Search for: All records

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.

 

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.

 

Electron–phonon interactions play an essential role in charge transport and transfer processes in semiconductors. For most structures, tailoring electron–phonon interactions for specific functionality remains elusive. Here, it is shown that, in hybrid perovskites, coherent phonon modes can be used to manipulate charge transfer. In the 2D double perovskite, (AE2T)₂AgBiI₈(AE2T: 5,5“‐diylbis(amino‐ethyl)‐(2,2”‐(2)thiophene)), the valence band maximum derived from the [Ag_0.5Bi_0.5I₄]^2–framework lies in close proximity to the AE2T‐derived HOMO level, thereby forming a type‐II heterostructure. During transient absorption spectroscopy, pulsed excitation creates sustained coherent phonon modes, which periodically modulate the associated electronic levels. Thus, the energy offset at the organic–inorganic interface also oscillates periodically, providing a unique opportunity for modulation of interfacial charge transfer. Density‐functional theory corroborates the mechanism and identifies specific phonon modes as likely drivers of the coherent charge transfer. These observations are a striking example of how electron–phonon interactions can be used to manipulate fundamentally important charge and energy transfer processes in hybrid perovskites.

 

Crystalline metal halide perovskites (MHPs) have provided unprecedented advances in interdisciplinary fields of materials, electronics, and photonics. While crystallinity offers numerous advantages, the ability to access a glassy state with distinct properties provides unique opportunities to extend the associated structure–property relationship, as well as broaden the application space for MHPs. Amorphous analogs for MHPs have so far been restricted to high pressures, limiting detailed studies and applications. Here, a 2D MHP is structurally tailored using bulky chiral organic cations to exhibit an unusual confluence of exceptionally low melting temperature (175 °C) and inhibited crystallization. The chiral MHP can thus be melt‐quenched into a stable glassy state, otherwise inhibited in the analogous racemic MHP. Facile and reversible switching between glassy and crystalline states is demonstrated for the chiral MHP, each with distinct optoelectronic character, opening new opportunities for applications including, for example nonvolatile memory, optical communication, and neuromorphic computing.

 

Hybrid perovskites incorporating conjugated organic cations enable unusual charge carrier interactions among organic and inorganic structural components, but are difficult to prepare as films due to disparate component chemical/physical characteristics ( e.g. , solubility, thermal stability). Here we demonstrate that resonant infrared matrix-assisted pulsed laser evaporation (RIR-MAPLE) mitigates these challenges, enabling facile deposition of lead-halide-based perovskite films incorporating variable-length oligothiophene cations. Density functional theory (DFT) predicts suitable organic and inorganic moieties that form quantum-well-like structures with targeted luminescence or exciton separation/quenching. RIR-MAPLE-deposited films enable confirmation of these predictions by optical measurements, which further display excited state behavior transcending traditional quantum-well models— i.e. , with appropriate selection of specially synthesized organic/inorganic moieties, intercomponent carrier transfer efficiently converts excitons from singlet to triplet states in organics for which intersystem crossing cannot ordinarily compete with recombination. These observations demonstrate the uniquely versatile excited-state behavior in hybrid perovskite quantum wells, and the value of integrating DFT, organic synthesis, RIR-MAPLE and spectroscopy for screening/preparing rationally devised complex structures.