Hyperthermal organic thin film growth on surfaces terminated with self-assembled monolayers. I. The dynamics of trapping.

We have examined the initial stages of growth of a crystalline small molecule organic thin film, diindenoperylene (DIP), on SiO(2) surfaces terminated with a series of self-assembled monolayers (SAMs). In this study we make use of supersonic molecular beam techniques to vary the incident kinetic energy of the DIP molecules, and we use in situ, real time synchrotron x-ray scattering to monitor the buildup of each molecular layer in the growing thin film. We find that the effects of the SAMs are most apparent concerning growth in the sub-monolayer regime, before the substrate is entirely covered by the DIP thin film. In this coverage regime on bare SiO(2), and SiO(2) terminated with either hexamethyldisilazane or perflurooctyltrichlorosilane the adsorption dynamics are consistent with trapping-mediated adsorption as observed in more simple systems, where the probability of adsorption decreases significantly with increasing kinetic energy. Once these surfaces are covered with DIP, however, the adsorption probability increases, particularly at the highest incident kinetic energy, and the probability of adsorption exhibits only a weak dependence on the incident kinetic energy. In contrast, on surfaces terminated by octyl- (OTS) and octadecyltrichlorosilane (ODTS) the trapping probability is high and exhibits little dependence on the incident kinetic energy, essentially the same as what is observed on these same surfaces covered by DIP. We postulate, which is backed by the results of molecular dynamics simulations, that direct molecular insertion into the OTS and ODTS layers is a primary explanation for efficient trapping on these surfaces.

Coverage dependent adsorption dynamics in hyperthermal organic thin film growth.

We have examined the dynamics of adsorption of diindenoperylene (DIP) on SiO(2) and SiO(2) modified with an interfacial organic layer using in situ real time synchrotron x-ray scattering, focusing on the effects of coverage. On both surfaces we observe a substantial increase in the probability of adsorption with increasing coverage, which is most dramatic at the highest incident kinetic energies. On the initially uncovered surfaces, we observe a smooth decrease in the probability of adsorption with increasing incident kinetic energy, indicative of trapping-mediated adsorption. Once both surfaces are covered by DIP, the effects of incident kinetic energy are greatly reduced, and trapping is very efficient over the range of kinetic energies examined. Possible reasons for efficient trapping at high coverage and at high incident kinetic energy include more efficient momentum transfer due to mass matching, and possibly direct molecular insertion. Comparison to results on another small-molecule, pentacene, suggests that this behavior should be common to hyperthermal growth of a variety of other small-molecule thin films.