Anthra[2,1‐ <i>b</i> :3,4‐ <i>b</i> ']Dithiophene‐7,12‐Dione‐Based Polymer Donors: Boosting Responsivity and Thermal Stability for Organic Photodetectors

Abstract Polymer photodetectors hold great promise for applications in the field of flexible electronics. However, there is currently a notable absence of suitable polymer donors that can simultaneously meet the demands for high performance and thermal stability. Herein, a new optoelectronic building block, anthra[2,1‐ b :3,4‐ b ']dithiophene‐7,12‐dione (ADTD), is synthesized. Subsequently, ADTD is used to construct quinone‐containing polymers. Combined with the benefits of quinone characteristics and extended conjugation structure, this approach enhances molecular planarity and promotes π‐electron delocalization. It effectively boosts charge transport capabilities. As a result, the chlorine‐mediated polymer (ADTD‐Cl) demonstrates a superior specific detectivity of up to 6.89×10 13 Jones and an outstanding responsivity of 0.561 A W⁻ 1 , which is currently the outstanding responsivity value reported in binary organic photodetectors. More intriguingly, the lower trap state density and energy disorder of ADTD‐Cl‐based device contribute to its exceptional thermal stability, which can maintain over 80% of its initial value even after continuous heating at 65 °C for 1000 h. These findings indicate that the polymer donors with new ADTD functional units can facilitate attaining two key objectives for organic photodetectors: high performance and thermal stability. The emergence of those materials will undoubtedly greatly promote the further practical development of organic photodetectors.