On the electron-phonon coupling of individual single-walled carbon nanotubes

We show that the phonon coupling to the electronic system in individual metallic single-walled carbon nanotubes is not due to coupling to low-energy plasmons. The evidence stems from the measured Raman-Stokes G-mode, which for metallic and semiconducting tubes could be fitted well by the superposition of only two Lorentzian lines associated with vibrational modes along the nanotube axis and the nanotube circumference. In the case of metallic tubes the lower-energy G mode is significantly broadened, however maintaining the Lorentzian line shape, in contrast to the theoretically expected asymmetric Breit-Wigner-Fano line shape from phonon-plasmon coupling. The results were obtained by studying 25 individual metallic and semiconducting single-walled carbon nanotubes with atomic force microscopy, electron transport measurements, and resonant Raman spectroscopy.     

Non-adiabatic phonon dispersion of metallic single-walled carbon nanotubes

Non-adiabatic effects can considerably modify the phonon dispersion of low-dimensional metallic systems. Here, these effects are studied for the case of metallic single-walled carbon nanotubes using a perturbative approach within a density-functional-based non-orthogonal tight-binding model. The adiabatic phonon dispersion was found to have logarithmic Kohn anomalies at the Brillouin zone center and at two mirror points inside the zone. The obtained dynamic corrections to the adiabatic phonon dispersion essentially modify and shift the Kohn anomalies as exemplified in the case of nanotube (8, 5). Large corrections have the longitudinal optical phonon, which gives rise to the so-called G- band in the Raman spectra, and the carbon hexagon breathing phonon. The results obtained for the G- band for all nanotubes in the diameter range from 0.8 to 3.0 nm can be used for assignment of the high-frequency features in the Raman spectra of nanotube samples.     

An atlas of carbon nanotube optical transitions

Electron-electron interactions are significantly enhanced in one-dimensional systems, and single-walled carbon nanotubes provide a unique opportunity for studying such interactions and the related many-body effects in one dimension. However, single-walled nanotubes can have a wide range of diameters and hundreds of different structures, each defined by its chiral index (n,m), where n and m are integers that can have values from zero up to 30 or more. Moreover, one-third of these structures are metals and two-thirds are semiconductors, and they display optical resonances at many different frequencies. Systematic studies of many-body effects in nanotubes would therefore benefit from the availability of a technique for identifying the chiral index of a nanotube based on a measurement of its optical resonances, and vice versa. Here, we report the establishment of a structure-property 'atlas' for nanotube optical transitions based on simultaneous electron diffraction measurements of the chiral index and Rayleigh scattering measurements of the optical resonances of 206 different single-walled nanotube structures. The nanotubes, which were suspended across open slit structures on silicon substrates, had diameters in the range 1.3-4.7?nm. We also use this atlas as a starting point for a systematic study of many-body effects in the excited states of single-walled nanotubes. We find that electron-electron interactions shift the optical resonance energies by the same amount for both metallic and semiconducting nanotubes, and that this shift (which corresponds to an effective Fermi velocity renormalization) increases monotonically with nanotube diameter. This behaviour arises from two sources: an intriguing cancellation of long-range electron-electron interaction effects, and the dependence of short-range electron-electron interactions on diameter.     

Frequency dependence of the dielectrophoretic separation of single-walled carbon nanotubes

Dielectrophoresis on single-walled carbon nanotubes in surfactant suspensions has been demonstrated to separate metallic from semiconducting tubes by their different electric field-induced polarisabilities. Here we report that the interaction between SWNTs and the surfactant induces a nanotube surface conductance which gives rise to a unique electric field frequency dependence of the dielectrophoretic force acting on semiconducting SWNTs. We observe a surfactant concentration dependent crossover frequency enabling separation of metallic from semiconducting SWNTs at high frequency and deposition of metallic and semiconducting SWNTs at low frequency. Proof for the effectiveness of separation is given by a comparative Raman spectroscopy study on dielectrophoretically deposited tubes excited with two different wavelengths.     

Effect of mixture ratios and nitrogen carrier gas flow rates on the morphology of carbon nanotube structures grown by CVD

We report on the growth of carbon nanotubes (CNTs) by thermal Chemical Vapor Deposition (CVD) and investigate the effects of nitrogen carrier gas flow rates and mixture ratios on the morphology of CNTs on a silicon substrate by vaporizing the camphor/ferrocene mixture at 750 °C in a nitrogen atmosphere. Carbon layers obtained after each CVD growth run of 15 min are characterized by scanning electron microscopy (SEM) and Raman spectroscopy. Growth of CNTs is found to occur on silicon substrates. The SEM micrographs helped better understand the nanotube growth morphology while Raman Spectroscopy was used to detect the presence of nanotubes and also identify their nature vizely semiconducting or metallic, single-walled or multi-walled. Raman Spectra was also useful to estimate the quality of the samples as a ratio of nanotube to non-nanotube content. The length and diameters of the aligned CNTs were found to depend on the pyrolysis temperatures, mixture ratio, and the nitrogen carrier gas flow rates.     

Influence of structural and dielectric anisotropy on the dielectrophoresis of single-walled carbon nanotubes

We report on a carbon nanotube network which is composed of aligned metallic and randomly oriented semiconducting single-walled carbon nanotubes. The material is formed by using a novel radio frequency dielectrophoresis setup, which generates very large dielectrophoretic force fields and allows dielectrophoretic assembling of nanotube films up to 100 nm thickness. Polarization dependent absorption measurements provide experimental evidence for the electronic type specific alignment behavior. We explain the experimental data with an advanced model for nanotube dielectrophoresis, which explicitly takes into account both the longitudinal and transversal polarizability. On the basis of this model, we calculate the dielectrophoretic force fields and show that semiconducting nanotubes deposit under very large fields due to their transversal polarizability even for high field frequencies.     

Label-free imaging of semiconducting and metallic carbon nanotubes in cells and mice using transient absorption microscopy

As interest in the potential biomedical applications of carbon nanotubes increases, there is a need for methods that can image nanotubes in live cells, tissues and animals. Although techniques such as Raman, photoacoustic and near-infrared photoluminescence imaging have been used to visualize nanotubes in biological environments, these techniques are limited because nanotubes provide only weak photoluminescence and low Raman scattering and it remains difficult to image both semiconducting and metallic nanotubes at the same time. Here, we show that transient absorption microscopy offers a label-free method to image both semiconducting and metallic single-walled carbon nanotubes in vitro and in vivo, in real time, with submicrometre resolution. By using appropriate near-infrared excitation wavelengths, we detect strong transient absorption signals with opposite phases from semiconducting and metallic nanotubes. Our method separates background signals generated by red blood cells and this allows us to follow the movement of both types of nanotubes inside cells and in the blood circulation and organs of mice without any significant damaging effects.     

The BN-pair impurity in carbon nanotubes and the possibility for disorder-induced frustration of gap formation

We study the BN-pair impurity complex inside a metallic and a semiconducting single-walled carbon nanotube host. For the single impurity in the semiconducting tube, we find that no electron or hole bound states can be sustained because the distance between the B and the N is less than the effective Fermi-Teller radius for that system. If the BN pairs are incorporated at stoichiometric concentrations (BC(10)N nanotubes), achievable for example with a borabenzene-pyridine adduct C(10)H(10)BN precursor, the metallic tube becomes semiconducting for an ordered arrangement of the impurities, but the introduction of disorder restores a finite density of states at the Fermi level. Thus, in the mechanism presented here, disorder effectively restores the symmetry of the nanotube, returning the nanotube to its original metallic character.     

Doping and phonon renormalization in carbon nanotubes

We show that the Raman frequency associated with the vibrational mode at approximately 1,580 cm(-1) (the G mode) in both metallic and semiconducting carbon nanotubes shifts in response to changes in the charge density induced by an external gate field. These changes in the Raman spectra provide us with a powerful tool for probing local doping in carbon nanotubes in electronic device structures, or charge carrier densities induced by environmental interactions, on a length scale determined by the light diffraction limit. The G mode shifts to higher frequency and narrows in linewidth in metallic carbon nanotubes at large fields. This behaviour is analogous to that observed recently in graphene. In semiconducting carbon nanotubes, on the other hand, induced changes in the charge density only shift the phonon frequency, but do not affect its linewidth. These spectral changes are quantitatively explained by a model that involves the renormalization of the carbon nanotube phonon energy by the electron-phonon interaction as the carrier density in the carbon nanotube is changed.     

Transition of single-walled carbon nanotubes from metallic to semiconducting in field-effect transistors by hydrogen plasma treatment

We report hydrogen plasma treatment results on converting the metallic single-walled carbon nanotubes to semiconducting single-walled carbon nanotubes. We found that the as-grown single-walled carbon nanotubes (SWNTs) can be sorted as three groups which behave as metallic, as-metallic, and semiconducting SWNTs. These three groups have different changes under hydrogen plasma treatment and successive annealing process. The SWNTs can be easily hydrogenated in the hydrogen plasma environment and the as-metallic SWNTs can be transformed to semiconducting SWNTs. The successive annealing process can break the C-H bond, so the conversion is reversible.     

Nickel-cobalt nanoparticles supported on single-walled carbon nanotubes and their catalytic hydrogenation activity

Single-walled carbon nanotubes were synthesized from graphite using the arc discharge technique. A nickel/yttrium/graphite mixture was used as the catalyst. After purification by sonication in a Triton X-100 solution, nickel-cobalt metal nanoparticles were deposited on the surface of the single-walled carbon nanotubes. The resulting material and/or the nanotubes themselves were characterized by physisorption, Raman spectroscopy, high-resolution transition electron microscopy and X-ray diffraction. Raman spectroscopy indicates that the nanotubes, prepared by the arc discharge technique, are semi-conducting with a diameter centering at 1.4 nm. The average nickel-cobalt particle size is estimated to be in the region of 8 nm. The catalytic activity of the material was examined for the hydrogenation of unsaturated fatty acid methyl esters obtained from avocado oil. The carbon nanotube supported nickel-cobalt particles effectively hydrogenate polyunsaturated methyl linoleate to monounsaturated methyl oleate. In contrast to a conventional nickel on kieselghur catalyst, further hydrogenation of methyl oleate to undesired methyl stearate was not observed.     

Absorption spectroscopy of individual single-walled carbon nanotubes

Current methods for producing single-walled carbon nanotubes (SWNTs) lead to heterogeneous samples containing mixtures of metallic and semiconducting species with a variety of lengths and defects. Optical detection at the single nanotube level should thus offer the possibility to examine these heterogeneities provided that both SWNT species are equally well detected. Here, we used photothermal heterodyne detection to record absorption images and spectra of individual SWNTs. Because this photothermal method relies only on light absorption, it readily detects metallic nanotubes as well as the emissive semiconducting species. The first and second optical transitions in individual semiconducting nanotubes have been probed. Comparison between the emission and absorption spectra of the lowest-lying optical transition reveal mainly small Stokes shifts. Side bands in the near-infrared absorption spectra are observed and assigned to exciton-phonon bound states. No such sidebands are detected around the lowest transition of metallic nanotubes.     

Direct identification of metallic and semiconducting single-walled carbon nanotubes in scanning electron microscopy

Because of their excellent electrical and optical properties, carbon nanotubes have been regarded as extremely promising candidates for high-performance electronic and optoelectronic applications. However, effective and efficient distinction and separation of metallic and semiconducting single-walled carbon nanotubes are always challenges for their practical applications. Here we show that metallic and semiconducting single-walled carbon nanotubes on SiO(2) can have obviously different contrast in scanning electron microscopy due to their conductivity difference and thus can be effectively and efficiently identified. The correlation between conductivity and contrast difference has been confirmed by using voltage-contrast scanning electron microcopy, peak force tunneling atom force microscopy, and field effect transistor testing. This phenomenon can be understood via a proposed mechanism involving the e-beam-induced surface potential of insulators and the conductivity difference between metallic and semiconducting SWCNTs. This method demonstrates great promise to achieve rapid and large-scale distinguishing between metallic and semiconducting single-walled carbon nanotubes, adding a new function to conventional SEM.     

Electric field-assisted deposition of nanowires on carbon nanotubes for nanoelectronics and sensor applications

Manipulation and control of matter at the nanoscale and atomic scale levels are crucial for the success of nanoscale sensors and actuators. The ability to control and synthesize multilayer structures using carbon nanotubes that will enable the building of electronic devices within a nanotube is still in its infancy. In this paper, we present results on selective electric field-assisted deposition of metals on carbon nanotubes realizing metallic nanowire structures. Silver and platinum nanowires have been fabricated using this approach for their applications in chemical sensing as catalytic materials to sniff toxic agents and in the area of biomedical nanotechnology for construction of artificial muscles. Electric field-assisted deposition allows the deposition of metals with a high degree of selectivity on carbon nanotubes by manipulating the charges on the surface of the nanotubes and forming electrostatic double-layer supercapacitors. Deposition of metals primarily occurred due to electrochemical reduction, electrophoresis, and electro-osmosis inside the walls of the nanotube. SEM and TEM investigations revealed silver and platinum nanowires between 10 nm and 100 nm in diameter. The present technique is versatile and enables the fabrication of a host of different types of metallic and semiconducting nanowires using carbon nanotube templates for nanoelectronics and a myriad of sensor applications.     

Logic circuits based on individual semiconducting and metallic carbon-nanotube devices

Nanoscale transistors employing an individual semiconducting carbon nanotube as the channel hold great potential for logic circuits with large integration densities that can be manufactured on glass or plastic substrates. Carbon nanotubes are usually produced as a mixture of semiconducting and metallic nanotubes. Since only semiconducting nanotubes yield transistors, the metallic nanotubes are typically not utilized. However, integrated circuits often require not only transistors, but also resistive load devices. Here we show that many of the metallic carbon nanotubes that are deposited on the substrate along with the semiconducting nanotubes can be conveniently utilized as load resistors with favorable characteristics for the design of integrated circuits. We also demonstrate the fabrication of arrays of transistors and resistors, each based on an individual semiconducting or metallic carbon nanotube, and their integration on glass substrates into logic circuits with switching frequencies of up to 500 kHz using a custom-designed metal interconnect layer.     

Progress towards monodisperse single-walled carbon nanotubes

The defining characteristic of a nanomaterial is that its properties vary as a function of its size. This size dependence can be clearly observed in single-walled carbon nanotubes, where changes in structure at the atomic scale can modify the electronic and optical properties of these materials in a discontinuous manner (for example, changing metallic nanotubes to semiconducting nanotubes and vice versa). However, as most practical technologies require predictable and uniform performance, researchers have been aggressively seeking strategies for preparing samples of single-walled carbon nanotubes with well-defined diameters, lengths, chiralities and electronic properties (that is, uniformly metallic or uniformly semiconducting). This review highlights post-synthetic approaches for sorting single-walled carbon nanotubes - including selective chemistry, electrical breakdown, dielectrophoresis, chromatography and ultracentrifugation - and progress towards selective growth of monodisperse samples.     

Hydrogen storage in carbon nanotubes through the formation of stable C-H bonds

To determine if carbon-based materials can be used for hydrogen storage, we have studied hydrogen chemisorption in single-walled carbon nanotubes. Using atomic hydrogen as the hydrogenation agent, we demonstrated that maximal degree of nanotube hydrogenation depends on the nanotube diameter, and for the diameter values around 2.0 nm nanotube-hydrogen complexes with close to 100% hydrogenation exist and are stable at room temperature. This means that specific carbon nanotubes can have a hydrogen storage capacity of more than 7 wt % through the formation of reversible C-H bonds.     

Production and characterization of polymer nanocomposites with highly aligned single-walled carbon nanotubes

We report the production and characterization of polymer nanocomposites with single-walled carbon nanotubes having improved mechanical properties and exceptional nanotube alignment. High-pressure carbon monoxide nanotubes (HiPco) were efficiently distributed in polystyrene (PS) and polyethylene (PE) with a twin-screw compounder. Nanotube concentrations were 1, 5, 10, and 20 wt% in PE composites and 0.7 wt% in PS composites. PE composites were melt-spun into fibers to achieve highly aligned nanotubes. Polarized Raman spectroscopy shows that the degree of alignment increases with decreasing fiber diameter and decreases with increasing nanotube loading. The orientation distribution function of a 1 wt% HiPco/PE composite had a full width at half-maximum of approximately 5 degrees. The elastic modulus increases up to 450% relative to PE fibers for 20 wt% nanotube loading at an intermediate fiber diameter of 100 microns.     

A microcavity-controlled, current-driven, on-chip nanotube emitter at infrared wavelengths

Recent studies of the optical properties of semiconducting single-walled carbon nanotubes suggest that these truly nanometre-scale systems have a promising future in nanophotonics, in addition to their well-known potential in electronics. Semiconducting single-walled nanotubes have a direct, diameter-dependent bandgap and can be excited readily by current injection, which makes them attractive as nano-emitters. The electroluminescence is spectrally broad, spatially non-directional, and the radiative yield is low. Here we report the monolithic integration of a single, electrically excited, semiconducting nanotube transistor with a planar lambda/2 microcavity, thus taking an important first step in the development of nanotube-based nanophotonic devices. The spectral full-width at half-maximum of the emission is reduced from approximately 300 to approximately 40 nm at a cavity resonance of 1.75 microm, and the emission becomes highly directional. The maximum enhancement of the radiative rate is estimated to be 4. We also show that both the optically and electrically excited luminescence of single-walled nanotubes involve the same E11 excitonic transition.     

载气种类对单壁碳纳米管管径的影响研究

单壁碳纳米管的管径对其性能、特别是储氢性能有极其重要的影响,但至今未见制备过程中系统控制单壁碳纳米管管径的报道.本文分别以氦气、氮气和氩气为载气,采用催化裂解法制备了不同直径范围的单壁碳纳米管.HRTEM和Raman光谱分析表明,以氦气、氩气为载气制得的碳管直径分布范围相对较窄,平均直径分别约为1.6和5.0nm.以氮气为载气时碳管直径分布相对较宽,约为2.0～4.5nm.氮气与碳反应生成氮化碳可能是导致单壁碳纳米管直径分布相对较宽的主要原因.分别以氦气、氮气和氩气为载气制得的单壁碳纳米管,在273K,15MPa时质量储氢分数依次为4.21%、6.30%和8.05%.