We present atomic-scale, video-rate environmental transmission electron microscopy and in situ time-resolved X-ray photoelectron spectroscopy of surface-bound catalytic chemical vapor deposition of single-walled carbon nanotubes and nanofibers. We observe that transition metal catalyst nanoparticles on SiOx support show crystalline lattice fringe contrast and high deformability before and during nanotube formation. A single-walled carbon nanotube nucleates by lift-off of a carbon cap. Cap stabilization and nanotube growth involve the dynamic reshaping of the catalyst nanocrystal itself. For a carbon nanofiber, the graphene layer stacking is determined by the successive elongation and contraction of the catalyst nanoparticle at its tip.

The growth of vertically aligned carbon nanotubes using a direct current plasma enhanced chemical vapor deposition system is reported. The growth properties are studied as a function of the Ni catalyst layer thickness, bias voltage, deposition temperature, C 2 H 2 :NH 3 ratio, and pressure. It was found that the diameter, growth rate, and areal density of the nanotubes are controlled by the initial thickness of the catalyst layer. The alignment of the nanotubes depends on the electric field. Our results indicate that the growth occurs by diffusion of carbon through the Ni catalyst particle, which rides on the top of the growing tube.

We report the first successful application of an ordered bicontinuous gyroid semiconducting network in a hybrid bulk heterojunction solar cell. The freestanding gyroid network is fabricated by electrochemical deposition into the 10 nm wide voided channels of a self-assembled, selectively degradable block copolymer film. The highly ordered pore structure is ideal for uniform infiltration of an organic hole transporting material, and solid-state dye-sensitized solar cells only 400 nm thick exhibit up to 1.7% power conversion efficiency. This patterning technique can be readily extended to other promising heterojunction systems and is a major step toward realizing the full potential of self-assembly in the next generation of device technologies.

The remarkable optical properties of metal nanoparticles are governed by the excitation of localized surface plasmon resonances (LSPRs). The sensitivity of each LSPR mode, whose spatial distribution and resonant energy depend on the nanoparticle structure, composition and environment, has given rise to many potential photonic, optoelectronic, catalytic, photovoltaic, and gas- and bio-sensing applications. However, the precise interplay between the three-dimensional (3D) nanoparticle structure and the LSPRs is not always fully understood and a spectrally sensitive 3D imaging technique is needed to visualize the excitation on the nanometre scale. Here we show that 3D images related to LSPRs of an individual silver nanocube can be reconstructed through the application of electron energy-loss spectrum imaging, mapping the excitation across a range of orientations, with a novel combination of non-negative matrix factorization, compressed sensing and electron tomography. Our results extend the idea of substrate-mediated hybridization of dipolar and quadrupolar modes predicted by theory, simulations, and electron and optical spectroscopy, and provide experimental evidence of higher-energy mode hybridization. This work represents an advance both in the understanding of the optical response of noble-metal nanoparticles and in the probing, analysis and visualization of LSPRs.

Nano-structured silicon anodes are attractive alternatives to graphitic carbons in rechargeable Li-ion batteries, owing to their extremely high capacities. Despite their advantages, numerous issues remain to be addressed, the most basic being to understand the complex kinetics and thermodynamics that control the reactions and structural rearrangements. Elucidating this necessitates real-time in situ metrologies, which are highly challenging, if the whole electrode structure is studied at an atomistic level for multiple cycles under realistic cycling conditions. Here we report that Si nanowires grown on a conducting carbon-fibre support provide a robust model battery system that can be studied by 7 Li in situ NMR spectroscopy. The method allows the (de)alloying reactions of the amorphous silicides to be followed in the 2nd cycle and beyond. In combination with density-functional theory calculations, the results provide insight into the amorphous and amorphous-to-crystalline lithium-silicide transformations, particularly those at low voltages, which are highly relevant to practical cycling strategies.

No abstract

Hybrid glasses connect the emerging field of metal-organic frameworks (MOFs) with the glass formation, amorphization and melting processes of these chemically versatile systems. Though inorganic zeolites collapse around the glass transition and melt at higher temperatures, the relationship between amorphization and melting has so far not been investigated. Here we show how heating MOFs of zeolitic topology first results in a low density ‘perfect' glass, similar to those formed in ice, silicon and disaccharides. This order–order transition leads to a super-strong liquid of low fragility that dynamically controls collapse, before a subsequent order–disorder transition, which creates a more fragile high-density liquid. After crystallization to a dense phase, which can be remelted, subsequent quenching results in a bulk glass, virtually identical to the high-density phase. We provide evidence that the wide-ranging melting temperatures of zeolitic MOFs are related to their network topologies and opens up the possibility of ‘melt-casting' MOF glasses.

Improving the solar light harvesting and photon-to-electron conversion efficiency for hybrid, organic-inorganic photovoltaics are critical challenges. Titania based solid-state hybrid solar cells are moderately efficient at converting visible photons to electrons, but major electrical losses still remain. A material based paradigm shift is required to dramatically enhance the performance of these devices. Here, we present an investigation into solid-state dye-sensitized solar cells (SDSCs) incorporating a molecular hole-transporter and mesoporous tin oxide electrodes, in place of titania usually employed. We investigate the influence of treating the surface of the SnO(2) with different oxides and find that MgO "passivated" SnO(2) electrodes demonstrate an unprecedented absorbed photon-to-electron conversion efficiency of near unity across a broad spectral range. A dual surface treatment of TiO(2) followed by MgO enables tuning of the solar cell photovoltage, fill factor, and efficiency with visible light absorbing cells delivering 3% solar-to-electrical full sun power conversion efficiency.