Force Spectroscopy Revealed a High-Gas-Density State near the Graphite Substrate inside Surface Nanobubbles

The absorption of gas molecules at hydrophobic surfaces may have a special state and play an important role in many processes in interfacial physics, which has been rarely considered in previous theory. In this paper, force spectroscopic experiments were performed by a nanosized AFM probe penetrated into individual surface nanobubbles and contacted with a highly ordered pyrolytic graphite (HOPG) substrate. The results showed that the adhesion force at the gas/solid interface was much smaller than that in air measured with the same AFM probe. The adhesion data were further analyzed by the van der Waals force theory, and the result implied that the gas density near the substrate inside the surface nanobubbles was about 3 orders of magnitude higher than that under the standard pressure and temperature (STP). Our MD simulation indicated that the gas layers near the substrate exhibited a high-density state inside the surface nanobubbles. This high-density state may provide new insight into the understanding of the abnormal stability and contact angle of nanobubbles on hydrophobic surfaces, and have significant impact on their applications.