Effects of Ar and O2 additives on SiO2 etching in C4F8-based plasmas (2002)

Gas mixtures based on C4F8 are promising for the development of high-performance SiO2 plasma etching processes. Measurements of important gas phase species, thin film etching rates and surface chemistry changes were performed for inductively coupled plasmas fed with C4F8/Ar and C4F8/O2 gas mixtures. The addition of Ar to C4F8 causes a strong increase of the plasma density relative to that of pure C4F8 (by up to a factor of 4× at 90% Ar). For O2 addition the changes in plasma density are small up to 90% O2 relative to pure C4F8. Infrared laser absorption spectroscopy was used to determine the absolute densities of neutral CF, CF2 and COF2 radical species as a function of the gas composition. The densities of CF and CF2 were enhanced for certain operating conditions when Ar was added to C4F8 as long as the amount of Ar remained below 20%. For instance, the partial pressure of CF was 0.1 mTorr for a 20 mTorr 1400 W source power discharge for pure C4F8, and increased to 0.13 mTorr at 20% Ar. Above 20% Ar it decreased, roughly following the gas dilution. The CF2 partial pressure was about 5 mTorr for the same conditions, and increased by about 10% at 20% Ar. Above 20% Ar the CF2 partial pressure decreased roughly linearly with the amount of Ar added, to about 2 mTorr at 50% Ar. Of particular interest was the analysis of the difference in behavior of CF, CF2 and COF2 partial pressures over SiO2 and Si surfaces, with and without rf bias power (in the latter case a self-bias voltage of −100 V was used). For pure C4F8 discharges at 20 mTorr and 1400 W inductive power without rf bias the partial pressures of CF, CF2 and COF2 radicals are comparable over SiO2 and Si surfaces. Upon applying a rf bias, the CF2 partial pressure over a SiO2 surface is reduced much more strongly than for a Si surface. The overall reduction appears to be consistent with the relative SiO2/Si etch rate ratios observed for these conditions. These results indicate that CF2 is consumed during the etching of SiO2 and Si. We also measured fluorocarbon deposition rates without rf bias and etching rates of blanket SiO2, silicon, resist and deposited fluorocarbon films as a function of the rf bias and feed gas composition. Important differences in the response of the etching rates of those materials upon the addition of O2 and Ar to C4F8 were observed. In particular, we show that the SiO2/Si and SiO2/resist etching selectivities can be doubled by adding up to 90% Ar to C4F8, without inducing an unacceptably large reduction of the SiO2 etching rate. The change in etch rate ratios is at least in part due to strong surface chemical changes seen for Ar-rich fluorocarbon gas mixtures. The surface chemical changes of Si and SiO2 surfaces were investigated by real-time ellipsometry and x-ray photoelectron spectroscopy. A strong reduction of the fluorine content of the fluorocarbon steady-state layer and an increase in thickness is seen when up to 90% Ar was added to C4F8, and this coincides with an increase of the SiO2/Si etching selectivity. The change in fluorocarbon surface chemistry can be explained by the strongly increased ion/neutral flux ratio that is characteristic of Ar-rich C4F8/Ar gas mixtures.