Determination of the cation site distribution of the spinel in multiferroic CoFe2O4 / BaTiO3 layers by X-ray photoelectron spectroscopy

International audienceThe properties of CoFe2O4/BaTiO3 artificial multiferroic multilayers strongly depend on the crystalline structure, the stoichiometry and the cation distribution between octahedral (Oh) and tetrahedral (Td) sites (inversion factor). In the present study, we have investigated epitaxial CoFe2O4 layers grown on BaTiO3, with different Co/Fe ratios. We determined the cation distribution in our samples by X-ray magnetic circular dichroism (XMCD), a well accepted method to do so, and by X-ray photoelectron spectroscopy (XPS), using a fitting method based on physical considerations. We observed that our XPS approach converged on results consistent with XMCD measurements made on the same samples. Thus, within a careful decomposition based on individual chemical environments it is shown that XPS is fully able to determine the actual inversion factor

Antiferromagnetic long-range spin ordering in Fe- and NiFe2-doped BaTiO3 multiferroic layers

International audienceWe report on the Fe doping and on the comparative Ni-Fe codoping with composition close to NiFe2 of fully oxidized BaTiO3 layers (similar to 20 nm) elaborated by atomic oxygen plasma assisted molecular beam epitaxy; specifically any role of oxygen vacancies can be excluded in our films. Additionally to the classical in situ laboratory tools, the films were thoroughly characterized by synchrotron radiation x-ray diffraction and x-ray absorption spectroscopy. For purely Fe-doped layers, the native tetragonal perovskite structure evolves rapidly toward cubiclike up to 5% doping level above which the crystalline order disappears. On the contrary, low codoping levels (similar to 5% NiFe2) fairly improve the thin film crystalline structure and surface smoothness; high levels (similar to 27%) lead to more crystallographically disordered films, although the tetragonal structure is preserved. Synchrotron radiation magnetic dichroic measurements reveal that metal clustering does not occur, that the Fe valence evolves from Fe2+ for low Fe doping levels to Fe3+ for high doping levels, and that the introduction of Ni favors the occurrence of the Fe2+ valence in the films. For the lower codoping levels it seems that Fe2+ substitutes Ba2+, whereas Ni2+ always substitutes Ti4+. Ferromagnetic long-range ordering can be excluded with great sensitivity in all samples as deduced from our x-ray magnetic absorption circular dichroic measurements. On the contrary, our linear dichroic x-ray absorption results support antiferromagnetic long-range ordering while piezoforce microscopy gives evidence of a robust ferroelectric long-range ordering showing that our films are excellent candidates for magnetic exchange coupled multiferroic applications