Control of Molecular Orientation in Organic Semiconductors Using Weak Iodine-Iodine Interactions

Controlling the molecular orientation of materials is a key issue for improving the performance of organic semiconductor devices. Herein, we demonstrate the structure-property relationships of iodinated and noniodinated molecules based on an asymmetric thienoacene framework. The noniodinated molecule formed an antiparallel slip-stack structure with small orbital overlap between molecules. In contrast, the iodinated molecule formed a head-to-head layered-herringbone structure, and as a result, the transfer integrals became larger and the hole mobility increased significantly compared with the noniodinated material. The iodinated molecule was made into a stable and solution-processable p-type organic semiconductor with a mobility of 2.2 cm V s , which was 2 orders of magnitude higher than that of the noniodinated molecule. This study reveals that controlling molecular orientations using iodine-iodine interactions is a promising strategy for accelerating the development of organic semiconductor materials.