Tunable bandgap and luminescence characters in single-phase two-dimensional perovskite AVA2PbClxBr4-x alloys

Abstract

Two-dimensional (2D) lead halide perovskites have garnered increasing interest due to their high photoluminescence quantum yields and tunable luminescence characters, making them excellent materials in light-emitting, especially for white-light emission. In contrast to their 3D analogues, they are formed by inserting large organic cations between the anionic layers of lead halide octahedra. Herein, we designed and prepared AVA2PbClxBr4-x (x = 0, 1, 2, 3, 4) alloy perovskites, in which AVA (5-aminovaleric acid) was used as an organic cation to separate the layers of chlorine-substituted lead bromide 2D perovskite, in order to identify the role of Cl substitution in tuning the bandgap and luminescence characters of the 2D AVA2PbBr4 perovskite. X-ray diffraction measurements revealed achievement of single-phase thin films of AVA2PbClxBr4-x perovskites with a (001) orientation. With increasing Cl/Br ratio from 0 to 1, the lattice constant c was found to decrease from 1.672 nm to 1.597 nm following c(x) = 1.674 – 0.076x, while the bandgap increased from 3.11 eV to 3.76 eV as approximated with Eg(x) = 3.08 + 0.62x. Correspondingly, the alloy luminescence character evolved from narrow-band blue-violet to broadband white-light emission, which was attributed to transformation from free-exciton to self-trapped-exciton emission with increasing octahedral distortion caused by Cl substitution. Based on an alloy system with continuously varying content designed for the first time, the work highlighted the role of Cl incorporation in changing the crystal lattice structure, and tuning bandgap as well as the light emission characters in 2D lead halide perovskites.

Keywords

• Two-dimensional
• Perovskite alloys
• Bandgap tuning
• Luminescence
• Self-trapped excitons