Chiral Zn‐Based Organic‐Inorganic Hybrid Ferroelectrics with Large Polarization and Luminescence

Abstract

Multi‐functionalized lead‐free organic‐inorganic hybrid ferroelectrics have recently realized diverse applications especially for optoelectronics and photovoltaics. Herein, the chiral Zn‐based organic−inorganic hybrids are discovered: [(R)‐(−)‐2‐methylpiperazine‐1,4‐diium][Zn(H2O)6]•(SO4)2 (RMPZnS2, space group P21) and [(S)‐(+)‐2‐methylpiperazine‐1,4‐diium]2[Zn(H2O)6]•(SO4)3 (SMP2ZnS3, space group P21212). Through experimental and computational investigations, it is found that RMPZnS2 is a ferroelectric with considerable large polarization value (P ≈ 9.5 µC cm−2) along b–axis, and its ferroelectric‐paraelectric phase transition is switched by rotation of organic cations. Meanwhile, it also possesses a fascinating photovoltaic effect driven by the polar charges at solar‐blind UV region, endowing it with the potential of self‐driven photodetection. In addition, white‐light emissions of the RMPZnS2 and SMP2ZnS3 are observed. The enhanced luminescence by heating is especially suitable for the application in white light‐emitting diodes. Overall, these chiral emission ferroelectrics at the supramolecular level will largely expand their applications in multidisciplinary fields.

Two-Dimensional Organic–Inorganic Hybrid Materials with Dielectric Switching and Photoluminescence Properties

“…Organic–inorganic hybrid materials − have attracted considerable attention because of their flexible structure and remarkable properties, such as photovoltaic, ferroelectric − and. piezoelectric, and nonlinear optical (NLO) properties. − Among them, layered two-dimensional (2D) organic–inorganic halide perovskites − (as an emerging semiconducting materials, they possess a strong quantum confinement effect to achieve high PLQYs and, moreover, photochromism can also be adjusted by halogen) have widespread applications in solar cells, , light emitting diodes (LEDs), − and photodetectors. − …”

Lead-Free Hybrid Organic–Inorganic Ferroelectric: (3,3-Difluoropyrrolidinium)2ZnCl4·H2O

“…31 Another example is that Wu et al synthesized zinc-based chiral hybrid organic−inorganic RMPZnS 2 and SMP 2 ZnS 3 single crystals, in which the RMPZnS 2 crystal is ferroelectric. 32 In addition, Jiao et al also reported a H/F-substituted HOIF (C 4 H 8 NF 2 ) 2 CdCl 4 , in which two different solvents were used to obtain a ferroelectric and a non-ferroelectric. 33 At present, the number of zinc-based ferroelectrics is still relatively small.…”

“…Chen et al reported an HOIF [(CH 3 ) 3 NCH 2 F]­ZnCl 3 with a zinc chloride ABX 3 structure, in which the organic molecules were substituted with H/F to optimize ferroelectricity . Another example is that Wu et al synthesized zinc-based chiral hybrid organic–inorganic RMPZnS 2 and SMP 2 ZnS 3 single crystals, in which the RMPZnS 2 crystal is ferroelectric . In addition, Jiao et al also reported a H/F-substituted HOIF (C 4 H 8 NF 2 ) 2 CdCl 4 , in which two different solvents were used to obtain a ferroelectric and a non-ferroelectric .…”

Metal ion induced dual switchable dielectric and luminescent properties in hybrid halides

“…In order to obtain such multifunctional materials, [22][23][24] great efforts have been made to explore the relationship between their inherent structure and potential properties. For example, Wu et al 25 reported chiral Zn-based organicinorganic hybrid RMPZnS 2 and SMP 2 ZnS 3 single crystals with a large polarization value of 9.5 μC cm −2 and luminescence characteristics. In addition, Zhang et al 26 synthesized a temperature-triggered dielectric switch nanocomposite (ODA for short), in which the dielectric switch showed good stability after multiple temperature cycles, indicating that the material is an excellent switchable dielectric material.…”