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Abstract Semiconducting polymers are of interest due to their solution processibility and broad electronic applications. Electrochemistry allows these wide bandgap semiconductors to be converted to conducting polymers by doping such polymers at various potentials. When polymers arep‐doped to improve their conductivity via electrochemical oxidation, various positively‐charged carriers are created, including polarons (singly‐charged) and bipolarons (doubly‐charged). Carrier creation is accompanied by anion intercalation from the electrolyte for charge balance, and this insertion requires ion mobility. In this work, poly(3‐hexylthiophene) (P3HT) with different regioregularities is used to understand the relationship between solvent swelling, which affects anion intercalation, and electrochemical doping. Cyclic voltammetry, optical absorption spectroscopy, and grazing incidence wide‐angle X‐ray scattering (GIWAXS) measurements are used to correlate the doping level with structural changes. In situ electrochemical quartz crystal microbalance (EQCM) measurements are used to quantify the swelling of the polymers dynamically during electrochemical cycling. Lastly, in situ conductivity measurements are done to measure the effect of swelling on the ionic and electronic conductivity. The results indicate that solvent swelling is required for bipolaron formation, and that swelling facilitates both the small structural changes need for polaron formation and the disordering required for bipolaron formation. 

Abstract The relaxation of photoexcited polarons in doped conjugated polymers is studied with ultrafast transient absorption (TA) spectroscopy to examine the effect of polymer morphology and counterion size on polaron mobility. Processing conditions are first used to create F₄TCNQ‐doped (2,3,5,6‐tetrafluoro‐tetracyanoquinodimethane) poly(3‐hexylthiophene‐2,5‐diyl) (P3HT) films with different morphologies and thus free and trapped polarons in different ratios. We find that less crystalline films have a higher fraction of trapped polarons, but, remarkably, that free and trapped polarons have the same relaxation times in all films. Films doped with a large dodecaborane (DDB) cluster‐based dopant are then used to show that trapping is based on Coulomb interactions between polarons and counterions; no trapped polarons are observed in TA due to the reduced Coulomb interaction between the polarons and the DDB counterion. Indeed, the relaxation of polarons in these films is an order of magnitude faster than that in F₄TCNQ‐doped films, consistent with reduced trapping. Finally, the results are used to argue that counterion size has a greater effect on polaron mobility than polymer morphology and crystallinity. All of the experiments show that pump/probe spectroscopy provides a straightforward way to determine the local mobilities and degree of carrier trapping in doped conjugated polymer films.