Abstract: The field of discrete tomography focuses on the reconstruction of samples that consist of only a few different materials. Ideally, a three-dimensional (3D) reconstruction of such a sample should contain only one grey level for each of the compositions in the sample. By exploiting this property in the reconstruction algorithm, either the quality of the reconstruction can be improved significantly, or the number of required projection images can be reduced. The discrete reconstruction typically contains fewer artifacts and does not have to be segmented, as it already contains one grey level for each composition. Recently, a new algorithm, called discrete algebraic reconstruction technique (DART), has been proposed that can be used effectively on experimental electron tomography datasets. In this paper, we propose discrete tomography as a general reconstruction method for electron tomography in materials science. We describe the basic principles of DART and show that it can be applied successfully to three different types of samples, consisting of embedded ErSi2 nanocrystals, a carbon nanotube grown from a catalyst particle and a single gold nanoparticle, respectively.

Abstract: The idea of this Review is to introduce newly developed possibilities of advanced electron microscopy to the materials science community. Over the last decade, electron microscopy has evolved into a full analytical tool, able to provide atomic scale information on the position, nature, and even the valency atoms. This information is classically obtained in two dimensions (2D), but can now also be obtained in 3D. We show examples of applications in the field of nanoparticles and interfaces.

Abstract: Cobalt nanorods possess ideal magnetic properties for applications requiring magnetically hard nanoparticles. However, their exploitation is undermined by their sensitivity toward oxygen and water, which deteriorates their magnetic properties. The development of a continuous metal shell inert to oxidation could render them stable, opening perspectives not only for already identified applications but also for uses in which contact with air and/or aqueous media is inevitable. However, the direct growth of a conformal noble metal shell on magnetic metals is a challenge. Here, we show that prior treatment of Co nanorods with a tin coordination compound is the crucial step that enables the subsequent growth of a continuous noble metal shell on their surface, rendering them air- and water-resistant, while conserving the monocrystallity, metallicity and the magnetic properties of the Co core. Thus, the as-synthesized coreshell ferromagnetic nanorods combine high magnetization and strong uniaxial magnetic anisotropy, even after exposure to air and water, and hold promise for successful implementation in in vitro biodiagnostics requiring probes of high magnetization and anisotropic shape.

Abstract: Annular objective apertures are fabricated for a CM300 transmission electron microscope using a focused ion beam system. A central beam stop in the back focal plane of the objective lens of the microscope blocks all electrons scattered up to a semi-angle of approximately 20 mrad. In this manner, contributions to the image from Bragg scattering are largely reduced and the image contrast is sensitive to the atomic number Z. Experimentally, we find that single atom scattering cross sections measured with this technique are close to Rutherford scattering values. A comparison between this new method and STEM-HAADF shows that both techniques result in qualitatively similar images although the resolution of ADF-TEM is limited by contrast delocalization caused by the spherical aberration of the objective lens. This problem can be overcome by using an aberration corrected microscope.

Abstract: Nano-sized ZnO particles with a narrow size distribution and high crystallinity were prepared from aqueous solutions with high concentrations of Zn2+ containing salts and citric acid in a conventional spray pyrolysis setup. Structure, morphology and size of the produced material were compared to ZnO material produced by simple spray pyrolysis of zinc nitrates in the same experimental setup. Using transmission electron microscopy and electron tomography it has been shown that citric acid-assisted spray pyrolysed material is made up of micron sized secondary particles comprising a shell of lightly agglomerated, monocrystalline primary ZnO nanoparticles with sizes in the 2030 nm range, separable by a simple ultrasonic treatment step.

Abstract: Highly ordered and self supported anatase TiO2 nanoparticle chains were fabricated by calcining conformally TiO2 coated multi-walled carbon nanotubes (MWCNTs). During annealing, the thin tubular TiO2 coating that was deposited onto the MWCNTs by atomic layer deposition (ALD) was transformed into chains of TiO2 nanoparticles ([similar]12 nm diameter) with an ultrahigh surface area (137 cm2 per cm2 of substrate), while at the same time the carbon from the MWCNTs was removed. Photocatalytic tests on the degradation of acetaldehyde proved that these forests of TiO2 nanoparticle chains are highly photoactive under UV light because of their well crystallized anatase phase.

Abstract: It is widely accepted that the physical properties of nanostructures depend on the type of surface facets1, 2. For Au nanorods, the surface facets have a major influence on crucial effects such as reactivity and ligand adsorption and there has been controversy regarding facet indexing3, 4. Aberration-corrected electron microscopy is the ideal technique to study the atomic structure of nanomaterials5, 6. However, these images correspond to two-dimensional (2D) projections of 3D nano-objects, leading to an incomplete characterization. Recently, much progress was achieved in the field of atomic-resolution electron tomography, but it is still far from being a routinely used technique. Here we propose a methodology to measure the 3D atomic structure of free-standing nanoparticles, which we apply to characterize the surface facets of Au nanorods. This methodology is applicable to a broad range of nanocrystals, leading to unique insights concerning the connection between the structure and properties of nanostructures.

Abstract: An epitaxial PbTiO3 thin film grown on self-organized crystalline SrRuO3 nanowires deposited on a DyScO3 substrate with ordered DyO and ScO2 chemical terminations is investigated by transmission electron microscopy. In this PbTiO3/SrRuO3/DyScO3 heterostructure, the SrRuO3 nanowires are assumed to grow on only one type of substrate termination. Here, we report on the structure, morphology, and chemical composition analysis of this heterostructure. Electron energy loss spectroscopy reveals the exact termination sequence in this complex structure. The energy loss near-edge structure of the Ti-L-2,L-3, Sc-L-2,L-3, and O K edges shows intrinsic interfacial electronic reconstruction. Furthermore, PbTiO3 domain walls are observed to start at the end of the nanowires resulting in atomic steps on the film surface. (C) 2013 AIP Publishing LLC.

Abstract: Nanometer sized ZnO clusters are produced in the gas phase and subsequently deposited on clean Au(111) surfaces under ultra-high vacuum conditions. The zinc blende atomic structure of the approximately spherical ZnO clusters is resolved by high resolution scanning transmission electron microscopy. The large band gap and weak n-type conductivity of individual clusters are determined by scanning tunnelling microscopy and spectroscopy at cryogenic temperatures. The conduction band is found to exhibit clear quantization into discrete energy levels, which can be related to finite-size effects reflecting the zero-dimensional confinement. Our findings illustrate that gas phase cluster production may provide unique possibilities for the controlled fabrication of high purity quantum dots and heterostructures that can be size selected prior to deposition on the desired substrate under controlled ultra-high vacuum conditions.

Abstract: Zeogrids and Zeotiles are hierarchical materials built from assembled MFI zeolite precursor units. Permanent secondary porosity in these materials is obtained through self assembly of nanoparticles encountered in MFI zeolite synthesis in the presence of supramolecular templates. Hereon, the aggregated species are termed nanoslabs. Zeogrids are layered materials with lateral spacings between nanoslabs creating galleries qualifying as supermicropores. Zeotiles present a diversity of tridimensional nanoslab assemblies with mesopores. Zeotile-1, -4 and -6 are hexagonal mesostructures. Zeotile-1 has triangular and hexagonal channels; Zeotile-4 has hexagonal channels interconnected via slits. Zeotile-2 has a cubic structure with gyroid type mesoporosity. The behavior of Zeogrids and Zeotiles in adsorption, membrane and chromatographic separation and catalysis has been characterized and compared with zeolites and mesoporous materials derived from unstructured silica sources. Shape selectivity was detected via adsorption of n- and iso-alkanes. The mesoporosity of Zeotiles can be exploited in chromatographic separation of biomolecules. Zeotiles present attractive separation properties relevant to CO2 sequestration. Because of its facile synthesis procedure without hydrothermal steps Zeogrid is convenient for membrane synthesis. The performance of Zeogrid membrane in gas separation, nanofiltration and pervaporation is reported. In the Beckmann rearrangement of cyclohexanone oxime Zeogrids and Zeotiles display a catalytic activity characteristic of silicalite-1 zeolites. Introduction of acidity and redox catalytic activity can be achieved via incorporation of Al and Ti atoms in the nanoslabs during synthesis. Zeogrids are active in hydrocracking, catalytic cracking, alkylation and epoxidation reactions. Zeogrids and Zeotiles often behave differently from ordered mesoporous materials as well as from zeolites and present a valuable extension of the family of hierarchical silicate based materials.

Abstract: We report the solution phase synthesis, the structural analysis, and the magnetic properties of hybrid nanostructures combining two magnetic metals. These nano-objects are characterized by a remarkable shape, combining Fe nanocubes on Co nanorods. The topological composition, the orientation relationship, and the growth steps have been studied by advanced electron microscopy techniques, such as HRTEM, electron tomography, and state-of-the-art 3-dimensional elemental mapping by EDX tomography. The soft iron nanocubes behave as easy nucleation centers that induce the magnetization reversal of the entire nanohybrid, leading to a drastic modification of the overall effective magnetic anisotropy.

Abstract: Metamorphic buffers (M-buffers) consisting of graded InAlAs or bulk InP were employed for the production of InP-based epiwafers on GaAs substrates by molecular-beam epitaxy. The graded InAlAs is the standard for production metamorphic high electron mobility transistors (M-HEMTs), while the bulk InP offers superior thermal properties for higher current density circuits. The surface morphology and crystal structure of the two M-buffers showed different relaxation mechanisms. The graded InAlAs gave a cross-hatched pattern with nearly full relaxation and very effective dislocation filtering, while the bulk InP had a uniform isotropic surface with dislocations propagating further up towards the active layers. Both types of M-buffers had atomic force microscopy root-mean-square roughness values around 2030 Å. The Hall transport properties of high electron mobility transistors (HEMTs) grown on the InAlAs M-buffer, and a baseline HEMT grown lattice matched on InP, both had room-temperature mobilities >10 000 cm2/V s, while the M-HEMT on the InP M-buffer showed a decrease to 9000 cm2/V  s. Similarly, the dc parameters of a double heterojunction bipolar transistor (DHBT) grown on the InAlAs M-buffer were much closer to the baseline heterojunction bipolar transistor than a DHBT grown on the InP M-buffer. A high breakdown voltage of 11.3 V was achieved on an M-DHBT with the InAlAs M-buffer. We speculate that the degradation in device characteristics on the InP M-buffer was related to the incomplete dislocation filtering.

Abstract: Changes in the size distribution and composition of bimetallic Pd-Au nanoclusters have been observed after hydrogen exposure. This effect is caused by hydrogen-induced Ostwald ripening whereby the hydrogen reduces the binding energy of the cluster atoms leading to their detachment from the cluster. The composition changes due to a difference in mobility of the detached palladium and gold atoms on the surface. Fast palladium atoms contribute to the formation of larger nanoclusters, while the slower gold atoms are confined to the smaller nanoclusters. These transformations in the Pd-Au nanocluster size and composition set a limit for chemical reactions in which such nanoclusters are involved together with hydrogen.

Abstract: Currently, ultrathin colloidal CdSe semiconductor nanoplatelets (NPLs) with a uniform thickness that is controllable up to the atomic scale can be prepared. The optical properties of these 2D semiconductor systems are the subject of extensive research. Here, we reveal their natural morphology and atomic arrangement. Using cryo-TEM (cryo-transmission electron microscopy), we show that the shape of rectangular NPLs in solution resembles a helix. Fast incorporation of these NPLs in silica preserves and immobilizes their helical shape, which allowed us to perform an in-depth study by high angle annular dark field scanning transmission electron microscopy (HAADF-STEM). Electron tomography measurements confirm and detail the helical shape of these systems. Additionally, high-resolution HAADF-STEM shows the thickness of the NPLs on the atomic scale and furthermore that these are consistently folded along a ?110? direction. The presence of a silica shell on both the top and bottom surfaces shows that Cd atoms must be accessible for silica precursor (and ligand) molecules on both sides.