High‐Performance n‐Channel Organic Transistors Using High‐Molecular‐Weight Electron‐Deficient Copolymers and Amine‐Tailed Self‐Assembled Monolayers

While high‐performance p‐type semiconducting polymers are widely reported, their n‐type counterparts are still rare in terms of quantity and quality. Here, an improved Stille polymerization protocol using chlorobenzene as the solvent and palladium(0)/copper(I) as the catalyst is developed to synthesize high‐quality n‐type polymers with number‐average molecular weight up to 10⁵ g mol^?1. Furthermore, by sp²‐nitrogen atoms (sp²‐N) substitution, three new n‐type polymers, namely, pBTTz, pPPT, and pSNT, are synthesized, and the effect of different sp²‐N substitution positions on the device performances is studied for the first time. It is found that the incorporation of sp²‐N into the acceptor units rather than the donor units results in superior crystalline microstructures and higher electron mobilities. Furthermore, an amine‐tailed self‐assembled monolayer (SAM) is smoothly formed on a Si/SiO₂ substrate by a simple spin‐coating technique, which can facilitate the accumulation of electrons and lead to more perfect unipolar n‐type transistor performances. Therefore, a remarkably high unipolar electron mobility up to 5.35 cm² V^?1 s^?1 with a low threshold voltage (≈1 V) and high on/off current ratio of ≈10⁷ is demonstrated for the pSNT‐based devices, which are among the highest values for unipolar n‐type semiconducting polymers.