LAUSR

Bendable organic single crystals are promising candidates for flexible electronics owing to their superior charge‐transport properties. However, large‐area high‐quality organic single crystals are rarely available on the polymer substrates generally used in flexible electronics. Here, a surface‐assisted assembly strategy based on a polymer modification, poly(amic acid) (PAA), is developed to grow large‐area organic singe crystals on polymer substrates using a simple drop‐casting method. The unique surface properties of PAA that enable molecular solution superwetting and promote molecular ordered assembly produce an extraordinary self‐driven “meniscus‐guided coating” behavior, enabling the fabrication of millimeter‐sized, highly aligned organic single crystals for a variety of organic semiconductors. Organic field‐effect transistors based on a mode molecule of 2,7‐dioctyl[1]benzothieno[3,2‐b][1]benzothiophene demonstrate the highest (average) mobility of 18.6 cm2 V−1 s−1 (15.9 cm2 V−1 s−1), attractively low operating voltage of −3 V, and high flexible durability. The results shed light on the large‐area fabrication of organic single crystals on polymer dielectrics toward high‐performance and integrated plastic electronics.