Surfactant Control of Coffee Ring Formation in Carbon Nanotube Suspensions

The coffee ring effect regularly occurs during the evaporation of colloidal droplets and is often undesirable. Here we show that adding a specific concentration of a surfactant can mitigate this effect. We have conducted experiments on aqueous suspensions of carbon nanotubes that were prepared with cationic surfactant dodecyltrimethylammonium bromide added at 0.2, 0.5, 1, 2, 5, and 10 times the critical micelle concentration. Colloidal droplets were deposited on candidate substrates for printed electronics with varying wetting characteristics: glass, polyethylene terephthalate, fluoroethylene propylene copolymer, and polydimethylsiloxane. Following drying, four pattern types were observed in the final deposits: dot-like, uniform, coffee ring deposits, and combined patterns (coffee ring with a dot-like central deposit). Evaporation occurred predominantly in constant contact radius mode for most pattern types, except for some cases that led to uniform deposits in which early stage receding of the contact line occurred. Image analysis and profilometry yielded deposit thicknesses, allowing us to identify a coffee ring subfeature in all uniform deposits and to infer the percentage coverage in all cases. Importantly, a critical surfactant concentration was identified for the generation of highly uniform deposits across all substrates. This concentration resulted in visually uniform deposits consisting of a coffee ring subfeature with a densely packed center, generated from two distinct evaporative phases.