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The Python package mlreflect is demonstrated, which implements an optimized pipeline for the automated analysis of reflectometry data using machine learning. The package combines several training and data treatment techniques discussed in previous publications. The predictions made by the neural network are accurate and robust enough to serve as good starting parameters for an optional subsequent least-mean-squares (LMS) fit of the data. For a large data set of 242 reflectivity curves of various thin films on silicon substrates, the pipeline reliably finds an LMS minimum very close to a fit produced by a human researcher with the application of physical knowledge and carefully chosen boundary conditions. The differences between simulated and experimental data and their implications for the training and performance of neural networks are discussed. The experimental test set is used to determine the optimal noise level during training. The extremely fast prediction times of the neural network are leveraged to compensate for systematic errors by sampling slight variations in the data.

Chemistry of materials 34(5), 2333-2341 (2022). doi:10.1021/acs.chemmater.1c04220, Polymer film capacitors are ubiquitous in modern electronics and electric systems, but the relatively low working temperatures of polymer dielectrics limit their application in next-generation capacitors. The currently reported high-temperature polymer dielectrics rely on the construction of nanocomposites with wide band gap fillers and cross-linked networks to achieve high breakdown strength and high efficiencies. However, generating the optimal chain structure with intrinsic great high-temperature capacitive properties using a one-component polymer is still challenging. Herein, a giant discharged energy density in neat polymer has been demonstrated in a series of linear poly(arylene ether amide) (PNFA) at 150 °C, which greatly surpass all the current free-standing dielectric polymer films measured in 10 Hz. The maximum discharged energy density with efficiency above 90% of the PNFA is 2.7 J cm–3, which is about 3 times that of the state-of-the-art commercial high-temperature polymer films. The architectures of the amorphous polymers have been identified by synchrotron X-ray diffraction combined with density functional theory calculations. The origins of superior high-temperature capacitive properties are traced to the increased packing density by the curly-packed chain structure. In addition, the reported polymer could be produced using existing industrial-grade processes, which are economical and practical for large-scale applications., Published by American Chemical Society, Washington, DC

Materials 15(1), 46 (2022). doi:10.3390/ma15010046, Here, we present the (element-specific) magnetic properties and cation ordering for ultrathin Co-rich cobalt ferrite films. Two Co-rich Co$_x$Fe$_{3−x}$O$_4$ films with different stoichiometry (x=1.1 and x=1.4) have been formed by reactive solid phase epitaxy due to post-deposition annealing from epitaxial CoO/Fe$_3$O$_4$ bilayers deposited before on Nb-doped SrTiO$_3$(001). The electronic structure, stoichiometry and homogeneity of the cation distribution of the resulting cobalt ferrite films were verified by angle-resolved hard X-ray photoelectron spectroscopy. From X-ray magnetic circular dichroism measurements, the occupancies of the different sublattices were determined using charge-transfer multiplet calculations. For both ferrite films, a partially inverse spinel structure is found with increased amount of Co$^{3+}$ cations in the low-spin state on octahedral sites for the Co$_{1.4}$Fe$_{1.6}$O$_4$ film. These findings concur with the results obtained by superconducting quantum interference device measurements. Further, the latter measurements revealed the presence of an additional soft magnetic phase probably due to cobalt ferrite islands emerging from the surface, as suggested by atomic force microscope measurements., Published by MDPI, Basel

The journal of physical chemistry / C 125(42), 23327 - 23337 (2021). doi:10.1021/acs.jpcc.1c05274, In this work, we present a study about the chemical and magnetic properties of thin magnetite/cobalt ferrite bilayers deposited on MgO(001). Two series of samples with different CoxFe$_{3���x}$O$_4$ stoichiometries (x = 1 and x = 0.5) in combination with Fe$_3$O$_4$ layers of varying thickness were prepared by reactive molecular beam epitaxy. The quality of the respective films were controlled by means of in situ X-ray photelectron spectroscopy and low energy electron diffraction. Stoichiometry and electronic structure were carried out by hard X-ray photoelectron spectroscopy. To determine the cationic distribution and magnetic moments, X-ray magnetic circular dichroism measurements were performed and charge transfer multiplet and sum rule calculations were applied. Here we find an enhanced interface magnetization for the bilayers. Additionally, superconducting quantum interference device measurements showed characteristic exchange-spring behavior., Published by Soc., Washington, DC

In order to explore an alternative pathway to prepare ultrathin CoFe2O4 films, epitaxial CoO/Fe3O4 bilayers with varying film thickness of the CoO film were grown on Nb-doped SrTiO3(001) substrates...

Detailed in operando studies of electrochemically induced PbBrF deposition at the liquid mercury/liquid electrolyte interface are presented. The nucleation and growth were monitored using time-reso...

Journal of synchrotron radiation 27(5), 1200 - 1208 (2020). doi:10.1107/S1600577520009789, Nanoprobe X-ray diffraction (nXRD) using focused synchrotron radiation is a powerful technique to study the structural properties of individual semiconductor nanowires. However, when performing the experiment under ambient conditions, the required high X-ray dose and prolonged exposure times can lead to radiation damage. To unveil the origin of radiation damage, a comparison is made of nXRD experiments carried out on individual semiconductor nanowires in their as-grown geometry both under ambient conditions and under He atmosphere at the microfocus station of the P08 beamline at the third-generation source PETRA III. Using an incident X-ray beam energy of 9 keV and photon flux of 10$^{10}$ s$^{−1}$, the axial lattice parameter and tilt of individual GaAs/In$_{0.2}$Ga$_{0.8}$As/GaAs core–shell nanowires were monitored by continuously recording reciprocal-space maps of the 111 Bragg reflection at a fixed spatial position over several hours. In addition, the emission properties of the (In,Ga)As quantum well, the atomic composition of the exposed nanowires and the nanowire morphology were studied by cathodoluminescence spectroscopy, energy-dispersive X-ray spectroscopy and scanning electron microscopy, respectively, both prior to and after nXRD exposure. Nanowires exposed under ambient conditions show severe optical and morphological damage, which was reduced for nanowires exposed under He atmosphere. The observed damage can be largely attributed to an oxidation process from X-ray-induced ozone reactions in air. Due to the lower heat-transfer coefficient compared with GaAs, this oxide shell limits the heat transfer through the nanowire side facets, which is considered as the main channel of heat dissipation for nanowires in the as-grown geometry., Published by Wiley-Blackwell, [S.l.]

In this work, we present a comprehensive study on real-time monitoring the growth of epitaxial CoxFe3−xO4 thin films grown on SrTiO3(001) substrates via reactive molecular beam epitaxy. The growth process was monitored during evaporation by means of time resolved operando hard X-ray photoelectron spectroscopy (HAXPES). We prepared ultrathin ferrite films using different oxygen partial pressures, showing pure metallic, light oxidic, and cobalt ferrite-like growth. Additional X-ray diffraction measurements confirm HAXPES results.

The Python package

It is demonstrated by a detailed structural analysis that the crystallinity and the efficiency of small molecule based organic photovoltaics can be tuned by solvent vapor annealing (SVA). Blends made of the small molecule donor 2,2′-[(3,3′″,3″″,4′-tetraoctyl[2,2′:5′,2″:5″,2′″:5′″,2″″-quinquethiophene]-5,5″″-diyl)bis[(Z)-methylidyne(3-ethyl-4-oxo-5,2-thiazolidinediylidene)]]bis-propanedinitrile (DRCN5T) and the acceptor [6,6]-phenyl C71 butyric acid methyl ester (PC71BM) were annealed using solvent vapors with either a high solubility for the donor (tetrahydrofuran), the acceptor (carbon disulfide) or both (chloroform). The samples were analyzed by grazing-incidence wide-angle X-ray scattering (GIWAXS), electron diffraction, X-ray pole figures, and time-of-flight secondary ion mass spectrometry (ToF-SIMS). A phase separation of DRCN5T and PC71BM is induced by SVA leading to a crystallization of DRCN5T and the formation of a DRCN5T enriched layer. The DRCN5T crystallites possess the two dimensional oblique crystal system with the lattice parameters a = 19.2 Å, c = 27.1 Å, and β = 111.1° for the chloroform case. No major differences in the crystal structure for the other solvent vapors were observed. However, the solvent choice strongly influences the size of the DRCN5T enriched layer. Missing periodicity in the [010]-direction leads to the extinction of all Bragg reflections with k ≠ 0. The annealed samples are randomly orientated with respect to the normal of the substrate (fiber texture).

ACS catalysis 9(7), 6530 - 6539 (2019). doi:10.1021/acscatal.9b01402, Sophisticated $\mathrm{IrO_{2}(110)}$-based model electrodes are prepared by deposition of a 10 nm thick single-crystalline $\mathrm{IrO_{2}(110)}$ layer supported on a structure-directing $\mathrm{IrO_{2}(110)-RuO_{2}(110)/Ru(0001)}$ template, exposing a regular array of mesoscopic rooflike structures. With this model electrode together with the dedicated in situ synchrotron based techniques (SXRD, XRR) and ex situ characterization techniques (SEM, ToF-SIMS, XPS), the corrosion process of $\mathrm{IrO_{2}(110)}$ in an acidic environment (pH 0.4) is studied on different length scales. Potential-induced pitting corrosion starts at 1.48 V vs SHE and is initiated at so-called surface grain boundaries, where three rotational domains of $\mathrm{IrO_{2}(110)}$ meet. The most surprising result is, however, that even when the electrode potential is increased to 1.94 V vs SHE 60–70% of the $\mathrm{IrO_{2}}$ film still stays intact down to the mesoscale and atomic scale and no uniform thinning of the $\mathrm{IrO_{2}(110)}$ layer is encountered. Neither flat$\mathrm{IrO_{2}(110)}$ terraces nor single steps are attacked. Ultrathin single-crystalline $\mathrm{IrO_{2}(110)}$ layers seem to be much more stable to anodic corrosion than hitherto expected., Published by ACS, Washington, DC

We report on the influence of oxygen partial pressure for the development of surface oxides covering the industrial aluminum alloy standard 6063 at temperatures ranging from room temperature to 500° C. Using an array of synchrotron-based techniques, we followed the change in oxide thickness, chemical composition, and the lateral distribution of alloying elements. The impact of the oxygen chemical potential is most visible at high temperatures where the oxide composition changes from mostly Al based to mostly Mg based. This is in stark contrast to the ultra-high vacuum (UHV) conditions where only a partial compositional transition is observed. The microscopy data demonstrate that in the UHV case, Mg segregation onto the surface occurs firstly at grain boundaries at 300° C and secondly at sites over the entire surface at 400° C. Further, the initial oxide thickness is 45 A, as determined by XPS and XRR, decreases in all observed cases after heating to 300° C. At higher temperatures, however, the oxygen partial pressure highly influences the resulting oxide thickness as evident from our X-ray reflectivity data. (Less)

Nature Communications 12(1), 5046 (2021). doi:10.1038/s41467-021-25320-0, The original version of this Article contained an error in the Acknowledgements section, which was previously incorrectly given as���The authors gratefully acknowledge funding by the Austrian Science Fund (FWF) through project P4509-N16 as well as DESY(Hamburg, Germany), a member of the Helmholtz Association HGF, for the allocation of beamtime and provision of experimentalfacilities.���. The correct version states ���The authors gratefully acknowledge funding by the Austrian Science Fund (FWF) through projectF4509-N16 as well as DESY (Hamburg, Germany), a member of the Helmholtz Association HGF, for the allocation of beamtime andprovision of experimental facilities.��� in place of the incorrect text. This has been corrected in both the PDF and HTML versions of theArticle., Published by Nature Publishing Group UK, [London]

The catalytic oxidation of CO on transition metals, such as Pt, is commonly viewed as a sharp transition from the CO-inhibited surface to the active metal, covered with O. However, we find that minor amounts of O are present in the CO-poisoned layer that explain why, surprisingly, CO desorbs at stepped and flat Pt crystal planes at once, regardless of the reaction conditions. Using near-ambient pressure X-ray photoemission and a curved Pt(111) crystal we probe the chemical composition at surfaces with variable step density during the CO oxidation reaction. Analysis of C and O core levels across the curved crystal reveals that, right before light-off, subsurface O builds up within (111) terraces. This is key to trigger the simultaneous ignition of the catalytic reaction at different Pt surfaces: a CO-Pt-O complex is formed that equals the CO chemisorption energy at terraces and steps, leading to the abrupt desorption of poisoning CO from all crystal facets at the same temperature., We acknowledge financial support from the Spanish Ministry of Science and Innovation (Grants MAT-2017-88374-P, PID2019-107338RB-C63, PID2019-107338RB-C66), the Basque Government (Grants IT-1255-19, IT-1246-19), the Knut and Alice Wallenberg foundation (DNR KAW 2015.0058 „Atomistic Design of new Catalysts“) and the Swedish Research Council (DNR 349-2011-6491 „Catalysis on the atomic scale“).

The mechanism behind the stability of organic nanoparticles prepared by liquid antisolvent (LAS) precipitation without a specific stabilizing agent is poorly understood. In this work, we propose that the organic solvent used in the LAS process rapidly forms a molecular stabilizing layer at the interface of the nanoparticles with the aqueous dispersion medium. To confirm this hypothesis, n-octadecyltrichlorosilane (OTS)-functionalized silicon wafers in contact with water-solvent mixtures were used as a flat model system mimicking the solid-liquid interface of the organic nanoparticles. We studied the equilibrium structure of the interface by X-ray reflectometry (XRR) for water-solvent mixtures (methanol, ethanol, 1-propanol, 2-propanol, acetone, and tetrahydrofuran). The formation of an organic solvent-rich layer at the solid-liquid interface was observed. The layer thickness increases with the organic solvent concentration and correlates with the polar and hydrogen bond fraction of Hansen solubility parameters. We developed a self-consistent adsorption model via complementing adsorption isotherms obtained from XRR data with molecular dynamics simulations.

We have investigated the structure of an ultrathin iron oxide phase grown on Ag(100) using surface x-ray diffraction in combination with Hubbard-corrected density functional theory (DFT+U) calculations. The film exhibits a novel structure composed of one close-packed layer of octahedrally coordinated Fe

Typically, core–shell–shell semiconductor nanowires (NWs) made from III–V materials with low lattice mismatch grow pseudomorphically along the growth axis, i.e. the axial lattice parameters of the core and shell materials are the same. Therefore, both the structural composition and interface strain of the NWs are encoded along directions perpendicular to the growth axis. Owing to fluctuations in the supplied growth species during molecular beam epitaxy (MBE) growth, structural parameters such as local shell thickness, composition and strain may differ between NWs grown onto the same substrate. This requires structural analysis of single NWs instead of measuring NW ensembles. In this work, the complete structure of single GaAs/(In,Ga)As/GaAs core–shell–shell NW heterostructures is determined by means of X-ray nanodiffraction using synchrotron radiation. The NWs were grown by MBE on a prepatterned silicon (111) substrate with a core diameter of 50 nm and an (In,Ga)As shell thickness of 20 nm with a nominal indium concentration of 15%, capped by a 30 nm GaAs outer shell. In order to access single NWs with the X-ray nanobeam being incident parallel to the surface of the substrate, a single row of holes with a separation of 10 µm was defined by electron-beam lithography to act as nucleation centres for MBE NW growth. These well separated NWs were probed sequentially by X-ray nanodiffraction, recording three-dimensional reciprocal-space maps of Bragg reflections with scattering vectors parallel (out-of-plane) and perpendicular (in-plane) to the NW growth axis. From the out-of-plane 111 Bragg reflection, deviations from hexagonal symmetry were derived, together with the diameters of probed NWs grown under the same conditions. The radial NW composition and interface strain became accessible when measuring the two-dimensional scattering intensity distributions of the in-plane 2{\overline 2}0 and 22{\overline 4} reflections, exhibiting well pronounced thickness fringes perpendicular to the NW side planes (truncation rods, TRs). Quantitative values of thickness, composition and strain acting on the (In,Ga)As and GaAs shells were obtained via finite-element modelling of the core–shell–shell NWs and subsequent Fourier transform, simulating the TRs measured along the three different directions of the hexagonally shaped NWs simultaneously. Considering the experimental constraints of the current experiment, thicknesses and In content have been evaluated with uncertainties of ±2 nm and ±0.01, respectively. Comparing data taken from different single NWs, the shell thicknesses differ from one to another.

We present results from the anodization of single crystal Al(100) and Al(111) surfaces and the aluminum alloy AA 6063 studied in situ by X-ray reflectivity and electrochemical impedance spectroscopy. We observe that the anodic oxide layer grows linearly with the anodization potential and that the thicknesses are similar for all samples. However, the thicknesses obtained from X-ray reflectivity are higher than that obtained from electrochemical impedance spectroscopy. We attribute the higher thicknesses to an outer porous oxide layer, which is not detected by electrochemical impedance spectroscopy. Both, electrochemical impedance spectroscopy and X-ray reflectivity suggests that a more heterogeneous and rough oxide is formed on AA 6063 due to the influence of the alloying elements and intermetallic particles during the growth.

Anodization of aluminum alloys AA 6082 and AA 7075 was investigated in-situ with integrated electrochemical and synchrotron-based X-ray reflectivity (XRR) methods providing complementary information about the anodic processes taking place on the alloys. The stepwise potentiostatic polarization measurements reveal dynamic processes of the anodic oxide formation and dissolution, and the following electrochemical impedance spectroscopy measurements detect the break of the native oxide and the growth of typical two-layer anodic oxide film, while the XRR measurements show the growth of entire anodic oxide film whose thickness increases linearly with the increasing applied potential. The results indicate that while a stable anodic oxide can be formed on the both alloys with a similar growth factor, AA 7075 shows a thinner thickness of the barrier layer and a lower resistance of the oxide film. The electrochemical results suggest both localized and uniform anodic dissolution processes, which are more pronounced on AA 7075, demonstrating the effect of alloying elements on the growth of anodic oxides.

Nanotechnology 31(21), 1-7 (2020). doi:10.1088/1361-6528/ab7590, We report on the direct correlation between the structural and optical properties of single, as-grown core-multi-shell GaAs/In$_{0.15}$Ga$_{0.85}$As/GaAs/AlAs/GaAs nanowires. Fabricated by molecular beam epitaxy on a pre-patterned Si(111) substrate, on a row of well separated nucleation sites, it was possible to access individual nanowires in the as-grown geometry. The polytype distribution along the growth axis of the nanowires was revealed by synchrotron-based nanoprobe x-ray diffraction techniques monitoring the axial 111 Bragg reflection. For the same nanowires, the spatially-resolved emission properties were obtained by cathodoluminescence hyperspectral linescans in a scanning electron microscope. Correlating both measurements, we reveal a blueshift of the shell quantum well emission energy combined with an increased emission intensity for segments exhibiting a mixed structure of alternating wurtzite and zincblende stacking compared with the pure crystal polytypes. The presence of this mixed structure was independently confirmed by cross-sectional transmission electron microscopy., Published by IOP Publ., Bristol

Applied physics letters 117(1), 011601 - (2020). doi:10.1063/5.0013925, Ni$_x$Fe$_{3���x}$O$_4$ thin films with varying Ni amount (0 ��� x ��� 1.5) were deposited on MgO(001) via reactive molecular beam epitaxy. The growth process was monitored during film deposition by means of X-ray diffraction. All prepared films exhibit a well-ordered structure with complete vertical crystallinity throughout the whole film growth and flat surfaces of the final films independent of the Ni amount. An enhancement of the vertical compression in the initial growth continuously decreases up to a film thickness of 8 nm. During further growth, all films exhibit residual and constant vertical compression with lateral adaption of the final films to the substrate lattice, as observed by high energy surface X-ray diffraction experiments. Hard X-ray photoelectron spectroscopy measurements of the final films reveal increasing Fe$^{3+}$:Fe$^{2+}$ ratios for higher Ni content and point to additional NiO agglomerations within the films exceeding the stoichiometric Ni amount of x = 1., Published by American Inst. of Physics, Melville, NY

Applied physics letters 118(8), 089901 (2021). doi:10.1063/5.0045052, Published by American Inst. of Physics, Melville, NY

Understanding how specific atom sites on metal surfaces lower the energy barrier for chemical reactions is vital in catalysis. Studies on simplified model systems have shown that atoms arranged as steps on the surface play an important role in catalytic reactions, but a direct comparison of how the light-off temperature is affected by the atom orientation on the step has not yet been possible due to methodological constraints. Here we report in situ spatially resolved measurements of the CO production over a cylindrical-shaped Pd catalyst and show that the light-off temperature at different parts of the crystal depends on the step orientation of the two types of steps (named A and B). Our finding is supported by density functional theory calculations, revealing that the steps, in contrast to what has been previously reported in the literature, are not directly involved in the reaction onset but have the role of releasing stress., The authors thank the Knut and Alice Wallenberg Foundation, the Swedish Research Council, the Swedish Foundation for Strategic Research, and the Crafoord Foundation. Support by the MAX IV staff is gratefully acknowledged. The calculations were performed at C3SE through a SNIC grant. J.E.O. acknowledges support from the Spanish Ministry of Economy (MAT2013-46593-C6-4-P) and the Basque Government (IT621-13).

The journal of physical chemistry letters 10(7), 1634 - 1638 (2019). doi:10.1021/acs.jpclett.9b00331, Films of carbon tetrachloride (CCl$_4$) confined in slit geometry between two flat diamond substrates down to a few tens of Angstroms are studied by combining X-ray reflectivity with in-plane and out-of-plane X-ray scattering. The confined films form a heterogeneous structure with coexisting regions of liquid and crystalline phases. The liquid phase shows short-range ordering normal to the surfaces of the substrates. The experiments directly show the ability of the confinement to induce crystal objects, which is a long-discussed issue in the literature. The surface structure and morphology of the substrates may influence the actual realization of the crystalline phase in confinement., Published by ACS, Washington, DC

The journal of chemical physics 152(11), 114705 (1-9) (2020). doi:10.1063/1.5142558, We have investigated the structure of an ultrathin iron oxide phase grown on Ag(100) using surface x-ray diffraction in combination with Hubbard-corrected density functional theory (DFT+U) calculations. The film exhibits a novel structure composed of one close-packed layer of octahedrally coordinated Fe$^{2+}$ sandwiched between two close-packed layers of tetrahedrally coordinated Fe$^{3+}$ and an overall stoichiometry of Fe$_3$O$_4$. As the structure is distinct from bulk iron oxide phases and the coupling with the silver substrate is weak, we propose that the phase should be classified as a metastable two-dimensional oxide. The chemical and physical properties are potentially interesting, thanks to the predicted charge ordering between atomic layers, and analogy with bulk ferrite spinels suggests the possibility of synthesis of a whole class of two-dimensional ternary oxides with varying electronic, optical, and chemical properties., Published by American Institute of Physics, Melville, NY

Journal of synchrotron radiation 25, 1664 - 1672 (2018). doi:10.1107/S1600577518013218, Since the properties of functional materials are highly dependent on their specific structure, and since the structural changes, for example during crystallization, induced by coating and annealing processes are significant, the study of structure and its formation is of interest for fundamental and applied science. However, structure analysis is often limited to ex situ determination of final states due to the lack of specialized sample cells that enable real-time investigations. The lack of such cells is mainly due to their fairly complex design and geometrical restrictions defined by the beamline setups. To overcome this obstacle, an advanced sample cell has been designed and constructed; it combines automated doctor blading, solvent vapor annealing and sample hydration with real-time grazing-incidence wide- and small-angle scattering (GIWAXS/GISAXS) and X-ray reflectivity (XRR). The sample cell has limited spatial requirements and is therefore widely usable at beamlines and laboratory-scale instruments. The cell is fully automatized and remains portable, including the necessary electronics. In addition, the cell can be used by interested scientists in cooperation with the Institute for Crystallography and Structural Physics and is expandable with regard to optical secondary probes. Exemplary research studies are presented, in the form of coating of P3HT:PC$_{61}$PM thin films, solvent vapor annealing of DRCN5T:PC$_{71}$BM thin films, and hydration of supported phospholipid multilayers, to demonstrate the capabilities of the in situ cell., Published by IUCr, [S.l.]

We present a comparative study of the morphology and structural as well as magnetic properties of crystalline Fe3O4/NiO bilayers grown on both MgO(001) and SrTiO3(001) substrates by reactive molecular beam epitaxy. These structures were investigated by means of X-ray photoelectron spectroscopy, low-energy electron diffraction, X-ray reflectivity and diffraction, as well as vibrating sample magnetometry. While the lattice mismatch of NiO grown on MgO(001) was only 0.8%, it was exposed to a lateral lattice mismatch of −6.9% if grown on SrTiO3. In the case of Fe3O4, the misfit strain on MgO(001) and SrTiO3(001) amounted to 0.3% and −7.5%, respectively. To clarify the relaxation process of the bilayer system, the film thicknesses of the magnetite and nickel oxide films were varied between 5 and 20 nm. While NiO films were well ordered on both substrates, Fe3O4 films grown on NiO/SrTiO3 exhibited a higher surface roughness as well as lower structural ordering compared to films grown on NiO/MgO. Further, NiO films grew pseudomorphic in the investigated thickness range on MgO substrates without any indication of relaxation, whereas on SrTiO3 the NiO films showed strong strain relaxation. Fe3O4 films also exhibited strong relaxation, even for films of 5 nm thickness on both NiO/MgO and NiO/SrTiO3. The magnetite layers on both substrates showed a fourfold magnetic in-plane anisotropy with magnetic easy axes pointing in 100 directions. The coercive field was strongly enhanced for magnetite grown on NiO/SrTiO3 due to the higher density of structural defects, compared to magnetite grown on NiO/MgO.

We present a comparative study of the morphology and structural as well as magnetic properties of crystalline Fe₃O₄/NiO bilayers grown on both MgO(001) and SrTiO₃(001) substrates by reactive molecular beam epitaxy. These structures were investigated by means of X-ray photoelectron spectroscopy, low-energy electron diffraction, X-ray reflectivity and diffraction, as well as vibrating sample magnetometry. While the lattice mismatch of NiO grown on MgO(001) was only 0.8%, it was exposed to a lateral lattice mismatch ofminus;6.9% if grown on SrTiO₃. In the case of Fe₃O₄, the misfit strain on MgO(001) and SrTiO₃(001) amounted to 0.3% andminus;7.5%, respectively. To clarify the relaxation process of the bilayer system, the film thicknesses of the magnetite and nickel oxide films were varied between 5 and 20 nm. While NiO films were well ordered on both substrates, Fe₃O₄ films grown on NiO/SrTiO₃ exhibited a higher surface roughness as well as lower structural ordering compared to films grown on NiO/MgO. Further, NiO films grew pseudomorphic in the investigated thickness range on MgO substrates without any indication of relaxation, whereas on SrTiO₃ the NiO films showed strong strain relaxation. Fe₃O₄ films also exhibited strong relaxation, even for films of 5 nm thickness on both NiO/MgO and NiO/SrTiO₃. The magnetite layers on both substrates showed a fourfold magnetic in-plane anisotropy with magnetic easy axes pointing in 100 directions. The coercive field was strongly enhanced for magnetite grown on NiO/SrTiO₃ due to the higher density of structural defects, compared to magnetite grown on NiO/MgO.

Journal of synchrotron radiation 25(5), 1389 - 1394 (2018). doi:10.1107/S1600577518010597, High-energy surface X-ray diffraction (HESXRD) provides surface structural information with high temporal resolution, facilitating the understanding of the surface dynamics and structure of the active phase of catalytic surfaces. The surface structure detected during the reaction is sensitive to the composition of the gas phase close to the catalyst surface, and the catalytic activity of the sample itself may affect the surface structure, which in turn may complicate the assignment of the active phase. For this reason, planar laser-induced fluorescence (PLIF) and HESXRD have been combined during the oxidation of CO over a Pd(100) crystal. PLIF complements the structural studies with an instantaneous two-dimensional image of the CO$_2$ gas phase in the vicinity of the active model catalyst. Here the combined HESXRD and PLIF operando measurements of CO oxidation over Pd(100) are presented, allowing for an improved assignment of the correlation between sample structure and the CO$_2$ distribution above the sample surface with sub-second time resolution., Published by Wiley-Blackwell, [S.l.]

The journal of physical chemistry / A 122(49), 28075 - 28084 (2018). doi:10.1021/acs.jpcc.8b08205, Doping with halide ions is a popular method toalter the properties of metal phthalocyanines (MPcs),particularly magnetic and electrical nature of organic semiconductorsfor applications in spintronic or electronic devices.Doping can cause a structural rearrangement in MPc packing,and the physical properties may be correlated with molecularpacking. Films of a planar and magnetic MPc, manganese-(II)phthalocyanine (MnPc), are chosen for iodine dopingstudy. The optical, magnetic, and electrical properties ofpristine- and iodine-doped MnPc thin films are investigatedand can be directly associated with their molecular structure.Two-dimensional grazing incidence synchrotron X-ray diffractionreveals structural disorder in MnPc films upon iodineinfusion induced by the reorientation of ordered, edge-on molecular configuration to tilted and face-on configurations in arandom fashion. The film morphology changes accordingly, where in the uniform crystallites reorganize in a disordered manner.The ferromagnetic nature of the pristine film gets weakened because of iodine species and favors antiferromagnetic coupling.The study of electrical properties at room temperature by conducting atomic force microscopy reveals that the conductance isenhanced independently of the film thickness because of the disorder induced by iodine inclusion., Published by ACS, Washington, DC

Catalysis letters 148(9), 2901 - 2910 (2018). doi:10.1007/s10562-018-2487-0, Liquid organic hydrogen carriers (LOHCs) have great potential as a hydrogen storage medium needed for a future sustainable energy system. Dehydrogenation of LOHCs requires a catalyst, such as supported Pd nanoparticles. Under reaction conditions, hydrogen and carbon may diffuse into the bulk of supported Pd catalyst particles and affect their activity and selectivity. The detailed understanding of this process is critical for the use of LOHCs in future hydrogen storage technologies. In this work, we studied these processes in-situ on a Pd model catalyst using high-energy grazing incidence X-ray diffraction. Pd nanoparticles were evaporated in ultra-high vacuum on a polished $α$-Al$_2$O$_3$(0001) substrate. The particles, with an initial average size of ~ 3.4 nm, were investigated at elevated temperature during their interaction with H$_2$ and methylcyclohexane (MCH) representing a model LOHC. The interaction with H$_2$ was studied in-situ at partial pressures up to 1 bar and temperatures between 300 and 500 K. At 300 K, the Pd nanoparticles (NPs) show a transition from $α$-PdH to $β$-PdH as a function of the H$_2$ pressure. The transition occurs gradually, which is attributed to the heterogeneity of the NP system. The hydrogen uptake in $β$-PdH$_x$ at 300 K and 1 bar is estimated to be XH ~ 0.37 ± 0.03 indicating that the miscibility gap is narrowed for the nanoparticular system. With increasing temperature, X$_H$ decreases until no $β$-PdH phase is formed anymore at 500 K. At the same temperature, we studied the interaction of the Pd/sapphire model catalyst with MCH, both in the presence and in the absence of H$_2$. In the absence of H$_2$, carbon is formed and diffuses into the bulk yielding PdC$_x$ with a C concentration of around x ~ 0.05 ± 0.01. In the presence of H$_2$ in the gas phase, bulk carbon formation in the Pd/sapphire model catalyst is completely suppressed. These results show that Pd nanoparticles act as an adequate catalyst for the dehydrogenation of MCH., Published by Springer Science + Business Media B.V, Dordrecht [u.a.]

Understanding nanoparticle catalysis requires novel approaches in which adjoining crystal orientations can be studied under the same reactive conditions. Here we use a curved palladium crystal and near-ambient pressure X-ray photoemission spectroscopy to characterize chemical species during the catalytic oxidation of CO in a whole set of surfaces vicinal to the (111) direction simultaneously. By stabilizing the reaction at fixed temperatures around the ignition point, we observe a strong variation of the catalytic activity across the curved surface. Such spatial modulation of the reaction stage is straightforwardly mapped through the photoemission signal from active oxygen species and poisoning CO, which are shown to coexist in a transient regime that depends on the vicinal angle. Line-shape analysis and direct comparison with ultrahigh vacuum experiments help identifying and quantifying all such surface species, allowing us to reveal the presence of surface oxides during reaction ignition and cooling-off., We acknowledge financial support from the Spanish Ministry of Economy (Grants MAT-2012-38567-C02-02, MAT-2016-78293-C6, MAT-2017-88374-P) and Basque Government (Grant IT-1255-19).

Topics in catalysis 60(6-7), 492 - 502 (2017). doi:10.1007/s11244-016-0714-8, One layer thick iron oxide films are attractive from both applied and fundamental science perspectives. The structural and chemical properties of these systems can be tuned by changing the substrate, making them promising materials for heterogeneous catalysis. In the present work, we investigate the structure of FeO(111) monolayer films grown on Ag(100) and Ag(111) substrates by means of microscopy and diffraction techniques and compare it with the structure of FeO(111) grown on other substrates reported in literature. We also study the NO adsorption properties of FeO(111)/Ag(100) and FeO(111)/Ag(111) systems utilizing different spectroscopic techniques. We discuss similarities and differences in the data obtained from adsorption experiments and compare it with previous results for FeO(111)/Pt(111)., Published by Baltzer, Bussum