On the possibility of hybrid chalcogenide perovskite photovoltaics

TL;DR

This study uses first-principles calculations to explore hybrid chalcogenide perovskites, identifying N2H6ZrSe3 as a promising stable, lead-free photovoltaic candidate with a 1.31 eV band gap and 24.5% efficiency potential.

Contribution

First comprehensive computational assessment of hybrid chalcogenide perovskites, highlighting the hydrazinium cation as a stable A-site candidate for photovoltaic applications.

Findings

N2H6ZrSe3 has a quasi-direct band gap of 1.31 eV.

Most hybrid candidates are structurally unstable.

N2H6ZrSe3 exhibits a theoretical maximum efficiency of 24.5%.

Abstract

Chalcogenide perovskites are an emerging class of photovoltaic absorbers offering stable, lead-free structures and promising optoelectronic properties. To date, the literature on chalcogenide perovskites has focused primarily on fully inorganic systems such as \ce{BaZrS3}. This contrasts with the halide perovskites, for which hybrid organic-inorganic systems exhibit record performance. In this work, we assess the viability of hybrid chalcogenide perovskite absorbers using first-principles calculations. We screen a wide range of monovalent and divalent organic cations within the A-site to evaluate their electronic, optical, and thermodynamic properties. Our analysis reveals that the majority of candidates are structurally unstable; however, we identify the hydrazinium cation (\ce{N2H6^{2+}}) as a unique candidate that maintains a stable perovskite structure. Specifically, we identify \ce{N2H6ZrSe3} as the most promising candidate, exhibiting a quasi-direct band gap of \SI{1.31}{eV} and a theoretical maximum efficiency of \SI{24.5}{\percent} for a \SI{200}{\nm} thin film. This study represents the first comprehensive computational report on hybrid chalcogenide perovskites, opening new avenues for the development of Earth-abundant photovoltaic materials.