Multiple Wetting–Dewetting States of a Water Droplet on Dual-Scale Hierarchical Structured Surfaces

Surfaces with microscale roughness can entail dual-scale hierarchical structures such as the recently reported nano/microstructured surfaces produced in the laboratory (Wang et al. Nature 2020, 582, 55−57). However, how the dual-scale hierarchical structured surface affects the apparent wetting/dewetting states of a water droplet, and the transitions between the states are still largely unexplored. Here, we report a systematic large-scale molecular dynamics (MD) simulation study on the wetting/dewetting states of water droplets on various dual-scale nano/near-submicrometer structured surfaces. To this end, we devise slab-water/slab-substrate model systems with a variety of dual-scale surface structures and with different degrees of intrinsic wettability (as measured based on the counterpart smooth surface). The dual-scale hierarchical structure can be described as “nanotexture-on-near-submicrometer-hill”. Depending on three prototypical nanotextures, our MD simulations reveal five possible wetting/dewetting states for a water droplet: (i) Cassie state; (ii) infiltrated upper-valley state; (iii) immersed nanotexture-on-hill state; (iv) infiltrated valley state; and (v) Wenzel state. The transitions between these wetting/dewetting states are strongly dependent on the intrinsic wettability (E_in), the initial location of the water droplet, the height of the nanotextures (H₁), and the spacing between nanotextures (W₁). Notably, E_in–H₁ and E_in–W₁ diagrams show that regions of rich wetting/dewetting states can be identified, including regions where between one to five states can coexist.