Defect chemistry of Ti and Fe impurities and aggregates in Al2O3

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dc.contributor.authorBristow, Jessica K.
dc.contributor.authorTiana, Davide
dc.contributor.authorParker, Stephen C.
dc.contributor.authorWalsh, Aron
dc.contributor.funderEngineering and Physical Sciences Research Councilen
dc.contributor.funderRoyal Societyen
dc.contributor.funderEuropean Research Councilen
dc.contributor.funderSeventh Framework Programmeen
dc.contributor.funderResearch Councils UKen
dc.date.accessioned2018-07-05T11:06:14Z
dc.date.available2018-07-05T11:06:14Z
dc.date.issued2014-02-05
dc.date.updated2018-07-03T11:21:12Z
dc.description.abstractWe report a theoretical evaluation of the properties of iron and titanium impurities in sapphire (corundum structured α-Al2O3). Calculations using analytical force fields have been performed on the defect structure with the metals present in isolated, co-doped and tri-cluster configurations. Crystal field parameters have been calculated with good agreement to available experimental data. When titanium and iron are present in neighbouring face and edge-sharing orientations, the overlap of the d-orbitals facilitates an intervalence charge transfer (FeIII/TiIII → FeII/TiIV) with an associated optical excitation energy of 1.85 eV and 1.76 eV in the respective configurations. Electronic structure calculations based on density functional theory confirm that FeIII/TiIII is the ground-state configuration for the nearest-neighbour pairs, in contrast to the often considered FeII/TiIV pair. Homonuclear intervalence charge transfer energies between both FeIII/FeII and TiIV/TiIII species have also been calculated, with the energy lying in the infra-red region. Investigation of multiple tri-clusters of iron and titanium identified one stable configuration, TiIII–(TiIV/FeII), with the energy of electron transfer remaining unchanged.en
dc.description.sponsorshipRoyal Society (University Research Fellowship scheme); University of Bath (Access to the HECToR supercomputer was facilitated through membership of the HPC Materials Chemistry Consortium (EP/F067496))en
dc.description.statusPeer revieweden
dc.description.versionPublished Versionen
dc.format.mimetypeapplication/pdfen
dc.identifier.citationBristow, J. K., Tiana, D., Parker, S. C. and Walsh, A. (2014) 'Defect chemistry of Ti and Fe impurities and aggregates in Al2O3', Journal of Materials Chemistry A, 2(17), pp. 6198-6208. doi: 10.1039/c3ta15322cen
dc.identifier.doi10.1039/c3ta15322c
dc.identifier.endpage6208en
dc.identifier.issn2050-7488
dc.identifier.journaltitleJournal of Materials Chemistry Aen
dc.identifier.startpage6198en
dc.identifier.urihttps://hdl.handle.net/10468/6416
dc.identifier.volume2en
dc.language.isoenen
dc.publisherRoyal Society of Chemistry (RSC)en
dc.relation.projectinfo:eu-repo/grantAgreement/RCUK/EPSRC/EP/G03768X/1/GB/Doctoral Training Centre in Sustainable Chemical Technologies/en
dc.relation.projectinfo:eu-repo/grantAgreement/EC/FP7::SP2::ERC/277757/EU/Hybrid Semiconductors: Design Principles and Material Applications/HYBRIDSen
dc.relation.projectinfo:eu-repo/grantAgreement/RCUK/EPSRC/EP/F067496/1/GB/Modelling of Advanced Functional Materials using Terascale Computing/en
dc.relation.urihttp://pubs.rsc.org/en/content/articlepdf/2014/ta/c3ta15322c
dc.rights© The Royal Society of Chemistry 2014. This article is licensed under a Creative Commons Attribution 3.0 Unported Licenceen
dc.rights.urihttps://creativecommons.org/licenses/by/3.0/en
dc.subjectGeneralized gradient approximationen
dc.subjectTransition-metal ionsen
dc.subjectCharge-transfer banden
dc.subjectSapphire thin-filmsen
dc.subjectDoped sapphireen
dc.subject1st-principles calculationsen
dc.subjectElectron localizationen
dc.subjectPolycrystalline AL2O3en
dc.subjectOptical-spectraen
dc.subjectBlue sapphireen
dc.titleDefect chemistry of Ti and Fe impurities and aggregates in Al2O3en
dc.typeArticle (peer-reviewed)en
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