Solution properties of single-walled carbon nanotubes

Naked metallic and semiconducting single-walled carbon nanotubes (SWNTs) were dissolved in organic solutions by derivatization with thionychloride and octadecylamine. Both ionic (charge transfer) and covalent solution-phase chemistry with concomitant modulation of the SWNT band structure were demonstrated. Solution-phase near-infrared spectroscopy was used to study the effects of chemical modifications on the band gaps of the SWNTs. Reaction of soluble SWNTs with dichlorocarbene led to functionalization of the nanotube walls.     

Crystalline Ropes of Metallic Carbon Nanotubes

Fullerene single-wall nanotubes (SWNTs) were produced in yields of more than 70 percent by condensation of a laser-vaporized carbon-nickel-cobalt mixture at 1200degreesC. X-ray diffraction and electron microscopy showed that these SWNTs are nearly uniform in diameter and that they self-organize into "ropes," which consist of 100 to 500 SWNTs in a two-dimensional triangular lattice with a lattice constant of 17 angstroms. The x-ray form factor is consistent with that of uniformly charged cylinders 13.8 +/- 0.2 angstroms in diameter. The ropes were metallic, with a single-rope resistivity of <10(-4) ohm-centimeters at 300 kelvin. The uniformity of SWNT diameter is attributed to the efficient annealing of an initial fullerene tubelet kept open by a few metal atoms; the optimum diameter is determined by competition between the strain energy of curvature of the graphene sheet and the dangling-bond energy of the open edge, where growth occurs. These factors strongly favor the metallic (10,10) tube with C5v symmetry and an open edge stabilized by triple bonds.     

Nanotube molecular wires as chemical sensors

Chemical sensors based on individual single-walled carbon nanotubes (SWNTs) are demonstrated. Upon exposure to gaseous molecules such as NO(2) or NH(3), the electrical resistance of a semiconducting SWNT is found to dramatically increase or decrease. This serves as the basis for nanotube molecular sensors. The nanotube sensors exhibit a fast response and a substantially higher sensitivity than that of existing solid-state sensors at room temperature. Sensor reversibility is achieved by slow recovery under ambient conditions or by heating to high temperatures. The interactions between molecular species and SWNTs and the mechanisms of molecular sensing with nanotube molecular wires are investigated.     

Structure-assigned optical spectra of single-walled carbon nanotubes

Spectrofluorimetric measurements on single-walled carbon nanotubes (SWNTs) isolated in aqueous surfactant suspensions have revealed distinct electronic absorption and emission transitions for more than 30 different semiconducting nanotube species. By combining these fluorimetric results with resonance Raman data, each optical transition has been mapped to a specific (n,m) nanotube structure. Optical spectroscopy can thereby be used to rapidly determine the detailed composition of bulk SWNT samples, providing distributions in both tube diameter and chiral angle. The measured transition frequencies differ substantially from simple theoretical predictions. These deviations may reflect combinations of trigonal warping and excitonic effects.     

Band gap fluorescence from individual single-walled carbon nanotubes

Fluorescence has been observed directly across the band gap of semiconducting carbon nanotubes. We obtained individual nanotubes, each encased in a cylindrical micelle, by ultrasonically agitating an aqueous dispersion of raw single-walled carbon nanotubes in sodium dodecyl sulfate and then centrifuging to remove tube bundles, ropes, and residual catalyst. Aggregation of nanotubes into bundles otherwise quenches the fluorescence through interactions with metallic tubes and substantially broadens the absorption spectra. At pH less than 5, the absorption and emission spectra of individual nanotubes show evidence of band gap-selective protonation of the side walls of the tube. This protonation is readily reversed by treatment with base or ultraviolet light.     

A rubberlike stretchable active matrix using elastic conductors

By using an ionic liquid of 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, we uniformly dispersed single-walled carbon nanotubes (SWNTs) as chemically stable dopants in a vinylidene fluoride-hexafluoropropylene copolymer matrix to form a composite film. We found that the SWNT content can be increased up to 20 weight percent without reducing the mechanical flexibility or softness of the copolymer. The SWNT composite film was coated with dimethyl-siloxane-based rubber, which exhibited a conductivity of 57 siemens per centimeter and a stretchability of 134%. Further, the elastic conductor was integrated with printed organic transistors to fabricate a rubberlike active matrix with an effective area of 20 by 20 square centimeters. The active matrix sheet can be uniaxially and biaxially stretched by 70% without mechanical or electrical damage. The elastic conductor allows for the construction of electronic integrated circuits, which can be mounted anywhere, including arbitrary curved surfaces and movable parts, such as the joints of a robot's arm.     

Macroscopic, neat, single-walled carbon nanotube fibers

Well-aligned macroscopic fibers composed solely of single-walled carbon nanotubes (SWNTs) were produced by conventional spinning. Fuming sulfuric acid charges SWNTs and promotes their ordering into an aligned phase of individual mobile SWNTs surrounded by acid anions. This ordered dispersion was extruded via solution spinning into continuous lengths of macroscopic neat SWNT fibers. Such fibers possess interesting structural composition and physical properties.     

Self-sorted, aligned nanotube networks for thin-film transistors

To find use in electronics, single-walled carbon nanotubes need to be efficiently separated by electronic type and aligned to ensure optimal and reproducible electronic properties. We report the fabrication of single-walled carbon nanotube (SWNT) network field-effect transistors, deposited from solution, possessing controllable topology and an on/off ratio as high as 900,000. The spin-assisted alignment and density of the SWNTs are tuned by different surfaces that effectively vary the degree of interaction with surface functionalities in the device channel. This leads to a self-sorted SWNT network in which nanotube chirality separation and simultaneous control of density and alignment occur in one step during device fabrication. Micro-Raman experiments corroborate device results as a function of surface chemistry, indicating enrichment of the specific SWNT electronic type absorbed onto the modified dielectric.     

Conductance-controlled point functionalization of single-walled carbon nanotubes

We used covalent attachments to single-walled carbon nanotubes (SWNTs) to fabricate single-molecule electronic devices. The technique does not rely on submicrometer lithography or precision mechanical manipulation, but instead uses circuit conductance to monitor and control covalent attachment to an electrically connected SWNT. Discrete changes in the circuit conductance revealed chemical processes happening in real time and allowed the SWNT sidewalls to be deterministically broken, reformed, and conjugated to target species. By controlling the chemistry through electronically controlled electrochemical potentials, we were able to achieve single chemical attachments. We routinely functionalized pristine, defect-free SWNTs at one, two, or more sites and demonstrated three-terminal devices in which a single attachment controls the electronic response.     

Selective etching of metallic carbon nanotubes by gas-phase reaction

Metallic and semiconducting carbon nanotubes generally coexist in as-grown materials. We present a gas-phase plasma hydrocarbonation reaction to selectively etch and gasify metallic nanotubes, retaining the semiconducting nanotubes in near-pristine form. With this process, 100% of purely semiconducting nanotubes were obtained and connected in parallel for high-current transistors. The diameter- and metallicity-dependent "dry" chemical etching approach is scalable and compatible with existing semiconductor processing for future integrated circuits.     

Chemical detection with a single-walled carbon nanotube capacitor

We show that the capacitance of single-walled carbon nanotubes (SWNTs) is highly sensitive to a broad class of chemical vapors and that this transduction mechanism can form the basis for a fast, low-power sorption-based chemical sensor. In the presence of a dilute chemical vapor, molecular adsorbates are polarized by the fringing electric fields radiating from the surface of a SWNT electrode, which causes an increase in its capacitance. We use this effect to construct a high-performance chemical sensor by thinly coating the SWNTs with chemoselective materials that provide a large, class-specific gain to the capacitance response. Such SWNT chemicapacitors are fast, highly sensitive, and completely reversible.     

Computational design of virus-like protein assemblies on carbon nanotube surfaces

There is a general need for the engineering of protein-like molecules that organize into geometrically specific superstructures on molecular surfaces, directing further functionalization to create richly textured, multilayered assemblies. Here we describe a computational approach whereby the surface properties and symmetry of a targeted surface define the sequence and superstructure of surface-organizing peptides. Computational design proceeds in a series of steps that encode both surface recognition and favorable intersubunit packing interactions. This procedure is exemplified in the design of peptides that assemble into a tubular structure surrounding single-walled carbon nanotubes (SWNTs). The geometrically defined, virus-like coating created by these peptides converts the smooth surfaces of SWNTs into highly textured assemblies with long-scale order, capable of directing the assembly of gold nanoparticles into helical arrays along the SWNT axis.     

Extreme oxygen sensitivity of electronic properties of carbon nanotubes

The electronic properties of single-walled carbon nanotubes are shown here to be extremely sensitive to the chemical environment. Exposure to air or oxygen dramatically influences the nanotubes' electrical resistance, thermoelectric power, and local density of states, as determined by transport measurements and scanning tunneling spectroscopy. These electronic parameters can be reversibly "tuned" by surprisingly small concentrations of adsorbed gases, and an apparently semiconducting nanotube can be converted into an apparent metal through such exposure. These results, although demonstrating that nanotubes could find use as sensitive chemical gas sensors, likewise indicate that many supposedly intrinsic properties measured on as-prepared nanotubes may be severely compromised by extrinsic air exposure effects.     

DNA-templated carbon nanotube field-effect transistor

The combination of their electronic properties and dimensions makes carbon nanotubes ideal building blocks for molecular electronics. However, the advancement of carbon nanotube-based electronics requires assembly strategies that allow their precise localization and interconnection. Using a scheme based on recognition between molecular building blocks, we report the realization of a self-assembled carbon nanotube field-effect transistor operating at room temperature. A DNA scaffold molecule provides the address for precise localization of a semiconducting single-wall carbon nanotube as well as the template for the extended metallic wires contacting it.     

Crossed nanotube junctions

Junctions consisting of two crossed single-walled carbon nanotubes were fabricated with electrical contacts at each end of each nanotube. The individual nanotubes were identified as metallic (M) or semiconducting (S), based on their two-terminal conductances; MM, MS, and SS four-terminal devices were studied. The MM and SS junctions had high conductances, on the order of 0.1 e(2)/h (where e is the electron charge and h is Planck's constant). For an MS junction, the semiconducting nanotube was depleted at the junction by the metallic nanotube, forming a rectifying Schottky barrier. We used two- and three-terminal experiments to fully characterize this junction.     

Diameter-Selective Raman Scattering from Vibrational Modes in Carbon Nanotubes

Single wall carbon nanotubes (SWNTs) that are found as close-packed arrays in crystalline ropes have been studied by using Raman scattering techniques with laser excitation wavelengths in the range from 514.5 to 1320 nanometers. Numerous Raman peaks were observed and identified with vibrational modes of armchair symmetry (n, n) SWNTs. The Raman spectra are in good agreement with lattice dynamics calculations based on C-C force constants used to fit the two-dimensional, experimental phonon dispersion of a single graphene sheet. Calculated intensities from a nonresonant, bond polarizability model optimized for sp2 carbon are also in qualitative agreement with the Raman data, although a resonant Raman scattering process is also taking place. This resonance results from the one-dimensional quantum confinement of the electrons in the nanotube.     

Optical spectroscopy of individual single-walled carbon nanotubes of defined chiral structure

We simultaneously determined the physical structure and optical transition energies of individual single-walled carbon nanotubes by combining electron diffraction with Rayleigh scattering spectroscopy. These results test fundamental features of the excited electronic states of carbon nanotubes. We directly verified the systematic changes in transition energies of semiconducting nanotubes as a function of their chirality and observed predicted energy splittings of optical transitions in metallic nanotubes.     

Separation of metallic from semiconducting single-walled carbon nanotubes

We have developed a method to separate metallic from semiconducting single-walled carbon nanotubes from suspension using alternating current dielectrophoresis. Our method takes advantage of the difference of the relative dielectric constants of the two species with respect to the solvent, resulting in an opposite movement of metallic and semiconducting tubes along the electric field gradient. Metallic tubes are attracted toward a microelectrode array, leaving semiconducting tubes in the solvent. Proof of the effectiveness of separation is given by a comparative Raman spectroscopy study on the dielectrophoretically deposited tubes and on a reference sample.     

Covalently bridging gaps in single-walled carbon nanotubes with conducting molecules

Molecular electronics is often limited by the poorly defined nature of the contact between the molecules and the metal surface. We describe a method to wire molecules into gaps in single-walled carbon nanotubes (SWNTs). Precise oxidative cutting of a SWNT produces carboxylic acid-terminated electrodes separated by gaps of 相似文献   

Single-Electron Transport in Ropes of Carbon Nanotubes

The electrical properties of individual bundles, or "ropes," of single-walled carbon nanotubes have been measured. Below about 10 kelvin, the low-bias conductance was suppressed for voltages less than a few millivolts. In addition, dramatic peaks were observed in the conductance as a function of a gate voltage that modulated the number of electrons in the rope. These results are interpreted in terms of single-electron charging and resonant tunneling through the quantized energy levels of the nanotubes composing the rope.