In-Situ Spectro-Electrochemistry of Conductive Polymers Using Plasmonics to Reveal Doping Mechanisms

Conducting polymers are a key component for developing wearable organic electronics, but tracking their redox processes at the nanoscale to understand their doping mechanism remains challenging. Here we present an in-situ spectro-electrochemical technique to observe redox dynamics of conductive polymers in an extremely localized volume (<100 nm³). Plasmonic nanoparticles encapsulated by thin shells of different conductive polymers provide actively tuned scattering color through switching their refractive index. Surface-enhanced Raman scattering in combination with cyclic voltammetry enables detailed studies of the redox/doping process. Our data intriguingly show that the doping mechanism varies with polymer conductivity: a disproportionation mechanism dominates in more conductive polymers, while sequential electron transfer prevails in less conductive polymers.