Ion-assisted precursor dissociation and surface diffusion : enabling rapid, low-temperature growth of carbon nanofibers

Growth kinetics of carbon nanofibers in a hydrocarbon plasma is studied. In addition to gas-phase and surface processes common to chemical vapor deposition, the model includes (unique to plasma-exposed catalyst surfaces) ion-induced dissociation of hydrocarbons, interaction of adsorbed species with incoming hydrogen atoms, and dissociation of hydrocarbon ions. It is shown that at low, nanodevice-friendly process temperatures the nanofibers grow via surface diffusion of carbon adatoms produced on the catalyst particle via ion-induced dissociation of a hydrocarbon precursor. These results explain a lower activation energy of nanofiber growth in a plasma and can be used for the synthesis of other nanoassemblies. © 2007 American Institute of Physics.

Plasma-controlled adatom delivery and (re)distribution: Enabling uninterrupted, low-temperature growth of ultralong vertically aligned single walled carbon nanotubes

Large-scale (∼109 atoms) numerical simulations reveal that plasma-controlled dynamic delivery and redistribution of carbon atoms between the substrate and nanotube surfaces enable the growth of ultralong single walled carbon nanotubes (SWCNTs) and explain the common experimental observation of slower growth at advanced stages. It is shown that the plasma-based processes feature up to two orders of magnitude higher growth rates than equivalent neutral-gas systems and are better suited for the SWCNT synthesis at low nanodevice friendly temperatures. © 2008 American Institute of Physics.

Distribution of ion-current density on substrate between carbon nanotubes grown from low-temperature plasma

Using Monte Carlo simulation technique, we have calculated the distribution of ion current extracted from low-temperature plasmas and deposited onto the substrate covered with a nanotube array. We have shown that a free-standing carbon nanotube is enclosed in a circular bead of the ion current, whereas in square and hexagonal nanotube patterns, the ion current is mainly concentrated along the lines connecting the nearest nanotubes. In a very dense array (with the distance between nanotubes/nanotube-height ratio less than 0.05), the ions do not penetrate to the substrate surface and deposit on side surfaces of the nanotubes.

Inductively coupled Ar/CH₄/H₂plasmas for low-temperature deposition of ordered carbon nanostructures

The study of inductively coupled Ar/CH 4/H 2 plasmas in the plasma enhanced chemical vapor deposition (PECVD) of self-assembled carbon nanostructures (CN) was presented. A spatially averaged (global) discharge model was developed to study the densities and fluxes of the radical neutrals and charged species, the effective electron temperature, and methane conversion factors under various conditions. It was found that the deposited cation fluxes in the PECVD of CNs generally exceed those of the radical neutrals. The agreement with the optical emission spectroscopy (OES) and quadrupole mass spectrometry (QMS) was also derived through numerical results.

Electron transport across magnetic field in low-temperature plasmas : an alternative approach for obtaining evidence of Bohm mechanism

A comparative study involving both experimental and numerical investigations was made to resolve a long-standing problem of understanding electron conductivity mechanism across magnetic field in low-temperature plasmas. We have calculated the plasma parameters from experimentally obtained electric field distribution, and then made a 'back' comparison with the distributions of electron energy and plasma density obtained in the experiment. This approach significantly reduces an influence of the assumption about particular phenomenology of the electron conductivity in plasma. The results of the experiment and calculations made by this technique have showed that the classical conductivity is not capable of providing realistic total current and electron energy, whereas the phenomenological anomalous Bohm mobility has demonstrated a very good agreement with the experiment. These results provide an evidence in favor of the Bohm conductivity, thus making it possible to clarify this pressing long-living question about the main driving mechanism responsible for the electron transport in low-temperature plasmas.

Rapid, low-temperature synthesis of nc-Si in high-density, non-equilibrium plasmas : enabling nanocrystallinity at very low hydrogen dilution

Nanocrystalline silicon thin films were deposited on single-crystal silicon and glass substrates simultaneously by inductively coupled plasma-assisted chemical vapor deposition from the reactive silane reactant gas diluted with hydrogen at a substrate temperature of 200 °C. The effect of hydrogen dilution ratio X (X is defined as the flow rate ratio of hydrogen to silane gas), ranging from 1 to 20, on the structural and optical properties of the deposited films, is extensively investigated by Raman spectroscopy, X-ray diffraction, Fourier transform infrared absorption spectroscopy, UV/VIS spectroscopy, and scanning electron microscopy. Our experimental results reveal that, with the increase of the hydrogen dilution ratio X, the deposition rate Rd and hydrogen content CH are reduced while the crystalline fraction Fc, mean grain size δ and optical bandgap ETauc are increased. In comparison with other plasma enhanced chemical vapor deposition methods of nanocrystalline silicon films where a very high hydrogen dilution ratio X is routinely required (e.g. X > 16), we have achieved nanocrystalline silicon films at a very low hydrogen dilution ratio of 1, featuring a high deposition rate of 1.57 nm/s, a high crystalline fraction of 67.1%, a very low hydrogen content of 4.4 at.%, an optical bandgap of 1.89 eV, and an almost vertically aligned columnar structure with a mean grain size of approximately 19 nm. We have also shown that a sufficient amount of atomic hydrogen on the growth surface essential for the formation of nanocrystalline silicon is obtained through highly-effective dissociation of silane and hydrogen molecules in the high-density inductively coupled plasmas. © 2009 The Royal Society of Chemistry.

Self-assembled low-dimensional nanomaterials via low-temperature plasma processing

Examples of successful fabrication of low-dimensional semiconducting nanomaterials in the Integrated Plasma-Aided Nanofabrication Facility are shown. Self-assembled size-uniform ZnO nanoparticles, ultra-high-aspect ratio Si nanowires, vertically aligned cadmium sulfide nanostructures, and quarternary semiconducting SiCAlN nanomaterial have been synthesized using inductively coupled plasma-assisted RF magnetron sputtering deposition. The observed increase in crystallinity and growth rates of the nanostructures are explained by using a model of plasma-enhanced adatom surface diffusion under conditions of local energy exchange between the ion flux and the growth surface. Issues related to plasma-based growth of low-dimensional semiconducting nanomaterials are discussed as well. © 2007 Elsevier B.V. All rights reserved.

Low-temperature PECVD of nanodevice-Grade nc-3C-SiC

In this work, we report a plasma-based synthesis of nanodevice-grade nc-3C-SiC films, with very high growth rates (7-9 nm min-1) at low and ULSI technology-compatible process temperatures (400-550 °C), featuring: (i) high nanocrystalline fraction (67% at 550 °C); (ii) good chemical purity; (iii) excellent stoichiometry throughout the entire film; (iv) wide optical band gap (3.22-3.71 eV); (v) refractive index close to that of single-crystalline 3C-SiC, and; (vi) clear, uniform, and defect-free Si-SiC interface. The counter-intuitive low SiC hydrogenation in a H2-rich plasma process is explained by hydrogen atom desorption-mediated crystallization.

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.

Low-temperature assembly of ordered carbon nanotip arrays in low-frequency, high-density inductively coupled plasmas

High-density inductively coupled plasma (ICP)-assisted self-assembly of the ordered arrays of various carbon nanostructures (NS) for the electron field emission applications is reported. Carbon-based nano-particles, nanotips, and pyramid-like structures, with the controllable shape, ordering, and areal density are grown under remarkably low process temperatures (260-350 °C) and pressures (below 0.1 Torr), on the same Ni-based catalyst layers, in a DC bias-controlled floating temperature regime. A high degree of positional and directional ordering, elevated sp2 content, and a well-structured graphitic morphology are achieved without the use of pre-patterned or externally heated substrates.

Nanoparticle manipulation in the near-substrate areas of low-temperature, high-density rf plasmas

Manipulation of a single nanoparticle in the near-substrate areas of high-density plasmas of low-temperature glow discharges is studied. It is shown that the nanoparticles can be efficiently manipulated by the thermophoretic force controlled by external heating of the substrate stage. Particle deposition onto or repulsion from nanostructured carbon surfaces critically depends on the values of the neutral gas temperature gradient in the near-substrate areas, which is directly measured in situ in different heating regimes by originally developed temperature gradient probe. The measured values of the near-surface temperature gradient are used in the numerical model of nanoparticle dynamics in a variable-length presheath. Specific conditions enabling the nanoparticle to overcome the repulsive potential and deposit on the substrate during the discharge operation are investigated. The results are relevant to fabrication of various nanostructured films employing structural incorporation of the plasma-grown nanoparticles, in particular, to nanoparticle deposition in the plasma-enhanced chemical-vapor deposition of carbon nanostructures in hydrocarbon-based plasmas.

Low-temperature growth of large area, vertically aligned carbon nanotubes for field emission applications

Large area, highly uniform vertically aligned carbon nanotips (VACNTP) and other nanostructures have been grown on silicon (100) substrates with Ni catalyst in the low-temperature, low-frequency, high-density inductively coupled plasmas (ICP) of methane-hydrogen-argon gas mixtures. The control strategies for the morphology, crystalline structure and chemical states of the resulting nanostructures by varying the growth conditions are proposed. XRD and Roman analyses confirm that the nanotips are well graphitized, which is favorable for the field emission applications.

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.

Cost efficiency of Japanese steam power generation companies : a Bayesian comparison of random and fixed frontier models

This study analyses and compares the cost efficiency of Japanese steam power generation companies using the fixed and random Bayesian frontier models. We show that it is essential to account for heterogeneity in modelling the performance of energy companies. Results from the model estimation also indicate that restricting CO2 emissions can lead to a decrease in total cost. The study finally discusses the efficiency variations between the energy companies under analysis, and elaborates on the managerial and policy implications of the results.

Regulation, pollution and heterogeneity in Japanese steam power generation companies

In this paper, the random stochastic frontier model is used to estimate the technical efficiency of Japanese steam power generation companies taking into regulation and pollution. The companies are ranked according to their productivity for the period 1976-2003 and homogenous and heterogeneous variables in the cost function are disentangled. Policy implication is derived.