Azaisoindigo-Based Polymers with a Linear Hybrid Siloxane-Based Side Chain for High-Performance Semiconductors Processable with Nonchlorinated Solvents

Developing nonchlorinated solvent-processed polymeric semiconductors to avoid environmental concerns and health hazards caused by chlorinated solvents is especially urgent. Here, a molecular design strategy, composed of backbone fluorination and side chain optimization, is used for preparing high-solubility and high-performance azaisoindigo-based polymers. The effects of different backbones and side chains on the solubility, film crystallinity, molecular stacking, and charge transport properties are mainly investigated. A long linear hybrid siloxane-based chain (C6-Si7) is chosen to improve the solubility, while the incorporation of fluorine (F) is used to enhance the film crystallinity and charge mobility. By optimizing the backbone and side chain, both solubility and charge mobility of the azaisoindigo-based polymer are significantly improved. As a result, PAIIDBFT-Si films processed with toluene, tetrahydrofuran, ether, and alkanes, achieved charge mobilities of 4.14, 3.78, 2.14, and 2.34 cm2 V–1 s–1, respectively. The current study provides an effective strategy for the design and synthesis of high-performance polymeric semiconductors processed with nonchlorinated solvents.