Journal of Chemical Physics, Vol.116, No.23, 10402-10410, 2002
CF3I on a silicon surface: Adsorption, temperature-programmed desorption, and electron-stimulated desorption
CF3I adsorption on a silicon surface and the effect of low-energy electron bombardment of a CF3I-covered silicon surface are relevant to plasma etching. Dissociative chemisorption of CF3I on Si(100) surface is observed at 370 K. Uptake measurements corroborated by work-function change measurements and temperature-programmed desorption (TPD) gives a sticking probability of at least 0.34+/-0.05. Molecular orbital calculations yield an adsorption energy greater than 3 eV for dissociative chemisorption of CF3X (X=F, Cl, Br, and I) on Si(100) (modeled by Si9H12) with X transferred to a silicon atom. We conclude that the variation in the sticking probability across the CF3X family is a consequence of the activation energy barrier for C-X bond cleavage. In TPD, SiF4 desorbs at 370 and 840 K, SiF3 radical at 770 K, and atomic iodine at 790 K. The parent CF3I does not desorb. Electron-stimulated desorption (ESD) yields F+, F- and a trace of I+. The threshold for the appearance of F+ is 20 eV and for F- is 29 eV. Dissociative ionization and dipolar dissociation are possible mechanisms for ESD of F+. Dipolar dissociation and harpooning are possible mechanisms for ESD of F-. There is evidence that iodine on the surface quenches the electronically excited states that lead to desorption of F-.