Abstract: 'Colossal magnetoresistance' in perovskite manganites such as La0.7Ca0.3MnO3 (LCMO), is caused by the interplay of ferro-paramagnetic, metal-insulator and structural phase transitions. Moreover, different electronic phases can coexist on a very fine scale resulting in percolative electron transport. Here we report on (LCMO)(1-x):(MgO)(x) (0 < x less than or equal to 0.8) epitaxial nano-composite films in which the structure and magnetotransport properties of the manganite nanoclusters can be tuned by the tensile stress originating from the MgO second phase. With increasing x, the lattice of LCMO was found to expand, yielding a bulk tensile strain. The largest colossal magnetoresistance of 10(5)% was observed at the percolation threshold in the conductivity at x(c) approximate to 0.3, which is coupled to a structural phase transition from orthorhombic (0 < x less than or equal to 0.1) to rhombohedral R (3) over barc structure (0.33 less than or equal to x less than or equal to 0.8). An increase of the Curie temperature for the R (3) over barc phase was observed. These results may provide a general method for controlling the magnetotransport properties of manganite-based composite films by appropriate choice of the second phase.

Abstract: Oriented attachment of PbSe nanocubes can result in the formation of two-dimensional (2D) superstructures with long-range nanoscale and atomic order. This questions the applicability of classic models in which the superlattice grows by first forming a nucleus, followed by sequential irreversible attachment of nanocrystals, as one misaligned attachment would disrupt the 2D order beyond repair. Here, we demonstrate the formation mechanism of 2D PbSe superstructures with square geometry by using in situ grazing-incidence X-ray scattering (small angle and wide angle), ex situ electron microscopy, and Monte Carlo simulations. We observed nanocrystal adsorption at the liquid/gas interface, followed by the formation of a hexagonal nanocrystal monolayer. The hexagonal geometry transforms gradually through a pseudo-hexagonal phase into a phase with square order, driven by attractive interactions between the {100} planes perpendicular to the liquid substrate, which maximize facet-to-facet overlap. The nanocrystals then attach atomically via a necking process, resulting in 2D square superlattices.

Abstract: Solid films of colloidal quantum dots show promise in the manufacture of photodetectors and solar cells. These devices require high yields of photogenerated charges and high carrier mobilities, which are difficult to achieve in quantum-dot films owing to a strong electronhole interaction and quantum confinement. Here, we show that the quantum yield of photogenerated charges in strongly coupled PbSe quantum-dot films is unity over a large temperature range. At high photoexcitation density, a transition takes place from hopping between localized states to band-like transport. These strongly coupled quantum-dot films have electrical properties that approach those of crystalline bulk semiconductors, while retaining the size tunability and cheap processing properties of colloidal quantum dots.

Abstract: It remains a challenge to identify the active sites of bismuth catalysts in the electrochemical CO2 reduction reaction. Here we show through in situ characterization that the activation of bismuth oxyhalide electrocatalysts to metallic bismuth is guided by the halides. In situ X-ray diffraction results show that bromide promotes the selective exposure of planar bismuth surfaces, whereas chloride and iodide result in more disordered active sites. Furthermore, we find that bromide-activated bismuth catalysts outperform the chloride and iodide counterparts, achieving high current density (>100 mA cm(-2)) and formic acid selectivity (>90%), suggesting that planar bismuth surfaces are more active for the electrochemical CO2 reduction reaction. In addition, in situ X-ray absorption spectroscopy measurements reveal that the reconstruction proceeds rapidly in chloride-activated bismuth and gradually when bromide is present, facilitating the formation of ordered planar surfaces. These findings show the pivotal role of halogens on selective facet exposure in activated bismuth-based electrocatalysts during the electrochemical CO2 reduction reaction.

Abstract: A high dispersion of the active metal phase of transition metals on oxide supports is important when designing efficient heterogeneous catalysts. Besides nanoparticles, clusters and even single metal atoms can be attractive for a wide range of reactions. However, many industrially relevant catalytic transformations suffer from structure sensitivity, where reducing the size of the metal particles below a certain size substantially lowers catalytic performance. A case in point is the low activity of small cobalt nanoparticles in the hydrogenation of CO and CO2. Here we show how engineering of catalytic sites at the metal–oxide interface in cerium oxide–zirconium dioxide (ceria–zirconia)-supported cobalt can overcome this structure sensitivity. Few-atom cobalt clusters dispersed on 3 nm cobalt(II)-oxide particles stabilized by ceria–zirconia yielded a highly active CO2 methanation catalyst with a specific activity higher than that of larger particles under the same conditions.

Abstract: Oriented attachment of synthetic semiconductor nanocrystals is emerging as a route for obtaining new semiconductors that can have Dirac-type electronic bands like graphene, but also strong spin-orbit coupling. The two-dimensional assembly geometry will require both atomic coherence and long-range periodicity of the superlattices. We show how the interfacial self-assembly and oriented attachment of nanocrystals results in two-dimensional (2D) metal chalcogenide semiconductors with a honeycomb superlattice. We present an extensive atomic and nanoscale characterization of these systems using direct imaging and wave scattering methods. The honeycomb superlattices are atomically coherent, and have an octahedral symmetry that is buckled; the nanocrystals occupy two parallel planes. Considerable necking and large-scale atomic motion occurred during the attachment process.

Abstract: Our study compares short-range order parameters refined from the diffuse scattering in single-crystal X-ray and single-crystal electron diffraction data. Nb0.84CoSb was chosen as a reference material. The correlations between neighbouring vacancies and the displacements of Sb and Co atoms were refined from the diffuse scattering using a Monte Carlo refinement in DISCUS. The difference between the Sb and Co displacements refined from the diffuse scattering and the Sb and Co displacements refined from the Bragg reflections in single-crystal X-ray diffraction data is 0.012 (7) angstrom for the refinement on diffuse scattering in single-crystal X-ray diffraction data and 0.03 (2) angstrom for the refinement on the diffuse scattering in single-crystal electron diffraction data. As electron diffraction requires much smaller crystals than X-ray diffraction, this opens up the possibility of refining short-range order parameters in many technologically relevant materials for which no crystals large enough for single-crystal X-ray diffraction are available.

Abstract: LNMO (LiNi0.5Mn1.5O4-delta) is a high-energy density positive electrode material for lithium ion batteries. Unfortunately, it suffers from capacity loss and impedance rise during cycling due to electrolyte oxidation and electrode/electrolyte interface instabilities at high operating voltages. Here, a solution-gel synthesis route was used to coat 0.5-2.5 mu m LNMO particles with amorphous Li-Ti-O (LTO) for improved Li conduction, surface structural stability and cyclability. High-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) analysis coupled with energy dispersive X-ray (EDX) showed Ti-rich amorphous coatings/islands or Ti-rich spinel layers on many of the LTO-modified LNMO facets, with a thickness varying from about 1 to 10 nm. The surface modification in the form of amorphous islands was mostly possible on high-energy crystal facets. Physicochemical observations were used to propose a molecular mechanism for the surface modification, combining insights from metalorganic chemistry with the crystallographic properties of LNMO. The improvements in functional properties were investigated in half cells. The cell impedance increased faster for the bare LNMO compared to amorphous LTO modified LNMO, resulting in R-ct values as high as 1247 Omega (after 1000 cycles) for bare LNMO, against 216 Omega for the modified material. At 10C, the modified material boosted a 15% increase in average discharge capacity. The improvements in electrochemical performance were attributed to the increase in electrochemically active surface area, as well as to improved HF-scavenging, resulting in the formation of protective byproducts, generating a more stable interface during prolonged cycling.

Abstract: The determination of the mechanical properties of serpentinites is essential toward the understanding of the mechanics of faulting and subduction. Here we present the first in situ tensile tests on antigorite in a transmission electron microscope. A push‐to‐pull deformation device is used to perform quantitative tensile tests, during which force and displacement are measured, while the evolving microstructure is imaged with the microscope. The experiments have been performed at room temperature on 2 × 1 × 0.2 μm3 beams prepared by focused ion beam. The specimens are not single crystals despite their small sizes. Orientation mapping indicated that several grains were well oriented for plastic slip. However, no dislocation activity has been observed even though the engineering tensile stress went up to 700 MPa. We show also that antigorite does not exhibit a purely elastic‐brittle behavior since, despite the presence of defects, the specimens accumulate permanent deformation and did not fail within the elastic regime. Instead, we observe that strain localizes at grain boundaries. All observations concur to show that under these experimental conditions, grain boundary sliding is the dominant deformation mechanism. This study sheds a new light on the mechanical properties of antigorite and calls for further studies on the structure and properties of grain boundaries in antigorite and more generally in phyllosilicates.

Abstract: We present the GW band structure of ZnO in its wurtzite (WZ), zincblende (ZB) and rocksalt (RS) phases at the Γ point, calculated within the GW approximation. We have used a Zn20+ pseudopotential which is essential for the adequate treatment of the exchange interaction in the self-energy. The accuracy of the pseudopotential used is also discussed. The effect of the pd hybridization on the GW corrections to the band gap is correlated by comparing the ZB and RS phase.

Abstract: In contrast to perfectly periodic crystals, materials with short-range order produce diffraction patterns that contain both Bragg reflections and diffuse scattering. To understand the influence of short-range order on material properties, current research focuses increasingly on the analysis of diffuse scattering. This article verifies the possibility to refine the short-range order parameters in submicrometre-sized crystals from diffuse scattering in single-crystal electron diffraction data. The approach was demonstrated on Li_1.2Ni_0.13Mn_0.54Co_0.13O₂, which is a state-of-the-art cathode material for lithium-ion batteries. The intensity distribution of the 1D diffuse scattering in the electron diffraction patterns of Li_1.2Ni_0.13Mn_0.54Co_0.13O₂depends on the number of stacking faults and twins in the crystal. A model of the disorder in Li_1.2Ni_0.13Mn_0.54Co_0.13O₂was developed and both the stacking fault probability and the percentage of the different twins in the crystal were refined using an evolutionary algorithm in<italic>DISCUS</italic>. The approach was applied on reciprocal space sections reconstructed from 3D electron diffraction data since they exhibit less dynamical effects compared with in-zone electron diffraction patterns. A good agreement was achieved between the calculated and the experimental intensity distribution of the diffuse scattering. The short-range order parameters in submicrometre-sized crystals can thus successfully be refined from the diffuse scattering in single-crystal electron diffraction data using an evolutionary algorithm in<italic>DISCUS</italic>.

Abstract: In this article we report on the synthesis and characterization of a system of colloidal spheres suspended in an aqueous solvent which can be refractive index-matched, thus allowing for investigations of the particle near-wall dynamics by evanescent wave dynamic light scattering at concentrations up to the isotropic to ordered transition and beyond. The particles are synthesized by copolymerization of a fluorinated acrylic ester monomer with a polyethylene-glycol (PEG) oligomer by surfactant free emulsion polymerization. Static and dynamic light scattering experiments in combination with cryo transmission electron microscopy reveal that the particles have a core shell structure with a significant enrichment of the PEG chains on the particles surface. In index-matching DMSO/water suspensions the particles arrange in an ordered phase at volume fraction above 7%, if no additional electrolyte is present. The near-wall dynamics at low volume fraction are quantitatively described by the combination of electrostatic repulsion and hydrodynamic interaction between the particles and the wall. At volume fractions close to the isotropic to ordered transition, the near-wall dynamics are more complex and qualitatively reminiscent of the behaviour which was observed in hard sphere suspensions at high concentrations.

Abstract: Adsorption of sulfide ions onto a surface of starch capped silver nanoparticles upon addition of thioacetamide was investigated. UVvis absorption spectroscopy revealed that the adsorption of the sulfide ion on the surface of the silver nanoparticles induced damping as well as blue shift of the silver surface plasmon resonance band. Further increase in thioacetamide concentration led to shift of the resonance band toward higher wavelengths indicating the formation of the continuous Ag2S layer on the silver surface. Thus fabricated nanoparticles were investigated using electron microscopy techniques (TEM, HRTEM, and HAADF-STEM) and X-ray photoelectron spectroscopy (XPS), which confirmed their coreshell structure.

Abstract: In this work we present an alternative way to look at electron diffraction in a transmission electron microscope.
Instead of writing the scattering amplitude in Fourier space as a set of plane waves,we use the cylindrical Fourier transform to describe the scattering amplitude in a basis of orbital angular momentum (OAM) eigenstates. We show how working in this framework can be very convenient when investigating, e.g., rotation and screw-axis symmetries. For the latter we find selection rules on the OAM coefficients that unambiguously reveal the handedness of the screw axis. Detecting the OAM coefficients of the scattering amplitude thus offers the possibility to detect the handedness of crystals without the need for dynamical simulations, the thickness of the sample, nor the exact crystal structure. We propose an experimental setup to measure the OAM components where an image of the crystal is taken after inserting a spiral phase plate in the diffraction plane and perform multislice simulations on α quartz to demonstrate how the method indeed reveals the chirality. The experimental feasibility of the technique is discussed together with its main advantages with respect to chirality determination of screw axes. The method shows how the use of a spiral phase plate can be extended from a simple phase imaging technique to a tool to measure the local OAM decomposition of an electron wave, widening the field of interest well beyond chiral space group determination.

Abstract: Bi2Se3 is a three-dimensional topological insulator which has been extensively studied because it has a single Dirac cone on the surface, inside a relatively large bulk band gap. However, the effect of two-dimensional topological insulator Bi bilayers on the properties of Bi2Se3 and vice versa, has not been explored much. Bi bilayers are often present between the quintuple layers of Bi2Se3, since (Bi2)n(Bi2Se3)m form stable ground-state structures. Moreover, Bi2Se3 is a good substrate for growing ultrathin Bi bilayers. By first-principles techniques, we first show that there is no preferable surface termination by either Bi or Se. Next, we investigate the electronic structure of Bi bilayers on top of, or inside a Bi2Se3 slab. If the Bi bilayers are on top, we observe a charge transfer to the quintuple layers that increases the binding energy of the surface Dirac cones. The extra states, originating from the Bi bilayers, were declared to form a topological Dirac cone, but here we show that these are ordinary Rashba-split states. This result, together with the appearance of a new Dirac cone that is localized slightly deeper, might necessitate the reinterpretation of several experimental results. When the Bi bilayers are located inside the Bi2Se3 slab, they tend to split the slab into two topological insulators with clear surface states. Interface states can also be observed, but an energy gap persists because of strong coupling between the neighboring quintuple layers and the Bi bilayers.