Methylhydrazine Lone‐Pair Engineering for Polar Lead‐Free Perovskite Enables Self‐Powered X‐Ray Detection

Lead‐free A3Bi2I9‐type perovskites demonstrate excellent performance in direct X‐ray detection owing to their high bulk resistivity and reduced ion migration. However, the reported centrosymmetric A3Bi2I9 can only operate with external voltage, inevitably resulting in energy consumption and bulky mo...

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Main Authors: Ruiqing Li, Jianbo Wu, Zeng‐Kui Zhu, Yaru Geng, Xinling Li, Yifei Wang, Bohui Xu, Zheshuai Lin, Junhua Luo
Format: Article
Language:English
Published: Wiley-VCH 2025-05-01
Series:Small Science
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Online Access:https://doi.org/10.1002/smsc.202400508
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author Ruiqing Li
Jianbo Wu
Zeng‐Kui Zhu
Yaru Geng
Xinling Li
Yifei Wang
Bohui Xu
Zheshuai Lin
Junhua Luo
author_facet Ruiqing Li
Jianbo Wu
Zeng‐Kui Zhu
Yaru Geng
Xinling Li
Yifei Wang
Bohui Xu
Zheshuai Lin
Junhua Luo
author_sort Ruiqing Li
collection DOAJ
description Lead‐free A3Bi2I9‐type perovskites demonstrate excellent performance in direct X‐ray detection owing to their high bulk resistivity and reduced ion migration. However, the reported centrosymmetric A3Bi2I9 can only operate with external voltage, inevitably resulting in energy consumption and bulky monolithic circuits, limiting their further development. Herein, exploiting the methylhydrazine (MHy) cation with 2s2 lone‐pair electrons (LPEs), a chiral‐polarity perovskite MHy3Bi2I9 are obtained and explored its self‐powered X‐ray detection properties. Where MHy forms the strong hydrogen bond interaction with the inorganic framework, resulting in the asymmetric Bi2I9 unit. Meanwhile, the 2s2 LPEs contribute to generating MHy dipole moments, leading to spontaneous polarization. On the one hand, spontaneous polarization acts as a driving force to realize the X‐ray‐generated carriers’ separation and transport to acquire self‐powered detection ability. On the other hand, the reduced noise current and dark current under zero bias further increase the signal‐to‐noise ratio and lower the detection limit. Notably, the MHy3Bi2I9 single‐crystal‐based detector displays a considerable sensitivity (106 μC Gy−1 cm−2) and an ultralow detection limit (55 nGy s−1) in self‐powered mode. Herein, new insights for constructing polar lead‐free perovskite and realizing unprecedented A3Bi2I9‐type self‐powered X‐ray detectors are provided.
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spelling doaj-art-34ecacc928c849e2a7d1fa53711f7a202025-08-20T02:55:32ZengWiley-VCHSmall Science2688-40462025-05-0155n/an/a10.1002/smsc.202400508Methylhydrazine Lone‐Pair Engineering for Polar Lead‐Free Perovskite Enables Self‐Powered X‐Ray DetectionRuiqing Li0Jianbo Wu1Zeng‐Kui Zhu2Yaru Geng3Xinling Li4Yifei Wang5Bohui Xu6Zheshuai Lin7Junhua Luo8State Key Laboratory of Structural Chemistry Fujian Institute of Research on the Structure of Matter Chinese Academy of Sciences, Fuzhou Fujian 350002 P. R. ChinaState Key Laboratory of Structural Chemistry Fujian Institute of Research on the Structure of Matter Chinese Academy of Sciences, Fuzhou Fujian 350002 P. R. ChinaState Key Laboratory of Structural Chemistry Fujian Institute of Research on the Structure of Matter Chinese Academy of Sciences, Fuzhou Fujian 350002 P. R. ChinaState Key Laboratory of Structural Chemistry Fujian Institute of Research on the Structure of Matter Chinese Academy of Sciences, Fuzhou Fujian 350002 P. R. ChinaState Key Laboratory of Structural Chemistry Fujian Institute of Research on the Structure of Matter Chinese Academy of Sciences, Fuzhou Fujian 350002 P. R. ChinaState Key Laboratory of Structural Chemistry Fujian Institute of Research on the Structure of Matter Chinese Academy of Sciences, Fuzhou Fujian 350002 P. R. ChinaSchool of Chemical Sciences College of Materials Science and Opto‐electronic Technology University of Chinese Academy of Sciences Beijing 100049 ChinaSchool of Chemical Sciences College of Materials Science and Opto‐electronic Technology University of Chinese Academy of Sciences Beijing 100049 ChinaState Key Laboratory of Structural Chemistry Fujian Institute of Research on the Structure of Matter Chinese Academy of Sciences, Fuzhou Fujian 350002 P. R. ChinaLead‐free A3Bi2I9‐type perovskites demonstrate excellent performance in direct X‐ray detection owing to their high bulk resistivity and reduced ion migration. However, the reported centrosymmetric A3Bi2I9 can only operate with external voltage, inevitably resulting in energy consumption and bulky monolithic circuits, limiting their further development. Herein, exploiting the methylhydrazine (MHy) cation with 2s2 lone‐pair electrons (LPEs), a chiral‐polarity perovskite MHy3Bi2I9 are obtained and explored its self‐powered X‐ray detection properties. Where MHy forms the strong hydrogen bond interaction with the inorganic framework, resulting in the asymmetric Bi2I9 unit. Meanwhile, the 2s2 LPEs contribute to generating MHy dipole moments, leading to spontaneous polarization. On the one hand, spontaneous polarization acts as a driving force to realize the X‐ray‐generated carriers’ separation and transport to acquire self‐powered detection ability. On the other hand, the reduced noise current and dark current under zero bias further increase the signal‐to‐noise ratio and lower the detection limit. Notably, the MHy3Bi2I9 single‐crystal‐based detector displays a considerable sensitivity (106 μC Gy−1 cm−2) and an ultralow detection limit (55 nGy s−1) in self‐powered mode. Herein, new insights for constructing polar lead‐free perovskite and realizing unprecedented A3Bi2I9‐type self‐powered X‐ray detectors are provided.https://doi.org/10.1002/smsc.202400508lead‐freelone‐pair engineeringlow detection limitpolar A3Bi2I9‐type perovskiteself‐powered X‐ray detection
spellingShingle Ruiqing Li
Jianbo Wu
Zeng‐Kui Zhu
Yaru Geng
Xinling Li
Yifei Wang
Bohui Xu
Zheshuai Lin
Junhua Luo
Methylhydrazine Lone‐Pair Engineering for Polar Lead‐Free Perovskite Enables Self‐Powered X‐Ray Detection
Small Science
lead‐free
lone‐pair engineering
low detection limit
polar A3Bi2I9‐type perovskite
self‐powered X‐ray detection
title Methylhydrazine Lone‐Pair Engineering for Polar Lead‐Free Perovskite Enables Self‐Powered X‐Ray Detection
title_full Methylhydrazine Lone‐Pair Engineering for Polar Lead‐Free Perovskite Enables Self‐Powered X‐Ray Detection
title_fullStr Methylhydrazine Lone‐Pair Engineering for Polar Lead‐Free Perovskite Enables Self‐Powered X‐Ray Detection
title_full_unstemmed Methylhydrazine Lone‐Pair Engineering for Polar Lead‐Free Perovskite Enables Self‐Powered X‐Ray Detection
title_short Methylhydrazine Lone‐Pair Engineering for Polar Lead‐Free Perovskite Enables Self‐Powered X‐Ray Detection
title_sort methylhydrazine lone pair engineering for polar lead free perovskite enables self powered x ray detection
topic lead‐free
lone‐pair engineering
low detection limit
polar A3Bi2I9‐type perovskite
self‐powered X‐ray detection
url https://doi.org/10.1002/smsc.202400508
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