Robust surface-bound insulating polymer films with controlled thickness in <5 nm range are important for technological advances in diverse disciplines such as electrochemical sensors, molecular electronics, separations, and anticorrosive coatings. Creating these films by simple methods from readily available materials has been a significant challenge. Here we report a newly synthesized molecule combining styrene and thiol moieties, joined via a short linker, that binds to the gold surface, polymerizes, and cross-links polymer chains to form robust films with uniform and controlled thickness and complete surface coverage. Additional layers can be deposited. These films that bridge two- and three-dimensional materials show excellent stability and insulating properties.

In this work we demonstrated controlled formation of robust nanometer-thin films from a newly synthesized compound 1 that combines a styrene moiety and a thiol group joined by a short linker. The thiol group binds the filmto the surface and enables its growth by cross-linking polystyrene chains. Films can be deposited in layers, which opens opportunities for creating multilayer films with programmed functionality. The films are uniform in thickness and provide a complete surface coverage with no noticeable pinholes. Films are insulating and stable under a broad range of conditions, making them suitable for a variety of applications. One can envision using molecular imprinting to create pores for use in electrochemical sensors or as docking sites in molecular electronics. The film deposition begins with a well-established SAM technology. The possibility of combining SAM patterning techniques such as dip-pen nanolithography (e.g., patterning 1, masking the rest of the surface, and building up a robust patterned film) with our robust film fabrication further enhance these films? utility.