Thermal desorption induced by kiloelectronvolt ion bombardment of thiol-bound self-assembled monolayers on gold

Time distributions of neutral molecules desorbed from a chemisorbed self-assembled monolayer of phenylethanethiol on gold have been measured subsequent to 8 keV Ar+ and H-2(+) ion bombardment. These distributions show that, regardless of the projectile used, most of the ejected molecules leave the surface with thermal kinetic energies (similar to 0.03 eV). The shapes of the distributions have a strong surface temperature dependence over the range 240-300 K. This behavior is well described by a convolution of the Maxwell-Boltzmann distribution and the rate equation for first-order desorption. The results imply that kiloelectronvolt ion bombardment initiates a process which breaks the adsorbate-surface bond, leaving the resulting physisorbed molecules to evaporate after attaining thermal equilibrium with the substrate. A mechanism for this gentle cleavage of the adsorbate-substrate bond is proposed.