Origin of the magnetic transition at 100 K in ε-Fe₂O₃ nanoparticles studied by x-ray absorption fine structure spectroscopy

The current study unveils the structural origin of the magnetic transition of the ε-Fe₂O₃ polymorph from an incommensurate magnetic order to a collinear ferrimagnetic state at low temperature. The high crystallinity of the samples and the absence of other iron oxide polymorphs have allowed us to carry out temperature-dependent x-ray absorption fine structure spectroscopy experiments out. The deformation of the structure is followed by the Debye–Waller factor for each selected Fe–O and Fe–Fe sub-shell. For nanoparticle sizes between 7 and 15 nm, the structural distortions between the Fe_te and Fe-D1_oc sites are localized in a temperature range before the magnetic transition starts. On the contrary, the inherent interaction between the other sub-shells (named Fe–O1,2 and Fe–Fe1) provokes cooperative magneto-structural changes in the same temperature range. This means that the Fe_te with Fe-D1_oc polyhedron interaction seems to be uncoupled with temperature dealing with these nanoparticle sizes wherein the structural distortions are likely moderate due to surface effects. (paper)