Synthesis of Ilmenite-type ε-Mn2O3 and Its Properties

doi:10.1021/acs.inorgchem.1c01666

. 2021 Sep 6;60(17):13348-13358.

doi: 10.1021/acs.inorgchem.1c01666. Epub 2021 Aug 20.

Synthesis of Ilmenite-type ε-Mn₂O₃ and Its Properties

Affiliations

¹ Bayerisches Geoinstitut, Universität Bayreuth, Universitätsstrasse 30, 95440 Bayreuth, Germany.
² Institute for Solid State Chemistry of Ural Branch of Russian Academy of Sciences, 91 Pervomayskaya Str., 620219 Yekaterinburg, Russia.
³ Experimental Physics VI, Center for Electronic Correlations and Magnetism, Institute of Physics, University of Augsburg, 86135 Augsburg, Germany.
⁴ M. N. Miheev Institute of Metal Physics of Ural Branch of Russian Academy of Sciences, 18 S. Kovalevskaya Str., 620137 Yekaterinburg, Russia.
⁵ The University of Chicago, Center for Advanced Radiation Sources, 60637 Chicago, Illinois, United States.
⁶ Material Physics and Technology at Extreme Conditions, Laboratory of Crystallography, Universität Bayreuth, 95440 Bayreuth, Germany.
⁷ Photon Science, Deutsches Elektronen-Synchrotron, Notkestrasse 85, 22607 Hamburg, Germany.
⁸ European Synchrotron Radiation Facility, 71, avenue des Martyrs CS 40220, 38043 Grenoble Cedex 9, France.

PMID: 34415155
DOI: 10.1021/acs.inorgchem.1c01666

Synthesis of Ilmenite-type ε-Mn₂O₃ and Its Properties

Sergey V Ovsyannikov et al. Inorg Chem. 2021.

. 2021 Sep 6;60(17):13348-13358.

doi: 10.1021/acs.inorgchem.1c01666. Epub 2021 Aug 20.

Affiliations

¹ Bayerisches Geoinstitut, Universität Bayreuth, Universitätsstrasse 30, 95440 Bayreuth, Germany.
² Institute for Solid State Chemistry of Ural Branch of Russian Academy of Sciences, 91 Pervomayskaya Str., 620219 Yekaterinburg, Russia.
³ Experimental Physics VI, Center for Electronic Correlations and Magnetism, Institute of Physics, University of Augsburg, 86135 Augsburg, Germany.
⁴ M. N. Miheev Institute of Metal Physics of Ural Branch of Russian Academy of Sciences, 18 S. Kovalevskaya Str., 620137 Yekaterinburg, Russia.
⁵ The University of Chicago, Center for Advanced Radiation Sources, 60637 Chicago, Illinois, United States.
⁶ Material Physics and Technology at Extreme Conditions, Laboratory of Crystallography, Universität Bayreuth, 95440 Bayreuth, Germany.
⁷ Photon Science, Deutsches Elektronen-Synchrotron, Notkestrasse 85, 22607 Hamburg, Germany.
⁸ European Synchrotron Radiation Facility, 71, avenue des Martyrs CS 40220, 38043 Grenoble Cedex 9, France.

PMID: 34415155
DOI: 10.1021/acs.inorgchem.1c01666

Abstract

In contrast to the corundum-type A₂X₃ structure, which has only one crystallographic site available for trivalent cations (e.g., in hematite), the closely related ABX₃ ilmenite-type structure comprises two different octahedrally coordinated positions that are usually filled with differently charged ions (e.g., in Fe²⁺Ti⁴⁺O₃ ilmenite). Here, we report a synthesis of the first binary ilmenite-type compound fabricated from a simple transition-metal oxide (Mn₂O₃) at high-pressure high-temperature (HP-HT) conditions. We experimentally established that, at normal conditions, the ilmenite-type Mn²⁺Mn⁴⁺O₃ (ε-Mn₂O₃) is an n-type semiconductor with an indirect narrow band gap of E_g = 0.55 eV. Comparative investigations of the electronic properties of ε-Mn₂O₃ and previously discovered quadruple perovskite ζ-Mn₂O₃ phase were performed using X-ray absorption near edge spectroscopy. Magnetic susceptibility measurements reveal an antiferromagnetic ordering in ε-Mn₂O₃ below 210 K. The synthesis of ε-Mn₂O₃ indicates that HP-HT conditions can induce a charge disproportionation in simple transition-metal oxides A₂O₃, and potentially various mixed-valence polymorphs of these oxides, for example, with ilmenite-type, LiNbO₃-type, perovskite-type, and other structures, could be stabilized at HP-HT conditions.

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Synthesis of Ilmenite-type ε-Mn₂O₃ and Its Properties

Affiliations

Synthesis of Ilmenite-type ε-Mn₂O₃ and Its Properties

Authors

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Abstract

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