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

The electronic and optical properties of α-(Fe V ) O 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 ∼0.5...

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Veröffentlicht in:Physical chemistry chemical physics : PCCP 2017-01, Vol.19 (2), p.1097-1107
Hauptverfasser: Nayyar, Iffat H, Chamberlin, Sara E, Kaspar, Tiffany C, Govind, Niranjan, Chambers, Scott A, Sushko, Peter V
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Sprache:eng
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Zusammenfassung:The electronic and optical properties of α-(Fe V ) O 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 ∼0.5 eV (i.e., nearly 1.6 eV lower than that in pure α-Fe O ) 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 Fe O /V O hetero-structures is as low as ∼0.3 eV and the corresponding peak is at ∼0.7 eV. In contrast, in the case of solid solutions this peak has lower intensity and is shifted to higher energy (∼1.2 eV). Analysis of the orbital character of electronic excitation suggests that Fe O /V O hetero-structures absorb light much more effectively than random alloys, thus promoting efficient photo-induced carrier generation. These predictions can be tested in α-(Fe V ) O thin films synthesized with well-controlled spatial distribution of Fe and V species.
ISSN:1463-9076
1463-9084
DOI:10.1039/C6CP06087K