Switching Colloidal Superstructures by Critical Casimir Forces

Abstract

Recent breakthroughs in colloidal synthesis promise the bottom-up assembly of superstructures on nano- and micrometer length scales, offering molecular analogues on the colloidal scale. However, a structural control similar to that in supramolecular chemistry remains very challenging. Here, colloidal superstructures are built and controlled using critical Casimir forces on patchy colloidal particles. These solvent-mediated forces offer direct analogues of molecular bonds, allowing patch-to-patch binding with exquisite temperature control of bond strength and stiffness. Particles with two patches are shown to form linear chains undergoing morphological changes with temperature, resembling a polymer collapse under poor-solvent conditions. This reversible temperature switching carries over to particles with higher valency, exhibiting a variety of patch-to-patch bonded structures. Using Monte Carlo simulations, it is shown that the collapse results from the growing interaction range favoring close-packed configurations. These results offer new opportunities for the active control of complex structures at the nano and micrometer scale, paving the way to novel temperature-switchable materials.