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Title: Electronic structure of lanthanum copper oxychalcogenides LaCuOCh (Ch=S, Se, Te) by X-ray photoelectron and absorption spectroscopy

Abstract

X-ray photoelectron spectroscopy (XPS) and X-ray absorption near-edge spectroscopy (XANES) have been applied to examine the electronic structures of lanthanum copper oxychalcogenides LaCuOCh (Ch=S, Se, Te), whose structure has been conventionally viewed as consisting of nominally isolated [LaO] and [CuCh] layers. However, there is evidence for weak La-Ch interactions between these layers, as seen in small changes in the satellite intensity of the La 3d XPS spectra as the chalcogen is changed and as supported by band structure calculations. The O 1s and Cu 2p XPS spectra are insensitive to chalcogen substitution. Lineshapes in the Cu 2p XPS spectra and fine-structure in the Cu L- and M-edge XANES spectra support the presence of Cu{sup +} species. The Ch XPS spectra show negative BE shifts relative to the elemental chalcogen, indicative of anionic species; these shifts correlate well with greater difference in electronegativity between the Cu and Ch atoms, provided that an intermediate electronegativity is chosen for Se. - Graphical abstract: The presence of anionic chalcogen atoms in LaCuOCh is supported by the Ch binding energies, which undergo negative shifts proportional to the polarity of the Cu-Ch bonds. Highlights: > La 3d XPS confirms La-Ch interlayer interactions between [LaO] and [CuCh]more » layers. > O 1s and Cu 2p XPS are insensitive to chalcogen substitution. > Cu XANES spectra support the presence of Cu{sup +} species. > Negative shifts in Ch binding energies imply anionic chalcogen atoms.« less

Authors:
; ;  [1];  [1]
  1. Department of Chemistry, University of Alberta, Edmonton, Alberta, T6G 2G2 (Canada)
Publication Date:
OSTI Identifier:
21580166
Resource Type:
Journal Article
Journal Name:
Journal of Solid State Chemistry
Additional Journal Information:
Journal Volume: 184; Journal Issue: 7; Other Information: DOI: 10.1016/j.jssc.2011.05.005; PII: S0022-4596(11)00226-X; Copyright (c) 2011 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Journal ID: ISSN 0022-4596
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ABSORPTION; ABSORPTION SPECTROSCOPY; BINDING ENERGY; COPPER; COPPER IONS; ELECTRONEGATIVITY; ELECTRONIC STRUCTURE; FINE STRUCTURE; INTERACTIONS; LANTHANUM; LANTHANUM OXIDES; SPECTRA; X RADIATION; X-RAY PHOTOELECTRON SPECTROSCOPY; X-RAY SPECTROSCOPY; CHALCOGENIDES; CHARGED PARTICLES; ELECTROMAGNETIC RADIATION; ELECTRON SPECTROSCOPY; ELEMENTS; ENERGY; IONIZING RADIATIONS; IONS; LANTHANUM COMPOUNDS; METALS; OXIDES; OXYGEN COMPOUNDS; PHOTOELECTRON SPECTROSCOPY; RADIATIONS; RARE EARTH COMPOUNDS; RARE EARTHS; SORPTION; SPECTROSCOPY; TRANSITION ELEMENTS

Citation Formats

Rudyk, Brent W, Blanchard, Peter E.R., Cavell, Ronald G, and Mar, Arthur. Electronic structure of lanthanum copper oxychalcogenides LaCuOCh (Ch=S, Se, Te) by X-ray photoelectron and absorption spectroscopy. United States: N. p., 2011. Web. doi:10.1016/j.jssc.2011.05.005.
Rudyk, Brent W, Blanchard, Peter E.R., Cavell, Ronald G, & Mar, Arthur. Electronic structure of lanthanum copper oxychalcogenides LaCuOCh (Ch=S, Se, Te) by X-ray photoelectron and absorption spectroscopy. United States. https://doi.org/10.1016/j.jssc.2011.05.005
Rudyk, Brent W, Blanchard, Peter E.R., Cavell, Ronald G, and Mar, Arthur. Fri . "Electronic structure of lanthanum copper oxychalcogenides LaCuOCh (Ch=S, Se, Te) by X-ray photoelectron and absorption spectroscopy". United States. https://doi.org/10.1016/j.jssc.2011.05.005.
@article{osti_21580166,
title = {Electronic structure of lanthanum copper oxychalcogenides LaCuOCh (Ch=S, Se, Te) by X-ray photoelectron and absorption spectroscopy},
author = {Rudyk, Brent W and Blanchard, Peter E.R. and Cavell, Ronald G and Mar, Arthur},
abstractNote = {X-ray photoelectron spectroscopy (XPS) and X-ray absorption near-edge spectroscopy (XANES) have been applied to examine the electronic structures of lanthanum copper oxychalcogenides LaCuOCh (Ch=S, Se, Te), whose structure has been conventionally viewed as consisting of nominally isolated [LaO] and [CuCh] layers. However, there is evidence for weak La-Ch interactions between these layers, as seen in small changes in the satellite intensity of the La 3d XPS spectra as the chalcogen is changed and as supported by band structure calculations. The O 1s and Cu 2p XPS spectra are insensitive to chalcogen substitution. Lineshapes in the Cu 2p XPS spectra and fine-structure in the Cu L- and M-edge XANES spectra support the presence of Cu{sup +} species. The Ch XPS spectra show negative BE shifts relative to the elemental chalcogen, indicative of anionic species; these shifts correlate well with greater difference in electronegativity between the Cu and Ch atoms, provided that an intermediate electronegativity is chosen for Se. - Graphical abstract: The presence of anionic chalcogen atoms in LaCuOCh is supported by the Ch binding energies, which undergo negative shifts proportional to the polarity of the Cu-Ch bonds. Highlights: > La 3d XPS confirms La-Ch interlayer interactions between [LaO] and [CuCh] layers. > O 1s and Cu 2p XPS are insensitive to chalcogen substitution. > Cu XANES spectra support the presence of Cu{sup +} species. > Negative shifts in Ch binding energies imply anionic chalcogen atoms.},
doi = {10.1016/j.jssc.2011.05.005},
url = {https://www.osti.gov/biblio/21580166}, journal = {Journal of Solid State Chemistry},
issn = {0022-4596},
number = 7,
volume = 184,
place = {United States},
year = {2011},
month = {7}
}