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.