This title appears in the Scientific Report :
2019
Please use the identifier:
http://hdl.handle.net/2128/22568 in citations.
Please use the identifier: http://dx.doi.org/10.1063/1.5109955 in citations.
Anion-mediated electronic effects in reducible oxides: Tuning the valence band of ceria via fluorine doping
Anion-mediated electronic effects in reducible oxides: Tuning the valence band of ceria via fluorine doping
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 in...
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Personal Name(s): | Kettner, Miroslav (Corresponding author) |
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Duchoň, Tomáš / Wolf, Matthew J. / Kullgren, Jolla / Senanayake, Sanjaya D. / Hermansson, Kersti / Veltruská, Kateřina / Nehasil, Václav | |
Contributing Institute: |
Elektronische Eigenschaften; PGI-6 |
Published in: | The journal of chemical physics, 151 (2019) 4, S. 044701 - |
Imprint: |
Melville, NY
American Institute of Physics
2019
|
PubMed ID: |
31370552 |
DOI: |
10.1063/1.5109955 |
Document Type: |
Journal Article |
Research Program: |
Controlling Spin-Based Phenomena |
Link: |
Published on 2019-07-22. Available in OpenAccess from 2020-07-22. Published on 2019-07-22. Available in OpenAccess from 2020-07-22. |
Publikationsportal JuSER |
Please use the identifier: http://dx.doi.org/10.1063/1.5109955 in citations.
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 |