Abstract
Two-dimensional (2D) Ruddlesden–Popper perovskites (RPPs) of the form PEA2Pb1–x Sn x I4 can be used as the tunable active layer in photovoltaics, as the passivating layer for 3D perovskite photovoltaics or in light emitting diodes. Here, we show a nonlinear band gap behavior with Sn content in mixed phase 2D RPPs. Density functional theory calculations (with and without spin–orbit coupling) are employed to study the effects of the short-range ordering of Pb and Sn in PEA2Pb1–x Sn x I4 compositions with x = 0, 0.25, 0.5, 0.75, and 1. Analysis of the partial density of states shows that the energy mismatch of the Pb 6s and Sn 5s states in the valence band maximum determines the nonlinearity of the band gap, leading to a bowing parameter of 0.35–0.38 eV. This research provides a critical insight for the design of future metal alloy 2D perovskite materials. The positions of the tunable energy band discontinuity may point to intraband transitions of interest to device engineers.