Photon-stimulated desorption of F(-) ions from CF(3)Cl adsorbed on Si(111)-7x7.

We report the photon-stimulated desorption of negative ions induced by direct dipolar dissociation and dissociative electron attachment. The photon-stimulated desorption of F(-) ions from CF(3)Cl physisorbed on a Si(111)-7x7 surface at 30 K in the photon energy range 12-35 eV was studied. The F(-) ion yield exhibits four resonances, at 12.8, 16.2, 19.5, and 22.3 eV, quite unlike the gas phase photodissociation cross section. The intensities of these resonances depend strongly on the CF(3)Cl coverage in a manner which varies from peak to peak. The resonances at 19.5 and 22.3 eV, which have a significant enhancement in the monolayer regime, are due to electron mediated dipolar dissociation of adsorbed CF(3)Cl molecules. The enhancement is attributed to surface electron attachment following molecular excitation. A significant enhancement in the monolayer regime has also been observed for the resonances at 12.8 and 16.2 eV. These two resonances are ascribable to a combination of electron mediated dipolar dissociation and dissociative electron attachment driven by photoelectrons generated in the neighboring molecules.