Directed Assembly of Ordered Mixed-Spacer Quasi-2D Halide Perovskites through Homomeric Chains of Intermolecular Bonds.

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.

Nonlinear Optical Switching in a Tin-Based Multilayered Halide Perovskite Activated by Stereoactive Lone Pairs and Confined Rotators.

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.

Centimeter-Size Single Crystals of Halide Perovskite Photoferroelectric Solid Solution with Ultrahigh Pyroelectricity Boosted Photodetection.

Photoferroelectrics, especially emerging halide perovskite ferroelectrics, have motivated tremendous interests owing to their fascinating bulk photovoltaic effect (BPVE) and cross-coupled functionalities. However, solid solutions of halide perovskite photoferroelectrics with controllable structure and enhanced performance are scarcely explored. Herein, through mixing cage cation, a homogeneous halide perovskite photoferroelectric PA2 FAx MA1-x Pb2 Br7 solid solution (PA, FA and MA are CH3 CH2 CH2 NH3 + , NH2 CHNH2 + and CH3 NH3 + , 0≤x≤1) has been developed, which demonstrates tunable Curie temperature in a wide range of 263-323 K and excellent optoelectrical features. As the component adjusted to x=0.7, the bulk crystal demonstrates ultrahigh pyroelectric coefficient up to 1.48 µC cm-2 K-1 around room temperature. Strikingly, benefiting from the light-induced pyroelectricity and remarkable BPVE, a self-powered and sensitive photodetector based solid solution crystals with boosted responsivity and detectivity over than 1300 % has been achieved. This pioneering work sheds light on the exploration of photoferroelectric solid solutions towards high-performance photoelectronic devices.