Chien-Te Chen, Antoine Maignan, Christine Martin, Françoise Damay, François Fauth, Xiao Wang, Hong-Ji Lin, Elodie Tailleur, Zhiwei Hu, Emmanuelle Suard, Liu Hao Tjeng, Maxim Mostovoy, Theory of Condensed Matter, Laboratoire de cristallographie et sciences des matériaux (CRISMAT), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche sur les Matériaux Avancés (IRMA), Normandie Université (NU)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Rouen Normandie (UNIROUEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS), Laboratoire Léon Brillouin (LLB - UMR 12), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), University of Groningen [Groningen], Max Planck Institute for Chemical Physics of Solids (CPfS), Max-Planck-Gesellschaft, Max Planck Institute for chemical Physics of Solids, Ministry of Science and Technology of the People’s Republic of China, Institut Laue-Langevin (ILL), and ALBA Synchrotron light source [Barcelone]
International audience; Fe4Nb2O9 and Co4Nb2O9 are antiferromagnetic compounds belonging to the M4M′2O9 series (M = Mn, Fe, Co; M′ = Nb, Ta), whose structure (P[3 with combining macron]c1) derives from the Cr2O3 corundum one. By mixing cobalt and iron in a 1 : 1 ratio, an Fe2Co2Nb2O9 oxide has been synthesized. Its structural, magnetic and electric characterization studies confirm that its unit cell volume (V = 331.19(1) Å3), Néel temperature (TN = 58 K) and dielectric permittivity are intermediate between those of the Fe4Nb2O9 and Co4Nb2O9 end members. The neutron diffraction study evidences an Fe:Co random occupation of the (4d) Wyckoff sites. Its antiferromagnetic structure, refined in the C2/c′ magnetic space group, shows magnetic moments in the planes of the honeycomb (HC) layers of the M4M′2O9 structure, and stacked along c, as for Fe4Nb2O9 and Co4Nb2O9. However, the magnetic field induced magnetization M(H) of Fe2Co2Nb2O9 below TN differs strongly from both end members, exhibiting a sublinear dependence. A similar rounded shape of the electric polarization P(H) curve is evidenced, in marked contrast to the linear M(H) and P(H) behaviours observed below the spin-flop magnetic field for this class of linear magnetoelectric materials. As a result, Fe2Co2Nb2O9 exhibits larger P values and steeper P responses to H at low H than both Fe4Nb2O9 and Co4Nb2O9 end members. This result is explained by a microscopic model based on the Fe and Co mixed occupation. Substitutional disorder locally allows for stronger magnetoelectric couplings and its effect does not cancel on average. This chemical substitution effect opens a new route to enhance the magnetoelectric response of honeycomb antiferromagnets.