Dimensionally and environmentally ultra-stable polymer composites reinforced with carbon fibres.

The quest to develop materials that enable the manufacture of dimensionally ultra-stable structures for critical-dimension components in spacecraft has led to much research over many decades and the evolution of carbon fibre reinforced polymer materials. This has resulted in structural designs that feature a near-zero coefficient of thermal expansion. However, the dimensional instabilities that result from moisture ingression and release remain the fundamental vulnerability of the matrix, which restricts many applications. Here, we address this challenge by developing a space-qualifiable physical surface barrier that blends within the mechanical properties of the composite, thus becoming part of the composite itself. The resulting enhanced composite features mechanical integrity and a strength that is superior to the underlying composite, while remaining impervious to moisture and outgassing. We demonstrate production capability for a model-sized component for the Sentinel-5 mission and demonstrate such capability for future European Space Agency (ESA) and National Aeronautics and Space Administration (NASA) programmes such as Copernicus Extension, Earth Explorer and Science Cosmic Visions.

Publisher Correction: Dimensionally and environmentally ultra-stable polymer composites reinforced with carbon fibres.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Publisher Correction: Dimensionally and environmentally ultra-stable polymer composites reinforced with carbon fibres.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Solution processable multi-channel ZnO nanowire field-effect transistors with organic gate dielectric.

The present work focuses on nanowire (NW) applications as semiconducting elements in solution processable field-effect transistors (FETs) targeting large-area low-cost electronics. We address one of the main challenges related to NW deposition and alignment by using dielectrophoresis (DEP) to select multiple ZnO nanowires with the correct length, and to attract, orientate and position them in predefined substrate locations. High-performance top-gate ZnO NW FETs are demonstrated on glass substrates with organic gate dielectric layers and surround source-drain contacts. Such devices are hybrids, in which inorganic multiple single-crystal ZnO NWs and organic gate dielectric are synergic in a single system. Current-voltage (I-V) measurements of a representative hybrid device demonstrate excellent device performance with high on/off ratio of ~10(7), steep subthreshold swing (s-s) of ~400 mV/dec and high electron mobility of ~35 cm(2) V(-1) s(-1) in N2 ambient. Stable device operation is demonstrated after 3 months of air exposure, where similar device parameters are extracted including on/off ratio of ~4 × 10(6), s-s ~500 mV/dec and field-effect mobility of ~28 cm(2) V(-1) s(-1). These results demonstrate that DEP can be used to assemble multiples of NWs from solvent formulations to enable low-temperature hybrid transistor fabrication for large-area inexpensive electronics.

Design of double-walled carbon nanotubes for biomedical applications.

Double-walled carbon nanotubes (DWNTs) prepared by catalytic chemical vapour deposition were functionalized in such a way that they were optimally designed as a nano-vector for the delivery of small interfering RNA (siRNA), which is of great interest for biomedical research and drug development. DWNTs were initially oxidized and coated with a polypeptide (Poly(Lys:Phe)), which was then conjugated to thiol-modified siRNA using a heterobifunctional cross-linker. The obtained oxDWNT-siRNA was characterized by Raman spectroscopy inside and outside a biological environment (mammalian cells). Uptake of the custom-designed nanotubes was not associated with detectable biochemical perturbations in cultured cells, but transfection of cells with DWNTs loaded with siRNA targeting the green fluorescent protein (GFP) gene, serving as a model system, as well as with therapeutic siRNA targeting the survivin gene, led to a significant gene silencing effect, and in the latter case a resulting apoptotic effect in cancer cells.

The effect of pH on the functionalization of nylon fabric with carbon nanotubes.

Single walled carbon nanotubes (SWCNTs) were dispersed in water and attached to nylon fabrics by a dip-drying procedure; scanning electron microscopy and Raman spectroscopy suggest the attachment of the SWCNTs. The electrical resistance of the functionalized fabrics is found to be pH-dependent, which is correlated with the quantity of SWCNTs dispersed in water at different values of pH. This can be further ascribed to the influence of the pK(a) of the acid (e.g., acetic acid in this study) used to tune pH. The acid may affect the dispersion of SWCNTs through two different mechanisms: (1) the free protons may protonate the amine and/or sulfonate group in the dye molecules, resulting in a variety of interactions among the dye molecules, SWCNTs and water molecules and (2) the resulting ions may increase the ionic strength of the solution, compressing the electric double layers of SWCNT colloids and thus impairing their stability. The former possibility is ruled out by data obtained using X-ray photoelectron spectroscopy, Raman spectroscopy, and ultraviolet-visible-near infrared spectroscopy; thus the latter is proposed to account for the experimental results. The colour strength of the functionalized fabrics increases with increasing pH, which is in agreement with their measured electrical properties.

Porphyrin-Nanocarbon Complexes to Control the Photodegradation of Rhodamine.

Porphyrin-nanocarbon systems were used to generate a photocatalyst for the control of rhodamine B and rhodamine 6G photodegradation. Carboxylic functionalized multi-walled carbon nanotubes (o-MWCNTs) were decorated by two different porphyrin moieties: 5-(4-aminophenyl)-10,15,20-(triphenyl)porphyrin (a-TPP) with an amine linker and 5-(4-carboxyphenyl)-10,15,20-(triphenyl)porphyrin (c-TPP) with a carboxyl linker to the o-MWCNT, respectively, with their photocatalyst performances investigated. The optical properties of the mixed nanocomposite materials were investigated to reveal the intrinsic energy levels and mechanisms of degradation. The charge-transfer states of the o-MWCNTs were directly correlated with the performance of the complexes as well as the affinity of the porphyrin moiety to the o-MWCNT anchor, thus extending our understanding of energy-transfer kinetics in porphyrin-CNT systems. Both a-TPP and c-TPP o-MWCNT complexes offered improved photocatalytic performance for both RhB and Rh6G compared to the reference o-MWCNTs and both porphyrins in isolated form. The photocatalytic performance improved with higher concentration of o-MWCNTs in the complexed sample, indicating the presence of greater numbers of -H/-OH groups necessary to more efficient photodegradation. The large presence of the -H/-OH group in the complexes was expected and was related to the functionalization of the o-MWCNTs needed for high porphyrin attachment. However, the photocatalytic efficiency was affected at higher o-MWCNT concentrations due to the decomposition of the porphyrins and changes to the size of the CNT agglomerates, thus reducing the surface area of the reactant. These findings demonstrate a system that displays solar-based degradation of rhodamine moieties that are on par, or an improvement to, state-of-the-art organic systems.

Dispersive hole transport in polymer:carbon nanotube composites.

The hole transport properties of poly(2-methoxy, 5-(2'-ethyl-hexoxy)-p-phenylene vinylene) (MEH-PPV) blended with acid oxidized multiwall carbon nanotubes (COOH-MWCNTs) were investigated in a diode configuration using the time-of-flight (TOF) photocurrent method. While the room temperature hole mobility in pure MEH-PPV films was non-dispersive with positive field dependent mobility, MEH-PPV:COOH-MWCNT blended devices exhibited dispersive transport and negative field dependent mobility. This indicates that the hole mobility in this composite is influenced by positional disorder caused by the presence of COOH-MWCNTs in the MEH-PPV matrix. These results strongly suggest that the distribution of COOH-MWCNTs optimising in the organic matrix is important for charge transport in the high mobility nanotube component to be activated, when used in hybrid material systems.

High-rate low-temperature growth of vertically aligned carbon nanotubes.

We report the low-temperature growth of vertically aligned carbon nanotubes (CNTs) at high growth rates by a photo-thermal chemical vapour deposition (PTCVD) technique using a Ti/Fe bilayer film as the catalyst. The bulk growth temperature of the substrate is as low as 370 °C and the growth rate is up to 1.3 µm min(-1), at least eight times faster than the values reported by traditional thermal CVD methods. Transmission electron microscopy observations reveal that as-grown CNTs are uniformly made of highly crystalline 5-6 graphene shells with an approximately 10 nm outer diameter and a 5-6 nm inner diameter. The low-temperature rapid growth of CNTs is strongly related to the unique top-down heating mode of PTCVD and the use of a Ti/Fe bimetallic solid solution catalyst. The present study will advance the development of CNTs as interconnects in nanoelectronics, through a CMOS-compatible low-temperature deposition method suitable for back-end-of-line processes.

Laser-assisted hydrothermal growth of size-controlled ZnO nanorods for sensing applications.

Pulsed laser irradiation is used to seed the low-temperature hydrothermal growth of ZnO nanorods. UV laser irradiation produces ZnO nanoparticles in solution that act as nucleation seeds for the subsequent hydrothermal growth of the nanorods. By systematically varying the seed density and/or the concentration of the reactants, the diameter of the nanorods can be controlled over a wide range with a narrow size distribution. The nanorods are linked into multi-pod structures, due to nucleation at a central seed, but ultrasonic processing of the solutions is shown to yield isolated nanorods. Three-dimensional networks of these multi-pod structures are fabricated by drop-casting the solutions onto inter-digitated electrodes. These devices are used to detect ethanol, water vapour and UV light exposure.

The growth of silica and silica-clad nanowires using a solid-state reaction mechanism on Ti, Ni and SiO(2) layers.

A large area compatible and solid-state process for growing silica nanowires is reported using nickel, titanium and silicon dioxide layers on silicon. The silica nanowires also contain silicon, as indicated by Raman spectroscopy. The phonon confinement model is employed to measure the diameter of the Si rich tail for our samples. The measured Raman peak shift and full width at half-maximum variation with the nanowire diameter qualitatively match with data available in the literature. We have investigated the effect of the seedbed structure on the nanowires, and the effect of using different gas conditions in the growth stages. From this, we have obtained the growth mechanism, and deduced the role of each individual substrate seedbed layer in the growth of the nanowires. We report a combined growth mechanism, where the growth is initiated by a solid-liquid-solid process, which is then followed by a vapour-liquid-solid process. We also report on the formation of two distinct structures of nanowires (type I and type II). The growth of these can be controlled by the use of titanium in the seedbed. We also observe that the diameter of the nanowires exhibits an inverse relation with the catalyst thickness.

Top-down heating for low substrate temperature synthesis of carbon nanotubes.

A top-down heating method to allow for low-temperature large area synthesis of carbon nanotubes using plasma-enhanced chemical vapour deposition is introduced in this paper. The approach utilizes top-down electromagnetic heating rather than conventional heating from a substrate heater under the electrode. A temperature gradient is created between the Ni catalyst surface and the substrate using a metal thermal control barrier layer, on which carbon nanotubes are grown as a function of the bias voltage, hydrocarbon concentrations and growth conditions. The heat during growth is provided by the plasma or energy coupling to the catalyst via top-down heating, which based on the coupled power density and the cooling of the substrate, in addition to the thermal 'barrier layer' properties will dictate the temperature of the growth surface. This unique approach of top-down heating with suitable cooling schemes, coupled with thermal barriers allows for the low substrate temperature synthesis of carbon nanotubes, scalable to large areas.

Charge transfer between acenes and PbS nanocrystals.

Organic-inorganic hybrid heterojunctions have potential as the basis for future photovoltaic devices. Herein, we report the results of investigations exploring the possibility of using pentacene and tetracene as photoelectron donors in conjunction with PbS nanocrystals (PbS-NCs). Photoinduced charge transfer was probed using external quantum efficiency measurements on acene:PbS-NC hybrid photovoltaic devices in conjunction with photoluminescence studies of the corresponding bilayer films. It is shown that photoelectron transfer from pentacene to the PbS-NCs is inefficient as compared to that between tetracene and PbS-NCs. The latter case can be rationalized in terms of the energy level alignment at the heterojunction assuming a common vacuum level. However, in the case of pentacene:PbS-NC junctions an interfacial energy level shift must be considered in order to explain the observations.

The fabrication and analysis of a PbS nanocrystal:C(60) bilayer hybrid photovoltaic system.

A near-infrared sensitive hybrid photovoltaic system between PbS nanocrystals (PbS-NCs) and C(60) is demonstrated. Up to 0.44% power conversion efficiency is obtained under AM1.5G with a short circuit current density (J(sc)) of 5 mA cm(-2) when the PbS-NC layer is treated in anhydrous methanol. The observed J(sc) is found be approximately one-third of the maximum expected from this hybrid configuration, indicating the potential for further optimization. Crucial for device operation, a smooth film of nanocrystals is seen to form on the hole transporting poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) layer deposited on the transparent electrode, facilitated through an ionic interaction between nanocrystal capping ligands and the PEDOT:PSS. The formation of the open circuit voltage in this system is seen to be influenced by an interfacial dipole formed at the hole-extracting electrode, providing insights for further optimization.

Electron transfer from a carbon nanotube into vacuum under high electric fields.

The transfer of an electron from a carbon nanotube (CNT) tip into vacuum under a high electric field is considered beyond the usual one-dimensional semi-classical approach. A model of the potential energy outside the CNT cap is proposed in order to show the importance of the intrinsic CNT parameters such as radius, length and vacuum barrier height. This model also takes into account set-up parameters such as the shape of the anode and the anode-to-cathode distance, which are generically portable to any modelling study of electron emission from a tip emitter. Results obtained within our model compare well to experimental data. Moreover, in contrast to the usual one-dimensional Wentzel-Kramers-Brillouin description, our model retains the ability to explain non-standard features of the process of electron field emission from CNTs that arise as a result of the quantum behaviour of electrons on the surface of the CNT.

High sensitivity organic inorganic hybrid X-ray detectors with direct transduction and broadband response.

X-ray detectors are critical to healthcare diagnostics, cancer therapy and homeland security, with many potential uses limited by system cost and/or detector dimensions. Current X-ray detector sensitivities are limited by the bulk X-ray attenuation of the materials and consequently necessitate thick crystals (~1 mm-1 cm), resulting in rigid structures, high operational voltages and high cost. Here we present a disruptive, flexible, low cost, broadband, and high sensitivity direct X-ray transduction technology produced by embedding high atomic number bismuth oxide nanoparticles in an organic bulk heterojunction. These hybrid detectors demonstrate sensitivities of 1712 µC mGy-1 cm-3 for "soft" X-rays and ~30 and 58 µC mGy-1 cm-3 under 6 and 15 MV "hard" X-rays generated from a medical linear accelerator; strongly competing with the current solid state detectors, all achieved at low bias voltages (-10 V) and low power, enabling detector operation powered by coin cell batteries.

Electron field emission properties of Co quantum dots in SiO2 matrix synthesised by ion implantation.

In this work, Co ions were implanted into thermally oxidised SiO2 layers on silicon substrates. The implantation energy was 50 keV and the doses were 1, 3, 5 and 7 x 10(16) Co+/cm2. The field emission (FE) properties of these layers were studied and correlated with results from atomic force microscopy and transmission electron microscopy measurements. Other than that for the lowest dose sample, crystallised Co nanoclusters, with sizes ranging from 1.8 to 5.7 nm, are observed in these Co-implanted layers. The higher dose samples exhibit excellent FE properties and give an emission current of 1 nA at electric fields as low as 5 V/microm, for a dose of 5 x 10(16) Co+/cm2, compared with 120 V/microm for the lowest dose samples. We attribute the excellent FE properties of these layers to the formation of Co nanoclusters, with the electrical inhomogeneity giving rise to local field enhancement. Finally, repeatable staircase-like current-field (I-F) characteristics are observed in FE measurements of these higher dose samples as compared to conventional Fowler-Nordheim-type I-F characteristics in the lower dose sample. We believe this data may be a result of Coulomb blockade effects arising from the isolated low-capacitance metal quantum dots formed by controlled ion implantation.

Energy loss spectroscopic profiling across linear interfaces: the example of amorphous carbon superlattices.

Energy loss spectroscopic profiling is a way to acquire, in parallel, spectroscopic information across a linear feature of interest, using a Gatan imaging filter (GIF) fitted to a transmission electron microscope (TEM). This technique is capable of translating the high spatial resolution of a bright field image into a sampling of the spectral information with similar resolution. Here we evaluate the contributions of chromatic aberration and the various acquisition parameters to the spatial sampling resolution of the spectral information, and show that this can reach 0.5 nm, in a system not ordinarily capable of forming electron probes smaller than 2 nm. We use this high spatial sampling resolution to study the plasmon energy variation across amorphous carbon superlattices, in order to extract information about their structure and electronic properties. By modelling the interaction of the relativistic incident electrons with a dielectric layer sandwiched between outer layers, we show that, due to the screening of the interfaces and at increased collection angles, the plasmon energy in the sandwiched layer can still be identified for layer thicknesses down to 5 A. This allows us to measure the change in the well bandgap as a function of well width and to interpret it in terms of the changes in the sp2 -fractions due to the deposition method, as measured from the carbon K-edges, and in terms of quantum confinement of the well wavefunction by the adjacent barriers.

Coherent quantum transport features in carbon superlattice structures.

Whilst resonant transmission is well understood and can be fully harnessed for crystalline superlattices, a complete picture has not yet emerged for disordered superlattices. It has proven difficult to tune resonant transmission in disordered diamond-like carbon (DLC) superlattices as conventional models are not equipped to incorporate significant structural disorder. In this work, we present concurrent experimental and theoretical analysis which addresses resonant transmission in DLC superlattices. Devices were fabricated by growing alternate layers of DLC with different percentages of sp3 hybridized carbon.Coherent quantum transport effects were demonstrated in these structurally disordered DLC superlattices through distinct current modulation with negative differential resistance (NDR) in the current-voltage (I-V) measurements. A model was developed using tight-binding calculations assuming a random variation of the hopping integral to simulate structural (bond-length) disorder. Calculations of the I-V characteristics compliment the interpretation of the measurements and illustrate that while DLC superlattice structures are unlike their classical counterparts, the near-field structural order will help with the confinement of quantised states. The present model provides an empirical guide for tailoring the properties of future devices, giving rise to much hope that carbon electronics operating at high frequencies over large areas can now be developed.

Carbon Nanotube Interconnects Realized through Functionalization and Sintered Silver Attachment.

Carbon nanotubes (CNTs) in the form of interconnects have many potential applications, and their ability to perform at high temperatures gives them a unique capability. We show the development of a novel transfer process using CNTs and sintered silver that offers a unique high-temperature, high-conductivity, and potentially flexible interconnect solution. Arrays of vertically aligned multiwalled carbon nanotubes of approximately 200 µm in length were grown on silicon substrates, using low-temperature photothermal chemical vapor deposition. Oxygen plasma treatment was used to introduce defects, in the form of hydroxyl, carbonyl, and carboxyl groups, on the walls of the carbon nanotubes so that they could bond to palladium (Pd). Nanoparticle silver was then used to bind the Pd-coated multiwalled CNTs to a copper substrate. The silver-CNT-silver interconnects were found to be ohmic conductors, with resistivity of 6.2 × 10(-4) Ωm; the interconnects were heated to temperatures exceeding 300 °C (where common solders fail) and were found to maintain their electrical performance.