Structural, Optical, and Electronic Properties of Wide Bandgap Perovskites: Experimental and Theoretical Investigations

Abstract

Wide bandgap hybrid halide perovskites based on bromine and chlorine halide anions have emerged as potential candidates for various optoelectronic devices. However, these materials are relatively less explored than the iodine-based perovskites for microscopic details. We present experiment and first-principles calculations to understand the structural, optical, and electronic structure of wide bandgap CH₃NH₃Pb(Br_1–xCl_x)₃ (x = 0, 0.33, 0.66, and 1) 3D hybrid perovskite materials. We substituted Br^– with Cl^– to tune the bandgap from 2.4 eV (green emissive) to 3.2 eV (blue (UV) emissive) of these materials. We correlate our experimental results with first-principles theory and provide an insight into important parameters like lattice constants, electronic structure, excitonic binding energy (E_X), dielectric constant, and reduced effective mass (μ_r) of charge carriers in these perovskite semiconductors. Electronic structure calculations reveal that electronic properties are mainly governed by Pb 6p and halide p orbitals. Our estimates of E_X within a hydrogen model suggest that an increase in E_X by increasing the Cl^– (chlorine) concentration is mainly due to a decrease in the dielectric constant with x and almost constant value of μ_r close to the range of 0.07m_e.