Negative ion formation in electron-stimulated desorption of CF2Cl2 coadsorbed with polar NH3 on Ru(0001)

Photon-induced dissociation of CF2Cl2 (freon-12) in the stratosphere contributes substantially to atmospheric ozone depletion. We report recent results on dissociation and negative ion formation in electron-stimulated desorption (ESD) of CF2Cl2 on Ru(0001), when CF2Cl2 is coadsorbed with a polar molecule (NH3), for electron energies ranging from 50 to 300 eV. Two different time-of-flight methods are used in this investigation: (a) an ESD ion angular distribution detector with wide collection angle and (b) a quadrupole mass spectrometer with narrow collection angle and high mass resolution. Many negative ESD fragments are seen (F-, Cl-, FCl-, CF-, F2-, and Cl2-), whose intensities depend on the surface preparation. Using both detectors we observe a giant enhancement of Cl- and F- yields for ESD of CF2Cl2 coadsorbed with approximately 1 ML of NH3; this enhancement (>10(3) for Cl-) is specific to certain ions, and is attributed to an increased probability of dissociative electron attachment due to "trapped" low-energy secondary electrons, i.e., precursor states of the solvated electron in NH3. In further studies, the influence of polar NH3 spacer layers (1-10 ML) on ESD of top-layer CF2Cl2 is determined, and compared with thick films of condensed CF2Cl2. The magnitudes and energy dependences of the Cl- yields are different in these cases, due to several contributing factors.