Cl atom recombination on silicon oxy-chloride layers deposited on chamber walls in chlorine–oxygen plasmas

Abstract

Chlorine atom recombination coefficients were measured on silicon oxy-chloride surfaces deposited in a chlorine inductively coupled plasma (ICP) with varying oxygen concentrations, using the spinning wall technique. A small cylinder embedded in the walls of the plasma reactor chamber was rapidly rotated, repetitively exposing its surface to the plasma chamber and a differentially pumped analysis chamber housing a quadruple mass spectrometer for line-of-sight desorbing species detection, or an Auger electron spectrometer for in situ surface analysis. The spinning wall frequency was varied from 800 to 30 000 rpm resulting in a detection time, t (the time a point on the surface takes to rotate from plasma chamber to the position facing the mass or Auger spectrometer), of ∼1–40 ms. Desorbing Cl2, due to Langmuir–Hinshelwood (LH) Cl atom recombination on the reactor wall surfaces, was detected by the mass spectrometer and also by a pressure rise in one of the differentially pumped chambers. LH Cl recombination coefficients were calculated by extrapolating time-resolved desorption decay curves to t = 0. A silicon-covered electrode immersed in the plasma was either powered at 13 MHz, creating a dc bias of −119 V, or allowed to electrically float with no bias power. After long exposure to a Cl2 ICP without substrate bias, slow etching of the Si wafer coats the chamber and spinning wall surfaces with an Si-chloride layer with a relatively small amount of oxygen (due to a slow erosion of the quartz discharge tube) with a stoichiometry of Si:O:Cl = 1:0.38:0.38. On this low-oxygen-coverage surface, any Cl2 desorption after LH recombination of Cl was below the detection limit. Adding 5% O2 to the Cl2 feed gas stopped etching of the Si wafer (with no rf bias) and increased the oxygen content of the wall deposits, while decreasing the Cl content (Si:O:Cl = 1:1.09:0.08). Cl2 desorption was detectable for Cl recombination on the spinning wall surface coated with this layer, and a recombination probability of γCl = 0.03 was obtained. After this surface was conditioned with a pure oxygen plasma for ∼60 min, γCl increased to 0.044 and the surface layer was slightly enriched in oxygen fraction (Si:O:Cl = 1:1.09:0.04). This behavior is attributed to a mechanism whereby Cl LH recombination occurs mainly on chlorinated oxygen sites on the silicon oxy-chloride surface, because of the weak Cl–O bond compared to the Cl–Si bond.