Mass and Auger electron spectroscopy studies of the interactions of atomic and molecular chlorine on a plasma reactor wall

We have investigated the interactions of Cl and Cl2 with an anodized Al surface in an inductively coupled chlorine plasma. The cylindrical substrate is rapidly rotated within a differentially pumped wall and is exposed to the plasma 35% of the time through a conical skimmer. On the opposite side of the substrate, a second skimmer and differential pumping allows the surface and desorbing products to be analyzed by Auger electron spectroscopy (AES), line-of-sight mass spectrometry (MS), and through pressure rise measurements. In a 600 W Cl2 plasma at 5 mTorr, the surface becomes covered with a layer with the overall stoichiometry of about Al2Si2O10Cl3, with Si being the result of the slow erosion of the quartz discharge tube. The surface layer composition (specifically Cl coverage) does not change as a function of the delay time (1 ms-10 min) between plasma exposure and AES characterization. In contrast to AES measurements, the MS signals from Cl2 desorption, resulting from recombination of Cl atoms, decrease by about a factor of 10 over the 1-38 ms probed by varying the substrate rotation frequency. Substantial adsorption and desorption of Cl2 are also observed with the plasma off. Cl recombination coefficients (γCl) derived from an analysis of the time-dependent MS signals range from 0.01 to 0.1 and increase with increasing Cl-to-Cl2 number density ratio, suggesting a competition for adsorption sites between Cl2 and Cl