Metallic nanoparticle contacts for high-yield, ambient-stable molecular-monolayer devices

Accessing the intrinsic functionality of molecules for electronic applications(1-3), light emission(4) or sensing(5) requires reliable electrical contacts to those molecules. A self-assembled monolayer (SAM) sandwich architecture(6) is advantageous for technological applications, but requires a non-destructive, top-contact fabrication method. Various approaches ranging from direct metal evaporation(6) over poly(3,4-ethylenedioxythiophene) polystyrene sulfonate(7) (PEDOT: PSS) or graphene(8) interlayers to metal transfer printing(9) have been proposed. Nevertheless, it has not yet been possible to fabricate SAM-based devices without compromising film integrity, intrinsic functionality or mass-fabrication compatibility. Here we develop a top-contact approach to SAM-based devices that simultaneously addresses all these issues, by exploiting the fact that a metallic nanoparticle can provide a reliable electrical contact to individual molecules(10). Our fabrication route involves first the conformal and non-destructive deposition of a layer of metallic nanoparticles directly onto the SAM (itself laterally constrained within circular pores in a dielectric matrix, with diameters ranging from 60 nanometres to 70 micrometres), and then the reinforcement of this top contact by direct metal evaporation. This approach enables the fabrication of thousands of identical, ambientstable metal-molecule-metal devices. Systematic variation of the composition of the SAM demonstrates that the intrinsic molecular properties are not affected by the nanoparticle layer and subsequent top metallization. Our concept is generic to densely packed layers of molecules equipped with two anchor groups, and provides a route to the large-scale integration of molecular compounds into solid-state devices that can be scaled down to the single-molecule level.