Preferential substitution at cationic sites in 9-4-9 Zintl phase Ca9− yEuyZn4.5+ δ Sb9

Ca9Zn4.5Sb9 Zintl compound is one of the promising thermoelectric materials with excellent performance, which can be further improved by Eu alloying. In this work, a series of Ca9−yEuyZn4.5+δSb9 compounds is investigated by using the advanced Cs-corrected high-angle annular dark field scanning transmission electron microscope (HAADF-STEM) imaging technique at an atomic level. The HAADF-STEM images show that alloying Eu will lead to preferential substitution of Eu atoms at Ca(1) and Ca(5) sites. The further structural analysis and first-principles density functional theory calculation elucidate the origin that the Eu atoms are prone to replace Ca(1) and Ca(5) sites in Ca9−yEuyZn4.5+δSb9. The preferential substitutions may provide a new insight into revealing the structural transformation commonly found in Zintl phase thermoelectric materials.