Structural evolution of nanocrystalline silicon thin films synthesized in high-density, low-temperature reactive plasmas

Silicon thin films with a variable content of nanocrystalline phase were deposited on single-crystal silicon and glass substrates by inductively coupled plasma-assisted chemical vapor deposition using a silane precursor without any hydrogen dilution in the low substrate temperature range from 100 to 300 °C. The structural and optical properties of the deposited films are systematically investigated by Raman spectroscopy, x-ray diffraction, Fourier transform infrared absorption spectroscopy, UV/vis spectroscopy, scanning electron microscopy and high-resolution transmission electron microscopy. It is shown that the structure of the silicon thin films evolves from the purely amorphous phase to the nanocrystalline phase when the substrate temperature is increased from 100 to 150 °C. It is found that the variations of the crystalline fraction fc, bonded hydrogen content CH, optical bandgap ETauc, film microstructure and growth rate Rd are closely related to the substrate temperature. In particular, at a substrate temperature of 300 °C, the nanocrystalline Si thin films of our interest feature a high growth rate of 1.63nms-1, a low hydrogen content of 4.0at.%, a high crystalline fraction of 69.1%, a low optical bandgap of 1.55eV and an almost vertically aligned columnar structure with a mean grain size of approximately 10nm. It is also shown that the low-temperature synthesis of nanocrystalline Si thin films without any hydrogen dilution is attributed to the outstanding dissociation ability of the high-density inductively coupled plasmas and effective plasma-surface interactions during the growth process. Our results offer a highly effective yet simple and environmentally friendly technique to synthesize high-quality nanocrystalline Si films, vitally needed for the development of new-generation solar cells and other emerging nanotechnologies.

High-rate, room temperature plasma-enhanced deposition of aluminum-doped zinc oxide nanofilms for solar cell applications

A custom-designed inductively coupled plasma (ICP)-assisted radio-frequency magnetron sputtering deposition system has been employed to synthesize aluminium-doped zinc oxide (ZnO:Al) nanofilms on glass substrates at room temperature. The effects of film thickness and ZnO target (partially covered by Al chips) power on the structural, electrical and optical properties of the ZnO:Al nanofilms are studied. A high growth rate (∼41 nm/min), low electrical sheet resistance (as low as 30 Ω/□) and high optical transparency (>80%) over the visible spectrum has been achieved at a film thickness of ∼615 nm and ZnO target power of 150 W. The synthesis of ZnO:Al nanofilms at room temperature and with high growth rates is attributed to the unique features of the ICP-assisted radio-frequency magnetron sputtering deposition approach. The results are relevant to the development of photovoltaic thin-film solar cells and flat panel displays.

Plasma heating effects in catalyzed growth of carbon nanofibres

A theoretical model describing the plasma-assisted growth of carbon nanofibres (CNFs) that accounts for the nanostructure heating by ion and etching gas fluxes from the plasma is developed. Using the model, it is shown that fluxes from the plasma environment can substantially increase the temperature of the catalyst nanoparticle located on the top of the CNF with respect to the substrate temperature. The difference between the catalyst and the substrate temperatures depends on the substrate width, the length of the CNF, the neutral gas density and temperature as well as the densities of the ions and atoms of the etching gas. In addition to the heating of the nanostructure, the ions and etching gas atoms from the ionized gas environment also strongly affect the CNF growth rates. Due to ion bombardment, the CNF growth rates in plasma enhanced chemical vapour deposition may be much higher than the rates in similar neutral gas-based thermal processes. The CNF growth model, which accounts for the nanostructure heating by the plasma-generated species, provides the growth rates that are in better agreement with the available experimental data on CNF growth than the models in which the heating effects are ignored.

High-rate, low-temperature synthesis of composition controlled hydrogenated amorphous silicon carbide films in low-frequency inductively coupled plasmas

It is commonly believed that in order to synthesize high-quality hydrogenated amorphous silicon carbide (a-Si1-xCx : H) films at competitive deposition rates it is necessary to operate plasma discharges at high power regimes and with heavy hydrogen dilution. Here we report on the fabrication of hydrogenated amorphous silicon carbide films with different carbon contents x (ranging from 0.09 to 0.71) at high deposition rates using inductively coupled plasma (ICP) chemical vapour deposition with no hydrogen dilution and at relatively low power densities (∼0.025 W cm -3) as compared with existing reports. The film growth rate R d peaks at x = 0.09 and x = 0.71, and equals 18 nm min-1 and 17 nm min-1, respectively, which is higher than other existing reports on the fabrication of a-Si1-xCx : H films. The extra carbon atoms for carbon-rich a-Si1-xCx : H samples are incorporated via diamond-like sp3 C-C bonding as deduced by Fourier transform infrared absorption and Raman spectroscopy analyses. The specimens feature a large optical band gap, with the maximum of 3.74 eV obtained at x = 0.71. All the a-Si1-xCx : H samples exhibit low-temperature (77 K) photoluminescence (PL), whereas only the carbon-rich a-Si1-xCx : H samples (x ≥ 0.55) exhibit room-temperature (300 K) PL. Such behaviour is explained by the static disorder model. High film quality in our work can be attributed to the high efficiency of the custom-designed ICP reactor to create reactive radical species required for the film growth. This technique can be used for a broader range of material systems where precise compositional control is required. © 2008 IOP Publishing Ltd.

Nanocrystalline vanadium oxide films synthesized by plasma-assisted reactive rf sputtering deposition

Plasma-assisted reactive rf magnetron sputtering deposition is used to fabricate vanadium oxide films on glass, silica and silicon substrates. The process conditions are optimized to synthesize phase-pure vanadium pentoxide (V2O5) featuring a nanocrystalline structure with the predominant (0 0 1) crystallographic orientation, surface morphology with rod-like nanosized grains and very uniform (the non-uniformity does not exceed 4%) coating thickness over large surface areas. The V2O5 films also show excellent and temperature-independent optical transmittance in a broad temperature range (20-95 °C). The results are relevant to the development of smart functional coatings with temperature-tunable properties. © 2007 IOP Publishing Ltd.

Chemical and bioanalytical assessment of coal seam gas associated water

A comprehensive study was undertaken involving chemical (inorganic and organic) and bioanalytical (a suite of 14 in vitro bioassays) assessments of coal seam gas (coal bed methane) associated water (CSGW) in Queensland, Australia. CSGW is a by-product of the gas extraction process and is generally considered as water of poor quality. This was done to better understand what is known about the potential biological and environmental effects associated with the organic constituents of CSGW in Australia. In Queensland, large amounts of associated water must be withdrawn from coal seams to allow extraction of the gas. CSGW is disposed of via release to surface water, reinjected to groundwater or reused for irrigation of crops or pasture, supplied for power station cooling and or reinjected specifically to augment drinking water aquifers. Groundwater samples were collected from private wells tapping into the Walloon Coal Measures, the same coal aquifer exploited for coal seam gas production in the Surat Basin, Australia. The inorganic characteristics of these water samples were almost identical to the CSGW entering the nearby gas company operated Talinga-Condabri Water Treatment Facility. The water is brackish with a pH of 8 to 9, high sodium, bicarbonate and chloride concentrations but low calcium, magnesium and negligible sulphate concentrations. Only low levels of polyaromatic hydrocarbons (PAHs) were detected in the water samples, and neither phenols nor volatile organic compounds were found. Results from the bioassays showed no genotoxicity, protein damage, or activation of hormone receptors (with the exception of the estrogen receptor). However, five of the 14 bioassays gave positive responses: an arylhydrocarbon-receptor gene activation assay (AhR-CAFLUX), estrogenic endocrine activity (ERα-CALUX), oxidative stress response (AREc32), interference with cytokine production (THP1-CPA) and non-specific toxicity (Microtox). The observed effects were benchmarked against known water sources and were similar to secondary treated wastewater effluent, stormwater and surface water. As mixture toxicity modelling demonstrated, the detected PAHs explained less than 5% of the observed biological effects.

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.

Two-dimensional simulation of nanoparticle deposition from high-density plasmas on microstructured surfaces

Selective and controlled deposition of plasma-grown nanoparticles is one of the pressing problems of plasma-aided nanofabrication. The results of advanced numerical simulations of motion of charge-variable nanoparticles in the plasma presheath and sheath areas and in localized microscopic electric fields created by surface microstructures are reported. Conditions for site-selective deposition of such nanoparticles onto individual microstructures and open surface areas within a periodic micropattern are formulated. The effects of plasma parameters, surface potential, and micropattern features on nanoparticle deposition are investigated and explained using particle charging and plasma force arguments. The results are generic and applicable to a broad range of nanoparticle-generating plasmas and practical problems ranging from management of nanoparticle contamination in microelectronics to site-selective nanoparticle deposition into specified device locations, and synthesis of advanced microporous materials and nanoparticle superlattices. © 2007 American Institute of Physics.

Plasma-controlled nanocrystallinity and phase composition of TiO2 : a smart way to enhance biomimetic response

This contribution sheds light on the role of crystal size and phase composition in inducing biomimetic apatite growth on the surface of nanostructured titania films synthesized by reactive magnetron sputtering of Ti targets in Ar+O2 plasmas. Unlike most existing techniques, this method enables one to deposit highly crystalline titania films with a wide range of phase composition and nanocrystal size, without any substrate heating or postannealing. Moreover, by using this dry plasma-based method one can avoid surface hydroxylation at the deposition stage, almost inevitable in wet chemical processes. Results of this work show that high phase purity and optimum crystal size appear to be the essential requirement for efficient apatite formation on magnetron plasma-fabricated bioactive titania coatings. © 2006 Wiley Periodicals, Inc.

Nanofabrication of single-crystalline flat-panel display microemitters : a plasma-building unit approach

This contribution is focused on plasma-enhanced chemical vapor deposition systems and their unique features that make them particularly attractive for nanofabrication of flat panel display microemitter arrays based on ordered patterns of single-crystalline carbon nanotip structures. The fundamentals of the plasma-based nanofabrication of carbon nanotips and some other important nanofilms and nanostructures are examined. Specific features, challenges, and potential benefits of using the plasma-based systems for relevant nanofabrication processes are analyzed within the framework of the "plasma-building unit" approach that builds up on extensive experimental data on plasma diagnostics and nanofilm/nanostructure characterization, and numerical simulation of the species composition in the ionized gas phase (multicomponent fluid models), ion dynamics and interaction with ordered carbon nanotip patterns, and ab initio computations of chemical structure of single crystalline carbon nanotips. This generic approach is also applicable for nanoscale assembly of various carbon nanostructures, semiconductor quantum dot structures, and nano-crystalline bioceramics. Special attention is paid to most efficient control strategies of the main plasma-generated building units both in the ionized gas phase and on nanostructured deposition surfaces. The issues of tailoring the reactive plasma environments and development of versatile plasma nanofabrication facilities are also discussed.

Nanoparticle manipulation in plasma-assisted nanofabrication of electron field emitters based on single crystalline carbon nanotip patterns

Nanoparticle manipulation by various plasma forces in near-substrate areas of the Integrated Plasma-Aided Nanofabrication Facility (IPANF) is investigated. In the IPANF, high-density plasmas of low-temperature rf glow discharges are sustained. The model near-substrate area includes a variable-length pre-sheath, where a negatively charged nanoparticle is accelerated, and a self-consistent collisionless sheath with a repulsive electrostatic potential. Conditions enabling the nanoparticle to overcome the repulsive barrier and deposit onto the substrate are investigated numerically and experimentally. Under certain conditions the momentum gained by the nanoparticle in the pre-sheath area appears to be sufficient for the driving ion drag force to outbalance the repulsive electrostatic and thermophoretic forces. Numerical results are applied for the explanation of size-selective nanoparticle deposition in the Ar+H2+CH4 plasma-assisted chemical vapor deposition of various carbon nanostructure patterns for electron field emitters and are cross-referenced by the field emission scanning electron microscopy. It is shown that the nanoparticles can be efficiently manipulated by the temperature gradient-controlled thermophoretic force. Experimentally, the temperature gradients in the near-substrate areas are measured in situ by means of the temperature gradient probe and related to the nanofilm fabrication conditions. The results are relevant to plasma-assisted synthesis of numerous nanofilms employing structural incorporation of the plasma-grown nanoparticles, including but not limited to nanofabrication of ordered single-crystalline carbon nanotip arrays for electron field emission applications.

Nanostructured copper oxide semiconductors : a perspective on materials, synthesis methods and applications

The oxides of copper (CuxO) are fascinating materials due to their remarkable optical, electrical, thermal and magnetic properties. Nanostructuring of CuxO can further enhance the performance of this important functional material and provide it with unique properties that do not exist in its bulk form. Three distinctly different phases of CuxO, mainly CuO, Cu2O and Cu4O3, can be prepared by numerous synthesis techniques including, vapour deposition and liquid phase chemical methods. In this article, we present a review of nanostructured CuxO focusing on their material properties, methods of synthesis and an overview of various applications that have been associated with nanostructured CuxO.

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.

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.

RF plasma sputtering deposition of hydroxyapatite bioceramics : synthesis, performance, and biocompatibility

Hydroxyapatite (HA) coatings have numerous applications in orthopedics and dentistry, owing to their excellent ability to promote stronger implant fixation and faster bone tissue ingrowth and remodeling. Thermal plasma spray and other plasma-assisted techniques have recently been used to synthesize various calcium phosphate-based bioceramics. Despite notable recent achievements in the desired stoichiometry, phase composition, mechanical, structural, and bio-compatible properties, it is rather difficult to combine all of the above features in a single coating. For example, many existing plasma-sprayed HA coatings fall short in meeting the requirements of grain size and crystallinity, and as such are subject to enhanced resorption in body fluid. On the other hand, relatively poor interfacial bonding and stability is an obstacle to the application of the HA coatings in high load bearing Ti6Al4V knee joint implants. Here, we report on an alternative: a plasma-assisted, concurrent, sputtering deposition technique for high performance biocompatible HA coatings on Ti6Al4V implant alloy. The plasma-assisted RF magnetron co-sputtering deposition method allows one to simultaneously achieve most of the desired attributes of the biomimetic material and overcome the aforementioned problems. This article details the film synthesis process specifications, extensive analytical characterization of the material's properties, mechanical testing, simulated body fluid assessments, biocompatibility and cytocompatibility of the HA-coated Ti6Al4V orthopedic alloy. The means of optimization of the plasma and deposition process parameters to achieve the desired attributes and performance of the HA coating, as well as future challenges in clinical applications are also discussed.