Plasma-enabled, catalyst-free growth of carbon nanotubes on mechanically-written Si features with arbitrary shape

Simple, rapid, catalyst-free synthesis of complex patterns of long, vertically aligned multiwalled carbon nanotubes, strictly confined within mechanically-written features on a Si(1 0 0) surface is reported. It is shown that dense arrays of the nanotubes can nucleate and fully fill the features when the low-temperature microwave plasma is in a direct contact with the surface. This eliminates additional nanofabrication steps and inevitable contact losses in applications associated with carbon nanotube patterns. Using metal catalyst has long been considered essential for the nucleation and growth of surface-supported carbon nanotubes (CNTs) [1] and [2]. Only very recently, the possibility of CNT growth using non-metallic (e.g., oxide [3] and SiC [4]) catalysts or artificially created carbon-enriched surface layers [5] has been demonstrated. However, successful integration of carbon nanostructures into Si-based nanodevice platforms requires catalyst-free growth, as the catalyst nanoparticles introduce contact losses, and their catalytic activity is very difficult to control during the growth [6]. Furthermore, in many applications in microfluidics, biological and molecular filters, electronic, sensor, and energy conversion nanodevices, the CNTs need to be arranged in specific complex patterns [7] and [8]. These patterns need to contain the basic features (e.g., lines and dots) written using simple procedures and fully filled with dense arrays of high-quality, straight, yet separated nanotubes. In this paper, we report on a completely metal or oxide catalyst-free plasma-based approach for the direct and rapid growth of dense arrays of long vertically-aligned multi-walled carbon nanotubes arranged into complex patterns made of various combinations of basic features on a Si(1 0 0) surface written using simple mechanical techniques. The process was conducted in a plasma environment [9] and [10] produced by a microwave discharge which typically generates the low-temperature plasmas at the discharge power below 1 kW [11]. Our process starts from mechanical writing (scribing) a pattern of arbitrary features on pre-treated Si(1 0 0) wafers. Before and after the mechanical feature writing, the Si(1 0 0) substrates were cleaned in an aqueous solution of hydrofluoric acid for 2 min to remove any possible contaminations (such as oil traces which could decompose to free carbon at elevated temperatures) from the substrate surface. A piece of another silicon wafer cleaned in the same way as the substrate, or a diamond scriber were used to produce the growth patterns by a simple arbitrary mechanical writing, i.e., by making linear scratches or dot punctures on the Si wafer surface. The results were the same in both cases, i.e., when scratching the surface by Si or a diamond scriber. The procedure for preparation of the substrates did not involve any possibility of external metallic contaminations on the substrate surface. After the preparation, the substrates were loaded into an ASTeX model 5200 chemical vapour deposition (CVD) reactor, which was very carefully conditioned to remove any residue contamination. The samples were heated to at least 800 °C to remove any oxide that could have formed during the sample loading [12]. After loading the substrates into the reactor chamber, N2 gas was supplied into the chamber at the pressure of 7 Torr to ignite and sustain the discharge at the total power of 200 W. Then, a mixture of CH4 and 60% of N2 gases were supplied at 20 Torr, and the discharge power was increased to 700 W (power density of approximately 1.49 W/cm3). During the process, the microwave plasma was in a direct contact with the substrate. During the plasma exposure, no external heating source was used, and the substrate temperature (∼850 °C) was maintained merely due to the plasma heating. The features were exposed to a microwave plasma for 3–5 min. A photograph of the reactor and the plasma discharge is shown in Fig. 1a and b.

Kinetics of low-pressure, low-temperature graphene growth : toward single-layer, single-crystalline structure

Graphene grown on metal catalysts with low carbon solubility is a highly competitive alternative to exfoliated and other forms of graphene, yet a single-layer, single-crystal structure remains a challenge because of the large number of randomly oriented nuclei that form grain boundaries when stitched together. A kinetic model of graphene nucleation and growth is developed to elucidate the effective controls of the graphene island density and surface coverage from the onset of nucleation to the full monolayer formation in low-pressure, low-temperature CVD. The model unprecedentedly involves the complete cycle of the elementary gas-phase and surface processes and shows a precise quantitative agreement with the recent low-energy electron diffraction measurements and also explains numerous parameter trends from a host of experimental reports. These agreements are demonstrated for a broad pressure range as well as different combinations of precursor gases and supporting catalysts. The critical role of hydrogen in controlling the graphene nucleation and monolayer formation is revealed and quantified. The model is generic and can be extended to even broader ranges of catalysts and precursor gases/pressures to enable the as yet elusive effective control of the crystalline structure and number of layers of graphene using the minimum amounts of matter and energy.

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.

Property-performance control of multidimensional, hierarchical, single-crystalline ZnO nanoarchitectures

Diverse morphologies of multidimensional hierarchical single-crystalline ZnO nanoarchitectures including nanoflowers, nanobelts, and nanowires are obtained by use of a simple thermal evaporation and vapour-phase transport deposition technique by placing Au-coated silicon substrates in different positions inside a furnace at process temperatures as low as 550 °C. The nucleation and growth of ZnO nanostructures are governed by the vapour–solid mechanism, as opposed to the commonly reported vapour–liquid–solid mechanism, when gold is used in the process. The morphological, structural, compositional and optical properties of the synthesized ZnO nanostructures can be effectively tailored by means of the experimental parameters, and these properties are closely related to the local growth temperature and gas-phase supersaturation at the sample position. In particular, room-temperature photoluminescence measurements reveal an intense near-band-edge ultraviolet emission at about 386 nm for nanobelts and nanoflowers, which suggests that these nanostructures are of sufficient quality for applications in, for example, optoelectronic devices.

Room-temperature, atmospheric plasma needle reduces adenovirus gene expression in HEK 293A host cells

Room-temperature, atmospheric-pressure plasma needle treatment is used to effectively minimize the adenovirus (AdV) infectivity as quantified by the dramatic reduction of its gene expression in HEK 293A primary human embryonic kidney cells studied by green fluorescent protein imaging. The AdV titer is reduced by two orders of magnitude within only 8 min of the plasma exposure. This effect is due to longer lifetimes and higher interaction efficacy of the plasma-generated reactive species in confined space exposed to the plasma rather than thermal effects commonly utilized in pathogen inactivation. This generic approach is promising for the next-generation anti-viral treatments and imunotherapies.

Effect of Coulomb blockade, gold resistance, and thermal expansion on the electrical resistance of ultrathin gold films

Controlling the electrical resistance of granular thin films is of great importance for many applications, yet a full understanding of electron transport in such films remains a major challenge. We have studied experimentally and by model calculations the temperature dependence of the electrical resistance of ultrathin gold films at temperatures between 2 K and 300 K. Using sputter deposition, the film morphology was varied from a discontinuous film of weakly coupled meandering islands to a continuous film of strongly coupled coalesced islands. In the weak-coupling regime, we compare the regular island array model, the cotunneling model, and the conduction percolation model with our experimental data. We show that the tunnel barriers and the Coulomb blockade energies are important at low temperatures and that the thermal expansion of the substrate and the island resistance affect the resistance at high temperatures. At low temperatures our experimental data show evidence for a transition from electron cotunneling to sequential tunneling but the data can also be interpreted in terms of conduction percolation. The resistivity and temperature coefficient of resistance of the meandering gold islands are found to resemble those of gold nanowires. We derive a simple expression for the temperature at which the resistance changes from non-metal-like behavior into metal-like behavior. In the case of strong island coupling, the total resistance is solely determined by the Ohmic island resistance.

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.

Plasma nanoscience : setting directions, tackling grand challenges

This review paper presents historical perspectives, recent advances and future directions in the multidisciplinary research field of plasma nanoscience. The current status and future challenges are presented using a three-dimensional framework. The first and the largest dimension covers the most important classes of nanoscale objects (nanostructures, nanofeatures and nanoassemblies/nanoarchitectures) and materials systems, namely carbon nanotubes, nanofibres, graphene, graphene nanoribbons, graphene nanoflakes, nanodiamond and related carbon-based nanostructures; metal, silicon and other inorganic nanoparticles and nanostructures; soft organic nanomaterials; nano-biomaterials; biological objects and nanoscale plasma etching. In the second dimension, we discuss the most common types of plasmas and plasma reactors used in nanoscale plasma synthesis and processing. These include low-temperature non-equilibrium plasmas at low and high pressures, thermal plasmas, high-pressure microplasmas, plasmas in liquids and plasma–liquid interactions, high-energy-density plasmas, and ionized physical vapour deposition as well as some other plasma-enhanced nanofabrication techniques. In the third dimension, we outline some of the 'Grand Science Challenges' and 'Grand Socio-economic Challenges' to which significant contributions from plasma nanoscience-related research can be expected in the near future. The urgent need for a stronger focus on practical, outcome-oriented research to tackle the grand challenges is emphasized and concisely formulated as from controlled complexity to practical simplicity in solving grand challenges.

Minimizing the Gibbs–Thomson effect in the low-temperature plasma synthesis of thin Si nanowires

An advanced combination of numerical models, including plasma sheath, ion- and radical-induced species creation and plasma heating effects on the surface and within a Au catalyst nanoparticle, is used to describe the catalyzed growth of Si nanowires in the sheath of a low-temperature and low-pressure plasma. These models have been used to explain the higher nanowire growth rates, low-energy barriers, much thinner Si nanowire nucleation and the less effective Gibbs–Thomson effect in reactive plasma processes, compared with those of neutral gas thermal processes. The effects of variation in the plasma sheath parameters and substrate potential on Si nanowire nucleation and growth have also been investigated. It is shown that increasing the plasma-related effects leads to decreases in the nucleation energy barrier and the critical nanoparticle radius, with the Gibbs–Thomson effect diminished, even at low temperatures. The results obtained are consistent with available experimental results and open a path toward the energy- and matter-efficient nucleation and growth of a broad range of one-dimensional quantum structures.

Temperature-dependent growth mechanisms of low-dimensional ZnO nanostructures

One-dimensional ZnO nanostructures were successfully synthesized on single-crystal silicon substrates via a simple thermal evaporation and vapour-phase transport method under different process temperatures from 500 to 1000 °C. The detailed and in-depth analysis of the experimental results shows that the growth of ZnO nanostructures at process temperatures of 500, 800, and 1000 °C is governed by different growth mechanisms. At a low process temperature of 500 °C, the ZnO nanostructures feature flat and smooth tips, and their growth is primarily governed by the vapour-solid mechanism. At an intermediate process temperature of 800 °C, the ZnO nanostructures feature cone-shape tips, and their growth is primarily governed by the self-catalyzed and saturated vapour–liquid–solid mechanism. At a high process temperature of 1000 °C, the alloy tip appears on the front side of the ZnO nanostructures, and their growth is primarily governed by the common catalyst-assisted vapour–liquid–solid mechanism. It is also shown that the morphological, structural, optical, and compositional properties of the synthesized ZnO nanostructures are closely related to the process temperature. These results are highly relevant to the development of light-emitting diodes, chemical sensors, energy conversion devices, and other advanced applications.

Deterministic plasma-aided synthesis of high-quality nanoislanded nc-SiC films

Despite major advances in the fabrication and characterization of SiC and related materials, there has been no convincing evidence of the synthesis of nanodevice-quality nanoislanded SiC films at low, ultralarge scale integration technology-compatible process temperatures. The authors report on a low-temperature (400 °C) plasma-assisted rf magnetron sputtering deposition of high-quality nanocrystalline SiC films made of uniform-size nanoislands that almost completely cover the Si(100) surface. These nanoislands are chemically pure, highly stoichiometric, have a typical size of 20-35 nm, and contain small (∼5 nm) nanocrystalline inclusions. The properties of nanocrystalline SiC films can be effectively controlled by the plasma parameters.

Self-organized quantum dot arrays : kinetic mapping of adatom capture

Deterministic synthesis of self-organized quantum dot arrays for renewable energy, biomedical, and optoelectronic applications requires control over adatom capture zones, which are presently mapped using unphysical geometric tessellation. In contrast, the proposed kinetic mapping is based on simulated two-dimensional adatom fluxes in the array and includes the effects of nucleation, dissolution, coalescence, and process parameters such as surface temperature and deposition rate. This approach is generic and can be used to control the nanoarray development in various practical applications. © 2009 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.

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.

Low-pressure planar magnetron discharge for surface deposition and nanofabrication

Current-voltage characteristics of the planar magnetron are studied experimentally and by numerical simulation. Based on the measured current-voltage characteristics, a model of the planar magnetron discharge is developed with the background gas pressure and magnetic field used as parameters. The discharge pressure was varied in a range of 0.7-1.7 Pa, the magnetic field of the magnetron was of 0.033-0.12 T near the cathode surface, the discharge current was from 1 to 25 A, and the magnetic field lines were tangential to the substrate surface in the region of the magnetron discharge ignition. The discharge model describes the motion of energetic secondary electrons that gain energy by passing the cathode sheath across the magnetic field, and the power required to sustain the plasma generation in the bulk. The plasma electrons, in turn, are accelerated in the electric field and ionize effectively the background gas species. The model is based on the assumption about the prevailing Bohm mechanism of electron conductivity across the magnetic field. A criterion of the self-sustained discharge ignition is used to establish the dependence of the discharge voltage on the discharge current. The dependence of the background gas density on the current is also observed from the experiment. The model is consistent with the experimental results. © 2010 American Institute of Physics.