Large-Scale Synthesis of Aligned Carbon Nanotubes

Large-scale synthesis of aligned carbon nanotubes was achieved by using a method based on chemical vapor deposition catalyzed by iron nanoparticles embedded in mesoporous silica. Scanning electron microscope images show that the nanotubes are approximately perpendicular to the surface of the silica and form an aligned array of isolated tubes with spacings between the tubes of about 100 nanometers. The tubes are up to about 50 micrometers long and well graphitized. The growth direction of the nanotubes may be controlled by the pores from which the nanotubes grow.     

Electronic structures of single-walled carbon nanotubes determined by NMR

Single-walled carbon nanotubes were studied by (13)C nuclear magnetic resonance (NMR). Two types of (13)C nuclear spins were identified with different spin-lattice relaxation rates. The fast-relaxing component, assigned to metallic tubes, followed the relaxation behavior expected in metals, and the density-of-states at the Fermi level increased with decreasing tube diameter. The slow-relaxing component has a significantly lower density-of-states at the Fermi level. Exposure to oxygen has a substantial effect on relaxation rates of both components.     

Aligned carbon nanotube films: production and optical and electronic properties

Carbon nanotube material can now be produced in macroscopic quantities. However, the raw material has a disordered structure, which restricts investigations of both the properties and applications of the nanotubes. A method has been developed to produce thin films of aligned carbon nanotubes. The tubes can be aligned either parallel or perpendicular to the surface, as verified by scanning electron microscopy. The parallel aligned surfaces are birefringent, reflecting differences in the dielectric function along and normal to the tubes. The electrical resistivities are anisotropic as well, being smaller along the tubes than perpendicular to them, because of corresponding differences in the electronic transport properties.     

An integrated logic circuit assembled on a single carbon nanotube

Single-walled carbon nanotubes (SWCNTs) have been shown to exhibit excellent electrical properties, such as ballistic transport over several hundred nanometers at room temperature. Field-effect transistors (FETs) made from individual tubes show dc performance specifications rivaling those of state-of-the-art silicon devices. An important next step is the fabrication of integrated circuits on SWCNTs to study the high-frequency ac capabilities of SWCNTs. We built a five-stage ring oscillator that comprises, in total, 12 FETs side by side along the length of an individual carbon nanotube. A complementary metal-oxide semiconductor-type architecture was achieved by adjusting the gate work functions of the individual p-type and n-type FETs used.     

Electrostatic deflections and electromechanical resonances of carbon nanotubes

Static and dynamic mechanical deflections were electrically induced in cantilevered, multiwalled carbon nanotubes in a transmission electron microscope. The nanotubes were resonantly excited at the fundamental frequency and higher harmonics as revealed by their deflected contours, which correspond closely to those determined for cantilevered elastic beams. The elastic bending modulus as a function of diameter was found to decrease sharply (from about 1 to 0.1 terapascals) with increasing diameter (from 8 to 40 nanometers), which indicates a crossover from a uniform elastic mode to an elastic mode that involves wavelike distortions in the nanotube. The quality factors of the resonances are on the order of 500. The methods developed here have been applied to a nanobalance for nanoscopic particles and also to a Kelvin probe based on 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.     

Self-assembly of subnanometer-diameter single-wall MoS2 nanotubes

We report on the synthesis, structure, and self-assembly of single-wall subnanometer-diameter molybdenum disulfide tubes. The nanotubes are up to hundreds of micrometers long and display diverse self-assembly properties on different length scales, ranging from twisted bundles to regularly shaped "furry" forms. The bundles, which contain interstitial iodine, can be readily disassembled into individual molybdenum disulfide nanotubes. The synthesis was performed using a novel type of catalyzed transport reaction including C(60) as a growth promoter.     

Microscopic Growth Mechanisms for Carbon Nanotubes

The uncatalyzed edge growth of carbon nanotubes was investigated by first-principles molecular dynamics simulations. At experimental temperatures the open end of single-walled nanotubes closed spontaneously into a graphitic dome, which may explain why these nanotubes do not grow in the absence of transition metal catalysts. On the other hand, chemical bonding between the edges of adjacent coaxial tubes ("lip-lip" interactions) trapped the end of a double-walled nanotube in a metastable energy minimum, thus preventing dome closure. These calculations show that this end geometry exhibits a high degree of chemical activity and easily accommodates incoming carbon fragments, supporting a model of growth by chemisorption from the vapor phase.     

Nanocapillarity and Chemistry in Carbon Nanotubes

Open carbon nanotubes were filled with molten silver nitrate by capillary forces. Only those tubes with inner diameters of 4 nanometers or more were filled, suggesting a capillarity size dependence as a result of the lowering of the nanotube-salt interface energy with increasing curvature of the nanotube walls. Nanotube cavities should also be less chemically reactive than graphite and may serve as nanosize test tubes. This property has been illustrated by monitoring the decomposition of silver nitrate within nanotubes in situ in an electron microscope, which produced chains of silver nanobeads separated by high-pressure gas pockets.     

Energy gaps in "metallic" single-walled carbon nanotubes

Metallic single-walled carbon nanotubes have been proposed to be good one-dimensional conductors. However, the finite curvature of the graphene sheet that forms the nanotubes and the broken symmetry due to the local environment may modify their electronic properties. We used low-temperature atomically resolved scanning tunneling microscopy to investigate zigzag and armchair nanotubes, both thought to be metallic. "Metallic" zigzag nanotubes were found to have energy gaps with magnitudes that depend inversely on the square of the tube radius, whereas isolated armchair tubes do not have energy gaps. Additionally, armchair nanotubes packed in bundles have pseudogaps, which exhibit an inverse dependence on tube radius. These observed energy gaps suggest that most "metallic" single-walled nanotubes are not true metals, and they have implications for our understanding of the electronic properties and potential applications of carbon nanotubes.     

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.     

Boron nitride nanotubes

The successful synthesis of pure boron nitride (BN) nanotubes is reported here. Multi-walled tubes with inner diameters on the order of 1 to 3 nanometers and with lengths up to 200 nanometers were produced in a carbon-free plasma discharge between a BN-packed tungsten rod and a cooled copper electrode. Electron energy-loss spectroscopy on individual tubes yielded B:N ratios of approximately 1, which is consistent with theoretical predictions of stable BN tube structures.     

Growth and sintering of fullerene nanotubes

Carbon nanotubes produced in arcs have been found to have the form of multiwalled fullerenes, at least over short lengths. Sintering of the tubes to each other is the predominant source of defects that limit the utility of these otherwise perfect fullerene structures. The use of a water-cooled copper cathode minimized such defects, permitting nanotubes longer than 40 micrometers to be attached to macroscopic electrodes and extracted from the bulk deposit. A detailed mechanism that features the high electric field at (and field-emission from) open nanotube tips exposed to the arc plasma, and consequent positive feedback effects from the neutral gas and plasma, is proposed for tube growth in such arcs.     

Aligned multiwalled carbon nanotube membranes

An array of aligned carbon nanotubes (CNTs) was incorporated across a polymer film to form a well-ordered nanoporous membrane structure. This membrane structure was confirmed by electron microscopy, anisotropic electrical conductivity, gas flow, and ionic transport studies. The measured nitrogen permeance was consistent with the flux calculated by Knudsen diffusion through nanometer-scale tubes of the observed microstructure. Data on Ru(NH3)6(3+) transport across the membrane in aqueous solution also indicated transport through aligned CNT cores of the observed microstructure. The lengths of the nanotubes within the polymer film were reduced by selective electrochemical oxidation, allowing for tunable pore lengths. Oxidative trimming processes resulted in carboxylate end groups that were readily functionalized at the entrance to each CNT inner core. Membranes with CNT tips that were functionalized with biotin showed a reduction in Ru(NH3)6(3+) flux by a factor of 15 when bound with streptavidin, thereby demonstrating the ability to gate molecular transport through CNT cores for potential applications in chemical separations and sensing.     

冷原子吸收法选用石英管的研究

冷原子吸收法(CAAS),常用石英管内径是12.0,10.0,8.0mm。直径越小,灵敏度越高,故一般多用8.0mm。本文作者进一步用8.0,6.5,5.0mm石英管对砷、汞进行了对比分析。试验结果:其绝对灵敏度:砷为0.220,0.029,0.088ng/0.0044A;汞为0.295,0.197,0.231ng/0.0044A。变异系数:砷为5.0％,6.3％,8.9％;汞为6.3％(6.5mm)。回收率:砷为93％,92％,90％;汞为94.7％(6.5mm)。试验证明石英管的直径为6.5mm时,灵敏度较高,分析质量亦较好。     

h/e magnetic flux modulation of the energy gap in nanotube quantum dots

We report experiments on quantum dot single-electron-tunneling (SET) transistors made from short multiwall nanotubes and threaded by magnetic flux. Such systems allow us to probe the electronic energy spectrum of the nanotube and its dependence on the magnetic field. Evidence is provided for the interconversion between gapped (semiconducting) and ungapped (metallic) states. Our tubes exhibit h/e-period magnetic flux dependence, in agreement with simple tight-binding calculations.     

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.     

Coalescence of single-walled carbon nanotubes

The coalescence of single-walled nanotubes is studied in situ under electron irradiation at high temperature in a transmission electron microscope. The merging process is investigated at the atomic level, using tight-binding molecular dynamics and Monte Carlo simulations. Vacancies induce coalescence via a zipper-like mechanism, imposing a continuous reorganization of atoms on individual tube lattices along adjacent tubes. Other topological defects induce the polymerization of tubes. Coalescence seems to be restricted to tubes with the same chirality, explaining the low frequency of occurrence of this event.     

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.     

Tubular structures associated with turnip yellow mosaic virus in vivo

Plants infected with a necrotic strain of turnip yellow mosaic virus contain tubes averaging about 80 millimicrons in diameter and attaining 3 microns in length. The main constituent of these tubes is a protein that is related chemically and immunologically to the protein of the virus. The tubes are composed of hexagonally packed hexagonal subunits resembling the hexamer protein subunits of the virus particles and are probably helical in construction.