Substrate contact angle governs microgel shape, stiffness and deposition pattern

Abstract

Soft microgels are widely used as deformable building blocks for two-dimensional assemblies, yet solid substrates are often treated as passive supports after interfacial deposition. Here, we show that substrate wettability mechanically preconditions soft microgels before drying. Using in-liquid force-volume atomic force microscopy, we find that the same microgels adopt markedly different hydrated shapes and stiffness profiles depending on substrate contact angle: hydrophobic substrates induce spreading, flattening, and internal stiffening, whereas hydrophilic substrates preserve taller, softer microgels with smaller contact areas. These single-microgel states can explain how Langmuir-Blodgett-deposited monolayers respond during drying. On hydrophilic substrates, the observed assemblies are consistent with soft and weakly immobilized microgels rearranging under immersion-capillary forces, producing distinct corona-corona and core-core contact states and an apparent isostructural transition. On hydrophobic substrates, the flattened and stiffened microgels are more strongly immobilized, likely suppressing capillary-driven rearrangements and largely preserving the transferred interfacial assembly structure. These findings establish substrate-controlled microgel mechanics as the missing link between interfacial self-assembly and the final structures observed after transfer and drying.