Hierarchical Surface Instability in Polymer Films

This study demonstrates hierarchical instabilities in thin films. The hierarchical instabilities display three morphological characteristics: (1) windmill-like patterns at the macroscale, (2) Bénard cells and striations at the microscale, and (3) holes at the mesoscale. Such hierarchical instabilities occurred when spin coating was performed on high-volatile solutions under a high relative humidity (RH) but were suppressed when spin coating was performed on low-volatile solutions regardless of the RH. The high-volatile solutions comprise poly­(4-vinylpyridine) (P4VP) in methanol or ethanol. The low-volatility solutions comprise P4VP in propanol or butanol. P4VP molecular weights, P4VP concentrations, spin rates, and film thicknesses are not vital factors in forming hierarchical instability in spin-coated P4VP films. Instead, the formation of hierarchical instabilities depends on the RH and solvent types. Namely, the hierarchical instabilities are driven by Bénard–Marangoni convection, water vapor condensation, and disturbance of spin-up and spin-off stages during spin coating of highly volatile solutions under high RH. Mechanisms of hierarchical instabilities are interpreted in detail.