Structural and Magnetic properties of Ge0.5Mn0.5Co2O4 using neutron diffraction

Abstract: The structural and magnetic properties of Ge0.5Mn0.5Co2O4 (GMCO) have been investigated in detail utilizing neutron powder diffraction (NPD), x-ray diffraction (XRD), DC magnetometry, and heat capacity analysis and compared with GeCo2O4. Despite both compounds exhibiting a cubic structure at room temperature, a substantial difference on low temperature structural properties have been observed for GMCO, indicating the effect of Mn substitution on crystal structure. The magnetic and heat capacity data reveal a ferrimagnetic ordering around 108 K in GMCO. A minor secondary phase is confirmed which undergoes long range AFM ordering at further lower temperatures. This secondary phase remains undetected in XRD due to identical lattice parameters. Furthermore, the analysis of heat capacity data indicates a broadening of the high-temperature transition, attributing to the short-range correlation persisting up to higher temperatures. The estimated magnetic entropy amounts is 63% of the value expected for GMCO. The missing entropy is likely linked with the short-range magnetic correlations persisting well above the transition temperature. Cation distribution at the A and B sites has been estimated in GMCO using NPD. Magnetic structures are also confirmed in the main phase as well as in the secondary phase using NPD analysis. The high-temperature transition corresponds to the ferrimagnetic ordering of A and B site cations in the main phase. A collinear ferrimagnetic arrangement of A and B site spins aligned parallel to c axis is observed. The average values of A and B site moments in the ferrimagnetic phase at 5 K are 2.31(3) and 1.82(3)mB, respectively, with the temperature dependence of moments following the expected power law behavior. The low-temperature ordering is attributed to the antiferromagnetic ordering of B site ions associated with the secondary phase, something similar to GeCo2O4.