Effects of Regioregularity and Molecular Weight on the Growth of Polythiophene Nanofibrils and Mixes of Short and Long Nanofibrils To Enhance the Hole Transport.

Morphological control over polythiophenes has been widely studied; however the impacts of regioregularity (RR) and molecular weight (MW) on their structural development have not been investigated systematically. This study examined a representative polythiophene, poly(3-hexylthiophene) (P3HT), to reveal that small differences in the RR can produce a large difference in the growth of nanofibrils. Low-RR P3HTs generated neat long nanofibrils (LNFs), whereas high-RR P3HTs formed short nanofibrils (SNFs). This study identified a critical RR (96-98%) depending on their MW, below which P3HT grew into LNFs and above which P3HT grew into SNFs. This study also found that the mixing ratio between high-RR P3HT and a low-RR P3HT in the solution phase is strongly correlated with the relative populations of SNF and LNF in the coated film. This study suggested that mixing high-RR and low-RR polymers may be a good strategy to optimize the electrical properties of polythiophenes for target applications. As an example, a mixture of high-RR (75%) P3HT and low-RR P3HT (25%) improved considerably the power conversion efficiency of bulk heterojunction polymer solar cells compared with the values obtained from the pure high-RR P3HT and the pure low-RR P3HT.