{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,4,30]],"date-time":"2026-04-30T19:01:41Z","timestamp":1777575701358,"version":"3.51.4"},"reference-count":51,"publisher":"MDPI AG","issue":"21","license":[{"start":{"date-parts":[[2024,11,1]],"date-time":"2024-11-01T00:00:00Z","timestamp":1730419200000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100001871","name":"FCT\u2014Funda\u00e7\u00e3o para a Ci\u00eancia e Tecnologia","doi-asserted-by":"publisher","award":["UIDB\/04564\/2020"],"award-info":[{"award-number":["UIDB\/04564\/2020"]}],"id":[{"id":"10.13039\/501100001871","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100001871","name":"FCT\u2014Funda\u00e7\u00e3o para a Ci\u00eancia e Tecnologia","doi-asserted-by":"publisher","award":["UIDP\/04564\/2020"],"award-info":[{"award-number":["UIDP\/04564\/2020"]}],"id":[{"id":"10.13039\/501100001871","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100001871","name":"FCT\u2014Funda\u00e7\u00e3o para a Ci\u00eancia e Tecnologia","doi-asserted-by":"publisher","award":["ICT_2009_02_012_1890"],"award-info":[{"award-number":["ICT_2009_02_012_1890"]}],"id":[{"id":"10.13039\/501100001871","id-type":"DOI","asserted-by":"publisher"}]},{"name":"QREN-Mais Centro project","award":["UIDB\/04564\/2020"],"award-info":[{"award-number":["UIDB\/04564\/2020"]}]},{"name":"QREN-Mais Centro project","award":["UIDP\/04564\/2020"],"award-info":[{"award-number":["UIDP\/04564\/2020"]}]},{"name":"QREN-Mais Centro project","award":["ICT_2009_02_012_1890"],"award-info":[{"award-number":["ICT_2009_02_012_1890"]}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Applied Sciences"],"abstract":"<jats:p>This paper reports the results of a systematic investigation into the magnetic properties of Bi1\u2212yCayFe1\u2212xMnxO3 (0.1 \u2264 y \u2264 0.175, 0.35 \u2264 x \u2264 0.45) solid solutions. The substitution of Bi3+ with Ca2+ and the concurrent introduction of Mn3+\/Mn4+ ions result in the stabilization of various structural phases, with each exhibiting distinct magnetic characteristics. The investigation indicates that the samples containing the polar rhombohedral phase display metamagnetic transitions at low temperatures, characterized by pronounced jumps in magnetization. Single-phase samples with a nonpolar orthorhombic structure exhibit weak ferromagnetic behavior without metamagnetic features. The observed metamagnetic behavior, accompanied by anomalies in temperature-dependent magnetization and significant remnant magnetization at low temperatures, particularly in samples near the polar-anti(non)polar phase boundary, highlighted the presence of both antiferromagnetic and glassy magnetic components.<\/jats:p>","DOI":"10.3390\/app14219991","type":"journal-article","created":{"date-parts":[[2024,11,5]],"date-time":"2024-11-05T08:25:14Z","timestamp":1730795114000},"page":"9991","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":1,"title":["Correlation Between the Crystal Structure and Magnetic Properties of Bi1\u2212yCayFe1\u2212xMnxO3 Multiferroics near the Polar-Anti(non)polar Phase Boundary"],"prefix":"10.3390","volume":"14","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-5867-3297","authenticated-orcid":false,"given":"Vladimir A.","family":"Khomchenko","sequence":"first","affiliation":[{"name":"CFisUC, Department of Physics, University of Coimbra, P-3004-516 Coimbra, Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5973-7443","authenticated-orcid":false,"given":"Mithila","family":"Das","sequence":"additional","affiliation":[{"name":"CFisUC, Department of Physics, University of Coimbra, P-3004-516 Coimbra, Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-4634-7395","authenticated-orcid":false,"given":"Jos\u00e9 Ant\u00f3nio","family":"Paix\u00e3o","sequence":"additional","affiliation":[{"name":"CFisUC, Department of Physics, University of Coimbra, P-3004-516 Coimbra, Portugal"}]}],"member":"1968","published-online":{"date-parts":[[2024,11,1]]},"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":"010901","DOI":"10.1063\/5.0076106","article-title":"Recent developments and the future perspectives in magnetoelectric nanocomposites for memory applications","volume":"10","author":"Wu","year":"2022","journal-title":"APL Mater."},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"046801","DOI":"10.1103\/PhysRevLett.133.046801","article-title":"Electric control of magnetism in multiferroic rare-earth-substituted BiFeO3 with ferrielectricity","volume":"133","author":"Xu","year":"2024","journal-title":"Phys. Rev. Lett."},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"81","DOI":"10.1007\/s40820-020-00420-6","article-title":"Structure, performance, and application of BiFeO3 nanomaterials","volume":"12","author":"Wang","year":"2020","journal-title":"Nano-Micro Lett."},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"170569","DOI":"10.1016\/j.jmmm.2023.170569","article-title":"Multiferroic perovskite bismuth ferrite nanostructures: A review on synthesis and applications","volume":"572","author":"Kharbanda","year":"2023","journal-title":"J. Magn. Magn. Mater."},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"1256","DOI":"10.1016\/j.ceramint.2016.10.074","article-title":"BiFeO3 perovskites: A multidisciplinary approach to multiferroics","volume":"43","author":"Zagorac","year":"2017","journal-title":"Ceram. Int."},{"key":"ref_7","doi-asserted-by":"crossref","unstructured":"Tiwari, A., and Turner, A.P.F. (2014). Structural, electrical and magnetic properties of pure and substituted BiFeO3 multiferroics. Biosensors Nanotechnology, Wiley-Scrivener. [1st ed.].","DOI":"10.1002\/9781118773826"},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"20","DOI":"10.1103\/Physics.2.20","article-title":"Classifying multiferroics: Mechanisms and effects","volume":"2","author":"Khomskii","year":"2009","journal-title":"Physics"},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"4835","DOI":"10.1088\/0022-3719\/15\/23\/020","article-title":"Spiral magnetic ordering in bismuth ferrite","volume":"15","author":"Sosnowska","year":"1982","journal-title":"J. Phys. C Solid State Phys."},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"217206","DOI":"10.1103\/PhysRevLett.110.217206","article-title":"X-ray imaging and multiferroic coupling of cycloidal magnetic domains in ferroelectric monodomain BiFeO3","volume":"110","author":"Johnson","year":"2013","journal-title":"Phys. Rev. Lett."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"373","DOI":"10.1103\/PhysRev.124.373","article-title":"Relationship between crystal symmetry and magnetic properties of ionic compounds containing Mn3+","volume":"124","author":"Goodenough","year":"1961","journal-title":"Phys. Rev."},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"1051","DOI":"10.7567\/JJAPS.24S2.1051","article-title":"Measurement of the quadratic magnetoelectric effect on single crystalline BiFeO3","volume":"24","author":"Rivera","year":"1985","journal-title":"Jpn. J. Appl. Phys."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"024408","DOI":"10.1103\/PhysRevMaterials.1.024408","article-title":"Successive field-induced transitions in BiFeO3 around room temperature","volume":"1","author":"Kawachi","year":"2017","journal-title":"Phys. Rev. Mater."},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"134417","DOI":"10.1103\/PhysRevB.80.134417","article-title":"Magnetization and magnetoelectric effect in Bi1\u2212xLaxFeO3 (0 \u2264 x \u2264 0.15)","volume":"80","author":"Colson","year":"2009","journal-title":"Phys. Rev. B"},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"1901","DOI":"10.1002\/pssb.200945030","article-title":"Structural transformations and magnetic properties of Bi1\u2212xLnxFeO3 (Ln = La, Nd, Eu) multiferroics","volume":"246","author":"Troyanchuk","year":"2009","journal-title":"Phys. Status Solidi B"},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"014407","DOI":"10.1103\/PhysRevB.86.014407","article-title":"Spin cycloid quenching in Nd3+-substituted BiFeO3","volume":"86","author":"Chen","year":"2012","journal-title":"Phys. Rev. B"},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"1025","DOI":"10.1134\/S1063776111140196","article-title":"Morphotropic phase boundary, weak ferromagnetism, and strong piezoelectric effect in Bi1\u2212xCaxFeO3\u2212x\/2 compounds","volume":"113","author":"Troyanchuk","year":"2011","journal-title":"J. Exp. Theor. Phys."},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"536","DOI":"10.1016\/j.ssc.2011.01.018","article-title":"Enhanced ferroelectric, magnetic and magnetoelectric properties of Bi1\u2212xCaxFe1\u2212xTixO3 solid solutions","volume":"151","author":"Karpinsky","year":"2011","journal-title":"Solid State Commun."},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"114102","DOI":"10.1063\/1.3594251","article-title":"Enhanced piezoelectric and magnetic properties of Bi1\u2212xCaxFe1-x\/2Nbx\/2O3 solid solutions","volume":"109","author":"Troyanchuk","year":"2011","journal-title":"J. Appl. Phys."},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"12572","DOI":"10.1021\/ic502183t","article-title":"Introducing a large polar tetragonal distortion into Ba-doped BiFeO3 by low-temperature fluorination","volume":"53","author":"Clemens","year":"2014","journal-title":"Inorg. Chem."},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"064103","DOI":"10.1103\/PhysRevB.97.064103","article-title":"Magnetic enhancement of ferroelectric polarization in a self-grown ferroelectric-ferromagnetic composite","volume":"97","author":"Kumar","year":"2018","journal-title":"Phys. Rev. B"},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"022902","DOI":"10.1063\/1.5059550","article-title":"Ferromagnetism in the multiferroic alloy systems BiFeO3-BaTiO3 and BiFeO3-SrTiO3: Intrinsic or extrinsic?","volume":"114","author":"Kumar","year":"2019","journal-title":"Appl. Phys. Lett."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"064101","DOI":"10.1063\/5.0133733","article-title":"Inducing ferromagnetism and magnetoelectric coupling in the ferroelectric alloy system BiFeO3\u2013PbTiO3 via additives","volume":"133","author":"Saha","year":"2023","journal-title":"J. Appl. Phys."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"245","DOI":"10.1134\/S1063776108080086","article-title":"Crystal-structure and magnetic phase transformations in solid solutions of BiFeO3-AFe0.5Nb0.5O3 (A = Ca, Sr, Ba, Pb)","volume":"107","author":"Troyanchuk","year":"2008","journal-title":"J. Exp. Theor. Phys."},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"19","DOI":"10.4283\/JMAG.2011.16.1.019","article-title":"Effects of Mn doping on structural and magnetic properties of multiferroic BiFeO3 nanograins made by sol-gel method","volume":"16","author":"Raghavender","year":"2011","journal-title":"J. Magn."},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"40258","DOI":"10.1016\/j.ceramint.2023.09.361","article-title":"Optimizing physical properties of BiFe1\u2212xMnxO3 perovskite thin films via a low-temperature sol-gel method","volume":"49","author":"Hosseini","year":"2023","journal-title":"Ceram. Int."},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"953","DOI":"10.1002\/crat.201000050","article-title":"Effect of Ba ions substitution on multiferroic properties of BiFeO3 perovskite","volume":"45","author":"Gautam","year":"2010","journal-title":"Cryst. Res. Technol."},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"32711","DOI":"10.1016\/j.ceramint.2023.07.238","article-title":"Dielectric and magnetic properties of (Pb, Ti) co-doped BiFeO3 multiferroic ceramics","volume":"49","author":"Abdelmadjid","year":"2023","journal-title":"Ceram. Int."},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"1764","DOI":"10.1007\/s10854-024-13531-2","article-title":"Effect of Ca and Nb co-doping on optical and magnetoelectric properties of polycrystalline BiFeO3 ceramics","volume":"35","author":"Sutha","year":"2024","journal-title":"J. Mater. Sci. Mater. Electron."},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"174169","DOI":"10.1016\/j.jallcom.2024.174169","article-title":"Weak ferromagnetism in morphotropic phase boundary of BiFeO3-based materials","volume":"986","author":"Long","year":"2024","journal-title":"J. Alloys Compd."},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"8132","DOI":"10.1016\/j.ceramint.2022.10.336","article-title":"Enhanced multiferroic effect in multi-phased Eu substituted Bi\u2013Fe\u2013Mn perovskite oxides","volume":"49","author":"Wadne","year":"2023","journal-title":"Ceram. Int."},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"2050","DOI":"10.1007\/s10854-023-11464-w","article-title":"Investigations on structural, magnetic, and dielectric properties of Gd-substituted perovskite BiFeO3 multiferroics","volume":"34","author":"Sharma","year":"2023","journal-title":"J. Mater. Sci. Mater. Electron."},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"109612","DOI":"10.1016\/j.jpcs.2020.109612","article-title":"Magnetic structure and properties of Ca, Mn-doped bismuth ferrites near the polar\/nonpolar phase boundary","volume":"146","author":"Khomchenko","year":"2020","journal-title":"J. Phys. Chem. Solids"},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"163682","DOI":"10.1016\/j.jallcom.2022.163682","article-title":"Structural and magnetic phase transitions in Ca-substituted bismuth ferromanganites","volume":"901","author":"Khomchenko","year":"2022","journal-title":"J. Alloys Compd."},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"959","DOI":"10.1007\/s10854-021-07367-3","article-title":"Influence of Sr and Mn co-doping on the structural, optical, dielectric, multiferroic properties and band gap tuning in bismuth ferrite ceramics","volume":"33","author":"Salmani","year":"2022","journal-title":"J. Mater. Sci. Mater. Electron."},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"22266","DOI":"10.1021\/acs.jpcc.0c05778","article-title":"Effect of Mn and Ba codoping on a magnetic spin cycloid of multiferroic bismuth ferrite nanoparticles","volume":"124","author":"Dubey","year":"2020","journal-title":"J. Phys. Chem. C"},{"key":"ref_37","doi-asserted-by":"crossref","first-page":"1122","DOI":"10.1063\/1.4973007","article-title":"Magnetic properties of the multiferroics Bi1\u2212xCaxFe1\u2212xMnxO3 and Bi1\u2212xCaxFe1\u2212xTixO3","volume":"42","author":"Troyanchuk","year":"2016","journal-title":"Low Temp. Phys."},{"key":"ref_38","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":"Phys. B"},{"key":"ref_39","doi-asserted-by":"crossref","first-page":"698","DOI":"10.1107\/S0108768190006887","article-title":"Structure of a ferroelectric and ferroelastic monodomain crystal of the perovskite BiFeO3","volume":"46","author":"Kubel","year":"1990","journal-title":"Acta Cryst. B"},{"key":"ref_40","doi-asserted-by":"crossref","first-page":"054601","DOI":"10.7566\/JPSJ.88.054601","article-title":"Effect of Ca doping on modulated structures in multiferroic Bi1\u2212xCaxFeO3","volume":"88","author":"Hiroyama","year":"2019","journal-title":"J. Phys. Soc. Jpn."},{"key":"ref_41","doi-asserted-by":"crossref","unstructured":"Karpinsky, D.V., Silibin, M.V., Latushka, S.I., Zhaludkevich, D.V., Sikolenko, V.V., Al-Ghamdi, H., Almuqrin, A.H., Sayyed, M.I., and Belik, A.A. (2022). Structural and magnetic phase transitions in BiFe1\u2212xMnxO3 solid solution driven by temperature. Nanomaterials, 12.","DOI":"10.3390\/nano12091565"},{"key":"ref_42","doi-asserted-by":"crossref","unstructured":"Belik, A.A. (2024). Two perovskite modifications of BiFe0.6Mn0.4O3 prepared by high-pressure and post-synthesis annealing at ambient pressure. Inorganics, 12.","DOI":"10.3390\/inorganics12080226"},{"key":"ref_43","doi-asserted-by":"crossref","first-page":"71","DOI":"10.1016\/0022-4596(82)90292-4","article-title":"Structure determination of CaMnO3 and CaMnO2.5 by X-ray and neutron methods","volume":"45","author":"Poeppelmeier","year":"1982","journal-title":"J. Solid State Chem."},{"key":"ref_44","doi-asserted-by":"crossref","first-page":"254","DOI":"10.1016\/j.jallcom.2009.08.099","article-title":"Magnetic and electrical properties of Bi0.8Ca0.2Fe1\u2212xMnxO3 (0 \u2264 x \u2264 0.5)","volume":"488","author":"Yin","year":"2009","journal-title":"J. Alloys Compd."},{"key":"ref_45","doi-asserted-by":"crossref","first-page":"339","DOI":"10.1016\/j.jmmm.2004.09.118","article-title":"The effect of Fe substitution on magnetic and transport properties of LaMnO3","volume":"288","author":"De","year":"2005","journal-title":"J. Magn. Magn. Mater."},{"key":"ref_46","doi-asserted-by":"crossref","first-page":"830","DOI":"10.1016\/j.jssc.2011.02.006","article-title":"Structure and magnetic order in the series BixRE1\u2212xFe0.5Mn0.5O3 (RE = La,Nd)","volume":"184","author":"Bridges","year":"2011","journal-title":"J. Solid State Chem."},{"key":"ref_47","doi-asserted-by":"crossref","first-page":"453","DOI":"10.1146\/annurev.ms.24.080194.002321","article-title":"Strongly geometrically frustrated magnets","volume":"24","author":"Ramirez","year":"1994","journal-title":"Annu. Rev. Mater. Sci."},{"key":"ref_48","doi-asserted-by":"crossref","first-page":"127470","DOI":"10.1016\/j.matlet.2020.127470","article-title":"Effect of Mn substitution on the crystal and magnetic structure of Bi1\u2212xCaxFeO3\u2212x\/2 multiferroics","volume":"266","author":"Khomchenko","year":"2020","journal-title":"Mater. Lett."},{"key":"ref_49","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_50","doi-asserted-by":"crossref","first-page":"233","DOI":"10.1016\/j.scriptamat.2020.07.045","article-title":"Magnetic contributions in multiferroic gadolinium modified bismuth ferrite ceramics","volume":"188","author":"Walker","year":"2020","journal-title":"Scr. Mater."},{"key":"ref_51","doi-asserted-by":"crossref","first-page":"160178","DOI":"10.1016\/j.jallcom.2021.160178","article-title":"Chemical pressure exerted by rare earth substitution in BiFeO3: Effect on crystal symmetry, band structure and magnetism","volume":"876","author":"Mumtaz","year":"2021","journal-title":"J. Alloys Compd."}],"container-title":["Applied Sciences"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/2076-3417\/14\/21\/9991\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,10]],"date-time":"2025-10-10T16:26:24Z","timestamp":1760113584000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/2076-3417\/14\/21\/9991"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2024,11,1]]},"references-count":51,"journal-issue":{"issue":"21","published-online":{"date-parts":[[2024,11]]}},"alternative-id":["app14219991"],"URL":"https:\/\/doi.org\/10.3390\/app14219991","relation":{},"ISSN":["2076-3417"],"issn-type":[{"value":"2076-3417","type":"electronic"}],"subject":[],"published":{"date-parts":[[2024,11,1]]}}}