Wire-desorbed radicals present during hot-wire chemical vapor deposition growth have been measured by quadrupole mass spectrometry. New wires produce Si as the predominant radical for temperatures above 1500 K, with a minor contribution from SiH3, consistent with previous measurements; the activation energy for the SiH3 signal suggests its formation is catalyzed. Aged wires also produce Si as the predominant radical (above 2100 K), but show profoundly different radical desorption kinetics. In particular, the Si signal exhibits a high temperature activation energy consistent with evaporation from liquid silicon. The relative abundance of the other SiHx species suggests that heterogeneous pyrolysis of SiH4 on the wire may be occurring to some extent. Chemical analysis of aged wires by Auger electron spectroscopy suggests that the aging process is related to the formation of a silicide at the surface, with silicon surface concentrations as high as 15 at. %. A limited amount (2 at. %) of silicon is observed in the interior as well, suggesting that diffusion into the wire occurs. Calculation of the relative rates for the various wire kinetic processes, coupled with experimental observations, reveals that silicon diffusion through the silicide is the slowest process, followed by Si evaporation, with SiH4 decomposition being the fastest
