Interplay of Cation Ordering and Ferroelectricity in Perovskite Tin Iodides: Designing a Polar Halide Perovskite for Photovoltaic Applications

Owing to its ideal semiconducting band gap and good carrier-transport properties, the fully inorganic perovskite CsSnI₃ has been proposed as a visible-light absorber for photovoltaic (PV) applications. However, compared to the organic-inorganic lead halide perovskite CH₃NH₃PbI₃, CsSnI₃ solar cells display very low energy conversion efficiency. In this work, we propose a potential route to improve the PV properties of CsSnI₃. Using first-principles calculations, we examine the crystal structures and electronic properties of CsSnI₃, including its structural polymorphs. Next, we purposefully order Cs and Rb cations on the A site to create the double perovskite (CsRb)Sn₂I₆. We find that a stable ferroelectric polarization arises from the nontrivial coupling between polar displacements and octahedral rotations of the SnI₆ network. These ferroelectric double perovskites are predicted to have energy band gaps and carrier effective masses similar to those of CsSnI₃. More importantly, unlike nonpolar CsSnI₃, the electric polarization present in ferroelectric (CsRb)Sn₂I₆ can effectively separate the photoexcited carriers, leading to novel ferroelectric PV materials with potentially enhanced energy conversion efficiency.