Structural and magnetic properties of Cu–Ni–Cr spinel oxides

Abstract

The compounds CuCr 2O 4 and NiCr 2O 4 crystallize at room temperature in a tetragonal distorted spinel structure, s.g. I4 1/amd, with axes ratio c/ a<1 and >1, respectively. The distortion is caused by the Jahn–Teller ions Cu 2+ and Ni 2+ which flatten or elongate their surrounding oxygen tetrahedron. CuCr 2O 4 and NiCr 2O 4 form a complete solid solution series Cu 1− x Ni x Cr 2O 4 where for 0.825< x<0.875 members with orthorhombic symmetry were found. Using neutron powder diffraction and thermal analysis methods several members of the solid solution series were investigated. On cooling, all samples showed a temperature-dependent crystallographic phase transition from cubic to tetragonal symmetry between 865 K (CuCr 2O 4) and 310 K (NiCr 2O 4). The phase Cu 0.15Ni 0.85Cr 2O 4 undergoes a second crystallographic transition to orthorhombic symmetry, space group Fddd, at T=300 K. The neutron diffraction experiments as well as SQUID measurements reveal magnetic ordering of the ions between 150 and 50 K which partially occurs as a two-step mechanism.