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Title: Structural descriptor for enhanced spin-splitting in 2D hybrid perovskites

Two-dimensional (2D) hybrid metal halide perovskites have emerged as outstanding optoelectronic materials and are potential hosts of Rashba/Dresselhaus spin-splitting for spin-selective transport and spin-orbitronics. However, a quantitative microscopic understanding of what controls the spin-splitting magnitude is generally lacking. Through crystallographic and first-principles studies on a broad array of chiral and achiral 2D perovskites, we demonstrate that a specific bond angle disparity connected with asymmetric tilting distortions of the metal halide octahedra breaks local inversion symmetry and strongly correlates with computed spin-splitting. This distortion metric can serve as a crystallographic descriptor for rapid discovery of potential candidate materials with strong spin-splitting. Our work establishes that, rather than the global space group, local inorganic layer distortions induced via appropriate organic cations provide a key design objective to achieve strong spin-splitting in perovskites. New chiral perovskites reported here couple a sizeable spin-splitting with chiral degrees of freedom and offer a unique paradigm of potential interest for spintronics.

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Nature Communications
Nature Publishing Group
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National Science Foundation
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  1. Abstract

    Translation of chirality and asymmetry across structural motifs and length scales plays a fundamental role in nature, enabling unique functionalities in contexts ranging from biological systems to synthetic materials. Here, we introduce a structural chirality transfer across the organic–inorganic interface in two-dimensional hybrid perovskites using appropriate chiral organic cations. The preferred molecular configuration of the chiral spacer cations,R-(+)- orS-(−)-1-(1-naphthyl)ethylammonium and their asymmetric hydrogen-bonding interactions with lead bromide-based layers cause symmetry-breaking helical distortions in the inorganic layers, otherwise absent when employing a racemic mixture of organic spacers. First-principles modeling predicts a substantial bulk Rashba-Dresselhaus spin-splitting in the inorganic-derived conduction band with opposite spin textures betweenR- andS-hybrids due to the broken inversion symmetry and strong spin-orbit coupling. The ability to break symmetry using chirality transfer from one structural unit to another provides a synthetic design paradigm for emergent properties, including Rashba-Dresselhaus spin-polarization for hybrid perovskite spintronics and related applications.

  2. Abstract

    The two-dimensional (2D) Ruddlesden−Popper organic-inorganic halide perovskites such as (2D)-phenethylammonium lead iodide (2D-PEPI) have layered structure that resembles multiple quantum wells (MQW). The heavy atoms in 2D-PEPI contribute a large spin-orbit coupling that influences the electronic band structure. Upon breaking the inversion symmetry, a spin splitting (‘Rashba splitting’) occurs in the electronic bands. We have studied the spin splitting in 2D-PEPI single crystals using the circular photogalvanic effect (CPGE). We confirm the existence of Rashba splitting at the electronic band extrema of 35±10 meV, and identify the main inversion symmetry breaking direction perpendicular to the MQW planes. The CPGE action spectrum above the bandgap reveals spin-polarized photocurrent generated by ultrafast relaxation of excited photocarriers separated in momentum space. Whereas the helicity dependent photocurrent with below-gap excitation is due to spin-galvanic effect of the ionized spin-polarized excitons, where spin polarization occurs in the spin-split bands due to asymmetric spin-flip.

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