Multiscale assembly of solution-processed organic electronics: the critical roles of confinement, fluid flow, and interfaces.

Organic semiconducting small molecules and polymers provide a rich phase space for investigating the fundamentals of molecular and hierarchical assembly. Stemming from weak intermolecular interactions, their assembly sensitively depends on processing conditions, which in turn drastically modulate their electronic properties. Much work has gone into molecular design strategies that maximize intermolecular interactions and encourage close packing. Less understood, however, is the non-equilibrium assembly that occurs during the fabrication process (especially solution coating and printing) which is critical to determining thin film morphology across length scales. This encompasses polymorphism and molecular packing at molecular scale, assembly of π-bonding aggregates at the tens of nanometers scale, and the formation of domains at the micron-millimeter device scale. Here, we discuss three phenomena ubiquitous in solution processing of organic electronic thin films: the confinement effect, fluid flows, and interfacial assembly and the role they play in directing assembly. This review focuses on the mechanistic understanding of how assembly outcomes couple closely to the solution processing environment, supported by salient examples from the recent literature.