Crucial Role Of The Co Cations On The Destabilization Of The Ferrimagnetic Alignment In Co-Ferrite Nanoparticles With Tunable Structural Defects

The key role of the structural defects on the magnetic properties of cobalt ferrite nanoparticles (NPs) is investigated by complementary local probes: element- and site-specific X-ray magnetic circular dichroism (XMCD) combined with high-resolution transmission electron microscopy of individual NPs. A series of monodisperse samples of 8 nm NPs with a tunable amount of structural defects were prepared by thermal decomposition of Fe(III) and Co(II) acetylacetonates in the presence of a variable concentration of 1,2-hexadecanediol. The particles show a partial inverse spinel structure, and their stoichiometry and cation distribution are comparable along the series. Element-specific XMCD hysteresis loops at all the cationic sites show a decrease in squareness and an increase in both the closure field and the high-field susceptibility as the NPs become more structurally defective, suggesting the progressive loss of the collinear ferrimagnetism. However, the Co2+ cations in octahedral sites are significantly more affected by the structural defects than the rest of the cations. This is because structural defects cause local distortions of the crystal field acting on the orbital component of the cations, yielding effective local anisotropy axes that cause a prevalent Co2+ spin canting through the spin-orbit coupling, owing to the relatively large value of the partially unquenched moment of these cations, as found by XMCD. All in all, our results emphasize the crucial role of the Co2+ cations on the destabilization of the collinear ferrimagnetism with the inclusion of structural defects in cobalt ferrite NPs.