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Growing patterned, crosslinked nanoscale polymer films from organic and inorganic surfaces using ring-opening metathesis polymerization.

The ability to modify substrates with thin polymer films allows for the tailoring of surface properties, and through combination of patterning finds use in a large variety of applications such as electronics and lab-on-chip devices. Although many techniques can be used to afford polymer-modified surfaces such as surface initiated polymerization or layer-by-layer methodologies, their stability in a wide range of environments as well as their ability to target specific chemistry are critical factors to enable their successful application. In this paper we report a facile technique in creating nanoscale polymer thin films using solid-state continuous assembly of polymers via ring opening metathesis polymerization (ssCAPROMP) directly from surfaces functionalized through silanization. Using a polymeric precursor that includes norbornene moieties, a highly-dense crosslinked network of polymer can be grown in a bottom-up fashion to afford thin films from an olefin-terminated silanized planar surface. Such nanotechnology affords films retaining the desirable qualities of previously reported methods while at the same time being covalently bound to the substrate: they are virtually pinhole free, and can be reinitiated multiple times. By combining this process with micro-contact printing, patterned films can be created by either the patterned deposition of catalyst, or by controlling the surface silanization chemistry and placement of olefin-terminated and non-reactive silanes. Additionally, patterned ssCAPROMP films were grown from SU-8 by selectively functionalizing the surface through masking and lift-off processes after the silanization step, thereby spatially controlling the surface-initiation, and subsequent polymer film formation. These patterned films expand the capabilities of the CAPROMP process and offer advantages over other film formation techniques in processes where patterned substrates and modified but robust surface chemistries are utilized.