The band structure of WO3 and non-rigid-band behaviour in Na0.67WO3 derived from soft x-ray spectroscopy and density functional theory

B. Chen, J. Laverock, L. F.J. Piper, A. R.H. Preston, Sangwan Cho, A. Demasi, K. E. Smith, D. O. Scanlon, G. W. Watson, R. G. Egdell, P. A. Glans, J. H. Guo

Research output: Contribution to journalArticle

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Abstract

The electronic structure of single-crystal WO3 and Na 0.67WO3 (a sodium-tungsten bronze) has been measured using soft x-ray absorption and resonant soft x-ray emission oxygen K-edge spectroscopies. The spectral features show clear differences in energy and intensity between WO3 and Na0.67WO3. The x-ray emission spectrum of metallic Na0.67WO3 terminates in a distinct Fermi edge. The rigid-band model fails to explain the electronic structure of Na0.67WO3 in terms of a simple addition of electrons to the conduction band of WO3. Instead, Na bonding and Na 3s-O 2p hybridization need to be considered for the sodium-tungsten bronze, along with occupation of the bottom of the conduction band. Furthermore, the anisotropy in the band structure of monoclinic γ-WO3 revealed by the experimental spectra with orbital-resolved geometry is explained via density functional theory calculations. For γ-WO3 itself, good agreement is found between the experimental O K-edge spectra and the theoretical partial density of states of O 2p orbitals. Indirect and direct bandgaps of insulating WO3 are determined from extrapolating separations between spectral leading edges and accounting for the core-hole energy shift in the absorption process. The O 2p non-bonding states show upward band dispersion as a function of incident photon energy for both compounds, which is explained using the calculated band structure and experimental geometry.

Original languageEnglish
Article number165501
JournalJournal of Physics Condensed Matter
Volume25
Issue number16
DOIs
Publication statusPublished - 2013 Apr 24

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Band structure
x ray spectroscopy
Density functional theory
Tungsten
Bronze
Spectroscopy
density functional theory
Conduction bands
X rays
Electronic structure
bronzes
Sodium
conduction bands
tungsten
Geometry
sodium
electronic structure
orbitals
x ray spectra
Energy gap

All Science Journal Classification (ASJC) codes

  • Materials Science(all)
  • Condensed Matter Physics

Cite this

Chen, B. ; Laverock, J. ; Piper, L. F.J. ; Preston, A. R.H. ; Cho, Sangwan ; Demasi, A. ; Smith, K. E. ; Scanlon, D. O. ; Watson, G. W. ; Egdell, R. G. ; Glans, P. A. ; Guo, J. H. / The band structure of WO3 and non-rigid-band behaviour in Na0.67WO3 derived from soft x-ray spectroscopy and density functional theory. In: Journal of Physics Condensed Matter. 2013 ; Vol. 25, No. 16.
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abstract = "The electronic structure of single-crystal WO3 and Na 0.67WO3 (a sodium-tungsten bronze) has been measured using soft x-ray absorption and resonant soft x-ray emission oxygen K-edge spectroscopies. The spectral features show clear differences in energy and intensity between WO3 and Na0.67WO3. The x-ray emission spectrum of metallic Na0.67WO3 terminates in a distinct Fermi edge. The rigid-band model fails to explain the electronic structure of Na0.67WO3 in terms of a simple addition of electrons to the conduction band of WO3. Instead, Na bonding and Na 3s-O 2p hybridization need to be considered for the sodium-tungsten bronze, along with occupation of the bottom of the conduction band. Furthermore, the anisotropy in the band structure of monoclinic γ-WO3 revealed by the experimental spectra with orbital-resolved geometry is explained via density functional theory calculations. For γ-WO3 itself, good agreement is found between the experimental O K-edge spectra and the theoretical partial density of states of O 2p orbitals. Indirect and direct bandgaps of insulating WO3 are determined from extrapolating separations between spectral leading edges and accounting for the core-hole energy shift in the absorption process. The O 2p non-bonding states show upward band dispersion as a function of incident photon energy for both compounds, which is explained using the calculated band structure and experimental geometry.",
author = "B. Chen and J. Laverock and Piper, {L. F.J.} and Preston, {A. R.H.} and Sangwan Cho and A. Demasi and Smith, {K. E.} and Scanlon, {D. O.} and Watson, {G. W.} and Egdell, {R. G.} and Glans, {P. A.} and Guo, {J. H.}",
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Chen, B, Laverock, J, Piper, LFJ, Preston, ARH, Cho, S, Demasi, A, Smith, KE, Scanlon, DO, Watson, GW, Egdell, RG, Glans, PA & Guo, JH 2013, 'The band structure of WO3 and non-rigid-band behaviour in Na0.67WO3 derived from soft x-ray spectroscopy and density functional theory', Journal of Physics Condensed Matter, vol. 25, no. 16, 165501. https://doi.org/10.1088/0953-8984/25/16/165501

The band structure of WO3 and non-rigid-band behaviour in Na0.67WO3 derived from soft x-ray spectroscopy and density functional theory. / Chen, B.; Laverock, J.; Piper, L. F.J.; Preston, A. R.H.; Cho, Sangwan; Demasi, A.; Smith, K. E.; Scanlon, D. O.; Watson, G. W.; Egdell, R. G.; Glans, P. A.; Guo, J. H.

In: Journal of Physics Condensed Matter, Vol. 25, No. 16, 165501, 24.04.2013.

Research output: Contribution to journalArticle

TY - JOUR

T1 - The band structure of WO3 and non-rigid-band behaviour in Na0.67WO3 derived from soft x-ray spectroscopy and density functional theory

AU - Chen, B.

AU - Laverock, J.

AU - Piper, L. F.J.

AU - Preston, A. R.H.

AU - Cho, Sangwan

AU - Demasi, A.

AU - Smith, K. E.

AU - Scanlon, D. O.

AU - Watson, G. W.

AU - Egdell, R. G.

AU - Glans, P. A.

AU - Guo, J. H.

PY - 2013/4/24

Y1 - 2013/4/24

N2 - The electronic structure of single-crystal WO3 and Na 0.67WO3 (a sodium-tungsten bronze) has been measured using soft x-ray absorption and resonant soft x-ray emission oxygen K-edge spectroscopies. The spectral features show clear differences in energy and intensity between WO3 and Na0.67WO3. The x-ray emission spectrum of metallic Na0.67WO3 terminates in a distinct Fermi edge. The rigid-band model fails to explain the electronic structure of Na0.67WO3 in terms of a simple addition of electrons to the conduction band of WO3. Instead, Na bonding and Na 3s-O 2p hybridization need to be considered for the sodium-tungsten bronze, along with occupation of the bottom of the conduction band. Furthermore, the anisotropy in the band structure of monoclinic γ-WO3 revealed by the experimental spectra with orbital-resolved geometry is explained via density functional theory calculations. For γ-WO3 itself, good agreement is found between the experimental O K-edge spectra and the theoretical partial density of states of O 2p orbitals. Indirect and direct bandgaps of insulating WO3 are determined from extrapolating separations between spectral leading edges and accounting for the core-hole energy shift in the absorption process. The O 2p non-bonding states show upward band dispersion as a function of incident photon energy for both compounds, which is explained using the calculated band structure and experimental geometry.

AB - The electronic structure of single-crystal WO3 and Na 0.67WO3 (a sodium-tungsten bronze) has been measured using soft x-ray absorption and resonant soft x-ray emission oxygen K-edge spectroscopies. The spectral features show clear differences in energy and intensity between WO3 and Na0.67WO3. The x-ray emission spectrum of metallic Na0.67WO3 terminates in a distinct Fermi edge. The rigid-band model fails to explain the electronic structure of Na0.67WO3 in terms of a simple addition of electrons to the conduction band of WO3. Instead, Na bonding and Na 3s-O 2p hybridization need to be considered for the sodium-tungsten bronze, along with occupation of the bottom of the conduction band. Furthermore, the anisotropy in the band structure of monoclinic γ-WO3 revealed by the experimental spectra with orbital-resolved geometry is explained via density functional theory calculations. For γ-WO3 itself, good agreement is found between the experimental O K-edge spectra and the theoretical partial density of states of O 2p orbitals. Indirect and direct bandgaps of insulating WO3 are determined from extrapolating separations between spectral leading edges and accounting for the core-hole energy shift in the absorption process. The O 2p non-bonding states show upward band dispersion as a function of incident photon energy for both compounds, which is explained using the calculated band structure and experimental geometry.

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U2 - 10.1088/0953-8984/25/16/165501

DO - 10.1088/0953-8984/25/16/165501

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JO - Journal of Physics Condensed Matter

JF - Journal of Physics Condensed Matter

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