Controllable Synthesis of Organic Microcrystals with Tunable Emission Color and Morphology Based on Molecular Packing Mode

Abstract Organic microcrystals are of essential importance for high fluorescence efficiency, ordered molecular packing mode, minimized defects, and smooth shapes, which are extensively applied in organic optoelectronics. The molecular packing mode significantly influences the optical/electrical properties of organic microcrystals, which makes the controllable preparation of organic microcrystals with desired molecular packing mode extremely important. In the study, yellow‐emissive α phase organic microcrystals with rectangular morphology and green‐emissive β phase perylene microcrystals with rhombic morphology are separately prepared by simply controlling the solution concentration. The distinct molecular staking modes of the H / J ‐aggregate are found in these two types of perylene microcrystals, which contribute to the different emission color, morphology, and radiative decay rate. What is more interesting, the α‐doped β phase and the β‐doped α phase organic microcrystals can also be fabricated by modulating the evaporation rate from 100 to 10 µL min −1 . The findings can contribute to the future development of organic optoelectronics at the microscale.