Radical surface interactions in industrial silicon plasma etch reactors

Silicon etching in Cl-2-based plasmas is an important step for the fabrication of IC circuits but the plasma surface interactions involved in this process remain poorly understood. Based on the developments in plasma and reactor wall diagnostics, this paper reviews the recent progress in the understanding of radicals' interactions with surfaces during silicon etching processes. X-ray photoelectron spectroscopy analysis of the reactor walls shows that during Si etching in Cl-2/O-2 plasmas, the initial Al2O3 chamber walls are coated with a thin SiOCl layer. Broadband absorption spectroscopy with UV light emitting diodes is used to measure the densities of SiClX radicals (X = 0-2) and Cl-2 molecules in steady state plasmas running with the chamber walls coated with different materials. To estimate the surface sticking/recombination probability of these radicals on different surfaces, we have performed time-resolved absorption measurements in the afterglow of pulsed discharges. Our work, in agreement with previous results, shows that the Cl-2/Cl density ratio in the discharge is driven mainly by the chemical nature of the chamber walls explaining why process drifts are often observed in Cl-2/O-2 plasmas. The recombination coefficient of Cl atoms on SiOCl surfaces is about 0.007, while it is about 0.1 on clean walls (AlF3). Based on these results, we discuss the best strategy leading to reproducible process control, the present strategy being a systematic reactor cleaning/conditioning between wafers. The SiOCl layer deposition mechanism is then discussed in detail. The sticking coefficient of SiCl on this surface is near unity, while SiCl2 appears to be weakly reactive toward it. Therefore, SiCl (and SiCl+ ions) are the main vectors of Si deposition on the reactor walls, where their subsequent oxidization by O atoms leads to the formation of a SiOCl deposit. Furthermore, we show that SiCl reaction in the plasma volume with Cl-2, through the exchange reaction SiCl + Cl-2 -> SiCl2 + Cl, is very important for the control of radical densities. Finally, time-resolved measurements of the gas temperature by laser-absorption Doppler spectroscopy show that in the afterglow of pulsed discharges the transport of particles is affected by the convection phenomenon. The very fast electron temperature cooling in the early afterglow generates a pressure gradient in the reactor which induces a rapid gas movement from the cold regions of the reactor toward the reactor center, where the plasma was generated. This leads to an increase in the density of stable molecules in the volume previously occupied by the plasma.