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.

Nanoscale plasma chemistry enables fast, size-selective nanotube nucleation

The possibility of fast, narrow-size/chirality nucleation of thin single-walled carbon nanotubes (SWCNTs) at low, device-tolerant process temperatures in a plasma-enhanced chemical vapor deposition (CVD) is demonstrated using multiphase, multiscale numerical experiments. These effects are due to the unique nanoscale reactive plasma chemistry (NRPC) on the surfaces and within Au catalyst nanoparticles. The computed three-dimensional process parameter maps link the nanotube incubation times and the relative differences between the incubation times of SWCNTs of different sizes/chiralities to the main plasma- and precursor gas-specific parameters and explain recent experimental observations. It is shown that the unique NRPC leads not only to much faster nucleation of thin nanotubes at much lower process temperatures, but also to better selectivity between the incubation times of SWCNTs with different sizes and chiralities, compared to thermal CVD. These results are used to propose a time-programmed kinetic approach based on fast-responding plasmas which control the size-selective, narrow-chirality nucleation and growth of thin SWCNTs. This approach is generic and can be used for other nanostructure and materials systems.

Plasma enables edge-to-center-oriented graphene nanoarrays on Si nanograss

The formation of clearly separated vertical graphenenanosheets on silicon nanograss support is demonstrated. The plasma-enabled, two-stage mask-free process produced self-organized vertical graphenes of a few carbon layers (as confirmed by advanced microanalysis), prominently oriented in the substrate center–substrate edge direction. It is shown that the width of the alignment zone depends on the substrate conductivity, and thus the electric field in the vicinity of the growth surface is responsible for the graphene alignment. This finding is confirmed by the Monte Carlo simulations of the ion flux distribution in the silicon nanograss pattern.

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.

Plasma control of morpho-dimensional selectivity of hematite nanostructures

Highly controllablefabrication of the nanowire, nanocone, and mixed nanowire/nanowall arrays of iron oxide (hematite, α-Fe2O3) nanostructures in a simple, environment-friendly process is achieved by exposing the metal foils to low-temperature oxygen plasmas. Very dense forests of thin (≈50 nm) and long (up to several μm) nanowires are grown on the electrically biased substrates, whereas the use of the electrically insulated substrate resulted in the formation of a mixed array of nanowires and nanowalls. The proposed mechanism of the nanostructure growth is supported by the numerical simulations demonstrating the key role of the plasma environment in the growth morphology selection.

Plasma-enabled growth of single-crystalline SiC/AlSiC Core–Shell nanowires on porous alumina templates

We report the catalyst-free synthesis of the arrays of core–shell, ultrathin, size-uniform SiC/AlSiC nanowires on the top of a periodic anodic aluminum oxide template. The nanowires were grown using an environmentally friendly, silane-free process by exposing the silicon supported porous alumina template to CH4 + H2 plasmas. High-resolution scanning and transmission electron microscopy studies revealed that the nanowires have a single-crystalline core with a diameter of about 10 nm and a thin (1–2 nm) amorphous AlSiC shell. Because of their remarkable length, high aspect ratio, and very high surface area-to-volume ratio, these unique structures are promising for nanoelectronic and nanophotonic applications that require efficient electron emission, light scattering, etc. A mechanism for nanowire growth is proposed based upon the reduction of the alumina template to nanosized metallic aluminum droplets forming between nanopores. The subsequent incorporation of silicon and carbon atoms from the plasma leads to nucleation and growth from the top of the alumina template.

Room-temperature photoluminescence from nitrogenated carbon nanotips grown by plasma-enhanced hot filament chemical vapor deposition

Nitrogenated carbon nanotips with a low atomic concentration of nitrogen have been synthesized by using a custom-designed plasma-enhanced hot-filament plasma chemical vapor deposition system. The properties (including morphology, structure, composition, photoluminescence, etc.) of the synthesized nitrogenated carbon nanotips are investigated using advanced characterization tools. The room-temperature photoluminescence measurements show that the nitrogenated carbon nanotips can generate two distinct broad emissions located at ∼405 and ∼507 nm, respectively. Through the detailed analysis, it is shown that these two emission bands are attributed to the transition between the lone pair valence and bands, which are related to the sp3 and sp2 C-N bonds, respectively. These results are highly relevant to advanced applications of nitrogenated carbon nanotips in light emitting 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.

Highly efficient silicon nanoarray solar cells by a single-step plasma-based process

Highly efficient solar cells (conversion efficiency 11.9%, fill factor 70%) based on the vertically aligned single-crystalline nanostructures are fabricated without any pre-fabricated p-n junctions in a very simple, single-step process of Si nanoarray formation by etching p-type Si(100) wafers in low-temperature environment-friendly plasmas of argon and hydrogen mixtures.

Control of density of self-organized carbon nanotube arrays by catalyst pretreatment through plasma immersion ion implantation

A simple and effective method of controlling the growth of vertically aligned carbon nanotube arrays in a lowerature plasma is presented. Ni catalyst was pretreated by plasma immersion ion implantation prior to the nanotube growth by plasma-enhanced chemical vapor deposition. Both the size distribution and the areal density of the catalyst nanoparticles decrease due to the ion-surface interactions. Consequently, the resulting size distribution of the vertically aligned carbon nanotubes is reduced to 50 ∼ 100 nm and the areal density is lowered (by a factor of ten) to 10 8 cm -2, which is significantly different from the very-high-density carbon nanotube forests commonly produced by thermal chemical vapor deposition. The efficiency of this pretreatment is compared with the existing techniques such as neutral gas annealing and plasma etching. These results are highly relevant to the development of the next-generation nanoelectronic and optoelectronic devices that require effective control of the density of nanotube arrays.

Enhancement of electron field emission of vertically aligned carbon nanotubes by nitrogen plasma treatment

The electron field emission (EFE) characteristics from vertically aligned carbon nanotubes (VACNTs) without and with treatment by the nitrogen plasma are investigated. The VACNTs with the plasma treatment showed a significant improvement in the EFE property compared to the untreated VACNTs. The morphological, structural, and compositional properties of the VACNTs are extensively examined by scanning electron microscopy, transmission electron microscopy, Raman spectroscopy, and energy dispersive X-ray spectroscopy. It is shown that the significant EFE improvement of the VACNTs after the nitrogen plasma treatment is closely related to the variation of the morphological and structural properties of the VACNTs. The high current density (299.6 μA/cm2) achieved at a low applied field (3.50 V/μm) suggests that the VACNTs after nitrogen plasma treatment can serve as effective electron field emission sources for numerous applications.

Made-to-order nanocarbons through deterministic plasma nanotechnology

Through a combinatorial approach involving experimental measurement and plasma modelling, it is shown that a high degree of control over diamond-like nanocarbon film sp3/sp2 ratio (and hence film properties) may be exercised, starting at the level of electrons (through modification of the plasma electron energy distribution function). Hydrogenated amorphous carbon nanoparticle films with high percentages of diamond-like bonds are grown using a middle-frequency (2 MHz) inductively coupled Ar + CH4 plasma. The sp3 fractions measured by X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy in the thin films are explained qualitatively using sp3/sp2 ratios 1) derived from calculated sp3 and sp2 hybridized precursor species densities in a global plasma discharge model and 2) measured experimentally. It is shown that at high discharge power and lower CH4 concentrations, the sp3/sp2 fraction is higher. Our results suggest that a combination of predictive modeling and experimental studies is instrumental to achieve deterministically grown made-to-order diamond-like nanocarbons suitable for a variety of applications spanning from nano-magnetic resonance imaging to spin-flip quantum information devices. This deterministic approach can be extended to graphene, carbon nanotips, nanodiamond and other nanocarbon materials for a variety of applications

Control of morphology and electrical properties of self-organized graphenes in a plasma

The possibility of effective control of morphology and electrical properties of self-organized graphene structures on plasma-exposed Si surfaces is demonstrated. The structures are vertically standing nanosheets and can be grown without any catalyst and any external heating upon direct contact with high-density inductively coupled plasmas at surface temperatures not exceeding 673–723 K. Study of nucleation and growth dynamics revealed the possibility to switch-over between the two most common (turnstile- and maze-like) morphologies on the same substrates by a simple change of the plasma parameters. This change leads to the continuous or discontinuous native oxide layer that supports self-organized patterns of small carbon nanoparticles on which the structures nucleate. It is shown that by tailoring the nanoparticle arrangement one can create various three-dimensional architectures and networks of graphene nanosheet structures. We also demonstrate effective control of the degree of graphitization of the graphene nanosheet structures from the initial through the final growth stages. This makes it possible to tune the electrical resistivity properties of the produced three-dimensional patterns/networks from strongly dielectric to semiconducting. Our results contribute to enabling direct integration of graphene structures into presently dominant Si-based nanofabrication platform for next-generation nanoelectronic, sensor, biomedical, and optoelectronic components and nanodevices.

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.

Graphene and carbon nanotubes from arc plasmas : experiment and plasma modeling

Graphene and carbon nanotubes are the most promising nanomaterials for application in various modern nanodevices. The successful production of the nanotubes and graphene in a single process was achieved by using a magnetically enhanced arc discharge in helium atmosphere between carbon and metal electrodes. A 3-D fluid model has been used to investigate the discharge parameters.