Dual cation-anion substitution in phosphorus-based perovskites A 3 PX 3 (A = Ca, Sr; X = Cl, F): structural, mechanical, electronic, and optical properties

Abstract We present a comprehensive density functional theory investigation of cubic perovskites A 3 PX 3 (A = Ca, Sr; X = Cl, F) to explore the influence of cation-anion substitution on their structural, mechanical, electronic, and optical properties. Structural optimization confirms lattice expansion when substituting Ca with Sr and F with Cl. Electronic band structure calculations reveal direct band gaps at the Γ point, with values 1.85 eV (2.90 eV) for Ca 3 PF 3 , 2.06 eV (2.97 eV) for Sr 3 PF 3 , 1.96 eV (2.77 eV) for Sr 3 PCl 3 , using the PBE (HSE06) functional, respectively. These results demonstrate that substituting both the A-site cation and the X-site anion provides a straightforward route for tuning the band gap within the visible range. Optical analyses show that substitution also modulates dielectric response, absorption onset, and optical conductivity, while mechanical calculations confirm elastic stability with higher stiffness for Ca–F rich compounds compared to Sr–Cl systems. Overall, this dual substitutional strategy underscores the promise of A 3 PX 3 perovskites as stable and tunable candidates for photovoltaic and optoelectronic applications.