Catalytic stamp lithography for sub-100 nm patterning of organic monolayers

A stamp-based nanoscale patterning technique of organic monolayers, termed catalytic stamp lithography, is described. The surface of poly(dimethylsiloxane) was patterned with catalytic Pd nanoparticles (NPs) via the use of self-assembled block copolymers. Using this catalytic stamp, catalytic hydrosilylations of terminal alkenes/alkynes were performed on H-terminated Si(111) or Si(100) surfaces to create nanoscale patterns of organic monolayers. Since the reaction takes place exclusively underneath the patterned Pd NPs (localized catalysis), the pattern formation is less susceptible to ink diffusion and stamp deformation, even at this sub-100 nm scale. A range of different molecular inks can be utilized to produce monolayer patterns of different chemical functionalities, and the stamps can be reused multiple times. The potential utility of this kind of chemically patterned surfaces as the basis for more complicated nanoarchitectures was demonstrated through gold nanoparticle capture, with a thiol-terminated nanopatterned silicon surface.