A DFT Study of Alkaline Earth Metal-Doped FAPbI3 (111) and (100) Surfaces

Density functional theory calculations have been performed to study the effect of replacing lead by alkaline earth metals on the stability, electronic and optical properties of the formamidinium lead triiodide (FAPbI₃) (111) and (100) surfaces with different terminations in the form of FAPb_1-xAE_xI₃ structures, where AE is Be, Mg or Ca. It is revealed that the (111) surface is more stable, indicating metallic characteristics. The (100) surfaces exhibit a suitable bandgap of around 1.309 and 1.623 eV for PbI₅ and PbI₆ terminations, respectively. Increases in the bandgaps as a result of Mg- and Ca-doping of the (100) surface were particularly noted in FAPb_0.96Ca_0.04I₃ and FAPb_0.8Ca_0.2I₃ with bandgaps of 1.459 and 1.468 eV, respectively. In the presence of Be, the band gap reduces critically by about 0.315 eV in the FAPb_0.95Be_0.05I₃ structure, while increasing by 0.096 eV in FAPb_0.96Be_0.04I₃. Optimal absorption, high extinction coefficient and light harvesting efficiency were achieved for plain and doped (100) surfaces in the visible and near UV regions. In order to improve the optical properties of the (111)-PbI₃ surface in initial visible areas, we suggest calcium-doping in this surface to produce FAPb_0.96Ca_0.04I₃, FAPb_0.92Ca_0.08I₃, and FAPb_0.88Ca_0.12I₃ structures.