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

• Published in: Advanced optical materials 2022-02, Vol.10 (4), p.n/a
• Main Authors: Wu, Yuying, Jiang, Haidong, Jiao, Shulin, Li, Dong, Gao, Zhangran, Niu, Ben, Wu, Di, Chen, Shuang, Cai, Hong‐Ling, Wu, Xiaoshan
• Format: Article
• Language: English
• Subjects: Ferroelectric materials; Ferroelectricity; Ferroelectrics; Light emission; Light emitting diodes; Luminescence; Materials science; Optics; Optoelectronics; organic‐inorganic hybrids; Phase transitions; Photovoltaic cells; Photovoltaic effect; Polarization; White light
• ISSN: 2195-1071; 2195-1071
• DOI: 10.1002/adom.202101905

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. Chiral Zn‐based organic−inorganic hybrid RMPZnS2 and SMP2ZnS3 monocrystals are obtained via introducing the chiral organic cations. The experimental and computational investigations confirm the ferroelectricity of RMPZnS2 with considerable large polarization value along b–axis. The polar charges endow it with the potential of self‐driven photodetection at solar‐blind UV region.