In situ Low-Energy Electron Microscopy of Chemical Waves on a Composite V-oxide/Rh(110) Surface.

Chemical wave patterns and V-oxide redistribution in catalytic methanol oxidation on a VOx/Rh(110) surface have been investigated in the 10-4 mbar range with low-energy electron microscopy (LEEM) and micro spot low-energy electron diffraction (micro-LEED) as in situ methods. V coverages of θV=0.2 and 0.4 MLE (monolayer equivalents) were studied. Pulses display a c(2×2) pattern in the reduced part and (1×2) and c(2×8) structures in the oxidized part of the surface. At θV=0.4 MLE (1×2)/(1×4) patterns with streaks along the [001]-direction at the 1/8 positions are present on the oxidized part of the surface. This phase can be assigned to V-oxide. On a tentative basis, an excitation mechanism for pulses is presented, Annealing the surface to 990 K under reaction conditions results in a macroscopic hole pattern in which holes of low VOx coverage are surrounded by a V-oxide layer. Chemical waves propagate inside the holes as well as on the VOx covered parts of the surface. The results demonstrate for the first time that also in supported oxidic overlayers selforganization processes can take place leading to chemical waves and a large scale redistribution of the oxide.

Unraveling van der Waals epitaxy: A real-time in-situ study of MoSe2 growth on graphene/Ru(0001).

In the present work we investigate the growth of monolayer MoSe2 on selenium-intercalated graphene on Ru(0001), a model layered heterostructure combining a transition metal dichalcogenide with graphene, using low energy electron microscopy and micro-diffraction. Real-time observation of MoSe2 on graphene growth reveals the island nucleation dynamics at the nanoscale. Upon annealing, larger islands are formed by sliding and attachment of multiple nanometer-sized MoSe2 flakes. Local micro-spot angle-resolved photoemission spectroscopy reveals the electronic structure of the heterostructure, indicating that no charge transfer occurs within adjacent layers. The observed behavior is attributed to intercalation of Se at the graphene/Ru(0001) interface. The unperturbed nature of the proposed heterostructure therefore renders it as a model system for investigations of graphene supported TMD nanostructures.

Preparation and stability of the hexagonal phase of samarium oxide on Ru(0001).

We have used low-energy electron microscopy (LEEM), micro-illumination low-energy electron diffraction (µLEED) supported by ab initio calculations, and X-ray absorption spectroscopy (XAS) to investigate in-situ and in real-time the structural properties of Sm2O3 deposits grown on Ru(0001), a rare-earth metal oxide model catalyst. Our results show that samarium oxide grows in a hexagonal A-Sm2O3 phase on Ru(0001), exhibiting a (0001) oriented-top facet and (113) side facets. Upon annealing, a structural transition from the hexagonal to cubic phase occurs, in which the Sm cations exhibit the +3 oxidation state. The unexpected initial growth in the A-Sm2O3 hexagonal phase and its gradual transition to a mixture with cubic C-Sm2O3 showcases the complexity of the system and the critical role of the substrate in the stabilization of the hexagonal phase, which was previously reported only at high pressures and temperatures for bulk samaria. Besides, these results highlight the potential interactions that Sm could have with other catalytic compounds with respect to the here gathered insights on the preparation conditions and the specific compounds with which it interacts.

Low-energy electron microscopy intensity-voltage data - Factorization, sparse sampling and classification.

Low-energy electron microscopy (LEEM) taken as intensity-voltage (I-V) curves provides hyperspectral images of surfaces, which can be used to identify the surface type, but are difficult to analyse. Here, we demonstrate the use of an algorithm for factorizing the data into spectra and concentrations of characteristic components (FSC3 ) for identifying distinct physical surface phases. Importantly, FSC3 is an unsupervised and fast algorithm. As example data we use experiments on the growth of praseodymium oxide or ruthenium oxide on ruthenium single crystal substrates, both featuring a complex distribution of coexisting surface components, varying in both chemical composition and crystallographic structure. With the factorization result a sparse sampling method is demonstrated, reducing the measurement time by 1-2 orders of magnitude, relevant for dynamic surface studies. The FSC3 concentrations are providing the features for a support vector machine-based supervised classification of the surface types. Here, specific surface regions which have been identified structurally, via their diffraction pattern, as well as chemically by complementary spectro-microscopic techniques, are used as training sets. A reliable classification is demonstrated on both example LEEM I-V data sets.

The morphology of VO2/TiO2(001): terraces, facets, and cracks.

Vanadium dioxide (VO2) features a pronounced, thermally-driven metal-to-insulator transition at 340 K. Employing epitaxial stress on rutile [Formula: see text] substrates, the transition can be tuned to occur close to room temperature. Striving for applications in oxide-electronic devices, the lateral homogeneity of such samples must be considered as an important prerequisite for efforts towards miniaturization. Moreover, the preparation of smooth surfaces is crucial for vertically stacked devices and, hence, the design of functional interfaces. Here, the surface morphology of [Formula: see text] films was analyzed by low-energy electron microscopy and diffraction as well as scanning probe microscopy. The formation of large terraces could be achieved under temperature-induced annealing, but also the occurrence of facets was observed and characterized. Further, we report on quasi-periodic arrangements of crack defects which evolve due to thermal stress under cooling. While these might impair some applicational endeavours, they may also present crystallographically well-oriented nano-templates of bulk-like properties for advanced approaches.

Wafer-Scale Synthesis of Graphene on Sapphire: Toward Fab-Compatible Graphene.

The adoption of graphene in electronics, optoelectronics, and photonics is hindered by the difficulty in obtaining high-quality material on technologically relevant substrates, over wafer-scale sizes, and with metal contamination levels compatible with industrial requirements. To date, the direct growth of graphene on insulating substrates has proved to be challenging, usually requiring metal-catalysts or yielding defective graphene. In this work, a metal-free approach implemented in commercially available reactors to obtain high-quality monolayer graphene on c-plane sapphire substrates via chemical vapor deposition is demonstrated. Low energy electron diffraction, low energy electron microscopy, and scanning tunneling microscopy measurements identify the Al-rich reconstruction 31 × 31 R ± 9 ° of sapphire to be crucial for obtaining epitaxial graphene. Raman spectroscopy and electrical transport measurements reveal high-quality graphene with mobilities consistently above 2000 cm2 V-1 s-1 . The process is scaled up to 4 and 6 in. wafers sizes and metal contamination levels are retrieved to be within the limits for back-end-of-line integration. The growth process introduced here establishes a method for the synthesis of wafer-scale graphene films on a technologically viable basis.

Dynamics of the Interaction Between Ceria and Platinum During Redox Processes.

The work is focused on understanding the dynamics of the processes which occur at the interface between ceria and platinum during redox processes, by investigating an inverse catalytic model system made of ceria epitaxial islands and ultrathin films supported on Pt(111). The evolution of the morphology, structure and electronic properties is analyzed in real-time during reduction and oxidation, using low-energy electron microscopy and spatially resolved low-energy electron diffraction. The reduction is induced using different methods, namely thermal treatments in ultra-high vacuum and in H2 as well as deposition of Ce on the oxide surface, while re-oxidation is obtained by exposure to oxygen at elevated temperature. The use of two different epitaxial systems, continuous films and nanostructures, allows determining the influence of platinum proximity on the stabilization of the specific phases observed. The factors that limit the reversibility of the observed modifications with the different oxidation treatments are also discussed. The obtained results highlight important aspects of the cerium oxide/Pt interaction that are relevant for a complete understanding of the behavior of Pt/CeO2 catalysts.

Exploiting micro-scale structural and chemical observations in real time for understanding chemical conversion: LEEM/PEEM studies over CeOx-Cu(111).

Proper consideration of length-scales is critical for elucidating active sites/phases in heterogeneous catalysis, revealing chemical function of surfaces and identifying fundamental steps of chemical reactions. Using the example of ceria thin films deposited on the Cu(111) surface, we demonstrate the benefits of multi length-scale experimental framework for understanding chemical conversion. Specifically, exploiting the tunable sampling and spatial resolution of photoemission electron microscopy, we reveal crystal defect mediated structures of inhomogeneous copper-ceria mixed phase that grow during preparation of ceria/Cu(111) model systems. The density of the microsized structures is such that they are relevant to the chemistry, but unlikely to be found during investigation at the nanoscale or with atomic level investigations. Our findings highlight the importance of accessing micro-scale when considering chemical pathways over heteroepitaxially grown model systems.

The cubic-to-hexagonal phase transition of cerium oxide particles: dynamics and structure.

Cerium oxide is often applied in today's catalysts due to its remarkable oxygen storage capacity. The changes in stoichiometry during reaction are linked to structural modifications, which in turn affect its catalytic activity. We present a real-time in situ study of the structural transformations of cerium oxide particles on ruthenium(0001) at high temperatures of 700 °C in ultra-high vacuum. Our results demonstrate that the reduction from CeO2 to cubic Ce2O3 proceeds via ordered intermediary phases. The final reduction step from cubic to hexagonal Ce2O3 is accompanied by a lattice expansion, the formation of two new surface terminations, a partial dissolution of the cerium oxide particles, and a massive mass transport of cerium from the particles to the substrate. The conclusions allow for new insights into the structure, stability, and dynamics of cerium oxide nanoparticles in strongly reducing environments.

Growth and structure of ultrathin praseodymium oxide layers on ruthenium(0001).

The growth, morphology, structure, and stoichiometry of ultrathin praseodymium oxide layers on Ru(0001) were studied using low-energy electron microscopy and diffraction, photoemission electron microscopy, atomic force microscopy, and X-ray photoelectron spectroscopy. At a growth temperature of 760 °C, the oxide is shown to form hexagonally close-packed (A-type) Pr2O3(0001) islands that are up to 3 nm high. Depending on the local substrate step density, the islands either adopt a triangular shape on sufficiently large terraces or acquire a trapezoidal shape with the long base aligned along the substrate steps.

Growth and characterization of epitaxially stabilized ceria(001) nanostructures on Ru(0001).

We have studied (001) surface terminated cerium oxide nanoparticles grown on a ruthenium substrate using physical vapor deposition. Their morphology, shape, crystal structure, and chemical state are determined by low-energy electron microscopy and micro-diffraction, scanning probe microscopy, and synchrotron-based X-ray absorption spectroscopy. Square islands are identified as CeO2 nanocrystals exhibiting a (001) oriented top facet of varying size; they have a height of about 7 to 10 nm and a side length between about 50 and 500 nm, and are terminated with a p(2 × 2) surface reconstruction. Micro-illumination electron diffraction reveals the existence of a coincidence lattice at the interface to the ruthenium substrate. The orientation of the side facets of the rod-like particles is identified as (111); the square particles are most likely of cuboidal shape, exhibiting (100) oriented side facets. The square and needle-like islands are predominantly found at step bunches and may be grown exclusively at temperatures exceeding 1000 °C.

Role of RuO2(100) in surface oxidation and CO oxidation catalysis on Ru(0001).

We have studied the oxidation of the Ru(0001) surface by in situ microscopy during exposure to NO2, an efficient source of atomic oxygen, at elevated temperatures. In a previous investigation [Flege et al., Phys. Rev. B: Condens. Matter Mater. Phys., 2008, 78, 165407], at O coverages exceeding 1 monolayer, using the combination of intensity-voltage (I(V)) low-energy electron microscopy (LEEM) and multiple scattering calculations for the (00) beam in the very-low-energy range (E≤ 50 eV) we identified three surface components during the initial Ru oxidation: a (1 × 1)-O chemisorption phase, the RuO2(110) oxide phase, and a surface oxide structure characterized by a trilayer O-Ru-O stacking. Here, we use dark-field LEEM imaging and micro-illumination low-energy electron diffraction in the range of 100 to 400 eV to show that this trilayer phase is actually a RuO2(100)-(1 × 1) phase with possibly mixed O and Ru surface terminations. This identification rationalizes the thermodynamic stability of this phase at elevated temperatures and is consistent with the observation of catalytic activity of the phase in CO oxidation.

Nanoscale Origin of Mesoscale Roughening: Real-Time Tracking and Identification of Three Distinct Ruthenium Oxide Phases in Ruthenium Oxidation.

The structural modification of the Ru(0001) surface is followed in real-time using low-energy electron microscopy at elevated temperatures during exposure to molecular oxygen. We observe the nucleation and growth of three different RuO2 facets, which are unambiguously identified by single-domain microspot low-energy electron diffraction (µLEED) analysis from regions of 250 nm in diameter. Structural identification is then pushed to the true nanoscale by employing very-low-energy electron reflectivity spectra R(E) from regions down to 10 nm for structural fingerprinting of complex reactions such as the oxidation of metal surfaces. Calculations of R(E) with an ab initio scattering theory confirm the growth of (110), (100), and (101) orientations of RuO2 and explain the shape of the R(E) spectra in terms of the conducting band structure. This methodology is ideally suited to identify the structure of supported ultrathin films and dynamic transformations at multicomponent interfaces down to few nanometer lateral resolution at elevated temperature and in reactive environments.

Insights into the gas phase oxidation of Ru(0001) on the mesoscopic scale using molecular oxygen.

We present an extensive mesoscale study of the initial gas phase oxidation of Ru(0001), employing in situ low-energy electron microscopy (LEEM), micro low-energy electron diffraction (µ-LEED) and scanning tunneling microscopy (STM). The initial oxidation was investigated in a temperature range of 500-800 K at a constant oxygen pressure of p(O2) = 4 × 10(-5) mbar. Depending to the preparation temperature a dramatic change of the growth morphology of the RuO2 film was observed. At lower temperature (580 K) the RuO2(110) film grows anisotropically oriented along the high symmetry directions of the Ru(0001) substrate. At higher temperature (680 K), new rotational domains of RuO2(110) begin to appear, which are slightly rotated by up to 20° with respect to the high symmetry direction. These rotated RuO2(110) domains grow along slightly rotated step edges and reveal an isotropic growth morphology. Both the growth speed and the nucleation rate differ from that of the oxide growth at lower temperature (580 K).

Oxidation-state analysis of ceria by X-ray photoelectron spectroscopy.

Three different methods to determine the oxide-phase concentration in mixed cerium oxide by hard X-ray photoelectron spectroscopy are applied and quantitatively compared. Synchrotron-based characterization of the O 1s region was used as a benchmark to introduce a method based on the weighted superposition of the Ce 3d spectra of the pure Ce(3+) and Ce(4+) phases, which was shown to lead to reliable and highly accurate determination of the mean oxidation state in mixed cerium oxides. The results obtained reveal a linear relation between the third distinct final state (u''') satellite peak intensity of the Ce(4+) phase and the Ce(4+) concentration by proper inclusion of Ce(3+)-related plasmon satellite peaks, which contradicts previous claims of nonlinear behavior. In contrast, quantitative conventional peak-fitting procedures were shown to be well suited for the Ce 2p region due to its relatively simple structure. Additional satellite features observed in the Ce 3d spectrum of CeO2 were proposed to originate from plasmon contributions.

Interactions of oxygen and ethylene with submonolayer Ag films supported on Ni(111).

We investigate the oxidation of, and the reaction of ethylene with, Ni(111) with and without sub-monolayer Ag adlayers as a function of temperature. The addition of Ag to Ni(111) is shown to enhance the activity towards the ethylene epoxidation reaction, and increase the temperature at which ethylene oxide is stable on the surface. We present a systematic study of the formation of chemisorbed oxygen on the Ag-Ni(111) surfaces and correlate the presence and absence of O(1-) and O(2-) surface species with the reactivity towards ethylene. By characterizing the samples with low-energy electron microscopy (LEEM) in combination with X-ray photoelectron spectroscopy (XPS), we have identified specific growth of silver on step-edge sites and successfully increased the temperature at which the produced ethylene oxide remains stable, a trait which is desirable for catalysis.