Reconstruction of Block Copolymer Micelles to Long-Range Ordered Dense Nanopatterns Via Light-Tunable Hydrogen-Bonding Association

Controlling the orientation and long-range order of nanostructures is a key issue in the self-assembly of block copolymer micelles. Herein, a versatile strategy is presented to transform one-component oxime-based block copolymer micelles into long-range ordered dense nanopatterns. Photoisomerization provides a straightforward and versatile approach to convert the hydrogen-bonding association from inward dimerization (E-type oxime motifs, slightly desolvated in ethyl acetate) into outward interchain association (Z-type ones, highly desolvated in ethyl acetate). This increases the glass transition temperature in bulk and converts swollen micelles into compact spherical micelles in solution. The reconstruction of these micelles on various substrates demonstrates that the phase transformation enables reconstruction of spherical micelles into mesoscopic sheets, nanorods, nanoworms, nanowires, networks, and eventually into long-range ordered and densely packed textile-like and lamellar nanopatterns on a macroscopic scale by adjusting E/Z-oxime ratio and solvent-evaporation rate.