Intrinsic Rashba Effect in Stable Configurations of Two-Dimensional (PEA)2PbI4

Halide perovskites (HPs) are crystalline solids that feature a unique softness, absent in conventional semiconducting materials. In recent years, this softness has been pivotal to many properties in these materials, in both static and dynamic regimes. Here, we focus on the two-dimensional (2D) (PEA)₂PbI₄ crystal. We employ extensive density functional theory calculations and structural analysis to uncover a rich mosaic of ground-state configurations, identifying several stable configurations with distinct electronic properties. Our study uncovers an intrinsic Rashba effect within a structure traditionally considered as globally centrosymmetric, presenting a challenge to conventional understanding in the field. The observed effect emerges from a local symmetry-breaking induced by specific spatial orientations of the organic PEA molecules. This intrinsic Rashba effect, observed in select configurations, underscores the nuanced symmetrical complexities of 2D HPs and highlights their potential for spin-related applications. Additionally, our investigation demonstrates the exceptional flexibility of 2D HPs, as evidenced by an observed significant tolerance toward single-molecule rotations. This flexibility suggests potential pathways for smoother transitions between different molecular domains within these materials. Overall, our findings emphasize the intricate interplay between the organic/inorganic counterparts and the electronic properties in 2D HPs, paving the way for further exploration and exploitation of their unique characteristics in various optoelectronic and spintronic applications.