Magnetic circular dichroism at the oxygen K-edge in microcrystals of spinels grown on Ru(0001)

We have measured the circular magnetic dichroism in the x-ray absorption at the K-edge of oxygen in microcrystals of different spinel oxides. The microcrystals are islands of micrometric size and nanometric thickness, grown on Ru(0001) substrates using high-temperature oxygen-assisted molecular beam epitaxy. The domains observed in the oxygen K-edge dichroism have the same distribution and orientation as those observed in x-ray magnetic circular dichroism at the L₃edge of the octahedral cations. Integrating the area from a single domain, x-ray magnetic circular dichroic spectra of oxygen were measured and, by the application of the K-edge sum rule, non vanishing orbital magnetic moments aligned with the octahedral cations were found. Density functional theory calculations, which did not show any orbital moment at the oxygen anions, indicate that the energy ranges where oxygen dichroism is observed correspond to those with significant hybridization with the cations d bands. They also show a correlation between the magnitude of the measured value of the oxygen orbital moment and the theoretical one for the cations, and demonstrate that this trend is preserved in the presence of Fe excess in the samples. Our experimental XMCD suggest, following the density functional theory calculations, that the origin of the oxygen magnetic moment lies in the hybridization of the oxygen unoccupied p-derived bands with the cation bands, mostly with the d-derived ones and does not correspond to a localized orbital magnetic moment in the oxygen in spinels.