Antiferromagnetic long-range spin ordering in Fe- andNiFe2-dopedBaTiO3multiferroic layers

We report on the Fe doping and on the comparative Ni-Fe codoping with composition close to $\mathrm{NiF}{\mathrm{e}}_{2}$ of fully oxidized $\mathrm{BaTi}{\mathrm{O}}_{3}$ layers (\ensuremath{\sim}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 $(\ensuremath{\sim}5%\mathrm{NiF}{\mathrm{e}}_{2})$ fairly improve the thin film crystalline structure and surface smoothness; high levels (\ensuremath{\sim}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 ${\mathrm{Fe}}^{2+}$ for low Fe doping levels to ${\mathrm{Fe}}^{3+}$ for high doping levels, and that the introduction of Ni favors the occurrence of the ${\mathrm{Fe}}^{2+}$ valence in the films. For the lower codoping levels it seems that ${\mathrm{Fe}}^{2+}$ substitutes ${\mathrm{Ba}}^{2+}$, whereas ${\mathrm{Ni}}^{2+}$ always substitutes ${\mathrm{Ti}}^{4+}$. 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.