Materials science: The ultrasmoothness of diamond-like carbon surfaces

The ultrasmoothness of diamond-like carbon coatings is explained by an atomistic/continuum multiscale model. At the atomic scale, carbon ion impacts induce downhill currents in the top layer of a growing film. At the continuum scale, these currents cause a rapid smoothing of initially rough substrates by erosion of hills into neighboring hollows. The predicted surface evolution is in excellent agreement with atomic force microscopy measurements. This mechanism is general, as shown by similar simulations for amorphous silicon. It explains the recently reported smoothing of multilayers and amorphous transition metal oxide films and underlines the general importance of impact-induced downhill currents for ion deposition, polishing, and nanopattering.

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.

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.

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.

Chemical sputtering of ta-C: Implications for the deposition of carbon nitride

The majority of attempts to synthesize the theoretically predicted superhard phase β-C3N4 have been driven towards the use of techniques which maximize both the carbon sp3 levels and the amount of nitrogen incorporated within the film. However, as yet no attempt has been made to understand the mechanism behind the resultant chemical sputter process and its obvious effect upon film growth. In this work, however, the chemical sputtering process has been investigated through the use of an as-deposited tetrahedrally bonded amorphous carbon film with a high density nitrogen plasma produced using an rf-based electron cyclotron wave resonance source. The results obtained suggested the presence of two distinct ion energy dependent regimes. The first, below 100 eV, involves the chemical sputtering of carbon from the surface, whereas the second at ion energies in excess of 100 eV exhibits a drop in sputter rate associated with the subplantation of nitrogen within the carbon matrix. Furthermore, as the sample temperature is increased there is a concomitant decrease in sputter rate suggesting that the rate is controlled by the adsorption and desorption of additional precursor species rather than the thermal desorption of CN. A simple empirical model has been developed in order to elucidate some of the primary reactions involved in the sputter process. Through the incorporation of various previously determined experimental parameters including electron temperature, ion current density, and nitrogen partial pressure the results indicated that molecular nitrogen physisorbed at the ta-C surface was the dominant precursor involved in the chemical sputter process. However, as the physisorption enthalpy of molecular nitrogen is low this suggests that activation of this molecular species takes place only through ion impact at the surface. The obtained results therefore provide important information for the modeling and growth of high density carbon nitride. © 2001 American Institute of Physics.

Properties of a-C:H films deposited from a methane electron cyclotron wave resonant plasma

An electron cyclotron wave resonant methane plasma discharge was used for the high rate deposition of hydrogenated amorphous carbon (a-C:H). Deposition rates of up to ∼400 Å/min were obtained over substrates up to 2.5 in. in diameter with a film thickness uniformity of ∼±10%. The deposited films were characterised in terms of their mass density, sp3 and hydrogen contents, C-H bonding, intrinsic stress, scratch resistance and friction properties. The deposited films possessed an average sp3 content, mass density and refractive index of ∼58%, 1.76 g/cm3 and 2.035 respectively.Mechanical characterisation indicated that the films possessed very low steady-state coefficients of friction (ca. 0.06) and a moderate shear strength of ∼141 MPa. Nano-indentation measurements also indicated a hardness and elastic modulus of ∼16.1 and 160 GPa respectively. The critical loads required to induce coating failure were also observed to increase with ion energy as a consequence of the increase in degree of ion mixing at the interface. Furthermore, coating failure under scratch test conditions was observed to take place via fracture within the silicon substrate itself, rather than either in the coating or at the film/substrate interface. © 2003 Elsevier B.V. All rights reserved.

Effect of deposition conditions on the chemical bonding in sputtered carbon nitride films

A balanced planar r.f. powered magnetron sputter source has been used to deposit carbon nitride films from a graphite target under various conditions. Sample temperature, bias voltage and nitrogen content in the gas mixture were varied. The effects of oxygen, methane and ammonia on the film growth were also studied. Special attention was paid to the effects of the deposition parameters on the structure of the films, in particular the hybridisation of the carbon and nitrogen bonding. The chemical bonding of the carbon and nitrogen atoms was studied by electron energy loss spectroscopy (EELS). The chemical composition was evaluated by Rutherford back-scattering. The intensity of transitions to π antibonding orbitals, as revealed by EELS, was found to increase with the nitrogen content in the films. Ion bombardment of the films during growth and the addition of oxygen or hydrogen-rich gases further increased the proportion of π bonds of both the carbon and nitrogen atoms. It is suggested that the increase in the transitions to μ antibond orbitals is to be explained by increased sp2 or possibly sp hybridisation of the carbon and nitrogen. Also, the effect of annealing on the bonding of nitrogen rich films after deposition was tested. The changes caused by nitrogen and deposition conditions are consistent with previous reports on the formation of paracyanogen structures.