Adsorption energy as a metric for wettability at the nanoscale.

Wettability is the affinity of a liquid for a solid surface. For energetic reasons, macroscopic drops of liquid form nearly spherical caps. The degree of wettability is then captured by the contact angle where the liquid-vapor interface meets the solid-liquid interface. As droplet volumes shrink to the scale of attoliters, however, surface interactions become significant, and droplets assume distorted shapes. In this regime, the contact angle becomes ambiguous, and a scalable metric for quantifying wettability is needed, especially given the emergence of technologies exploiting liquid-solid interactions at the nanoscale. Here we combine nanoscale experiments with molecular-level simulation to study the breakdown of spherical droplet shapes at small length scales. We demonstrate how measured droplet topographies increasingly reveal non-spherical features as volumes shrink. Ultimately, the nanoscale droplets flatten out to form layer-like molecular assemblies at the solid surface. For the lack of an identifiable contact angle at small scales, we introduce a droplet's adsorption energy density as a new metric for a liquid's affinity for a surface. We discover that extrapolating the macroscopic idealization of a drop to the nanoscale, though it does not geometrically resemble a realistic droplet, can nonetheless recover its adsorption energy if line tension is included.

A Platform for Analysis of Nanoscale Liquids with an Array of Sensor Devices Based on Two-Dimensional Material.

Analysis of nanoscale liquids, including wetting and flow phenomena, is a scientific challenge with far reaching implications for industrial technologies. We report the conception, development, and application of an integrated platform for the experimental characterization of liquids at the nanometer scale. The platform combines the functionalities of a two-dimensional electronic array of sensor devices with in situ application of highly sensitive optical microspectroscopy and atomic force microscopy. We demonstrate the performance capabilities of the platform with an embodiment based on an array of optically transparent graphene sensors. The application of electronic and optical sensing in the platform allows for differentiating between liquids electronically, for determining a liquid's molecular fingerprint, and for monitoring surface wetting dynamics in real time. In order to explore the platform's sensitivity limits, we record topographies and optical spectra of individual, spatially isolated sessile oil emulsion droplets having volumes of less than ten attoliters. The results demonstrate that integrated measurement functionalities based on two-dimensional materials have the potential to push lab-on-chip based analysis from the microscale to the nanoscale.