ABSTRACT
Two-dimensional (2D) halide perovskites (HPs) are of significant interest to researchers because of their natural structural frameworks and intriguing optoelectronic properties. However, the direct fabrication of ordered mixed-spacer quasi-2D HPs remains challenging. Herein, a synthetic strategy inspired by the principle of supramolecular synthons is employed for the self-assembly of a series of ordered mixed-spacer bilayered HPs. The key innovation involves the introduction of intermolecular hydrogen bonds using a bifunctional 3-aminopropionitrile cation. Three homogeneous n = 2 structures are obtained, with a subtly ordered perovskite connected by two distinct types of organic cation layers, resulting in a recurrent ABAB' stacking sequence. These three compounds exhibit attractive semiconducting properties. Moderate bandgaps in the range of 2.70 to 2.76 eV with an absorption wavelength range of 448-459 nm exhibit excellent photoelectric response. Moreover, the ordered structures facilitate excellent polarization-sensitive photodetection, with an impressive on/off ratio of 103. The response speed ranged from 298 to 381 µs, and the out-of-plane polarization-related dichroism ratio is determined to be 1.19. Such ordered mixed-spacer bilayered perovskites have not been reported. These results enrich the HPs system and play a significant role in the direct assembly of novel perovskites with ordered structures.
ABSTRACT
In recent years, there has been a surge in research enthusiasm on searching for solid-state nonlinear optical (NLO) switching materials in halide perovskites owing to their exceptional structural flexibility, compositional diversity, and broad property tenability. However, the majority of reported halide perovskite NLO switching materials contain toxic elements (e.g., Pb), which raise significant environmental concerns. Herein, we present a novel lead-free multilayered halide perovskite NLO switching material, (BA)2(EA)2Sn3Br10 (1, where BA is butylammonium and EA is ethylammonium). Driven by the stereochemically active lone-pair electrons of the Sn2+ cation and the cage-confined effect of EA rotators, 1 undergoes a phase transition with symmetry breaking from P4/mnc to Cmc21, which gives rise to a highly efficient modulation of the quadratic NLO property (0.7 times that of KH2PO4) at a high temperature of 353 K. Furthermore, crystallographic investigation combined with theoretical calculations reveals that the efficient modulation of NLO properties in 1 stems from the synergistic effects between stereochemically active lone pair-induced octahedral distortions and order/disorder transformation of organic cations. This study opens up an instructive avenue for designing and advancing environmentally friendly solid-state NLO switches in halide perovskites.
ABSTRACT
Circularly polarized light (CPL) detection has sparked overwhelming research interest for its widespread chiroptoelectronic and spintronic applications. Ferroelectric materials, especially emerging layered hybrid perovskite ferroelectrics, exhibiting striking bulk photovoltaic effect (BPVE) present significant possibilities for CPL detection by a distinctive working concept. Herein, for the first time, we demonstrate the realization of robust angular anisotropy of CPL detection in a new layered hybrid perovskite ferroelectric crystal (CPA)2FAPb2Br7 (1, CPA is chloropropylammonium, FA is formamidinium), which crystallized in an optically active achiral polar point group. Benefiting from the notable spontaneous polarization (5.1 µC/cm2) and excellent semiconducting characteristics, single crystals of 1 exhibit remarkable BPVE under light illumination, with a high current on/off switching ratio (ca. 103). More intriguingly, driven by the angular carrier drift originating from spin-dependent BPVE in optically active ferroelectrics, 1 displays highly sensitive self-powered CPL detection performance, showing a robust angular anisotropy factor up to 0.98, which is far more than those achieved by material intrinsic chirality. This work provides an unprecedented approach for realizing highly sensitive CPL detection, which sheds light on the further design of optically active ferroelectrics for chiral photonic applications.
ABSTRACT
Birefringent crystals that can modulate the polarization of light play a significant role in modern optical devices including polarizing microscopes, optical isolators, and achromatic quarter-wave plates. To date, commercial birefringent crystals are exclusively limited to purely inorganic compounds. Here we report a new organic-inorganic hybrid halide, MLAPbBr4 (MLA=melamine), which features a (110)-oriented layered perovskite structure. Although the 6s2 lone-pair electrons of Pb2+ cations are stereochemically inert, MLAPbBr4 exhibits a birefringence of 0.322@550â nm, which exceeds those of all commercial birefringent crystals. The first-principles calculations reveal that this birefringence should be ascribed to the highly dislocated π-conjugation of MLA cations and high distortion of PbBr6 octahedra. This work highlights the persistently neglected great potential of hybrid halide perovskites as birefringent crystals.
