Structural phase transitions of HfV2 at low temperatures

Abstract

We report a high-resolution synchrotron X-ray powder diffraction study on HfV2, hafnium divanadium, at low temperatures. In this work we show, for the first time, a complete sequence of structural phase transitions of HfV2 from cubic (Fd3m) to tetragonal (I41/amd) to orthorhombic (Imma) in succession as temperature decreases. Peak splitting and extra diffraction peaks owing to lattice distortion can be clearly distinguished for the low-symmetry phases. The atomic positions and lattice parameters were obtained by Rietveld refinement. The bond lengths and angles of the HfV2 crystal structure at the low-symmetry phases were correctly determined from the structure refinement. The face-centered cubic (Fd3m) unit cell (Z = 24) transforms to a body-centered tetragonal (I41/amd) phase with a 45° rotation relative to the cubic cell and with a reduced number of atoms (Z = 12) in the unit cell at a temperature of T = 112 K. The orthorhombic phase occurs at T = 102 K and it keeps the body-centered symmetry (Imma) and Z = 12 in the unit cell. The refinement results indicate that there may be a small amount of untransformed cubic phase left over in the lower symmetry phases. The abnormal thermal contraction of both tetragonal phase and orthorhombic phase marks the significance of structural change in HfV2.