Pressure-Driven Metallization in Hafnium Diselenide

Abstract

The quest for new transition metal dichalcogenides (TMDs) with outstanding electronic properties operating under ambient conditions draws us to investigate the 1T-HfSe₂ polytype under hydrostatic pressure. Diamond anvil cell (DAC) devices coupled to in situ synchrotron X-ray, Raman, and optical (VIS-NIR) absorption experiments along with density functional theory (DFT)-based calculations prove that (i) bulk 1T-HfSe₂ exhibits strong structural and vibrational anisotropies, being the interlayer direction especially sensitive to pressure changes, (ii) the indirect gap of 1T-HfSe₂ tends to vanish by a -0.1 eV/GPa pressure rate, slightly faster than MoS₂ or WS₂, (iii) the onset of the metallic behavior appears at P_met ∼10 GPa, which is to date the lowest pressure among common TMDs, and finally, (iv) the electronic transition is explained by the bulk modulus B₀-P_met correlation, along with the pressure coefficient of the band gap, in terms of the electronic overlap between chalcogenide p-type and metal d-type orbitals. Overall, our findings identify 1T-HfSe₂ as a new efficient TMD material with potential multipurpose technological applications.