We study the macroscopic and microscopic conductivity of doped polythiophenes and vary the electrostatic environment with polar side chains or anion exchange of the dopant. Optimized doping of P3HT with a strong oxidant and anion exchange increases the conductivity to up to 190 S/cm mainly by increasing the number of contributing charges. Furthermore, oligo ethylene glycol side chains increase the conductivity to up to 750 S/cm by increasing (i) the number of contributing charges and (ii) also their mobility in comparison to P3HT with alkyl side chains. We dynamically investigate the spectral changes in absorbance during chemical doping and correlate the conductivity to an ideal ratio between polarons and bipolarons. Understanding the macroscopic and microscopic conductivity as well as the doping dynamics are keys for designing efficient transistors based on doped organic semiconductors.
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