Phase-Selective Synthesis of Rhombohedral WS₂ Multilayers by Confined-Space Hybrid Metal–Organic Chemical Vapor Deposition

Rhombohedral polytype transition metal dichalcogenide (TMDC) multilayers exhibit non-centrosymmetric interlayer stacking, which yields intriguing properties such as ferroelectricity, a large second-order susceptibility coefficient χ⁽²⁾, giant valley coherence, and a bulk photovoltaic effect. These properties have spurred significant interest in developing phase-selective growth methods for multilayer rhombohedral TMDC films. Here, we report a confined-space, hybrid metal-organic chemical vapor deposition method that preferentially grows 3R-WS₂ multilayer films with thickness up to 130 nm. We confirm the 3R stacking structure via polarization-resolved second-harmonic generation characterization and the 3-fold symmetry revealed by anisotropic H₂O₂ etching. The multilayer 3R WS₂ shows a dendritic morphology, which is indicative of diffusion-limited growth. Multilayer regions with large, stepped terraces enable layer-resolved evaluation of the optical properties of 3R-WS₂ via Raman, photoluminescence, and differential reflectance spectroscopy. These measurements confirm the interfacial quality and suggest ferroelectric modification of the exciton energies.