Pressure‐Induced Metallization and Isostructural Transitions in 3R‐MoS₂

At ambient conditions 3R-polytypes of transition metal dichalcogenides (TMDs) demonstrate fascinating properties because of their unique layer stacking. Understanding the structure-property relationship is essential for the realization of their use in spintronic, valleytronic, and optoelectronic applications. Herein, after the high pressure-temperature synthesis of 3R-MoS₂ in a large volume cubic press, a concomitant experimental and theoretical high-pressure study of 3R-MoS₂ is reported, leading to the discovery of pressure-induced reversible isostructural phase transitions without symmetry breaking. Concurrent with the isostructural transitions, a semiconductor-to-metal transition is observed, owing to strong interlayer interaction and charge redistribution across the van der Waals gap under pressure. The pressure-induced enhancement of interlayer interactions together with the robust intrinsic layer stacking in 3R-MoS₂ prevent the layers from sliding under pressure and hinder a corresponding volume collapse. This study on continuous pressure-tuning of crystal and electronic structure in 3R-MoS₂ will play a vital role in developing the next-generation devices involving coupling of structural, optical, and electrical properties of 3R-polytypes of TMDs and other layered materials.