Gruber Mathias, Jung Seok-Heon, Schott Sam, Venkateshvaran Deepak, Kronemeijer Auke Jisk, Andreasen Jens Wenzel, McNeill Christopher R, Wong Wallace W H, Shahid Munazza, Heeney Martin, Lee Jin-Kyun, Sirringhaus Henning
Cavendish Laboratory , University of Cambridge , J J Thomson Avenue , Cambridge , CB3 0HE , UK . Email:
Department of Polymer Science & Engineering , Inha University , Incheon , 402-751 , South Korea . Email:
Chem Sci. 2015 Dec 1;6(12):6949-6960. doi: 10.1039/c5sc01326g. Epub 2015 Aug 12.
In this article we discuss the synthesis of four new low band-gap co-polymers based on the diketopyrrolopyrrole (DPP) and benzotriazole (BTZ) monomer unit. We demonstrate that the BTZ unit allows for additional solubilizing side-chains on the co-monomer and show that the introduction of a linear side-chain on the DPP-unit leads to an increase in thin-film order and charge-carrier mobility if a sufficiently solubilizing, branched, side chain is attached to the BTZ. We compare two different synthetic routes, direct arylation and Suzuki-polycondensation, by a direct comparison of polymers obtained the two routes and show that direct arylation produces polymers with lower electrical performance which we attribute to a higher density of chain Furthermore we demonstrate that a polymer utilizing this design motif and synthesized Suzuki-polycondensation () exhibits exceptionally high and near balanced average electron and hole mobilities >2 cm V s which are among the highest, robustly extracted mobility values reported for DPP copolymers in a top-gate configuration to date. Our results demonstrate clearly that linear side chain substitution of the DPP unit together with co-monomers that allow for the use of sufficiently long or branched solubilizing side chains can be an attractive design motif for solution processable, high mobility DPP copolymers.
在本文中,我们讨论了基于二酮吡咯并吡咯(DPP)和苯并三唑(BTZ)单体单元的四种新型低带隙共聚物的合成。我们证明,BTZ单元允许在共聚单体上有额外的增溶侧链,并且表明如果在BTZ上连接一个足够增溶的支化侧链,在DPP单元上引入线性侧链会导致薄膜有序度和电荷载流子迁移率增加。我们通过直接比较由这两种路线得到的聚合物,比较了两种不同的合成路线,即直接芳基化和铃木缩聚反应,并表明直接芳基化产生的聚合物具有较低的电学性能,我们将其归因于更高的链密度。此外,我们证明了一种利用这种设计 motif 并通过铃木缩聚反应合成的聚合物()表现出异常高且近乎平衡的平均电子和空穴迁移率>2 cm V s,这是迄今为止在顶栅配置中报道的DPP共聚物中最高且可靠提取的迁移率值之一。我们的结果清楚地表明,DPP单元的线性侧链取代以及允许使用足够长或支化增溶侧链的共聚单体,对于可溶液加工的高迁移率DPP共聚物来说可能是一种有吸引力的设计 motif。