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Title: Effect of doping and chemical ordering on the optoelectronic properties of complex oxides: Fe 2 O 3 –V 2 O 3 solid solutions and hetero-structures

Abstract

The electronic and optical properties of a-(Fe1xVx)2O3 at low (x = 0.04) and high (x = 0.5) doping levels are investigated using a combination of periodic and embedded cluster approaches, and time dependent density functional theory. At low V concentrations the onset of the optical absorption is B0.5 eV (i.e., nearly 1.6 eV lower than that in pure a-Fe2O3) and corresponds to the electron transitions from V 3d to Fe 3d* orbitals. At high V concentrations, optical absorption energies and intensities are sensitive to specific arrangements of Fe and V atoms and their spin configuration that determine Fe–V hybridization. The onset of the lowest inter-vanadium absorption band in the case of Fe2O3/V2O3 hetero-structures is as low as B0.3 eV and the corresponding peak is at B0.7 eV. In contrast, in the case of solid solutions this peak has lower intensity and is shifted to higher energy (B1.2 eV). Analysis of the orbital character of electronic excitation suggests that Fe2O3/V2O3 hetero-structures absorb light much more effectively than random alloys, thus promoting efficient photo-induced carrier generation. These predictions can be tested in a-(Fe1xVx)2O3 thin films synthesized with well-controlled spatial distribution of Fe and V species.

Authors:
; ; ; ; ;
Publication Date:
Research Org.:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
Sponsoring Org.:
USDOE Office of Science (SC), Biological and Environmental Research (BER) (SC-23); USDOE Office of Science (SC), Advanced Scientific Computing Research (ASCR) (SC-21); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1339801
Report Number(s):
PNNL-SA-122741
Journal ID: ISSN 1463-9076; 48341; KC0203020
DOE Contract Number:
AC05-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: Physical Chemistry Chemical Physics. PCCP (Print); Journal Volume: 19; Journal Issue: 2
Country of Publication:
United States
Language:
English
Subject:
Environmental Molecular Sciences Laboratory

Citation Formats

Nayyar, Iffat H., Chamberlin, Sara E., Kaspar, Tiffany C., Govind, Niranjan, Chambers, Scott A., and Sushko, Peter V. Effect of doping and chemical ordering on the optoelectronic properties of complex oxides: Fe 2 O 3 –V 2 O 3 solid solutions and hetero-structures. United States: N. p., 2017. Web. doi:10.1039/C6CP06087K.
Nayyar, Iffat H., Chamberlin, Sara E., Kaspar, Tiffany C., Govind, Niranjan, Chambers, Scott A., & Sushko, Peter V. Effect of doping and chemical ordering on the optoelectronic properties of complex oxides: Fe 2 O 3 –V 2 O 3 solid solutions and hetero-structures. United States. doi:10.1039/C6CP06087K.
Nayyar, Iffat H., Chamberlin, Sara E., Kaspar, Tiffany C., Govind, Niranjan, Chambers, Scott A., and Sushko, Peter V. Sun . "Effect of doping and chemical ordering on the optoelectronic properties of complex oxides: Fe 2 O 3 –V 2 O 3 solid solutions and hetero-structures". United States. doi:10.1039/C6CP06087K.
@article{osti_1339801,
title = {Effect of doping and chemical ordering on the optoelectronic properties of complex oxides: Fe 2 O 3 –V 2 O 3 solid solutions and hetero-structures},
author = {Nayyar, Iffat H. and Chamberlin, Sara E. and Kaspar, Tiffany C. and Govind, Niranjan and Chambers, Scott A. and Sushko, Peter V.},
abstractNote = {The electronic and optical properties of a-(Fe1xVx)2O3 at low (x = 0.04) and high (x = 0.5) doping levels are investigated using a combination of periodic and embedded cluster approaches, and time dependent density functional theory. At low V concentrations the onset of the optical absorption is B0.5 eV (i.e., nearly 1.6 eV lower than that in pure a-Fe2O3) and corresponds to the electron transitions from V 3d to Fe 3d* orbitals. At high V concentrations, optical absorption energies and intensities are sensitive to specific arrangements of Fe and V atoms and their spin configuration that determine Fe–V hybridization. The onset of the lowest inter-vanadium absorption band in the case of Fe2O3/V2O3 hetero-structures is as low as B0.3 eV and the corresponding peak is at B0.7 eV. In contrast, in the case of solid solutions this peak has lower intensity and is shifted to higher energy (B1.2 eV). Analysis of the orbital character of electronic excitation suggests that Fe2O3/V2O3 hetero-structures absorb light much more effectively than random alloys, thus promoting efficient photo-induced carrier generation. These predictions can be tested in a-(Fe1xVx)2O3 thin films synthesized with well-controlled spatial distribution of Fe and V species.},
doi = {10.1039/C6CP06087K},
journal = {Physical Chemistry Chemical Physics. PCCP (Print)},
number = 2,
volume = 19,
place = {United States},
year = {Sun Jan 01 00:00:00 EST 2017},
month = {Sun Jan 01 00:00:00 EST 2017}
}