低成本溶液法制备厘米级Cs3Cu2I5单晶及其闪烁发光性能

doi:10.15541/jim20220028

无机材料学报 ›› 2022, Vol. 37 ›› Issue (10): 1129-1134.DOI: 10.15541/jim20220028

低成本溶液法制备厘米级Cs₃Cu₂I₅单晶及其闪烁发光性能

徐婷婷¹^,²(), 李云云²(), 王谦²^,³, 王京康²^,⁴, 任国浩², 孙大志¹, 吴云涛²()

1.上海师范大学化学与材料科学学院, 上海 200234
2.中国科学院上海硅酸盐研究所, 上海200050
3.上海大学材料科学与工程学院, 上海 200444
4.上海理工大学材料与化学学院, 上海 200082

收稿日期:2022-01-18 修回日期:2022-02-14 出版日期:2022-10-20 网络出版日期:2022-07-08
通讯作者: 吴云涛, 研究员. E-mail: ytwu@mail.sic.ac.cn;
李云云, 博士. E-mail: liyunyun@mail.sic.ac.cn
作者简介:徐婷婷(1997-), 女, 硕士研究生. E-mail: chris1183047422@163.com
基金资助:
国家自然科学基金(12005288);国家自然科学基金(11975303);国家自然科学基金(11775290);上海市自然科学基金(20ZR1473900);上海市自然科学基金(21TS1400100);上海硅酸盐所集成计算材料中心所创新项目(2020年度)

Centimeter-sized Cs₃Cu₂I₅ Single Crystal: Synthesized by Low-cost Solution Method and Optical and Scintillation Properties

XU Tingting¹^,²(), LI Yunyun²(), WANG Qian²^,³, WANG Jingkang²^,⁴, REN Guohao², SUN Dazhi¹, WU Yuntao²()

1. College of Chemistry and Materials Science, Shanghai Normal University, Shanghai 200234, China
2. Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China
3. School of Materials Science and Engineering, Shanghai University, Shanghai 200444, China
4. School of Materials and Chemistry, University of Shanghai for Science and Technology, Shanghai 200082, China

Received:2022-01-18 Revised:2022-02-14 Published:2022-10-20 Online:2022-07-08
Contact: WU Yuntao, professor. E-mail: ytwu@mail.sic.ac.cn;
LI Yunyun, PhD. E-mail: liyunyun@mail.sic.ac.cn
About author:XU Tingting (1997-), female, Master candidate. E-mail: chris1183047422@163.com
Supported by:
National Natural Science Foundation of China(12005288);National Natural Science Foundation of China(11975303);National Natural Science Foundation of China(11775290);Shanghai Municipal Natural Science Foundation(20ZR1473900);Shanghai Municipal Natural Science Foundation(21TS1400100);Innovation Project of the Center for Integrated Computational Materials of Shanghai Institute of Ceramics(2020)

摘要/Abstract

摘要：

近年来, 拥有高发光量子效率的低维钙钛矿/类钙钛矿结构金属卤化物在辐射探测领域展现出潜在的应用前景。本工作利用反溶剂扩散法生长了高光学质量的厘米级尺寸零维结构Cs₃Cu₂I₅单晶, 并系统研究了其光学吸收、透过、光致激发和发射、时间分辨光致发光、X射线辐照发光、余辉、热释光以及伽马射线探测性能。溶液法制备的Cs₃Cu₂I₅晶体的光学带隙为3.68 eV。在X射线激发下, Cs₃Cu₂I₅单晶的蓝光发射峰位于448 nm, 来源于自陷激子发光。闪烁衰减时间主分量为947 ns (96%)。Cs₃Cu₂I₅单晶的余辉水平与商用BGO晶体相当。此外, 该晶体作为伽马射线闪烁体也表现出29000 photons/MeV的高光产额, 与熔体法制备的Cs₃Cu₂I₅晶体闪烁性能相当。本研究证实了低成本制备高性能Cs₃Cu₂I₅闪烁晶体的可行性。

关键词: 零维钙钛矿, 闪烁体, Cs₃Cu₂I₅单晶, 反溶剂扩散法, 布里奇曼法

Abstract:

In recent years, low-dimensional metal halide perovskites/quasi-perovskites with high photoluminescence quantum yield have shown potential application prospects in nuclear radiation detection. In this paper, centimeter- sized zero-dimensional perovskite Cs₃Cu₂I₅ single crystals with high optical quality was grown by the anti solvent diffusion method. The optical absorption, transmittance photoluminescence excitation (PLE) and emission (PL), time-resolved photoluminescence, X-ray excited radioluminescence (XEL), afterglow, thermoluminescence (TL) and γ-ray detection performance of Cs₃Cu₂I₅ single crystals were comprehensively investigated. The optical bandgap of as-prepared Cs₃Cu₂I₅ single crystals is 3.68 eV. Under the excitation of X-ray, Cs₃Cu₂I₅single crystals show blue emission peaking at 448 nm originated from self-trapped exciton emission, and the principal scintillation decay time is 947 ns (96%). The afterglow level of Cs₃Cu₂I₅ single crystals is comparable to that of commercial BGO crystal. In addition, Cs₃Cu₂I₅single crystals exhibit a high light yield of 29000 photons/MeV as γ-ray scintillators, and their scintillation properties are comparable to that of Cs₃Cu₂I₅ single crystals prepared by the melt growth method. Therefore, this work demonstrates the feasibility of low-cost crystal growth of high-performance Cs₃Cu₂I₅ single crystals.

Key words: zero-dimensional perovskites, scintillators, Cs₃Cu₂I₅ single crystal, anti-solvent diffusion method, Bridgman method

中图分类号:

O782

徐婷婷, 李云云, 王谦, 王京康, 任国浩, 孙大志, 吴云涛. 低成本溶液法制备厘米级Cs₃Cu₂I₅单晶及其闪烁发光性能[J]. 无机材料学报, 2022, 37(10): 1129-1134.

XU Tingting, LI Yunyun, WANG Qian, WANG Jingkang, REN Guohao, SUN Dazhi, WU Yuntao. Centimeter-sized Cs₃Cu₂I₅ Single Crystal: Synthesized by Low-cost Solution Method and Optical and Scintillation Properties[J]. Journal of Inorganic Materials, 2022, 37(10): 1129-1134.

图/表 4

图1 用反相溶剂扩散法生长Cs3Cu2I5晶体示意图

Fig. 1 Schematic diagram of Cs3Cu2I5 crystal grown by anti, solvent diffusion method

图2 Cs3Cu2I5晶体照片和结构

Fig. 2 Photographs and structures of Cs3Cu2I5 crystals (a-b) Photographs of millimeter-sized rod-like Cs3Cu2I5 crystals and centimeter-sized bulk Cs3Cu2I5 crystals grown by solution method under sunlight and 254 nm ultraviolet light; (c) Photographs of Cs3Cu2I5 crystals grown by solution method for comparative study; (d) Photographs of Cs3Cu2I5 crystals grown by melt method for comparative study; (e) Structure of [Cu2I5]3- where blue and purple spheres represent Cu and I atoms, respectively; (f) X-ray powder diffraction (XRD) pattern of crystals grown by solution method

图3 Cs3Cu2I5晶体的光学性能

Fig. 3 Optical properties of Cs3Cu2I5 crystals (a) Absorption spectra of Cs3Cu2I5 crystals grown by solution method; (b) Transmittance spectra of Cs3Cu2I5 crystals grown by solution method; (c) Photoluminescence excitation (PLE) and emission (PL) spectra of Cs3Cu2I5 crystals grown by solution method; (d) PL and PLE contour mappings of Cs3Cu2I5 crystals grown by solution method; (e) Photoluminescence decay profiles of Cs3Cu2I5 crystals grown by solution method when λex=308 nm and λem=448 nm excited by nanoLED

图4 Cs3Cu2I5晶体的闪烁性能

Fig. 4 Scintillation properties of Cs3Cu2I5 crystals (a) X-ray excited RL spectra of Cs3Cu2I5 crystals grown by solution method and melt method with BGO as reference sample; (b) X-ray afterglow curves of Cs3Cu2I5 grown by solution method and melt method compared with that of BGO and CsI:Tl; (c) Thermoluminescence glow curves of Cs3Cu2I5 grown by solution method and melt method compared with that of CsI:Tl; (d) Pulse height spectra of Cs3Cu2I5 grown by solution method and melt method under 137Cs gamma-ray radiation as well as that of BGO; (e) Scintillation decay profiles of Cs3Cu2I5 grown by solution method and melt method under 137Cs gamma-ray radiation===Colorful figures are available on website

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低成本溶液法制备厘米级Cs₃Cu₂I₅单晶及其闪烁发光性能

Centimeter-sized Cs₃Cu₂I₅ Single Crystal: Synthesized by Low-cost Solution Method and Optical and Scintillation Properties

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