Exceptionally high saturation magnetisation in Eu-doped magnetite stabilised by spin–orbit interaction

Abstract

The significance of the spin–orbit interaction is very well known in compounds containing heavier elements such as the rare-earth Eu ion. Here, through density functional calculations, we investigated the effect of the spin–orbit interaction on the magnetic ground state of Eu doped magnetite (Fe₃O₄:Eu_Fe). By examining all possible spin alignments between Eu and magnetite's Fe, we demonstrate that Eu, which is most stable when doped at the tetrahedral site, adapts a spin almost opposite the substituted Fe. Consequently, because of smaller spin cancellation between the cations on the tetrahedral site (Fe_Tet and Eu_Tet) and the cations on the octahedral sites (Fe_Oct), Fe₃O₄:Eu_Fe exhibits a maximum saturation magnetisation of 9.451 μ_B per f.u. which is significantly larger than that of undoped magnetite (calculated to be 3.929 μ_B per f.u.). We further show that this large magnetisation persists through additional electron doping. However, additional hole doping, which may unintentionally occur in Fe deficient magnetite, can reduce the magnetisation to values smaller than that of the undoped magnetite. The results presented here can aid in designing highly efficient magnetically recoverable catalysts for which both magnetite and rare earth dopants are common materials.