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We present x-ray resonant magnetic reflectivity (XRMR) as a very sensitive tool to detect proximity induced interface spin polarization in Pt/FM heterostructures. Different XRMR experiments are carried out and the results are evaluated for their dependence on the magneto-optical depth profile, the photon energy, the optical parameters, and the ferromagnetic material. We demonstrate that a detailed analysis of the reflected x-ray intensity gives insight into the spatial distribution of the spin polarization of a nonmagnetic metal across the interface to a ferromagnetic layer. The evaluation of the experimental results with simulations based on optical data from ab initio calculations provides the induced magnetic moment per Pt atom in the spin-polarized volume adjacent to the ferromagnet. For a series with different ferromagnetic materials consisting of Pt/Fe, $\text{Pt}/{\mathrm{Ni}}_{33}{\mathrm{Fe}}_{67}, \text{Pt}/{\mathrm{Ni}}_{81}{\mathrm{Fe}}_{19}$ (permalloy), and Pt/Ni bilayers we find the largest spin polarization in Pt/Fe and a much smaller magnetic proximity effect in Pt/Ni. Additional XRMR experiments with varying photon energy are in good agreement with the theoretical predictions for the energy dependence of the magneto-optical parameters and allow identifying the optical dispersion $\ensuremath{\delta}$ and absorption $\ensuremath{\beta}$ across the $\mathrm{Pt}\phantom{\rule{0.28em}{0ex}}{\mathrm{L}}_{3}$-absorption edge.

We study the structure–function relationship of alumina supported platinum during the formation of ammonia from nitrogen oxide and dihydrogen by employing in situ X-ray absorption and Fourier transform infrared spectroscopy. Particular focus has been directed towards the effect of oxygen on the reaction as a model system for emerging technologies for passive selective catalytic reduction of nitrogen oxides. The suppressed formation of ammonia observed as the feed becomes net-oxidizing is accompanied by a considerable increase in the oxidation state of platinum as well as the formation of surface nitrates and the loss of NH-containing surface species. In the presence of (excess) oxygen, the ammonia formation is proposed to be limited by weak interaction between nitrogen oxide and the oxidized platinum surface. This leads to a slow dissociation rate of nitrogen oxide and thus low abundance of the atomic nitrogen surface species that can react with the adsorbed hydrogen species. In this case the consumption of hydrogen through the competing water formation reaction and decomposition/oxidation of ammonia are of less importance for the net ammonia formation.

This work is licensed under a Creative Commons Attribution 4.0 International License.-- et al., Surface chemistry and catalysis studies could significantly gain from the systematic variation of surface active sites, tested under the very same conditions. Curved crystals are excellent platforms to perform such systematics, which may in turn allow to better resolve fundamental properties and reveal new phenomena. This is demonstrated here for the carbon monoxide/platinum system. We curve a platinum crystal around the high-symmetry (111) direction and carry out photoemission scans on top. This renders the spatial core-level imaging of carbon monoxide adsorbed on a 'tunable' vicinal surface, allowing a straightforward visualization of the rich chemisorption phenomenology at steps and terraces. Through such photoemission images we probe a characteristic elastic strain variation at stepped surfaces, and unveil subtle stress-release effects on clean and covered vicinal surfaces. These results offer the prospect of applying the curved surface approach to rationally investigate the chemical activity of surfaces under real pressure conditions., We acknowledge financial support from the Spanish Ministry of Economy (Grants MAT2013-46593-C6-4-P and MAT2013-46593-C6-2-P ), Basque Government (Grants IT621-13 and IT756-13). A.L.W. acknowledges support from the US Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-SC0012704. AXBR acknowledges support from the Basque Departamento de Educación and the UPV/EHU through the Zabalduz program. AXBR, PCS and DSP acknowledge the Deutsche Forschungsgemeinschaft through the Sonderforschungsbereich 1083.

The spin polarization of Pt in Pt/NiFe2O4 and Pt/Fe bilayers is studied by interface-sensitive x-ray resonant magnetic reflectivity to investigate static magnetic proximity effects. The asymmetry ratio of the reflectivity is measured at the Pt L3 absorption edge using circular polarized x-rays for opposite directions of the magnetization at room temperature. The results of the 2% asymmetry ratio for Pt/Fe bilayers are independent of the Pt thickness between 1.8 and 20 nm. By comparison with ab initio calculations, the maximum magnetic moment per spin polarized Pt atom at the interface is determined to be (0.6±0.1) μB for Pt/Fe. For Pt/NiFe2O4 the asymmetry ratio drops below the sensitivity limit of 0.02 μB per Pt atom. Therefore, we conclude, that the longitudinal spin Seebeck effect recently observed in Pt/NiFe2O4 is not influenced by a proximity induced anomalous Nernst effect.

Iron oxide films with different thicknesses (7.6–30 nm) were grown on clean MgO(001) substrates using reactive molecular beam epitaxy at 250 °C depositing Fe in a 5 × 10−5 mbar oxygen atmosphere. X-ray photoelectron spectra and low energy electron diffraction experiments indicate the stoichiometry and the surface structure of magnetite (Fe3O4). Film thicknesses and the lattice constants were analyzed ex situ by x-ray reflectometry and x-ray diffraction, respectively. These experiments reveal the single crystalline and epitactic state of the iron oxide films. However, the obtained vertical layer distances are too small to be strained magnetite and would rather suit to maghemite. Although Raman spectroscopy carried out to analyze the present iron oxide phase showed that the films might have slightly been oxidized in ambient conditions, a posteriori performed XPS measurements exclude a strong oxidation of the surface. Therefore we consider the presence of anti phase boundaries to explain the low vertical layer distances of the magnetite films. Further magnetooptic Kerr measurements were performed to investigate the magnetic properties. While the thinnest film shows a magnetic isotropic behavior, the thicker films exhibit a fourfold magnetic in-plane anisotropy. The magnetic easy axes are in the Fe3O4 directions. We propose that the magnetocrystalline anisotropy is too weak for very thin iron oxide films to form fourfold anisotropy related to the cubic crystal structure.

We present results from measurements of the native oxide film thickness on four different industrial aluminum alloys and three different aluminum single crystals. The thicknesses were determined using X-ray reflectivity, X-ray photoelectron spectroscopy, and electrochemical impedance spectroscopy. In addition, atomic force microscopy was used for micro-structural studies of the oxide surfaces. The reflectivity measurements were performed in ultra-high vacuum, vacuum, ambient, nitrogen and liquid water conditions. The results obtained using X-ray reflectivity and X-ray photoelectron spectroscopy demonstrate good agreement. However, the oxide thicknesses determined from the electrochemical impedance spectroscopy show a larger discrepancy from the above two methods. In the present contribution the reasons for this discrepancy are discussed. We also address the effect of the substrate type and the presence of water on the resultant oxide thickness.

International audience; We present results from the anodization of an aluminum single crystal [Al(111)] and an aluminum alloy [Al 6060] studied by in situ x-ray reflectivity, in situ electrochemical impedance spectroscopy and ex situ scanning electron microscopy. For both samples, a linear increase of oxide film thickness with increasing anodization voltage was found. However, the slope is much higher in the single crystal case, and the break-up of the oxide film grown on the alloy occurs at a lower anodization potential than on the single crystal. The reasons for these observations are discussed as are the measured differences observed for x-ray reflectivity and electrochemical impedance spectroscopy. (C) 2014 Author(s)

It is shown that ultrathin, highly ordered, continuous films of cerium dioxide may be prepared on silicon following substrate prepassivation using an atomic layer of chlorine. The as-deposited, few-nanometer-thin Ce2O3 film may very effectively be converted at room temperature to almost fully oxidized CeO2 by simple exposure to air, as demonstrated by hard X-ray photoemission spectroscopy and X-ray diffraction. This post-oxidation process essentially results in a negligible loss in film crystallinity and interface abruptness.

X-ray photoelectron emission microscopy (XPEEM) was used in combination with other microscopic and spectroscopic techniques to follow the surface development of an aluminum brazing sheet during heating. The studied aluminum alloy sheet is a composite material designed for vacuum brazing. Its surface is covered with a native aluminum oxide film. Changes in the chemical state of the alloying elements and the composition of the surface layer were detected during heating to the melting temperature. It was found that Mg segregates to the surface upon heating, and the measurements indicate the formation of magnesium aluminate. During the heating the aluminum oxide as well as the silicon is observed to disappear from the surface. Our measurements is in agreement with previous studies observing a break-up of the oxide and the outflow of the braze cladding onto the surface, a process assisted by the Mg segregation and reaction with surface oxygen. This study also demonstrates how XPEEM can be utilized to study complex industrial materials.

Journal of applied physics 109(9), 093907 (2011). doi:10.1063/1.3576135, Thin Co films of different thickness deposited on glass are investigated by magnetooptic Kerr effect to study the uniaxial magnetic anisotropy of these films. The direction of the uniaxial magnetic anisotropy is determined from the azimuthal dependence of the magnetic remanence and differs with increasing thickness of the Co film investigated by x-ray reflectivity. Our experiments reveal that preparation conditions like temperature, deposition rate, or obliqueness of deposition cannot be the reason for this rotation effect of the uniaxial magnetic anisotropy. Also, strain in the substrate and possible textures in the filmstructure can be excluded as the origin of the magnetic behavior as studied by grazing incidence wide angle x-ray scattering. Thus, probably only the substrate shape in connection with the amorphous or polycrystalline filmstructure can explain the rotation of the uniaxial magnetic anisotropy., Published by American Inst. of Physics, Melville, NY

Iron oxide films were reactively grown on iron buffer films, which were deposited before on MgO(001) substrates to analyze the influence of the initial iron buffer layers on the magnetic properties of the magnetite films. X-ray photoelectron spectroscopy and low energy electron dif-fraction showed that magnetite films of high crystalline quality in the surface near region were formed by this two-step deposition procedure. The underlying iron film, however, was completely oxidized as proved by x-ray reflectometry and diffraction. The structural bulk quality of the iron oxide film is poor compared to magnetite films directly grown on MgO(001). Although the iron film was completely oxidized, we found drastically modified magnetic properties for these films using the magnetooptic Kerr effect. The magnetite films had strongly increased coercive fields, and their magnetic in-plane anisotropy is in-plane rotated by 45° compared to magnetite films formed directly by one step reactive growth on MgO(001).

Journal of applied physics 105, 124108 (2009). doi:10.1063/1.3152796, Films of hexagonal praseodymium sesquioxide (h-Pr$_2$O$_3$) were deposited on Si(111) by molecular beam epitaxy and thereafter annealed in 1 atm oxygen at different temperatures, ranging from 100 to 700 °C. The films of the samples annealed at 300 °C or more were transformed to PrO2 with B-oriented Fmˉ3m structure, while films annealed at lower temperatures kept the hexagonal structure. The films are composed of PrO2 and PrO2−δ species, which coexist laterally and are tetragonally distorted due to the interaction at the interface between oxide film and Si substrate. Compared to PrO$_2$, PrO$_2$−δ has the same cubic structure but with oxygen vacancies. The oxygen vacancies are partly ordered and increase the vertical lattice constant of the film, whereas the lateral lattice constant is almost identical for both species and on all samples. The latter lattice constant matches the lattice constant of the originally crystallized hexagonal praseodymium sesquioxide. That means that no long range reordering of the praseodymium atoms takes place during the phase transformation, Published by American Institute of Physics, Melville, NY

Ultra thin heteroepitaxial PrO2 films on Si(111) were annealed under UHV conditions and investigated by x-ray diffraction (XRD), x-ray reflectometry (XRR) and spot profile analysis low energy electron diffraction (SPALEED) with regard to structural stability and phase transitions due to the high oxygen mobility of the oxide. This gives information about the manageability of the material and its application as a model catalyst system in surface science. While the samples are stable in UHV at room temperature, annealing at 300 ◦ C exhibits a terminated phase transition from PrO2 and PrO2−� to cub-Pr2O3 with an increase in the silicate at the interface and a decrease in the crystalline praseodymia layer mainly due to atomic diffusion of silicon into the oxide film. Strain effects during the phase transition also cause mosaic formation at the surface. Further annealing up to 600 ◦ C shows only little change in the film structure. This will finally lead to a model of the film structure during the annealing process. (Some figures in this article are in colour only in the electronic version)