skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Structural perturbations of epitaxial α-(Fe1-xVx)2O3 thin films driven by excess oxygen near the surface

Journal Article · · Journal of Applied Physics, 116(23):Article No. 233702
DOI:https://doi.org/10.1063/1.4903839· OSTI ID:1188913

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 may have an impact on local bonding geometries, and could be highly significant in this material’s efficiency as a photocatalyst.

Research Organization:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
Sponsoring Organization:
USDOE
Grant/Contract Number:
AC05-76RL01830
OSTI ID:
1188913
Report Number(s):
PNNL-SA-105900; 48144; KC0304030
Journal Information:
Journal of Applied Physics, 116(23):Article No. 233702, Journal Name: Journal of Applied Physics, 116(23):Article No. 233702
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 9 works
Citation information provided by
Web of Science

References (39)

A magnetic and neutron diffraction study of the Fe2O3-V2O3 system∗ journal July 1962
Optical absorption and spectral photoconductivity in α-(Fe 1− x Cr x ) 2 O 3 solid-solution thin films journal September 2013
X-ray photoelectron and Auger spectroscopy study of some vanadium oxides journal August 1979
New Benchmark for Water Photooxidation by Nanostructured α-Fe 2 O 3 Films journal December 2006
Single Crystalline Hematite Films for Solar Water Splitting: Ti-Doping and Thickness Effects journal January 2014
Atomic subshell photoionization cross sections and asymmetry parameters: 1 ⩽ Z ⩽ 103 journal January 1985
Determination of the V2p XPS binding energies for different vanadium oxidation states (V5+ to V0+) journal April 2004
Optical Absorption and Band Gap Reduction in (Fe 1– x Cr x ) 2 O 3 Solid Solutions: A First-Principles Study journal November 2013
XPS studies of V2O5, V6O13, VO2 and V2O3 journal April 1995
Photoemission and STM study of the electronic structure of Nb-doped TiO 2 journal May 2000
Syntheses, Structures, and Characterization of 5-Layer BaVO3-x (x = 0.2, 0.1, 0.0) journal June 1994
Noncummutative band offset at α Cr 2 O 3 / α Fe 2 O 3 ( 0001 ) heterojunctions journal May 2000
Oxides Which Show a Metal-to-Insulator Transition at the Neel Temperature journal July 1959
Strong hybridization in vanadium oxides: evidence from photoemission and absorption spectroscopy journal June 1998
Synthesis of epitaxial films of Fe3O4 and α-Fe2O3 with various low-index orientations by oxygen-plasma-assisted molecular beam epitaxy journal March 1997
K -edge absorption spectra of selected vanadium compounds journal November 1984
An XPS study on the surface reduction of V2O5(001) induced by Ar+ ion bombardment journal September 2006
Structural chemistry of vanadium oxides with open frameworks journal October 1999
Electronic and optical properties of new multifunctional materials via half-substituted hematite: first principles calculations journal January 2012
Hard X-ray core level photoemission of vanadium oxides journal June 2005
Hybrid density functional theory band structure engineering in hematite journal June 2011
Synthesis and properties of V2O3–Fe2O3 magnetic ceramic nanostructures journal September 2013
Increased metal-insulator transition temperatures in epitaxial thin films of V2O3 prepared in reduced oxygen environments journal April 2011
First-principles study of the mixed oxide α Fe Cr O 3 journal November 2007
WO 3 −Fe 2 O 3 Photoanodes for Water Splitting: A Host Scaffold, Guest Absorber Approach journal July 2009
Bulk screening in core-level photoemission from Mott-Hubbard and charge-transfer systems journal April 2005
The remarkable effect of vanadium doping on the adsorption and catalytic activity of magnetite in the decolorization of methylene blue journal June 2010
Band-gap narrowing in α -(Cr x Fe 1- x ) 2 O 3 solid-solution films journal December 2011
Photoelectrochemical water splitting over ordered honeycomb hematite electrodes stabilized by alumina shielding journal January 2012
V2O3(0001) surface terminations: from oxygen- to vanadium-rich journal April 2004
New Insights into Water Splitting at Mesoporous α-Fe 2 O 3 Films: A Study by Modulated Transmittance and Impedance Spectroscopies journal December 2011
The probing depth of total electron yield in the sub-keV range: TEY-XAS and X-PEEM journal July 2003
Impact of lattice mismatch and stoichiometry on the structure and bandgap of (Fe,Cr) 2 O 3 epitaxial thin films journal March 2014
Crystal Chemical Aspects of Vanadium:  Polyhedral Geometries, Characteristic Bond Valences, and Polymerization of (VO n ) Polyhedra journal May 2000
Sn-Doped Hematite Nanostructures for Photoelectrochemical Water Splitting journal May 2011
Layered perovskite compounds Sr n + 1 V n O 3 n + 1 ( n =1, 2, 3, and ∞) journal January 1991
Observations and interpretation of x-ray absorption edges in iron compounds and proteins journal May 1976
Electrical transport properties of Ti-doped Fe 2 O 3 (0001) epitaxial films journal December 2011
V2O3() on Au() and W(): growth, termination and electronic structure journal August 2003

Similar Records

Structural perturbations of epitaxial α-(Fe 1-x V x ) 2 O 3 thin films driven by excess oxygen near the surface
Journal Article · Sun Dec 21 00:00:00 EST 2014 · Journal of Applied Physics · OSTI ID:1188913

Structural perturbations of epitaxial α-(Fe{sub 1−x}V{sub x}){sub 2}O{sub 3} thin films driven by excess oxygen near the surface
Journal Article · Sun Dec 21 00:00:00 EST 2014 · Journal of Applied Physics · OSTI ID:1188913

Electronic structure and optical properties of α-(Fe1-xVx)2O3 solid-solution thin films
Journal Article · Mon Jan 26 00:00:00 EST 2015 · Applied Physics Letters, 106(4):041905 · OSTI ID:1188913