TY - JOUR
T1 - Centimeter-Sized 2D Perovskitoid Single Crystals for Efficient X-ray Photoresponsivity
AU - Ma, Chuang
AU - Gao, Lili
AU - Xu, Zhuo
AU - Li, Xiaotong
AU - Song, Xin
AU - Liu, Yucheng
AU - Yang, Tinghuan
AU - Li, Haojin
AU - Du, Yachao
AU - Zhao, Guangtao
AU - Liu, Xinmei
AU - Kanatzidis, Mercouri G.
AU - Liu, Shengzhong Frank
AU - Zhao, Kui
N1 - Funding Information:
This work was funded by the National Natural Science Foundation of China (61974085 and 62004121), the National Key Research and Development Program of China (2017YFA0204800), the 111 Project (Grant No. B21005), and National 1000-talent-plan program (1110010341), and the Fundamental Research Funds for the Central Universities (Grant No. GK202103109). At the Northwestern University, research on hard radiation detectors was supported in part by the Department of the Defense Threat Reduction Agency under award HDTRA1-20-2-0002.
Publisher Copyright:
© 2022 American Chemical Society
PY - 2022/2/22
Y1 - 2022/2/22
N2 - Metal-halide perovskitoids with corner-, edge-, and face-sharing octahedra provide a fertile “playground” for structure modulation. With low defect density, low ion migration, and high intrinsic stability, two-dimensional (2D) perovskitoid single crystals are expected to be ideal materials for room-temperature semiconductor detectors (RTSDs) as high-energy radiation. However, there is no report yet on the use of 2D perovskitoid single crystals for X-ray detection, as well as on how the halide-modulated molecular assembly would affect their structure and properties. Herein, based on an amidino-based organic spacer, we successfully synthesized a novel family of centimeter-sized 2D perovskitoid single crystals, (3AP)PbX4 (3AP = 3-amidinopyridine, X = Cl, Br, and I). This is the first time that centimeter-sized 2D perovskitoid single crystals are demonstrated for X-ray photoresponse. Detailed investigations reveal a unique crystal packing with corner-sharing and edge-sharing octahedra of inorganic frameworks and 3AP cations lying between adjacent inorganic layers in a parallel and antisymmetric manner. Changing the halide from I to Br and Cl results in greater Pb-X-Pb angles and stronger hydrogen bonding in perovskitoids and therefore consequently a better elastic recovery under stress, a more efficient charge transport in the inorganic layer, and a lower ionic migration. By varying halide substitution, an efficient X-ray photoresponse is achieved with a sensitivity up to 791.8 μC Gyair-1 cm-2 for (3AP)PbCl4 and a low detection limit of 1.54 μGyair s-1. These results reveal that the large 2D perovskitoid single crystals provide a promising platform for high performance optoelectronics.
AB - Metal-halide perovskitoids with corner-, edge-, and face-sharing octahedra provide a fertile “playground” for structure modulation. With low defect density, low ion migration, and high intrinsic stability, two-dimensional (2D) perovskitoid single crystals are expected to be ideal materials for room-temperature semiconductor detectors (RTSDs) as high-energy radiation. However, there is no report yet on the use of 2D perovskitoid single crystals for X-ray detection, as well as on how the halide-modulated molecular assembly would affect their structure and properties. Herein, based on an amidino-based organic spacer, we successfully synthesized a novel family of centimeter-sized 2D perovskitoid single crystals, (3AP)PbX4 (3AP = 3-amidinopyridine, X = Cl, Br, and I). This is the first time that centimeter-sized 2D perovskitoid single crystals are demonstrated for X-ray photoresponse. Detailed investigations reveal a unique crystal packing with corner-sharing and edge-sharing octahedra of inorganic frameworks and 3AP cations lying between adjacent inorganic layers in a parallel and antisymmetric manner. Changing the halide from I to Br and Cl results in greater Pb-X-Pb angles and stronger hydrogen bonding in perovskitoids and therefore consequently a better elastic recovery under stress, a more efficient charge transport in the inorganic layer, and a lower ionic migration. By varying halide substitution, an efficient X-ray photoresponse is achieved with a sensitivity up to 791.8 μC Gyair-1 cm-2 for (3AP)PbCl4 and a low detection limit of 1.54 μGyair s-1. These results reveal that the large 2D perovskitoid single crystals provide a promising platform for high performance optoelectronics.
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U2 - 10.1021/acs.chemmater.1c03832
DO - 10.1021/acs.chemmater.1c03832
M3 - Article
AN - SCOPUS:85124569042
VL - 34
SP - 1699
EP - 1709
JO - Chemistry of Materials
JF - Chemistry of Materials
SN - 0897-4756
IS - 4
ER -