High-Pressure and High-Temperature Synthesis and In Situ High-Pressure Synchrotron X-ray Diffraction Study of HfSi₂

High-quality hafnium disilicide (HfSi₂) has been successfully synthesized using a high-pressure and high-temperature (HPHT) method at 3 GPa and 1573 K in a DS6 × 10 MN cubic press. The modest synthesis temperature is aided by significant decreases in both liquidus and solidus temperatures at high pressure for the Si-rich portion of the Hf-Si binary system. The in situ high-pressure X-ray diffraction study yielded a bulk modulus of B₀ = 124.4 ± 0.8 GPa with a fixed B₀^' = 4.0 for HfSi₂, which exhibits a dramatically anisotropic compressibility, with a and c axes nearly twice as incompressible as the b axis. The bulk HfSi₂ as synthesized has a Vickers hardness of 6.9 ± 0.1 GPa and high thermal stability of 1163 K in air, indicating its hard and refractory ceramic properties. The core-level XPS data of Hf 4f and Si 2p have been collected on the bulk samples of HfSi₂, HfSi, and Hf, as well as Si powder to examine the Hf-Si bonding in hafnium silicides. The Hf 4f_7/2 binding energies are 15.0 and 14.8 eV for bulk HfSi₂ and HfSi, respectively.