The enhanced negative thermal expansion in less-oxygen-vacancies copper pyrophosphate

摘要

For oxides,controlling the concentration of oxygen vacancy is a useful way to optimize their functional properties.However,when it comes to the field of negative thermal expansion(NTE),much less attention has been paid to the effect of oxygen vacancy on NTE,though oxide-typed NTE materials account for more than 40%of the total NTE materials.Here,we report that the linear coefficient of thermal expansion at 250–350 K of copper pyrophosphate(i.e.,Cu_(2)P_(2)O_(7))can be significantly improved from–13.88 to–36.60 ppm/K when the synthesis temperature is raised from 1073 to 1373 K.The combined study including X-ray absorption near edge structure,neutron powder diffraction,and X-ray diffraction has confirmed the selective vacancies in the O1 site for low-temperature synthesized samples,which suppress both the phase-transition and framework-structure driven NTE simultaneously.Our result proposes a new approach for optimizing the NTE effect of oxides.