Sn/Ge substitution in ((C$_\textrm{n}$H$_{2\textrm{n}-1}$NH$_3$)$_2$PbI$_4$; n=3): An emerging 2D layered hybrid perovskites with enhanced optoelectronic properties$^†$ (2204.04738v1)

Abstract: Two-dimensional (2D) perovskites show higher stability in comparison to their three-dimensional (3D) counterparts. Therefore, 2D perovskites have invoked remarkable attention in basic understanding of their physical properties and optoelectronic applications. Here we present a low-dimensional naturally self-assembled inorganic-organic (IO) hybrid systems based on primary cyclic ammonium-based (C${\textrm{n}}$H${2\textrm{n}-1}$NH${3}$) semiconductor series [viz. ((C${\textrm{n}}$H$_{2\textrm{n}-1}$ NH$_3$)$_2$PbI$_4$; n=3-6)]. However, the wide bandgap nature and presence of toxicity due to lead (Pb) prohibit their applications. Therefore, in the present work, we study the role of Ge/Sn substitution and Pb-vacancy (Pb-$\boxtimes$) to reduce concentration of Pb and to enhance solar cell efficiency by the formation of mixed perovskite structures. We have discussed the effect of spin-orbit coupling (SOC) using state-of-the-art hybrid density functional theory (DFT). We find the mixed conformers with Pb-$\boxtimes$ do not possess structural stability. Moreover, they have indirect bandgap, which is not good for solar cell applications. Only those conformers, which have favourable thermodynamics and structural stability, are considered for further study of optical properties. Our results infer that Sn substitution is more favorable than that of Ge in replacing Pb and enhancing the efficiency. Exciton binding energies calculated using Wannier-Mott approach for pristine and substituted conformers are larger than lead halide perovskites, while the electron-phonon coupling is smaller in the former. From computed spectroscopic limited maximum efficiency (SLME), these 2D perovskites show enough promise as alternatives to conventional lead halide perovskites.