{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,3,26]],"date-time":"2026-03-26T20:42:07Z","timestamp":1774557727116,"version":"3.50.1"},"reference-count":27,"publisher":"MDPI AG","issue":"19","license":[{"start":{"date-parts":[[2021,10,4]],"date-time":"2021-10-04T00:00:00Z","timestamp":1633305600000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100006769","name":"Russian Science Foundation","doi-asserted-by":"publisher","award":["21-19-00386"],"award-info":[{"award-number":["21-19-00386"]}],"id":[{"id":"10.13039\/501100006769","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Materials"],"abstract":"<jats:p>The crystal structure of BiMnO3+\u03b4 ceramics has been studied as a function of nominal oxygen excess and temperature using synchrotron and neutron powder diffraction, magnetometry and differential scanning calorimetry. Increase in oxygen excess leads to the structural transformations from the monoclinic structure (C2\/c) to another monoclinic (P21\/c), and then to the orthorhombic (Pnma) structure through the two-phase regions. The sequence of the structural transformations is accompanied by a modification of the orbital ordering followed by its disruption. Modification of the orbital order leads to a rearrangement of the magnetic structure of the compounds from the long-range ferromagnetic to a mixed magnetic state with antiferromagnetic clusters coexistent in a ferromagnetic matrix followed by a frustration of the long-range magnetic order. Temperature increase causes the structural transition to the nonpolar orthorhombic phase regardless of the structural state at room temperature; the orbital order is destroyed in compounds BiMnO3+\u03b4 (\u03b4 \u2264 0.14) at temperatures above 470 \u00b0C.<\/jats:p>","DOI":"10.3390\/ma14195805","type":"journal-article","created":{"date-parts":[[2021,10,10]],"date-time":"2021-10-10T21:37:29Z","timestamp":1633901849000},"page":"5805","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":6,"title":["Crystal and Magnetic Structure Transitions in BiMnO3+\u03b4 Ceramics Driven by Cation Vacancies and Temperature"],"prefix":"10.3390","volume":"14","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-1046-543X","authenticated-orcid":false,"given":"Dmitry V.","family":"Karpinsky","sequence":"first","affiliation":[{"name":"Laboratory of Technology and Physics of Crystals Growth, Scientific-Practical Materials Research Centre of NAS of Belarus, 220072 Minsk, Belarus"},{"name":"Institute for Advanced Materials and Technologies, National Research University of Electronic Technology \u201cMIET\u201d, 124498 Zelenograd, Russia"},{"name":"Department of Materials Science and Physico-Chemistry of Materials, South Ural State University, av. Lenina, 76, 454080 Chelyabinsk, Russia"}]},{"given":"Maxim V.","family":"Silibin","sequence":"additional","affiliation":[{"name":"Institute for Advanced Materials and Technologies, National Research University of Electronic Technology \u201cMIET\u201d, 124498 Zelenograd, Russia"},{"name":"Scientific-Manufacturing Complex \u201cTechnological Centre\u201d, 124498 Zelenograd, Russia"},{"name":"Institute for Bionic Technologies and Engineering, I.M. Sechenov First Moscow State Medical University, 119991 Moscow, Russia"}]},{"given":"Dmitry V.","family":"Zhaludkevich","sequence":"additional","affiliation":[{"name":"Laboratory of Technology and Physics of Crystals Growth, Scientific-Practical Materials Research Centre of NAS of Belarus, 220072 Minsk, Belarus"},{"name":"Institute for Advanced Materials and Technologies, National Research University of Electronic Technology \u201cMIET\u201d, 124498 Zelenograd, Russia"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-0008-0525","authenticated-orcid":false,"given":"Siarhei I.","family":"Latushka","sequence":"additional","affiliation":[{"name":"Laboratory of Technology and Physics of Crystals Growth, Scientific-Practical Materials Research Centre of NAS of Belarus, 220072 Minsk, Belarus"},{"name":"Institute for Advanced Materials and Technologies, National Research University of Electronic Technology \u201cMIET\u201d, 124498 Zelenograd, Russia"}]},{"given":"Vadim V.","family":"Sikolenko","sequence":"additional","affiliation":[{"name":"Institute for Advanced Materials and Technologies, National Research University of Electronic Technology \u201cMIET\u201d, 124498 Zelenograd, Russia"},{"name":"Frank Laboratory of Neutron Physics, Joint Institute for Nuclear Research, 141980 Dubna, Russia"},{"name":"Institute of Applied Geosciences, Karlsruhe Institute of Technology, 76131 Karlsruhe, Germany"}]},{"given":"Daniel M.","family":"T\u00f6bbens","sequence":"additional","affiliation":[{"name":"Department Structure and Dynamics of Energy Materials, Helmholtz-Zentrum Berlin f\u00fcr Materialien und Energie, 14109 Berlin, Germany"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-3001-6586","authenticated-orcid":false,"given":"Denis","family":"Sheptyakov","sequence":"additional","affiliation":[{"name":"Laboratory for Neutron Scattering and Imaging, Paul Scherrer Institut, 5232 Villigen, Switzerland"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5867-3297","authenticated-orcid":false,"given":"Vladimir A.","family":"Khomchenko","sequence":"additional","affiliation":[{"name":"CFisUC, Department of Physics, University of Coimbra, 3004-516 Coimbra, Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9031-2355","authenticated-orcid":false,"given":"Alexei A.","family":"Belik","sequence":"additional","affiliation":[{"name":"International Center for Materials Nanoarchitectonics (WPI-MANA), National Institute for Materials Science (NIMS), Namiki 1-1, Tsukuba, Ibaraki 305-0044, Japan"}]}],"member":"1968","published-online":{"date-parts":[[2021,10,4]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"203","DOI":"10.1038\/s41563-018-0275-2","article-title":"Advances in magnetoelectric multiferroics","volume":"18","author":"Spaldin","year":"2019","journal-title":"Nat. Mater."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"12772","DOI":"10.1038\/ncomms12772","article-title":"A novel perovskite oxide chemically designed to show multiferroic phase boundary with room-temperature magnetoelectricity","volume":"7","author":"Castro","year":"2016","journal-title":"Nat. Commun."},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"060401","DOI":"10.1103\/PhysRevB.71.060401","article-title":"Weak ferromagnetism and magnetoelectric coupling in bismuth ferrite","volume":"71","author":"Ederer","year":"2005","journal-title":"Phys. Rev. B"},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"044610","DOI":"10.1088\/1468-6996\/12\/4\/044610","article-title":"Local distortions in multiferroic BiMnO3 as a function of doping","volume":"12","author":"Belik","year":"2011","journal-title":"Sci. Technol. Adv. Mater."},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"180401","DOI":"10.1103\/PhysRevB.67.180401","article-title":"Magnetocapacitance effect in multiferroic BiMnO3","volume":"67","author":"Kimura","year":"2003","journal-title":"Phys. Rev. B"},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"167","DOI":"10.1080\/000187399243455","article-title":"Mixed-valence manganites","volume":"48","author":"Coey","year":"1999","journal-title":"Adv. Phys."},{"key":"ref_7","doi-asserted-by":"crossref","unstructured":"Karoblis, D., Diliautas, R., Raudonyte-Svirbutaviciene, E., Mazeika, K., Baltrunas, D., Beganskiene, A., Zarkov, A., and Kareiva, A. (2020). The Synthesis and Characterization of Sol-Gel-Derived SrTiO3-BiMnO3 Solid Solutions. Crystals, 10.","DOI":"10.3390\/cryst10121125"},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"126655","DOI":"10.1016\/j.matlet.2019.126655","article-title":"Structural, morphological, optical, dielectric and magnetic field sensing characteristics of Bi1-xKxMnO3 and BiMn1-yCoyO3 nanopowders: A comparative study","volume":"256","author":"Revathi","year":"2019","journal-title":"Mater. Lett."},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"8","DOI":"10.1016\/j.jssc.2016.10.025","article-title":"Structural, magnetic, and dielectric properties of solid solutions between BiMnO3 and YMnO3","volume":"246","author":"Belik","year":"2017","journal-title":"J. Solid State Chem."},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"96","DOI":"10.1016\/j.matchemphys.2016.11.052","article-title":"Sr doped BiMO3 (M = Mn, Fe, Y) perovskites: Structure correlated thermal and electrical properties","volume":"187","author":"Thakur","year":"2017","journal-title":"Mater. Chem. Phys."},{"key":"ref_11","first-page":"030014","article-title":"Critical behavior and non-universal low-field magnetic scaling in La1-xBixMnO3 (x=0.4 & 0.6) perovskite manganite oxide","volume":"1665","author":"Kumar","year":"2015","journal-title":"AIP Conf. Proc."},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"1177","DOI":"10.1016\/j.jmmm.2006.10.287","article-title":"Magnetic and structural properties of BiFe1\u2212xMnxO3","volume":"310","author":"Azuma","year":"2007","journal-title":"J. Magn. Magn. Mater."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"064425","DOI":"10.1103\/PhysRevB.66.064425","article-title":"Orbital ordering as the determinant for ferromagnetism in biferroic BiMnO3","volume":"66","author":"Cheetham","year":"2002","journal-title":"Phys. Rev. B"},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"1335","DOI":"10.1039\/C6CP07682C","article-title":"Novel multiferroic state and ME enhancement by breaking the AFM frustration in LuMn1\u2212xO3","volume":"19","author":"Figueiras","year":"2017","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"8137","DOI":"10.1021\/ja102014n","article-title":"Crystal and Magnetic Structures and Properties of BiMnO3+\u03b4","volume":"132","author":"Belik","year":"2010","journal-title":"J. Am. Chem. Soc."},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"A49","DOI":"10.17815\/jlsrf-2-65","article-title":"KMC-2: An X-ray beamline with dedicated diffraction and XAS endstations at BESSY II","volume":"2","author":"Zander","year":"2016","journal-title":"JLSRF"},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"146","DOI":"10.1016\/S0921-4526(99)01399-X","article-title":"High-resolution powder diffractometer HRPT for thermal neutrons at SINQ","volume":"276\u2013278","author":"Fischer","year":"2000","journal-title":"Physica B"},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"55","DOI":"10.1016\/0921-4526(93)90108-I","article-title":"Recent advances in magnetic structure determination by neutron powder diffraction","volume":"192","year":"1993","journal-title":"Physica B"},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"65","DOI":"10.1107\/S0021889869006558","article-title":"A profile refinement method for nuclear and magnetic structures","volume":"2","author":"Rietveld","year":"1969","journal-title":"J. Appl. Crystallogr."},{"key":"ref_20","first-page":"87","article-title":"The extinction rule for reflexions in symmetrical electron-diffraction spot patterns","volume":"14","author":"Cowley","year":"1961","journal-title":"Acta Crystallogr. Sect. A"},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"2191","DOI":"10.1039\/b803118p","article-title":"Crucial role of oxygen stoichiometry in determining the structure and properties of BiMnO3","volume":"18","author":"Sundaresan","year":"2008","journal-title":"J. Mater. Chem. C"},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"13519","DOI":"10.1039\/C6CP01562J","article-title":"Breaking the geometric magnetic frustration in controlled off-stoichiometric LuMn1+zO3+\u03b4 compounds","volume":"18","author":"Figueiras","year":"2016","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"7112","DOI":"10.1063\/1.1667855","article-title":"Vacancies at Mn-sites in LaMn1-xO3 manganites: Interplay between ferromagnetic interactions and hydrostatic pressure","volume":"95","author":"Markovich","year":"2004","journal-title":"J. Appl. Phys."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"e640","DOI":"10.1016\/j.jmmm.2007.03.053","article-title":"Ferromagnetic ordering in LaMn1\u2212xO3 manganites: EMR probing","volume":"316","author":"Shames","year":"2007","journal-title":"J. Magn. Magn. Mater."},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"287","DOI":"10.1016\/0022-3697(58)90107-0","article-title":"An interpretation of the magnetic properties of the perovskite-type mixed crystals La1-xSrxCoO3\u2212\u03bb","volume":"6","author":"Goodenough","year":"1958","journal-title":"J. Phys. Chem. Solids"},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"87","DOI":"10.1016\/0022-3697(59)90061-7","article-title":"Superexchange interaction and symmetry properties of electron orbitals","volume":"10","author":"Kanamori","year":"1959","journal-title":"J. Phys. Chem. Solids"},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"3993","DOI":"10.1088\/0953-8984\/12\/17\/307","article-title":"Magnetic properties and the phase diagram of La1-xSrxMnO3 for x <=0.2","volume":"12","author":"Paraskevopoulos","year":"2000","journal-title":"J. Phys. Condens. Matter."}],"container-title":["Materials"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1996-1944\/14\/19\/5805\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,11]],"date-time":"2025-10-11T07:09:22Z","timestamp":1760166562000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1996-1944\/14\/19\/5805"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2021,10,4]]},"references-count":27,"journal-issue":{"issue":"19","published-online":{"date-parts":[[2021,10]]}},"alternative-id":["ma14195805"],"URL":"https:\/\/doi.org\/10.3390\/ma14195805","relation":{},"ISSN":["1996-1944"],"issn-type":[{"value":"1996-1944","type":"electronic"}],"subject":[],"published":{"date-parts":[[2021,10,4]]}}}