Nitrogen Incorporation In Carbon Nitride Films Produced By Direct And Dual Ion Beam Sputtering

Carbon (C) and carbon nitride (CNx) films were grown on Si(100) substrates by direct ion beam sputtering (IBS) of a carbon target at different substrate temperatures (RT-450°C) and Ar/N2 sputtering gas mixtures. Additionally, the effect of concurrent nitrogen ion assistance during the growth of CNx films by IBS was also investigated. The samples were analyzed by elastic recoil detection analysis (ERDA) and x-ray near edge absorption spectroscopy (XANES). ERDA results showed that significant nitrogen amount (up to 20 at. %) was incorporated in the films, without any other nitrogen source but the N2-containing sputtering gas. The nitrogen concentration is proportional to the N2 content in the sputtering beam and no saturation limit is reached under the present working conditions. The film areal density derived from ERDA revealed a decrease in the amount of deposited material at increasing the growth temperature, with a correlation between the C and N losses. XANES results indicate that N atoms are efficiently incorporated into the carbon network and can be found in different bonding environments, such as pyridine-like, nitrile-like, graphite-like, and embedded N2 molecules. The contribution of molecular and pyridine-like nitrogen decreases when the temperature increases while the contribution of the nitrile-like nitrogen increases. The concurrent nitrogen ion assistance resulted in the significant increase of the nitrogen content in the film but it induced a further reduction of the deposited material. Additionally, the assisting ions inhibited the formation of the nitrile-like configurations while promoting nitrogen environments in graphite-like positions. The nitrogen incorporation and release mechanisms are discussed in terms of film growth precursors, ion bombardment effects and chemical sputtering.