High-pressure syntheses, crystal structures, and magnetic properties of novel quadruple perovskite oxides LaMn3Ru2Mn2O12 and LaMn3Ru2Fe2O12

Abstract

Quadruple perovskite oxides LaMn3Ru2M2O12 (M = Mn, Fe) have been synthesized under high-pressure and high-temperature conditions of 8 GPa and 1373 K. Synchrotron X-ray powder diffraction study demonstrates that both oxides crystallized in AA'3B4O12-type cubic quadruple perovskite structures, where the Ru and M ions did not form the special ordering at B-site. X-ray absorption spectroscopy reveals that the valence states are represented as LaMn3+3Ru3+2M3+2O12 (M = Mn, Fe) in the ionic models, indicating that the isovalent states of Ru3+ and M3+ ions disturb the B-site ordering. Magnetization, heat capacity, and neutron diffraction data prove that short-range magnetic orderings are predominant for both compounds instead of long-range magnetic orderings. We conclude that the competition between ferromagnetic and antiferromagnetic superexchange interactions between Ru3+ and M3+ ions at B-site prevent the long-range magnetic ordering Mn3+ ions at A′-site, although the A'- and B-site magnetic sublattices are expected to be intrinsically independent in A′-Mn quadruple perovskite system. This finding represents that the atomic ordering of the B-site is essential for the precise design of magnetic structures for the LaMn3M2M′2O12 quadruple perovskite series.