Cubic Fluorite-Type CaH with a Small Bandgap.

A cubic variant of CaH adopting a fluorite-type crystal structure was synthesized by cationic substitution with La or Y, yielding the first alkaline earth hydride-based with fluorite-type framework. The material has a bandgap of ∼2.5 eV (greenish yellow in color), which is much smaller than that of orthorhombic PbCl-type CaH (4.4 eV) and is, in fact, the smallest among alkaline or alkaline earth metal hydrides reported to date. Analysis of the density functional theory band structure of cubic-CaH indicates that its conduction band minimum is formed mainly by the interaction between the Ca 3d e orbitals around the crystallographic cavity defined by cubes of H ions. The use of such cavities in the creation of low-lying conduction band minima by semiconductors is extremely rare, and has similarities to inorganic electrides.