From Fe₃O₄/NiO bilayers to NiFe₂O₄-like thin films through Ni interdiffusion

Ferrites with (inverse) spinel structure display a large variety of electronic and magnetic properties making some of them interesting for potential applications in spintronics. We investigate the thermally induced interdiffusion of Ni$^{2+}$ ions out of NiO into Fe$_3$O$_4$ ultrathin films resulting in off-stoichiometric nickelferrite-like thin layers. We synthesized epitaxial Fe$_3$O$_4$/NiO bilayers on Nb-doped SrTiO$_3$(001) substrates by means of reactive molecular beam epitaxy. Subsequently, we performed an annealing cycle comprising three steps at temperatures of 400\,$^{\circ}$C, 600\,$^{\circ}$C, and 800\,$^{\circ}$C under an oxygen background atmosphere. We studied the changes of the chemical and electronic properties as result of each annealing step with help of hard x-ray photoelectron spectroscopy and found a rather homogenous distribution of Ni and Fe cations throughout the entire film after the overall annealing cycle. For one sample we observed a cationic distribution close to that of the spinel ferrite NiFe$_2$O$_4$. Further evidence comes from low energy electron diffraction patterns indicating a spinel type structure at the surface after annealing. Site and element specific hysteresis loops performed by x-ray magnetic circular dichroism uncovered the antiferrimagnetic alignment between the octahedral coordinated Ni$^{2+}$ and Fe$^{3+}$ ions and the Fe$^{3+}$ in tetrahedral coordination. We find a quite low coercive field of 0.02\,T, indicating a rather low defect concentration within the thin ferrite films.