Nanoscale lithography on silicon is of interest for applications ranging from computer chip design to tissue interfacing. Block copolymer-based self-assembly, also called directed self-assembly (DSA) within the semiconductor industry, can produce a variety of complex nanopatterns on silicon, but these polymeric films typically require transformation into functional materials. Here we demonstrate how gold nanopatterns, produced <i>via</i> block copolymer self-assembly, can be incorporated into an optically transparent flexible PDMS stamp, termed a plasmonic stamp, and used to directly functionalize silicon surfaces on a sub-100 nm scale. We propose that the high intensity electric fields that result from the localized surface plasmons of the gold nanoparticles in the plasmonic stamps upon illumination with low intensity green light, lead to generation of electron–hole pairs in the silicon that drive spatially localized hydrosilylation. This approach demonstrates how localized surface plasmons can be used to enable functionalization of technologically relevant surfaces with nanoscale control
