Nanoscale size effect on surface spin canting in iron oxide nanoparticles synthesized by the microemulsion method

Uniformly sized and crystalline iron oxide nanoparticles (IONPs) with spinel structure and mean diameters of about 3, 6 and 9 nm were synthesized in high yield using the microemulsion route at room temperature. The nanoparticles (NPs) were stabilized in situ by organic surfactant molecules which acted both as a stabilizer of the microemulsion system and as a capping layer of the NP surface. NP size control was attained by careful adjustment of the preparation conditions. The structure, morphology and NP size distribution were investigated by x-ray diffraction, transmission electron microscopy and scanning electron microscopy. A particular effort was devoted in this work to study the effect of size and capping of these NPs on their magnetic structure by in-field Mossbauer spectroscopy at 4.2 K. The mean canting angle (relative to the applied field direction) of the Fe spins was observed to increase with decreasing NP size due to the enhanced surface-to-volume ratio. Comparing bare and capped NPs of the same diameter, we verified that the spin canting was not affected by the organic capping. This implied almost identical magnetic orientations of bare and capped NPs. Simultaneously, the capping material was capable of preventing agglomeration effects which can occur in case of direct particle contact. Using a core/shell model, we showed that spin canting originated from the surface shell of the NPs. Furthermore, the Mossbauer spectral parameters provided evidence for the existence of a high fraction of Fe3O4 (magnetite) in the IONP.