Anion Ordering and Phase Stability Govern Optical Band Gaps in BaZr(S,Se)3

TL;DR

This study investigates how anion ordering and phase stability in BaZr(S,Se)3 influence its optical band gaps, revealing that composition and crystal structure enable tunable optoelectronic properties.

Contribution

It combines simulations and microscopy to identify an unusual ordered structure and maps the phase diagram, showing how anion ordering affects the band gap in BaZr(S,Se)3.

Findings

An unusual layered S/Se ordering persists at room temperature.

Composition and ordering jointly control the optical band gap, tunable from 1.6 to 1.9 eV.

Anion ordering reduces the band gap by approximately 0.12 eV.

Abstract

Chalcogenide perovskites have emerged as promising lead free materials for photovoltaic and thermoelectric applications. Among them, BaZrS3 has attracted particular attention due to its thermal and chemical stability, favorable optoelectronic properties, and low thermal conductivity. Here, we combine molecular dynamics and Monte Carlo simulations based on machine learned interatomic potentials with scanning transmission electron microscopy to investigate mixing thermodynamics and phase stability in the BaZr(S,Se)3 system. We identify an unusual ordered structure that persists at room temperature, most prominently at 33% S, where S and Se atoms form alternating layers within the crystal. Free energy calculations yield the temperature composition phase diagram, including a nonperovskite delta phase in the Se rich limit and a perovskite phase in the S rich limit, separated by a broad two phase region. Analysis of the dielectric function and the absorption coefficient demonstrates that composition, crystal structure, and anion ordering jointly control the optical band gap. Selenium alloying enables tuning between approximately 1.6 and 1.9eV, while anion ordering within a given composition reduces the gap by about 0.12eV. Lastly, variations between structural polymorphs give rise to band gap differences of up to 0.4eV.