WS₂ Nanotubes, 2D Nanomeshes, and 2D In-Plane Films through One Single Chemical Vapor Deposition Route

We demonstrate a versatile, catalyst free chemical vapor deposition process on insulating substrates capable of producing in one single stream one-dimensional (1D) WO_{3- x} suboxides leading to a wide range of substrate-supported 2H-WS₂ polymorphs: a tunable class of out-of-plane (of the substrate) nanophases, with 1D nanotubes and a pure WS₂, two-dimensional (2D) nanomesh (defined as a network of webbed, micron-size, few-layer 2D sheets) at its extremes; and in-plane (parallel to the substrate) mono- and few-layer 2D domains. This entails a two-stage approach in which the 2WO₃ + 7S → 2WS₂ + 3SO₂ reaction is intentionally decoupled. First, various morphologies of nanowires or nanorods of high stoichiometry, WO_2.92/WO_2.9 suboxides (belonging to the class of Magnéli phases) were formed, followed by their sulfurization to undergo reduction to the aforementioned WS₂ polymorphs. The continuous transition of WS₂ from nanotubes to the out-of-plane 2D nanomesh, via intermediary, mixed 1D-2D phases, delivers tunable functional properties, for example, linear and nonlinear optical properties, such as reflectivity (linked to optical excitations in the material), and second harmonic generation (SHG) and onset of saturable absorption. The SHG effect is very strong across the entire tunable class of WS₂ nanomaterials, weakest in nanotubes, and strongest in the 2D nanomesh. Furthermore, a mechanism via suboxide (WO_{3- x}) intermediate as a possible path to 2D domain growth is demonstrated. 2D, in-plane WS₂ domains grow via "self-seeding and feeding" where short WO_2.92/WO_2.9 nanorods provide both the nucleation sites and the precursor feedstock. Understanding the reaction path (here, in the W-O-S space) is an emerging approach toward controlling the nucleation, growth, and morphology of 2D domains and films of transition-metal dichalcogenides.