Abstract
Hybrid organic–inorganic perovskite solar cells (HOIPs), especially CH3NH3PbI3 (MAPbI3), have received tremendous attention due to their excellent power conversion efficiency (25.2%). However, two fundamental hurdles, long-term stability and lead (Pb) toxicity, prevent HOIPs from practical applications in the solar industry. To overcome these issues, compositional engineering has been used to modify cations at A- and B-sites and anions at the X-site in the general form ABX3. In this work, we used the density functional theory (DFT) to incorporate Rb, Cs, and FA at the A-site to minimize the volatile nature of MA, while the highly stable Ca2+ and Sr2+ were mixed with the less stable Ge2+ and Sn2+ at the B-site to obtain a Pb-free perovskite. To further enhance the stability, we mixed the X-site anions (I/Br). Through this approach, we introduced 20 new perovskite species to the lead-free perovskite family and 7 to the lead-containing perovskite family. The molecular dynamic (MD) simulations, enthalpy formation, and tolerance and octahedral factor study confirm that all of the perovskite alloys we introduced here are as stable as pristine MAPbI3. All Pb-free perovskites have suitable and direct band gaps (1.42–1.77 eV) at the Γ-point, which are highly desirable for solar cell applications. Most of our Pb-free perovskites have smaller effective masses and exciton binding energies. Finally, we show that the introduced perovskites have high absorption coefficients (105 cm–1) and strong absorption efficiencies (above 90%) in a wide spectral range (300–1200 nm), reinforcing their significant potential applications. This study provides a new way of searching for stable lead-free perovskites for sustainable and green energy applications.