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Title: Photochemical Properties, Composition, and Structure in Molecular Beam Epitaxy Grown Fe “Doped” and (Fe,N) Codoped Rutile TiO2(110)

Abstract

We have investigated the surface photochemical properties of Fe "doped" and (Fe,N) co-doped homoepitaxial rutile TiO2 (110) films grown by plasma assisted molecular beam epitaxy. Fe does not incorporate as an electronic dopant in the rutile lattice, but rather segregates to the film surface. However, co-deposition of Fe with N enhances the solubility of Fe, and DFT calculations suggest that co-dopant complex formation is the driving force behind the enhanced solubility. The co-doped films, in which a few atomic percent of Ti (O) are replaced with Fe (N), exhibit significant disorder compared to undoped films grown under the same conditions, presumably due to dopant-induced strain. Co-doping redshifts the rutile bandgap into the visible. However, the film surfaces are photochemically inert with respect to hole-mediated decomposition of adsorbed trimethyl acetate. The absence of photochemical activity may result from dopant-induced trap and/or recombination sites within the film. This study indicates that enhanced visible light absorptivity in TiO2 does not necessarily result in visible light initiated surface photochemistry.

Authors:
; ; ; ; ; ;
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
Sponsoring Org.:
USDOE
OSTI Identifier:
1023108
Report Number(s):
PNNL-SA-79027
Journal ID: ISSN 1932-7447; 35197; KC0301010; TRN: US201118%%756
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Journal of Physical Chemistry C, 115(31):15416-15424
Additional Journal Information:
Journal Volume: 115; Journal Issue: 31; Journal ID: ISSN 1932-7447
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; ABSORPTIVITY; MOLECULAR BEAM EPITAXY; PHOTOCHEMISTRY; PLASMA; RECOMBINATION; RUTILE; SOLUBILITY; Environmental Molecular Sciences Laboratory

Citation Formats

Mangham, Andrew N, Govind, Niranjan, Bowden, Mark E, Shutthanandan, V, Joly, Alan G, Henderson, Michael A, and Chambers, Scott A. Photochemical Properties, Composition, and Structure in Molecular Beam Epitaxy Grown Fe “Doped” and (Fe,N) Codoped Rutile TiO2(110). United States: N. p., 2011. Web. doi:10.1021/jp203061n.
Mangham, Andrew N, Govind, Niranjan, Bowden, Mark E, Shutthanandan, V, Joly, Alan G, Henderson, Michael A, & Chambers, Scott A. Photochemical Properties, Composition, and Structure in Molecular Beam Epitaxy Grown Fe “Doped” and (Fe,N) Codoped Rutile TiO2(110). United States. https://doi.org/10.1021/jp203061n
Mangham, Andrew N, Govind, Niranjan, Bowden, Mark E, Shutthanandan, V, Joly, Alan G, Henderson, Michael A, and Chambers, Scott A. 2011. "Photochemical Properties, Composition, and Structure in Molecular Beam Epitaxy Grown Fe “Doped” and (Fe,N) Codoped Rutile TiO2(110)". United States. https://doi.org/10.1021/jp203061n.
@article{osti_1023108,
title = {Photochemical Properties, Composition, and Structure in Molecular Beam Epitaxy Grown Fe “Doped” and (Fe,N) Codoped Rutile TiO2(110)},
author = {Mangham, Andrew N and Govind, Niranjan and Bowden, Mark E and Shutthanandan, V and Joly, Alan G and Henderson, Michael A and Chambers, Scott A},
abstractNote = {We have investigated the surface photochemical properties of Fe "doped" and (Fe,N) co-doped homoepitaxial rutile TiO2 (110) films grown by plasma assisted molecular beam epitaxy. Fe does not incorporate as an electronic dopant in the rutile lattice, but rather segregates to the film surface. However, co-deposition of Fe with N enhances the solubility of Fe, and DFT calculations suggest that co-dopant complex formation is the driving force behind the enhanced solubility. The co-doped films, in which a few atomic percent of Ti (O) are replaced with Fe (N), exhibit significant disorder compared to undoped films grown under the same conditions, presumably due to dopant-induced strain. Co-doping redshifts the rutile bandgap into the visible. However, the film surfaces are photochemically inert with respect to hole-mediated decomposition of adsorbed trimethyl acetate. The absence of photochemical activity may result from dopant-induced trap and/or recombination sites within the film. This study indicates that enhanced visible light absorptivity in TiO2 does not necessarily result in visible light initiated surface photochemistry.},
doi = {10.1021/jp203061n},
url = {https://www.osti.gov/biblio/1023108}, journal = {Journal of Physical Chemistry C, 115(31):15416-15424},
issn = {1932-7447},
number = 31,
volume = 115,
place = {United States},
year = {Thu Aug 11 00:00:00 EDT 2011},
month = {Thu Aug 11 00:00:00 EDT 2011}
}