Self-Assembly under Confinement: Nanocorrals for Understanding Fundamentals of 2D Crystallization

[Image: see text] Nanocorrals with different size, shape, and orientation are created on covalently modified highly oriented pyrolytic graphite surfaces using scanning probe nanolithography, i.e., nanoshaving. Alkylated diacetylene molecules undergo laterally confined supramolecular self-assembly within these corrals. When nanoshaving is performed in situ, at the liquid–solid interface, the orientation of the supramolecular lamellae structure is directionally influenced by the gradual graphite surface exposure. Careful choice of the nanoshaving direction with respect to the substrate symmetry axes promotes alignment of the supramolecular lamellae within the corral. Self-assembly occurring inside corrals of different size and shape reveals the importance of geometric and kinetic constraints controlled by the nanoshaving process. Finally, seed-mediated crystallization studies demonstrate confinement control over nucleation and growth principles.