Functionality-Directed Screening of Pb-Free Hybrid Organic–Inorganic Perovskites with Desired Intrinsic Photovoltaic Functionalities

The material class of hybrid organic–inorganic perovskites has risen rapidly from a virtually unknown material in photovoltaic applications a short 7 years ago into an ∼20% efficient thin-film solar cell material. As promising as this class of materials is, however, there are limitations associated with its poor long-term stability, nonoptimal band gap, presence of environmentally toxic Pb element, etc. We herein apply a functionality-directed theoretical materials selection approach as a filter for initial screening of the compounds that satisfy the desired intrinsic photovoltaic functionalities and might overcome the above limitations. First-principles calculations are employed to systemically study thermodynamic stability and photovoltaic-related properties of hundreds of candidate hybrid perovskites. We have identified in this materials selection process 14 Ge- and Sn-based materials with potential superior bulk-material-intrinsic photovoltaic performance. A distinct class of compounds containing NH3COH+ with the organic molecule derived states intriguingly emerging at band-edges is found. Comparison of various candidate materials offers insights on how composition variation and microscopic structural changes affect key photovoltaic relevant properties in this family of materials.