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Title: Structural perturbations of epitaxial α-(Fe 1-x V x ) 2 O 3 thin films driven by excess oxygen near the surface

Abstract

We examine the structure and composition of phase-pure epitaxial α-(Fe1-xVx)2O3 thin films deposited on α-Al2O3(0001) substrates by oxygen-plasma-assisted molecular beam epitaxy for 0 ≤ x ≤ ~0.5. The films crystallize in the corundum lattice, with vanadium substituting for iron throughout. Vanadium cations exhibit the expected 3+ charge state in the bulk, but exhibit higher valences nearer to the surface, most likely because of excess oxygen in interstitial sites near the surface. The extent of vanadium oxidation beyond the 3+ state is inversely proportional to x. The gradation of vanadium valence with depth has an impact on local bonding geometries, and could be highly significant in this material's efficiency as a photocatalyst.

Authors:
; ; ; ; ; ; ;
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science - Office of Basic Energy Sciences - Chemical Sciences, Geosciences, and Biosciences Division; USDOE Office of Science - Office of Biological and Environmental Research
OSTI Identifier:
1392580
DOE Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article
Journal Name:
Journal of Applied Physics
Additional Journal Information:
Journal Volume: 116; Journal Issue: 23; Journal ID: ISSN 0021-8979
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Chamberlin, S. E., Kaspar, T. C., Bowden, M. E., Shutthanandan, V., Kabius, B., Heald, S., Keavney, D. J., and Chambers, S. A. Structural perturbations of epitaxial α-(Fe 1-x V x ) 2 O 3 thin films driven by excess oxygen near the surface. United States: N. p., 2014. Web. doi:10.1063/1.4903839.
Chamberlin, S. E., Kaspar, T. C., Bowden, M. E., Shutthanandan, V., Kabius, B., Heald, S., Keavney, D. J., & Chambers, S. A. Structural perturbations of epitaxial α-(Fe 1-x V x ) 2 O 3 thin films driven by excess oxygen near the surface. United States. doi:10.1063/1.4903839.
Chamberlin, S. E., Kaspar, T. C., Bowden, M. E., Shutthanandan, V., Kabius, B., Heald, S., Keavney, D. J., and Chambers, S. A. Sun . "Structural perturbations of epitaxial α-(Fe 1-x V x ) 2 O 3 thin films driven by excess oxygen near the surface". United States. doi:10.1063/1.4903839.
@article{osti_1392580,
title = {Structural perturbations of epitaxial α-(Fe 1-x V x ) 2 O 3 thin films driven by excess oxygen near the surface},
author = {Chamberlin, S. E. and Kaspar, T. C. and Bowden, M. E. and Shutthanandan, V. and Kabius, B. and Heald, S. and Keavney, D. J. and Chambers, S. A.},
abstractNote = {We examine the structure and composition of phase-pure epitaxial α-(Fe1-xVx)2O3 thin films deposited on α-Al2O3(0001) substrates by oxygen-plasma-assisted molecular beam epitaxy for 0 ≤ x ≤ ~0.5. The films crystallize in the corundum lattice, with vanadium substituting for iron throughout. Vanadium cations exhibit the expected 3+ charge state in the bulk, but exhibit higher valences nearer to the surface, most likely because of excess oxygen in interstitial sites near the surface. The extent of vanadium oxidation beyond the 3+ state is inversely proportional to x. The gradation of vanadium valence with depth has an impact on local bonding geometries, and could be highly significant in this material's efficiency as a photocatalyst.},
doi = {10.1063/1.4903839},
journal = {Journal of Applied Physics},
issn = {0021-8979},
number = 23,
volume = 116,
place = {United States},
year = {2014},
month = {12}
}

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