Sub-nanometer free electrons with topological charge

The holographic mask technique is used to create freely moving electrons with quantized angular momentum. With electron optical elements they can be focused to vortices with diameters below the nanometer range. The understanding of these vortex beams is important for many applications. Here we present a theory of focused free electron vortices. The agreement with experimental data is excellent. As an immediate application, fundamental experimental parameters like spherical aberration and partial coherence are determined.Comment: 4 pages, 5 figure

A novel vortex generator and mode converter for electrons

A mode converter for electron vortex beams is described. Numerical simulations, confirmed by experiment, show that the converter transforms a vortex beam with topological charge $m=\pm 1$ into beams closely resembling Hermite-Gaussian HG$_{10}$ and HG$_{01}$ modes. The converter can be used as a mode discriminator or filter for electron vortex beams. Combining the converter with a phase plate turns a plane wave into modes with topological charge $m=\pm 1$. This combination serves as a generator of electron vortex beams of high brilliance

Electron microscopy investigations of metal-support interaction effects in M/Y2O3 and M/ZrO2 thin films (M=Cu, Ni)

Model systems of the clean and pure oxides Y2O3 and ZrO2, as well as Cu/Cu2O and Ni/NiO particles embedded in the respective oxides have been used to study the reduction behavior of the oxides and the eventually associated metal-support interaction effects in oxide-supported systems. Particular emphasis has also been given to the influence of the phase transformation in ZrO2-containing systems on metal-support interaction. Whereas Y2O3 has been found to be an outstandingly structurally and thermally stable oxide even upon reduction in hydrogen up to 1073 K, ZrO2 was found to undergo a series of phase transformations from amorphous ZrO2 to polycrystalline tetragonal ZrO2 (673 K) and subsequently to monoclinic ZrO2 (above 873 K). Both phase transformations were found to be basically dependent on gas partial pressure and annealing rate. However, substantial reduction of the oxides did not take place during the phase transformations. In turn, both Cu- and Ni-containing systems were not observed to be substantially affected by any (strong) metal-support interaction effects such as encapsulation by sub-stoichiometric oxides or reductive formation of intermetallic phases, at least up to temperatures of 1073 K. Equally, for the ZrO2-containing systems, also the phase transformations occurring at elevated temperatures did not cause structural or thermo-chemical alterations of the Cu or Ni-particles. Differences in the metal-support interaction between Cu- and Ni-particles have only been obtained in the structural “reference” systems, that is, if supported on SiO2. Whereas Cu/Cu2O particles on SiO2 are basically unaffected by the reductive treatment at elevated temperatures, a Ni3Si2 intermetallic phase is formed if SiO2-supported Ni/NiO particles are treated in hydrogen at 673 K and above.(VLID)2852394Accepted versio

The Crystallographic and Electronic Phase Diagrams of Yttria-Stabilized Zirconia Model Electrolytes

Yttria-stabilized zirconia model electrolyte systems with four different compositions are analyzed regarding their crystallographic and electronic structure. By investigating the unit cell height, obtained from electron diffraction patterns, it is shown that a phase transformation between the tetragonal and cubic polymorphs takes place between 8 and 9.3 mol%. Furthermore, the direct band gaps are shown to exhibit the same behavior as the lattice parameter, featuring a discontinuity at the phase transition. By measuring the emitted Čerenkov radiation, an electronic transition that is smaller than the band gaps is found, suggesting that localized defect states are present within the band gap, which is in agreement with UV photoelectron spectra.(VLID)2852382Accepted versio

Methane Decomposition and Carbon Growth on Y₂O₃, Yttria-Stabilized Zirconia, and ZrO₂

Carbon deposition following thermal methane decomposition under dry and steam reforming conditions has been studied on yttria-stabilized zirconia (YSZ), Y2O3 and ZrO2 by a range of different chemical, structural and spectroscopic characterization techniques, including aberration-corrected electron microscopy, Raman spectroscopy, electric impedance spectroscopy and volumetric adsorption techniques. Concordantly, all experimental techniques reveal the formation of a conducting layer of disordered nanocrystalline graphite covering the individual grains of the respective pure oxides after treatment in dry methane at temperatures T ≥ 1000 K. In addition, treatment under moist methane conditions causes additional formation of carbon-nanotube-like architectures by partial detachment of the graphite layers. All experiments show that during carbon growth, no substantial reduction of any of the oxides takes place. Our results therefore indicate that these pure oxides can act as efficient nonmetallic substrates for methane-induced growth of different carbon species with potentially important implications regarding their use in solid oxide fuel cells. By comparison of the three oxides we could moreover elucidate differences in the methane reactivities of the respective SOFC-relevant purely oxidic surfaces under typical SOFC operation conditions without the presence of metallic constituents

Formation and Stability of small well-defined Cu- and Ni oxide particles

Well-defined and -structured Cu/Cu2O and Ni/NiO composite nanoparticles have been prepared by physical-vapor deposition on vacuum-cleaved NaCl(001) single crystal facets. Epitaxial growth has been observed due to the close crystallographic matching of the respective cubic crystal lattices. Distinct particle morphologies have only been obtained for the Ni/NiO particles, comprising truncated half-octahedral, rhombohedral- and pentagonal-shaped outlines. Oxidation of the particles in the temperature range 473-673 K in both cases led to the formation of well-defined CuO and NiO particles with distinct morphologies. Whereas CuO possibly adopts its thermodynamical equilibrium shape, NiO formation is accompanied by entering a Kirkendall-like state, that is, a hollow core-shell structure is obtained. The difference in the formation of the oxides is also reflected by their stability under reducing conditions. CuO transforms back to a polycrystalline mixture of Cu metal, Cu2O and CuO after reduction in hydrogen at 673 K. In contrast, as expected from theoretical stability considerations, the formation of the hollow NiO structure is reversed upon annealing in hydrogen at 673 K and moreover results in the formation of a Ni-rich silicide structure Ni3Si2. The discussed systems present a convenient way to tackle and investigate various problems in nanotechnology or catalysis, including phase transformations, establishing structure/activity relationships or monitoring intermetallic particles, starting from well-defined and simple models.(VLID)2852386Accepted versio

Energy-loss magnetic chiral dichroism (EMCD): Magnetic chiral dichroism in the electron microscope

A new technique called energy-loss magnetic chiral dichroism (EMCD) has recently been developed [P. Schattschneider, et al. Nature 441, 486 (2006)] to measure magnetic circular dichroism in the transmission electron microscope (TEM) with a spatial resolution of 10 nm. This novel technique is the TEM counterpart of x-ray magnetic circular dichroism, which is widely used for the characterization of magnetic materials with synchrotron radiation. In this paper we describe several experimental methods that can be used to measure the EMCD signal [P. Schattschneider, et al. Nature 441, 486 (2006); C. Hébert, et al. Ultramicroscopy 108(3), 277 (2008); B. Warot-Fonrose, et al. Ultramicroscopy 108(5), 393 (2008); L. Calmels, et al. Phys. Rev. B 76, 060409 (2007); P. van Aken, et al. Microsc. Microanal. 13(3), 426 (2007)] and give a review of the recent improvements of this new investigation tool. The dependence of the EMCD on several experimental conditions (such as thickness, relative orientation of beam and sample, collection and convergence angle) is investigated in the transition metals iron, cobalt, and nickel. Different scattering geometries are illustrated; their advantages and disadvantages are detailed, together with current limitations. The next realistic perspectives of this technique consist of measuring atomic specific magnetic moments, using suitable spin and orbital sum rules, [L. Calmels, et al. Phys. Rev. B 76, 060409 (2007); J. Rusz, et al. Phys. Rev. B 76, 060408 (2007)] with a resolution down to 2 to 3 n

Line defects in epitaxial silicon films grown at 560 C

We present an investigation of line defects in epitaxially grown silicon layers using Secco defect etching and transmission electron microscopy TEM . 1 m thick layers were deposited onto Si 100 wafers at a substrate temperature of 560 C using electron cyclotron resonance chemical vapour deposition ECRCVD . Defect etching reveals a variety of etch pits related to extended defects. A detailed analysis of the orientations and shapes of etch pits related to line defects is carried out. Using this information it is then possible to assign different types of etch pits to line defects observed by TEM. The investigations show, that one type of defect are extended dislocations parallel to lt;112 gt;, while the direction of two other types are lt;110 gt; as well as lt;314 gt;, a direction uncommon for line defects in silico

Pattern Formation in Catalytic H₂ Oxidation on Rh: Zooming in by Correlative Microscopy

Spatio-temporal nonuniformities in H2 oxidation on individual Rh(h k l) domains of a polycrystalline Rh foil were studied in the 10–6 mbar pressure range by photoemission electron microscopy (PEEM), X-ray photoemission electron microscopy (XPEEM), and low-energy electron microscopy (LEEM). The latter two were used for in situ correlative microscopy to zoom in with significantly higher lateral resolution, allowing detection of an unusual island-mediated oxygen front propagation during kinetic transitions. The origin of the island-mediated front propagation was rationalized by model calculations based on a hybrid approach of microkinetic modeling and Monte Carlo simulations