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

TL;DR

This study uses density functional calculations to show that Eu doping in magnetite, stabilized by spin-orbit interaction, significantly enhances its saturation magnetisation, with potential applications in magnetically recoverable catalysts.

Contribution

It reveals the role of spin-orbit interaction in Eu-doped magnetite, demonstrating a substantial increase in saturation magnetisation and analyzing effects of electron and hole doping.

Findings

Eu doping at tetrahedral sites maximizes magnetisation.

Maximum saturation magnetisation reaches 9.451 μB/f.u., much higher than undoped magnetite.

Electron doping maintains high magnetisation, while hole doping reduces it.

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 ($\mathrm{Fe_3O_4:Eu_{Fe}}$). 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 ($\mathrm{Fe_{Tet}}$ and $\mathrm{Eu_{Tet}}$) and the cations on the octahedral sites ($\mathrm{Fe_{Oct}}$), $\mathrm{Fe_3O_4:Eu_{Fe}}$ exhibits a maximum saturation magnetisation of 9.451 $\mu_B/$f.u. which is significantly larger than that of undoped magnetite (calculated to be 3.929 $\mu_B/$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.