Surface-Adsorbed Nanodroplets of Symmetric Diblock Copolymers Form Versatile and Stimuli-Responsive Nanostructures

Abstract

Block copolymers often create droplets when placed on a substrate. Such nanostructured droplets can be arranged into regular microstructured arrays, thereby forming hierarchically organized materials that can be used in microelectronics, plasmonics, sensing, photonics, metamaterials production, and even cryptography. However, it is unclear if such materials can be stimuli-responsive, i.e., be able to change their nanostructure on a single droplet level upon applying external stimuli. In this work, we discovered that small (10-100 nm) surface-adsorbed droplets of symmetric diblock copolymers can form a multitude of different externally switchable nanostructures. We obtained a near-equilibrium, comprehensive 4D diagram of droplet morphologies by performing large-scale self-consistent field theory (SCFT) calculations under various wetting and phase separation conditions. The SCFT modeling was augmented with a computational algorithm that established an equilibrium droplet morphology in a given system without assuming potentially equilibrium structures prior to simulation. The discovered droplet nanostructures agreed excellently with previously published experimental data. Crucially, we showed that direct and reversible transitions between different droplet morphologies are possible upon changing the interaction strength between components, which can be tuned externally in experiments by adding surfactants or controlling temperature. We confirmed experimental realizability of such stimuli-responsiveness by modeling surfactant addition that led to a switch between droplet nanostructures. This work demonstrates that even the simplest symmetric diblock copolymers are able to produce versatile and stimuli-responsive structures on a surface when confined to a small nanodroplet. This opens the possibility to produce smart coatings with externally switchable hierarchical micro- and nanostructures.