Observation of enhanced negative-ion formation in ArF–excimer–laser irradiated silane was reported in a recent paper [L. A. Pinnaduwage, M. Z. Martin, and L. G. Christophorou, Appl. Phys. Lett.65, 2571 (1994)]. In that paper, preliminary evidence was presented to show that highly excited electronic states of silane or its photofragments could be responsible for the observed enhanced negative-ion formation. In the present paper, we report evidence, obtained using a new experimental technique, that the electron attaching species are high-Rydberg (HR) states of silane indirectly populated via laser irradiation and show that an absolute lower bound for the corresponding electron attachment rate constant is∼4×10−7 cm3 s−1.The initial capture of the electron by the HR states is likely to be a diabatic process and the large polarizabilities associated with the HR states appear to be responsible for the observed large electron attachment rate constants. We also measured electron attachment to thermally excited vibrational states of the ground electronic state of silane, which showed no measurable electron attachment up to 750 K. Implications of these observations in modeling of silane discharges used for plasma processing of amorphous silicon are discussed. It is also pointed out that large negative ion formation observed in many “weakly electronegative” plasma processing gas discharges could be due to enhanced electron attachment to HR states: such states could be populated via direct electron impact and/or via excitation transfer from the metastable states of rare gases that are commonly used in these processing discharges. ©1997 American Institute of Physics.