Zn²⁺ Ion Surface Enrichment in Doped Iron Oxide Nanoparticles Leads to Charge Carrier Density Enhancement

Here, we report the development of monodisperse Zn-doped iron oxide nanoparticles (NPs) with different amounts of Zn (Zn_xFe_3–xO₄, 0 < x < 0.43) by thermal decomposition of a mixture of zinc and iron oleates. The as-synthesized NPs show a considerable fraction of wüstite (FeO) which is transformed to spinel upon 2 h oxidation of the NP reaction solutions. At any Zn doping amounts, we observed the enrichment of the NP surface with Zn²⁺ ions, which is enhanced at higher Zn loadings. Such a distribution of Zn²⁺ ions is attributed to the different thermal decomposition profiles of Zn and Fe oleates, with Fe oleate decomposing at much lower temperature than that of Zn oleate. The decomposition of Zn oleate is, in turn, catalyzed by a forming iron oxide phase. The magnetic properties were found to be strongly dependent on the Zn doping amounts, showing the saturation magnetization to decrease by 9 and 20% for x = 0.05 and 0.1, respectively. On the other hand, X-ray photoelectron spectroscopy near the Fermi level demonstrates that the Zn_0.05Fe_2.95O₄ sample displays a more metallic character (a higher charge carrier density) than undoped iron oxide NPs, supporting its use as a spintronic material.