Thermal and electrical cross-plane conductivity at the nanoscale in poly(3,4-ethylenedioxythiophene):trifluoromethanesulfonate thin films

Cross-plane electrical and thermal transport in thin films of a conducting polymer (poly(3,4-ethylenedioxythiophene), PEDOT) stabilized with trifluoromethanesulfonate (OTf) is investigated in this study. We explore their electrical properties by conductive atomic force microscopy (C-AFM), which reveals the presence of highly conductive nano-domains. Thermal conductivity in the cross-plane direction is measured by null-point scanning thermal microscopy (NP-SThM). PEDOT:OTf indeed demonstrates a non-negligible electronic contribution to the thermal transport. We further investigate the correlation between electrical and thermal conductivity by applying post-treatment: chemical reduction (de-doping) to lower charge carrier concentration and hence, electrical conductivity and acid treatment (over-doping) to increase the latter. From our measurements, we find a vibrational thermal conductivity of 0.34 ± 0.04 W m^-1 K^-1. From the linear dependence or the electronic contribution of thermal conductivity vs. the electronic conductivity (Wiedemann-Franz law), we infer a Lorenz number 6 times larger than the classical Sommerfeld value as also observed in many organic materials for in-plane thermal transport. By applying the recently proposed molecular Wiedemann-Franz law, we deduced a reorganization energy of 0.53 ± 0.06 eV.