Dimethyl sulfide on Cu{111}: Molecular self-assembly and submolecular resolution imaging

The literature contains many studies of thiol-based, self-assembled monolayers (RSH); however, thioethers (RSR) have barely begun to be explored, despite having the potential advantages of being more resistant to oxidation and allowing for the control of self-assembly parallel to the surface. This paper describes a low-temperature scanning tunneling microscopy investigation of dimethyl sulfide on Cu{111}. Previous work on the adsorption of dibutyl sulfide on Cu{111} revealed that intermolecular van der Waals interactions directed the parallel ordering of dibutyl sulfide molecules in linear rows. Upon annealing to 120 K, small dibutyl sulfide domains reordered into very large, ordered domains free of defects. The current study reveals the effect of the shorter alkyl chain length of dimethyl sulfide on both the rate of diffusion and the packing structure of the molecule. At a medium surface coverage and at 78 K, it was found that dimethyl sulfide is mobile and forms large, ordered islands without the 120 K annealing that was required for dibutyl sulfide to arrange. Also, the molecular packing structure evolves from quadrupole-quadrupole interactions and results in a perpendicular arrangement of neighboring molecules instead of the parallel arrangement observed for dibutyl sulfide. We show high-resolution images of the dimethyl sulfide islands in which submolecular features are revealed. These high-resolution data allow us to propose a structural model for the adsorption site of each dimethyl sulfide molecule within the ordered structures. These results demonstrate that the length of the alkyl side chain is an important factor in determining how thioethers self-assemble on metal surfaces.