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Tetrahedral semiconductors such as Si adopt a diamond-type crystal structure with low packing density arising from open cavities in the crystallographic space. By taking LiAlGe as an example, we propose a zincblende-type framework as a platform for semiconductors possessing electroactive cavities. LiAlGe adopts a half-Heusler-type crystal structure including an ordered diamond-type sublattice (zincblende-type) (AlGe) and is an indirect semiconductor with a band gap of ∼0.1 eV. The conduction band minimum (CBM) is uniquely located at the