Higher PEDOT Molecular Weight Giving Rise to Higher Thermoelectric Property of PEDOT:PSS: A Comparative Study of Clevios P and Clevios PH1000

Poly­(3,4-ethylenedioxythiophene):poly­(styrenesulfonate) (PEDOT:PSS) is a promising candidate as the next-generation thermoelectric (TE) material. Its TE properties are strongly dependent on its chemical and electronic structures. In this paper, we investigated the effect of PEDOT molecular weight on the TE properties of PEDOT:PSS films by a comparative study on two commercial grades of PEDOT:PSS, Clevios P, and Clevios PH1000. Dynamic light scattering (DLS) and Raman spectra imply that the PEDOT of Clevios PH1000 possesses longer conjugated chains than that of Clevios P. The TE properties of both the Clevios P and Clevios PH1000 films can be significantly enhanced through various post treatments, including solvent treatment, germinal diol treatment, organic solution treatment, and acid treatment. After these treatments, the treated Clevios PH1000 films constantly show both superior Seebeck coefficients and electrical conductivities over the treated Clevios P films. It is attributed to the higher molecular weight of PEDOT for the former than the latter. For the treated Clevios PH1000, longer PEDOT chains result in large PEDOT domains, facilitating the charge conduction a semimetallic behavior. Tuning the oxidation level of PEDOT:PSS is a facile way to enhance their TE property. A base treatment with sodium hydroxide was subsequently performed on both the treated Clevios P and Clevios PH1000 films. The power factors of both grades of PEDOT:PSS films were remarkably increased by a factor of 1.2–3.6. Still, both the conductivity and the Seebeck coefficient of a based-treated Clevios PH1000 film are superior over those of a control Clevios P film. The highest power factor the former is 334 μW/(m K²) for the former while only 11.4 μW/(m K²) for the latter. They are different by a factor of about 30 times