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.

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.

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.

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.

Multi-Functional Carbon Fibre Composites using Carbon Nanotubes as an Alternative to Polymer Sizing.

Carbon fibre reinforced polymers (CFRP) were introduced to the aerospace, automobile and civil engineering industries for their high strength and low weight. A key feature of CFRP is the polymer sizing - a coating applied to the surface of the carbon fibres to assist handling, improve the interfacial adhesion between fibre and polymer matrix and allow this matrix to wet-out the carbon fibres. In this paper, we introduce an alternative material to the polymer sizing, namely carbon nanotubes (CNTs) on the carbon fibres, which in addition imparts electrical and thermal functionality. High quality CNTs are grown at a high density as a result of a 35 nm aluminium interlayer which has previously been shown to minimise diffusion of the catalyst in the carbon fibre substrate. A CNT modified-CFRP show 300%, 450% and 230% improvements in the electrical conductivity on the 'surface', 'through-thickness' and 'volume' directions, respectively. Furthermore, through-thickness thermal conductivity calculations reveal a 107% increase. These improvements suggest the potential of a direct replacement for lightning strike solutions and to enhance the efficiency of current de-icing solutions employed in the aerospace industry.

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.

Adsorbent 2D and 3D carbon matrices with protected magnetic iron nanoparticles.

We report on the synthesis of two and three dimensional carbonaceous sponges produced directly from graphene oxide (GO) into which functionalized iron nanoparticles can be introduced to render it magnetic. This simple, low cost procedure, wherein an iron polymeric resin precursor is introduced into the carbon framework, results in carbon-based materials with specific surface areas of the order of 93 and 66 m(2) g(-1), compared to approx. 4 m(2) g(-1) for graphite, decorated with ferromagnetic iron nanoparticles giving coercivity fields postulated to be 216 and 98 Oe, values typical for ferrite magnets, for 3.2 and 13.5 wt% Fe respectively. The strongly magnetic iron nanoparticles are robustly anchored to the GO sheets by a layer of residual graphite, on the order of 5 nm, formed during the pyrolysis of the precursor material. The applicability of the carbon sponges is demonstrated in their ability to absorb, store and subsequently elute an organic dye, Rhodamine B, from water as required. It is possible to regenerate the carbon-iron hybrid material after adsorption by eluting the dye with a solvent to which it has a high affinity, such as ethanol. The use of a carbon framework opens the hybrid materials to further chemical functionalization, for enhanced chemical uptake of contaminants, or co-decoration with, for example, silver nanoparticles for bactericidal properties. Such analytical properties, combined with the material's magnetic character, offer solutions for environmental decontamination at land and sea, wastewater purification, solvent extraction, and for the concentration of dilute species.

Self-Heating Effects In Polysilicon Source Gated Transistors.

Source-gated transistors (SGTs) are thin-film devices which rely on a potential barrier at the source to achieve high gain, tolerance to fabrication variability, and low series voltage drop, relevant to a multitude of energy-efficient, large-area, cost effective applications. The current through the reverse-biased source barrier has a potentially high positive temperature coefficient, which may lead to undesirable thermal runaway effects and even device failure through self-heating. Using numerical simulations we show that, even in highly thermally-confined scenarios and at high current levels, self-heating is insufficient to compromise device integrity. Performance is minimally affected through a modest increase in output conductance, which may limit the maximum attainable gain. Measurements on polysilicon devices confirm the simulated results, with even smaller penalties in performance, largely due to improved heat dissipation through metal contacts. We conclude that SGTs can be reliably used for high gain, power efficient analog and digital circuits without significant performance impact due to self-heating. This further demonstrates the robustness of SGTs.

On-chip fabrication of high performance nanostructured ZnO UV detectors.

Developing rationally controlled bottom-up device fabrication processes is essential for the achievement of high performance optimal devices. We report a controlled, seedless and site-selective hydrothermal technique to fabricate high-performance nanostructured ZnO UV-detectors directly on-chip. We demonstrate that by controlling the nanowire growth process, via tuning the experimental parameters such as the concentration of reactants and the growth time, and by introducing a refresh of the growth solution, the device structure efficiency can be enhanced to significantly improve its performance. The on-chip fabricated bridging nanosyringe ultraviolet detector demonstrates improved sensitivity (~10(5)), nanowatts detectability, and ultrafast response-time (90 ms) and recovery-time (210 ms). The improvement in response-time and recovery-time is attributed to the unique nanowire-nanowire junction barrier dominated resistance and the direct contact between ZnO and Au electrodes. Furthermore, the enhanced sensitivity and nanowatts detectability of the bridging nanosyringe device are due to the reduction in dimensionality and ultrahigh surface-to-volume ratio. This work paves the way toward low cost, large scale, low temperature, seedless and site-selective fabrication of high performance ZnO nanowire sensors on flexible and transparent substrates.

Source-gated transistors for order-of-magnitude performance improvements in thin-film digital circuits.

Ultra-large-scale integrated (ULSI) circuits have benefited from successive refinements in device architecture for enormous improvements in speed, power efficiency and areal density. In large-area electronics (LAE), however, the basic building-block, the thin-film field-effect transistor (TFT) has largely remained static. Now, a device concept with fundamentally different operation, the source-gated transistor (SGT) opens the possibility of unprecedented functionality in future low-cost LAE. With its simple structure and operational characteristics of low saturation voltage, stability under electrical stress and large intrinsic gain, the SGT is ideally suited for LAE analog applications. Here, we show using measurements on polysilicon devices that these characteristics lead to substantial improvements in gain, noise margin, power-delay product and overall circuit robustness in digital SGT-based designs. These findings have far-reaching consequences, as LAE will form the technological basis for a variety of future developments in the biomedical, civil engineering, remote sensing, artificial skin areas, as well as wearable and ubiquitous computing, or lightweight applications for space exploration.

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.

Role of the Exposed Polar Facets in the Performance of Thermally and UV Activated ZnO Nanostructured Gas Sensors.

ZnO nanostructures with different morphologies (nanowires, nanodisks, and nanostars) were synthesized hydrothermally. Gas sensing properties of the as-grown nanostructures were investigated under thermal and UV activation. The performance of the ZnO nanodisk gas sensor was found to be superior to that of other nanostructures (Sg ∼ 3700% to 300 ppm ethanol and response time and recovery time of 8 and 13 s). The enhancement in sensitivity is attributed to the surface polarities of the different structures on the nanoscale. Furthermore, the selectivity of the gas sensors can be achieved by controlling the UV intensity used to activate these sensors. The highest sensitivity value for ethanol, isopropanol, acetone, and toluene are recorded at the optimal UV intensity of 1.6, 2.4, 3.2, and 4 mW/cm2, respectively. Finally, the UV activation mechanism for metal oxide gas sensors is compared with the thermal activation process. The UV activation of analytes based on solution processed ZnO structures pave the way for better quality gas sensors.

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.

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.