Pressure-dependent electronic, optical, and mechanical properties of antiperovskite X₃NP (X = Ca, Mg): A first-principles study

Abstract

Hydrostatic pressure provides an efficient way to tune and optimize the properties of solid materials without changing their composition. In this work, we investigate the electronic, optical, and mechanical properties of antiperovskite X3NP (X2+ = Ca, Mg) upon compression by first-principles calculations. Our results reveal that the system is anisotropic, and the lattice constant a of X3NP exhibits the fastest rate of decrease upon compression among the three directions, which is different from the typical Pnma phase of halide and chalcogenide perovskites. Meanwhile, Ca3NP has higher compressibility than Mg3NP due to its small bulk modulus. The electronic and optical properties of Mg3NP show small fluctuations upon compression, but those of Ca3NP are more sensitive to pressure due to its higher compressibility and lower unoccupied 3d orbital energy. For example, the band gap, lattice dielectric constant, and exciton binding energy of Ca3NP decrease rapidly as the pressure increases. In addition, the increase in pressure significantly improves the optical absorption and theoretical conversion efficiency of Ca3NP. Finally, the mechanical properties of X3NP are also increased upon compression due to the reduction in bond length, while inducing a brittle-to-ductile transition. Our research provides theoretical guidance and insights for future experimental tuning of the physical properties of antiperovskite semiconductors by pressure.