International audienceRoom temperature flexible heat harvesters based on conducting polymers are ideally suited to cover the energy demands of the modern nomadic society. The optimization of their thermoelectric efficiency is usually sought by tuning the oxidation levels of the conducting polymers, even if such methodology is detrimental to the Seebeck coefficient (S) as both the Seebeck coefficient and the electrical conductivity (σ) are antagonistically related to the carrier concentration. Here we report a concurrent increase of S and σ and we experimentally derive the dependence of Seebeck coefficient on charge carrier mobility for the first time in organic electronics. Through specific control of the conducting polymer synthesis, we enabled the formation of a denser percolation network that facilitated the charge transport and the thermodiffusion of the charge carriers inside the conducting polymer layer, while the material shifted from a Fermi glass towards a semi-metal, as its crystallinity increased. This work sheds light upon the origin of the thermoelectric properties of conducting polymers, but also underlines the importance of enhanced charge carrier mobility for the design of efficient thermoelectric polymers

Due to the rising need for clean energy, thermoelectricity has raised as a potential alternative to reduce dependence on fossil fuels. Specifically, thermoelectric devices based on polymers could offer an efficient path for near-room temperature energy harvesters. Thus, control over thermoelectric properties of conducting polymers is crucial and, herein, the structural, electrical and thermoelectric properties of poly(3,4-ethylenedioxythiophene) (PEDOT) thin films doped with p-toluenesulfonate (Tos) molecules were investigated with regards to thin film processing. PEDOT:Tos thin films were prepared by in-situ polymerization of (3,4-ethylenedioxythiophene) monomers in presence of iron(III) p-toluenesulfonate with different co-solvents in order to tune the film structure. While the Seebeck coefficient remained constant, a large improvement in the electrical conductivity was observed for thin films processed with high boiling point additives. The increase of electrical conductivity was found to be solely in-plane mobility-driven. Probing the thin film structure by Grazing Incidence Wide Angle X-ray Scattering has shown that this behavior is dictated by the structural properties of the PEDOT:Tos films; specifically by the thin film crystallinity combined to the preferential edge-on orientation of the PEDOT crystallites. Consequentially enhancement of the power factor from 25 to 78.5 μW/mK² has been readily obtained for PEDOT:Tos thin films following this methodology.