Plasmon-directed polymerization: Regulating polymer growth with light

Plasmon-induced polymerization can facilitate the site-selectivity and orientation of polymer growth, which enriches the toolbox of polymerization and nanofabrication. Here, we demonstrate plasmon-induced polymerization, accomplished by low-power laser excitation of gold nanoparticles (NPs). We selectively control the growth of polymers around single plasmonic NPs while monitoring the polymerization using dark field spectroscopy and subsequent scanning electron microscopy. This plasmon-induced polymerization, generated by hot electron initiation, not only precisely controls the thickness and composition of the polymer coatings but also regulates the location and orientation of the growth, which are strongly influenced by the laser polarization and near-field distribution around the plasmonic NPs. A saturation increase in the polymer thickness provides a strong support for our mechanism. This facile approach of nanoscale polymerization directed by light not only provides new opportunities in nanosynthesis and nanofabrication for functional devices, but also opens many routes for polymer physics and chemistry at the nanoscale level.