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

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 Ce 3+ 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 Ce 4+ ion giving rise to F 2p states which overlap the top of the O 2p band. The nature of this adsorbate F –Ce 4+ 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.

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [5]; ORCiD logo [4]; ORCiD logo [6]; ORCiD logo [6]
  1. Charles Univ., Prague (Czech Republic); Friedrich-Alexander-Univ. Erlangen-Nürnberg, Erlangen (Germany)
  2. Charles Univ., Prague (Czech Republic); Forschungszentrum Jülich, Julich (Germany)
  3. Uppsala Univ., Uppsala (Sweden); Univ. of Bath, Bath (United Kingdom)
  4. Uppsala Univ., Uppsala (Sweden)
  5. Brookhaven National Lab. (BNL), Upton, NY (United States)
  6. Charles Univ., Prague (Czech Republic)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1557709
Report Number(s):
[BNL-211941-2019-JAAM]
[Journal ID: ISSN 0021-9606]
Grant/Contract Number:  
[SC0012704]
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
[ Journal Volume: 151; Journal Issue: 4]; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY

Citation Formats

Kettner, Miroslav, Duchoň, Tomáš, Wolf, Matthew J., Kullgren, Jolla, Senanayake, Sanjaya D., Hermansson, Kersti, Veltruská, Kateřina, and Nehasil, Václav. Anion-mediated electronic effects in reducible oxides: Tuning the valence band of ceria via fluorine doping. United States: N. p., 2019. Web. doi: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. United States. doi:10.1063/1.5109955.
Kettner, Miroslav, Duchoň, Tomáš, Wolf, Matthew J., Kullgren, Jolla, Senanayake, Sanjaya D., Hermansson, Kersti, Veltruská, Kateřina, and Nehasil, Václav. Mon . "Anion-mediated electronic effects in reducible oxides: Tuning the valence band of ceria via fluorine doping". United States. doi:10.1063/1.5109955.
@article{osti_1557709,
title = {Anion-mediated electronic effects in reducible oxides: Tuning the valence band of ceria via fluorine doping},
author = {Kettner, Miroslav and Duchoň, Tomáš and Wolf, Matthew J. and Kullgren, Jolla and Senanayake, Sanjaya D. and Hermansson, Kersti and Veltruská, Kateřina and Nehasil, Václav},
abstractNote = {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.},
doi = {10.1063/1.5109955},
journal = {Journal of Chemical Physics},
number = [4],
volume = [151],
place = {United States},
year = {2019},
month = {7}
}

Journal Article:
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