From diamond to crystalline silicon carbonitride: effect of introduction of nitrogen in CH4/H2 gas mixture using MW-PECVD

Microwave plasma enhanced chemical vapor deposition (MW-PECVD) is considered as one of the most successful growth techniques in recent diamond and crystalline carbon nitride investigations. In this study, we tried to synthesize crystalline carbon nitride film using MW-PECVD by gradually increasing the content of nitrogen into H₂/CH₄ gas mixture. Well-faceted crystalline diamond films could be synthesized with a H₂/CH₄ gas ratio of 198:2. With the gradual increase of nitrogen content up to 3% in the gas mixture diamond film quality deteriorates seriously, and the morphological crystal size and growth rate of diamond coatings decreased significantly. With the nitrogen gas content increased to approximately 6–22%, a lot of separated round diamond or diamond-like carbon particles formed on the surface rather than a continuous film. Only with the nitrogen content increased above 72%, could some tiny crystals with a type of hexagonal facet form on the silicon surface, together with many large, round diamond particles. With the further increase of nitrogen gas content above 90%, many large, well-faceted hexagonal crystals formed on Si surface. However, XRD, energy dispersive X-ray spectrometry, X-ray photoelectron spectroscopy and nano-indentation analysis indicated that these crystals were actually silicon carbonitride (Si–C–N) with a crystalline structure of Si₃N₄ modified with the introduction of carbon atoms, rather than carbonitride as expected and regarded.