To achieve high-performance polymer semiconductors, it is crucially important to explore novel and effective synthesis strategies. Here, chain-extending polymerization as a synthesis strategy to design polymer semiconductors is introduced. Furthermore, we demonstrate its superiority over a conventional synthesis strategy─one-pot polymerization. Diketopyrrolopyrrole-thieno[3,2-b]thiophene-containing polymers (PDPPTT and PDPPTT-vinylene) are used in this study. PDPPTT and PDPPTT-vinylene are synthesized through one-pot polymerization and chain-extending polymerization, respectively. The utilization of this novel strategy enhances the hole/electron mobilities of PDPPTT-vinylene to up to 3.70/2.96 cm2 V-1 s-1 (compared to 2.71/0.63 cm2 V-1 s-1 for PDPPTT), thereby achieving the required performance for organic circuits like inverters and ring oscillators. The significant improvement in the transistor performance of PDPPTT-vinylene is attributed to the introduced vinylene linking units during the polymerization process, which can fine-tune the electronic structure, expand π-conjugation, and induce stronger intermolecular π-π interactions with more significant crystallization. These results demonstrate that chain-extending polymerization is an effective synthesis strategy for developing high-performance polymer semiconductors.
Keywords: chain-extending polymerization; charge-carrier mobility; molecular packing; organic thin-film transistor; polymer semiconductor.