Field induced metamagnetic transition and mixed charge transfer Mott-Hubbard character in nanocrystalline FeCo2O4 spinel oxide: A combined study using experimental and first principles techniques

Abstract

Unusual magnetic behavior of nanocrystalline FeCo2O4 (FCO) has been observed at different annealing temperatures. FCO nanoparticles have been prepared by co-precipitation method and the prepared sample annealed at different temperatures to vary its crystallite size. The powder x-ray diffraction analysis confirms the presence of pure spinel phase in the samples annealed at 900 ℃ and 1000℃. The increase in particle size with annealing temperature has been confirmed by field emission scanning electron microscopy (FESEM) analysis. High resolution x-ray photoelectron spectroscopy (HRXPS) analysis reveals the presence of mixed oxidation states of Fe+2/ Fe+3 and Co+3/Co+2 in the sample annealed at 900℃. The as-synthesized sample at 80 °C shows strong antiferromagnetic behavior due to their smaller particle size, but all the annealed samples have strong ferromagnetic behavior with large coercive field and remanence due to their larger particle size. We have observed a sharp rise in magnetization near small field values in the virgin curve and also the presence of virgin curve completely outside the main hysteresis loop in the M(H) curves measured at 5 K for the samples annealed at and above 1000 ℃ reveal the characteristic of first order nature of field induced metamagnetic transition. Structural parameters obtained after Rietveld refinement of powder x-ray diffraction pattern for sample annealed at 900 ℃ have been used for investigating the magnetic properties using first principles density functional theory. Our calculations using hybrid exchange-correlation functional, HSE06 captures the correct insulating ferromagnetic ground state and band gap for inverse spinel structure in broad agreement with our experimental results while calculations within GGA+U leads to a wrong half metallic ferromagnetic ground state. The partial density of states obtained for inverse spinel structure with HSE06 functional suggests a mixed charge transfer and Mott-Hubbard character in our system. We have explored the interplay among structural, magnetic and transport properties of FCO using experiment as well as first principles density functional theory.