Pressure-induced novel ZrN₄ semiconductor materials with high dielectric constants: a first-principles study

In addition to Zr₃N₄ and ZrN₂ compounds, zirconium nitrides with a rich family of phases always exhibit metal phases. By employing an evolutionary algorithm approach and first-principles calculations, we predicted seven novel semiconductor phases for the ZrN₄ system at 0-150 GPa. Through calculating phonon dispersions, we identified four dynamically stable semiconductor structures under ambient pressure, namely, α-P1̄, β-P1̄, γ-P1̄, and β-P1 (with bandgaps of 1.03 eV, 1.10 eV, 2.33 eV, and 1.49 eV calculated using the HSE06 hybrid density functional, respectively). The calculated work functions and dielectric functions show that the four dynamically stable semiconductor structures are all high dielectric constant (high-k) materials, among which the β-P1̄ phase has the largest static dielectric constant (3.9 times that of SiO₂). Furthermore, we explored band structures using the HSE06 functional and density of states (DOS) and the response of bandgaps to pressure using the PBE functional for the four new semiconductor configurations. The results show that the bandgap responses of the four structures exhibit significant differences when hydrostatic pressure is applied from 0 to 150 GPa.