribution to journalArticle

Abstract

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. Our results demonstrate the versatility of anion doping as a potential means of tuning the valence band electronic structure of ceria.

Original languageEnglish
Article number044701
Pages (from-to)1-9
Number of pages9
JournalJournal of Chemical Physics
Volume151
Issue number4
Early online date22 Jul 2019
DOIs
Publication statusPublished - 28 Jul 2019

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

Kettner, M., Duchoň, T., Wolf, M. J., Kullgren, J., Senanayake, S. D., Hermansson, K., ... Nehasil, V. (2019). Anion-mediated electronic effects in reducible oxides: Tuning the valence band of ceria via fluorine doping. Journal of Chemical Physics, 151(4), 1-9. [044701]. https://doi.org/10.1063/1.5109955

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.

In: Journal of Chemical Physics, Vol. 151, No. 4, 044701, 28.07.2019, p. 1-9.

Research output: Contribution to journalArticle

Kettner, M, Duchoň, T, Wolf, MJ, Kullgren, J, Senanayake, SD, Hermansson, K, Veltruská, K & Nehasil, V 2019, 'Anion-mediated electronic effects in reducible oxides: Tuning the valence band of ceria via fluorine doping', Journal of Chemical Physics, vol. 151, no. 4, 044701, pp. 1-9. https://doi.org/10.1063/1.5109955
Kettner, Miroslav ; Duchoň, Tomáš ; Wolf, Matthew J. ; Kullgren, Jolla ; Senanayake, Sanjaya D. ; Hermansson, Kersti ; Veltruská, Kateřina ; Nehasil, Václav. / Anion-mediated electronic effects in reducible oxides : Tuning the valence band of ceria via fluorine doping. In: Journal of Chemical Physics. 2019 ; Vol. 151, No. 4. pp. 1-9.
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