Uniformity of postprocessing of dense nanotube arrays by neutral and ion fluxes

The advantages of using low-temperature plasma environments for postprocessing of dense nanotube arrays are shown by means of multiscale hybrid numerical simulations. By controlling plasma-extracted ion fluxes and varying the plasma and sheath parameters, one can selectively coat, dope, or functionalize different areas on nanotube surfaces. Conditions of uniform deposition of ion fluxes over the entire nanotube surfaces are obtained for different array densities. The plasma route enables a uniform processing of lateral nanotube surfaces in very dense (with a step-to-height ratio of 1:4) arrays, impossible via the neutral gas process wherein radical penetration into the internanotube gaps is poor. © 2006 American Institute of Physics.

Microscopic ion fluxes in plasma-aided nanofabrication of ordered carbon nanotip structures

Three-dimensional topography of microscopic ion fluxes in the reactive hydrocarbon-based plasma-aided nanofabrication of ordered arrays of vertically aligned single-crystalline carbon nanotip microemitter structures is simulated by using a Monte Carlo technique. The individual ion trajectories are computed by integrating the ion equations of motion in the electrostatic field created by a biased nanostructured substrate. It is shown that the ion flux focusing onto carbon nanotips is more efficient under the conditions of low potential drop Us across the near-substrate plasma sheath. Under low- Us conditions, the ion current density onto the surface of individual nanotips is higher for higher-aspect-ratio nanotips and can exceed the mean ion current density onto the entire nanopattern in up to approximately five times. This effect becomes less pronounced with increasing the substrate bias, with the mean relative enhancement of the ion current density ξi not exceeding ∼1.7. The value of ξi is higher in denser plasmas and behaves differently with the electron temperature Te depending on the substrate bias. When the substrate bias is low, ξi decreases with Te, with the opposite tendency under higher- Us conditions. The results are relevant to the plasma-enhanced chemical-vapor deposition of ordered large-area nanopatterns of vertically aligned carbon nanotips, nanofibers, and nanopyramidal microemitter structures for flat-panel display applications. © 2005 American Institute of Physics.

Effective control of ion fluxes over large areas by magnetic fields : from narrow beams to highly uniform fluxes

An effective control of the ion current distribution over large-area (up to 103 cm2) substrates with the magnetic fields of a complex structure by using two additional magnetic coils installed under the substrate exposed to vacuum arc plasmas is demonstrated. When the magnetic field generated by the additional coils is aligned with the direction of the magnetic field generated by the guiding and focusing coils of the vacuum arc source, a narrow ion density distribution with the maximum current density 117 A m-2 is achieved. When one of the additional coils is set to generate the magnetic field of the opposite direction, an area almost uniform over the substrate of 103 cm2 ion current distribution with the mean value of 45 A m-2 is achieved. Our findings suggest that the system with the vacuum arc source and two additional magnetic coils can be effectively used for the effective, high throughput, and highly controllable plasma processing.

Ion impact distribution over plasma exposed nanocone arrays

The effect of an ordered array of nanocones on a conducting substrate immersed in the plasma on the transport of the plasma ions is investigated. The real conical shape of the cones is rigorously incorporated into the model. The movement of 10^5 CH3+ ions in the plasma sheath modified by the nanocone array is simulated. The ions are driven by the electric fields produced by the sheath and the nanostructures. The surface charge density and the total charge on the nanotips with different aspect ratios are computed. The ion transport simulation provides important characteristics of the displacement and velocity of the ions. The relative ion distribution along the lateral surfaces of the carbon nanotips is computed as well. It is shown that a rigorous account of the realistic nanostructure shape leads to very different distribution of the ion fluxes on the nanostructured surfaces compared to the previously reported works. The ion flux distribution is a critical factor in the nucleation process on the substrate and determines the nanostructure growth patterns.

Control of ion density distribution by magnetic traps for plasma electrons

The effect of a magnetic field of two magnetic coils on the ion current density distribution in the setup for low-temperature plasma deposition is investigated. The substrate of 400 mm diameter is placed at a distance of 325 mm from the plasma duct exit, with the two magnetic coils mounted symmetrically under the substrate at a distance of 140 mm relative to the substrate centre. A planar probe is used to measure the ion current density distribution along the plasma flux cross-sections at distances of 150, 230, and 325 mm from the plasma duct exit. It is shown that the magnetic field strongly affects the ion current density distribution. Transparent plastic films are used to investigate qualitatively the ion density distribution profiles and the effect of the magnetic field. A theoretical model is developed to describe the interaction of the ion fluxes with the negative space charge regions associated with the magnetic trapping of the plasmaelectrons. Theoretical results are compared with the experimental measurements, and a reasonable agreement is demonstrated.

Nanosphere monolayer-templated, ion-assisted nanofeature etching in dielectric materials : a numerical simulation of nanoscale ion flux topography

The results of numerical simulations of nanometer precision distributions of microscopic ion fluxes in ion-assisted etching of nanoscale features on the surfaces of dielectric materials using a self-assembled monolayer of spherical nanoparticles as a mask are presented. It is shown that the ion fluxes to the substrate and nanosphere surfaces can be effectively controlled by the plasma parameters and the external bias applied to the substrate. By proper adjustment of these parameters, the ion flux can be focused onto the areas uncovered by the nanospheres. Under certain conditions, the ion flux distributions feature sophisticated hexagonal patterns, which may lead to very different nanofeature etching profiles. The results presented are generic and suggest viable ways to overcome some of the limitations of the existing plasma-assisted nanolithography.

Effect of ambipolar fluxes on nanoparticle charging in low-pressure glow discharges

The effect of ambipolar fluxes on nanoparticle charging in a typical low-pressure parallel-plate glow discharge is considered. It is shown that the equilibrium values of the nanoparticle charge in the plasma bulk and near-electrode areas are strongly affected by the ratio S ath i of the ambipolar flux and the ion thermal velocities. Under typical experimental conditions the above ratio is neither S ath i≪ 1 nor S ath i≫1, which often renders the commonly used approximations of the purely thermal or "ion wind" ion charging currents inaccurate. By using the general approximation for the ambipolar drift-affected ion flux on the nanoparticle surface, it appears possible to obtain more accurate values of the nanoparticle charge that usually deviate within 10-25 % from the values obtained without a proper accounting for the ambipolar ion fluxes. The implications of the results obtained for glow discharge modeling and nanoparticle manipulation in low-pressure plasmas are discussed.

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.

Ion-assisted functional monolayer coating of nanorod arrays in hydrogen plasmas

Uniformity of postprocessing of large-area, dense nanostructure arrays is currently one of the greatest challenges in nanoscience and nanofabrication. One of the major issues is to achieve a high level of control in specie fluxes to specific surface areas of the nanostructures. As suggested by the numerical experiments in this work, this goal can be achieved by manipulating microscopic ion fluxes by varying the plasma sheath and nanorod array parameters. The dynamics of ion-assisted deposition of functional monolayer coatings onto two-dimensional carbon nanorod arrays in a hydrogen plasma is simulated by using a multiscale hybrid numerical simulation. The numerical results show evidence of a strong correlation between the aspect ratios and nanopattern positioning of the nanorods, plasma sheath width, and densities and distributions of microscopic ion fluxes. When the spacing between the nanorods and/or their aspect ratios are larger, and/or the plasma sheath is wider, the density of microscopic ion current flowing to each of the individual nanorods increases, thus reducing the time required to apply a functional monolayer coating down to 11 s for a 7-μm-wide sheath, and to 5 s for a 50-μm-wide sheath. The computed monolayer coating development time is consistent with previous experimental reports on plasma-assisted functionalization of related carbon nanostructures [B. N. Khare et al., Appl. Phys. Lett. 81, 5237 (2002)]. The results are generic in that they can be applied to a broader range of plasma-based processes and nanostructures, and contribute to the development of deterministic strategies of postprocessing and functionalization of various nanoarrays for nanoelectronic, biomedical, and other emerging applications.

Simulation of ion flux distribution in conductive and nonconductive nanotip patterns

The distribution of flux of carbon-bearing cations over nanopatterned surfaces with conductive nanotips and nonconductive nanoislands is simulated using the Monte-Carlo technique. It is shown that the ion current is focused to nanotip surfaces when the negative substrate bias is low and only slightly perturbed at higher substrate biases. In the low-bias case, the mean horizontal ion displacement caused by the nanotip electric field exceeds 10 nm. However, at higher substrate biases, this value reduces down to 2 nm. In the nonconductive nanopattern case, the ion current distribution is highly nonuniform, with distinctive zones of depleted current density around the nanoislands. The simulation results suggest the efficient means to control ion fluxes in plasma-aided nanofabrication of ordered nanopatterns, such as nanotip microemitter structures and quantum dot or nanoparticle arrays. © World Scientific Publishing Company.

Crystalline Si nanoparticles below crystallization threshold : effects of collisional heating in non-thermal atmospheric-pressure microplasmas

Nucleation and growth of highly crystalline silicon nanoparticles in atmospheric-pressure low-temperature microplasmas at gas temperatures well below the Si crystallization threshold and within a short (100 μs) period of time are demonstrated and explained. The modeling reveals that collision-enhanced ion fluxes can effectively increase the heat flux on the nanoparticle surface and this heating is controlled by the ion density. It is shown that nanoparticles can be heated to temperatures above the crystallization threshold. These combined experimental and theoretical results confirm the effective heating and structure control of Si nanoparticles at atmospheric pressure and low gas temperatures.

Pulsed i-PVD of dielectric nanodot arrays using a nanoporous template

The results of multi-scale numerical simulations of pulsed i-PVD template-assisted nanofabrication of ZnO nanodot arrays on a silicon substrate are presented. The ratios and spatial distributions of the ion fluxes deposited on the lateral and bottom surfaces of the nanopores are computed as a function of the external bias and plasma parameters. The results show that the pulsed bias plays a significant role in the ion current distribution inside the nanopores. The results of numerical experiments of this work suggest that by finely adjusting the pulse voltage, the pulse duration and the duty cycle of the external pulsed bias, the nanopore clogging can be successfully avoided during the deposition and the shapes of the deposited ZnO nanodots can be effectively controlled. A figure is presented.

Effects of ions and atomic hydrogen in plasma-assisted growth of single-walled carbon nanotubes

The growth of single-walled carbon nanotubes (SWCNTs) in plasma-enhanced chemical vapor deposition (PECVD) is studied using a surface diffusion model. It is shown that at low substrate temperatures (≤1000 K), the atomic hydrogen and ion fluxes from the plasma can strongly affect nanotube growth. The ion-induced hydrocarbon dissociation can be the main process that supplies carbon atoms for SWCNT growth and is responsible for the frequently reported higher (compared to thermal chemical vapor deposition) nanotube growth rates in plasma-based processes. On the other hand, excessive deposition of plasma ions and atomic hydrogen can reduce the diffusion length of the carbon-bearing species and their residence time on the nanotube lateral surfaces. This reduction can adversely affect the nanotube growth rates. The results here are in good agreement with the available experimental data and can be used for optimizing SWCNT growth in PECVD.

Modes of nanotube growth in plasmas and reasons for single-walled structure

The conditions for carbon nanotube synthesis in the bulk of arc discharges and on plasma-exposed solid surfaces are compared to reveal the main distinguishing features of the growth kinetics and explain the striking difference between the growth of the nanotubes in both cases. It is shown that this difference is due to very different exposure of the discharge-synthesized and surface-bound nanotubes to ion fluxes, with the ratio of the ion fluxes collected per nanotube in the two cases reaching up to six orders of magnitude. Depending on the plasma parameters and the sizes of the nanotubes and metal catalyst particles, four distinct growth modes of the nanotubes in the plasma bulk have been identified. These results shed light on why single-walled carbon nanotube growth is more favourable in the bulk of arc plasmas rather than on plasma-exposed surfaces.

Plasma-assembled carbon nanotubes : electric field–related effects

The paper presents results of comparative investigation of carbon nanotubes growth processes in dense low-temperature plasma and on substrate surface. Hybrid/Monte-Carlo numerical simulations were used to demonstrate the differences in the ion fluxes, growth rates and kinetics of adsorbed atoms re-distribution on substrate and nanotubes surfaces. We show that the plasma parameters significantly affect the nanotubes growth kinetics. We demonstrate that the growth rates of the nanotubes in plasma and on surface can differ by three orders, and the specific fluxes to the nanotube in the plasma can exceed the flux to surface-grown nanotube by six orders. We also show that the metal catalyst used for the nanotubes production on surface and in arc is a subject to very different conditions and this may be a key factor for the nanotube growth mode. The obtained dependencies for the ion fluxes to the nanotubes and nanotubes growth rates on the plasma parameters may be useful for selection of the production methods.