Micro to Nanoscale Engineering of Surface Precipitates Using Reconfigurable Contact Lines

Nanoscale engineering has traditionally adopted the chemical route of synthesis or optochemical techniques such as lithography requiring large process times, expensive equipment, and an inert environment. Directed self-assembly using evaporation of nanocolloidal droplet can be a potential low-cost alternative across various industries ranging from semiconductors to biomedical systems. It is relatively simple to scale and reorient the evaporation-driven internal flow field in an evaporating droplet which can direct dispersed matter into functional agglomerates. The resulting functional precipitates not only exhibit macroscopically discernible changes but also nanoscopic variations in the particulate assembly. Thus, the evaporating droplet forms an autonomous system for nanoscale engineering without the need for external resources. In this article, an indigenous technique of interfacial re-engineering, which is both simple and inexpensive to implement, is developed. Such re-engineering widens the horizon for surface patterning previously limited by the fixed nature of the droplet interface. It involves handprinting hydrophobic lines on a hydrophilic substrate to form a confinement of any selected geometry using a simple document stamp. Droplets cast into such confinements get modulated into a variety of shapes. The droplet shapes control the contact line behavior, evaporation dynamics, and complex internal flow pattern. By exploiting the dynamic interplay among these variables, we could control the deposit's macro- as well as nanoscale assembly not possible with simple circular droplets. We provide a detailed mechanism of the coupling at various length scales enabling a predictive capability in custom engineering, particularly useful in nanoscale applications such as photonic crystals.