  In this paper we study, both with theoretical and experimental approach, the
effect of iron doping in zirconia. Combining density functional theory (DFT)
simulations with the experimental characterization of thin films, we show that
iron is in the Fe3+ oxidation state and accordingly that the films are rich in
oxygen vacancies (VO). VO favor the formation of the tetragonal phase in doped
zirconia (ZrO2:Fe) and affect the density of state at the Fermi level as well
as the local magnetization of Fe atoms. We also show that the Fe(2p) and Fe(3p)
energy levels can be used as a marker for the presence of vacancies in the
doped system. In particular the computed position of the Fe(3p) peak is
strongly sensitive to the VO to Fe atoms ratio. A comparison of the theoretical
and experimental Fe(3p) peak position suggests that in our films this ratio is
close to 0.5. Besides the interest in the material by itself, ZrO2:Fe
constitutes a test case for the application of DFT on transition metals
embedded in oxides. In ZrO2:Fe the inclusion of the Hubbard U correction
significantly changes the electronic properties of the system. However the
inclusion of this correction, at least for the value U = 3.3 eV chosen in the
present work, worsen the agreement with the measured photo-emission valence
band spectra.
