Hierarchical 3D Patterns with Dynamic Wrinkles Produced by a Photocontrolled Diels–Alder Reaction on the Surface

Abstract Three‐dimensional (3D) reconfigurable patterns with dynamic morphologies enable the on‐demand control of surface properties, such as optical, wetting, and adhesive properties, to achieve smart surfaces. Here, a simple yet general strategy is developed for fabricating 3D patterns with reversible wrinkles on the surface, in which a Diels–Alder (D‐A) reaction in the top layer, which consists of a reversible cross‐linked polymer network composed of a furan‐containing copolymer (PSFB) and bismaleimide (BMI), can be spatially controlled by the photodimerization of BMI. When a photomask is used during irradiation with ultraviolet (UV) light, selective photodimerization of the maleimide leads to the diffusion of maleimide from the unexposed region to the exposed region, resulting in the generation of a diffused relief pattern. By controlling the reversible D‐A reaction at different temperatures, orthogonal wrinkles can be sequentially and reversibly generated or erased in both the exposed and unexposed regions on the surface. Theoretical modeling with boundary effects reveals that the orientation of the wrinkle in the exposed region is perpendicular to the boundary, whereas the wrinkle in the unexposed region is parallel to the boundary. This strategy, based on a photocontrolled D‐A reaction, provides an important and robust alternative for fabricating 3D patterned surfaces with dynamic topographies.