%0 Journal Article %A Ding, Tao %A Mertens, Jan %A Lombardi, Anna %A Scherman, Oren A. %A Baumberg, Jeremy J. %D 2017 %T Light-Directed Tuning of Plasmon Resonances via Plasmon-Induced Polymerization Using Hot Electrons %U https://acs.figshare.com/articles/journal_contribution/Light-Directed_Tuning_of_Plasmon_Resonances_via_Plasmon-Induced_Polymerization_Using_Hot_Electrons/4996718 %R 10.1021/acsphotonics.7b00206.s001 %2 https://acs.figshare.com/ndownloader/files/8413034 %K Selective control %K Plasmon Resonances %K noble-metal nanostructures controls %K show light-triggered chain growth %K polymer chemistry %K plasmonic nanoparticles %K Plasmon-Induced Polymerization %K Light-Directed Tuning %K show photocatalytic plasmon-induced polymerization %K gap size %K polymer growth %K plasmon resonances %K nanoscale gaps %K dark-field spectroscopy %K polymerization process %K plasmon initiation %K hot-electron transfer %K Hot Electrons %K monomer %X The precise morphology of nanoscale gaps between noble-metal nanostructures controls their resonant wavelengths. Here we show photocatalytic plasmon-induced polymerization can locally enlarge the gap size and tune the plasmon resonances. We demonstrate light-directed programmable tuning of plasmons can be self-limiting. Selective control of polymer growth around individual plasmonic nanoparticles is achieved, with simultaneous real-time monitoring of the polymerization process in situ using dark-field spectroscopy. Even without initiators present, we show light-triggered chain growth of various monomers, implying plasmon initiation of free radicals via hot-electron transfer to monomers at the Au surface. This concept not only provides a programmable way to fine-tune plasmons for many applications but also provides a window on polymer chemistry at the sub-nanoscale. %I ACS Publications