Highly Crystalline Soluble Acene Crystal Arrays for Organic Transistors: Mechanism of Crystal Growth During Dip-Coating

The preparation of uniform large‐area highly crystalline organic semiconductor thin films that show outstanding carrier mobilities remains a challenge in the field of organic electronics, including organic field‐effect transistors. Quantitative control over the drying speed during dip‐coating permits optimization of the organic semiconductor film formation, although the kinetics of crystallization at the air–solution–substrate contact line are still not well understood. Here, we report the facile one‐step growth of self‐aligning, highly crystalline soluble acene crystal arrays that exhibit excellent field‐effect mobilities (up to 1.5 cm V−1 s−1) via an optimized dip‐coating process. We discover that optimized acene crystals grew at a particular substrate lifting‐rate in the presence of low boiling point solvents, such as dichloromethane (b.p. of 40.0 °C) or chloroform (b.p. of 60.4 °C). Variable‐temperature dip‐coating experiments using various solvents and lift rates are performed to elucidate the crystallization behavior. This bottom‐up study of soluble acene crystal growth during dip‐coating provides conditions under which one may obtain uniform organic semiconductor crystal arrays with high crystallinity and mobilities over large substrate areas, regardless of the substrate geometry (wafer substrates or cylinder‐shaped substrates). Self‐aligning, highly crystalline, uniform soluble acene crystal arrays are facilely grown via an optimized one‐step dip‐coating process. The optimized crystals grow only at a particular substrate lifting‐rate in the presence of low boiling point solvents. This is because the rate of input/output flows at the contact line is well‐balanced with the optimal substrate lifting rate. The study provides a simple and reproducible method for creating high‐performance uniform organic semiconductor thin films over large areas of substrates with a variety of geometries.