Direct evidence of Fe2+ - Fe3+ charge ordering in the ferrimagnetic hematite-ilmenite Fe1.35Ti0.65O3−δ thin films

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dc.contributor.author Bocher, L.
dc.contributor.author Popova, Elena
dc.contributor.author Nolan, Michael
dc.contributor.author Gloter, Alexandre
dc.contributor.author Chikoidze, Ekaterina
dc.contributor.author March, K.
dc.contributor.author Warot-Fonrose, B.
dc.contributor.author Berini, B.
dc.contributor.author Stephan, Odile
dc.contributor.author Keller, Niels
dc.contributor.author Dumont, Yves
dc.date.accessioned 2017-09-04T09:02:30Z
dc.date.available 2017-09-04T09:02:30Z
dc.date.issued 2013-10-14
dc.identifier.citation Bocher, L., Popova, E., Nolan, M., Gloter, A., Chikoidze, E., March, K., Warot-Fonrose, B., Berini, B., Stéphan, O., Keller, N. and Dumont, Y. (2013) ‘Direct evidence of Fe2+ - Fe3+ charge ordering in the ferrimagnetic hematite-ilmenite Fe1.35Ti0.65O3−δ thin films’, Physical Review Letters, 111(16), 167202 (6pp). doi: 10.1103/PhysRevLett.111.167202 en
dc.identifier.volume 111
dc.identifier.issued 16
dc.identifier.issn 0031-9007
dc.identifier.issn 1079-7114
dc.identifier.uri http://hdl.handle.net/10468/4615
dc.identifier.doi 10.1103/PhysRevLett.111.167202
dc.description.abstract In this Letter we highlight direct experimental evidence of Fe2+-Fe3+ charge ordering at room temperature in hematite-ilmenite Fe1.35Ti0.65O3-delta epitaxial thin films grown by pulsed laser deposition, using aberration-corrected scanning transmission electron microscopy coupled to high-resolution energy electron-loss spectroscopy. These advanced spectromicroscopy techniques demonstrate a strong modulation of the Fe2+ valence state along the c axis. Density functional theory calculations provide crucial information on the key role of oxygen vacancies in the observed charge distributions. Their presence at significant levels leads to the localization of extra electrons onto reduced Fe2+ sites, while Ti remains solely +4. The magnetic and transport properties of these films are reviewed in the light of the present results regarding their ferrimagnetic character correlated with the Fe2+ modulation and their semi-conducting behavior interpreted by an Efros-Shklovskii variable-range hopping conduction regime via Fe2+ and Fe3+ centers. The experimental evidence of only one type of mixed valence state, i.e., Fe2+ and Fe3+, in the Fe2-xTixO3-delta system will thus help to interpret further the origin of its geomagnetic properties and to illuminate fundamental issues regarding its spintronic potential. en
dc.description.sponsorship Centre de Compétences Nanosciences Ile-de-France (Project No. IF-08-1453/R); Université Paris-Saclay (LabEx CHARM3AT (Invited Professor grant); European Commission (COST Action CM1104 "Reducible Oxide Chemistry, Structure and Functions) en
dc.format.mimetype application/pdf en
dc.language.iso en en
dc.publisher American Physical Society en
dc.relation.uri https://journals.aps.org/prl/abstract/10.1103/PhysRevLett.111.167202
dc.rights © 2013, American Physical Society en
dc.subject Solid solution series en
dc.subject Weak ferromagnetism en
dc.subject Electrical properties en
dc.subject Electronic structure en
dc.subject Magnetic properties en
dc.subject Crystal structure en
dc.subject High temperature en
dc.subject Fetio3 en
dc.subject Interface en
dc.subject System en
dc.title Direct evidence of Fe2+ - Fe3+ charge ordering in the ferrimagnetic hematite-ilmenite Fe1.35Ti0.65O3−δ thin films en
dc.type Article (peer-reviewed) en
dc.internal.authorcontactother Michael Nolan, Tyndall National Institute, University College Cork, Cork, Ireland. +353-21-490-3000. Email: michael.nolan@tyndall.ie en
dc.internal.availability Full text available en
dc.description.version Published Version en
dc.internal.rssid 243943690
dc.internal.wokid WOS:000326119300015
dc.contributor.funder European Commission
dc.contributor.funder Seventh Framework Programme
dc.contributor.funder Université Paris-Saclay
dc.contributor.funder Irish Centre for High-End Computing
dc.contributor.funder Science Foundation Ireland
dc.contributor.funder Centre de Compétences Nanosciences Ile-de-France
dc.contributor.funder Commissariat à l'Énergie Atomique et aux Énergies Alternatives
dc.contributor.funder Centre National de la Recherche Scientifique
dc.contributor.funder European Cooperation in Science and Technology
dc.description.status Peer reviewed en
dc.identifier.journaltitle Physical Review Letters en
dc.internal.IRISemailaddress michael.nolan@tyndall.ie en
dc.identifier.articleid 167202
dc.relation.project info:eu-repo/grantAgreement/EC/FP7::SP4::INFRA/312483/EU/Enabling Science and Technology through European Electron Microscopy/ESTEEM 2
dc.relation.project info:eu-repo/grantAgreement/SFI/SFI Starting Investigator Research Grant (SIRG)/09/SIRG/I1620/IE/EMOIN: Engineering Metal Oxide Interfaces For Renewable Energy Photocatalysis/


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