Structural, morphological, and magnetic characterizations of (Fe0.25Mn0.75)2O3 nanocrystals: a comprehensive stoichiometric determination

TL;DR

This study comprehensively characterizes (Fe0.25Mn0.75)2O3 nanocrystals, revealing their structural, morphological, and magnetic properties, including phase composition, surface oxygen vacancies, and spin-glass behavior at low temperatures.

Contribution

It provides detailed insights into the nanocrystals' phase structure, surface chemistry, and magnetic behavior, especially the core-shell spin-glass transition, using multiple advanced characterization techniques.

Findings

Formation of bixbyite primary phase

Presence of surface oxygen vacancies and mixed oxidation states

Observation of spin-glass behavior below 50 K

Abstract

Iron manganese trioxide (Fe0.25Mn0.75)2O3 nanocrystals were synthesized by the sol-gel method. The 80 K Mossbauer spectrum was well-fitted using two doublets representing the 8b and 24d crystallographic sites of the (FexMn1-x)2O3 phase and two weak extra sextets which were attributed to crystalline and amorphous hematite. Our findings showed formation of a bixbyite primary phase. The Raman spectrum exhibits six Raman active modes, typical of (Fe,Mn)2O3, and two extra Raman modes associated with the secondary hematite phase. X-ray photoelectron spectroscopy analysis confirmed the presence of oxygen vacancy onto the (FexMn1-x)2O3 particle surface, with varying oxidation states. X-band magnetic resonance data revealed a single broad resonance line in the whole temperature range (3.8 K - 300 K). The temperature dependence of both resonance field and resonance linewidth shows a remarkable change in the range of 40 - 50 K, herein credited to surface spin glass behavior. The model picture used assumes (FexMn1-x)2O3 nanoparticles with a core-shell structure. Results indicate that below about 50 K the spin system of shell reveals a paramagnetic to spin glass-like transition upon cooling, with a critical temperature estimated at 43 K. In the higher temperature range, the superparamagnetic hematite (secondary) phase contributes remarkably to the temperature dependence of the resonance linewidth. Zero-field-cooled (ZFC) and fieldcooled (FC) data show strong irreversibility and a peak in the ZFC curve at 33 K, attributed to a paramagnetic-ferrimagnetic transition of the main phase. Hysteresis curve at 5 K shows a low coercive field of 4 kOe, with the magnetization not reaching saturation at 70 kOe, suggesting the occurrence of a ferrimagnetic core with a magnetic disorder at surface, characteristic of core-shell spin-glass-like behavior.