Stability Criteria and Optoelectronic Properties of Mg3ZBr3 (Z = As, Sb, Bi) Perovskites for Evaluating the Performance in PIN Photo Diode

Abstract

The toxicity and stability issues of lead-based perovskites motivate the search for non-toxic, durable alternatives. This work examines lead-free $\mathrm{Mg_3ZBr_3}$ ($Z=\mathrm{As,Sb,Bi}$) halide perovskites as optoelectronic materials, with emphasis on $\mathrm{Mg_3AsBr_3}$ and $\mathrm{Mg_3SbBr_3}$. First-principles calculations establish cubic $Pm\bar{3}m$ frameworks stabilized by strong Mg--Br linkages, and indirect band gaps of $2.0645\,\mathrm{eV}$ for $\mathrm{Mg_3AsBr_3}$ and $1.6533\,\mathrm{eV}$ for $\mathrm{Mg_3SbBr_3}$ obtained using hybrid functionals. Optical spectra show a rapid rise in absorption above the gap and an increasing static dielectric response along $\mathrm{As}\rightarrow\mathrm{Sb}\rightarrow\mathrm{Bi}$, indicating strengthened light--matter coupling. Phonon dispersions lack imaginary branches, confirming dynamical stability, and exhibit large mode anharmonicity (Gr\"uneisen signatures) consistent with soft-lattice heat transport. Moving down the pnictogen series expands the lattice and lowers the Goldschmidt tolerance factor, while enhanced pnictogen--Br $p$-orbital hybridization and stereochemically active $n\mathrm{s}^{2}$ lone pairs (Sb, Bi) narrow the band gap and increase the optical dielectric response. Elastic analyses confirm Born stability and moderate stiffness, with Hill-averaged bulk moduli decreasing from approximately $44\,\mathrm{GPa}$ ($\mathrm{Mg_3AsBr_3}$) to $35\,\mathrm{GPa}$ ($\mathrm{Mg_3BiBr_3}$). Drift--diffusion $p$--$i$--$n$ simulations qualitatively track band-edge-limited spectra, aligning with the computed gaps. Together, these results position these materials as promising lead-free candidates for stable thin-film photodiode and photovoltaic applications.