Molecular-Scale Geometric Design: Zigzag-Structured Intrinsically Stretchable Polymer Semiconductors

Orienting intelligence and multifunction, stretchable semiconductors are of great significance in constructing next-generation human-friendly wearable electronic devices. Nevertheless, rendering semiconducting polymers mechanical stretchability without compromising intrinsic electrical performance remains a major challenge. Combining geometry-innovated inorganic systems and structure-tailored organic semiconductors, a molecular-scale geometric design strategy is proposed to obtain high-performance intrinsically stretchable polymer semiconductors. Originating from the linear regioregular conjugated polymer and corresponding <i>para</i>-modified near-linear counterpart, a series of zigzag-structured semiconducting polymers are developed with diverse <i>ortho</i>-type and <i>meta</i>-type kinking units quantitatively incorporated. They showcase huge edges in realizing stretchability enhancement for conformational transition, likewise with long-range π-aggregation and short-range torsion disorder taking effect. Assisted by additional heteroatom embedment and flexible alkyl-chain attachment, mechanical stretchability and carrier mobility could afford a two-way promotion. Among zigzag-structured species, <i>o</i>-OC8-5% with the initial field-effect mobility up to 1.92 cm² V^-1 s^-1 still delivers 1.43 and 1.37 cm² V^-1 s^-1 under 100% strain with charge transport parallel and perpendicular to the stretching direction, respectively, accompanied by outstanding performance retention and cyclic stability. This molecular design strategy contributes to an in-depth exploration of prospective intrinsically stretchable semiconductors for cutting-edge electronic devices.