Study on pressure-induced band gap modulation and physical properties of direct band gap Ca3NX3 (X = Cl, Br) for optoelectronic and thermoelectric applications

Utilizing density functional theory, we have comprehensively analyzed the structural, electronic, mechanical, transport, and thermodynamic properties of Ca3NCl3 and Ca3NBr3 photovoltaic materials. Furthermore, we investigated the impact of pressures ranging from 0 to 80 GPa and observed that the applied pressure decreases the atomic distances, resulting in significant changes in the physical properties of both materials. We employed GGA-PBE and TB-mBJ functionals to calculate the band structures and density of states, confirming their semiconducting nature. At 0 GPa, both compounds initially display a direct bandgap (Gamma-Gamma) of 1.5 eV for Ca3NCl3 and 1.26 eV for Ca3NBr3 based on GGA-PBE calculations. In contrast, the TB-mBJ calculations show an increase in the bandgap to 2.25 eV for Ca3NCl3 and 1.84 eV for Ca3NBr3, respectively. When a pressure of 80 GPa was applied, the direct bandgap of Ca3NCl3 and Ca3NBr3 decreased to 0.23 eV and 0.12 eV with GGA-PBE, and to 0.92 eV and 0.74 eV with TB-mBJ, respectively. It was also observed that the effective mass decreases under applied pressure, making these materials promising candidates for solar cell applications. The mechanical stability of both perovskites was maintained up to 80 GPa. Poisson's ratio and Pugh's ratio indicate that both compounds are brittle at 0 GPa but tend to become more ductile under applied stress. The optical properties reveal that pressure alters the dielectric function, absorption spectra, and optical conductivity, causing a red shift from higher to lower photon energies. Several thermodynamic properties, including heat capacity, Debye temperature, thermal expansion coefficient, and entropy, have been calculated, with their dependencies on temperature and pressure illustrated. Finally, the thermoelectric response of these materials is evaluated by examining how various transport parameters - such as the Seebeck coefficient, electrical and thermal conductivity, and power factor depend on the temperature.