Two-dimensional layered materials have attracted extensive interest owing to their highly tunable electronic and optoelectronic properties associated with layer number and interlayer stacking. Tungsten disulfide (WS₂), a representative transition metal dichalcogenide, mainly adopts 2H and 3R stacking configurations in multilayer form, which exhibit distinct crystal symmetries and nonlinear optical responses. However, how template-guided stacking evolution influences the layer and morphology evolution of multilayer WS₂ during layer-by-layer epitaxy remains insufficiently understood. Herein, we demonstrate a WS₂-template-guided van der Waals epitaxial strategy to regulate the stacking propagation pathways and morphology evolution of multilayer WS₂. Under the combined effects of template-guided epitaxial regulation and deposition-temperature-dependent stacking evolution, distinct stacking propagation pathways preferentially lead to AB-stacked 2H-WS₂ and ABC-stacked 3R-WS₂. Notably, multilayer 2H-WS₂ exhibits asynchronous layer-dependent morphology evolution from triangular to hexagonal tower-like structures, whereas 3R-WS₂ maintains a self-similar pyramidal growth pathway with highly ordered stacking propagation. Atomic force microscopy (AFM) and second harmonic generation (SHG) mapping further establish the intrinsic correlation among stacking evolution, layer evolution, morphology evolution, and symmetry response in multilayer WS₂, including odd-even SHG oscillation in 2H-WS₂ and progressively enhanced SHG response in multilayer 3R-WS₂. These findings provide new insights into template-guided stacking regulation during multilayer van der Waals epitaxy, offering a potential strategy for the controllable structural engineering of layered transition metal dichalcogenide materials.

Twisted two-dimensional (2D) layered materials have attracted significant attention due to their twist angle-related superconductivity and moiré exciton phenomena. In twisted layered materials, supertwisted spirals exhibit multiple layers of continuous twisted structures, which give rise to their unique optoelectronic properties. Previous studies have primarily focused on the influence of conical non-Euclidean surfaces on the growth of twisted spirals, revealing their dominant role in determining the twist angle. However, few studies have systematically analyzed the additional factors influencing the variation of twist angles during the growth of such structures. In this work, we demonstrated the synthesis of supertwisted WS₂ spirals on the edges of WS₂ nanoribbons with nanoparticles, where the twist angle deviates from the theoretical value due to the additional influence of the nanoribbons during growth. Beyond the dominant role of nanoparticles in determining the twist angle of the spirals, we found that larger step heights or contact areas of the nanoribbons lead to larger twist angles. Furthermore, photoluminescence (PL) and Raman spectroscopy revealed the unique optical properties of the twisted spirals. PL spectra exhibited thickness-dependent abnormal variation in luminescence intensity, attributed to the decoupling and recoupling of interlayer interactions, while Raman spectra demonstrated the thickness-dependent and twist angle-dependent variations in the dominant atomic vibrations of interlayer van der Waals (vdW) interactions. These findings not only provide new insights into the regulation of twist angles in twisted spiral structures, but also contribute to a deeper understanding of the optical characteristics of twisted 2D layered materials, paving the way for their potential applications in various fields.