Identification of Lone-Pair Surface States on Indium Oxide

Daniel W. Davies, Aron Walsh, James J. Mudd, Chris F. McConville, Anna Regoutz, J. Matthias Kahk, David J. Payne, Vin R. Dhanak, David Hesp, Katariina Pussi, Tien Lin Lee, Russell G. Egdell, Kelvin H.L. Zhang

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Abstract

Indium oxide is widely used as a transparent electrode in optoelectronic devices and as a photocatalyst with activity for reduction of CO2. However, very little is known about the structural and electronic properties of its surfaces, particularly those prepared under reducing conditions. In this report, directional "lone-pair" surface states associated with filled 5s2 orbitals have been identified on vacuum-annealed In2O3(111) through a combination of hard and soft X-ray photoemission spectroscopy and density functional theory calculations. The lone pairs reside on indium ad-atoms in a formal +1 oxidation state, each of which traps two electrons into a localized hybrid orbital protruding away from the surface and lying just above the valence band maximum in photoemission spectra. The third electron associated with the ad-atoms is delocalized into the conduction band, thus producing the surface electron accumulation layer identified previously on vacuum-annealed In2O3(111) (1 × 1) surfaces. The surface structure is further supported by low-energy electron diffraction, but there is no chemical shift in indium core level X-ray photoelectron spectra between surface In(I) ad-atoms and bulk In(III). The 5s2 lone pairs confer Lewis basicity on the surface In sites and may have a pronounced impact on the catalytic or photocatalytic activity of reduced In2O3.

Original languageEnglish
Pages (from-to)1700-1709
Number of pages10
JournalJournal of Physical Chemistry C
Volume123
Issue number3
Early online date24 Dec 2018
DOIs
Publication statusPublished - 24 Jan 2019

ASJC Scopus subject areas

  • Electronic, Optical and Magnetic Materials
  • Energy(all)
  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films

Cite this

Davies, D. W., Walsh, A., Mudd, J. J., McConville, C. F., Regoutz, A., Kahk, J. M., ... Zhang, K. H. L. (2019). Identification of Lone-Pair Surface States on Indium Oxide. Journal of Physical Chemistry C, 123(3), 1700-1709. https://doi.org/10.1021/acs.jpcc.8b08623

Identification of Lone-Pair Surface States on Indium Oxide. / Davies, Daniel W.; Walsh, Aron; Mudd, James J.; McConville, Chris F.; Regoutz, Anna; Kahk, J. Matthias; Payne, David J.; Dhanak, Vin R.; Hesp, David; Pussi, Katariina; Lee, Tien Lin; Egdell, Russell G.; Zhang, Kelvin H.L.

In: Journal of Physical Chemistry C, Vol. 123, No. 3, 24.01.2019, p. 1700-1709.

Research output: Contribution to journalArticle

Davies, DW, Walsh, A, Mudd, JJ, McConville, CF, Regoutz, A, Kahk, JM, Payne, DJ, Dhanak, VR, Hesp, D, Pussi, K, Lee, TL, Egdell, RG & Zhang, KHL 2019, 'Identification of Lone-Pair Surface States on Indium Oxide', Journal of Physical Chemistry C, vol. 123, no. 3, pp. 1700-1709. https://doi.org/10.1021/acs.jpcc.8b08623
Davies DW, Walsh A, Mudd JJ, McConville CF, Regoutz A, Kahk JM et al. Identification of Lone-Pair Surface States on Indium Oxide. Journal of Physical Chemistry C. 2019 Jan 24;123(3):1700-1709. https://doi.org/10.1021/acs.jpcc.8b08623
Davies, Daniel W. ; Walsh, Aron ; Mudd, James J. ; McConville, Chris F. ; Regoutz, Anna ; Kahk, J. Matthias ; Payne, David J. ; Dhanak, Vin R. ; Hesp, David ; Pussi, Katariina ; Lee, Tien Lin ; Egdell, Russell G. ; Zhang, Kelvin H.L. / Identification of Lone-Pair Surface States on Indium Oxide. In: Journal of Physical Chemistry C. 2019 ; Vol. 123, No. 3. pp. 1700-1709.
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