Anisotropy-Driven Crystallization of Dimensionally Resolved Quasi-1D Van der Waals Nanostructures

[Image: see text] Unusual behavior in solids emerges from the complex interplay between crystalline order, composition, and dimensionality. In crystals comprising weakly bound one-dimensional (1D) or quasi-1D (q-1D) chains, properties such as charge density waves, topologically protected states, and indirect-to-direct band gap crossovers have been predicted to arise. However, the experimental demonstration of many of these nascent physics in 1D or q-1D van der Waals (vdW) crystals is obscured by the highly anisotropic bonding between the chains, stochasticity of top-down exfoliation, and the lack of synthetic strategies to control bottom-up growth. Herein, we report the directed crystallization of a model q-1D vdW phase, Sb(2)S(3), into dimensionally resolved nanostructures. We demonstrate the uncatalyzed growth of highly crystalline Sb(2)S(3) nanowires, nanoribbons, and quasi-2D nanosheets with thicknesses in the range of 10 to 100 nm from the bottom-up crystallization of [Sb(4)S(6)](n) chains. We found that dimensionally resolved nanostructures emerge from two distinct chemical vapor growth pathways defined by diverse covalent intrachain and anisotropic vdW interchain interactions and controlled precursor ratios in the vapor phase. At sub-100 nm nanostructure thicknesses, we observe the hardening of phonon modes, blue-shifting of optical band gaps, and the emergence of a new high-energy photoluminescence peak. The directional growth of weakly bound 1D ribbons or chains into well-resolved nanocrystalline morphologies provides opportunities to develop ordered nanostructures and hierarchical assemblies that are suitable for a wide range of optoelectronic and quantum devices.