Correlation between crystallite size, resistance to oxidation, and phase transformation of germanium-doped Fe3O4 nanocrystalline thin films by using a sputtering target of α-Fe2O3

We investigated the correlation between the crystallite size, resistance to oxidation, and phase transition of Ge-doped Fe3O4 nanocrystalline thin films. We prepared thin films on water-cooled glass substrates by radiofrequency sputtering with Ge-tipped α-Fe2O3 ceramic disks as targets. The addition of Ge caused a reductive phase transition from α-Fe2O3 with a corundum structure to Ge-doped Fe3O4 with an inverse spinel structure, resulting in a crystallite size of <10 nm. We annealed three samples with average sizes of 5, 8, and 10 nm by changing Ge addition concentrations at 673 K in air for up to 323 days until reaching near-thermal equilibrium. All samples maintained their magnetization at almost a constant value over long-term heat treatment. The results of Raman spectroscopy and optical transmittance spectroscopy suggest that there was a phase transition to Ge-doped γ-Fe2O3 at 5 nm, Ge-doped Fe3−δO4 with iron vacancies δ at 8 nm, and Ge-doped Fe3O4 at 10 nm. In other words, we retained Fe3O4 down to a relatively small crystallite size of 10 nm because of the improved oxidation resistance imparted by Ge doping.