Soft Templating of Water Aggregates Disrupts π–π Stacking in Crystalline Poly(3-hexylthiophene)
Soft Templating of Water Aggregates Disrupts π–π Stacking in Crystalline Poly(3-hexylthiophene)
复制标题
水聚集体的软模板化破坏了结晶聚（3-己基噻吩）中的堆积
DOI：
10.1021/acs.jpcc.7b09191
复制
发表时间：
2017
期刊：
影响因子：
--
通讯作者：
Tsige, Mesfin
中科院分区：
文献类型：
--
作者：
Jha, Kshitij C.;Weber, Alexander;Yimer, Yeneneh Y.;Tsige, Mesfin
光敏层的 π-π 堆叠稳健性是维持有机光伏 (OPV) 效率的关键。我们发现，结晶聚（3-己基噻吩）（P3HT）（OPV 中最常用的材料之一）的 π-π 堆叠平均发生超过 2 Å 的局部破坏，通过形成生长有限且大部分为五聚簇末端的链状水结构。相比之下，在无定形 P3HT 中观察到不断生长的 3D 聚集水簇。与无定形 P3HT 相比，结晶 P3HT 中形成最大聚集体的水分子动力学显示出有限迁移率的影响，这是由于烷基侧基和噻吩主链的双重限制。我们将这种双重限制称为软模板，并使用全原子分子动力学和内部开发的电位来量化其对结晶和无定形 P3HT 中水聚集体的性质、尺寸和氢键参与的影响，这些电位先前已被证明代表 P3HT 系统的界面和润湿行为，与实验非常一致。对 P3HT 破坏行为的检查将允许光敏层的智能分子设计。
The π–π stacking robustness of the photoactive layer is key to maintaining efficiency of organic photovoltaics (OPVs). We show local disruption more than 2 Å on average in the π–π stack of crystalline poly(3-hexylthiophene) (P3HT), one of the most common materials used in OPVs, through formation of a chainlike water structure with limited growth and mostly pentameric cluster ends. In contrast, a 3D aggregated water cluster with constant growth is observed in amorphous P3HT. Dynamics of water molecules that form the largest aggregates in crystalline P3HT show the effect of limited mobility, when compared to amorphous P3HT, due to dual confinement from both alkyl side groups and thiophene backbone. We term this dual confinementsoft templatingand quantify its effect on nature, size, and hydrogen bond participation of water aggregates in crystalline and amorphous P3HT using all-atom molecular dynamics with in-house developed potentials that were previously shown to represent the interfacial and wetting behavior of P3HT systems in good agreement with experiments. Examination of disruption behavior presented for P3HT would allow smart molecular design of photoactive layers.