Single-walled carbon nanotube network ultramicroelectrodes

Ultramicroelectrodes (UMEs) fabricated from networks of chemical vapor deposited single-walled carbon nanotubes (SWNTs) on insulating silicon oxide surfaces are shown to offer superior qualities over solid UMEs of the same size and dimensions. Disk shaped UMEs, comprising two-dimensional "metallic" networks of SWNTs, have been fabricated lithographically, with a surface coverage of <1% of the underlying insulating surface. The electrodes are long lasting and give highly reproducible responses (either for repeat runs with the same electrode or when comparing several electrodes with the same size). For redox concentrations 相似文献   

Assessment of the electrochemical behavior of two-dimensional networks of single-walled carbon nanotubes

Scanning electrochemical microscopy (SECM) has been employed in the feedback mode to assess the electrochemical behavior of two-dimensional networks of single-walled carbon nanotubes (SWNTs). It is shown that, even though the network comprises both metallic and semiconducting SWNTs, at high density (well above the percolation threshold for metallic SWNTs) and with approximately millimolar concentrations of redox species the network behaves as a thin metallic film, irrespective of the formal potential of the redox couple. This result is particularly striking since the fractional surface coverage of SWNTs is only approximately 1% and SECM delivers high mass transport rates to the network. Finite element simulations demonstrate that under these conditions diffusional overlap between neighboring SWNTs is significant so that planar diffusion prevails in the gap between the SECM tip and the underlying SWNT substrate. The SECM feedback response diminishes at higher concentrations of the redox species. However, wet gate measurements show that at the solution potentials of interest the conductivity is sufficiently high that lateral conductivity is not expected to be limiting. This suggests that reaction kinetics may be a limiting factor, especially since the low surface coverage of the SWNT network results in large fluxes to the SWNTs, which are characterized by a low density of electronic states. For electroanalytical purposes, significantly, two-dimensional SWNT networks can be considered as metallic films for typical millimolar concentrations employed in amperometry and voltammetry. Moreover, SWNT networks can be inexpensively and easily formed over large scales, opening up the possibility of further electroanalytical applications.     

Detection of a nerve agent simulant using single-walled carbon nanotube networks: dimethyl-methyl-phosphonate

Single-walled carbon nanotube (SWNT) networks were used to detect hazardous dimethyl-methyl-phosphonate (DMMP) gas in real time, employing two different metals as electrodes. Random networks of SWNTs were simply obtained by drop-casting a SWNT-containing solution onto a surface-oxidized Si substrate. Although the electrical responses to DMMP at room temperature were reversible for both metals, the Pd-contacting SWNT network sensors exhibited a higher response and a shorter response time than those of the Au-contacting SWNT network sensors at the same DMMP concentration, due to the stronger interactions between the SWNTs and Pd surface atoms. In Pd-contacting SWNT network sensors, the response increased linearly with increasing DMMP concentration and reproducible response curves were obtained for DMMP levels as low as 1 ppm. These results indicate that SWNT networks in contact with Pd electrodes can function as good DMMP sensors at room temperature with scalable and fast response and excellent recovery.     

Copper catalyzing growth of single-walled carbon nanotubes on substrates

Metallic copper, which is normally considered as a contaminant in the growth of single-walled carbon nanotubes (SWNTs), was found to be an efficient catalyst to grow SWNTs under suitable conditions. It showed very high catalytic activity for the growth of both random SWNT networks and horizontally aligned SWNT arrays. Especially, high-quality SWNT arrays were obtained when monodispersed copper nanoparticles were used. The catalytic behavior of copper for the growth of SWNTs was discussed. The weaker interaction between the copper and silica surfaces plays an important role in the growth of high-quality horizontally aligned SWNT arrays. This new synthesis process of SWNTs with a non-ferromagnetic catalyst brings more convenience to the study of magnetic properties of SWNTs and gives more insight in structure-controlled synthesis of SWNTs.     

Percolation in networks of aligned SWNTs formed with laminar flow deposition

Macroscopic networks of highly aligned SWNTs have been fabricated at room temperature by laminar flow deposition from aqueous suspensions. This deposition method allows the growth of a macroscopic two dimensional SWNT network through successive deposition cycles. AFM image analysis showed that each deposition cycle puts down a reproducible density of SWNTs, with the final density being directly proportional to the number of deposition cycles for a given solution. The macroscopic electronic behavior of these networks was characterized by DC conductance measurements taken after each deposition cycle. This showed that these networks could be described by two dimensional percolation models throughout the growth process.     

Chemical vapour deposition of single walled carbon nanotubes freely suspended over nanotube supports

Single walled carbon nanotubes (SWNTs) suspended above the substrate can be fabricated simply and rapidly by chemical vapour deposition growth over pre-grown multi-walled carbon nanotubes (MWNTs). SWNTs are suspended either on a randomly organized carbon nanotube network on an unpatterned substrate, or between organized pillars made from vertically aligned nanotube forests on a patterned substrate. All nanotubes are produced during a single growth run using a two step growth technique. This approach enables the fabrication of laterally suspended SWNT networks which are well suited for optical applications.     

Generation of single-walled carbon nanotubes from alcohol and generation mechanism by molecular dynamics simulations

Recent advances in high-purity and high-yield catalytic chemical vapor deposition (CVD) generation of single-walled carbon nanotubes (SWNTs) from alcohol are comprehensively presented and discussed on the basis of results obtained from both experimental and numerical investigations. We have uniquely adopted alcohol as a carbon feedstock, and this has resulted in high-quality, low-temperature synthesis of SWNTs. This technique can produce SWNTs even at a very low temperature of 550 degrees C, which is about 300 degrees C lower than the conventional CVD methods in which methane or acetylene is typically used. We demonstrate the excellence of the proposed alcohol catalytic CVD method for high-yield production of SWNTs when Fe-Co on USY-zeolite powder was used as a catalyst. At optimum CVD conditions, a SWNT yield of more than 40 wt % was achieved over the weight of the catalytic powder within the reaction time of 120 min. In addition to the advantages for mass production, this method is also suitable for the direct synthesis of high-quality SWNTs on Si and quartz substrates when combined with the newly developed liquid-based "dip-coat" technique to mount catalytic metals on the surface of substrates. This method allows easy and costless loading of catalytic metals without the need for any support or underlayer materials that were usually required in previous studies for the generation of a sufficient quantity of SWNTs on an Si surface. Finally, the result of molecular dynamics simulation for the SWNT growth process is presented to obtain a fundamental insight into the initial growth mechanism on the catalytic particles.     

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.     

Biocompatibility of native and functionalized single-walled carbon nanotubes for neuronal interface

Single-walled carbon nanotubes (SWNTs) have unique mechanical, electrical, and optical properties and can be easily chemically modified; features that make them excellent candidate materials for applications as sensors and stimulators in neuronal tissue engineering. The purpose of this study was to demonstrate that SWNTs can support neuronal attachment and growth, that simple chemical modifications can be employed to control cell growth, that SWNTs do not interfere with ongoing neuronal function, and that neurons can be electrically coupled to SWNTs. Growth and attachment of the neuroblastoma*glioma NG108, a model neuronal cell, was assessed on unmodified SWNT substrates or substrates from SWNTs modified with 4-benzoic acid or 4-tert-butylphenyl functional groups using a simple functionalization method. SWNT films support cell growth, but at a reduced level compared to tissue culture-treated polystyrene. The order of viability and cell attachment was tissue culture treated polystyrene > SWNTs > 4-tert-butylphenyl-functionalized SWNTs > 4-benzoic acid-functionalized SWNTs. Decreased cell growth after culture on untreated (non adherent) polystyrene suggested that cell attachment was a critical determinant of proliferation and cell growth on SWNTs. Fluorescence and scanning electron microscopy revealed decreased neurite outgrowth in NG108 grown on SWNT substrates. We are also among the first groups to demonstrate electrical coupling of SWNTs and neurons by demonstrating that NG108 and rat primary peripheral neurons showed robust voltage-activated currents when electrically stimulated through transparent, conductive SWNT films. Our data suggest that SWNTs are flexible resource materials for tissue engineering application involving electrically excitable tissues such as muscles and nerves.     

Methods for enhanced control over the density and electrical properties of SWNT networks

The formation of manufacturable electronic materials that incorporate single-walled carbon nanotubes (SWNTs) will most likely involve the use of networks of these molecular wires, due to the enhanced current drive and reproducibility of such films. Therefore, control over the density of SWNTs during the deposition of 2-D networks is of critical importance for the development of numerous enhanced electronic materials. Room temperature deposition methods are of particular interest as they allow separation, purification, and/or chemical modification of SWNTs before deposition. This article reports three iterative liquid-deposition techniques that allow control over the properties of three distinct types of SWNT networks. First, density control was obtained for 2-D networks of unbundled, high-aspect ratio SWNTs. Such networks exhibited semiconductive behavior, with tunable on/off ratios. Second, electrically continuous 2-D clusters of high aspect ratio SWNTs were formed by allowing capillary forces to develop in a sessile suspension droplet. These constructs displayed tunable metallic conductivity, and may have the applications as interconnects in microelectronics. Finally, highly conductive, 3-D networks of bundled SWNTs were formed via an evaporation method. For these three types of networks, the density of SWNTs, and thus the macroscopic conductance, was readily controlled via the number of deposition cycles used in their formation.     

Individual single-walled carbon nanotubes as nanoelectrodes for electrochemistry

We demonstrate the use of individual single-walled carbon nanotubes (SWNTs) as nanoelectrodes for electrochemistry. SWNTs were contacted by nanolithography, and cyclic voltammetry was performed in aqueous solutions. Interestingly, metallic and semiconducting SWNTs yielded similar steady-state voltammetric curves. We clarify this behavior through a model that considers the electronic structure of the SWNTs. Interfacial electron transfer to the SWNTs is observed to be very fast but can nonetheless be resolved due to the nanometer critical dimension of SWNTs. These studies demonstrate the potential of using a SWNT as a model carbon nanoelectrode for electrochemistry.     

Continued growth of single-walled carbon nanotubes

We demonstrate the continued growth of single-walled carbon nanotubes (SWNTs) from ordered arrays of open-ended SWNTs in a way analogous to epitaxy. Nanometer-sized metal catalysts were docked to the SWNT open ends and subsequently activated to restart growth. SWNTs thus grown inherit the diameters and chirality from the seeded SWNTs, as indicated by the closely matched frequencies of Raman radial breathing modes before and after the growth.     

Nanoscale Charge Percolation Analysis in Polymer‐Sorted (7,5) Single‐Walled Carbon Nanotube Networks

The current percolation in polymer‐sorted semiconducting (7,5) single‐walled carbon nanotube (SWNT) networks, processed from solution, is investigated using a combination of electrical field‐effect measurements, atomic force microscopy (AFM), and conductive AFM (C‐AFM) techniques. From AFM measurements, the nanotube length in the as‐processed (7,5) SWNTs network is found to range from ≈100 to ≈1500 nm, with a SWNT surface density well above the percolation threshold and a maximum surface coverage ≈58%. Analysis of the field‐effect charge transport measurements in the SWNT network using a 2D homogeneous random‐network stick‐percolation model yields an exponent coefficient for the transistors OFF currents of 16.3. This value is indicative of an almost ideal random network containing only a small concentration of metallic SWNTs. Complementary C‐AFM measurements on the other hand enable visualization of current percolation pathways in the xy plane and reveal the isotropic nature of the as‐spun (7,5) SWNT networks. This work demonstrates the tremendous potential of combining advanced scanning probe techniques with field‐effect charge transport measurements for quantification of key network parameters including current percolation, metallic nanotubes content, surface coverage, and degree of SWNT alignment. Most importantly, the proposed approach is general and applicable to other nanoscale networks, including metallic nanowires as well as hybrid nanocomposites.     

Thermal conductivity measurements of semitransparent single-walled carbon nanotube films by a bolometric technique

We introduce a new technique for measurement of the thermal conductivity of ultrathin films of single-walled carbon nanotubes (SWNTs) utilizing IR radiation as heat source and the SWNT film as thermometer. The technique is applied to study the temperature dependence of the thermal conductivity of an as-prepared SWNT film obtained in the electric arc discharge process and a film of purified SWNTs prepared by vacuum filtration. The interplay between thermal and electrical transport in SWNT networks is analyzed in relation to the type of intertube junctions and the possibility of optimizing the thermal and electrical properties of SWNT networks for specific applications is discussed.     

The importance of strong carbon-metal adhesion for catalytic nucleation of single-walled carbon nanotubes

Density functional theory is used to show that the adhesion between single-walled carbon nanotubes (SWNTs) and the catalyst particles from which they grow needs to be strong to support nanotube growth. It is found that Fe, Co, and Ni, commonly used to catalyze SWNT growth, have larger adhesion strengths to SWNTs than Cu, Pd, and Au and are therefore likely to be more efficient for supporting growth. The calculations also show that to maintain an open end of the SWNT it is necessary that the SWNT adhesion strength to the metal particle is comparable to the cap formation energy of the SWNT end. This implies that the difference between continued and discontinued SWNT growth to a large extent depends on the carbon-metal binding strength, which we demonstrate by molecular dynamics (MD) simulations. The results highlight that first principles computations are vital for the understanding of the binding strength's role in the SWNT growth mechanism and are needed to get accurate force field parameters for MD.     

Identifying and counting point defects in carbon nanotubes

The prevailing conception of carbon nanotubes and particularly single-walled carbon nanotubes (SWNTs) continues to be one of perfectly crystalline wires. Here, we demonstrate a selective electrochemical method that labels point defects and makes them easily visible for quantitative analysis. High-quality SWNTs are confirmed to contain one defect per 4 microm on average, with a distribution weighted towards areas of SWNT curvature. Although this defect density compares favourably to high-quality, silicon single-crystals, the presence of a single defect can have tremendous electronic effects in one-dimensional conductors such as SWNTs. We demonstrate a one-to-one correspondence between chemically active point defects and sites of local electronic sensitivity in SWNT circuits, confirming the expectation that individual defects may be critical to understanding and controlling variability, noise and chemical sensitivity in SWNT electronic devices. By varying the SWNT synthesis technique, we further show that the defect spacing can be varied over orders of magnitude. The ability to detect and analyse point defects, especially at very low concentrations, indicates the promise of this technique for quantitative process analysis, especially in nanoelectronics development.     

Lateral manipulation of single-walled carbon nanotubes on H-passivated Si(100) surfaces with an ultrahigh-vacuum scanning tunneling microscope

Ultrahigh-vacuum (UHV) scanning tunneling microscopy (STM) can be used for the manipulation of individual atoms and molecules into complex arrangements for sensitive electrical and structural characterization. However, the systematic UHV STM manipulation of single-walled carbon nanotubes (SWNTs), high-aspect-ratio molecular wires derived from graphene that exist in both semiconducting and metallic forms, has yet to be reported. In this work, we demonstrate the room-temperature lateral manipulation of approximately 1-nm-diameter SWNTs on UHV-prepared, hydrogen-passivated Si(100) surfaces. We show the reproducible actuation of SWNTs having lengths as small as 13 nm, along with the partial division of a two-tube bundle. Moreover, UHV STM desorption of H at the SWNT/Si interface is introduced as a means of locally strengthening the interaction between the tube and the surface. The UHV STM manipulation scheme described here is potentially extensible to the orientational control of SWNTs interfaced with atomically clean semiconducting surfaces, such as InAs(110), GaAs(110), and unpassivated Si(100), for which first-principles calculations based on density functional theory have been reported recently in the literature.     

Designing Catalysts for Chirality‐Selective Synthesis of Single‐Walled Carbon Nanotubes: Past Success and Future Opportunity

A major obstacle for the applications of single‐walled carbon nanotubes (SWNTs) in electronic devices is their structural diversity, ending in SWNTs with diverse electrical properties. Catalytic chemical vapor deposition has shown great promise in directly synthesizing high‐quality SWNTs with a high selectivity to specific chirality (n, m). During the growth process, the tube–catalyst interface plays crucial roles in regulating the SWNT nucleation thermodynamics and growth kinetics, ultimately governing the SWNT chirality distribution. Starting with the introduction of SWNT growth modes, this review seeks to extend the knowledge about chirality‐selective synthesis by clarifying the energetically favored SWNT cap nucleation and the threshold step for SWNT growth, which describes how the tube–catalyst interface affects both the nucleus energy and the new carbon atom incorporation. Such understandings are subsequently applied to interpret the (n, m) specific growth achieved on a variety of templates, such as SWNT segments or predefined molecular seeds, transition metal (Fe, Co and Ni)‐containing catalysts at low reaction temperatures, W‐based alloy catalysts, and metal carbides at relatively high reaction temperatures. The up to date achievements on chirality‐controlled synthesis of SWNTs is summarized and the remaining major challenges existing in the SWNT synthesis field are discussed.     

Mechanical properties of epoxy nanocomposites reinforced with very low content of amino-functionalized single-walled carbon nanotubes

Functionalized single-walled carbon nanotubes (SWNTs) with amino groups were prepared by oxidation, acylation, and amidation of SWNT surfaces. Epoxy/SWNT composite membranes were fabricated using a very low content of amino-grafted SWNTs (< or = 0.08 wt%) as fillers. SWNTs with amino groups acted as a curing agent, covalently bonding to the epoxy matrix. The influence of SWNT content on the mechanical properties of epoxy/amino-functionalized SWNT composite membrane was investigated. It is found that the tensile strength of composites is enhanced with the increase of SWNTs. Only 0.01 wt% of SWNT-R-NH, leads to improvement of the epoxy tensile strength by 9.5%, and 0.08 wt% of SWNT-R-NH2 increased tensile strength by 13.6%. For comparison purposes, epoxy/pristine-SWNT films were also prepared. The improvement of the tensile strength of the amino-functionalized SWNTs system is more remarkable than that of pristine SWNT system at very low weight-percentage loading. The amino groups on the surface of SWNTs can be covalently attached to the epoxy matrix, which effectively improves the dispersion and adhesion of SWNTs in epoxy. This leads to the enhancement in mechanical properties of the epoxy composite. Mechanical results between functionalized and pristine nanotubes are discussed in detail.     

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.