High‐Mobility Emissive n‐Type Polymer Semiconductors: Strong Synergy of Efficient Carrier‐Transporting Diketopyrrolopyrrole and Intense Light‐Emitting Phenylene‐Vinylene

Abstract

High‐mobility emissive n‐type polymer semiconductors (HMEN‐CPs) are essential for organic optoelectronic devices. However, due to the lack of highly electron‐deficient building blocks with excellent physicochemical properties and the molecular design trade‐offs, the development of HMEN‐CPs has significantly lagged behind that of p‐type counterparts. Here, a new electron‐deficient acceptor, TFBVDPP is developed, by integrating the efficient carrier‐transporting diketopyrrolopyrrole and intense light‐emitting phenylene‐vinylene into a single molecule system. A series of all‐acceptor‐type polymers are synthesized by Pd‐catalyzed Suzuki polycondensation. The introduction of a vinyl bridge induces intra‐/intermolecular non‐covalent interactions, significantly narrowing the optical bandgap while enhancing coplanarity and crystallinity of the conjugated backbone, thus one of the polymers P1 exhibits ideal ambipolar transports with hole and electron mobilities reaching 4.6 and 3.7 cm2 V−1 s−1, respectively. Additionally, by directly homopolymerizing TFBVDPP, the non‐radiative transition is effectively suppressed, maintaining high electron transport while enhancing emission. This system shows excellent unipolar electron mobility (µe) and high quantum yield (Φ), achieving a record Φ · µe value exceeding 10−2 cm2 V−1 s−1, which is at least three orders of magnitude higher than the reported values. This study provides a new approach for developing HMEN‐CPs, and demonstrates their great potential in advancing organic optoelectronic technologies.