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.

中文翻译：

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使用高分子量电子贫乏共聚物和胺尾自组装单分子膜的高性能n沟道有机晶体管

尽管高性能p型半导体聚合物得到了广泛报道，但其n型对应物在数量和质量上仍然很少。在这里，开发了一种改进的Stille聚合方案，该方案使用氯苯作为溶剂，并使用钯（0）/铜（I）作为催化剂，以合成数均分子量高达10 ⁵ g mol ^-1的高质量n型聚合物。此外，通过sp ^2-氮原子（sp ^2- N）取代，合成了三种新的n型聚合物，即pBTTz，pPPT和pSNT，并且不同sp ² -N取代位置对器件性能的影响是第一次研究。发现sp ²的掺入‐N进入受体单元而不是施主单元会产生出众的晶体微观结构和更高的电子迁移率。此外，通过简单的旋涂技术，可以在Si / SiO ₂衬底上平滑地形成胺尾自组装单分子层（SAM），这可以促进电子的积累并带来更理想的单极n型晶体管性能。因此，显着高的单极电子迁移率高达5.35厘米² V ^-1小号^-1具有低阈值电压（≈1V）和高开/关的≈10电流比⁷证明对于基于PSNT的设备，其是单极性n型半导体聚合物的最高值。