Effect of Heteroatom and Doping on the Thermoelectric Properties of Poly(3‐alkylchalcogenophenes)

Abstract This study reports on the thermoelectric properties of poly(3‐alkylchalcogenophene) thin films (500 nm) as a function of heteroatom (sulfur, selenium, tellurium), and how these properties change with dopant (ferric chloride) concentration. UV–vis–NIR spectroscopy shows that polaronic charge carriers are formed upon doping. Poly(3‐alkyltellurophene) (P3RTe) is most easily doped followed by poly(3‐alkylselenophene) (P3RSe) and poly(3‐alkylthiophene) (P3RT), where R = 3,7‐dimethyloctyl chain is the pendant alkyl group. Thermoelectric properties vary as functions of the heteroatom and doping level. At low dopant concentrations (≈1 × 10 −3 m ), P3RTe shows the highest power factor of 10 µW m −1 K −2 , while, at higher dopant concentrations (≈5 × 10 −3 m ), P3RSe shows the highest power factor of 13 µW m −1 K −2 . Most notably, it is found that the measured properties are consistent with Mott's polaron hopping model and not consistent with other transport models. Additionally, temperature‐dependent conductivity measurements show that for a given dopant concentration, the activation energies for electronic transport decrease as the heteroatom is changed from sulfur to selenium to tellurium. Overall, this work presents a systematic study of poly(chalcogenophenes) and indicates the potential of polymers beyond P3HT by tuning the heteroatom and doping level for optimized thermoelectric performance.