Crystal structures, elastic properties, and hardness of high-pressure synthesized CrB₂ and CrB₄

Chromium tetraboride (CrB₄), a recently proposed candidate for superhard materials, has been synthesized at high pressure and temperature by a solid-state reaction. As a byproduct, chromium diboride (CrB₂) also forms and co-exists with CrB₄ in the final product. The comparative studies of crystal structure, elastic property, and hardness of both phases have been conducted at the same sample environment conditions. The crystal structure of CrB₄ has been refined with an orthorhombic symmetry of Immm(space group no. 71) or Pnnm (space group no. 58) using X-ray diffraction data. Further simulations indicate that the structural distinction between Immm and Pnnm can be resolved by neutron diffraction, due to the high scattering cross-section of boron (¹¹B) by neutrons. Although CrB₂ and CrB₄ have close bulk modulus at about 230 GPa, the measured asymptotic Vickers hardness yields 16 GPa for CrB₂ but 30 GPa for CrB₄, which is nearly two times that of CrB₂. The dramatic enhancement in hardness in CrB₄ is attributed to the strong three-dimensional Cr-B network, in contrast to the layered lattice structure of hexagonal CrB₂.