One challenge in the production of nanometer-sized objects with given properties is to control their growth at a macroscopic scale in situ and in real time. A dedicated ultrahigh-vacuum grazing-incidence small-angle x-ray scattering setup has been developed, yielding high sensitivity and dynamics. Its capabilities to derive the average particle shape and size and the film growth mode and ordering and to probe both surfaces and buried interfaces are illustrated for two prototypical cases: the model catalyst Pd/MgO(100) and the self-organized Co/Au(111) system. A wide range of technologically important systems can potentially be investigated in various gaseous environments.

Using grazing-incidence x-ray diffraction, the p(2x2) surface structures of the single crystal NiO(111) and a 5 monolayer thick NiO(111) film on Au(111) were both shown to exhibit locally the theoretically predicted octopolar reconstruction, with some important differences. The single crystal exhibits a single Ni termination with double steps. The thin film exhibits both possible terminations (O and Ni) and single steps. These surfaces were found to be nonreactive with respect to hydroxylation.

International audienceUndoped and Ti-doped (2 at. %) epitaxial hematite thin films, in the thickness range 5–50 nm, were grown by atomic oxygen assisted molecular beam epitaxy (AO-MBE) on Pt(111) substrates in the framework of hydrogen harvesting from sunlight-induced water splitting. Such single crystalline samples are suitable model systems to study thickness and doping effects on the photoelectrochemical properties; we demonstrate that they also allow disentangling intrinsic transport properties from mingled overall properties due to the usually unknown contributions from morphology or crystalline structure defects. From their photoelectrochemical characteristics (I(V) curves, incident photon to current efficiency measurements, and electrochemical impedance spectroscopy), we evidence the existence of an optimum layer thickness, which is higher for Ti-doped samples (30 nm) as compared to undoped ones (20 nm). Our results suggest that this effect is due to an increase of the carrier concentration combined with higher carriers’ diffusion lengths in the doped samples stressing intrinsic modifications of the hematite layer upon titanium doping that cannot be accounted for by simple structural or electronic structure changes

International audienceWe provide an experimental surface phase diagram (surface termination versus chemical oxygen potential) of alpha-Fe2O3(0001) using a natural single crystal surface. In a partial reduction reoxidation cycle, we observe a sequence from oxygen-, to ferryl-, and again oxygen-terminated surfaces, in better agreement with recent density functional theory in the generalized gradient approximation calculations than with calculations taking into account on-site Fe 3d Coulomb repulsion. The nonreversible change in surface termination is accompanied by the formation of basal twins, which act as a sink for the extra Fe ions during the surface transformation processes

International audienceHematite (α-Fe 2 O 3) can be considered as one of the top candidates to act as photoanode in the framework of clean hydrogen production through solar water splitting. The O:Fe ratio, that in this material plays a crucial role in the definition of its photoelectrochemical properties, has been investigated in detail. For this purpose, we examined thermal magnetite oxidation and hematite reduction as two possible routes to produce semiconducting iron oxides layers with controlled stoichiometry. We report on properties of single crystalline nanometric films elaborated by atomic oxygen plasma assisted molecular beam epitaxy as model systems to disentangle structural phase transition effects from pure stoichiometry ones. We provide new insights into the mechanisms related to hematite properties modifications and their correlation with photocurrent changes upon the presence of oxygen vacancies and phase mixing with magnetite, with respect to the vacancies concentration regimes. We show on one hand that crystallographic structure mixing appears as strongly detrimental for photoanodes synthesis whatever the oxygen vacancies concentration. On the other hand, oxygen vacancies in the optimal concentration range, while preserving the α-Fe 2 O 3 corundum phase, is highly favorable for solar water splitting, inducing a substantial reduction of 0.2 V for the onset potential and an overall photocurrent increase of 50% with respect to stoichiometric hematite. The present study demonstrates more generally the possibility of using oxygen vacancies as a degree of freedom for the optimization of hematite photoanodes

The growth of hexagonal aluminum nitride directly on (111) silicon has been studied by grazing incidence x-ray diffraction and high resolution electron microscopy as a function of film thickness. Two epitaxial relationships were observed: (1) AlN (0001) [211¯0]//Si(111) [022̄], which prevails at deposition temperatures larger than 650 °C, and (2) AlN (0001) [101̄0]//Si(111) [022̄]. For a 40 Å thick layer, the average in-plane crystallite size is 162 Å, the in-plane rotation is ∼2° and the dislocations induce an average strain distribution of 0.8%. The Si/AlN interface is very sharp and complete relaxation (down to ∼0.2%) occurs within one bilayer. No long range order was observed at the interface. This implies a low mobility of the AlN species on Si, inhibiting any structural rearrangement. In particular the in-plane rotations originate from the early stage of the layer growth and decrease with the layer thickness, especially for thicknesses larger than 250 Å.

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.

Stable polar oxide surfaces must be simultaneously electrostatically compensated and in thermodynamic equilibrium with the environment. As a paradigm, the MgO(111)-p(2x2) reconstructed surface is shown to involve combinations of Mg-covered terminations with peculiar insulating electronic structure, favored in O-poor conditions, and the O-terminated octopole, stabler in more O-rich environments. Such a picture, which could not have been foreseen by either experiments or simulations separately, goes beyond the Wolf model and reconciles the theory with the experimental data taken in variable thermodynamic conditions.