Magnetic anisotropy engineering in onion-structured metal oxide nanoparticles combining dual exchange coupling and proximity effects

Abstract

A series of exchange-coupled magnetic nanoparticles combining several magnetic phases in an onion-type structure were synthesized by performing a three-step seed-mediated growth process. Iron and cobalt precursors were alternatively decomposed in high-boiling-temperature solvents (288–310 °C) to successively grow CoO and Fe_3−δO₄ shells (the latter in three stages) on the surface of Fe_3−δO₄ seeds. The structure and chemical composition of these nanoparticles were investigated in depth by combining a wide panel of advanced techniques, such as scanning transmission electron microscopy (STEM), electron energy-loss spectroscopy–spectrum imaging (EELS-SI), ⁵⁷Fe Mössbauer spectrometry, and X-ray circular magnetic dichroism (XMCD) techniques. The size of the nanoparticles increased progressively after each thermal decomposition step, but the crystal structure of core–shell nanoparticles was significantly modified during the growth of the second shell. Indeed, the antiferromagnetic CoO phase was progressively replaced by the CoFe₂O₄ ferrimagnet due to the concomitant processes of partial solubilization/crystallization and the interfacial cationic diffusion of iron. A much more complex chemical structure than that suggested by a simple size variation of the nanoparticles is thus proposed, namely Fe_3−δO₄@CoO-CoFe₂O₄@Fe_3−δO₄, where an intermediate Co-based layer was shown to progressively become a single, hybrid magnetic phase (attributed to proximity effects) with a reduction in the CoO amount. In turn, the dual exchange-coupling of this hybrid Co-based intermediate layer (with high anisotropy and ordering temperature) with the surrounding ferrite (core and outer shells) stabilized the particle moment well above room temperature. These effects allow for the production of Fe oxide-based magnetic nanoparticles with high effective anisotropy, thus revealing the potential of this strategy to design rare-earth-free permanent nanomagnets at room temperature.