Nematic ordering via vertical stratification in drying clay nanotube suspensions

Abstract

Evaporative self-assembly offers a simple, cost-effective method for producing functional nanostructured materials. However, achieving tunable and ordered assemblies remains challenging, especially when working with complex building blocks like nanoparticles that exhibit significant shape and size polydispersity. In this study, starting from an aqueous suspension of a polydisperse sample of rod-like Halloysite nanotubes, we present a physical protocol for producing a high degree of orientational ordering in the final dried deposit. By placing a sessile droplet on a substrate heated to 50{\deg}C, self-induced Marangoni flows suppress the coffee-ring effect, enabling more uniform deposition of colloidal rods. Subsequently, the vertical stratification during evaporation leads to the segregation of particles by aspect ratio, with longer rods (aspect ratio>=6.5) preferentially migrating to the top layers over the entire deposit. Since rods exceeding this threshold exhibit nematic ordering at high densities, the resulting top layer, spanning an area of the order of mm^2, displays a high degree of orientational order. Thus, our results highlight a robust strategy for engineering ordered structures from disordered colloidal suspensions despite the overall polydispersity of the system.