Influence of Magnetite Nanoparticles Shape and Spontaneous Surface Oxidation on the Electron Transport Mechanism

The spontaneous oxidation of a magnetite surface and shape design are major aspects of synthesizing various nanostructures with unique magnetic and electrical properties, catalytic activity, and biocompatibility. In this article, the roles of different organic modifiers on the shape and formation of an oxidized layer composed of maghemite were discussed and described in the context of magnetic and electrical properties. It was confirmed that Fe₃O₄ nanoparticles synthesized in the presence of triphenylphosphine could be characterized by cuboidal shape, a relatively low average particle size (9.6 ± 2.0 nm), and high saturation magnetization equal to 55.2 emu/g. Furthermore, it has been confirmed that low-frequency conductivity and dielectric properties are related to surface disordering and oxidation. The electric energy storage possibility increased for nanoparticles with a disordered and oxidized surface, whereas the dielectric losses in these particles were strongly related to their size. The cuboidal magnetite nanoparticles synthesized in the presence of triphenylphosphine had an ultrahigh electrical conductivity (1.02 × 10^-4 S/cm at 10 Hz) in comparison to the spherical ones. At higher temperatures, the maghemite content altered the behavior of electrons. The electrical conductivity can be described by correlated barrier hopping or overlapping large polaron tunneling. Interestingly, the activation energies of electrons transport by the surface were similar for all the analyzed nanoparticles in low- and high-temperature ranges.