Ga and In-based hybrid halide perovskites as an alternative to Pb: a first principles study

Lead-free hybrid halide perovskites have gained much attention in the field of photovoltaics due to their non-toxicity, stability and unique photo-physical properties. Sn and Ge-based ABX₃ perovskites have been widely studied due to their similar electronic properties to Pb-based materials. However, the unstable oxidation state of Sn is a major challenge for the commercialization of this class of materials. To overcome this problem, here, we have designed a series of novel Ga and In-based A₃B₂X₉-type perovskite materials incorporating the methylammonium (MA) organic cation in the A site and I^- as the halide ion in the X site. In this regard, we have investigated different structural, electronic, optical and photovoltaic properties by employing the density functional theory formalism. The formation of a stable three dimensional perovskite structure is determined by the observed values of tolerance factor (TF) and octahedral factor (μ). The observed negative values of formation enthalpy manifest that our studied materials are also thermodynamically stable. The obtained band gap values reveal that our designed perovskite materials can act as semiconducting materials for application in photovoltaics. We have also investigated the optical properties of our studied materials and the observed values of dielectric function and absorption coefficient in the visible range of the electromagnetic spectrum indicate their excellent photo absorption. The observed theoretical power conversion efficiency (PCE) values reveal that (MA)₃In₂I₉ (13.82%) and (MA)₃ (Ga_.50In_.50)₂I₉ (12.8%) can be chosen as potential candidates for application in perovskite-based photovoltaics. This research provides a pathway for the development of less toxic and efficient semiconducting materials, offering exciting prospects for their utilization in optoelectronics and contributing to the ongoing efforts to advance sustainable energy technologies.