Bringing Conducting Polymers to High Order: Toward Conductivities beyond 10⁵ S cm⁻¹ and Thermoelectric Power Factors of 2 mW m⁻¹ K⁻²

Here, an effective design strategy of polymer thermoelectric materials based on structural control in doped polymer semiconductors is presented. The strategy is illustrated for two archetypical polythiophenes, e.g., poly(2,5‐bis(3‐dodecyl‐2‐thienyl)thieno[3,2‐ b ]thiophene) (C 12 ‐PBTTT) and regioregular poly(3‐hexylthiophene) (P3HT). FeCl 3 doping of aligned films results in charge conductivities up to 2 × 10 5 S cm −1 and metallic‐like thermopowers similar to iodine‐doped polyacetylene. The films are almost optically transparent and show strongly polarized near‐infrared polaronic bands (dichroic ratio >10). The comparative study of structure–property correlations in P3HT and C 12 ‐PBTTT identifies three conditions to obtain conductivities beyond 10 5 S cm −1 : i) achieve high in‐plane orientation of conjugated polymers with high persistence length; ii) ensure uniform chain oxidation of the polymer backbones by regular intercalation of dopant molecules in the polymer structure without disrupting alignment of π‐stacked layers; and iii) maintain a percolating nanomorphology along the chain direction. The highly anisotropic conducting polymer films are ideal model systems to investigate the correlations between thermopower S and charge conductivity σ. A scaling law S ∝ σ −1/4 prevails along the chain direction, but a different S ∝ −ln(σ) relation is observed perpendicular to the chains, suggesting different charge transport mechanisms. The simultaneous increase of charge conductivity and thermopower along the chain direction results in a substantial improvement of thermoelectric power factors up to 2 mW m −1 K −2 in C 12 ‐PBTTT.