Contrasting 1D tunnel-structured and 2D layered polymorphs of V sub(2)O sub(5): relating crystal structure and bonding to band gaps and electronic structure

New V sub(2)O sub(5) polymorphs have risen to prominence as a result of their open framework structures, cation intercalation properties, tunable electronic structures, and wide range of applications. The application of these materials and the design of new, useful polymorphs requires understanding...

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Veröffentlicht in:Physical chemistry chemical physics : PCCP 2016-06, Vol.18 (23), p.15798-15806
Hauptverfasser: Tolhurst, Thomas M, Leedahl, Brett, Andrews, Justin L, Marley, Peter M, Banerjee, Sarbajit, Moewes, Alexander
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container_issue 23
container_start_page 15798
container_title Physical chemistry chemical physics : PCCP
container_volume 18
creator Tolhurst, Thomas M
Leedahl, Brett
Andrews, Justin L
Marley, Peter M
Banerjee, Sarbajit
Moewes, Alexander
description New V sub(2)O sub(5) polymorphs have risen to prominence as a result of their open framework structures, cation intercalation properties, tunable electronic structures, and wide range of applications. The application of these materials and the design of new, useful polymorphs requires understanding their defining structure-property relationships. We present a characterization of the band gap and electronic structure of nanowires of the novel zeta -phase and the orthorhombic alpha -phase of V sub(2)O sub(5) using X-ray spectroscopy and density functional theory calculations. The band gap is found to decrease from 1.90 plus or minus 0.20 eV in the alpha -phase to 1.50 plus or minus 0.20 eV in the zeta -phase, accompanied by the loss of the alpha -phase's characteristic split-off d sub()xyband in the zeta -phase. States of d sub()xyorigin continue to dominate the conduction band edge in the new polymorph but the inequivalence of the vanadium atoms and the increased local symmetry of [VO sub(6)] octahedra results in these states overlapping with the rest of the V 3d conduction band. zeta -V sub(2)O sub(5) exhibits anisotropic conductivity along the b direction, defining a 1D tunnel, in contrast to alpha -V sub(2)O sub(5) where the anisotropic conductivity is along the ablayers. We explain the structural origins of the differences in electronic properties that exist between the alpha - and zeta -phase.
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source Royal Society Of Chemistry Journals 2008-; Alma/SFX Local Collection
subjects Anisotropy
Cations
Conduction band
Electronic structure
Energy gaps (solid state)
Origins
Three dimensional
Vanadium pentoxide
title Contrasting 1D tunnel-structured and 2D layered polymorphs of V sub(2)O sub(5): relating crystal structure and bonding to band gaps and electronic structure
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