Pressure tuning of charge ordering in iron oxide

Sergey V. Ovsyannikov (), Maxim Bykov, Elena Bykova, Konstantin Glazyrin, Rudra Sekhar Manna, Alexander A. Tsirlin, Valerio Cerantola, Ilya Kupenko, Alexander V. Kurnosov, Innokenty Kantor, Anna S. Pakhomova, Irina Chuvashova, Aleksandr I. Chumakov, Rudolf Rüffer, Catherine McCammon and Leonid S. Dubrovinsky
Additional contact information
Sergey V. Ovsyannikov: Universität Bayreuth
Maxim Bykov: Universität Bayreuth
Elena Bykova: Universität Bayreuth
Konstantin Glazyrin: Deutsches Elektronen-Synchrotron (DESY)
Rudra Sekhar Manna: IIT Tirupati
Alexander A. Tsirlin: University of Augsburg
Valerio Cerantola: Universität Bayreuth
Ilya Kupenko: ESRF—The European Synchrotron
Alexander V. Kurnosov: Universität Bayreuth
Innokenty Kantor: ESRF—The European Synchrotron
Anna S. Pakhomova: Deutsches Elektronen-Synchrotron (DESY)
Irina Chuvashova: Universität Bayreuth
Aleksandr I. Chumakov: ESRF—The European Synchrotron
Rudolf Rüffer: ESRF—The European Synchrotron
Catherine McCammon: Universität Bayreuth
Leonid S. Dubrovinsky: Universität Bayreuth

Nature Communications, 2018, vol. 9, issue 1, 1-11

Abstract: Abstract A Verwey-type charge-ordering transition in magnetite at 120 K leads to the formation of linear units of three iron ions with one shared electron, called trimerons. The recently-discovered iron pentoxide (Fe4O5) comprising mixed-valent iron cations at octahedral chains, demonstrates another unusual charge-ordering transition at 150 K involving competing formation of iron trimerons and dimerons. Here, we experimentally show that applied pressure can tune the charge-ordering pattern in Fe4O5 and strongly affect the ordering temperature. We report two charge-ordered phases, the first of which may comprise both dimeron and trimeron units, whereas, the second exhibits an overall dimerization involving both the octahedral and trigonal-prismatic chains of iron in the crystal structure. We link the dramatic change in the charge-ordering pattern in the second phase to redistribution of electrons between the octahedral and prismatic iron chains, and propose that the average oxidation state of the iron cations can pre-determine a charge-ordering pattern.

Date: 2018
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DOI: 10.1038/s41467-018-06457-x

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