Tunability of electronic and optical properties of the Ba–Zr–S system via dimensional reduction

Abstract

Transition metal sulfide perovskites offer lower band gaps and greater tunability than oxides, along with other desirable properties for applications. Here, we explore dimensional reduction as a tuning strategy using the Ruddlesden–Popper phases in the Ba–Zr–S system as a model. The three-dimensional perovskite BaZrS₃ is a direct gap semiconductor, with a band gap of 1.5 eV suitable for solar photovoltaic application. However, the three known members of the Ruddlesden–Popper series, are all indirect gap materials, and additionally have lower fundamental band gaps. This is accompanied in the case of Ba₂ZrS₄ by a band structure that is more favorable for carrier transport for oriented samples. The layered Ruddlesden–Popper compounds show significantly anisotropic optical properties, as may be expected. The optical spectra show tails at low energy, which may complicate experimental characterization of these materials.