Bandgap Modulation of Cs2AgInX6 (X = Cl and Br) Double Perovskite Nano- and Microcrystals via Cu2+ Doping

Abstract

Recently, the double perovskite Cs2AgInCl6, which has high stability and low toxicity, has been proposed as a potential alternative to Pb-based perovskites. However, the calculated parity-allowed transition bandgap of Cs2AgInCl6 is 4.25 eV; this wide bandgap makes it difficult to use as an efficient solar absorber. In this study, we explored the effect of Cu doping on the optical properties of Cs2AgInCl6 double perovskite nano- and microcrystals (MCs), particularly in its changes of absorption profile from the ultraviolet (UV) to near-infrared (NIR) region. Undoped Cs2AgInCl6 showed the expected wide bandgap absorbance, but the Cu-doped sample showed a new sharp absorption peak at 419 nm and broad absorption bands near 930 nm, indicating bandgap reduction. Electron paramagnetic resonance (EPR) spectroscopy demonstrated that this bandgap reduction effect was due to the Cu doping in the double perovskite and confirmed that the Cu2+ paramagnetic centers were located on the surface of the nanocrystals (NCs) and at the center of the perovskite octahedrons (g(parallel to) > g(perpendicular to) > g(e)). Finally, we synthesized Cu-doped Cs2AgInCl6 MCs and observed results similar to those of the NCs, showing that the application range could be expanded to multidimensions.