School of Chemistry and Biochemistry & Center for Organic Photonics and Electronics, Georgia Institute of Technology, Atlanta, Georgia 30332-0400, USA.
J Am Chem Soc. 2010 Mar 17;132(10):3375-87. doi: 10.1021/ja908173x.
Perylene tetracarboxylic diimide (PTCDI) derivatives stand out as one of the most investigated families of air-stable n-type organic semiconductors for organic thin-film transistors. Here, we use density functional theory to illustrate how it is possible to control the charge-transport parameters of PTCDIs as a function of the type, number, and positions of the substituents. Specifically, two strategies of functionalization related to core and end substitutions are investigated. While end-substituted PTCDIs present the same functional molecular backbone, their molecular packing in the crystal significantly varies; as a consequence, this series of derivatives constitutes an ideal test bed to evaluate the models that describe charge-transport in organic semiconductors. Our results indicate that large bandwidths along with small effective masses can be obtained with the insertion of appropriate substituents on the nitrogens, in particular halogenated aromatic groups.
苝四羧酸二酰亚胺（PTCDI）衍生物是研究最多的空气稳定的 n 型有机半导体之一，适用于有机薄膜晶体管。在这里，我们使用密度泛函理论来说明如何通过取代基的类型、数量和位置来控制 PTCDI 的电荷输运参数。具体来说，研究了与核心和端取代相关的两种功能化策略。虽然端取代的 PTCDI 具有相同的功能分子主链，但它们在晶体中的分子堆积方式有很大差异；因此，这一系列衍生物构成了评估描述有机半导体电荷输运模型的理想试验台。我们的结果表明，通过在氮原子上插入适当的取代基，特别是卤代芳基，可获得大带宽和小有效质量。
