Spectroscopic study of low pressure, low temperature H2 CH4 CO2 microwave plasmas used for large area deposition of nanocrystalline diamond films. Part I: on temperature determination and energetic aspects
In a distributed antenna array (DAA) reactor, microwave H2 plasmas with admixtures of 2.5% CH4 and 1% CO2 used for the deposition of nanocrystalline diamond films have been studied by infrared absorption and optical emission spectroscopy (OES) techniques. The experiments were carried out in order to analyze the dependence of plasma chemical phenomena on power and pressure at relatively low pressures, up to 0.55 mbar, and power values, up to 3 kW. The evolution of the concentration of the methyl radical, CH3, and of five stable molecules, CH4, CO2, CO, C2H2 and C2H6, was monitored in the plasma processes by in situ infrared laser absorption spectroscopy using lead salt diode lasers (TDL) and external cavity quantum cascade lasers (EC QCL) as radiation sources. OES was applied simultaneously to obtain complementary information about the degree of dissociation of the H2 precursor gas and of its gas temperature. The experimental results are presented in two separate parts. In Part I, the present paper, the measurement of the gas (T gas) rotational (T rot) and vibrational (T vib) temperatures of the various species in the complex plasma was the main focus of interest. To achieve reliable values for the gas temperature inside and outside the plasma bulk as well as for the rotational and vibrational temperatures in the plasma hot zones, which are of great importance for calculation of species concentrations, five different methods based on the emission and absorption spectroscopy data of H2, CH4, CH3 and CO have been used. In these, line profile analysis has been combined with Boltzmann plot methods. Based on the wide tuning range of the EC QCL, a variety of CO lines in the ground and three excited states was measured enabling extensive temperature analysis providing new insight into the energetic aspects of this multi component plasma. Depending on the different plasma zones the gas temperature was found to range between about 360 and 1000 K inside the DAA reactor. In Part II, based on detailed concentration measurements general plasma chemical aspects will be analyzed and discussed.