Vacancy ordering induced topological electronic transition in bulk Eu2ZnSb2

Metal-semiconductor transitions from changes in edge chirality from zigzag to armchair were observed in many nanoribbon materials, especially those based on honeycomb lattices. Here, this is generalized to bulk complex Zintl semiconductors, exemplified by Eu2ZnSb2 where the Zn vacancy ordering plays an essential role. Five Eu2ZnSb2 structural models are proposed to guide transmission electron microscopy imaging. Zigzag vacancy ordering models show clear metallicity, while the armchair models are semiconducting with indirect bandgaps that monotonously increase with the relative distances between neighboring ZnSb2 chains. Topological electronic structure changes based on cation ordering in a Zintl compound point toward tunable and possibly switchable topological behavior, since cations in these are often mobile. Thus, their orderings can often be adjusted by temperature, minor alloying, and other approaches. We explain the electronic structure of an interesting thermoelectric and point the way to previously unidentified types of topological electronic transitions in Zintl compounds.