The performance of semiconducting polymers strongly depends on their intra- and intermolecular electronic interactions. Therefore, the morphology and particularly crystallinity and crystal structure play a crucial role in enabling a sufficient overlap between the orbitals of neighboring polymers. A new solution-based in situ polymerization for the fabrication of native polythiophene thin films is presented, which exploits the film formation process to influence the polymer crystal structure in the resulting thin films. The synthesis of the insoluble polythiophene is based on an oxidative reaction in which the oxidizing agent, iron(III) p-toluenesulfonate (FeTos), initially oxidizes the monomers to enable the polymer chain growth and secondly the final polymers, thereby chemically doping the polythiophene. To exploit the fact that the doped polythiophene has a different crystal packing structure compared to the undoped polythiophene, we investigate the structural effect of this inherent doping process by varying the amounts of FeTos in the reaction mixture, creating polythiophene thin films with different degrees of doping. The structural investigation performed by means of grazing incidence wide-angle X-ray scattering (GIWAXS) suggests that the strongly doped polymer chains aggregate in a π-stacked manner in the film formation process. Moreover, this π-stacking can be maintained after the removal of the dopant molecules. GIWAXS measurements, molecular dynamics simulations, and spectroscopic analysis suggest the presence of polythiophene in a novel and stable crystal structure with an enhanced intermolecular interaction.

中文翻译：

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在原位聚合过程中指导天然聚噻吩的聚集

半导体聚合物的性能在很大程度上取决于其分子内和分子间的电子相互作用。因此，形态，特别是结晶度和晶体结构在使相邻聚合物的轨道之间充分重叠方面起着至关重要的作用。提出了一种新的基于溶液的原位聚合方法，用于制备天然聚噻吩薄膜，该方法利用成膜过程影响所得薄膜中的聚合物晶体结构。不溶性聚噻吩的合成基于氧化反应，其中氧化剂铁（III）p-甲苯磺酸盐（FeTos）首先氧化单体以使聚合物链增长，其次氧化最终的聚合物，从而化学掺杂聚噻吩。为了利用与未掺杂的聚噻吩相比，掺杂的聚噻吩具有不同的晶体堆积结构这一事实，我们通过改变反应混合物中FeTos的量来研究这种固有的掺杂过程的结构效应，从而形成具有不同掺杂程度的聚噻吩薄膜。通过掠入射广角X射线散射（GIWAXS）进行的结构研究表明，在膜形成过程中，强掺杂的聚合物链以π堆积的方式聚集。而且，在去除掺杂剂分子之后可以保持这种π堆积。GIWAXS测量，分子动力学模拟，