Abstract: The phase problem can be considered as one of the cornerstones of quantum mechanics intimately connected to the detection process and the uncertainty relation. The latter impose fundamental limits on the manifold phase reconstruction schemes invented to date, in particular, at small magnitudes of the quantum wave. Here, we show that a rigorous solution of the transport of intensity reconstruction (TIE) scheme in terms of a linear elliptic partial differential equation for the phase provides reconstructions even in the presence of wave zeros if particular boundary conditions are given. We furthermore discuss how partial coherence hampers phase reconstruction and show that a modified version of the TIE reconstructs the curl-free current density at arbitrary (in)coherence. Our results open the way for TIE-based phase retrieval of arbitrary wave fields, eventually containing zeros such as phase vortices.

Abstract: In this study, the uptake and elimination of ZnO and CuO nanoparticles in Daphnia magna was tested. Daphnids were exposed during 10 days to sublethal concentrations of ZnO and CuO nanoparticles and corresponding metal salts (ZnCl2 and CuCl2.2H2O), after which they were transferred to unexposed medium for another 10 days. At different times during the exposure and none-exposure, the total and internal zinc or copper concentration of the daphnids was determined and the nanoparticles were localized in the organism using electron microscopy. The exposure concentrations were characterized by measuring the dissolved, nanoparticle and aggregated fraction in the medium. The results showed that the ZnO nanoparticles quickly dissolved after addition to the medium. Contrarily, only a small fraction (corresponding to the dissolved metal salt) of the CuO nanoparticles dissolved, while most of these nanoparticles formed large aggregates. Despite an initial increase in zinc and copper concentration during the first 48 hour to 5 day exposure, the body concentration reached a plateau level that was comparable for the ZnO nanoparticles and ZnCl2, but much higher for the CuO nanoparticles (with visible aggregates accumulating in the gut) than CuCl2.2H2O. During the remaining exposure and subsequent none-exposure phase, the zinc and copper concentration decreased fast to concentrations comparable with the unexposed daphnids. The results indicate that D. magna can regulate its internal zinc and copper concentration after exposure to ZnO and CuO nanoparticles, similar as after exposure to metal salts. The combined dissolution, accumulation and toxicity results confirm that the toxicity of ZnO and CuO nanoparticles is caused by the dissolved fraction. Keywords nano; zinc; copper; dissolution; aggregation; electron microscopy

Abstract: In this work, Yttria-stabilized zirconia (YSZ) thin films were deposited using dual reactive magnetron sputtering. By varying the deposition conditions, the film morphology and texture of the thin films are tuned and biaxial alignment is obtained. Studying the crystallographic and microstructural properties of the YSZ thin films, a tilted columnar growth was identified. This tilt is shown to be dependent on the compositional gradient of the sample. The variation of composition within a single YSZ column measured via STEM-EDX is demonstrated to be equal to the macroscopic variation on a full YSZ sample when deposited under the same deposition parameters. A simple stress model was developed to predict the tilt of the growing columns. The results indicate that this model not only determines the column bending of the growing film but also confirms that a macroscopic approach is sufficient to determine the compositional gradient in a single column of the YSZ thin films. (C) 2013 Elsevier B.V. All rights reserved.

Abstract: Ag/ZnO and Au/CuxO (x = 1, 2) nanocomposites supported on Si(100) and polycrystalline Al2O3 were synthesised by hybrid approaches, combining chemical vapor deposition (either thermal or plasma-assisted) of host oxide matrices and subsequent radio frequency-sputtering of guest metal particles. The influence of the adopted synthetic parameters on the nanocomposite morphological and compositional features was investigated by field emission-scanning electron microscopy, transmission electron microscopy, energy dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy. Results confirm the synthesis of ZnO and CuxO nanoarchitectures, characterized by a tailored morphology and an intimate metal/oxide contact. A careful control of the processing conditions enabled a fine tuning of the mutual constituent distribution, opening thus attractive perspectives for the engineering of advanced nanomaterials.

Abstract: Tailoring the properties of oxide-based nanocomposites is of great importance for a wide range of materials relevant for energy technology. YBa2Cu3O7−δ (YBCO) superconducting thin films containing nanosized BaHfO3 (BHO) particles yield a significant improvement of the magnetic flux pinning properties and a reduced anisotropy of the critical current density. These films were prepared by chemical solution deposition (CSD) on (100) SrTiO3 (STO) substrates yielding critical current densities up to 3.6 MA cm−2 at 77 K and self-field. Transport in-field J c measurements demonstrated a high pinning force maximum of around 6 GN/m3 for a sample annealed at T = 760 °C that has a doping of 12 mol% of BHO. This sample was investigated by scanning transmission electron microscopy (STEM) in combination with electron energy-loss spectroscopy (EELS) yielding strain and spectral maps. Spherical BHO nanoparticles of 15 nm in size were found in the matrix, whereas the particles at the interface were flat. A 2 nm diffusion layer containing Ti was found at the YBCO (BHO)/STO interface. Local lattice deformation mapping at the atomic scale revealed crystal defects induced by the presence of both sorts of BHO nanoparticles, which can act as pinning centers for magnetic flux lines. Two types of local lattice defects were identified and imaged: (i) misfit edge dislocations and (ii) Ba-Cu-Cu-Ba stacking faults (Y-248 intergrowths). The local electronic structure and charge transfer were probed by high energy resolution monochromated electron energy-loss spectroscopy. This technique made it possible to distinguish superconducting from non-superconducting areas in nanocomposite samples with atomic resolution in real space, allowing the identification of local pinning sites on the order of the coherence length of YBCO (~1.5 nm) and the determination of 0.25 nm dislocation cores.

Abstract: We present the ASTRA Toolbox as an open platform for 3D image reconstruction in tomography. Most of the software tools that are currently used in electron tomography offer limited flexibility with respect to the geometrical parameters of the acquisition model and the algorithms used for reconstruction. The ASTRA Toolbox provides an extensive set of fast and flexible building blocks that can be used to develop advanced reconstruction algorithms, effectively removing these limitations. We demonstrate this flexibility, the resulting reconstruction quality, and the computational efficiency of this toolbox by a series of experiments, based on experimental dual-axis tilt series.

Abstract: Directed assembly of gold nanorods through the use of dithiolated molecular linkers is one of the most efficient methodologies for the morphologically controlled tip-to-tip assembly of this type of anisotropic nanocrystals. However, in a direct analogy to molecular polymerization synthesis, this process is characterized by difficulties in chain-growth control over nanoparticle oligomers. In particular, it is nearly impossible to favor the formation of one type of oligomer, making the methodology hard to use for actual applications in nanoplasmonics. We propose here a light-controlled synthetic procedure that allows obtaining selected plasmonic oligomers in high yield and with reaction times in the scale of minutes by irradiation with low fluence near-infrared (NIR) femtosecond laser pulses. Selective inhibition of the formation of gold nanorod n-mers (trimers) with a longitudinal localized surface plasmon in resonance with a 800 nm Ti:sapphire laser, allowed efficient trapping of the (n – 1)-mers (dimers) by hot spot mediated photothermal decomposition of the interparticle molecular linkers. Laser irradiation at higher energies produced near-field enhancement at the interparticle gaps, which is large enough to melt gold nanorod tips, offering a new pathway toward tip-to-tip welding of gold nanorod oligomers with a plasmonic response at the NIR. Thorough optical and electron microscopy characterization indicates that plasmonic oligomers can be selectively trapped and welded, which has been analyzed in terms of a model that predicts with reasonable accuracy the relative concentrations of the main plasmonic species.

Abstract: Nanoparticle assemblies can be investigated in 3 dimensions using electron tomography. However, it is not straightforward to obtain quantitative information such as the number of particles or their relative position. This becomes particularly difficult when the number of particles increases. We propose a novel approach in which prior information on the shape of the individual particles is exploited. It improves the quality of the reconstruction of these complex assemblies significantly. Moreover, this quantitative Sparse Sphere Reconstruction approach yields directly the number of particles and their position as an output of the reconstruction technique, enabling a detailed 3D analysis of assemblies with as many as 10 000 particles. The approach can also be used to reconstruct objects based on a very limited number of projections, which opens up possibilities to investigate beam sensitive assemblies where previous reconstructions with the available electron tomography techniques failed.

Abstract: A new application which focuses on an artificial sphincter fabricated by Ni-Ti SMAs for human implantation is under investigation by applying the all-round shape memory effect with precise control of the phase transformation temperatures. In this study, a Ni51at.%-Ti alloy was fabricated by arc melting with fast solidification, followed by a proper strained aging which induces the two way shape memory effect needed for this particular application. Differential scanning calorimetry was used to investigate the thermal behavior and transmission electron microscopy was used for studying the microstructure of the alloys. With the latter the novel technique of automated crystal orientation microscopy is used and optimized to obtain phase and orientation mapping of the various structures.

Abstract: We present a time-dependent parametric model for reactive HiPIMS deposition of films. Specific features of HiPIMS discharges and a possible increase in the density of the reactive gas in front of the reactive gas inlets placed between the target and the substrate are considered in the model. The model makes it possible to calculate the compound fractions in two target layers and in one substrate layer, and the deposition rate of films at fixed partial pressures of the reactive and inert gas. A simplified relation for the deposition rate of films prepared using a reactive HiPIMS is presented. We used the model to simulate controlled reactive HiPIMS depositions of stoichiometric ZrO2 films, which were recently carried out in our laboratories with two different configurations of the O2 inlets in front of the sputtered target. The repetition frequency was 500 Hz at the deposition-averaged target power densities of 5 Wcm−2 and 50 Wcm−2 with a pulse-averaged target power density up to 2 kWcm−2. The pulse durations were 50 μs and 200 μs. Our model calculations show that the to-substrate O2 inlet provides systematically lower compound fractions in the target surface layer and higher compound fractions in the substrate surface layer, compared with the to-target O2 inlet. The low compound fractions in the target surface layer (being approximately 10% at the depositionaveraged target power density of 50 Wcm−2 and the pulse duration of 200 μs) result in high deposition rates of the films produced, which are in agreement with experimental values.

Abstract: Nanoscale materials are one of the few engineering materials that can be grown from the bottom up in a controlled manner. Here, the effects of nanostructure and nanoscale conformal coating on the mechanical behavior of vertically aligned carbon nanotube (CNT) arrays through experiments and simulation are systematically investigated. A modeling approach is developed and used to quantify the compressive strength and modulus of the CNT array under large deformation. The model accounts for the porous
nanostructure, which contains multiple CNTs with random waviness, van der Waals interactions, fracture strain, contacts, and frictional forces. CNT array micropillars are grown and their porous nanostructure is controlled by the infi ltration and deposition of thin conformal coatings using chemical vapor deposition. Flat-punch nanoindentation experiments reveal signifi cant changes in material properties as a function of coating thickness. The simulations explain the experimental results and show the novel failure transition regime that changes from collective CNT buckling toward structural collapse due to fracture. The compressive strength and the elastic
modulus increase exponentially as a function of the coating thickness and demonstrate a unique dependency on the CNT waviness. More interestingly, a design rule is identifi ed that predicts the optimum coating thickness for porous materials.

Abstract: The crystal structure of the K6.4Nb28.2Ta8.1O94 pseudo-tetragonal tungsten bronze-type oxide was determined using a combination of X-ray powder diffraction, neutron diffraction and transmission electron microscopy techniques, including electron diffraction, high angle annular dark field scanning transmission electron microscopy (HAADF-STEM), annular bright field STEM (ABF-STEM) and energy-dispersive X-ray compositional mapping (STEM-EDX). The compound crystallizes in the space group Pbam with unit cell parameters a = 37.468(9) A, b = 12.493(3) A, c = 3.95333(15) A. The structure consists of corner sharing (Nb,Ta)O6 octahedra forming trigonal, tetragonal and pentagonal tunnels. All tetragonal tunnels are occupied by K(+) ions, while 1/3 of the pentagonal tunnels are preferentially occupied by Nb(5+)/Ta(5+) and 2/3 are occupied by K(+) in a regular pattern. A fractional substitution of K(+) in the pentagonal tunnels by Nb(5+)/Ta(5+) is suggested by the analysis of the HAADF-STEM images. In contrast to similar structures, such as K2Nb8O21, also parts of the trigonal tunnels are fractionally occupied by K(+) cations.

Abstract: Hydrogen plays an essential role during the in situ assembly of tailored catalytic materials, and serves as key ingredient in multifarious chemical reactions promoted by these catalysts. Despite intensive debate for several decades, the existence and nature of hydrogen-involved mechanisms – such as hydrogen-spillover, surface migration – have not been unambiguously proven and elucidated up to date. Here, Pt-Ga alloy formation is used as a probe reaction to study the behavior and atomic transport of H and Ga, starting from Pt nanoparticles on hydrotalcite-derived Mg(Ga)(Al)Ox supports. In situ XANES spectroscopy, time-resolved TAP kinetic experiments, HAADF-STEM imaging and EDX mapping are combined to probe Pt, Ga and H in a series of H2 reduction experiments up to 650 degrees C. Mg(Ga)(Al)Ox by itself dissociates hydrogen, but these dissociated hydrogen species do not induce significant reduction of Ga3+ cations in the support. Only in the presence of Pt, partial reduction of Ga3+ into Gadelta+ is observed, suggesting that different reaction mechanisms dominate for Pt- and Mg(Ga)(Al)Ox-dissociated hydrogen species. This partial reduction of Ga3+ is made possible by Pt-dissociated H species which spillover onto non-reducible Mg(Al)Ox or partially reducible Mg(Ga)(Al)Ox and undergo long-range transport over the support surface. Moderately mobile Gadelta+Ox migrates towards Pt clusters, where Gadelta+ is only fully reduced to Ga0 on condition of immediate stabilization inside Pt-Ga alloyed nanoparticles.

Abstract: Lithium-ion (Li-ion) batteries that rely on cationic redox reactions are the primary energy source for portable electronics. One pathway toward greater energy density is through the use of Li-rich layered oxides. The capacity of this class of materials (>270 milliampere hours per gram) has been shown to be nested in anionic redox reactions, which are thought to form peroxo-like species. However, the oxygen-oxygen (O-O) bonding pattern has not been observed in previous studies, nor has there been a satisfactory explanation for the irreversible changes that occur during first delithiation. By using Li2IrO3 as a model compound, we visualize the O-O dimers via transmission electron microscopy and neutron diffraction. Our findings establish the fundamental relation between the anionic redox process and the evolution of the O-O bonding in layered oxides.

Abstract: Janus gold nanoparticles are of high interest because they allow directed self-assembly and display plasmonic properties. We succeeded in coating gold nanoparticles with two different polymers that form a Janus shell. The spontaneous segregation of two immiscible polymers at the surface of the nanoparticles was verified by NOESY NMR and most importantly by electron microscopy analysis in two and three dimensions. The Janus structure is additionally shown to affect the aggregation behavior of the nanoparticles.