All‐Scale Hierarchical Structure Contributing to Ultralow Thermal Conductivity of Zintl Phase CaAg(0.2)Zn(0.4)Sb

TiNiSi‐type Zintl phase CaAgSb can transform into LiGaGe‐type Zintl phase CaAg(x)Zn((1−) (x) ()/2)Sb when some of the Ag atoms are substituted by Zn atoms, leading to an ultralow thermal conductivity of ≈0.4 W m(−1) K(−1) in the whole measured temperature range of CaAg(0.2)Zn(0.4)Sb. The microstructure is then investigated by spherical aberration‐corrected electron microscopy on an atomic scale, which reveals an all‐scale hierarchical structure that can scatter the phonons in a wide frequency range. There exist a large quantity of CaAgSb nanometer precipitates as well as quite a lot of edge dislocations close to these nanometer precipitates, thus releasing the stress caused by the mismatch between the precipitates and the parent phase. Many twin boundaries also exist around the CaAgSb precipitates. High‐density point defects contain the randomly dispersed Ag vacancies and Zn atoms substituted for the Ag atoms. All these widely distributed multidimensional defects contribute to the decrease of lattice thermal conductivity in a wide temperature range.