Role of the Processing Solvent on the Electrical Conductivity of PEDOT:PSS

Abstract Poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) is one of the most studied conductive polymers, holding great potential in many applications such as thermoelectric generators, solar cells, and memristors. Great efforts have been invested in trying to improve its mechanical and electrical properties and to elucidate the structure–property relationship. In this work, a systematic and quantitative study of the effect of solvent polarity and solution processing on the film structure and conductivity is presented. By using grazing‐incidence wide‐angle X‐ray scattering (GIWAXS) together with atomic force microscopy (AFM), the importance of the quality of the PEDOT crystal packing is highlighted as a key factor to reach improved electrical conductivity, rather than the overall degree of crystallinity. Moreover, the (re)structuring mechanisms occurring during the film formation and film exposure processes are also studied by in situ GIWAXS. Different intermediate precursor stages and different pathways to reach improved crystallinity are reported depending on the used solvent. The structural results are interpreted looking at the solvent nature and the PSS/solvent affinity. With this contribution, a guidance is hoped to be given not only on how to improve the PEDOT:PSS electrical conductivity, but also on how to tune the film structural or electrical property for different applications.