Anisotropic dielectric behavior of layered perovskite-like Cs3Bi2I9 crystals in the terahertz region

Abstract

The ternary metal halide perovskites have gradually attracted attention for application in the optoelectronic field, owing to their tunable crystal structure and appropriate bandgap. Lead free Cs₃Bi₂I₉ perovskite, with a 0D layered structure containing molecular [Bi₂I₉]³⁻ dimers, exhibits prominent optical and electrical anisotropies. Here, the anisotropic properties of the Cs₃Bi₂I₉ crystals were evaluated using terahertz time-domain spectroscopy (THz-TDS); meanwhile, the effect of phonon vibration on the THz transmission was confirmed using density functional perturbation theory (DFPT). Accordingly, the refractive index and extinction coefficient are estimated using THz-TDS, thanks to the high transmission in the range of 0.2–0.9 THz. The anisotropic refractive index was observed for the Cs₃Bi₂I₉ crystals, and was found to be 3.2–3.7 for the (100) plane (CBI₍₁₀₀₎) in contrast to 2.8–3.2 for the (001) plane (CBI₍₀₀₁₎). Furthermore, the Lorentz model was employed to extract the dielectric constant of Cs₃Bi₂I₉, in which anisotropy is obviously indicated by the static dielectric constant and the high-frequency dielectric constant. These anisotropic behaviors are determined by the dipole moment, which is attributed to the anisotropic packing density of [Bi₂I₉]³⁻ dimers. This study is significant and provides a deeper insight into the anisotropic photoelectric properties of Cs₃Bi₂I₉, thus contributing to the development of metal halide perovskites in the field of optoelectronics.