Single-Crystalline γ-Ga₂S₃ Nanotubes via Epitaxial Conversion of GaAs Nanowires

The chemical transformation of nanowire templates into nanotubes is a promising avenue toward hollow one-dimensional (1D) nanostructures. To date, high-quality single crystalline tubes of nonlayered inorganic crystals have been obtained by solid-state reactions in diffusion couples of nanowires with deposited thin film shells, but this approach presents issues in achieving single-phase tubes with a desired stoichiometry. Chemical transformations with reactants supplied from the gas- or vapor-phase can avoid these complications, allowing single-phase nanotubes to be obtained through self-termination of the reaction once the sacrificial template has been consumed. Here, we demonstrate the realization of this scenario with the transformation of zincblende GaAs nanowires into single-crystalline cubic γ-Ga₂S₃ nanotubes by reaction with sulfur vapor. The conversion proceeds via the formation of epitaxial GaAs-Ga₂S₃ core-shell structures, vacancy injection and aggregation into Kirkendall voids, elastic relaxation of the detached Ga₂S₃ shell, and finally complete incorporation of Ga in a crystalline chalcogenide tube. Absorption and luminescence spectroscopy on individual nanotubes show optoelectronic properties, notably a ∼3.1 eV bandgap and intense band-edge and near band-edge emission consistent with high-quality single crystals, along with transitions between gap-states due to the inherent cation-vacancy defect structure of Ga₂S₃. Our work establishes the transformation of nanowires via vapor-phase reactions as a viable approach for forming single-crystalline hollow 1D nanostructures with promising properties.