Plasma–surface interactions at nanoscales : a combinatorial theoretical, process diagnostics and surface microanalysis approach

This paper introduces an integral approach to the study of plasma-surface interactions during the catalytic growth of selected nanostructures (NSs). This approach involves basic understanding of the plasma-specific effects in NS nucleation and growth, theoretical modelling, numerical simulations, plasma diagnostics, and surface microanalysis. Using an example of plasma-assisted growth of surface-supported single-walled carbon nanotubes, we discuss how the combination of these techniques may help improve the outcomes of the growth process. A specific focus here is on the effects of nanoscale plasma-surface interactions on the NS growth and how the available techniques may be used, both in situ and ex situ to optimize the growth process and structural parameters of NSs.

Structure- and composition-dependent electron field emission from nitrogenated carbon nanotips

The electron field emission (EFE) properties of nitrogenated carbon nanotips (NCNTPs) were studied under high-vacuum conditions. The NCNTPs were prepared in a plasma-assisted hot filament chemical vapor deposition system using CH4 and N2 as the carbon and nitrogen sources, respectively. The work functions of NCNTPs were measured using x-ray photoelectron spectroscopy. The morphological and structural properties of NCNTPs were studied by field emission scanning electron microscopy, micro-Raman spectroscopy, and x-ray photoelectron spectroscopy. The field enhancement factors of NCNTPs were calculated using relevant EFE models based on the Fowler-Nordheim approximation. Analytical characterization and modeling results were used to establish the relations between the EFE properties of NCNTPs and their morphology, structure, and composition. It is shown that the EFE properties of NCNTPs can be enhanced by the reduction of oxygen termination on the surface as well as by increasing the ratio of the NCNTP height to the radius of curvature at its top. These results also suggest that a significant amount of electrons is emitted from other surface areas besides the NCNTP tops, contrary to the common belief. The outcomes of this study advance our knowledge on the electron emission properties of carbonnanomaterials and contribute to the development of the next-generation of advanced applications in the fields of micro- and opto-electronics.

Solitary filamentary structures and nanosecond dynamics in atmospheric-pressure plasmas driven by tailored dc pulses

Nanosecond dynamics of two separated discharge cycles in an asymmetric dielectric barrier discharge is studied using time-resolved current and voltage measurements synchronized with high-speed (∼5 ns) optical imaging. Nanosecond dc pulses with tailored raise and fall times are used to generate solitary filamentary structures (SFSs) during the first cycle and a uniform glow during the second. The SFSs feature ∼1.5 mm thickness, ∼1.9 A peak current, and a lifetime of several hundred nanoseconds, at least an order of magnitude larger than in common microdischarges. This can be used in alternating localized and uniform high-current plasma treatments in various applications.

Plasma-made silicon nanograss and related nanostructures

Plasma-made nanostructures show outstanding potential for applications in nanotechnology. This paper provides a concise overview on the progress of plasma-based synthesis and applications of silicon nanograss and related nanostructures. The materials described here include black silicon, Si nanotips produced using a self-masking technique as well as self-organized silicon nanocones and nanograss. The distinctive features of the Si nanograss, two-tier hierarchical and tilted nanograss structures are discussed. Specific applications based on the unique features of the silicon nanograss are also presented.

Energy and matter-efficient size-selective growth of thin quantum wires in a plasma

It is shown that plasmas can minimize the adverse Gibbs-Thompson effect in thin quantum wire growth. The model of Si nanowirenucleation includes the unprecedented combination of the plasma sheath, ion- and radical-induced species creation and heating effects on the surface and within an Au catalyst nanoparticle. Compared to neutral gas thermal processes, much thinner, size-selective wires can nucleate at the same temperature and pressure while much lower energy and matter budget is needed to grow same-size wires. This explains the experimental observations and may lead to energy- and matter-efficient synthesis of a broader range of one-dimensional quantum structures.

Control of energy and matter at nanoscales : challenges and opportunities for plasma nanoscience in a sustainability age

Plasma nanoscience is an emerging multidisciplinary research field at the cutting edge of a large number of disciplines including but not limited to physics and chemistry of plasmas and gas discharges, materials science, surface science, nanoscience and nanotechnology, solid-state physics, space physics and astrophysics, photonics, optics, plasmonics, spintronics, quantum information, physical chemistry, biomedical sciences and related engineering subjects. This paper examines the origin, progress and future perspectives of this research field driven by the global scientific and societal challenges. The future potential of plasma nanoscience to remain a highly topical area in the global research and technological agenda in the age of fundamental-level control for a sustainable future is assessed using a framework of the five Grand Challenges for Basic Energy Sciences recently mapped by the US Department of Energy. It is concluded that the ongoing research is very relevant and is expected to substantially expand to competitively contribute to the solution of all of these Grand Challenges. The approach to controlling energy and matter at nano- and subnanoscales is based on identifying the prevailing carriers and transfer mechanisms of the energy and matter at the spatial and temporal scales that are most relevant to any particular nanofabrication process. Strong accent is made on the competitive edge of the plasma-based nanotechnology in applications related to the major socio-economic issues (energy, food, water, health and environment) that are crucial for a sustainable development of humankind. Several important emerging topics, opportunities and multidisciplinary synergies for plasma nanoscience are highlighted. The main nanosafety issues are also discussed and the environment- and human health-friendly features of plasma-based nanotech are emphasized.

Plasma nanofabrication and nanomaterials safety

The fast advances in nanotechnology have raised increasing concerns related to the safety of nanomaterials when exposed to humans, animals and the environment. However, despite several years of research, the nanomaterials safety field is still in its infancy owing to the complexities of structural and surface properties of these nanomaterials and organism-specific responses to them. Recently, plasma-based technology has been demonstrated as a versatile and effective way for nanofabrication, yet its health and environment-benign nature has not been widely recognized. Here we address the environmental and occupational health and safety effects of various zero- and one-dimensional nanomaterials and elaborate the advantages of using plasmas as a safe nanofabrication tool. These advantages include but are not limited to the production of substrate-bound nanomaterials, the isolation of humans from harmful nanomaterials, and the effective reforming of toxic and flammable gases. It is concluded that plasma nanofabrication can minimize the hazards in the workplace and represents a safe way for future nanofabrication technologies.

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.

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.

Controlled electronic transport in single-walled carbon nanotube networks : selecting electron hopping and chemical doping mechanisms

The electronic transport in both intrinsic and acid-treated single-walled carbon nanotube networks containing more than 90% semiconducting nanotubes is investigated using temperature-dependent resistance measurements. The semiconducting behavior observed in the intrinsic network is attributed to the three-dimensional electron hopping mechanism. In contrast, the chemical doping mechanism in the acid-treated network is found to be responsible for the revealed metal-like linear resistivity dependence in a broad temperature range. This effective method to control the electrical conductivity of single-walled carbon nanotube networks is promising for future nanoscale electronics, thermometry, and bolometry. © 2010 American Institute of Physics.

Single-step, catalyst-free plasma-assisted synthesis and growth mechanism of single-crystalline aluminum nitride nanorods

Synthesis of one-dimensional AlN nanostructures commonly requires high process temperatures (>900 °C), metal catalyst, and hazardous gas/powder precursors. We report on a simple, single-step, catalyst-free, plasma-assisted growth of dense patterns of size-uniform single-crystalline AlN nanorods at a low substrate temperature (∼650 °C) without any catalyst or hazardous precursors. This unusual growth mechanism is based on highly effective plasma dissociation of N2 molecules, localized species precipitation on AlN islands, and reduced diffusion on the nitrogen-rich surface. This approach can also be used to produce other high-aspect-ratio oxide and nitride nanostructures for applications in energy conversion, sensing, and optoelectronics. © 2010 American Institute of Physics.

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.

Control of core-shell structure and elemental composition of binary quantum dots

The possibility of initial stage control of the elemental composition and core/shell structure of binary SiC quantum dots by optimizing temporal variation of Si and C incoming fluxes and surface temperatures is shown via hybrid numerical simulations. Higher temperatures and influxes encourage the formation of a stoichiometric outer shell over a small carbon-enriched core, whereas lower temperatures result in a larger carbon-enriched core, Si-enriched undershell, and then a stoichiometric SiC outer shell. This approach is generic and is applicable to a broad range of semiconductor materials and nanofabrication techniques. © 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.

Hydrogen in plasma-nanofabrication : selective control of nanostructure heating and passivation

The possibility of independent control of the surface fluxes of energy and hydrogen-containing radicals, thus enabling selective control of the nanostructure heating and passivation, is demonstrated. In situ energy flux measurements reveal that even a small addition of H2 to low-pressure Ar plasmas leads to a dramatic increase in the energy deposition through H recombination on the surface. The heat release is quenched by a sequential addition of a hydrocarbon precursor while the surface passivation remains effective. Such selective control offers an effective mechanism for deterministic control of the growth shape, crystallinity, and density of nanostructures in plasma-aided nanofabrication. © 2010 American Institute of Physics.