Preparation, crystal and magnetic structure, and magnetotransport properties of the double perovskite CaCu2.5Mn4.5O12

作者:Sanchez Benitez J; Alonso JA*; Martinez Lope MJ; Casais MT; Martinez JL; de Andres A; Fernandez Diaz MT
来源:Chemistry of Materials, 2003, 15(11): 2193-2200.
DOI:10.1021/cm0212616

摘要

CaCu2.5Mn4.5O12 perovskite has been prepared in polycrystalline form under moderate pressure conditions of 20 kbar, in the presence of KClO4 as oxidizing agent. This material has been studied by X-ray and neutron powder diffraction (NPD), magnetic, magnetotransport, and thermopower measurements. The crystal structure is cubic, space group Im (3) over bar (No. 204), with a = 7.2279(l) Angstrom at room temperature (RT). In the ABO(3) perovskite superstructure, the A positions are occupied by Ca2+ and (Cu2.52+Mn0.53+), ordered in a 1:3 arrangement giving rise to the body-centering of the unit cell. At the B positions, Mn adopts a mixed oxidation state of 3.875+; MnO6 octahedra are considerably tilted by 19degrees, due to the relatively small size of the A-type cations. The Curie temperature is 345 K. Low temperature (2 K) NPD data show evidence for a ferrimagnetic coupling between Mn3.875+ and (Cu2.52+Mn0.53+) spins, with ordered magnetic moments of 2.32(5) and -0.54(3) mu(B), respectively. An additional canting effect of the Mn moments at B positions has been detected below 70 K, breaking down the body centered symmetry. We have developed a microscopic model that explains both the saturation magnetization values and the refined magnetic moments at A and B positions. Our results show that Cu2+ and Mn3+ spins at the A substructure are almost perpendicular to each other. A magnetoresistance (MR) of 34% has been observed at 5 K for H = 9 T; the low field MR at RT is as high as 2% and shows an appreciable temperature stability.

  • 出版日期2003-6-3