High-Speed Three-Dimensional Scanning Force Microscopy Visualization of Subnanoscale Hydration Structures on Dissolving Calcite Step Edges

Hydration at solid-liquid interfaces plays an essential role in a wide range of phenomena in biology and in materials and Earth sciences. However, the atomic-scale dynamics of hydration have remained elusive because of difficulties associated with their direct visualization. In this work, a high-speed three-dimensional (3D) scanning force microscopy technique that produces 3D images of solid-liquid interfaces with subnanoscale resolution at a rate of 1.6 s per 3D image was developed. Using this technique, direct 3D images of moving step edges were acquired during calcite dissolution in water, and hydration structures on transition regions were visualized. A Ca(OH)₂ monolayer was found to form along the step edge as an intermediate state during dissolution. This imaging process also showed that hydration layers extended from the upper terraces to the transition regions to stabilize adsorbed Ca(OH)₂. This technique provides information that cannot be obtained via conventional 1D/2D measurement methods.