Zero and controllable thermal expansion in HfMgMo3-xWxO12

HfMgMo3-xWxO12 with x = 0.5, 1.0, 1.5, 2.0, and 2.5 are developed with a simple solid state method. With increasing the content of W, solid solutions of Hf Mg Mo3-xWx O12 crystallize in an orthorhombic structure for x≤2.0 and a monoclinic structure for x>2.0. A near-zero thermal expansion（ZTE） is realized for HfMgMo2.5W0.5O12 and negative coefficients of thermal expansion（NCTE） are achieved for other compositions with different values. The ZTE and variation of NCTE are attributed to the difference in electronegativity between W and Mo and incorporation of a different amount of W, which cause variable distortion of the octahedra and softening of the MoO4 tetrahedra, and hence an enhanced NCTE in the a- and c-axis and reduced CTE in the b-axis as revealed by Raman spectroscopy and x-ray diffraction.