Formation of carbon oxides in CH4/O2 plasmas produced by inductively coupled RF discharges at low pressure

The formation of CO and CO2 has been studied in inductively coupled rf (13.56 MHz) discharges with varied mixtures of CH4 and O-2 as feed gases at a total pressure of 10 Pa, flow rates of <10 sccm, and input powers of <500 W. The primary diagnostic tool has been TDLAS (tunable diode laser absorption spectroscopy) to measure absolute concentrations of molecular species as well as their kinetic and rovibrational temperatures. Of particular interest is the sudden transition between different modes of power coupling (capacitive and inductive mode, resp.) and the related changes of the plasma composition. We have found that the power threshold for this transition exhibits a clear hysteresis and depends on the oxygen content. Comparing the ratio of the CO- and CO2-concentrations in capacitive mode with corresponding data from a parallel-plate discharge, clear differences have been observed. The findings can partly be explained on the basis of plasma-chemical reaction chains using tabulated cross-sections in combination with estimations of the electron energy distribution function. Some observations (as, e.g. the presence of CO in inductively coupled plasmas that are fed by pure oxygen) cannot be understood from volume reactions only but point to an important role of surface processes, which depend on the materials of the discharge chamber and on its history and cleaning method.