'Green barriers' for air pollutant capture: Leaf micromorphology as a mechanism to explain plants capacity to capture particulate matter.

Finding ways to mitigate atmospheric particulate matter (PM) is one of the key steps towards fighting air pollution and protecting people's health. The use of green infrastructure is one option that could help improving urban air quality and promoting more sustainable cities. Detailed knowledge of how plants capture particulate matter can support plant selection for this purpose. Previous studies have primarily focused on 2D techniques to assess the micromorphology of plant leaves. Here, 3D optical profilometry and SEM imaging (2D) are used to quantify leaf roughness and other micromorphological leaf traits of three contrasting plant species (Hedera helix 'Woerner', Thuja occidentalis 'Smaragd', and Phyllostachys nigra) located within a mixed-species green barrier. These techniques have allowed us to identify the relative distribution of adhered atmospheric PM with respect to the surface topography of leaves, with high spatial resolution. Leaf surface roughness did not show a direct relationship with PM deposition; however, the descriptors width, depth and frequency of the grooves are important to explain PM capture by the leaves. Additionally, the presence of wax on leaves was relevant for PM adherence. All species captured PM, with their overall PM capture efficiency ranked from highest to lowest as follows: Thuja occidentalis > Hedera helix > Phyllostachys nigra. All green barrier species contributed to air quality improvement, through PM capture, regardless of their location within the barrier. Having multiple species in a green barrier is beneficial due to the diverse range of leaf micromorphologies present, thus offering different mechanisms for particulate matter capture.

Visualization and Chemical Characterization of the Cathode Electrolyte Interphase Using He-Ion Microscopy and In Situ Time-of-Flight Secondary Ion Mass Spectrometry.

Unstable cathode electrolyte interphase (CEI) formation increases degradation in high voltage Li-ion battery materials. Few techniques couple characterization of nano-scale CEI layers on the macroscale with in situ chemical characterization, and thus, information on how the underlying microstructure affects CEI formation is lost. Here, the process of CEI formation in a high voltage cathode material, LiCoPO4, has been investigated for the first time using helium ion microscopy (HIM) and in situ time-of-flight (ToF) secondary ion mass spectrometry (SIMS). The combination of HIM and Ne-ion ToF-SIMS has been used to correlate the cycle-dependent morphology of the CEI layer on LiCoPO4 with a local cathode microstructure, including position, thickness, and chemistry. HIM imaging identified partial dissolution of the CEI layer on discharge resulting in in-homogenous CEI coverage on larger LiCoPO4 agglomerates. Ne-ion ToF-SIMS characterization identified oxyfluorophosphates from HF attack by the electrolyte and a Li-rich surface region. Variable thickness of the CEI layer coupled with inactive Li on the surface of LiCoPO4 electrodes contributes to severe degradation over the course of 10 cycles. The HIM-SIMS technique has potential to further investigate the effect of microstructures on CEI formation in cathode materials or solid electrolyte interphase formation in anodes, thus aiding future electrode development.

Giant Radiolytic Dissolution Rates of Aqueous Ceria Observed in Situ by Liquid-Cell TEM.

The dynamics of cerium oxide nanoparticle aqueous corrosion are revealed in situ. We use innovative liquid-cell transmission electron microscopy (TEM) combined with deliberate high-intensity electron-beam irradiation of nanoparticle suspensions. This enables life video-recording of materials reactions in liquid, with nm resolution. We introduce image quantification to measure detailed rates of dissolution as a function of time and particle size to be compared with literature data. Giant dissolution rates, exceeding any previous reports for chemical dissolution rates at room temperature by many orders of magnitude, are discovered. The reasons for this accelerated dissolution are outlined, including the importance of the radiolysis of water preceding the ceria attack. Electron-water interaction generates radicals, ions, and hydrated electrons, which assist in hydration and reductive dissolution of oxide minerals. The presented methodology has the potential to become a novel accelerated testing procedure to compare multiple nanoscale materials for relative aqueous durability. The ceria-water system is of crucial importance for the fields of catalysis, abrasive polishing, environmental remediation, and as simulant for actinide oxide behaviour in contact with liquid for nuclear engineering.

Mechanical properties of mesoporous ceria nanoarchitectures.

Architectural constructs are engineered to impart desirable mechanical properties facilitating bridges spanning a thousand meters and buildings nearly 1 km in height. However, do the same 'engineering-rules' translate to the nanoscale, where the architectural features are less than 0.0001 mm in size? Here, we calculate the mechanical properties of a porous ceramic functional material, ceria, as a function of its nanoarchitecture using molecular dynamics simulation and predict its yield strength to be almost two orders of magnitude higher than the parent bulk material. In particular, we generate models of nanoporous ceria with either a hexagonal or cubic array of one-dimensional pores and simulate their responses to mechanical load. We find that the mechanical properties are critically dependent upon the orientation between the crystal structure (symmetry, direction) and the pore structure (symmetry, direction).

Nanoscale characterization of 1D Sn-3.5Ag nanosolders and their application into nanowelding at the nanoscale.

One-dimensional Sn-3.5Ag alloy nanosolders have been successfully fabricated by a dc electrodeposition technique into nanoporous templates, and their soldering quality has been demonstrated in nanoscale electrical welding for the first time, which indicates that they can easily form remarkably reliable conductive joints. The electrical measurement shows that individual 1D Sn-3.5Ag nanosolders have a resistivity of 28.9 µΩ·cm. The morphology, crystal structure and chemistry of these nanosolders have been characterized at the nanoscale. It is found that individual 1D Sn-3.5Ag alloy nanosolders have a continuous morphology and smooth surface. XPS confirms the presence of tin and silver with a mass ratio of 96.54:3.46, and EDX elemental mappings clearly reveal that the Sn and Ag elements have a uniform distribution. Coveragent beam electron diffractions verify that the crystal phases of individual 1D Sn-3.5Ag alloy nanosolders consist of matrix ß-Sn and the intermetallic compound Ag3Sn. The reflow experiments reveal that the eutectic composition of the 1D Sn-Ag alloy nanowire is shifted to the Sn rich corner. This work may contribute one of the most important tin-based alloy nanosolders for future nanoscale welding techniques, which are believed to have broad applications in nanotechnology and the future nano-industry.

Nanopatterning by ion implantation through nanoporous alumina masks.

The important problem of how to generate lateral order for ion implantation patterning of substrates is solved by using a nanoporous anodic alumina membrane as a mask. Co and Pt implantation is used at two implantation doses. In order to observe the achieved implantation zones free from artifacts, electron transparent thin nitride and oxide films are used as substrates, which allows the quality of pattern transfer from the mask to the thin film to be assessed by plan-view transmission electron microscopy. Characteristic density variations of implanted elements across projected pore-regions of the mask, such as ring and dome shapes, and corresponding variation of cluster size are discussed, and therefore the method also serves as a suitable test bed for ion beam focusing studies by cylindrical or conical pores.

Characterization of worn alumina hip replacement prostheses.

Alumina hip replacement prostheses have been analyzed following in vitro simulated microseparation. The worn surfaces of the alumina acetabular cup and femoral head were investigated using scanning electron microscopy (SEM) and atomic force microscopy (AFM) which identified four different wear zones. Focused ion beam (FIB) cross-sectioning was used to section the worn surface and produce 3D reconstructions of the subsurface damage. This showed that the subsurface fracture was predominantly intergranular, with occasional intragranular fracture. Significantly, in all cases, fracture was restricted to the outer layer of grains. The wear mechanisms leading to the generation of the stripe wear region on the worn alumina hip prostheses are proposed and microseparation is believed to play a critical role.

Nanostructure and chemical characterisation of individual NiFe/Pt multilayer nanowires.

NiFe/Pt multilayer nanowires have been successfully fabricated by pulse electrodeposition into the channels of porous anodic aluminum oxide (AAO) templates, and characterized at the nanoscale. Individual nanowires have uniform structure and regular periodicity. The NiFe and Pt layers are polycrystalline, with random orientation fcc lattice structure crystallites and grain sizes 3-10 nm, and the average layer growth rate is 30 nm/s for NiFe and 4 nm/s for Pt. Nanoscale chemical analysis of individual NiFe/Pt nanowires by EDX and EELS shows that they contain alternating NiFe and Pt layers, with a small approximately 1% inclusion of Pt in the NiFe layer due to electrochemical co-deposition.

A piezoelectric goniometer inside a transmission electron microscope goniometer.

Piezoelectric nanoactuators, which can provide extremely stable and reproducible positioning, are rapidly becoming the dominant means for position control in transmission electron microscopy. Here we present a second-generation miniature goniometric nanomanipulation system, which is fully piezo-actuated with ultrafine step size for translation and rotation, programmable, and can be fitted inside a hollowed standard specimen holder for a transmission electron microscope (TEM). The movement range of this miniaturized drive is composed of seven degrees of freedom: three fine translational movements (X, Y, and Z axes), three coarse translational movements along all three axes, and one rotational movement around the X-axis with an integrated angular sensor providing absolute rotation feedback. The new piezoelectric system independently operates as a goniometer inside the TEM goniometer. In situ experiments, such as tomographic tilt without missing wedge and differential tilt between two specimens, are demonstrated.

Mechanical properties of ceria nanorods and nanochains; the effect of dislocations, grain-boundaries and oriented attachment.

We predict that the presence of extended defects can reduce the mechanical strength of a ceria nanorod by 70%. Conversely, the pristine material can deform near its theoretical strength limit. Specifically, atomistic models of ceria nanorods have been generated with full microstructure, including: growth direction, morphology, surface roughening (steps, edges, corners), point defects, dislocations and grain-boundaries. The models were then used to calculate the mechanical strength as a function of microstructure. Our simulations reveal that the compressive yield strengths of ceria nanorods, ca. 10 nm in diameter and without extended defects, are 46 and 36 GPa for rods oriented along [211] and [110] respectively, which represents almost 10% of the bulk elastic modulus and are associated with yield strains of about 0.09. Tensile yield strengths were calculated to be about 50% lower with associated yield strains of about 0.06. For both nanorods, plastic deformation was found to proceed via slip in the {001} plane with direction <110>--a primary slip system for crystals with the fluorite structure. Dislocation evolution for the nanorod oriented along [110] was nucleated via a cerium vacancy present at the surface. A nanorod oriented along [321] and comprising twin-grain boundaries with {111} interfacial planes was calculated to have a yield strength of about 10 GPa (compression and tension) with the grain boundary providing the vehicle for plastic deformation, which slipped in the plane of the grain boundary, with an associated <110> slip direction. We also predict, using a combination of atomistic simulation and DFT, that rutile-structured ceria is feasible when the crystal is placed under tension. The mechanical properties of nanochains, comprising individual ceria nanoparticles with oriented attachment and generated using simulated self-assembly, were found to be similar to those of the nanorod with grain-boundary. Images of the atom positions during tension and compression are shown, together with animations, revealing the mechanisms underpinning plastic deformation. For the nanochain, our simulations help further our understanding of how a crystallising ice front can be used to 'sculpt' ceria nanoparticles into nanorods via oriented attachment.

Electrical nanowelding and bottom-up nano-construction together using nanoscale solder.

A new bottom-up nanowelding technique enabling the welding of complex 3D nanoarchitectures assembled from individual building blocks using nanovolumes of metal solder is reported in this work. The building blocks of gold nanowires, (Co72Pt28/Pt)n multilayer nanowires, and nanosolder Sn99Au1 alloy nanowires were successfully fabricated by a template technique. Individual metallic nanowires dispersed on Si/SiO2(100 nm) wafers were manipulated and assembled together. Conductive nanostructures were then welded together by the new electrical nanowelding technique using nanovolumes of similar or dissimilar nanosolder. At the weld sites, nanoscale volumes of a chosen metal are deposited using nanosolder of a sacrificial nanowire, which ensures that the nanoobjects to be bonded retain their structural integrity. The whole nanowelding process is clean, controllable and reliable, and ensures both mechanically strong and electrically conductive contacts. The quality check of nanoweld achieve a resistance as low as 20 omega by using Sn99Au1 alloy solder. This technique should provide a promising way to conquer the challenge of the integration obstacle for bottom-up nanotechnology.

The effect of oxide overlayers on secondary electron dopant mapping.

The International Technology Roadmap for Semiconductors ranks dopant profiling as one of the most difficult challenges for analysis of semiconductors. Dopant mapping in the scanning electron microscope (SEM) has the potential to provide a solution. This technique has not yet found widespread application, however, mainly due to the lack of a comprehensive theoretical model, uncertain quantification, and its inability to differentiate doping levels in n-type silicon. Although a Monte Carlo model was recently published that closely matched experimental data obtained in p-doped silicon to data obtained from the theoretical model, a large discrepancy between experimental data obtained for n-type silicon was found. Here we present a Monte Carlo model that provides close matches between experimental and calculated data in both n- and p-type silicon, paving the way for a widespread application of SEM dopant contrast.

Spectroscopic electron tomography.

The elemental mapping techniques in analytical transmission electron microscopy (TEM), energy filtered imaging (EFTEM) and EDX-mapping, are shown to provide new routes for tomographic reconstructions of 3D chemical maps on the nanoscale. The inelastic scattering does not only provide chemical sensitivity but also improves the linear projection relationship between mass density and image intensity, which often fails in bright field TEM of crystalline materials due to diffraction contrast. Instrumental requirements and artefact sources within the contrast formation mechanisms and within the numerical reconstruction are assessed.