Interactions of chlorine plasmas with silicon chloride-coated reactor walls during and after silicon etching

The interplay between chlorine inductively coupled plasmas (ICP) and reactor walls coated with silicon etching products has been studied in situ by Auger electron spectroscopy and line-of-sight mass spectrometry using the spinning wall method. A bare silicon wafer mounted on a radio frequency powered electrode (-108 V dc self-bias) was etched in a 13.56 MHz, 400 W ICP. Etching products, along with some oxygen due to erosion of the discharge tube, deposit a Si-oxychloride layer on the plasma reactor walls, including the rotating substrate surface. Without Si-substrate bias, the layer that was previously deposited on the walls with Si-substrate bias reacts with Cl-atoms in the chlorine plasma, forming products that desorb, fragment in the plasma, stick on the spinning wall and sometimes react, and then desorb and are detected by the mass spectrometer. In addition to mass-to-charge (m/e) signals at 63, 98, 133, and 168, corresponding to SiClx (x = 1 - 4), many Si-oxychloride fragments with m/e = 107, 177, 196, 212, 231, 247, 275, 291, 294, 307, 329, 345, 361, and 392 were also observed from what appear to be major products desorbing from the spinning wall. It is shown that the evolution of etching products is a complex "recycling" process in which these species deposit and desorb from the walls many times, and repeatedly fragment in the plasma before being detected by the mass spectrometer. SiCl3 sticks on the walls and appears to desorb for at least milliseconds after exposure to the chlorine plasma. Notably absent are signals at m/e = 70 and 72, indicating little or no Langmuir-Hinshelwood recombination of Cl on this surface, in contrast to previous studies done in the absence of Si etching. (C) 2012 American Vacuum Society. [http://dx.doi.org/10.1116/1.4742319]