Ultrathin Polydiacetylene-Based Synergetic Composites with Plasmon-Enhanced Photoelectric Properties

Fabricating plasmon-enhanced organic nanomaterials with technologically relevant supporting architectures on planar solids remains a challenging task in the chemistry of thin films and interfaces. In this work, we report a bottom-up assembly of ultrathin layered composites of conductive polymers with photophysical properties enhanced by gold nanoparticles. The polydiacetylene component was formed by photopolymerization of a catanionic mixture of pentacosadiynoic surfactants on a surface of citrate-stabilized gold hydrosol monitored by a fiber optic spectrometer. Microscopic examination of the 3 nm thick solid-immobilized film showed that gold nanoparticles (AuNPs) do not aggregate within the monolayer upon polymerization. This polydiacetylene/AuNPs monolayer was coupled with 60 nm thick polyaniline-based layer deposited atop. The resulting polymer composite with an integrated 4-stripe electric cell showed nonadditive electric behavior due to the formation of electron-hole pairs with increased charge carrier mobility at the interface between the polymer layers. Under visible light irradiation of the composite film, a plasmonic effect of the gold nanoparticles was observed at the onset of photoconductivity, although neither polydiacetylene nor the polyaniline component alone are photoconductive polymers. The results indicate that our bottom-up strategy can be expanded to design other plasmon-enhanced ultrathin polymer composites with potential applications in optoelectronics and photovoltaics.