On the role of activation mode in the plasma- and hot filaments-enhanced catalytic chemical vapour deposition of vertically aligned carbon nanotubes

International audienceCatalytic chemical vapor deposition (CCVD) with different activation modes (thermal; hot filaments-enhanced; direct current plasma-enhanced and both hot filament and direct current plasma-enhanced) are achieved in order to grow vertically aligned carbon nanotubes (VA CNTs). By widely varying the power of the different activation sources of the gas (plasma, hot filaments, substrate heating) while keeping identical the substrate temperature (973 K) and the catalyst preparation, the results point out the important role of ions in the nucleation of carbon nanotubes (CNTs), as well as the etching behaviour of highly activated radicals such as H˙ in the selective growth of vertically aligned films of CNTs. Moreover, it is demonstrated that, within the deposition conditions (temperature, pressure, flow rate) used in this study, oriented carbon nanotubes can be grown only when both ions, mainly generated by the gas discharge plasma, and highly reactive radicals, mainly formed by the hot filaments, are produced in the gas phase. We propose that highly energetic ions are needed to nucleate the carbon nanotubes by increasing the carbon concentration gradient whereas the highly reactive radicals allow the selective growth of vertically aligned CNTs by preventing carbon deposition on the whole surface through chemical etching of edge carbons in graphene sheets

A new polarised hot filament chemical vapor deposition process for homogeneous diamond nucleation on Si(100)

International audienceA new hot filament chemical vapor deposition with direct current plasma assistance (DC HFCVD) chamber has been designed for an intense nucleation and subsequent growth of diamond films on Si(100).Growth process as well as the If(V) characteristics of the DC discharge are reported. Gas phase constituents activation was obtained by a stable glow discharge between two grid electrodes coupled with two sets of parallel hot filaments settled in-between and polarised at the corresponding plasma potential. The sample is negatively biased with a small 10-15 V extraction potential with respect to the cathode grid.Such design allows to create a high density of both ions and radicals that are extracted and focussed onto the surface of the sample.The current density onto the sample can be finely tuned independently of the primary plasma.A homogeneous plasma fully covering the sample surface is visualized. Consequently, a high-density nucleation (>1010 cm-2) occurs

Localized CVD growth of oriented and individual carbon nanotubes from nanoscaled dots prepared by lithographic sequences

International audienceUsing a combination of top-down lithographic techniques, isolated, individual and oriented multi-wall carbon nanotubes (MWNTs) were grown on nickel or iron nanoscaled dots. In the first step of the process, micron-sized catalytic metallic dots (either iron or nickel) were prepared using UV lithography. MWNTs were then synthesized from these catalysts using a direct current plasma-assistance and hot-filament-enhanced chemical vapor deposition (CVD) reactor. Samples were characterized by means of scanning electron microscopy. It turns out that the splitting up of the micron-sized dot is favored in the iron case and that the surface diffusion of the metal is enhanced using ammonia in the gaseous mixture during the CVD process. The results are discussed giving arguments for the understanding of the MWNT growth mechanism. In a second step, a focused ion beam (FIB) procedure is carried out in order to reduce the initial dot size down to submicronic scale and subsequently to grow one single MWNT per dot. It is found that nickel is most appropriate to control the size of the dot. Dots of size 200 nm ± 40 nm are then required to grow individual MWNTs

Aligned carbon nanotubes catalytically grown on iron-based nanoparticles obtained by laser-induced CVD

International audienceIron-based nanoparticles are prepared by a laser-induced chemical vapor deposition (CVD) process. They are characterized as body-centered Fe and Fe2O3 (maghemite/magnetite) particles with sizes ::;5 and 10 nm, respectively. The Fe particles are embedded in a protective carbon matrix. Both kind of particles are dispersed by spin-coating on SiO2/Si(1 0 0) flat substrates. They are used as catalyst to grow carbon nanotubes by a plasma- and filaments-assisted catalytic CVD process (PE-HF-CCVD). Vertically oriented and thin carbon nanotubes (CNTs) were grown with few differences between the two samples, except the diameter in relation to the initial size of the iron particles, and the density. The electron field emission of these samples exhibit quite interesting behavior with a low turn-on voltage at around 1 V/mm

A comparative study of the field emission properties of aligned carbon nanostructures films, from carbon nanotubes to diamond

International audienceThe electron field emission properties of different graphitic and diamond-like nanostructures films are compared. They are prepared in the same CVD chamber on SiO{2}/Si(100) and Si(100) flat surfaces, respectively. These nanostructures are thoroughly characterized by scanning electron emission (SEM), transmission electron microscopy (TEM), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES). Films of dense aligned carbon nanotubes by far display the lowest threshold fields around few V/μ m and the largest emission currents. Carbon nanofibers, with platelet arrangement of the graphitic planes parallel to the substrate, exhibit higher emission thresholds around 10 V/μ m. Diamond nanostructures, either modified through ammonia incorporation within the gas phase or not, exhibit the largest emission threshold around 25 V/μ m. The high enhancement factors, deduced from the Fowler-Nordheim plots, can explain the low emission thresholds whereas limitations to the electron transport ever occur through different processes (i) surface modifications of the surface, as the transformation of the SiO{2} barrier layer into SiN{x} in the presence of ammonia evidenced by XPS; (ii) different orientation of the graphitic basal planes relative to the direction of electron transport (carbon nanofiber) and (iii) presence of a graphitic nest at the interface of the carbon nanostructure and the substrate, observed when catalyst is deposited through mild evaporation

Synthesis of carbon nanotubes by plasma-enhanced CVD process: gas phase study of synthesis conditions

International audienceTo support experimental investigations, a model based on ChemkinTM software was used to simulate gas phase and surface chemistry during plasma-enhanced catalytic CVD of carbon nanotubes. According to these calculations, gas phase composition, etching process and growth rates are calculated. The role of several carbon species, hydrocarbon molecules and ions in the growth mechanism of carbon nanotubes is presented in this study. Study of different conditions of gas phase activation sources and pressure is performed