Buckling in solid thin films supported by soft substrates has been well-studied. Many of those buckling features discovered, however, are monotonous without any hierarchical organizations. We report our finding of a substantial 2D hierarchical buckling atop a molecular type of multistacks or lamellae. This multistacked structure is a direct self-assembly from aminopropyltriethoxysilane, in which the polar amine groups promote the absorption of a large amount of water. We found that the resulting soft structures are good candidates to allow the formation of a complex buckling along the surface normal. Revealed cauliflower-like, hierarchical patterns are modeled by considering rigid columns standing on a soft substrate. In return, the hierarchical structures demonstrated could find applications in nanofabrication and enrich emerging fields, such as flexible electronics or optics.
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