Uniform, dense arrays of vertically aligned, large-diameter single-walled carbon nanotubes

Precisely controlled reactive chemical vapor synthesis of highly uniform, dense arrays of vertically aligned single-walled carbon nanotubes (SWCNTs) using tailored trilayered Fe/Al2O3/SiO2 catalyst is demonstrated. More than 90% population of thick nanotubes (>3 nm in diameter) can be produced by tailoring the thickness and microstructure of the secondary catalyst supporting SiO2 layer, which is commonly overlooked. The proposed model based on the atomic force microanalysis suggests that this tailoring leads to uniform and dense arrays of relatively large Fe catalyst nanoparticles on which the thick SWCNTs nucleate, while small nanotubes and amorphous carbon are effectively etched away. Our results resolve a persistent issue of selective (while avoiding multiwalled nanotubes and other carbon nanostructures) synthesis of thick vertically aligned SWCNTs whose easily switchable thickness-dependent electronic properties enable advanced applications in nanoelectronic, energy, drug delivery, and membrane technologies.

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.

Self-organization in arrays of surface-grown nanoparticles : characterization, control, driving forces

Some important issues related to the self-organization in the arrays of nanoparticles on solid surfaces exposed to the low-temperature plasma are analysed and discussed. The available tools for the characterization of the size and position uniformity in nanoarrays are examined. The technique capable of revealing the realistic adsorbed atom and adsorbed radical capture zone pattern based on the surface physics is indicated as the most promising characterization tool. The processes responsible for the self-organization are analysed, the main driving forces of the self-organization are discussed, and possible ways to control the self-organization by controlling the plasma parameters are introduced. A view on the possible ways to further improve the methods of nanoarray characterization and self-organization is presented as well.

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.

Control of dense carbon nanotube arrays via hierarchical multilayer catalyst

Effective control of dense, high-quality carbon nanotube arrays using hierarchical multilayer catalyst patterns is demonstrated. Scanning/transmission electron microscopy, atomic force microscopy, Raman spectroscopy, and numerical simulations show that by changing the secondary and tertiary layers one can control the properties of the nanotube arrays. The arrays with the highest surface density of vertically aligned nanotubes are produced using a hierarchical stack of iron nanoparticles and alumina and silica layers differing in thickness by one order of magnitude from one another. The results are explained in terms of the catalyst structure effect on carbon diffusivity.

Effect of hydrophilicity of carbon nanotube arrays on the release rate and activity of recombinant human bone morphogenetic protein-2

Novel nanostructures such as vertically aligned carbon nanotube (CNT) arrays have received increasing interest as drug delivery carriers. In the present study, two CNT arrays with extreme surface wettabilities are fabricated and their effects on the release of recombinant human bone morphogenetic protein-2 (rhBMP-2) are investigated. It is found that the superhydrophilic arrays retained a larger amount of rhBMP-2 than the superhydrophobic ones. Further use of a poloxamer diffusion layer delayed the initial burst and resulted in a greater total amount of rhBMP-2 released from both surfaces. In addition, rhBMP-2 bound to the superhydrophilic CNT arrays remained bioactive while they denatured on the superhydrophobic surfaces. These results are related to the combined effects of rhBMP-2 molecules interacting with poloxamer and the surface, which could be essential in the development of advanced carriers with tailored surface functionalities.

Plasma/ion-controlled metal catalyst saturation : enabling simultaneous growth of carbon nanotube/nanocone arrays

It is shown that the simultaneous saturation of Ni nanoparticles used as catalyst for vertically aligned carbon nanotube and nanocone arrays can be improved in low-temperature plasma- or ion-assisted processes compared with neutral gas-based routes. The results of hybrid multiscale numerical simulations of the catalyst nanoarrays (particle sizes of 2 and 10 nm) saturation with carbon show the possibility of reducing the difference in catalyst incubation times for smallest and largest catalyst particles by up to a factor of 2. This approach is generic and provides process conditions for simultaneous nucleation and growth of uniform arrays of vertically aligned nanostructures. © 2008 American Institute of Physics.

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.

Plasma-driven self-organization of Ni nanodot arrays on Si(100)

The results of the combined experimental and numerical study suggest that nonequilibrium plasma-driven self-organization leads to better size and positional uniformity of nickel nanodot arrays on a Si(100) surface compared with neutral gas-based processes under similar conditions. This phenomenon is explained by introducing the absorption zone patterns, whose areas relative to the small nanodot sizes become larger when the surface is charged. Our results suggest that strongly nonequilibrium and higher-complexity plasma systems can be used to improve ordering and size uniformity in nanodot arrays of various materials, a common and seemingly irresolvable problem in self-organized systems of small nanoparticles. © 2008 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.

Hierarchical multilevel arrays of self-assembled gold nanoparticles : Control of resistivity-temperature dependence

The possibility to control the electric resistivity-temperature dependence of the nanosized resistive components made using hierarchical multilevel arrays of self-assembled gold nanoparticles prepared by multiple deposition/annealing is demonstrated. It is experimentally shown that the hierarchical three-level patterns, where the nanoparticles of sizes ranging from several nanometers to several tens of nanometer play a competitive roles in the electric conductivity, demonstrate sharp changes in the activation energy. These patterns can be used for the precise tuning of the resistivity-temperature behavior of nanoelectronic components.

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.

Plasma-assisted self-organized growth of uniform carbon nanocone arrays

The self-organized growth of uniform carbon nanocone arrays using low-temperature non-equilibrium Ar + H 2 + CH 4 plasma-enhanced chemical vapor deposition (PECVD) is studied. The experiment shows that size-, shape-, and position-uniform carbon nanocone arrays can develop even from non-uniformly fragmented discontinuous nickel catalyst films. A three-stage scenario is proposed where the primary nanocones grow on large catalyst particles during the first stage, and the secondary nanocones are formed between the primary ones at the second stage. Finally, plasma-related effects lead to preferential growth of the secondary nanocones and eventually a uniform nanopattern is formed. This does not happen in a CVD process with the same gas feedstock and surface temperature. The proposed three-stage growth scenario is supported by the numerical experiment which generates nanocone arrays very similar to the experimentally synthesized nanopatterns. The self-organization process is explained in terms of re-distribution of surface and volumetric fluxes of plasma-generated species in a developing nanocone array. Our results suggest that plasma-related self-organization effects can significantly reduce the non-uniformity of carbon nanostructure arrays which commonly arises from imperfections in fragmented Ni-based catalyst films.

Pulsed i-PVD of dielectric nanodot arrays using a nanoporous template

The results of multi-scale numerical simulations of pulsed i-PVD template-assisted nanofabrication of ZnO nanodot arrays on a silicon substrate are presented. The ratios and spatial distributions of the ion fluxes deposited on the lateral and bottom surfaces of the nanopores are computed as a function of the external bias and plasma parameters. The results show that the pulsed bias plays a significant role in the ion current distribution inside the nanopores. The results of numerical experiments of this work suggest that by finely adjusting the pulse voltage, the pulse duration and the duty cycle of the external pulsed bias, the nanopore clogging can be successfully avoided during the deposition and the shapes of the deposited ZnO nanodots can be effectively controlled. A figure is presented.

Deterministic control of plasma-assembled self-organized Ge/Si quantum dot arrays

Self-assembly of size-uniform and spatially ordered quantum dot (QD) arrays is one of the major challenges in the development of the new generation of semiconducting nanoelectronic and photonic devices. Assembly of Ge QD (in the ∼5-20 nm size range) arrays from randomly generated position and size-nonuniform nanodot patterns on plasma-exposed Si (100) surfaces is studied using hybrid multiscale numerical simulations. It is shown, by properly manipulating the incoming ion/neutral flux from the plasma and the surface temperature, the uniformity of the nanodot size within the array can be improved by 34%-53%, with the best improvement achieved at low surface temperatures and high external incoming fluxes, which are intrinsic to plasma-aided processes. Using a plasma-based process also leads to an improvement (∼22% at 700 K surface temperature and 0.1 MLs incoming flux from the plasma) of the spatial order of a randomly sampled nanodot ensemble, which self-organizes to position the dots equidistantly to their neighbors within the array. Remarkable improvements in QD ordering and size uniformity can be achieved at high growth rates (a few nms) and a surface temperature as low as 600 K, which broadens the range of suitable substrates to temperature-sensitive ultrathin nanofilms and polymers. The results of this study are generic, can also be applied to nonplasma-based techniques, and as such contributes to the development of deterministic strategies of nanoassembly of self-ordered arrays of size-uniform QDs, in the size range where nanodot ordering cannot be achieved by presently available pattern delineation techniques.