Suppression of coffee rings by controllable nanoparticle enrichment through superhydrophobicity-enabled dynamic evaporation.

ABSTRACT

Coffee rings formed by evaporation of analyte-containing droplets are widely observed in micropatterning, bio-arrays, and trace detection. The coffee-ring effect caused by contact line pinning significantly affects the detection uniformity and sensitivity. Here, we propose a simple and operable method to effectively suppress coffee rings through controllable nanoparticles aggregation by superhydrophobicity-enabled dynamic evaporation. The gold nanoparticles (AuNPs) deposition footprint formed after dynamic evaporation on an integrated superhydrophobic surface was reduced by ∼3 orders of magnitude compared to that of non-interventional evaporation. Detailed experiments, numerical simulations, and theoretical studies have revealed that substrate wettability, temperature and droplet motion behaviors play significant roles in suppressing coffee-ring effect. More critically, based on the force mechanism of AuNPs at the interface/contact line, universal mathematical models and regime maps were established to classify the different deposition modes for AuNPs under different evaporation conditions by introducing dimensionless parameter G, revealing the enrichment mechanism of AuNPs in droplets under superhydrophobicity-enabled dynamic evaporation. The accuracy of the theoretical model and enrichment mechanism was demonstrated through the single-molecule detection of rhodamine 6G with excellent sensitivity (10-17 M, enhancement factor ∼1013) and perfect uniformity (relative standard deviation ∼5.57 %), which provides a valuable guide for research and applications of nanoparticle aggregation.