Unraveling the Origin of Ferrimagnetic Signatures in (Fe,Mn,Ga)2O3 Bixbyites: The Role of Structurally-Undetectable Spinel Impurities
The cubic Fe2-xMnxO3 is an intriguing material that has recently been investigated for various applications, including lithium-ion battery anodes, catalysts, energy storage media, humidity sensors, and photocatalysts. Despite its wide range of promising applications, the magnetic properties of Fe2-xMnxO3 remain controversial, with different sources reporting conflicting information regarding the type of magnetic ordering, phase transition temperature, and magnetic moment of this compound. This work presents a study of the magnetic state of three Fe2-xMnxO3:Ga solid solutions with varying Mn:Fe:Ga ratios, along with one gallium-free Fe2-xMnxO3 reference sample. We performed a detailed analysis of the actual chemical composition and crystal structure of the synthesized samples using energy-dispersive X-ray spectroscopy (EDX), powder X-ray diffraction (XRD), and X-ray absorption spectroscopy (XAS) to evaluate compositional differences. The magnetic states of the three Fe2-xMnxO3:Ga samples and the gallium-free Fe2-xMnxO3 were investigated using magnetometry and Mossbauer spectroscopy. The low-temperature magnetic anomalies were found to be more consistent with spin-glass-like freezing than with conventional long-range antiferromagnetic ordering. Although variations in magnetic behavior were observed and found to depend on composition and the cooling rate during synthesis, our results demonstrate that these factors do not account for the drastically different magnetic properties reported for similar bixbyite-type oxides. Instead, the apparent room-temperature ferrimagnetism observed in one sample is most likely extrinsic and can be attributed to a trace spinel-type impurity phase, as supported by magnetizations and ESR measurements. Thus, the origin of these discrepancies lies primarily in the chemical purity of the samples and, to a significant extent, in the synthesis technique employed.