Carbon nanotubes (CNTs), due to their unique electronic and extraordinary mechanical properties, have been receiving much attention for a wide variety of applications. Recently, plasma enhanced chemical vapour deposition (PECVD) has emerged as a key growth technique to produce vertically-aligned nanotubes. This paper reviews various plasma sources currently used in CNT growth, catalyst preparation and growth results. Since the technology is in its early stages, there is a general lack of understanding of growth mechanisms, the role of the plasma itself, and the identity of key species responsible for growth. This review is aimed at the low temperature plasma research community that has successfully addressed such issues, through plasma and surface diagnostics and modelling, in semiconductor processing and diamond thin film growth.

A high density plasma from a methane–hydrogen mixture is generated in an inductively coupled plasma reactor, and multiwalled carbon nanotubes (MWNTs) are grown on silicon substrates with multilayered Al/Fe catalysts. The nanotubes are vertically aligned, and the alignment is better than the orientation commonly seen in thermally grown samples. A detailed parametric study varying inductive power, pressure, temperature, gas composition, catalyst thickness, and power to the substrate is undertaken. Transmission electron microscopy and Raman spectroscopy are used to characterize the nanotubes. Emission spectroscopy and a global model are used to characterize the plasma. The power in the lower electrode holding the substrate influences the morphology and results in a transition from MWNTs to nanofibers as the power is increased.

The effect of the plasma on heating the growth substrate in plasma enhanced chemical vapor deposition (PECVD) of carbon nanotubes is characterized for the first time. This effect, which is commonly ignored in the nanotube/nanofiber literature, is the sole heating mechanism in this work for catalyst pretreatment and growth of straight and vertically aligned multiwalled carbon nanofibers. Significant temperatures, as high as 700 °C, are induced from a C2H2:NH3 direct current (dc) plasma with no other heat source present. To model the behavior of the plasma-heated substrate platform, we have developed a 1-D dc discharge model that incorporates a cathode platform energy balance, including ion bombardment, thermal radiation, and solid and gas conduction. The predicted gas-phase species present are correlated with the morphology of nanofibers grown by exclusive plasma heating as well as by heating from plasma in combination with a conventional resistive heater. The understanding of plasma heating and its accurate modeling are essential for reactor design for wafer scale production of vertically aligned nanofibers.

For internal energy relaxation in rarefied gas mixtures, exact relationships are derived between the selection probability P employed in direct simulation Monte Carlo (DSMC) methods and the macroscopic relaxation rates dictated by collision number Z in Jeans’ equation. These expressions apply to the Borgnakke–Larsen model for internal energy exchange mechanics and are not limited to the assumption of constant Z. Although Jeans’ equation leads to adiabatic relaxation curves, which coalesce to a single solution when plotted against the cumulative number of collisions, it is shown that the Borgnakke–Larsen selection probabilities depend upon the intermolecular potential, the number of internal degrees of freedom, and the DSMC selection methodology. Furthermore, simulation results show that the common assumption P=1/Z is invalid, in general, and leads to considerably slower relaxation than stipulated by Z in Jeans’ equation. Moreover, inconsistent definitions of collision rates appearing in the literature can lead to considerable errors in DSMC models. Finally, for general gas mixtures, Borgnakke–Larsen DSMC kinetics match Jeans’ behavior exactly only when using a selection methodology, which prohibits multiple relaxation events during a single collision.

This paper presents the growth of vertically aligned carbon nanotubes by plasma-enhanced chemical vapor deposition (PECVD) using Ni catalyst and C2H2/NH3 feedstock. The role of plasma in aligning the carbon nanotubes during growth is investigated both experimentally and computationally, confirming that the field in the plasma sheath causes the nanotubes to be aligned. Experiments using a plasma analyzer show that C2H2 is the dominant precursor for carbon nanotube growth. The role of NH3 in the plasma chemistry is also investigated, and experimental results show how the interaction between NH3 and the C2H2 carbon feedstock in the gas phase explains the structural variation in deposited nanotubes for differing gas ratios. The effects of varying the plasma power during deposition on nanotube growth rate is also explored. Finally, the role of endothermic ion-molecule reactions in the plasma sheath is investigated by comparing measured data with simulation results.

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