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Defects in two-dimensional and layered materials have attracted interest for realizing properties different from those of perfect crystals. Even stronger links between defect formation, fast growth, and emerging functionality can be found in nanostructures of van der Waals crystals, but only a few prevalent morphologies and defect-controlled synthesis processes have been identified. Here, we show that in vapor-liquid-solid growth of 1D van der Waals nanostructures, the catalyst controls the selection of the predominant (fast-growing) morphologies. Growth of layered GeS over Bi catalysts leads to two coexisting nanostructure types: chiral nanowires carrying axial screw dislocations and bicrystal nanoribbons where a central twin plane facilitates rapid growth. While Au catalysts produce exclusively dislocated nanowires, their modification with an additive triggers a switch to twinned bicrystal ribbons. Nanoscale spectroscopy shows that, while supporting fast growth, the twin defects in the distinctive layered bicrystals are electronically benign and free of nonradiative recombination centers.

Many materials are known to exist in several stable polymorphs, but synthesis only provides access to a subset. This situation is exemplified by the dichalcogenide semiconductor GeSe

Among group IV monochalcogenides, layered GeSe is of interest for its anisotropic properties, 1.3 eV direct band gap, ferroelectricity, high mobility, and excellent environmental stability. Electronic, optoelectronic and photovoltaic applications depend on the development of synthesis approaches that yield large quantities of crystalline flakes with controllable size and thickness. Here, we demonstrate the growth of single-crystalline GeSe nanoribbons by a vapor-liquid-solid process over Au catalyst on different substrates at low thermal budget. The nanoribbons crystallize in a layered structure, with ribbon axis along the armchair direction of the van der Waals layers. The ribbon morphology is determined by catalyst driven fast longitudinal growth accompanied by lateral expansion

2D/layered semiconductors are of interest for fundamental studies and for applications in optoelectronics and photonics. Work to date focused on extended crystals, produced by exfoliation or growth and investigated by diffraction-limited spectroscopy. Processes such as vapor-liquid-solid (VLS) growth carry potential for mass-producing nanostructured van der Waals semiconductors with exceptionally high crystal quality and optoelectronic/photonic properties at least on par with those of extended flakes. Here, we demonstrate the synthesis, structure, morphology, and optoelectronics/photonics of GaSe van der Waals nanoribbons obtained by Au- and Ag-catalyzed VLS growth. Although all GaSe ribbons are high-quality basal-plane oriented single crystals, those grown at lower temperatures stand out with their remarkably uniform morphology and low edge roughness. Photoluminescence spectroscopy shows intense, narrow light emission at the GaSe bandgap energy. Nanophotonic experiments demonstrate traveling waveguide modes at visible/near-infrared energies and illustrate approaches for locally exciting and probing such photonic modes by cathodoluminescence in transmission electron microscopy.

Nanowires of layered van der Waals (vdW) crystals are of interest due to structural characteristics and emerging properties that have no equivalent in conventional 3D crystalline nanostructures. Here, vapor-liquid-solid growth, optoelectronics, and photonics of GaS vdW nanowires are studied. Electron microscopy and diffraction demonstrate the formation of high-quality layered nanostructures with different vdW layer orientation. GaS nanowires with vdW stacking perpendicular to the wire axis have ribbon-like morphologies with lengths up to 100 μm and uniform width. Wires with axial layer stacking show tapered morphologies and a corrugated surface due to twinning between successive few-layer GaS sheets. Layered GaS nanowires are excellent wide-bandgap optoelectronic materials with

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-Ga