Investigations on the effect of single or double A-site cation engineering on the photovoltaic performance of bismuth perovskite-inspired materials (A3Bi2I9) are rare. Herein, we report novel single- and double-cation based bismuth perovskite-inspired materials developed by (1) completely replacing CH3NH3+ (methylammonium, MA+) in MA3Bi2I9 with various organic cations such as CH(NH2)2+ (formamidinium, FA+), (CH3)2NH2+ (dimethylammonium, DMA+), C(NH2)3+ (guanidinium, GA+) and inorganic cations such as cesium (Cs+), rubidium (Rb+), potassium (K+), sodium (Na+) and lithium (Li+) and (2) partially replacing MA+ with Cs+ in different stoichiometric ratios. Compared to single-cation based bismuth perovskite devices, the double-cation bismuth perovskite device showed an increment in the device power conversion efficiency (PCE) up to 1.5% crediting to the reduction in the bandgap. This is the first study demonstrating double-cation based bismuth perovskite showing bandgap reduction and increment in device efficiency and opens up the possibilities towards compositional engineering for improved device performance. Graphic Abstract

Thermal co-evaporation is a promising method for large-scale uniform perovskite deposition. However, the optimization of deposition parameters is an intricate process and often not reproducible between different laboratories. In this...