Negative and zero thermal expansion in α-(Cu

Negative or zero thermal expansion (NTE or ZTE) of materials is intriguing for controllable thermal expansion. We report a series of orthorhombic α-Cu2-xZnxV2O7 (x = 0, 0.1, 0.2), in which the volumetric coefficients of thermal expansion are successfully tuned from -10.19 × 10-6 K-1 to -1.58 × 10-6 K-1 in the temperature range of 100-475 K by increasing the content of Zn2+. It has been revealed that the transverse vibrations of oxygen bonded with vanadium are dominant in the contraction of the bc plane, leading to the overall volume NTE in α-Cu2V2O7. The introduction of Zn2+ densifies the crystal structure, which is presumed to suppress the space of transverse vibrations and results in the ZTE in α-Cu1.8Zn0.2V2O7. This work presents an effective method to realize ZTE in anisotropic framework systems.