Electronic devices based on purified carbon nanotubes grown by high-pressure decomposition of carbon monoxide

The excellent properties of transistors, wires and sensors made from single-walled carbon nanotubes (SWNTs) make them promising candidates for use in advanced nanoelectronic systems. Gas-phase growth procedures such as the high-pressure decomposition of carbon monoxide (HiPCO) method yield large quantities of small-diameter semiconducting SWNTs, which are ideal for use in nanoelectronic circuits. As-grown HiPCO material, however, commonly contains a large fraction of carbonaceous impurities that degrade the properties of SWNT devices. Here we demonstrate a purification, deposition and fabrication process that yields devices consisting of metallic and semiconducting nanotubes with electronic characteristics vastly superior to those of circuits made from raw HiPCO. Source-drain current measurements on the circuits as a function of temperature and backgate voltage are used to quantify the energy gap of semiconducting nanotubes in a field-effect transistor geometry. This work demonstrates significant progress towards the goal of producing complex integrated circuits from bulk-grown SWNT material.     

Selective etching of metallic single-wall carbon nanotubes with hydrogen plasma

We present Raman scattering and scanning tunnelling microscopy (STM) measurements on hydrogen plasma etched single-wall carbon nanotubes (SWNTs). Interestingly, both the STM and Raman spectroscopy show that the metallic SWNTs are dramatically altered and highly defected by the plasma treatment. In addition, structural characterizations show that metal catalysts are detached from the ends of the SWNT bundles. For semiconducting SWNTs we observe no feature of defects or etching along the nanotubes. Raman spectra in the radial breathing mode region of plasma-treated SWNT material show that most of the tubes are semiconducting. These results show that hydrogen plasma treatment favours etching of metallic nanotubes over semiconducting ones and therefore could be used to tailor the electronic properties of SWNT raw materials.     

Structure‐Dependent Mitochondrial Dysfunction and Hypoxia Induced with Single‐Walled Carbon Nanotubes

Cytotoxicity of nanomaterials on living systems is known to be affected by their size, shape, surface chemistry, and other physicochemical properties. Exposure to a well‐characterized subpopulation of specific nanomaterials is therefore desired to reveal more detailed mechanisms. This study develops scalable density gradient ultracentrifugation sorting of highly dispersed single‐walled carbon nanotubes (SWNTs) into four distinct bands based on diameter, aggregation, and structural integrity, with greatly improved efficiency, yield, and reproducibility. With guarantee of high yield and stability of four SWNT fractions, it is possible for the first time, to investigate the structure‐dependent bioeffects of four SWNT fractions. it is possible Among these, singly‐dispersed integral SWNTs show no significant effects on the mitochondrial functions and hypoxia. The aggregated integral SWNTs show more significant effects on the mitochondrial dysfunction and hypoxia compared to the aggregated SWNTs with poor structure integrity. Then, it is found that the aggregated integral SWNTs induced the irregular mitochondria respiratory and pro‐apoptotic proteins activation, while aggregated SWNTs with poor structure integrity greatly enhanced reactive oxygen species (ROS) levels. This work supports the view that control of the distinct structure characteristics of SWNTs helps establish clearer structure‐bioeffect correlation and health risk assessment. It is also hoped that these results can help in the design of nanomaterials with higher efficiency and accuracy in subcellular translocation.     

A model for nucleation and growth of single wall carbon nanotubes via the HiPcO process: a catalyst concentration study

Using the High Pressure carbon monoxide (HiPco) reactor we conducted an experiment on the effects of changing the catalyst concentration. With each catalyst concentration tested the resulting raw HiPco material was characterized for average SWNT lengths, SWNT diameters, residual iron particle size, and large fullerene content. We were able to determine trends in each of these characteristics as the catalyst concentration was changed. As the catalyst concentration was decreased SWNT lengths increased, SWNT diameters increased, the residual iron particle size increased, and the large fullerene content decreased. From these trends we have developed a Competitive Growth model for nucleation and growth of SWNTs via the HiPco process.     

Ultrasonication study for suspending single-walled carbon nanotubes in water

A systematic calorimetry-based technique was developed to standardize single-walled carbon nanotube (SWNT) dispersion protocol. Simple calorimetric experiments were performed to benchmark the performance of the ultra-dismembrator. Temperature profiles for the sonication period were utilized to estimate energy input to the system. Energy loss profile was generated for the ultradismembrator in use and a calibration relationship was formulated that could standardize the sonication process. The standardized protocol was used to prepare aqueous SWNT suspensions-sonicating SWNTs in a varied range of input energy (18-100 kJ) in water. SWNT mass fractions suspended for each energy input was accurately measured and the suspended SWNT samples were characterized for morphology, surface potential, cluster size and structure, and chemical functionality using high resolution transmission electron microscopy (HRTEM), electrophoresis, dynamic and static light scattering (DLS/SLS), and Raman spectroscopy. The study demonstrated that suspended mass of SWNTs increased up to 18 kJ of energy input with no further increase upon continued energy input. The physicochemical properties showed similar trend for energy input. The aggregate cluster size, surface potential behavior, as well as the Raman defect properties plateaued after the initial energy input. The significant changes observed were limited to morphological properties, i.e., shorter length, debundled, and sharp edged SWNTs and fractal cluster formation (lower D(f)) with increased input energy.     

Design criteria for transparent single-wall carbon nanotube thin-film transistors

A study based on two-dimensional percolation theory yielding quantitative parameters for optimum connectivity of transparent single-wall carbon nanotube (SWNT) thin films is reported. Optimum SWNT concentration in the filtrated solution was found to be 0.1 mg/L with a volume of 30 mL. Such parameters lead to SWNT fractions in the films of approximately Phi = 1.8 x 10(-3), much below the metallic percolation threshold, which is found to be approximately PhiC = 5.5 x 10(-3). Therefore, the performance of transparent carbon nanotube thin-film transistors is limited by the metallic SWNTs, even below their percolation threshold. We show how this effect is related to hopping or tunneling between neighboring metallic tubes.     

Rheological behaviour and mechanical characterization of injectable poly(propylene fumarate)/single-walled carbon nanotube composites for bone tissue engineering

This work investigated the effects of the use of a surfactant or the functionalization of single-walled carbon nanotubes (SWNTs) on their dispersion in uncrosslinked poly(propylene fumarate) (PPF) and the mechanical reinforcement of crosslinked composites as a function of the SWNT concentration. Rheological measurements showed good dispersion of SWNTs in uncrosslinked PPF at low concentrations of 0.05?wt% and SWNT aggregation for higher concentrations for all formulations examined. Mechanical testing demonstrated significant reinforcement in the compressive and flexural mechanical properties of crosslinked nanocomposites which peaked for low SWNT concentrations of the order of 0.05?wt%. For example, a 74% increase was recorded for the compressive modulus and a 69% increase for the flexural modulus of nanocomposites with functionalized SWNTs at a 0.05?wt% loading. Nevertheless, this reinforcement was not related to the use of a surfactant or the functionalization of the SWNTs tested. Scanning electron microscopy examinations of fractured nanocomposite surfaces revealed the formation of SWNT aggregates at higher concentrations corroborating the rheological and mechanical data. These results suggest that the dispersion of individual SWNTs in a uncrosslinked formulation is pivotal to the development of injectable nanocomposites for bone tissue engineering applications.     

Computational modeling of the thermal conductivity of single-walled carbon nanotube-polymer composites

A computational model was developed to study the thermal conductivity of single-walled carbon nanotube (SWNT)-polymer composites. A random walk simulation was used to model the effect of interfacial resistance on the heat flow in different orientations of SWNTs dispersed in the polymers. The simulation is a modification of a previous model taking into account the numerically determined thermal equilibrium factor between the SWNTs and the composite matrix material. The simulation results agreed well with reported experimental data for epoxy and polymethyl methacrylate (PMMA) composites. The effects of the SWNT orientation, weight fraction and thermal boundary resistance on the effective conductivity of composites were quantified. The present model is a useful tool for the prediction of the thermal conductivity within a wide range of volume fractions of the SWNTs, so long as the SWNTs are not in contact with each other. The developed model can be applied to other polymers and solid materials, possibly even metals.     

Photoluminescence from intertube carrier migration in single-walled carbon nanotube bundles

Photoluminescence (PL) identifies spectroscopic signatures of intertube transfer of optically pumped carriers in single-walled carbon nanotube (SWNT) ensembles. Resonant photoexcitation of large band gap SWNTs produces strong PL from smaller band gap SWNTs. Magnetic alignment measurements associate the energy-transfer PL peaks with the formation of SWNT bundles, suggesting that efficient coupling results from physical contact.     

Fabrication and characterization of single walled nanotube supercapacitor electrodes with uniform pores using electrophoretic deposition

Well dispersed aqueous suspensions containing single walled carbon nanotubes (SWNTs) were prepared without surfactants by functionalizing SWNTs in an acid treatment. SWNT coated electrodes were prepared from the SWNT aqueous suspensions using various methods to create uniform nanoporous networks of SWNTs on stainless steel (SST) current collectors. The EPD process was identified as the primary tool for reliably producing uniform SWNT nanoporous networks on SST substrates. Optical and scanning electron microscopic images and the BET surface area analysis were used to evaluate the SWNT dispersion quality of the electrodes. The average SWNT nanopore size produced from the EPD process was found about 1 nm and was nearly unaffected by extended EPD processing times. The SWNT coated electrodes were characterized using the cyclic voltammetry and their capacitance was determined. A correlation between the extended EPD processing time and the electrode capacitance was quantified.     

Structural study of single-walled carbon nanotube films doped by a solution method

Herein, we have studied a structure of SWNT films doped by organic molecules. In this study, we reacted organic molecules with SWNT films by a vapor phase and a liquid phase, respectively. The structure of doped SWNT films was investigated using synchrotron X-ray powder diffraction measurements, and we found the clear difference between the vapor phase reaction (v-doped) and the liquid phase reaction (I-doped). In v-doped SWNT films, organic molecules are predominantly encapsulated inside SWNTs, although molecules adsorbed on the surface of SWNT bundles in l-doped SWNT films.     

Synthesis and Hydrogen Storage in Single—walled Carbon Nanotubes

Single=walled carbon nanotubes(SWNTs) were synthesized by a hydrogen arc discharge method.A high yield of gram quantity of SWNTs per hour was achieved.Tow kinds of SWNT products:web-like substancea and thin films in large slices were obtained. Results of resonant Raman scattering measurements indicate that the SWNTs prepared have a wider diameter distribution and a larger mean diameter.Hydrogen uptake measurements of the two kinds of SWNT samples(both as prepared and pretreated) were carried out using a high pressure volumetric method,respectively.And a hydrogen storage capacity of 4 wt pct could be repeatedly achieved for the suitably pretreated SWMNTs,whicb indicates that SWNTs may be a promising hydrogen storge material.     

Fluorescent Polymer—Single‐Walled Carbon Nanotube Complexes with Charged and Noncharged Dendronized Perylene Bisimides for Bioimaging Studies

Fluorescent nanomaterials are expected to revolutionize medical diagnostic, imaging, and therapeutic tools due to their superior optical and structural properties. Their inefficient water solubility, cell permeability, biodistribution, and high toxicity, however, limit the full potential of their application. To overcome these obstacles, a water‐soluble, fluorescent, cytocompatible polymer—single‐walled carbon nanotube (SWNT) complex is introduced for bioimaging applications. The supramolecular complex consists of an alkylated polymer conjugated with neutral hydroxylated or charged sulfated dendronized perylene bisimides (PBIs) and SWNTs as a general immobilization platform. The polymer backbone solubilizes the SWNTs, decorates them with fluorescent PBIs, and strongly improves their cytocompatibility by wrapping around the SWNT scaffold. In photophysical measurements and biological in vitro studies, sulfated complexes exhibit superior optical properties, cellular uptake, and intracellular staining over their hydroxylated analogs. A toxicity assay confirms the highly improved cytocompatibility of the polymer‐wrapped SWNTs toward surfactant‐solubilized SWNTs. In microscopy studies the complexes allow for the direct imaging of the SWNTs' cellular uptake via the PBI and SWNT emission using the 1st and 2nd optical window for bioimaging. These findings render the polymer‐SWNT complexes with nanometer size, dual fluorescence, multiple charges, and high cytocompatibility as valuable systems for a broad range of fluorescence bioimaging studies.     

Polymer electrolyte gating of carbon nanotube network transistors

Network behavior in single-walled carbon nanotubes (SWNTs) is examined by polymer electrolyte gating. High gate efficiencies, low voltage operation, and the absence of hysteresis in polymer electrolyte gating lead to a convenient and effective method of analyzing transport in SWNT networks. Furthermore, the ability to control carrier type with chemical groups of the host polymer allows us to examine both electron and hole conduction. Comparison to back gate measurements is made on channel length scaling. Frequency measurements are also made giving an upper limit of approximately 300 Hz switching speed for poly(ethylene oxide)/LiClO(4) gated SWNT thin film transistors.     

Temperature-mediated growth of single-walled carbon-nanotube intramolecular junctions

Single-walled carbon nanotubes (SWNTs) possess superior electronic and physical properties that make them ideal candidates for making next-generation electronic circuits that break the size limitation of current silicon-based technology. The first critical step in making a full SWNT electronic circuit is to make SWNT intramolecular junctions in a controlled manner. Although SWNT intramolecular junctions have been grown by several methods, they only grew inadvertently in most cases. Here, we report well-controlled temperature-mediated growth of intramolecular junctions in SWNTs. Specifically, by changing the temperature during growth, we found that SWNTs systematically form intramolecular junctions. This was achieved by a consistent variation in the SWNT diameter and chirality with changing growth temperature even though the catalyst particles remained the same. These findings provide a potential approach for growing SWNT intramolecular junctions at desired locations, sizes and orientations, which are important for making SWNT electronic circuits.     

Determination of the concentration of single-walled carbon nanotubes in aqueous dispersions using UV-visible absorption spectroscopy

Stable, homogeneous, aqueous dispersions of single-walled carbon nanotubes (SWNTs) are prepared by nonspecific physical adsorption of surfactants enhanced by sonication. Upon centrifugation, supernatant and precipitate phases are obtained. The initial weights of the SWNTs and the surfactant are divided between these two phases, and the respective SWNT concentration in each phase is unknown. The focus of this work is on the determination of the true concentration of raw, exfoliated HiPCO SWNTs in the supernatant phase. A UV-visible absorption-based approach is suggested for a direct measurement of the SWNT and the surfactant concentration in the supernatant. UV-visible absorbance spectra of SWNTs-surfactant dispersions and surfactants alone reveal that the intensity of a certain peak, attributed to the pi-plasmon resonance absorption, is unaffected by the presence of most surfactants. A calibration plot is then made by monitoring the intensity of the peak as a function of the true concentration of the exfoliated SWNTs. Thus, we are able to determine the unknown concentration of surfactant-dispersed HiPCO SWNTs in the supernatant solution, simply by measuring its optical absorbance. Moreover, we can now calculate the surfactant efficiency in dispersing SWNTs. Cryogenic-transmission electron microscopy and thermogravimetric analysis techniques are used for the characterization of these dispersions and to complement the UV-visible measurements.     

Charge Transfer from Carbon Nanotubes to Silicon in Flexible Carbon Nanotube/Silicon Solar Cells

Mechanical fragility and insufficient light absorption are two major challenges for thin flexible crystalline Si‐based solar cells. Flexible hybrid single‐walled carbon nanotube (SWNT)/Si solar cells are demonstrated by applying scalable room‐temperature processes for the fabrication of solar‐cell components (e.g., preparation of SWNT thin films and SWNT/Si p–n junctions). The flexible SWNT/Si solar cells present an intrinsic efficiency ≈7.5% without any additional light‐trapping structures. By using these solar cells as model systems, the charge transport mechanisms at the SWNT/Si interface are investigated using femtosecond transient absorption. Although primary photon absorption occurs in Si, transient absorption measurements show that SWNTs also generate and inject excited charge carriers to Si. Such effects can be tuned by controlling the thickness of the SWNTs. Findings from this study could open a new pathway for designing and improving the efficiency of photocarrier generation and absorption for high‐performance ultrathin hybrid SWNT/Si solar cells.     

The synergistic effect of nanocrystal integration and process optimization on solar cell efficiency

This paper investigates the roles of semiconducting single-walled carbon nanotubes (SWNTs) and metallic SWNTs in the SWNT/poly(3-hexylthiophene) (P3HT)-based photovoltaic conversion system. SWNTs containing different fractions of semiconducting nanotubes were conjugated with P3HT by virtue of π-π interaction. The energy transfer and carrier transport mechanisms in the photovoltaic composites were experimentally investigated by optical absorption spectroscopy, photoluminescence spectroscopy and carrier mobility measurements. At low loading of SWNTs, a high percentage of semiconducting nanotubes result in diminished non-radiative decay of exciton and lower carrier mobility, causing higher open circuit voltage and lower photocurrent. At an optimized morphology, SWNT/P3HT/phenyl-C61-butyric acid methyl ester (PCBM) hybrid-based solar cells demonstrated much higher photocurrent than a reference solar cell (P3HT:PCBM) due to the improved carrier mobility. Further thermal annealing of the devices significantly increased the open circuit voltage to 610?mV, resulting in an 80% increase of power conversion efficiency in comparison to the reference solar cell. These results are expected to lay a foundation for the integration of various nanocrystals into solar cells for efficient photovoltaic conversion.     

Single wall nanotube and vapor grown carbon fiber reinforced polymers processed by extrusion freeform fabrication

Single wall carbon nanotubes (SWNTs) and vapor grown carbon fibers (VGCFs) were compounded with poly(acrylonitrile-co-butadiene-co-styrene) (ABS) to create composite materials for use with Extrusion Freeform Fabrication (EFF). The composite materials possessed homogeneously dispersed fibers that were oriented with EFF processing. The VGCF and SWNT reinforced materials processed by EFF displayed improved tensile modulus compared to similarly processed ABS and composite material with isotropic fiber orientation, and the SWNT reinforced material displayed the highest properties, strength and modulus, of the materials studied. The materials containing oriented VGCFs and SWNTs showed modulus improvements of 44 and 93%, respectively.     

Structure of semidilute single-wall carbon nanotube suspensions and gels

The microscopic network structure of surfactant-stabilized single-wall carbon nanotubes (SWNTs) in water was investigated as a function of SWNT concentration in the semidilute (overlapping) regime using small-angle neutron scattering (SANS). Most of the samples exhibit rigid rod behavior (i.e., Q(-1) intensity variation) at large scattering wavevector, Q, and a crossover to network behavior (i.e., approximately Q(-2) intensity variation) at low Q. The mesh size, xi, of the network was determined from the crossover of rigid rod to network behavior in the SANS intensity profile and was found to decrease with increasing SWNT concentration. When the dispersion quality of these associating rigid rods was degraded, only approximately Q(-2) intensity variation was observed at both high and low Q. Small-angle X-ray scattering measurements of the same stable dispersions were relatively insensitive to network structure because of poor contrast between SWNTs and surfactant.