Neil P. Young

Three-dimensional atomic-scale structure of size-selected gold nanoclusters

An unambiguous determination of the three-dimensional structure of nanoparticles is challenging. Electron tomography requires a series of images taken for many different specimen orientations. This approach is ideal for stable and stationary structures. But ultrasmall nanoparticles are intrinsically structurally unstable and may interact with the incident electron beam, constraining the electron beam density that can be used and the duration of the observation. Here we use aberration-corrected scanning transmission electron microscopy, coupled with simple imaging simulation, to determine with atomic resolution the size, three-dimensional shape, orientation and atomic arrangement of size-selected gold nanoclusters that are preformed in the gas phase and soft-landed on an amorphous carbon substrate. The structures of gold nanoclusters containing 309±6 atoms can be identified with either Ino-decahedral, cuboctahedral or icosahedral geometries. Comparison with theoretical modelling of the system suggests that the structures are consistent with energetic considerations. The discovery that nanoscale gold particles function as active and selective catalysts for a variety of important chemical reactions has provoked much research interest in recent years. We believe that the detailed structure information we provide will help to unravel the role of these nanoclusters in size- and structure-specific catalytic reactions. We note that the technique will be of use in investigations of other supported ultrasmall metal cluster systems.

Nanogold: A Quantitative Phase Map

The development of the next generation of nanotechnologies requires precise control of the size, shape, and structure of individual components in a variety of chemical and engineering environments. This includes synthesis, storage, operational environments and, since these products will ultimately be discarded, their interaction with natural ecosystems. Much of the important information that determines these properties is contained within nanoscale phase diagrams, but quantitative phase maps that include surface effects and critical diameter (along with temperature and pressure) remain elusive. Here we present the first quantitative equilibrium phase map for gold nanoparticles together with experimental verification, based on relativistic ab initio thermodynamics and in situ high-resolution electron microscopy at elevated temperatures.

Atomic Imaging of Phase Transitions and Morphology Transformations in Nanocrystals

A newly developed SiN microhotplate allows specimens to be studied at temperatures up to 1000 K at a resolution of 100 picometer. Aberration-corrected transmission electron microscopy has become a commonplace tool to investigate stable crystals; however, imaging transient nanocrystals is much more demanding. Morphological transformations in gold nanoparticles and layer-by-layer sublimation of PbSe nanocrystals is imaged with atomic resolution.

Resolving strain in carbon nanotubes at the atomic level

Details of how atomic structure responds to strain are essential for building a deeper picture of mechanics in nanomaterials. Here, we provide the first experimental evidence of atomic displacements associated with shear strain in single-walled carbon nanotubes (SWNTs) by direct imaging using aberration-corrected transmission electron microscopy. The atomic structure of a zig-zag SWNT is resolved with unprecedented accuracy and the strain induced by bending is mapped in two dimensions. We show the existence of a dominant non-uniform shear strain that varies along the SWNT axis. The direction of shear is opposite to what would be expected from a simple force applied perpendicular to the axis to produce the bending. This highlights the complex atomistic strain behaviour of beam-bending mechanics in highly anisotropic SWNTs.

Characterization and Comparison of Mesoporous Silica Particles for Optimized Drug Delivery

In this study we have investigated the suitability of a number of different mesoporous silica nanoparticle structures for carrying a drug cargo. We have fully characterized the nanoparticles in terms of their physical parameters; size, surface area, internal pore size and structure. These data are all required if we are to make an informed judgement on the suitability of the structure for drug delivery in vivo. With these parameters in mind, we investigated the loading/unloading profile of a model therapeutic into the pore structure of the nanoparticles. We demonstrate that the release can be controlled by capping the pores on the nanoparticles to achieve temporal control of the unloading. We have also examined the rate and mechanism of the degradation of the nanoparticles over an extended period of time. The eventual dissolution of the nanoparticles after cargo release is a desirable property for a drug delivery system.

Transformations of gold nanoparticles investigated using variable temperature high-resolution transmission electron microscopy.

Recently designed advanced in-situ specimen holders for transmission electron microscopy (TEM) have been used in studies of gold nanoparticles. We report results of variable temperature TEM experiments in which structural transformations have been correlated with specimen temperature, allowing general trends to be identified. Transformation to a decahedral morphology for particles in the size range 5-12nm was observed for the majority of particles regardless of their initial structure. Following in-situ annealing, decahedra were found to be stable at room temperature, confirming this as the equilibrium morphology, in agreement with recently calculated phase diagrams. Other transitions at low temperature in addition to surface roughening have also been observed and correlated with the same nanoscale phase diagram. Investigations of gold particles at high temperature have revealed evidence for co-existing solid and liquid phases. Overall, these results are important in a more precise understanding of the structure and action of catalytic gold nanoparticles and in the experimental verification of theoretical calculations.

Spray processing of TiO2 nanoparticle/ionomer coatings on carbon nanotube scaffolds for solid-state supercapacitors

A one-step scalable spray technique was used to fabricate solid-state supercapacitors with multi-wall carbon nanotube/TiO2-nanoparticle/ionomer hybrid electrodes. The 3D electrode nanostructure was designed for mobile H+ ion generation and fast electron-ion dual conduction, achieving an unusual and highly attractive balance of energy (31.8 W h kg−1) and power (14.9 kW kg−1) densities at 1 A g−1 that are amongst highest reported for solid-state supercapacitors.

The development of a 200 kV monochromated field emission electron source

We report the development of a monochromator for an intermediate-voltage aberration-corrected electron microscope suitable for operation in both STEM and TEM imaging modes. The monochromator consists of two Wien filters with a variable energy selecting slit located between them and is located prior to the accelerator. The second filter cancels the energy dispersion produced by the first filter and after energy selection forms a round monochromated, achromatic probe at the specimen plane. The ultimate achievable energy resolution has been measured as 36 meV at 200 kV and 26 meV at 80 kV. High-resolution Annular Dark Field STEM images recorded using a monochromated probe resolve Si-Si spacings of 135.8 pm using energy spreads of 218 meV at 200 kV and 217 meV at 80 kV respectively. In TEM mode an improvement in non-linear spatial resolution to 64 pm due to the reduction in the effects of partial temporal coherence has been demonstrated using broad beam illumination with an energy spread of 134 meV at 200 kV.

The Electrochemical Characterization of Single Core–Shell Nanoparticles

We report the direct solution-phase characterization of individual gold-core silver-shell nanoparticles through an electrochemical means, with selectivity achieved between the core and shell components based on their different redox activities. The electrochemically determined core-shell sizes are in excellent agreement with electron microscopy-based results, successfully demonstrating the electrochemical characterization of individual core-shell nanoparticles.

Solid-state supercapacitors with rationally designed heterogeneous electrodes fabricated by large area spray processing for wearable energy storage applications

Supercapacitors are in demand for short-term electrical charge and discharge applications. Unlike conventional supercapacitors, solid-state versions have no liquid electrolyte and do not require robust, rigid packaging for containment. Consequently they can be thinner, lighter and more flexible. However, solid-state supercapacitors suffer from lower power density and where new materials have been developed to improve performance, there remains a gap between promising laboratory results that usually require nano-structured materials and fine-scale processing approaches, and current manufacturing technology that operates at large scale. We demonstrate a new, scalable capability to produce discrete, multi-layered electrodes with a different material and/or morphology in each layer, and where each layer plays a different, critical role in enhancing the dynamics of charge/discharge. This layered structure allows efficient utilisation of each material and enables conservative use of hard-to-obtain materials. The layered electrode shows amongst the highest combinations of energy and power densities for solid-state supercapacitors. Our functional design and spray manufacturing approach to heterogeneous electrodes provide a new way forward for improved energy storage devices.