双噻吩酰亚胺基n型高分子半导体的设计合成及其应用

有机高分子半导体材料因其质轻、可溶液加工、柔性以及可拉伸性等独特的优势从而在有机场效应晶体管（OFETs）和有机太阳能电池中受到广泛应用。有机高分子半导体可进一步分为p型高分子和n型高分子。由于有机材料更容易被氧化成有机正离子，而不容易被还原成有机阴离子，因此大部分的有机高分子半导体为p型，而高性能的n型高分子半导体无论在种类和数量上都远远落后，这在很大程度上限制了有机电子领域的整体发展和商业化应用。因此，如何设计合成高性能的n型高分子半导体是有机电子领域的关键科学问题。而n型高分子半导体的构筑取决于强缺电子单元的设计与合成。

  酰亚胺基团具有强吸电子特性以及可提供增溶的烷基侧链等优势，使得酰亚胺功能化成为构筑强缺电子单元的最有效方法之一。其中苝二酰亚胺和萘二酰亚胺是构筑n型高分子半导体最经典的构建单元。然而其大的位阻效应导致高分子骨架扭曲，限制了载流子传输，使得它们在器件性能上很难进一步提高。双噻吩酰亚胺（BTI）单元具有小的位阻和平面骨架，在有机电子器件中展现出优异的器件性能。但是噻吩环的引入使得高分子最低未占据分子轨道（LUMO）能级偏高，易表现出p型性能。因此，本论文在BTI单元基础之上，一方面通过引入拉电子基团（氯原子和吡嗪）构建更强的缺电子单元（ClBTI、ClBTI2和TPDI）；另一方面开发出了强受体单元锡化的策略（锡化双硒吩酰亚胺单体）。基于此，合成出系列给体-受体和受体-受体型高分子，从而有效地调控相应高分子的物理化学性质以及器件性能，并系统地研究了结构与性能之间的关系。

  本论文从受体单元结构出发，将高电负性氯原子引入到BTI单元中得到ClBTI以及并环策略进一步得到更缺电的ClBTI2单元。通过合理的引入，有效地避免了由于大范德华半径的氯原子所带来的位阻效应。理论计算发现，Cl···S之间存在非共价相互作用，从而促进了分子骨架的平面性。相应的并环ClBTI2基高分子表现出低位的LUMO能级并在OFETs中实现了高达0.48 cm2 V−1 s−1的电子迁移率。

  然而基于并环的BTI2单元具有较高地最高占据分子轨道（HOMO）能级，易展现出双极型传输。因此本文将中心并噻吩核用更加缺电的吡嗪环替代，从而实现LUMO/HOMO能级的大幅降低，相应的TPDI基高分子在OFETs中取得了0.44 cm2 V−1 s−1的电子迁移率。

  除了引入缺电子基团到受体单元策略之外，本文还开发出了强受体单元锡化的策略，成功地合成出高纯度的锡化双硒吩酰亚胺单体，使得其可以与不同的强缺电子单体共聚，得到系列受体-受体型高分子，包括均聚物PBSeI和共聚物P(BTI-BSeI)、P(BTI2-BSeI)、P(CNI-BSeI)和P(CNI2-BSeI)。通过增强共聚受体单元的缺电子性，可以实现LUMO能级的降低，其中P(CNI-BSeI)低至−3.86 eV。这些受体-受体型高分子在晶体管中表现出优异的电子迁移率，最高达到1.50 cm2 V−1 s−1。

  锡化单体的合成为构筑的n型高分子实现了合适的能级以及出色的电子迁移率，表明通过该锡化单体所开发的高分子也具有应用于全聚合物太阳能电池（all-PSCs）的潜力。因此，通过与单体Y5-2Br共聚得到的受体-受体型高分子Y5-BSeI具有窄的带隙（1.35 eV）、宽的吸收光谱以及高的电子迁移率，从而基于Y5-BSeI的all-PSCs实现了17.0%的能量转换效率，这也是二元all-PSCs的最高效率之一。

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