H. Magnan

Enhanced photoanode properties of epitaxial Ti doped α-Fe2O3 (0001) thin films

The growth, crystal and electronic structures, and photo-electrochemical properties of undoped and Ti doped hematite epitaxial films were studied. We evidence that Ti4+ substitutes Fe3+ in the hematite lattice inducing a slight modification of the oxygen octahedron. Ti doping is shown to induce a shift of the valence band toward higher binding energy due to a movement of the Fermi level toward the conduction band. The resulting modification of electrical conductivity appears as a possible origin of the improvement of photo-electrochemical properties in the doped sample.

A surface EXAFS study of thin nickel deposits on (110) TiO2 surfaces

Abstract The first stages of nickel deposition on a clean (110) TiO 2 surface were studied using surface extended X-ray absorption fine structure (EXAFS). Experiments were performed on two kinds of nickel deposits, one of 0.8 equivalent monolayers and another of 1.6 equivalent monolayers. Depositions were performed on well characterized TiO 2 (110)-p(1 × 1) surfaces. The correlation of Auger experiments with EXAFS results showed that no islands were present on the surface; only two-dimensional growth of nickel was observed. Moreover, it was shown, in the case of the thinner deposit, that a model with nickel atoms forming chains in the channels determined by oxygen atoms on the surface is consistent with the EXAFS data.

Resonant L2MV and L3MV Auger transitions in titanium dioxide

Abstract The ratio of the two components of the L 23 M 23 V Auger transition is currently used to determine the stoichiometry of titanium oxides. The reduction of Ti manifests itself by a relative increase (decrease) in intensity of the Auger component lying at high (low) kinetic energy, which is assigned to an intraatomic (interatomic) transition involving Tixa03d (O 2p) valence electrons. The LMV Auger transition is herein revisited via its resonant behaviour at the Ti L 23 absorption edge in TiO 2 . Resonances of the high energy component occurs exclusively at the L 2 edge, while resonances of the other component are seen at the L 3 edge, but also at the L 2 edge. The latter being attributed to a L 2 L 3 V Coster–Kronig transition, the low- and high-lying LMV are identified as L 3 MV (including those following CK) and L 2 MV transitions, respectively, at variance with the previous assignment.

Surface EXAFS study of metastable magnetic thin films

Epitaxial thin films provide new opportunities to explore the relationship between structure and magnetism. The bidimensionnal character of magnetic films deposited on single-crystal substrates and the occurrence of singular crystallographic structures often confer on these systems electronic and magnetic properties that cannot be found in the bulk solids. Although shape anisotropy would favour an in-plane easy axis of magnetization for thin films, Ni layers deposited on Cu(001) present a perpendicular magnetic anisotropy in a very wide thickness range. It is shown that this can be explained by a distorted structure of Ni, originating from the strain induced by the epitaxy on the Cu substrate. In the field of low-dimensional magnetism, nanostructures with a reduced lateral dimension are now being widely investigated in view of their technological applications. Thin Fe layers on MgO(001) can be cut into strips by the atomic saw method: a compression of the substrate induces a dislocation slipping which saws both the substrate and the Fe film into regular and separated ribbons. The observed magnetic anisotropy, with the easy axis perpendicular to the strips, is explained by a structural relaxation occurring during the structuration process. In these two studies, a precise structural characterization and simple magnetoelastic models allow the magnetic behaviour of the systems to be described. The structure of the films can be described as an elastic deformation of the bulk structure.

Cross-Correlation between Strain, Ferroelectricity, and Ferromagnetism in Epitaxial Multiferroic CoFe2O4/BaTiO3 Heterostructures

Multiferroic biphase systems with robust ferromagnetic and ferroelectric response at room temperature would be ideally suitable for voltage-controlled nonvolatile memories. Understanding the role of strain and charges at interfaces is central for an accurate control of the ferroelectricity as well as of the ferromagnetism. In this paper, we probe the relationship between the strain and the ferromagnetic/ferroelectric properties in the layered CoFe2O4/BaTiO3 (CFO/BTO) model system. For this purpose, ultrathin epitaxial bilayers, ranging from highly strained to fully relaxed, were grown by molecular beam epitaxy on Nb:SrTiO3(001). The lattice characteristics, determined by X-ray diffraction, evidence a non-intuitive cross-correlation: the strain in the bottom BTO layer depends on the thickness of the top CFO layer and vice versa. Plastic deformation participates in the relaxation process through dislocations at both interfaces, revealed by electron microscopy. Importantly, the switching of the BTO ferroelectric polarization, probed by piezoresponse force microscopy, is found dependent on the CFO thickness: the larger is the latter, the easiest is the BTO switching. In the thinnest thickness regime, the tetragonality of BTO and CFO has a strong impact on the 3d electronic levels of the different cations, which were probed by X-ray linear dichroism. The quantitative determination of the nature and repartition of the magnetic ions in CFO, as well as of their magnetic moments, has been carried out by X-ray magnetic circular dichroism, with the support of multiplet calculations. While bulklike ferrimagnetism is found for 5-15 nm thick CFO layers with a magnetization resulting as expected from the Co2+ ions alone, important changes occur at the interface with BTO over a thickness of 2-3 nm because of the formation of Fe2+ and Co3+ ions. This oxidoreduction process at the interface has strong implications concerning the mechanisms of polarity compensation and coupling in multiferroic heterostructures.

QUADRUPOLAR CHARACTER OF THE Ti K-EDGE PREPEAKS IN TiO2 BY RESONANT AUGER

Resonant spectroscopies offer a new opportunity to get more insight into excited electronic states by studying line shapes and intensities of decay processes. For photon excitations in the pre-K-edge region, the Ti KL2,3L2,3 Auger spectra in TiO2 show additional peaks when an electron is promoted in localized d-like states via a quadrupolar transition. This resonant process is used to unravel the respective contributions of quadrupolar and dipolar transitions to the absorption edge prepeaks.