Solution and displacement in monolayer and multilayer binary films of SF6 and CF4 on graphite.

Abstract

Infrared reflection absorption spectroscopy is used to study the evolution of binary physisorbed films on graphite. A predeposited monolayer of SF6 is exposed to slowly increasing pressure of CF4 at constant temperature between 80 and 113 K. Shifts in the frequencies of the dominant vibrational mode of each species due to resonant dipole-dipole coupling serve as proxies for the areal density of each species in the monolayer. If the initial SF6 film is far below saturation (coexistence with bulk solid), the SF6 can be largely displaced by continuous solution of CF4. However, if the initial SF6 layer is at or near saturation, a layer of CF4 condenses on top at a well defined CF4 pressure after only 2%-3% dilution of the SF6 layer. Simultaneously, most of the dissolved CF4 is withdrawn from the SF6 layer. With further increase in CF4 pressure, the CF4 layer is compressed and additional layers condense, while the SF6 layer is again diluted. Still, the SF6 layer retains about 90% concentration until the CF4 pressure is very close to saturation, at which point the SF6 is rapidly displaced, apparently going into dilute solution in the rapidly growing CF4 multilayer. Monte Carlo simulations are used to quantitatively relate measured frequency shifts to concentrations in the binary monolayer.