LAUSR

Abstract The discovery of electrides, in particular, inorganic electrides where electrons substitute anions, has inspired striking interests in the systems that exhibit unusual electronic and catalytic properties. So far, however, the experimental studies of such systems are largely restricted to ambient conditions, unable to understand their interactions between electron localizations and geometrical modifications under external stimuli, e.g., pressure. Here, pressure‐induced structural and electronic evolutions of Ca2N by in situ synchrotron X‐ray diffraction and electrical resistance measurements, and density functional theory calculations with particle swarm optimization algorithms are reported. Experiments and computation are combined to reveal that under compression, Ca2N undergoes structural transforms from R 3¯ m symmetry to I 4¯2d phase via an intermediate Fd 3¯ m phase, and then to Cc phase, accompanied by the reductions of electronic dimensionality from 2D, 1D to 0D. Electrical resistance measurements support a metal‐to‐semiconductor transition in Ca2N because of the reorganizations of confined electrons under pressure, also validated by the calculation. The results demonstrate unexplored experimental evidence for a pressure‐induced metal‐to‐semiconductor switching in Ca2N and offer a possible strategy for producing new electrides under moderate pressure.