Colloidal monolayers with cell-like tessellations via interface assisted evaporative assembly

Evaporating sessile drops containing surface active colloids is a promising route to self-assemble two-dimensional nanostructures. The standard protocol is to first self-assemble surface active nanoscale particles at the water-vapour interface and subsequently transfer it on to a solid surface. Colloidal monolayers with very few morphologies have been fabricated, exploiting this bottom-up self-assembly technique. However, the evaporation kinetics under controlled humidity conditions may dramatically alter the microstructure of self-assembled colloidal monolayers at the liquid-vapor interface and that on the solid surfaces, an aspect that has not been fully addressed in the prior studies.

To this end, we present an experimental study of evaporation driven self-assembly of soft poly(N-isopropylacrylamide) (pNIPAM) microgel particles loaded in a sessile drop. The surface-active microgel particles spontaneously populate the water-vapour interface facilitating the suppression of the coffee-ring effect and the formation of monolayer stains. The role of evaporation kinetics under controlled humidity conditions on the colloid's microstructure adsorbed to the solvent-air interface and on the morphology of the colloidal monolayer transferred onto the solid surface are studied in detail.

The formation of particle-free and particle-rich regions at the water-vapor interface is observed for sessile drops evaporated under saturated humidity conditions. We show that the evaporation induced shrinkage of the interface area and the enhancement of the areal density of microgel particles adsorbed onto the interface leads to a restructuring of the particle-laden interface. The rearrangement of microgel particles along the water-vapor interface resembling the de-wetting assisted patterns is transferred to the solid substrate upon complete evaporation of the solvent. The microgel particles in the deposit assemble into domains with enhanced crystalline order. The evolution of Voronoi entropy across the monolayer deposit patterns obtained by the standard and slow evaporation routes are presented.