Tuning of Optoelectronic Properties of Chalcohalides by Tailoring Pnictogen Composition for Sustainable Photovoltaics

Abstract This study investigates Sb 1‐x Bi x SeI pnictogen chalcohalides as lead‐free materials for photovoltaic and optoelectronic applications using density functional theory (DFT) calculations. Increasing Bi content from 0.5 to 0.6 reduces the bandgap from 1.60 to 1.43 eV, enhancing the light absorption and aligning with the optimal range for solar energy conversions. Structural analysis reveals that higher Bi substitution expands the lattice, reduces the hole effective mass, and improves the hole mobility, while the electron mobility decreases slightly. Sb 0.4 Bi 0.6 SeI demonstrates quasi‐direct bandgap characteristics attributed to Bi‐induced lattice distortion and strong spin–orbit coupling (SOC), which reduces the conduction band minimum and facilitate direct‐like electronic transitions. Enhanced absorption near the band edge and localized states contribute to higher sub‐bandgap absorption, broadening the spectral response. Reduced bandgap falls within the optimal range for single‐junction solar cells, increasing photocurrent generation. While defect‐induced recombination poses challenges, passivation and compositional tuning can optimize its performance. This study identifies the potential of Sb 0.4 Bi 0.6 SeI as a versatile absorber material in emerging solar cell architectures. The findings provide a pathway toward designing cost‐effective and sustainable materials with tailored properties for next‐generation photovoltaic and optoelectronic technologies.