Elucidating the Interplay between Symmetry Distortions in Passivated MAPbI3 and the Rashba Splitting Effect

Hybrid organic–inorganic perovskites play a critical role in modern optoelectronic applications, particularly as single photon sources due to their unusual bright ground state. However, the presence of trap states resulting from surface dangling bonds hinders their widespread commercial application. This work uses density functional theory (DFT) to study the effects of various passivating ligands and their binding sites on Rashba splitting, a phenomenon directly linked to the bright ground state. Our results predict that X2- and X4-type ligands that adsorb at acidic oxygen binding sites and zwitterionic binding sites efficiently eliminate trap states introduced by surface iodine vacancies. Furthermore, our results show that distortions from the nominally symmetric cubic structure of the perovskite predominantly determine the presence and magnitude of the Rashba splitting. Specifically, the loss of more symmetry elements consistently leads to Rashba splitting in both the valence band (VB) and the conduction band (CB) with small Rashba splitting coefficients. Conversely, although inversion symmetry breaking alone fails to guarantee the presence of pure Rashba splitting in both the VB and the CB, it significantly increases the degree of splitting. The adsorption of ligands not only mitigates trap states but also plays a critical role in altering the local symmetry, thus influencing Rashba splitting. DFT predicts a distinct Rashba–Dresselhaus splitting in the CB with X2 ligands, causing the largest splitting. The presence of local electric fields causes consistent Rashba splitting of the VB across all studied systems except for the X4 zwitterionic passivated systems (sulfobetaine and lecithin). Electric fields are predicted to cause significant splitting of the CB, particularly for MAPbI3 and SH passivated MAPbI3 surfaces that possess freely rotating ligand binding sites. This study reveals that the wavelength, tunability of Rashba splitting through an applied electric field, and nature of Rashba–Dresselhaus splitting are influenced by the characteristics of the ligand binding site. On the other hand, pure Rashba splitting is predicted to exhibit a greater susceptibility to symmetry distortion than to specific ligand binding sites. These findings elucidate how surface passivating ligands and symmetry distortions influence Rashba splitting, shaping the optoelectronic properties of perovskite nanocrystals.