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.