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.