Probing the Viscoelastic Property of Pseudo Free‐Standing Conjugated Polymeric Thin Films

The understanding of the structure‐mechanical property relationship for semiconducting polymers is essential for the application of flexible organic electronics. Herein pseudo free‐standing tensile testing, a technique that measures the mechanical property of thin films floating on the surface of water, is used to obtain the stress–strain behaviors of two semiconducting polymers, poly(3‐hexylthiophene) (P3HT) and poly(2,5‐bis(2‐decyltetradecyl)‐3,6‐di(thiophen‐2‐yl)diketopyrrolo[3,4‐c]pyrrole‐1,4‐dione‐ alt ‐thienovinylthiophene (DPP‐TVT) donor–acceptor (D–A) polymer. To our surprise, DPP‐TVT shows similar viscoelastic behavior to P3HT, despite DPP‐TVT possessing a larger conjugated backbone and much higher charge carrier mobility. The viscoelastic behavior of these polymers is due to sub room temperature glass transition temperatures ( T g ), as shown by AC chip calorimetry. These results provide a comprehensive understanding of the viscoelastic properties of conjugated D–A polymers by thickness‐dependent, strain rate dependent, hysteresis tests, and stress‐relaxation tests, highlighting the importance of T g for designing intrinsically stretchable conjugated polymers.