Torsion-Susceptible Conjugation-Break Spacers in Semiconducting Polymers: the Good, the Bad, and the Wonderful

Yan Zhao1,  Xikang Zhao1,  Yaping zang2,  Chongan Di2,  Ying Diao3,  Jianguo Mei1
1Purdue University, 2Chinese Academy of Sciences, 3University of Illinois at Urbana-Champaign


Abstract

Solution-processability plays a critical role from polymer purification to device fabrication in the development of polymer-based electronic devices. Tuning solution-processability of polymers is typically achieved by side chain engineering, which varies the size, shape and position of flexible side chains. In this study, we introduce a different approach to realize the modulation of solution processability and electronic performance through introducing flexible conjugation-break spacers (CBSs) along polymer backbones. A set of five polymers have been prepared by introducing the propyl spacer in the ratio of 100, 70, 50, 30 and 0% into the diketopyrrolopyrrole (DPP)-based polymer backbone. Thus, the backbones of these polymers are from flexible to rigid. We demonstrate that solution processability and charge carrier mobility of the polymers can be modulated. That is, solution-processability progressively increases with increasing the percentage of CBSs, while charge mobility inversely varies to the CBS ratio. For instance, the polymer DPP-30 with solubility of ~ 10 mg/mL in dichlorobenzene provides an average mobility over 1.4 cm2•V−1s−1, while DPP-0 exhibits an average mobility of 4.3 cm2•V−1s−1 with solubility of ~3 mg/mL. This result provides a practical guidance to design polymers with desired performance and solution-processability for large scale roll-to-roll processing. Most encouraging, we find that DPP-70 can be melt processed in air and provide hole mobilities up to 0.30 cm2•V−1s−1, substantially higher value than their solution-processed counterparts about 0.1 cm2•V−1s−1. The mobility boost in melt-processed devices, together with completely eliminating the need to use toxic solvent in the processing, encourages to design melt-processable polymers for electronic devices.