Rapid, simultaneous activation of thin nanowire growth in low-temperature, low-pressure chemically active plasmas

Multiscale numerical modeling of the species balance and transport in the ionized gas phase and on the nanostructured solid surface complemented by the heat exchange model is used to demonstrate the possibility of minimizing the Gibbs-Thompson effect in low-temperature, low-pressure chemically active plasma-assisted growth of uniform arrays of very thin Si nanowires, impossible otherwise. It is shown that plasma-specific effects drastically shorten and decrease the dispersion of the incubation times for the nucleation of nanowires on non-uniform Au catalyst nanoparticle arrays. The fast nucleation makes it possible to avoid a common problem of small catalyst nanoparticle burying by amorphous silicon. These results explain a multitude of experimental observations on chemically active plasma-assisted Si nanowire growth and can be used for the synthesis of a range of inorganic nanowires for environmental, biomedical, energy conversion, and optoelectronic applications.

Unidirectional arrays of vertically standing graphenes in reactive plasmas

The possibility for the switch-over of the growth mode from a continuous network to unidirectional arrays of well-separated, self-organized, vertically oriented graphene nanosheets has been demonstrated using a unique, yet simple plasma-based approach. The process enables highly reproducible, catalyst-free synthesis of arrays of graphene nanosheets with reactive open graphitic edges facing upwards. Effective control over the nanosheet length, number density, and the degree of alignment along the electric field direction is achieved by a simple variation of the substrate bias. These results are of interest for environment-friendly fabrication of next-generation nanodevices based on three-dimensional, ordered self-organized nanoarrays of active nanostructures with very large surface areas and aspect ratios, highly reactive edges, and controlled density on the substrate. Our simple and versatile plasma-based approach paves the way for direct integration of such nanoarrays directly into the Si-based nanodevice platform.

Real-time monitoring of nucleation-growth cycle of carbon nanoparticles in acetylene plasmas

Quantum cascade laserabsorption spectroscopy was used to measure the absolute concentration of acetylene in situ during the nanoparticle growth in Ar + C2H2 RF plasmas. It is demonstrated that the nanoparticle growth exhibits a periodical behavior, with the growth cycle period strongly dependent on the initial acetylene concentration in the chamber. Being 300 s at 7.5% of acetylene in the gas mixture, the growth cycle period decreases with the acetylene concentration increasing; the growth eventually disappears when the acetylene concentration exceeds 32%. During the nanoparticle growth, the acetylene concentration is small and does not exceed 4.2% at radio frequency (RF) power of 4 W, and 0.5% at RF power of 20 W. An injection of a single acetylene pulse into the discharge also results in the nanoparticlenucleation and growth. The absorption spectroscopy technique was found to be very effective for the time-resolved measurement of the hydrocarbon content in nanoparticle-generatingplasmas.

Control of morphology and nucleation density of iron oxide nanostructures by electric conditions on iron surfaces exposed to reactive oxygen plasmas

The possibility to control the morphology and nucleation density of quasi-one-dimensional, single-crystalline α -Fe2 O3 nanostructures by varying the electric potential of iron surfaces exposed to reactive oxygen plasmas is demonstrated experimentally. A systematic increase in the oxygen ion flux through rf biasing of otherwise floating substrates and then an additional increase of the ion/neutral density resulted in remarkable structural transformations of straight nanoneedles into nanowires with controlled tapering/aspect ratio and also in larger nucleation densities. Multiscale numerical simulations relate the microscopic ion flux topographies to the nanostructure nucleation and morphological evolution. This approach is applicable to other metal-oxide nanostructures.

Controlled-bandgap silicon nitride nanomaterials : deterministic nitrogenation in high-density plasmas

To overcome major problems associated with insufficient incorporation of nitrogen in hydrogenated amorphous silicon nitride (a-SiNx:H) nanomaterials, which in turn impedes the development of controlled-bandgap nanodevices, here we demonstrate the possibility to achieve effective bandgap control in a broad range by using high-density inductively coupled plasmas. This achievement is related to the outstanding dissociation ability of such plasmas. It is shown that the compositional, structural, optical, and morphological properties of the synthesized a-SiNx:H nanomaterials can be effectively tailored through the manipulation of the flow rate ratio of the silane to nitrogen gases X. In particular, a wide bandgap of 5.21 eV can be uniquely achieved at a low flow rate ratio of the nitrogen to silane gas of 1.0, whereas typically used values often exceed 20.0. These results are highly-relevant to the development of the next-generation nanodevices that rely on the effective control of the functional nano-layer bandgap energies.

Single-step, rapid low-temperature synthesis of Si quantum dots embedded in an amorphous SiC matrix in high-density reactive plasmas

A simple, effective and innovative approach based on low-pressure, thermally nonequilibrium, high-density inductively coupled plasmas is proposed to rapidly synthesize Si quantum dots (QDs) embedded in an amorphous SiC (a-SiC) matrix at a low substrate temperature and without any commonly used hydrogen dilution. The experimental results clearly demonstrate that uniform crystalline Si QDs with a size of 3-4 nm embedded in the silicon-rich (carbon content up to 10.7at.%) a-SiC matrix can be formed from the reactive mixture of silane and methane gases, with high growth rates of ∼1.27-2.34 nm s-1 and at a low substrate temperature of 200 °C. The achievement of the high-rate growth of Si QDs embedded in the a-SiC without any commonly used hydrogen dilution is discussed based on the unique properties of the inductively coupled plasma-based process. This work is particularly important for the development of the all-Si tandem cell-based third generation photovoltaic solar cells.

Silicon on silicon : self-organized nanotip arrays formed in reactive Ar+H2 plasmas

The formation of arrays of vertically aligned nanotips on a moderately heated (up to 500 degrees C) Si surface exposed to reactive low-temperature radio frequency (RF) Ar+H(2) plasmas is studied. It is demonstrated that the nanotip surface density, aspect ratio and height dispersion strongly depend on the substrate temperature, discharge power, and gas composition. It is shown that nanotips with aspect ratios from 2.0 to 4.0 can only be produced at a higher RF power density (41.7 mW cm(-3)) and a hydrogen content of about 60%, and that larger aspect ratios can be achieved at substrate temperatures of about 300 degrees C. The use of higher (up to 500 degrees C) temperatures leads to a decrease of the aspect ratio but promotes the formation of more uniform arrays with the height dispersion decreasing to 1.5. At lower (approximately 20 mW cm(-3)) RF power density, only semispherical nanodots can be produced. Based on these experimental results, a nanotip formation scenario is proposed suggesting that sputtering, etching, hydrogen termination, and atom/radical re-deposition are the main concurrent mechanisms for the nanostructure formation. Numerical calculations of the ion flux distribution and hydrogen termination profiles can be used to predict the nanotip shapes and are in a good agreement with the experimental results. This approach can be applied to describe the kinetics of low-temperature formation of other nanoscale materials by plasma treatment.

Low- and high-temperature controls in carbon nanofiber growth in reactive plasmas

A numerical growth model is used to describe the catalyzed growth of carbon nanofibers in the sheath of a low-temperature plasma. Using the model, the effects of variation in the plasma sheath parameters and substrate potential on the carbon nanofiber growth characteristics, such as the growth rate, the effective carbon flux to the catalyst surface, and surface coverages, have been investigated. It is shown that variations in the parameters, which change the sheath width, mainly affect the growth parameters at the low catalyst temperatures, whereas the other parameters such as the gas pressure, ion temperature, and percentages of the hydrocarbon and etching gases, strongly affect the carbon nanofiber growth at higher temperatures. The conditions under which the carbon nanofiber growth can still proceed under low nanodevice-friendly process temperatures have been formulated and summarized. These results are consistent with the available experimental results and can also be used for catalyzed growth of other high-aspect-ratio nanostructures in low-temperature plasmas.

From nucleation to nanowires : a single-step process in reactive plasmas

This feature article introduces a deterministic approach for the rapid, single-step, direct synthesis of metal oxide nanowires. This approach is based on the exposure of thin metal samples to reactive oxygen plasmas and does not require any intervening processing or external substrate heating. The critical roles of the reactive oxygen plasmas, surface processes, and plasma-surface interactions that enable this growth are critically examined by using a deterministic viewpoint. The essentials of the experimental procedures and reactor design are presented and related to the key process requirements. The nucleation and growth kinetics is discussed for typical solid-liquid-solid and vapor-solid-solid mechanisms related to the synthesis of the oxide nanowires of metals with low (Ga, Cd) and high (Fe) melting points, respectively. Numerical simulations are focused on the possibility to predict the nanowire nucleation points through the interaction of the plasma radicals and ions with the nanoscale morphological features on the surface, as well as to control the localized 'hot spots' that in turn determine the nanowire size and shape. This generic approach can be applied to virtually any oxide nanoscale system and further confirms the applicability of the plasma nanoscience approaches for deterministic nanoscale synthesis and processing.

Single-step synthesis and magnetic separation of graphene and carbon nanotubes in arc discharge plasmas

The unique properties of graphene and carbon nanotubes made them the most promising nanomaterials attracting enormous attention, due to the prospects for applications in various nanodevices, from nanoelectronics to sensors and energy conversion devices. Here we report on a novel deterministic, single-step approach to simultaneous production and magnetic separation of graphene flakes and carbon nanotubes in an arc discharge by splitting the high-temperature growth and low-temperature separation zones using a non-uniform magnetic field and tailor-designed catalyst alloy, and depositing nanotubes and graphene in different areas. Our results are very relevant to the development of commercially-viable, single-step production of bulk amounts of high-quality graphene.

Highly effective fungal inactivation in He+O2 atmospheric-pressure nonequilibrium plasmas

Highly effective (more than 99.9%) inactivation of a pathogenic fungus Candida albicans commonly found in oral, respiratory, digestive, and reproduction systems of a human body using atmospheric-pressure plasma jets sustained in He+ O2 gas mixtures is reported. The inactivation is demonstrated in two fungal culture configurations with open (Petri dish without a cover) and restricted access to the atmosphere (Petri dish with a cover) under specific experimental conditions. It is shown that the fungal inactivation is remarkably more effective in the second configuration. This observation is supported by the scanning and transmission electron microscopy of the fungi before and after the plasma treatment. The inactivation mechanism explains the experimental observations under different experimental conditions and is consistent with the reports by other authors. The results are promising for the development of advanced health care applications.

Effect of input power and gas pressure on the roughening and selective etching of SiO2/Si surfaces in reactive plasmas

We report on the application low-temperature plasmas for roughening Si surfaces which is becoming increasingly important for a number of applications ranging from Si quantum dots to cell and protein attachment for devices such as "laboratory on a chip" and sensors. It is a requirement that Si surface roughening is scalable and is a single-step process. It is shown that the removal of naturally forming SiO2 can be used to assist in the roughening of the surface using a low-temperature plasma-based etching approach, similar to the commonly used in semiconductor micromanufacturing. It is demonstrated that the selectivity of SiO2 /Si etching can be easily controlled by tuning the plasma power, working gas pressure, and other discharge parameters. The achieved selectivity ranges from 0.4 to 25.2 thus providing an effective means for the control of surface roughness of Si during the oxide layer removal, which is required for many advance applications in bio- and nanotechnology.

Dynamics of mode transitions in inductively-coupled plasmas

The dynamics of transitions between the electrostatic and electromagnetic discharge modes of the low-frequency (460 kHz) inductively coupled plasma (LF ICP) reactor is studied. A series of images of plasma glows in Ar and N2 gases taken in the process of continuous variation of the input power confirms the discharge bistability and hysteresis. The operation regimes and parameters making the LF ICP reactor attractive for materials synthesis and processing applications are discussed.

Temperature-dependent properties of nc-Si thin films synthesized in low-pressure, thermally nonequilibrium, high-density inductively coupled plasmas

Silicon thin films were synthesized simultaneously on single-crystal silicon and glass substrates by lowpressure, thermally nonequilibrium, high-density inductively coupled plasma-assisted chemical vapor deposition from the silane precursor gas without any additional hydrogen dilution in a broad range of substrate temperatures from 100 to 500 °C. The effect of the substrate temperature on the morphological, structural and optical properties of the synthesized silicon thin films is systematically studied by X-ray diffractometry, Raman spectroscopy, UV-vis spectroscopy, and scanning electron microscopy. It is shown that the formation of nanocrystalline silicon (nc-Si) occurs when the substrate temperature is higher than 200 °C and that all the deposited nc-Si films have a preferential growth along the (111) direction. However, the mean grain size of the (111) orientation slightly and gradually decreases while the mean grain size of the (220) orientation shows a monotonous increase with the increased substrate temperature from 200 to 500 °C. It is also found that the crystal volume fraction of the synthesized nc-Si thin films has a maximum value of ∼69.1% at a substrate temperature of 300 rather than 500 °C. This rather unexpected result is interpreted through the interplay of thermokinetic surface diffusion and hydrogen termination effects. Furthermore, we have also shown that with the increased substrate temperature from 100 to 500 °C, the optical bandgap is reduced while the growth rates tend to increase. The maximum rates of change of the optical bandgap and the growth rates occur when the substrate temperature is increased from 400 to 500 °C. These results are highly relevant to the development of photovoltaic thin-film solar cells, thin-film transistors, and flat-panel displays.

Nanopowder management and control of plasma parameters in electronegative SiH4 plasmas

The nanopowder management and control of plasma parameters in electronegative SiH4 plasmas were discussed. The spatial profiles of electron and positive/negative ion number densities, electron temperature and charge of the fine particles were obtained. It was found that management of powder charge distribution is also possible through control of the external parameters.