Crystal Engineering Under Residual Solvent Evaporation: A Journey Into Crystallization Chronicles of Soluble Acenes

Abstract

In the pursuit of achieving high‐performance and high‐throughput organic transistors, this study highlights two critical aspects: designing new soluble acenes and optimizing their solution processing. A fundamental understanding of the crystallization mechanism inherent to these customized soluble acenes, as they undergo a transformation during the evaporation of residual solvent, is deemed essential. Here, the pathway to crafting ideal solution processing conditions is elucidated, meticulously tailored to the molecular structure of soluble acenes when blended with polymers. Employing a comprehensive array of analytical and computational methodologies, this investigation delves directly into the intricate interplay between processing parameters and crystallization mechanisms, firmly rooted in the domains of thermodynamics and kinetics. Notably, a delicate equilibrium where the optimal weight of residual solvent harmoniously aligns is uncovered with the specific attributes of soluble acene molecules, exerting influence over vertical phase separation with the blended polymer and the crystallization process of soluble acenes at the surface. Consequently, transistors showcasing remarkable field‐effect mobility exceeding 8 cm2 V−1 s−1 are successfully developed. These findings provide invaluable guidance for navigating the path toward determining optimal solution processing conditions across a diverse array of soluble acene/polymer blend systems, all achieved through the strategic application of crystal and residual solvent engineering.