Pre‐Endcapping of Hyperbranched Polymers toward Intrinsically Stretchable Semiconductors with Good Ductility and Carrier Mobility

Abstract The advancement of semiconducting polymers stands as a pivotal milestone in the quest to realize wearable electronics. Nonetheless, endowing semiconductor polymers with stretchability without compromising their carrier mobility remains a formidable challenge. This study proposes a “pre‐endcapping” strategy for synthesizing hyperbranched semiconducting polymers (HBSPs), aiming to achieve the balance between carrier mobility and stretchability for organic electronics. The findings unveil that the aggregates formed by the endcapped hyperbranched network structure not only ensure efficient charge transport but also demonstrate superior tensile resistance. In comparison to linear conjugated polymers, HBSPs exhibit substantially larger crack onset strains and notably diminished tensile moduli. It is evident that the HBSPs surpass their linear counterparts in terms of both their semiconducting and mechanical properties. Among HBSPs, HBSP‐72h‐2.5 stands out as the preeminent candidate within the field of inherently stretchable semiconducting polymers, maintaining 93% of its initial mobility even when subjected to 100% strain (1.41 ± 0.206 cm 2 V −1 s −1 ). Furthermore, thin film devices of HBSP‐72h‐2.5 remain stable after undergoing repeated stretching and releasing cycles. Notably, the mobilities are independent of the stretching directions, showing isotropic charge transport behavior. The preliminary study makes this “pre‐endcapping” strategy a potential candidate for the future design of organic materials for flexible electronic devices.