Hierarchical Morphology of Polymer Blend Films Induced by Convection-Driven Solvent Evaporation

Homogeneous thin films of polymer blends with a desired morphology are necessary because of their applications in the fields such as optoelectronics, sensors, biomedicine, and so on. The frequently employed approach for the thin film preparation, spin coating is only able to achieve a homogeneous film for a small area because of the overwhelming spin-driven solvent evaporation with increased size. Here, a convection-guided morphology formation for polystyrene:poly(methyl methacrylate) blend films is reported. In situ observation shows that the morphology changed from homogeneous deposition with a scale less than 10 pm to a self organized cellular pattern with a scale of more than 100 pm after the fluid flow is involved. Selective dissolution of the hierarchical films reveals that the cellular morphology is attributed to the flow-field-guided deposition of sequentially generated precipitates. The coupling of phase separation and fluid convection results in the hierarchical morphology that includes Voronoi cellular division as the primary structure and the detailed heterogeneous inner-cell features as the secondary structure. Isolated modulation of either micro- or mesoscale in the hierarchical morphology could be carried out via adjusting phase interaction or the convection disturbance correspondingly, providing a flexible and straightforward strategy to construct designed hierarchical structures for polymer thin films toward desired function or property.