Effects of pre-treatment and plasma enhancement on chemical vapor deposition of carbon nanotubes from ultra-thin catalyst films

We report a detailed study of surface-bound chemical vapor deposition of carbon nanotubes and nanofibers from evaporated transition metal catalysts exposed to ammonia diluted acetylene. We show that a reduction of the Fe/Co catalyst film thickness below 3 nm results into a transition from large diameter (> 40 nm), bamboo-like nanofibers to small diameter (similar to 5 nm) multi-walled carbon nanotubes. The nanostructuring of ultrathin catalyst films critically depends on the gas atmosphere, with the resulting island distribution initiating the carbon nucleation. Compared to purely thermal chemical vapor deposition, we find that, for small diameter nanotube growth, DC plasma assistance is detrimental to graphitization and sample homogeneity and cannot prevent an early catalyst poisoning. (c) 2006 Elsevier B.V. All rights reserved.

The role of the catalytic particle in the growth of carbon nanotubes by plasma enhanced chemical vapor deposition

Vertically aligned carbon nanotubes were synthesized by plasma enhanced chemical vapor deposition using nickel as a metal catalyst. High resolution transmission electron microscopy analysis of the particle found at the tip of the tubes reveals the presence of a metastable carbide Ni3C. Since the carbide is found to decompose upon annealing at 600 degreesC, we suggest that Ni3C is formed after the growth is stopped due to the rapid cooling of the Ni-C interstitial solid solution. A detailed description of the tip growth mechanism is given, that accounts for the composite structure of the tube walls. The shape and size of the catalytic particle determine the concentration gradient that drives the diffusion of C atoms across and though the metal. (C) 2004 American Institute of Physics.

Semi-insulating layer for novel high voltage polysilicon thin film transistors

This work describes the deposition and characterisation of semi-insulating oxygen-doped silicon films for the development of high voltage polycrystalline silicon (poly-Si) circuitry on glass. The performance of a novel poly-Si High Voltage Thin Film Transistor (HVTFT) structure, incorporating a layer of semi-insulating material, has been investigated using a two dimensional device simulator. The semi-insulating layer increases the operating voltage of the HVTFT structure by linearising the potential distribution in the device offset region. A glass compatible semi-insulating layer, suitable for HVTFT applications, has been deposited by the Plasma Enhanced Chemical Vapour Deposition (PECVD) technique from silane (SiH4), nitrous oxide (N2O) and helium (He) gas mixtures. The as-deposited films are furnace annealed at 600°C which is the maximum process temperature. By varying the N2O/SiH4 ratio the conductivity of the annealed films can be accurately controlled up to a maximum of around 10-7 Ω-1cm-1. Helium dilution of the reactant gases improves both film uniformity and reproducibility. Raman analysis shows the as-deposited and annealed films to be completely amorphous. A model for the microstructure of these Semi-Insulating Amorphous Oxygen-Doped Silicon (SIAOS) films is proposed to explain the observed physical and electrical properties.

Low-temperature (≤600 °C) semi-insulating oxygen-doped silicon films by the PECVD technique for large-area power applications

This work describes the deposition, annealing and characterisation of semi-insulating oxygen-doped silicon films at temperatures compatible with polysilicon circuitry on glass. The semi-insulating layers are deposited by the plasma enhanced chemical vapour deposition technique from silane (SiH4), nitrous oxide (N2O) and helium (He) gas mixtures at a temperature of 350 °C. The as-deposited films are then furnace annealed at 600 °C which is the maximum process temperature. Raman analysis shows the as-deposited and annealed films to be completely amorphous. The most important deposition variable is the N2O SiH4 gas ratio. By varying the N2O SiH4 ratio the conductivity of the annealed films can be accurately controlled, for the first time, down to a minimum of ≈10-7Ω-1cm-1 where they exhibit a T -1 4 temperature dependence indicative of a hopping conduction mechanism. Helium dilution of the reactant gases is shown to improve both film uniformity and reproducibility. A model for the microstructure of these semi-insulating amorphous oxygen-doped silicon films is proposed to explain the observed physical and electrical properties. © 1995.

Low temperature (≤ 600°C) semi-insulating oxygen-doped silicon films by the PECVD technique for large area power applications

This work describes the annealing and characterisation of semi-insulating oxygen-doped silicon films deposited by the Plasma Enhanced Chemical Vapour Deposition (PECVD) technique from silane (SiH4), nitrous oxide (N2O) and helium (He) gas mixtures. The maximum process temperature is chosen to be compatible with large area polycrystalline silicon (poly-Si) circuitry on glass. The most important deposition variable is shown to be the N2O SiH4 gas ratio. Helium dilution results in improved film uniformity and reproducibility. Raman analysis shows the 'as-deposited' and annealed films to be completely amorphous. A model for the microstructure of these Semi-Insulating Amorphous Oxygen-doped Silicon (SIAOS) films is proposed to explain the observed physical and electrical properties. © 1995.

High rate deposition of ta-C:H using an electron cyclotron wave resonance plasma source

A compact electron cyclotron wave resonance (ECWR) source has been developed for the high rate deposition of hydrogenated tetrahedral amorphous carbon (ta-C:H). The ECWR provides growth rates of up to 1.5 nm/s over a 4-inch diameter and an independent control of the deposition rate and ion energy. The ta-C:H was deposited using acetylene as the source gas and was characterized as having an sp3 content of up to 77%, plasmon energy of 27 eV, refractive index of 2.45, hydrogen content of about 30%, optical gap of up to 2.1 eV and RMS surface roughness of 0.04 nm. © 1999 Elsevier Science S.A. All rights reserved.

High rate deposition of Ta-C:H using an electron cyclotron wave resonance plasma source

A compact electron cyclotron wave resonance (ECWR) source has been developed for the high rate deposition of hydrogenated tetrahedral amorphous carbon (ta-C:H). The ECWR provides growth rates of up to 900 angstrom/min and an independent control of the deposition rate and ion energy. The ta-C:H was deposited using acetylene as the source gas and was characterized in terms of its bonding, stress and friction coefficient. The results indicated that the ta-C:H produced using this source fulfills the necessary requirements for applications requiring enhanced tribological performance.

Material properties and tribological performance of rf-PECVD deposited DLC coatings

Diamond-like carbon (DLC) coatings were deposited on to silicon, glass and metal substrates, using an rf-plasma enhanced chemical vapour deposition (rf-PECVD) process. The resultant film properties were evaluated in respect of material and interfacial property control, based on bias voltage variation and the introduction of inert (He and Ar) and reactive (N2) diluting gases in a CH4 plasma. The analysis techniques used to assess the material properties of the films included AFM, EELS, RBS/ERDA, spectroscopic, electrical, stress, microhardness, and adhesion. These were correlated to the tribological performance of the coatings using wear measurements. The most important observation is that He dilution (>90%) promotes enhanced adhesion with respect to all substrate material studies. Coatings typically exhibit a microhardness of the order of 10-20 GPa in films 0.1vapour deposition (rf-PECVD) process. The resultant film properties were evaluated in respect of material and interfacial property control, based on bias voltage variation and the introduction of inert (He and Ar) and reactive (N2) diluting gases in a CH4 plasma. The analysis techniques used to assess the material properties of the films included AFM, EELS, RBS/ERDA, spectroscopic, electrical, stress, microhardness, and adhesion. These were correlated to the tribological performance of the coatings using wear measurements. The most important observation is that He dilution (>90%) promotes enhanced adhesion with respect to all substrate materials studied. Coatings typically exhibit a microhardness of the order of 10-20 GPa in films 0.1 < d < 2 μm thick, with associated electrical resistivity in the range 108 < ρ < 1012 Ω·cm, coefficient of friction <0.1 and surface RMS roughness as low as 2 A. The results are discussed with respect to surface pre-treatment, ion surface bombardment, interfacial reactivity and changes in plasma gas breakdown processes.

Amorphous carbon-silicon alloys prepared by a high plasma density source

The addition of silicon to hydrogenated amorphous carbon can have the advantageous effect of lowering the compressive stress, improving the thermal stability of its hydrogen and maintaining a low friction coefficient up to high humidity. Most experiments to date have been on a-C1-xSix:H alloys deposited by RF plasma enhanced chemical vapour deposition (PECVD). This method gives alloys with considerable hydrogen content and only moderate hardness. Here, we use a high plasma density source, the electron cyclotron wave resonance (ECWR) source, to prepare films with a high deposition rate. The composition and bonding in the alloys is determined by XPS, visible and UV Raman and FTIR spectroscopy. We find that it is possible to produce hard, low stress, low friction, almost humidity insensitive a-C1-xSix:H alloys with a good optical transparency and a band gap over 2 eV.

Deposition of carbon nitride films using an electron cyclotron wave resonance plasma source

Hydrogenated amorphous carbon nitride (a-C:N:H) has been synthesized using a high plasma density electron cyclotron wave resonance (ECWR) technique using N2 and C2H2 as source gases, at different ratios and a fixed ion energy (80 eV). The composition, structure and bonding state of the films were investigated and related to their optical and electrical properties. The nitrogen content in the film rises rapidly until the N2/C2H2 gas ratio reaches 2 and then increases more gradually, while the deposition rate decreases steeply, placing an upper limit for the nitrogen incorporation at 30 at%. For nitrogen contents above 20 at%, the band gap and sp3-bonded carbon fraction decrease from 1.7 to 1.1 eV and approximately 65 to 40%, respectively. Films with higher nitrogen content are less dense than the original hydrogenated tetrahedral amorphous carbon (ta-C:H) film but, because they have a relatively high band gap (1.1 eV), high resistivity (109 Ω cm) and moderate sp3-bonded carbon fraction (40%), they should be classed as polymeric in nature.