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.

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.

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.

Reactive plasmas as a versatile nanofabrication tool

The underlying physics of the application of low-temperature, low-pressure reactive plasmas in various nanoassembly processes is described. From the viewpoint of the "cause and effect" approach, this Colloquium focuses on the benefits and challenges of using plasma-based systems in nanofabrication of nanostructured silicon films, low-dimensional semiconducting quantum structures, ordered carbon nanotip arrays, highly crystalline TiO2 coatings, and nanostructured hydroxyapatite bioceramics. Other examples and future prospects of plasma-aided nanofabrication are also discussed. © 2005 The American Physical Society.

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.

Synthesis and characterization of ternary AL-C-N compound

Efficient hydrogenated diamond-like carbon (DLC) film deposition in a plasma reactor that features both the capacitive and inductively coupled operation regimes is reported. The hydrogenated DLC films have been prepared on silicon wafers using a low-frequency (500 kHz) inductively coupled plasma (LF 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. The films deposited in the electrostatic mode feature graphite-like structure. Above the mode transition threshold, the high-density inductively coupled plasma is produced in the electromagnetic (H) discharge regime. Raman spectrometry suggests the possibility to control relative proportions of sp2 and sp3 hybridized carbon. Variation of the DC substrate bias results in dramatic modification of the film structure from the polymeric (unbiased substrates) to the diamond-like (optimized bias). 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 20 m Torr H-mode CH4+Ar gas mixture discharge, the DLC film exhibits mechanical hardness of 18 GPa, Young's modulus of 170 GPa, and compressive stress of 1.3 GPa.

SiC-like phase and room-temperature photoluminescence of low-k SiOCH films

Carbon-doped hydrogenated silicon oxide (SiOCH) low-k films have been prepared using 13.56 MHz discharge in trimethylsilane (3MS) - oxygen gas mixtures at 3, 4, and 5 Torr sustained with RF power densities 1.3 - 2.6 W/cm2. The atomic structure of the SiOCH films appears to be a mixture the amorphous SiO2-like and the partially polycrystalline SiC-like phases. Results of the infra-red spectroscopy reflect the increment in the volume fraction of the SiC-like phase from 0.22 - 0.28 to 0.36 - 0.39 as the RF power increment. Steady-state near-UV laser-excited (364 nm wavelength, 40±2 mW) photoluminescence (PL) has been studied at room temperatures in the visible (1.8 eV - 3.1 eV) subrange of photon spectrum. Two main bands of the PL signal (at the photon energies of 2.5 - 2.6 eV and 2.8 - 2.9 eV) are observed. Intensities of the both bands are changed monotonically with RF power, whereas the bandwidth of ∼0.1 eV remains almost invariable. It is likely that the above lines are dumped by the non-radiative recombination involving E1-like centres in the amorphous-nanocrystalline SiC-like phases. Such explanation of the PL intensity dependences on the RF power density is supported by results of experimental studies of defect states spectrum in bandgap of the SiOCH films.

Nano-scale morphology and electron spectrum of defect states in low-k SiOCH films

Results of experimental investigations on the relationship between nanoscale morphology of carbon doped hydrogenated silicon-oxide (SiOCH) low-k films and their electron spectrum of defect states are presented. The SiOCH films have been deposited using trimethylsilane (3MS) - oxygen mixture in a 13.56 MHz plasma enhanced chemical vapor deposition (PECVD) system at variable RF power densities (from 1.3 to 2.6 W/cm2) and gas pressures of 3, 4, and 5 Torr. The atomic structure of the SiOCH films is a mixture of amorphous-nanocrystalline SiO2-like and SiC-like phases. Results of the FTIR spectroscopy and atomic force microscopy suggest that the volume fraction of the SiC-like phase increases from ∼0.2 to 0.4 with RF power. The average size of the nanoscale surface morphology elements of the SiO2-like matrix can be controlled by the RF power density and source gas flow rates. Electron density of the defect states N(E) of the SiOCH films has been investigated with the DLTS technique in the energy range up to 0.6 eV from the bottom of the conduction band. Distinct N(E) peaks at 0.25 - 0.35 eV and 0.42 - 0.52 eV below the conduction band bottom have been observed. The first N(E) peak is identified as originated from E1-like centers in the SiC-like phase. The volume density of the defects can vary from 1011 - 1017 cm-3 depending on specific conditions of the PECVD process.

Numerical simulation of nanoparticle-generating electronegative plasmas in the PECVD of nanostructured silicon film

The results of numerical simulation of the equilibrium parameters of a low pressure nanopowder-generating discharge in silane for the plasma enhanced chemical vapor deposition (PECVD) of nanostructured silicon-based films are presented. It is shown that a low electron temperature and a low density of negative SiH3 - ions are favorable for the PECVD process. This opens a possibility to predict the main parameters of the reactive plasma and plasma-nucleated nanoparticles, and hence, to control the quality of silicon nanofilms.

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.

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.

Plasma Enabled Fabrication of Silicon Carbide Nanostructures

Silicon carbide is one of the promising materials for the fabrication of various one- and two-dimensional nanostructures. In this chapter, we discuss experimental and theoretical studies of the plasma-enabled fabrication of silicon carbide quantum dots, nanowires, and nanorods. The discussed fabrication methods include plasma-assisted growth with and without anodic aluminium oxide membranes and with or without silane as a source of silicon. In the silane-free experiments, quartz was used as a source of silicon to synthesize the silicon carbide nanostructures in an environmentally friendly process. The mechanism of the formation of nanowires and nanorods is also discussed.

Development of gas sensing technology for ground and airborne applications powered by solar energy : methodology and experimental results

Monitoring gases for environmental, industrial and agricultural fields is a demanding task that requires long periods of observation, large quantity of sensors, data management, high temporal and spatial resolution, long term stability, recalibration procedures, computational resources, and energy availability. Wireless Sensor Networks (WSNs) and Unmanned Aerial Vehicles (UAVs) are currently representing the best alternative to monitor large, remote, and difficult access areas, as these technologies have the possibility of carrying specialised gas sensing systems, and offer the possibility of geo-located and time stamp samples. However, these technologies are not fully functional for scientific and commercial applications as their development and availability is limited by a number of factors: the cost of sensors required to cover large areas, their stability over long periods, their power consumption, and the weight of the system to be used on small UAVs. Energy availability is a serious challenge when WSN are deployed in remote areas with difficult access to the grid, while small UAVs are limited by the energy in their reservoir tank or batteries. Another important challenge is the management of data produced by the sensor nodes, requiring large amount of resources to be stored, analysed and displayed after long periods of operation. In response to these challenges, this research proposes the following solutions aiming to improve the availability and development of these technologies for gas sensing monitoring: first, the integration of WSNs and UAVs for environmental gas sensing in order to monitor large volumes at ground and aerial levels with a minimum of sensor nodes for an effective 3D monitoring; second, the use of solar energy as a main power source to allow continuous monitoring; and lastly, the creation of a data management platform to store, analyse and share the information with operators and external users. The principal outcomes of this research are the creation of a gas sensing system suitable for monitoring any kind of gas, which has been installed and tested on CH4 and CO2 in a sensor network (WSN) and on a UAV. The use of the same gas sensing system in a WSN and a UAV reduces significantly the complexity and cost of the application as it allows: a) the standardisation of the signal acquisition and data processing, thereby reducing the required computational resources; b) the standardisation of calibration and operational procedures, reducing systematic errors and complexity; c) the reduction of the weight and energy consumption, leading to an improved power management and weight balance in the case of UAVs; d) the simplification of the sensor node architecture, which is easily replicated in all the nodes. I evaluated two different sensor modules by laboratory, bench, and field tests: a non-dispersive infrared module (NDIR) and a metal-oxide resistive nano-sensor module (MOX nano-sensor). The tests revealed advantages and disadvantages of the two modules when used for static nodes at the ground level and mobile nodes on-board a UAV. Commercial NDIR modules for CO2 have been successfully tested and evaluated in the WSN and on board of the UAV. Their advantage is the precision and stability, but their application is limited to a few gases. The advantages of the MOX nano-sensors are the small size, low weight, low power consumption and their sensitivity to a broad range of gases. However, selectivity is still a concern that needs to be addressed with further studies. An electronic board to interface sensors in a large range of resistivity was successfully designed, created and adapted to operate on ground nodes and on-board UAV. The WSN and UAV created were powered with solar energy in order to facilitate outdoor deployment, data collection and continuous monitoring over large and remote volumes. The gas sensing, solar power, transmission and data management systems of the WSN and UAV were fully evaluated by laboratory, bench and field testing. The methodology created to design, developed, integrate and test these systems was extensively described and experimentally validated. The sampling and transmission capabilities of the WSN and UAV were successfully tested in an emulated mission involving the detection and measurement of CO2 concentrations in a field coming from a contaminant source; the data collected during the mission was transmitted in real time to a central node for data analysis and 3D mapping of the target gas. The major outcome of this research is the accomplishment of the first flight mission, never reported before in the literature, of a solar powered UAV equipped with a CO2 sensing system in conjunction with a network of ground sensor nodes for an effective 3D monitoring of the target gas. A data management platform was created using an external internet server, which manages, stores, and shares the data collected in two web pages, showing statistics and static graph images for internal and external users as requested. The system was bench tested with real data produced by the sensor nodes and the architecture of the platform was widely described and illustrated in order to provide guidance and support on how to replicate the system. In conclusion, the overall results of the project provide guidance on how to create a gas sensing system integrating WSNs and UAVs, how to power the system with solar energy and manage the data produced by the sensor nodes. This system can be used in a wide range of outdoor applications, especially in agriculture, bushfires, mining studies, zoology, and botanical studies opening the way to an ubiquitous low cost environmental monitoring, which may help to decrease our carbon footprint and to improve the health of the planet.

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.

Defect healing and enhanced nucleation of carbon nanotubes by low-energy ion bombardment

Structural defects inevitably appear during the nucleation event that determines the structure and properties of single-walled carbon nanotubes. By combining ion bombardment experiments with atomistic simulations we reveal that ion bombardment in a suitable energy range allows these defects to be healed resulting in an enhanced nucleation of the carbon nanotube cap. The enhanced growth of the nanotube cap is explained by a nonthermal ion-induced graphene network restructuring mechanism.