Origin of magnetism via cation vacancy defects in non-stoichiometric NiCo2O4 nanoparticles: A synchrotron-based x-ray absorption and x-ray magnetic circular dichroism spectroscopic study

Abstract

The present study probes the effect of cation distributions in the structural, optical, electronic, and magnetic properties of mixed-valent inverse-spinel NiCo2O4 (NCO) nanoparticles (NPs). NCO NPs were prepared using the sol–gel combustion method and the grain size was obtained in the magnetic exchange length range assumed to be from single-ion anisotropy. The Raman and photoluminescence spectroscopies confirm the presence of an inverse-spinel structure with different oxidation states, and vibrating sample magnetometry clarifies the existence of ferromagnetism with the presence of magnetic anisotropy among the cations. These NPs annealed at a higher grain-growth temperature accumulate ferrimagnetic properties and produce magneto-crystalline anisotropy making NCO an assuring material for spintronic applications. A detailed x-ray absorption spectroscopy and x-ray magnetic circular dichroism studies reveal an indestructible correlation between the distribution of the present cations and the element-specific origin of ferrimagnetic behavior. Ni is found to be accountable for the magnetic moment and electronic conduction, whereas Co is associated mainly with the generation of the magnetic anisotropy even in the polycrystalline NP form. This describes the anti-ferromagnetic coupling between Co and Ni ions that is pivotal in demonstrating the exchange interaction between these cations. The above result signifies the site-dependent cation valence states for the magnetic properties, and the extent of growing conditions are related to such cation-site dysfunction. This depicts further tunability in NCO as a functional oxide material.