Self-Assembly of Supramolecular Thin Films: Role of Small Molecule and Solvent Vapor Annealing

Block copolymer (BCP)-based supramolecules offer a versatile platform to generate hierarchically assembled nanostructures with inherent functions. However, the multicomponent supramolecular system is complex, and there is a limited understanding of the self-assembly process which is critical for precise control of the nanostructure. Here, the effect of small molecule loading and the solvent annealing condition on thin films of supramolecules on flat and patterned substrates were investigated. There is a superposition between the effect of the small molecule loading and solvent annealing condition that can be used to control the assembly rate, grain size, and feature size. The final film features are a result of the kinetic pathway taken during the assembly process. On patterned substrates with linear or circular trenches, the assembly is not driven by incommensurability as is commonly seen in BCP thin films but rather by the kinetic pathway. The present study offers insight into the importance of systematic studies in the kinetic process in self-assembly of multicomponent systems.