Comparative study of electron stimulated positive-ion desorption from LiCl and 1-ethyl-3-methylimidazolium bis[trifluoromethylsulfonyl]imide.

The mechanism of electron stimulated desorption (ESD) from LiCl has been investigated in comparison with that from a room-temperature ionic liquid, 1-ethyl-3-methylimidazolium bis[trifluoromethylsulfonyl]imide, [emim][Tf(2)N]. The bonding natures of these materials are discussed based on the matrix effect in positive-ion yields. The [emim](+) and fragment ions are emitted from the [emim][Tf(2)N] molecule unless it is in direct contact with a metal surface, suggesting that the ions are emitted provided that the electronic excitation can be localized in each molecule. In contrast, the electronic excitation tends to be delocalized over the LiCl film, as evidenced by a monotonic increase of a Li(+) yield in the multilayer regime. The Li(+) ion is created via gas-phase ionization of desorbed neutrals or emitted directly from the surface, in which self-trapped excitons or hot carriers created in the bulk play a role. The Li(+) and Li(+)(LiCl) ions are emitted efficiently from LiCl nanoclusters formed on a rare-gas solid film via Coulombic fission. The delocalized nature of hot holes is also manifested by steep decay of the ion yields with increasing LiCl coverage. The structural transformation of [emim][Tf(2)N] during the phase transition is also revealed based on ESD positive-ion yields as a function of temperature.