Nucleation Of Nanotubes Research Articles

Growth of Single‐Walled Carbon Nanotubes from Sharp Metal Tips

The nucleation and growth of single-walled carbon nanotubes is observed in situ in a transmission electron microscope. Carbon atoms are implanted into catalytically active metal particles by electron-beam sputtering. The metal particles are then shaped with a focused electron beam. Once the particles have a region of high surface curvature, spontaneous nucleation and growth of single-walled carbon nanotubes occurs on the metal particles. It is shown that the local solubility of carbon in the metal determines the nucleation of nanotubes. This is confirmed by atomistic computer simulations treating the solubility of carbon in a metal particle as a function of the size of the system.

Quantum Chemical Molecular Dynamics Simulation of Single-Walled Carbon Nanotube Cap Nucleation on an Iron Particle

The atomic scale details of single-walled carbon nanotube (SWNT) nucleation on metal catalyst particles are elusive to experimental observations. Computer simulation of metal-catalyzed SWNT nucleation is a challenging topic but potentially of great importance to understand the factors affecting SWNT diameters, chirality, and growth efficiency. In this work, we use nonequilibrium density functional tight-binding molecular dynamics simulations and report nucleation of sp(2)-carbon cap structures on an iron particle consisting of 38 atoms. One C(2) molecule was placed every 1.0 ps around an Fe(38) cluster for 30 ps, after which a further 410 ps of annealing simulation without carbon supply was performed. We find that sp(2)-carbon network nucleation and annealing processes occur in three sequential and repetitive stages: (A) polyyne chains on the metal surface react with each other to evolve into a Y-shaped polyyne junction, which preferentially form a five-membered ring as a nucleus; (B) polyyne chains on the first five-membered ring form an additional fused five- or six-membered ring; and (C) pentagon-to-hexagon self-healing rearrangement takes place with the help of short-lived polyyne chains, stabilized by the mobile metal atoms. The observed nucleation process resembles the formation of a fullerene cage. However, the metal particle plays a key role in differentiating the nucleation process from fullerene cage formation, most importantly by keeping the growing cap structure from closing into a fullerene cage and by keeping the carbon edge "alive" for the addition of new carbon material.

The dynamics of the nucleation, growth and termination of single-walled carbon nanotubes from in situ Raman spectroscopy during chemical vapor deposition

The dynamics of the chemical vapor deposition (CVD) of single-walled carbon nanotubes (SWNTs) is extracted experimentally using in situ Raman spectroscopy. Nanotubes are grown using a thin film cobalt catalyst and an ethanol precursor in a miniature hot walled reactor with optical access. Raman spectra at room temperature and at the growth temperature are compared for two growth temperatures. The evolution of the G-band, D-band, and radial breathing mode (RBM) is tracked at the growth temperature with time resolution of a few seconds. There are three identifiable phases in the evolution of the Raman signal intensity: an initial exponential increasing phase, a linear growth phase, and a saturation phase. In situ optical spectroscopy thus enables the study of nucleation, steady growth, and deactivation processes to be investigated separately in real time. The evolution curves for all bands (G, D, and RBM), when scaled, collapse onto the same curve, to within experimental uncertainty.

Milestones in molecular dynamics simulations of single-walled carbon nanotube formation: A brief critical review

We present a brief review of the most important efforts aimed at simulating single-walled carbon nanotube (SWNT) nucleation and growth processes using molecular dynamics (MD) techniques reported in the literature. MD simulations allow the spatio-temporal movement of atoms during nonequilibrium growth to be followed. Thus, it is hoped that a successful MD simulation of the entire SWNT formation process will assist in the design of chirality-specific SWNT synthesis techniques. We give special consideration to the role of the metal catalyst particles assumed in standard theories of SWNT formation, and describe the actual metal behavior observed in the reported MD simulations, including our own recent quantum chemical MD simulations. It is concluded that the use of a quantum potential is essential for a qualitatively correct description of the catalytic behavior of the metal cluster, and that carbide formation does not seem to be a necessary requirement for nucleation and growth of SWNTs according to our most recent quantum chemical MD simulations.

DFT and tight binding Monte Carlo calculations related to single-walled carbon nanotube nucleation and growth

Density-functional theory (DFT) calculations for idealized nucleation processes of (5, 5) and (10, 0) single-walled carbon nanotubes (SWCNTs) on a 55 atom nickel cluster (Ni 55) showed that it requires a larger chemical potential to grow a carbon island (which is the simplest structure that can lead to formation of the SWCNTs) on the cluster than to extend the island into a SWCNT or to have the carbon atoms dispersed on the cluster surface. Hence, in the thermodynamic limit the island will only form once the (surface of the) cluster is saturated with carbon, and the island will spontaneously form a SWCNT at the chemical potentials required to create the island. The DFT (zero Kelvin) and tight binding Monte Carlo (1000 K) also show that there is a minimum cluster size required to support SWCNT growth, and that this cluster size can be used to control the diameter, but probably not the chirality, of the SWCNT at temperatures relevant to carbon nanotube growth. It also imposes a minimum size of clusters that are used for SWCNT regrowth.

Hierarchical nanostructures by nanotube grafting on porous cellular surfaces

Natural biological systems make use of capillary-type hierarchical structures in order to enhance surface functionality within limited size. This paper discusses fabrication of similar synthetic structures by grafting carbon nanotubes (CNTs) on microcellular substrates such as graphitic foam. A major hurdle so far had been deposition of dense CNT layers inside uneven pores. This has been overcome in this study by pre-coating the porous surface with plasma-derived silica molecules. It is seen that the pre-coating not only increases the density of nanocatalyst attachment on the surface but also makes each nanocatalyst more effective in nucleation and growth of nanotubes. The CNT layers formed are strongly attached to the substrate, which makes them particularly suitable for use in robust hierarchical devices in the future.

Catalyst size effects on the growth of single-walled nanotubes in neutral and plasmasystems

The results of large-scale (∼109 atoms) numerical simulations of the growth of different-diameter vertically-alignedsingle-walled carbon nanotubes in plasma systems with different sheath widths and inneutral gases with the same operating parameters are reported. It is shown that thenanotube lengths and growth rates can be effectively controlled by varying the processconditions. The SWCNT growth rates in the plasma can be up to two orders of magnitudehigher than in the equivalent neutral gas systems. Under specific process conditions, thinSWCNTs can grow much faster than their thicker counterparts despite the higher energiesrequired for catalyst activation and nanotube nucleation. This selective growth of thinSWCNTs opens new avenues for the solution of the currently intractable problem ofsimultaneous control of the nanotube chirality and length during the growth stage.

Nanoscale Zirconia as a Nonmetallic Catalyst for Graphitization of Carbon and Growth of Single- and Multiwall Carbon Nanotubes

We report that nanoparticulate zirconia (ZrO(2)) catalyzes both growth of single-wall and multiwall carbon nanotubes (CNTs) by thermal chemical vapor deposition (CVD) and graphitization of solid amorphous carbon. We observe that silica-, silicon nitride-, and alumina-supported zirconia on silicon nucleates single- and multiwall carbon nanotubes upon exposure to hydrocarbons at moderate temperatures (750 degrees C). High-pressure, time-resolved X-ray photoelectron spectroscopy (XPS) of these substrates during carbon nanotube nucleation and growth shows that the zirconia catalyst neither reduces to a metal nor forms a carbide. Point-localized energy-dispersive X-ray spectroscopy (EDAX) using scanning transmission electron microscopy (STEM) confirms catalyst nanoparticles attached to CNTs are zirconia. We also observe that carbon aerogels prepared through pyrolysis of a Zr(IV)-containing resorcinol-formaldehyde polymer aerogel precursor at 800 degrees C contain fullerenic cage structures absent in undoped carbon aerogels. Zirconia nanoparticles embedded in these carbon aerogels are further observed to act as nucleation sites for multiwall carbon nanotube growth upon exposure to hydrocarbons at CVD growth temperatures. Our study unambiguously demonstrates that a nonmetallic catalyst can catalyze CNT growth by thermal CVD while remaining in an oxidized state and provides new insight into the interactions between nanoparticulate metal oxides and carbon at elevated temperatures.

Formation of Catalyst Nanoparticles and Nucleation of Carbon Nanotubes in Chemical Vapor Deposition

Multi-walled carbon nanotubes and other carbon nanostructures have been grown using catalytic thermal chemical vapor deposition method in a horizontal tubular quartz furnace at atmospheric pressure. The mechanisms of nanotubes/nanofibers nucleation and growth are analyzed. A new model explaining the nanotube nucleation as a specific instability occurring on the catalyst particle surface supersaturated with carbon is presented. It is also shown that an axially symmetric instability, giving rise to the nanotube nucleation, is developed when certain critical conditions such as temperature, supersaturation and catalyst volume are achieved. For smaller temperatures, another mechanism of carbon segregation from supersaturated catalyst particles has been observed. In this case, flat rather than tubular graphitic layers are formed. These findings are important for better understanding and control of the synthesis of different carbon nanoforms using chemical vapor deposition.

Substrate preparation techniques for direct investigation by TEM of single wall carbon nanotubes grown by chemical vapor deposition

We have investigated and evaluated different TEM sample preparation techniques for studying carbon single-walled nanotube (C-SWNT) nucleation and growth, issued from CVD processes when the catalyst is supported on a substrate. This kind of study requires means to observe individual and isolated tubes. It implies using synthesis conditions able to produce only a low density of tubes and to thin the substrate to electron transparency, to observe the nanotubes and the catalytic particles from which they have grown in their native state. We have tested two approaches, depending if the substrate is thinned after or before the synthesis. The low tube density requirement led us to exclude all the techniques where the substrate is thinned to electron transparency after the synthesis. We have shown, that, with this last approach, all TEM preparation techniques dramatically suffer from a lack of control of thin areas with respect to the location of the tubes, which is unknown. However we have demonstrated that the suitable approach is to perform synthesis directly on transparent substrates presenting several holes. We have tested the capabilities and the potentialities of these supports for studying the size distribution and composition of the catalytic particles, the nucleation mode, the diameter and helicity of the tubes. These results are very promising and represent an important step for performing specific nanoscale TEM analyses necessary for the study of the growth mechanism of nanotubes on substrates.

Early Stages in the Nucleation Process of Carbon Nanotubes

The early stages of carbon nanotube nucleation are investigated using field ion/electron microscopy along with in situ local chemical probing of a single nanosized nickel crystal. To go beyond experiments, tight-binding Monte Carlo simulations are performed on oriented Ni slabs. Real-time field electron imaging demonstrates a carbon-induced increase of the number density of steps in the truncated vertices of a polyhedral Ni nanoparticle. The necessary diffusion and step-site trapping of adsorbed carbon atoms are observed in the simulations and precede the nucleation of graphene-based sheets in these steps. Chemical probing of selected nanofacets of the Ni crystal reveals the occurrence of Cn (n=1-4) surface species. Kinetic studies prove C2+ species are formed from C1 with a delay time of several milliseconds at 623 K. Carbon dimers, C2, must not necessarily be formed on the Ni surface. Tight-binding Monte Carlo simulations reveal the high stability of such dimers in the first layer beneath the surface.

Relating carbon nanotube growth parameters to the size and composition of nanocatalysts

A gas-phase approach to studying carbon nanotube (CNT) nucleation and growth from nanoparticle catalysts has been developed. Dimensionally- and compositionally-tuned metal particles with mean diameters between 2 and 5 nm and standard deviations less than 15% are initially synthesized from metallocene vapors in an atmospheric-pressure microplasma. The nanocatalysts are continuously fed with acetylene and hydrogen into a flow furnace reactor to grow CNTs. Kinetic studies are performed by in situ aerosol size classification of the nanotubes to relate the CNT length and thus, the growth rate in our thermal process to the catalyst size and composition. We find that reducing the catalyst size results in an increase in the growth rate while varying the catalyst composition affects the growth rate, activation energy, and the onset temperature for CNT growth.

Tight-binding potential for atomistic simulations of carbon interacting with transition metals: Application to the Ni-C system

We present a tight-binding potential for transition metals, carbon, and transition-metal carbides, which has been optimized through a systematic fitting procedure. A minimal basis, including the $s$ and $p$ electrons of carbon and the $d$ electrons of the transition metal, is used to obtain a transferable tight-binding model of the carbon-carbon, metal-metal, and metal-carbon interactions applicable to binary systems. The Ni-C system is more specifically discussed. The successful validation of the potential for different atomic configurations indicates a good transferability of the model and makes it a good choice for atomistic simulations sampling a large configuration space. This approach appears to be very efficient to describe interactions in systems containing carbon and transition-metal elements. By way of example, we present results concerning the epitaxial growth of graphene sheets on (111) Ni surfaces, as well as the catalytic nucleation of carbon nanotubes.

Integration and characterization of aligned carbon nanotubes on metal/silicon substrates and effects of water

We report here a facile way to grow aligned multi-walled carbon nanotubes (MWCNTs) on various metal (e.g. gold, tungsten, vanadium and copper)/silicon electrically conductive substrates by aerosol-assisted chemical vapor deposition (AACVD). Without using any buffer layers, integration of high quality MWCNTs to the conductive substrates has been achieved by introducing appropriate amount of water vapor into the growth system. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) determination indicate tidy morphology and narrow diameter distribution of the nanotubes as well as promising growth rate suitable for industrial applications. Raman spectra analysis illustrates that the structural order and purity of the nanotubes are significantly improved in the presence of water vapor. The growth mechanism of the nanotubes has been discussed. It is believed that water vapor plays a key role in the catalyst-substrate interaction and nucleation of the carbon nanotubes on the conductive substrates. This synthesis approach is expected to be extended to other catalyst-conductive substrate systems and provide some new insight in the direct integration of carbon nanotubes onto conductive substrates, which promises great potential for applications in electrical interconnects, contacts for field emitters, and other electronic nanodevices.

Pulsed laser CVD investigations of single-wall carbon nanotube growth dynamics

The nucleation and rapid growth of single-wall carbon nanotubes (SWNTs) were explored by pulsed-laser assisted chemical vapor deposition (PLA-CVD). A special high-power, Nd:YAG laser system with tunable pulse width (>0.5 ms) was implemented to rapidly heat (>3×104°C/s) metal catalyst-covered substrates to different growth temperatures for very brief (sub-second) and controlled time periods as measured by in situ optical pyrometry. Utilizing growth directly on transmission electron microscopy grids, exclusively SWNTs were found to grow under rapid heating conditions, with a minimum nucleation time of >0.1 s. By measuring the length of nanotubes grown by single laser pulses, extremely fast growth rates (up to 100 microns/s) were found to result from the rapid heating and cooling induced by the laser treatment. Subsequent laser pulses were found not to incrementally continue the growth of these nanotubes, but instead activate previously inactive catalyst nanoparticles to grow new nanotubes. Localized growth of nanotubes with variable density was demonstrated through this process and was applied for the reliable direct-write synthesis of SWNTs onto pre-patterned, catalyst-covered metal electrodes for the synthesis of SWNT field-effect transistors.

Nucleation of carbon nanotubes and their bundles at the surface of catalyst melt

The kinetics of nanotube nucleation from a carbon-supersaturated nanodrop of a catalytic metal was considered. The problem of nucleation of the solid phase from a supersaturated melt was considered with allowance for the particular boundary conditions and the specificity of carbon structure. The solutions are obtained for the cases of extended and surface substrate nanopores, in which the carbon-supersaturated nanodrops are located. The threshold nucleation temperatures were determined for the single-and multiwall nanotubes and their bundles. The dependences of the nanotube size and the required supersaturation level on the temperature and nanodrop size are determined.

The reasons why metals catalyze the nucleation and growth of carbon nanotubes and other carbon nanomorphologies

Carbon nanotubes (CNTs) and other carbon nanomorphologies are grown using “typical” (Ni, Co, and Fe) and “atypical” (Al, In, Pt, Ti, Mg, Pd, K, Cs, Na, W, Mn, Mo, Ir, and Ni 3C) catalysts by chemical vapor deposition. X-ray diffraction analysis reveals the formation (and decomposition) of metal carbides at different stages of these growth reactions. Based on these results and various pieces of evidence gathered from the literature, we present a model that explains why different metals catalyze the nucleation and growth of CNTs or other carbon nanomorphologies, and in particular, why Ni, Co, and Fe display the highest catalytic activity. The catalytic activity of a metal strongly depends on its electronic structure. This property of the catalyst not only controls the decomposition of the carbon source, but also the formation and stability of metal carbides and, more importantly, the release of carbon atoms. Another property of significance is the enthalpy of formation of the carbon source because it enhances the activation of the catalyst.

Efficient diffusion barrier layers for the catalytic growth of carbon nanotubes on copper substrates

We have investigated the growth of carbon nanotube (CNT) films on copper substrates by the catalytic chemical vapour deposition route. Ferrocene was used as the catalyst precursor and toluene was the carbon feedstock. The copper substrates were coated with nitride and oxide amorphous ceramic barrier coatings in order to prevent diffusion of the iron catalyst during growth. It was found that virtually no CNT grew on pure copper, but long and densely packed mats of CNTs could be grown on TiN-coated copper. Copper substrates coated with SiN x and In 2O 3:Sn (ITO) also showed better results than pure copper, although the CNT density was much lower than that obtained from TiN/Cu. Auger electron spectroscopy (AES) showed that Fe diffusion occurred into SiN x /Cu and ITO/Cu substrates, which partially inhibited its catalyst activity. In contrast, AES did not detect the presence of diffused Fe into the TiN coating. The estimation of the diffusion coefficient by AES depth profiles for Fe in SiN x , was 3 · 10 −3 nm 2 s −1. This value establishes an upper limit for Fe diffusion on substrates for proper nanotube nucleation and growth. Secondary ion mass spectrometry provided complementary information on the composition profiles with depth.

A Tight-Binding Grand Canonical Monte Carlo Study of the Catalytic Growth of Carbon Nanotubes

The nucleation of carbon nanotubes on small nickel clusters is studied using a tight binding model coupled to grand canonical Monte Carlo simulations. This technique follows the conditions of the synthesis of carbon nanotubes by chemical vapor deposition. The possible formation of a carbon cap on the catalyst particle is studied as a function of the carbon chemical potential, for particles of different size, either crystalline or disordered. We show that these parameters strongly influence the structure of the cap/particle interface which in turn will have a strong effect on the control of the structure of the nanotube. In particular, we discuss the presence of carbon on surface or in subsurface layers.

Growth kinetics of MWCNTs synthesized by a continuous-feed CVD method

Unlike two-step chemical vapor deposition (CVD) methods using pre-deposited catalyst particles, in a continuous-feed CVD process, the liquid feed (consisting of catalytic precursor and hydrocarbon source) is continuously supplied into the reactor causing catalyst particle formation, nucleation of carbon nanotubes (CNTs) and CNT growth to occur simultaneously throughout the reaction period. In order to observe these processes, CVD experiments were conducted for different durations (30 s to 3 h) and the product multiwalled carbon nanotubes (MWCNTs) were characterized using scanning electron microscopy. It was found that the nanotubes did not grow in the vapor phase and that substrates played an important role in the growth by providing a place for them to anchor before growth took place. Based on transmission electron microscopy images, it has been suggested that MWCNTs grew by root-growth mechanism from the catalyst particles that were deposited on the substrate during the early stages. At long process times, continuously supplied feed gas produced additional catalyst particles which were deposited mostly on the growing nanotube mat. Due to weak catalyst–mat interaction, the additional nanotubes grew by tip growth. A comprehensive MWCNT growth model has been presented for the continuous-feed CVD.