High-Pressure Control of Vanadium Self-Intercalation and Enhanced Metallic Properties in 1T‑V1+xS2 Single Crystals

By means of high-pressure synthesis in the 4–6 GPa range, we report on the successful growth of high-quality 1T-V1+xS2 single crystals with controlled concentration, x = 0.09–0.17, of self-intercalated V atoms in the van der Waals gap. A systematic X-ray diffraction and energy-dispersive X-ray spectroscopy study unveils a linear decrease of x with the synthesis pressure, dx/dP = −0.042 GPa–1, suggesting that the stoichiometric (x = 0) phase is stable above 8 GPa. Transmission electron microscopy and electrical resistivity measurements show that, for all x values studied, the system is metallic up to 400 K, with no charge-density-wave order, contrary to the x = 0 composition. This finding clarifies the controversial electronic phase diagram of the 1T-V1+xS2 system and unveils a connection between the charge-density-wave phase observed at x = 0 and the itinerant antiferromagnetic phase stable for x > 0.25.