Imaging as-grown single-walled carbon nanotubes originated from isolated catalytic nanoparticles

Discrete catalytic nanoparticles with diameters in the range of 1–3 nm are obtained by placing controllable numbers of metal atoms into the cores of apoferritin. With nanoparticles placed on transmission electron microscope (TEM) grids coated with ultra-thin alumina membranes, isolated single-walled carbon nanotubes are grown by chemical vapor deposition and directly examined by TEM. The characterizations, carried out at single-tube and single-particle level, obtain clear evidence that the diameters of the nanotubes are determined by the diameters of catalytic nanoparticles. For the first time, both ends of an as-grown single-walled nanotube are imaged by TEM, leading to a microscopic picture of the nanotube-growth mechanism. Received: 19 September 2001 / Accepted: 3 December 2001 / Published online: 4 March 2002     

Effect of nickel,iron and cobalt on growth of aligned carbon nanotubes

The effect of pure nickel, iron and cobalt on growth of aligned carbon nanotubes was systematically studied by plasma-enhanced hot-filament chemical vapor deposition. It is found that the catalyst has a strong effect on the nanotube diameter, growth rate, wall thickness, morphology and microstructure. Ni yields the highest growth rate, largest diameter and thickest wall, whereas Co results in the lowest growth rate, smallest diameter and thinnest wall. The carbon nanotubes catalyzed by Ni have the best alignment and the smoothest and cleanest wall surface, whereas those from Co are covered with amorphous carbon and nanoparticles on the outer surface. The carbon nanotubes produced from Ni catalyst also exhibit a reasonably good graphitization. Therefore, Ni is considered as the most suitable catalyst for growth of aligned carbon nanotubes. Received: 30 November 2001 / Accepted: 3 December 2001 / Published online: 4 March 2002     

Growth of vertically aligned carbon-nanotube array on large area of quartz plates by chemical vapor deposition

A simple method has been developed for growth of well-aligned carbon nanotubes (CNTs) on nickel-film quartz plates by chemical vapor deposition (CVD) with organic ethylenediamine as a precursor. High-density carbon nanotubes were vertically aligned on a large area of the quartz plates. The height of the nanotube array could be controlled by varying the CVD time. High-resolution transmission electron microscopy analysis revealed that the multiwalled CNTs were composed of crystalline graphitic sheets with a bamboo structure. Received: 28 May 2001 / Accepted: 3 December 2001 / Published online: 4 March 2002     

Growth mechanisms for single-wall carbon nanotubes in a laser-ablation process

Mechanisms proposed in the literature are compared with a current scenario for the formation of single-wall carbon nanotubes in the laser-ablation process that is based on our spectral emission and laser-induced fluorescence measurements. It is suggested that the carbon which serves as feedstock for nanotube formation not only comes from the direct ablation of the target, but also from carbon particles suspended in the reaction zone. Fullerenes formed in the reaction zone may be photo-dissociated into C₂ and other low molecular weight species, and also may serve as feedstock for nanotube growth. Confinement of the nanotubes in the reaction zone within the laser beam allows the nanotubes to be ‘purified’ and annealed during the formation process by laser heating. Received: 2 November 2000 / Accepted: 3 November 2000 / Published online: 23 March 2001     

Electrochemical synthesis of polypyrrole/carbon nanotube nanoscale composites using well-aligned carbon nanotube arrays

Polypyrrole/carbon nanotube nanoscale composites were successfully fabricated by electrochemical deposition of polypyrrole over each of the carbon nanotubes in well-aligned large arrays. The thickness of the polypyrrole coating can be easily controlled by the value of the film-formation charge. For both thin (low film-formation charge) and thick (high film-formation charge) films, the polypyrrole coating on the surface of each nanotube is very uniform throughout the entire length, as observed by transmission electron microscopy. Received: 2 May 2001 / Accepted: 4 May 2001 / Published online: 20 June 2001     

Atomistic Failure Mechanism of Single Wall Carbon Nanotubes with Small Diameters

Single wall carbon nanotubes with small diameters （〈 5.0 A） subjected to bending deformation are simulated by orthogonal tight-binding molecular dynamics approach. Based on the calculations of C-C bond stretching and breaking in the bending nanotubes, we elucidate the atomistic failure mechanisms of nanotube with small diameters. In the folding zone of bending nanotube, a large elongation of C-C bonds occurs, accounting for the superelastic behaviour. The C-C bonds parallel to the axis direction of nanotube are broken firstly due to the sustained longitudinal stretching strain, giving rising to forming one-notch or two-notch bond-breaking mode depending on nanotube chirMities. The direct bond-breaking mechanism is responsible for the brittle fracture behaviour of nanotubes with small diameters.     

Carbon nanotubes: opportunities and challenges

Carbon nanotubes are graphene sheets rolled-up into cylinders with diameters as small as one nanometer. Extensive work carried out worldwide in recent years has revealed the intriguing electrical and mechanical properties of these novel molecular scale wires. It is now well established that carbon nanotubes are ideal model systems for studying the physics in one-dimensional solids and have significant potential as building blocks for various practical nanoscale devices. Nanotubes have been shown to be useful for miniaturized electronic, mechanical, electromechanical, chemical and scanning probe devices and materials for macroscopic composites. Progress in nanotube growth has facilitated the fundamental study and applications of nanotubes. Gaining control over challenging nanotube growth issues is critical to the future advancement of nanotube science and technology, and is being actively pursued by researchers.     

Altering the catalytic activity of thin metal catalyst films for controlled growth of chemical vapor deposited vertically aligned carbon nanotube arrays

The growth rate and terminal length of vertically aligned carbon nanotube arrays (VANTAs) grown by chemical vapor deposition have been dramatically improved through pulsed KrF excimer laser pretreatments of multilayer metal catalyst films. Silicon wafers coated with Al, Mo, and Fe layers were laser processed in air with single laser shots of varying fluence through circular apertures, then heated to ∼750°C and exposed to acetylene and ferrocene containing gas mixtures typically used to grow vertically aligned nanotube arrays. In situ videography was used to record the growth kinetics of the nanotube arrays in both patterned and unpatterned regions to understand the changes in catalytic activity, growth rates, and termination of growth. The height of the patterned regions varied with fluence, with the most successful treatment resulting in 1.4 cm tall posts of nanotubes embedded in a 0.4 cm tall nanotube carpet. High-resolution transmission electron microscopy images from the nanotubes in the posts revealed fewer walls, smaller diameters, and a much narrower distribution of diameters compared to the nanotubes grown in the carpet. This information, along with data obtained from weighing the material from each region, suggests that pulsed laser processing can also significantly increase the areal density of VANTAs. Research sponsored by the Division of Materials Sciences and Engineering, U.S. Department of Energy.     

Carbon nanotubes formed in graphite after mechanical grinding and thermal annealing

Multi-walled carbon nanotubes with cylindrical and bamboo-type structures are produced in a graphite sample after mechanical milling at ambient temperature and subsequent thermal annealing up to 1400 °C. The ball milling produces a precursor structure and the thermal annealing activates the nanotube growth. Different nanotubular structures indicate different formation mechanisms: multi-wall cylindrical carbon nanotubes are probably formed upon micropores and the bamboo tubes are produced because of the metal catalysts. A two-dimensional growth governed by surface diffusion is believed to be one important factor for the nanotube growth. A potential industrial production method is demonstrated with advantages of large production quantity and low cost. Received: 17 May 2002 / Accepted: 12 September 2002 / Published online: 4 December 2002 RID="*" ID="*"Corresponding author. Fax: +61-2/6125-8338, E-mail: ying.chen@anu.edu.au     

Selective growth of carbon nantoubes on SiO2/Si substrate

Three-step raising temperature process was employed to fabricate carbon nanotubes by pyrolysis of ferrocene/melamine mixtures on silica and single crystalline silicon wafers respectively. Then the morphologies, structures and compositions of obtained carbon nanotubes are investigated by scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray spectroscope (EDX) and electron energy-loss spectroscopy (EELS). TEM and SEM observation shows that on silica substrate, high-oriented carbon nanotube can grow compactly to form continuous film on both frontal and cross-section surfaces, but on silicon substrate, only can form on cross-section surface. These carbon nanotubes have much irregular cup-like structure, and with outer diameter varying from 25 nm to 35 nm. At the top end of carbon nanotube there is a catalyst particle. EDX analysis reveals that the particle are iron cluster, and EELS spectrum indicates that the nanotube is composed of pure carbon. Finally, the effect of substrate surface roughness on the growth behavior of carbon nanotubes has been discussed.     

Copper nanocluster diffusion in carbon nanotube

The diffusion of copper nanocluster in carbon nanotube was investigated using a classical molecular dynamics simulation and three empirical potential functions. The results indicated a growth mechanism of the copper-filled ultra-thin carbon nanotubes: the copper nanoclusters inserted into carbon nanotubes swiftly migrate along the tube axis, and then the copper nanowires grow in the ultra-thin carbon nanotubes. Periodic energy barriers in the carbon nanotubes induced the directional movement of copper nanoclusters in the carbon nanotubes. The diffusion speeds of copper nanocluster in the carbon nanotube showed the Arrherius relation.     

Thermal properties of carbon nanotubes and nanotube-based materials

The thermal properties of carbon nanotubes are directly related to their unique structure and small size. Because of these properties, nanotubes may prove to be an ideal material for the study of low-dimensional phonon physics, and for thermal management, both on the macro- and the micro-scale. We have begun to explore the thermal properties of nanotubes by measuring the specific heat and thermal conductivity of bulk SWNT samples. In addition, we have synthesized nanotube-based composite materials and measured their thermal conductivity. The measured specific heat of single-walled nanotubes differs from that of both 2D graphene and 3D graphite, especially at low temperatures, where 1D quantization of the phonon bandstructure is observed. The measured specific heat shows only weak effects of intertube coupling in nanotube bundling, suggesting that this coupling is weaker than expected. The thermal conductivity of nanotubes is large, even in bulk samples: aligned bundles of SWNTs show a thermal conductivity of >200 W/m K at room temperature. A linear K(T) up to approximately 40 K may be due to 1D quantization; measurement of K(T) of samples with different average nanotube diameters supports this interpretation. Nanotube–epoxy blends show significantly enhanced thermal conductivity, showing that nanotube-based composites may be useful not only for their potentially high strength, but also for their potentially high thermal conductivity. Received: 17 October 2001 / Accepted: 3 December 2001 / Published online: 4 March 2002     

Synthesis and morphology of boron nitride nanotubes and nanohorns

Boron nitride (BN) nanotubes have been synthesized by evaporating a mixture of boron and gallium oxide in the presence of ammonia gas. The synthesized BN nanotubes exhibit a well-crystallized concentric structure with diameters less than 30 nm, and no carbon contamination or defects could be observed, while the BN nanotubes with large diameters usually show a number of defects. Some BN nanohorn structures could also be observed in the product. The carbon-free growth of BN nanotubes was explained based on the vapor–liquid–solid growth mechanism, and the catalytic activity of liquid gallium for BN one-dimensional growth was also demonstrated. Received: 16 April 2002 / Accepted: 25 May 2002 / Published online: 19 July 2002     

Multiwalled carbon nanotubes are ballistic conductors at room temperature

Following the experiments of Frank et al. [1], which demonstrated quantum transport in multiwalled carbon nanotubes, there have been several experiments that appear to contradict the main conclusion of that paper, which is that the transport of a MWNT at room temperature is ballistic. Here we demonstrate that the intrinsic resistance of clean-arc-produced carbon nanotubes is at most 200 Ω/ μm, which implies that the momentum mean free path is greater than 30 μm, which in turn is much larger than the tube length. This implies that these tubes are ballistic, according to the standard definition of ballistic transport. We also show that the contact resistance with mercury is quite large: a nanotube in contact with Hg over 100 nm of its length still represents a 3000 Ω resistance. Received: 14 September 2001 / Accepted: 3 December 2001 / Published online: 4 March 2002     

Flame synthesis of single-walled carbon nanotubes

Flames offer potential for synthesis of carbon nanotubes in large quantities at considerably lower costs than that of other methods currently available. This study aims to examine conditions for carbon nanotube formation in premixed flames and to characterize the morphology of solid carbon deposits and their primary formation mechanisms in the combustion environment. Single-walled nanotubes have been observed in the post-flame region of a premixed acetylene/oxygen/15 mol% argon flame operated at 6.7 kPa with Fe(CO)₅ vapor used as a source of metallic catalyst necessary for nanotube growth. Thermophoretic sampling and transmission electron microscopy were used to characterize the solid material present in the flame at various heights above burner (HAB), giving a resolution of formation dynamics within the flame system. Catalyst particle formation and growth is observed to dominate the immediate post-flame region (10–40 mm HAB). Nanotubes were observed to be present after 40 mm HAB with nanotube inception occurring as early as 30 mm HAB. Between 40 and 70 mm HAB, nanotubes are observed to coalesce into clusters. A nanotube formation ‘window’ is evident with formation limited to fuel equivalence ratios between 1.5 and 1.9. A continuum of morphologies ranging from relatively clean clusters of nanotubes to amorphous material is observed between these lower and upper limits. High-resolution TEM and Raman spectroscopy revealed nanotube bundles with each nanotube being single-walled with diameters between 0.9 and 1.5 nm.     

Laser heating method for estimation of carbon nanotube purity

A new method of a carbon nanotube purity estimation has been developed on the basis of Raman spectroscopy. The spectra of carbon soot containing different amounts of nanotubes were registered under heating from a probing laser beam with a step-by-step increased power density. The material temperature in the laser spot was estimated from a position of the tangential Raman mode demonstrating a linear thermal shift (-0.012 cm^-1/K) from the position 1592 cm^-1 (at room temperature). The rate of the material temperature rise versus the laser power density (determining the slope of a corresponding graph) appeared to correlate strongly with the nanotube content in the soot. The influence of the experimental conditions on the slope value has been excluded via a simultaneous measurement of a reference sample with a high nanotube content (95 vol. %). After the calibration (done by a comparison of the Raman and the transmission electron microscopy data for the nanotube percentage in the same samples) the Raman-based method is able to provide a quantitative purity estimation for any nanotube-containing material. Received: 11 December 2001 / Accepted: 12 December 2001 / Published online: 4 March 2002     

Simple and accurate model for voltage-dependent resistance of metallic carbon nanotube interconnects: An ab initio study

In this work, development of a voltage dependent resistance model for metallic carbon nanotubes is aimed. Firstly, the resistance of metallic carbon nanotube interconnects are obtained from ab initio simulations and then the voltage dependence of the resistance is modeled through regression. Self-consistent non-equilibrium Green's function formalism combined with density functional theory is used for calculating the voltage dependent resistance of metallic carbon nanotubes. It is shown that voltage dependent resistances of carbon nanotubes can be accurately modeled as a polynomial function which enables rapid integration of carbon nanotube interconnect models into electronic design automation tools.     

Thinning and diluting aligned carbon nanotube films for uniform field emission

Aligned carbon nanotube (CNT) films are potential field emitters for large-area flat panel displays. However, the distribution of emission areas in the CNT films is quite non-uniform because of inhomogeneous nanotube growth, which is hard to avoid using the conventional chemical vapor deposition (CVD) method. Here we show that the emission uniformity of CNT films can be improved simply by reducing the film thickness (thinning) or the nanotube density (diluting). The thickness and density of CNT films could be controlled by controlling the CNT growth time and temperature. Received: 12 June 2001 / Accepted: 27 October 2001 / Published online: 23 January 2002     

Electrical transport and noise in semiconducting carbon nanotubes

We investigate electrical transport and noise in semiconducting carbon nanotubes. By studying carbon nanotube devices with various diameters and contact metals, we show that the ON-currents of CNFETs are governed by the heights of the Schottky barriers at the metal/nanotube interfaces. The current fluctuations are dominated by 1/f noise at low-frequencies and correlate with the number of transport carriers in the device regardless of contact metal.     

Effect of gas pressure on the growth and structure of carbon nanotubes by chemical vapor deposition

The effect of gas pressure on the structure of carbon nanotubes (CNTs) has been systematically investigated in the chemical vapor deposition process. The yield of CNTs (defined as the weight ratio of CNTs vs. catalyst) increases significantly with the gas pressure, reaches 600% at 600 Torr, then decreases with further increase of gas pressure. At low reacting gas pressure the CNTs have completely hollow cores, whereas at high pressure the CNTs have a bamboo structure. The density of the compartments in the bamboo-structured CNTs increases dramatically with the increase of the gas pressure. This result shows that the structure and yield of carbon nanotubes are strongly affected by the growth gas pressure. Received: 10 May 2001 / Accepted: 10 May 2001 / Published online: 20 June 2001