Growth of carbon nanocone arrays on a metal catalyst: The effect of carbon flux ionization

The growth of carbon nanocone arrays on metal catalyst particles by deposition from a low-temperature plasma is studied by multiscale Monte Carlo/surface diffusion numerical simulation. It is demonstrated that the variation in the degree of ionization of the carbon flux provides an effective control of the growth kinetics of the carbon nanocones, and leads to the formation of more uniform arrays of nanostructures. In the case of zero degree of ionization (neutral gas process), a width of the distribution of nanocone heights reaches 360 nm with the nanocone mean height of 150 nm. When the carbon flux of 75% ionization is used, the width of the distribution of nanocone heights decreases to 100 nm, i.e., by a factor of 3.6. A higher degree of ionization leads to a better uniformity of the metal catalyst saturation and the nanocone growth, thus contributing to the formation of more height-uniform arrays of carbon nanostructures.

Size-selected Ni catalyst islands for single-walled carbon nanotube arrays

Many properties of single-walled carbon nanotube (SWCNT) arrays are determined by the size and surface coverage of the metal catalyst islands from which they are nucleated. Methods using thermal fragmentation of continuous metal films frequently fail to produce size-uniform islands. Hybrid numerical simulations are used to propose a new approach to controlled self-assembly of Ni islands of the required size and surface coverage using tailored gas-phase generated nanocluster fluxes and adjusted surface temperatures. It is shown that a maximum surface coverage of 0.359 by 0.96-1.02 nm Ni catalyst islands can be achieved at a low surface temperature of 500 K. Optimized growth of Ni catalyst islands can lead to fabrication of size-uniform SWCNT arrays, suitable for numerous nanoelectronic applications. This approach is deterministic and is applicable to a range of nanoassemblies where high surface coverage and island size uniformity are required.

Multi-scale hybrid numerical simulation of the growth of high-aspect-ratio nanostructures

Recently, a variety high-aspect-ratio nanostructures have been grown and profiled for various applications ranging from field emission transistors to gene/drug delivery devices. However, fabricating and processing arrays of these structures and determining how changing certain physical parameters affects the final outcome is quite challenging. We have developed several modules that can be used to simulate the processes of various physical vapour deposition systems from precursor interaction in the gas phase to gas-surface interactions and surface processes. In this paper, multi-scale hybrid numerical simulations are used to study how low-temperature non-equilibrium plasmas can be employed in the processing of high-aspect-ratio structures such that the resulting nanostructures have properties suitable for their eventual device application. We show that whilst using plasma techniques is beneficial in many nanofabrication processes, it is especially useful in making dense arrays of high-aspect-ratio nanostructures.

Simulation of gas-phase nanoparticle dynamics in the plasma-enhanced chemical vapor deposition of carbon nanostructures

The results of 1D simulation of nanoparticle dynamics in the areas adjacent to nanostructured carbon-based films exposed to chemically active complex plasma of CH4 + H2 + Ar gas mixtures are presented. The nanoparticle-loaded near-substrate (including sheath and presheath) areas of a low-frequency (0.5 MHz) inductively coupled plasma facility for the PECVD growth of the ordered carbon-based nanotip structures are considered. The conditions allowing one to predict the size of particles that can pass through the plasma sheath and softly land onto the surface are formulated. The possibility of soft nano-cluster deposition without any additional acceleration common for some existing nano-cluster deposition schemes is demonstrated. The effect of the substrate heating power and the average atomic mass of neutral species is studied numerically and verified experimentally.

Angular distribution of carbon ion flux in a nanotube array during the plasma process by the Monte Carlo technique

Angular distribution of microscopic ion fluxes around nanotubes arranged into a dense ordered pattern on the surface of the substrate is studied by means of multiscale numerical simulation. The Monte Carlo technique was used to show that the ion current density is distributed nonuniformly around the carbon nanotubes arranged into a dense rectangular array. The nonuniformity factor of the ion current flux reaches 7 in dense (5× 1018 m-3) plasmas for a nanotube radius of 25 nm, and tends to 1 at plasma densities below 1× 1017 m-3. The results obtained suggest that the local density of carbon adatoms on the nanotube side surface, at areas facing the adjacent nanotubes of the pattern, can be high enough to lead to the additional wall formation and thus cause the single- to multiwall structural transition, and other as yet unexplained nanoscience phenomena.

Growth kinetics of carbon nanowall-like structures in low-temperature plasmas

The results of a hybrid numerical simulation of the growth kinetics of carbon nanowall-like nanostructures in the plasma and neutral gas synthesis processes are presented. The low-temperature plasma-based process was found to have a significant advantage over the purely neutral flux deposition in providing the uniform size distribution of the nanostructures. It is shown that the nanowall width uniformity is the best (square deviations not exceeding 1.05) in high-density plasmas of 3.0× 1018 m-3, worsens in lower-density plasmas (up to 1.5 in 1.0× 1017 m-3 plasmas), and is the worst (up to 1.9) in the neutral gas-based process. This effect has been attributed to the focusing of ion fluxes by irregular electric field in the vicinity of plasma-grown nanostructures on substrate biased with -20 V potential, and differences in the two-dimensional adatom diffusion fluxes in the plasma and neutral gas-based processes. The results of our numerical simulations are consistent with the available experimental reports on the effect of the plasma process parameters on the sizes and shapes of relevant nanostructures.

PECVD of carbon nanostructures in hydrocarbon-based RF plasmas

Different aspects of the plasma-enhanced chemical vapor deposition of various carbon nanostructures in the ionized gas phase of high-density, low-temperature reactive plasmas of Ar+H2+CH4 gas mixtures are studied. The growth techniques, surface morphologies, densities and fluxes of major reactive species in the discharge, and effects of the transport of the plasma-grown nanoparticles through the near-substrate plasma sheath are examined. Possible growth precursors of the carbon nanostructures are also discussed. In particular, the experimental and numerical results indicate that it is likely that the aligned carbon nanotip structures are predominantly grown by the molecular and radical units, whereas the plasma-grown nanoparticles are crucial components of polymorphous carbon films.

Optical emission characteristics and mode transitions in low-frequency inductively coupled plasmas

An attempt was made to investigate the optical emission spectra of atomic, molecular, and ionic species in low-frequency, high-density ICP discharges in pure nitrogen, ar con gases, and gas mixtures Ar+H2, N2+Ar, and N2+H2. The excited species were identified by in situ optical emission intensity (OEI) measurements in the discharge chamber. In general, significant results were obtained.

E and H regimes of plasma enhanced chemical vapor deposition of diamond-like carbon film in low frequency inductively coupled plasma reactor

This paper reports on the efficient deposition of hydrogenated diamond-like carbon (DLC) film in a plasma reactor that features both the capacitively and inductively coupled operation regimes. The hydrogenated DLC films have been prepared on silicon wafers using a low-frequency (500 kHz) inductively coupled plasma (ICP) chemical vapor deposition (CVD) system. At low RF powers, the system operates as an asymmetric capacitively coupled plasma source, and the film deposition process is undertaken in the electrostatic (E) discharge regime. Above the mode transition threshold, the high-density inductively coupled plasma is produced in the electromagnetic (H) discharge regime. It has been shown that the deposition rate and hardness of the DLC film are much higher in the H-mode deposition regime. For a 2.66-Pa H-mode CH4 + Ar gas mixture discharge, the deposited DLC film exhibits a mechanical hardness of 18 GPa, Young's modulus of 170 GPa, and compressive stress of 1.3 GPa.

Self-assembly of uniform carbon nanotip structures in chemically active inductively coupled plasmas

Self-assembly of carbon nanotip (CNTP) structures on Ni-based catalyst in chemically active inductively coupled plasmas of CH 4 + H 2 + Ar gas mixtures is reported. By varying the process conditions, it appears possible to control the shape, size, and density of CNTPs, content of the nanocrystalline phase in the films, as well as to achieve excellent crystallinity, graphitization, uniformity and vertical alignment of the resulting nanostructures at substrate temperatures 300-500°C and low gas pressures (below 13.2 Pa). This study provides a simple and efficient plasma-enhanced chemical vapor deposition (PECVD) technique for the fabrication of vertically aligned CNTP arrays for electron field emitters.

Self-organization and dynamics of nanoparticles in chemically active plasmas for low-temperature deposition of silicon and carbon-based nanostructured films

Self-organization and dynamic processes of nano/micron-sized solid particles grown in low-temperature chemically active plasmas as well as the associated physico-chemical processes are reviewed. Three specific reactive plasma chemistries, namely, of silane (SiH4), acetylene (C 2H2), and octafluorocyclobutane (c-C4F 8) RF plasma discharges for plasma enhanced chemical vapor deposition of amorphous hydrogenated silicon, hydrogenated and fluorinated carbon films, are considered. It is shown that the particle growth mechanisms and specific self-organization processes in the complex reactive plasma systems are related to the chemical organization and size of the nanoparticles. Correlation between the nanoparticle origin and self-organization in the ionized gas phase and improved thin film properties is reported. Self-organization and dynamic phenomena in relevant reactive plasma environments are studied for equivalent model systems comprising inert buffer gas and mono-dispersed organic particulate powders. Growth kinetics and dynamic properties of the plasma-assembled nanoparticles can be critical for the process quality in microelectronics as well as a number of other industrial applications including production of fine metal or ceramic powders, nanoparticle-unit thin film deposition, nanostructuring of substrates, nucleating agents in polymer and plastics synthesis, drug delivery systems, inorganic additives for sunscreens and UV-absorbers, and several others. Several unique properties of the chemically active plasma-nanoparticle systems are discussed as well.

The impact of fuser roller temperature on laser printer particle emission

The emission of particles in the ultrafine range (<100 nm) from laser printers has not been reported until recently (Uhde et al., 2006; He et al., 2007; Morawska et al., 2009). The research reported to date has provided a body of information about printer emissions and shed light on particle formation mechanisms. However, until now, the effect of fuser roller temperature on particle emissions had not been comprehensively investigated...

Large arrays and networks of carbon nanotubes : morphology control by process parameters

Large arrays and networks of carbon nanotubes, both single- and multi-walled, feature many superior properties which offer excellent opportunities for various modern applications ranging from nanoelectronics, supercapacitors, photovoltaic cells, energy storage and conversation devices, to gas- and biosensors, nanomechanical and biomedical devices etc. At present, arrays and networks of carbon nanotubes are mainly fabricated from the pre-fabricated separated nanotubes by solution-based techniques. However, the intrinsic structure of the nanotubes (mainly, the level of the structural defects) which are required for the best performance in the nanotube-based applications, are often damaged during the array/network fabrication by surfactants, chemicals, and sonication involved in the process. As a result, the performance of the functional devices may be significantly degraded. In contrast, directly synthesized nanotube arrays/networks can preclude the adverse effects of the solution-based process and largely preserve the excellent properties of the pristine nanotubes. Owing to its advantages of scale-up production and precise positioning of the grown nanotubes, catalytic and catalyst-free chemical vapor depositions (CVD), as well as plasma-enhanced chemical vapor deposition (PECVD) are the methods most promising for the direct synthesis of the nanotubes.

Steady state and transient dynamometer vehicle emission measurements using a DiSC

Analysis of the particulate size and number concentration emissions from a fleet of inner city medium duty CNG buses was conducted using the newly available Diffusion Size Classifier in comparison with more traditional SMPS's and CPC's. Studies were conducted at both steady state and transient driving modes on a vehicle dynamometer utilising a CVS dilution system. Comparative analysis of the results showed that the DiSC provided equivalent information during steady state conditions and was able to provide additional information during transient conditions, namely, the modal diameter of the particle size distribution.

Effect of plasma environment on synthesis of vertically aligned carbon nanofibers in plasma-enhanced chemical vapor deposition

We present a theoretical model describing a plasma-assisted growth of carbon nanofibers (CNFs), which involves two competing channels of carbon incorporation into stacked graphene sheets: via surface diffusion and through the bulk of the catalyst particle (on the top of the nanofiber), accounting for a range of ion- and radical-assisted processes on the catalyst surface. Using this model, it is found that at low surface temperatures, Ts, the CNF growth is indeed controlled by surface diffusion, thus quantifying the semiempirical conclusions of earlier experiments. On the other hand, both the surface and bulk diffusion channels provide a comparable supply of carbon atoms to the stacked graphene sheets at elevated synthesis temperatures. It is also shown that at low Ts, insufficient for effective catalytic precursor decomposition, the plasma ions play a key role in the production of carbon atoms on the catalyst surface. The model is used to compute the growth rates for the two extreme cases of thermal and plasma-enhanced chemical vapor deposition of CNFs. More importantly, these results quantify and explain a number of observations and semiempirical conclusions of earlier experiments.