Design of Two-Dimensional Hybrid Perovskites with Giant Spin Splitting and Persistent Spin Textures.

Semiconductors with large energetic separation Δ of energy sub-bands with distinct spin expectation values (spin textures) represent a key target to enable control over spin transport and spin-optoelectronic properties. While the paradigmatic case of symmetry-dictated Rashba spin splitting and associated spin textures remains the most explored pathway toward designing future spin-transport-based quantum information technologies, controlling spin physics beyond the Rashba paradigm by accessing strategically targeted crystalline symmetries holds significant promise. In this paper, we show how breaking the traditional paradigm of octahedron-rotation based structure distortions in 2D organic-inorganic perovskites (2D-OIPs) can facilitate exceptionally large spin splittings (Δ > 400 meV) and spin textures with extremely short spin helix lengths ( ∼ 5 nm).

Remote chirality transfer in low-dimensional hybrid metal halide semiconductors.

In hybrid metal halide perovskites, chiroptical properties typically arise from structural symmetry breaking by incorporating a chiral A-site organic cation within the structure, which may limit the compositional space. Here we demonstrate highly efficient remote chirality transfer where chirality is imposed on an otherwise achiral hybrid metal halide semiconductor by a proximal chiral molecule that is not interspersed as part of the structure yet leads to large circular dichroism dissymmetry factors (g) of up to 10. Density functional theory calculations reveal that the transfer of stereochemical information from the chiral proximal molecule to the inorganic framework is mediated by selective interaction with divalent metal cations.

Local Structure in Crystalline, Glass and Melt States of a Hybrid Metal Halide Perovskite.

The pursuit of structure-property relationships in crystalline metal halide perovskites (MHPs) has yielded an unprecedented combination of advantageous characteristics for wide-ranging optoelectronic applications. While crystalline MHP structures are readily accessible through diffraction-based structure refinements, providing a clear view of associated long-range ordering, the local structures in more recently discovered glassy MHP states remain unexplored. Herein, we utilize a combination of Raman spectroscopy, solid-state nuclear magnetic resonance (NMR), Fourier transform infrared spectroscopy, in situ X-ray diffraction (XRD) and pair distribution function (PDF) analysis to investigate the coordination environment in crystalline, glass and melt states of the 2D MHP [(S)-(-)-1-(1-naphthyl)ethylammonium]PbBr.

Hydrogen Bonding Analysis of Structural Transition-Induced Symmetry Breaking and Spin Splitting in a Hybrid Perovskite Employing a Synergistic Diffraction-DFT Approach.

Two-dimensional (2D) hybrid organic-inorganic perovskites (HOIPs) offer an outstanding opportunity for spin-related technologies owing in part to their tunable structural symmetry breaking and distortions driven by organic-inorganic hydrogen (H) bonds. However, understanding how H-bonds tailor inorganic symmetry and distortions and therefore enhance spin splitting for more effective spin manipulation remains imprecise due to challenges in measuring H atom positions using X-ray diffraction. Here, we report a thermally induced structural transition (at ∼209 K) for a 2D HOIP, (2-BrPEA)PbI [2-BrPEA = 2-(2-bromophenyl)ethylammonium], which induces inversion asymmetry and a strong spin splitting (Δ > 30 meV).