Negative Thermal Expansion in ABC(MoO4)3 Compounds

Abstract Negative thermal expansion (NTE) compounds provide a solution for the mismatch of coefficients of thermal expansion in highly integrated device design. However, the current NTE compounds are rare, and how to effectively design new NTE compounds is still challenging. Here, a new concept is proposed to design NTE compounds, that is, to increase the flexibility of framework structure by expanding the space in framework structure compounds. Taking the parent compound NaZr 2 (PO 4 ) 3 as a case, a new NTE system A I B II C III (MoO 4 ) 3 (A = Li, Na, K, and Rb; B = Mg and Mn; C = Sc, In, and Lu) is designed. In these compounds, the large volume of MoO 4 tetrahedron is used to replace the small volume of PO 4 tetrahedron in NaZr 2 (PO 4 ) 3 to enhance structural space and NTE performance. Simultaneously, a joint study of temperature‐dependent X‐ray diffraction, Raman spectroscopy, and the first principles calculation reveals that the NTE in A I B II C III (MoO 4 ) 3 series compounds arise from the coupled oscillation of polyhedral. Large‐radius ions are conducive to enhancing the space and softening the framework structure to achieve the enhancement of NTE. The current strategy for designing NTE compounds is expected to be adopted in other compounds to obtain more NTE compounds.