Ion-exchange doped polymers at the degenerate limit: what limits conductivity at 100% doping efficiency?

Doping of semiconducting polymers has seen a surge in research interest driven by emerging applications in sensing, bioelectronics and thermoelectrics. A recent breakthrough was a doping technique based on ion-exchange, which separates the redox and charge compensation steps of the doping process. The improved microstructural control this process allows enables us for the first time to systematically address a longstanding but still poorly understood question: what limits the electrical conductivity at high doping levels? Is it the formation of charge carrier traps in the Coulomb potentials of the counterions, or is it the structural disorder in the polymer lattice? Here, we apply ion-exchange doping to several classes of high mobility conjugated polymers and identify experimental conditions that achieve near 100% doping efficiency under degenerate conditions with nearly 1 charge per monomer. We demonstrate very high conductivities up to 1200 S/cm in semicrystalline polymer systems, and show that in this regime conductivity is poorly correlated with ionic size, but strongly correlated with paracrystalline disorder. This observation, backed by a detailed electronic structure model that incorporates ion-hole and hole-hole interactions and a carefully parameterized model of disorder, indicates that trapping by dopant ions is negligible, and that maximizing crystalline order is critical to improving conductivity.