Polycrystalline silicon wafers were etched in dc discharges of SF6. SFx species were extracted from the discharges and measured with a mass spectrometer. A systematic procedure was used to measure the SFx + signals such that they are indicators of events in the discharge close to the sample undergoing etching. The picture that emerges is remarkably simple and shows the relative stability of several SFx species including SF6, SF 4, $F2, and SF which are shown to be extracted from the discharge both in the presence and absence of the silicon sample. When silicon is being etched on the cathode of the discharge cell, the only significant additional products are SiF4 and $2F2. A comparison of blank and sample data for opposite substrate polarities shows that there is only a small cation-assisted etching effect and suggests that ions do not play an important role in the etching of silicon by SF6 discharges.
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