Anisotropy often leads to unexpected structures and properties in the solid state. In van der Waals (vdW) solids composed of 1D or quasi-1D (q-1D) building blocks, anisotropy in both intra- and inter-chain directions results in an abundance of crystalline packing motifs and drastically altered physical states. Among these, 1D/q-1D vdW solids that display topologically protected states, confined photonic modes, and direct band gap characteristics in few- to single-chains are highly sought after due to their tremendous potential as building blocks for next-generation quantum computing, spintronic, and telecommunication devices. Yet, access to such facet- and edge-specific physical states is still limited by the stochastic nature of micromechanical exfoliation. Here, we present two convergent efforts that address the growth of 1D and q-1D vdW crystals, which have closely related stoichiometric competing phases or exhibit rich polymorphism. First, I will describe the unique crystallization behavior of Bi4I4, a known topological insulator in bulk, in the presence of Au nanoparticle (NP) catalysts. Systematically varying Au NP diameters, Bi:I precursor ratios, and growth-deposition temperatures reveals that Au NPs generally act as nucleation sites for the vapor-solid (VS) growth of Bi4I4 nanowires. Strikingly, we discovered that post-synthesis analysis of 20 nm Au NPs, showing an equistochiometric 1:1 ratio of Bi to I within the Au NP, distinctly triggers the vapor-liquid-solid (VLS) growth of [001]-oriented quasi-2D nanosheets comprised of laterally-ordered [Bi4I4]n chains along the perpendicular [100] direction. Second, I will discuss how highly anisotropic and intrinsically strong covalent interactions along the long axis in 1D vdW crystals enable the uncatalyzed growth of record-long photonic nanowires (approximately 8 mm long with thicknesses ranging from 30 to 60 nm) via bottom-up vapor-phase routes. In both systems, we employ a series of structural and spectroscopic techniques to establish the structure, polytype, and physical properties of the well-defined nanowires and quasi-2D nanosheets that emerge from our synthetic routes.
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