Determination of gas temperature and C2 absolute density in Ar/H2/CH4 microwave discharges used for nanocrystalline diamond deposition from the C2 Mulliken system

Abstract

The spectroscopic characterization of Ar/H2/CH4 discharges suitable for the synthesis of nanocrystalline diamond using the microwave plasma assisted chemical vapour deposition process is reported. The experiments are realized in a moderate-pressure bell jar reactor, where discharges are ignited using a microwave cavity coupling system. The concentration of CH4 is maintained at 1% and the coupled set of hydrogen concentration/microwave power (MWP) ranges from 2%/500 W to 7%/800 W at a pressure of 200 mbar. Emission spectroscopy and broadband absorption spectroscopy studies are carried out on the Mulliken system and the C2(d 3Πg–a 3Πu) Swan system in order to determine the gas temperature and the C2 absolute density within the plasma. For this purpose, and since the Swan system is quite well-known, much importance is devoted to the achievement of a detailed simulation of the Mulliken system, which allows the determination of both the rotational temperature and the density of the ground state, as well as the rotational temperature of the state, from experimental data. All the experimental values are compared to those predicted by a thermochemical model developed to describe Ar/H2/CH4 microwave discharges under quasi-homogeneous plasma assumption. This comparison shows a reasonable agreement between the values measured from the C2 Mulliken system, those measured from the C2 Swan system and that calculated from plasma modelling, especially at low hydrogen concentration/MWP. These consistent results show that the use of the Mulliken system leads to fairly good estimates of the gas temperature and of the C2 absolute density. The relatively high gas temperatures found for the conditions investigated, typically between 3000 K and 4000 K, are attributed to the low thermal conductivity of argon that may limit thermal losses to the substrate surface and reactor wall. The measured C2 absolute densities range from 1013 to 1014 cm−3 depending on the experimental conditions. These high values may result from an enhanced thermal conversion of hydrocarbon species due to the high gas temperature.