Optimizing Lead-Free Chalcogenide Perovskites for High-Efficiency Photovoltaics via Alloying Strategies

Abstract

Lead-free chalcogenide perovskites are emerging as game-changers in the race for sustainable, high-performance photovoltaics. These materials offer a perfect trifecta: non-toxic elemental composition, exceptional phase stability, and outstanding optoelectronic properties. However, unlocking their full potential for solar cell applications requires advanced strategies to fine-tune their electronic and optical behavior. In this study, we take CaHfS${}_3$-a promising but underexplored candidate-and revolutionize its performance by introducing targeted substitutions: Ti at the cation site and Se at the anion site. Using cutting-edge computational techniques, including density functional theory, GW calculations, and the Bethe-Salpeter equation (BSE), we reveal how these substitutions transform the material's properties. Our findings highlight that alloyed compounds such as CaHfS${}_{3-x}$Se${}_x$ and CaHf${}_{1-y}$Ti${}_y$X${}_3$ (X = S, Se) are not only phase-stable but also feature adjustable direct G${}_0$W${}_0$@PBE bandgaps (1.29-2.67 eV), reduced exciton binding energies, and significantly improved polaron mobility. These modifications enable better light absorption, reduced electron-hole recombination, longer exciton lifetimes, and enhanced quantum yield. Impressively, the alloyed perovskites, specifically, for the Ti-rich Se-based perovskites, achieve a spectroscopic-limited maximum efficiency of up to 28.06%, outperforming traditional lead-based halide perovskites. Our results demonstrate that strategic alloying is a powerful tool to supercharge the optoelectronic properties of lead-free chalcogenide perovskites, positioning them as strong contenders for next-generation photovoltaic technologies.

16 pages, 6 figures, 4 tables

References in corpus (9)

• Necessary and Sufficient Elastic Stability Conditions in Various Crystal Systems
• Implementation strategies in phonopy and phono3py
• Efficient $\mathcal{O}(N^2)$ approach to solve the Bethe-Salpeter equation for excitonic bound states
• Ti-alloying of BaZrS3 chalcogenide perovskite for photovoltaics
• Phonon Screening of Excitons in Semiconductors: Halide Perovskites and Beyond
• Indirect band gap semiconductors for thin-film photovoltaics: High-throughput calculation of phonon-assisted absorption
• Chalcogenide Perovskites: An Emerging Class of Semiconductors for Optoelectronics
• Post-Transition Metal Sn-Based Chalcogenide Perovskites: A Promising Lead-Free and Transition Metal Alternative for Stable, High-Performance Photovoltaics
• Probing Optoelectronic Properties of Stable Vacancy-Ordered Double Perovskites: Insights from Many-Body Perturbation Theory

Cited by in corpus (1)

• Unveiling the impact of trivalent metal cation transmutation on Cs${}_2$AgM(III)Cl${}_6$ double perovskites using many-body perturbation theory