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

TL;DR

This study uses advanced computational methods to optimize lead-free chalcogenide perovskites through alloying, significantly enhancing their photovoltaic efficiency and stability for next-generation solar cells.

Contribution

It introduces targeted alloying strategies in CaHfS₃-based perovskites, demonstrating improved optoelectronic properties and high efficiency potential via computational analysis.

Findings

Alloyed perovskites are phase-stable with tunable bandgaps.

Reduced exciton binding energies and improved polaron mobility.

Achieved maximum efficiency of up to 28.06%.

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.