Influence of ion energy and substrate temperature on the optical and electronic properties of tetrahedral amorphous carbon (ta-C) films

The properties of amorphous carbon (a-C) deposited using a filtered cathodic vacuum arc as a function of the ion energy and substrate temperature are reported. The sp3 fraction was found to strongly depend on the ion energy, giving a highly sp3 bonded a-C denoted as tetrahedral amorphous carbon (ta-C) at ion energies around 100 eV. The optical band gap was found to follow similar trends to other diamondlike carbon films, varying almost linearly with sp2 fraction. The dependence of the electronic properties are discussed in terms of models of the electronic structure of a-C. The structure of ta-C was also strongly dependent on the deposition temperature, changing sharply to sp2 above a transition temperature, T1, of ≈200°C. Furthermore, T1 was found to decrease with increasing ion energy. Most film properties, such as compressive stress and plasmon energy, were correlated to the sp3 fraction. However, the optical and electrical properties were found to undergo a more gradual transition with the deposition temperature which we attribute to the medium range order of sp2 sites. We attribute the variation in film properties with the deposition temperature to diffusion of interstitials to the surface above T1 due to thermal activation, leading to the relaxation of density in context of a growth model. © 1997 American Institute of Physics.

Nature of disorder and localization in amorphous carbon

The electronic structure of amorphous diamond-like carbon is studied. Analysis of the participation ratio shows that π states within the σ-σ* gap are localized. The localization arises from dihedral angle disorder. The localization of π states causes the mobility gap to exceed the optical gap, which accounts for the low carrier mobility and the flat photoluminesence excitation spectrum. © 1998 Elsevier Science B.V. All rights reserved.

Doping mechanism in tetrahedral amorphous carbon

Doping in hydrogenated amorphous silicon occurs by a process of an ionised donor atom partially compensated by a charged dangling bond. The total energies of various dopant and dopant/bonding combinations are calculated for tetrahedral amorphous carbon. It is found that charged dangling bonds are less favoured because of the stronger Coulombic repulsion in ta-C. Instead the dopants can be compensated by weak bond states in the lower gap associated with odd-membered π-rings or odd-numbered π-chains. The effect is that the doping efficiency is low but there are not charged midgap recombination centres, to reduce photoconductivity or photoluminescence with doping, as occurs in a-Si:H.

Properties of tetrahedral amorphous carbon deposited by a filtered cathodic vacuum arc

The properties of a highly sp3 bonded form of amorphous carbon denoted ta-C deposited from a filtered cathodic vacuum arc (FCVA) are described as a function of ion energy and deposition temperature. The sp3 fraction depends strongly on ion energy and reaches 85% at an ion energy of 100 eV. Other properties such as density and band gap vary in a similar fashion, with the optical gap reaching a maximum of 2.3 eV. These films are very smooth with area roughness of order 1 nm. The sp3 fraction falls suddenly to almost zero for deposition above about 200 °C.

Doping mechanism in tetrahedral amorphous carbon

Doping in hydrogenated amorphous silicon occurs by a process of an ionized donor atom partially compensated by a charged dangling bond. The total energies of various dopant and dopant/bonding combinations are calculated for tetrahedral amorphous carbon. It is found that charged dangling bonds are less favored because of the stronger Coulombic repulsion in ta-C. Instead the dopants can be compensated by weak bond states in the lower gap associated with odd-membered π-rings or odd-numbered π-chains. The effect is that the doping efficiency is low but there are not charged midgap recombination centres, to reduce photoconductivity or photoluminescence with doping, as occurs in a-Si:H.

Surface atomic properties of tetrahedral amorphous carbon

The surface energy and surface atomic structure of tetrahedral amorphous carbon has been calculated by an ab-initio method. The surface atoms are found to reconstruct into sp2 sites often bonded in graphitic rings. Placing the dangling bonds on adjacent surface atoms lower their energy by π-bonding and this is the source of the low surface energy. The even lower surface energy of hydrogenated amorphous carbon (a-C:H) is due to the hydrogenation of all broken surface bonds. © 2005 Elsevier B.V. All rights reserved.

Cross-sectional structure of tetrahedral amorphous carbon thin films

A cross-sectional transmission electron microscope study of the low density layers at the surface and at the substrate-film interface of tetrahedral amorphous carbon (ta-C) films grown on (001) silicon substrates is presented. Spatially resolved electron energy loss spectroscopy is used to determine the bonding and composition of a tetrahedral amorphous carbon film with nanometre spatial resolution. For a ta-C film grown with a substrate bias of -300 V, an interfacial region approximately 5 nm wide is present in which the carbon is sp2 bonded and is mixed with silicon and oxygen from the substrate. An sp2 bonded layer observed at the surface of the film is 1.3 ± 0.3 nm thick and contains no detectable impurities. It is argued that the sp2 bonded surface layer is intrinsic to the growth process, but that the sp2 bonding in the interfacial layer at the substrate may be related to the presence of oxygen from the substrate.

Growth of highly-quality single-wall carbon nanotubes without amorphous carbon formation

A simple way to deposit single-wall carbon nanotubes by CVD without the co-deposition of unwanted a-C was demonstrated. It was found that the catalytic deposition of SWCNTs occurs at a substantial rate compared to the self-pyrolysis of the hydrocarbon gas used.

Stress reduction and bond stability during thermal annealing of tetrahedral amorphous carbon

A comprehensive study of the stress release and structural changes caused by postdeposition thermal annealing of tetrahedral amorphous carbon (ta-C) on Si has been carried out. Complete stress relief occurs at 600-700°C and is accompanied by minimal structural modifications, as indicated by electron energy loss spectroscopy, Raman spectroscopy, and optical gap measurements. Further annealing in vacuum converts sp3 sites to sp2 with a drastic change occurring after 1100°C. The field emitting behavior is substantially retained up to the complete stress relief, confirming that ta-C is a robust emitting material. © 1999 American Institute of Physics.

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.

Properties of amorphous carbon-silicon alloys deposited 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 hydrogenated amorphous carbon-silicon alloys (a-C1-xSix:H) deposited by rf plasma enhanced chemical vapor deposition. This method gives alloys with sizeable hydrogen content and only moderate hardness. Here we use a high plasma density source known as the electron cyclotron wave resonance source to prepare films with higher sp3 content and lower hydrogen content. The composition and bonding in the alloys is determined by x-ray photoelectron spectroscopy, Rutherford backscattering, elastic recoil detection analysis, visible and ultraviolet (UV) Raman spectroscopy, infrared spectroscopy, and x-ray reflectivity. We find that it is possible to produce relatively hard, low stress, low friction, almost humidity insensitive a-C1-xSix:H alloys with a good optical transparency and a band gap well over 2.5 eV. The friction behavior and friction mechanism of these alloys are studied and compared with that of a-C:H, ta-C:H, and ta-C. We show how UV Raman spectroscopy allows the direct detection of Si-C, Si-Hx, and C-Hx vibrations, not seen in visible Raman spectra. © 2001 American Institute of Physics.