Nanocrystal Superparticles with Whispering-Gallery Modes Tunable through Chemical and Optical Triggers.

Whispering-gallery microresonators have the potential to become the building blocks for optical circuits. However, encoding information in an optical signal requires on-demand tuning of optical resonances. Tuning is achieved by modifying the cavity length or the refractive index of the microresonator. Due to their solid, nondeformable structure, conventional microresonators based on bulk materials are inherently difficult to tune. In this work, we fabricate irreversibly tunable optical microresonators by using semiconductor nanocrystals. These nanocrystals are first assembled into colloidal spherical superparticles featuring whispering-gallery modes. Exposing the superparticles to shorter ligands changes the nanocrystal surface chemistry, decreasing the cavity length of the microresonator by 20% and increasing the refractive index by 8.2%. Illuminating the superparticles with ultraviolet light initiates nanocrystal photo-oxidation, providing an orthogonal channel to decrease the refractive index of the microresonator in a continuous fashion. Through these approaches, we demonstrate optical microresonators tunable by several times their free spectral range.

Evaporation-Driven Coassembly of Hierarchical, Multicomponent Networks.

Self-assembly is an increasingly popular approach to systematically control the formation of complex, multicomponent materials with structural features orders of magnitude larger than the constituent colloidal nanocrystals. Common approaches often involve templating via prefabricated patterns to control particle organization- or programming-specific interactions between individual building blocks. While effective, such fabrication methods suffer from major bottlenecks due to the complexity required in mask creation for patterning or surface modification techniques needed to program directed interactions between particles. Here, we propose an alternative strategy that aims to bypass such limitations. First, we design a ligand structure that can bridge two distinct nanocrystal types. Then, by leveraging the solvent's evaporative dynamics to drive particle organization, we direct a cross-linked, multicomponent system of nanocrystals to organize hierarchically into ordered, open-network structures with domain sizes orders of magnitude larger than the constituent building blocks. We employ simulation and theory to rationalize the driving forces governing this evaporation-driven process, showing excellent agreement across theory, simulations, and experiments. These results suggest that evaporation-driven organization can be a powerful approach to designing and fabricating hierarchical, multifunctional materials.