Breaking of Lateral Symmetry in Two-Dimensional Crystallization-Driven Self-Assembly on a Surface.

Symmetry breaking is prevalent in nature and provides distinctive access to hierarchical structures for artificial materials. However, it is rarely explored in two-dimensional (2D) entities, especially for lateral asymmetry. Herein, we describe a unique symmetry breaking process in surface-initiated 2D living crystallization-driven self-assembly. The 2D epitaxial growth occurs only at one lateral side of the immobilized cylindrical micelle seeds, accessing unilateral platelets with the yield increasing with the seed length, the growth temperature, and poly(2-vinylpyridine) corona length (maximum = 92%). Generally, the tilted immobilization of seeds blocks one lateral side and triggers the lateral symmetry breaking, where the intensity and spatial arrangement of seed-surface interactions dictate the regulation. Segmented unilateral platelets with segmented corona regions are further fabricated with the addition of different blended unimers. Remarkably, discrete slope-like and dense blade-like platelet arrays grow off the surface when seeds are compactly aligned either with spherical micelles or themselves. This strategy provides nanoscale insights into the symmetry breaking in long-range self-assembly and would be promising for the design of innovative colloids and smart surfaces.