Micro- and Nanocrystals of Organic Semiconductors

Organic semiconductors have attracted wide attention in recent decades, resulting in the rapid development of organic electronics. For example, the solution processibility of organic semiconductors allows researchers to use unconventional deposition methods (such as inkjet printing and stamping) to fabricate large area devices at low cost. The mechanical properties of organic semiconductors also allow for flexible electronics. However, the most distinguishing feature of organic semiconductors is their chemical versatility, which permits the incorporation of functionalities through molecular design. However, key scientific challenges remain before organic electronics technology can advance further, including both the materials' low charge carrier mobility and researchers' limited knowledge of structure-property relationships in organic semiconductors. We expect that high-quality organic single crystals could overcome these challenges: their purity and long-range ordered molecular packing ensure high device performance and facilitate the study of structure-property relationships. Micro- and nanoscale organic crystals could offer practical advantages compared with their larger counterparts. First, growing small crystals conserves materials and saves time. Second, devices based on the smaller crystals could maintain the functional advantages of larger organic single crystals but would avoid the growth of large crystals, leading to the more efficient characterization of organic semiconductors. Third, the effective use of small crystals could allow researchers to integrate these materials into micro- and nanoelectronic devices using a "bottom-up" approach. Finally, unique properties of crystals at micro- and nanometer scale lead to new applications, such as flexible electronics. In this Account, we focus on organic micro- and nanocrystals, including their design, the controllable growth of crystals, and structure-property studies. We have also fabricated devices and circuits based on these crystals. This interdisciplinary work combines techniques from the fields of synthetic chemistry, self-assembly, crystallography, and condensed matter physics. We have designed new molecules, including a macrocycle and polyaromatic compounds that self-assemble in a predictive manner into regular high-quality crystals. We have examined how the structure, particularly pi-pi interactions, determines the crystal growth and how the external conditions affect the crystal morphology. We have developed new methods, such as the gold wire mask, the organic ribbon mask, and the gold layer stamp techniques, to fabricate high-performance devices based on the small crystals and investigate their anisotropic charge transport properties. In addition, we have demonstrated small-crystal organic circuits that function with high performance and ultralow power consumption. We expect that organic micro- and nanocrystals have a bright future in organic electronics.