Multiferroism Induced by Spontaneous Structural Ordering in Antiferromagnetic Iron Perovskites

• Published in: Chemistry of materials 2019-08, Vol.31 (15), p.5993-6000
• Main Authors: Martínez de Irujo-Labalde, Xabier, Goto, Masato, Urones-Garrote, Esteban, Amador, Ulises, Ritter, Clemens, Amano Patino, Midori E, Koedtruad, Anucha, Tan, Zhenhong, Shimakawa, Yuichi, García-Martín, Susana
• Format: Article
• Language: English
• ISSN: 0897-4756; 1520-5002
• DOI: 10.1021/acs.chemmater.9b02716

Room-temperature multiferroism in polycrystalline antiferromagnetic Fe perovskites is reported for the first time. In the perovskite-type oxides RE1.2Ba1.2Ca0.6Fe3O8 (RE = Gd, Tb), the interplay of layered ordering of Gd­(Tb), Ba, and Ca atoms with the ordering of FeO4-tetrahedra (T) and FeO6-octahedra (O) results in a polar crystal structure. The layered structure consists of the stacking sequence of RE/Ca-RE/Ca-Ba-RE/Ca layers in combination with the TOOT sequence in a unit cell. A polar moment of 33.0 μC/cm2 for the Gd-oxide (23.2 μC/cm2 for the Tb one) is determined from the displacements of the cations, mainly Fe, and oxygen atoms along the b-axis. These oxides present antiferromagnetic ordering doubling the c-axis, and the magnetic structure in the Tb-compound remains up to 690 K, which is one of the highest transition temperatures reported in Fe perovskites.