填充LiF-CaF2:Eu共晶粉体的有机-无机复合闪烁体制备与表征

doi:10.15541/jim20250163

无机材料学报 ›› 2026, Vol. 41 ›› Issue (2): 201-207.DOI: 10.15541/jim20250163 CSTR: 32189.14.jim20250163

填充LiF-CaF₂:Eu共晶粉体的有机-无机复合闪烁体制备与表征

周琦¹^,²(), 李翔², 张开辉¹^,², 王泽亮³, 邓明雪², 贾文宝³, 王珂¹(), 陈俊锋¹^,²()

1.上海理工大学材料与化学学院, 上海 200093
2.中国科学院上海硅酸盐研究所, 功能晶体与器件全国重点实验室, 上海 201899
3.南京航空航天大学材料科学与技术学院, 南京 211106

收稿日期:2025-04-18 修回日期:2025-05-23 出版日期:2025-07-16 网络出版日期:2025-07-16
通讯作者: 陈俊锋, 研究员. E-mail: jfchen@mail.sic.ac.cn;
王珂, 副教授. E-mail: wangk2017@usst.edu.cn
作者简介:周琦(2000-), 男, 硕士研究生. E-mail: zqis97@163.com
基金资助:
中国科学院战略性先导科技专项(XDA25030600);国家重点研发计划(2022YFB3503902);强脉冲辐射环境模拟与效应国家重点实验室开放课题(SKLIPR1714)

Organic-Inorganic Composite Scintillators Loaded with LiF-CaF₂:Eu Eutectic Powder: Preparation and Characterization

ZHOU Qi¹^,²(), LI Xiang², ZHANG Kaihui¹^,², WANG Zeliang³, DENG Mingxue², JIA Wenbao³, WANG Ke¹(), CHEN Junfeng¹^,²()

1. School of Materials and Chemistry, University of Shanghai for Science and Technology, Shanghai 200093, China
2. State Key Laboratory of Functional Crystals and Devices, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 201899, China
3. College of Materials Science and Technology, Nanjing University of Aeronautics and Astronautics, Nanjing 211106, China

Received:2025-04-18 Revised:2025-05-23 Published:2025-07-16 Online:2025-07-16
Contact: CHEN Junfeng, professor. E-mail: jfchen@mail.sic.ac.cn;
WANG Ke, associate professor. E-mail: wangk2017@usst.edu.cn
About author:ZHOU Qi (2000-), male, Master candidate. E-mail: zqis97@163.com
Supported by:
Strategic Priority Research Program of Chinese Academy of Sciences(XDA25030600);National Key R&D Program of China(2022YFB3503902);Opening Program of State Key Lab of Intense Pulsed Radiation Simulation and Effect(SKLIPR1714)

摘要/Abstract

摘要：

热中子技术在核物理、核安全、核能开发、工业无损检测及国土安全等各个领域应用广泛, 亟需发展高效的热中子探测闪烁体。已商业化的许多热中子探测闪烁体, 在性能和生产成本方面仍面临诸多发展挑战。由于有机-无机复合闪烁体具有制备简易、成本低廉、组分组合灵活等突出优势, 近期受到越来越多的关注。本研究通过将固相合成的LiF-CaF₂:Eu共晶粉体, 以质量分数0~20%的含量均匀分散在有机聚苯乙烯基体中, 成功制备出一系列热中子敏感的有机-无机复合闪烁体, 分析了合成的LiF-CaF₂:Eu共晶粉体的X射线衍射图谱、扫描电子显微镜形貌和元素分布, 评价了该系列有机-无机复合闪烁体的辐射发光和光学透射特性。采用镉差法和脉冲形状甄别技术, 较为系统地评价了填充天然丰度Li的LiF-CaF₂:Eu和⁶Li富集度为95%的⁶LiF-CaF₂:Eu共晶粉体复合闪烁体的热中子探测性能。与填充LiF-CaF₂:Eu混合粉体相比, 填充LiF-CaF₂:Eu共晶粉体的复合闪烁体具有更好的光透过性能和更高的辐射发光强度。随着LiF-CaF₂:Eu共晶粉体填充量的增加, 复合闪烁体的辐射发光强度逐渐升高。增大⁶Li丰度能有效提高热中子探测效率, 复合闪烁体的热中子/伽马甄别品质因子可达到2.64。作为一种具有较好应用潜力的新型闪烁体, 填充LiF-CaF₂:Eu共晶粉体的复合闪烁体具有较为优异的热中子探测效率和热中子/伽马甄别能力。

关键词: 复合闪烁体, 热中子探测, LiF-CaF₂:Eu, 共晶, 甄别

Abstract:

Thermal neutron technology is widely applied in many fields, such as homeland security, nuclear non-proliferation, nuclear energy development, industrial nondestructive testing, and nuclear physics research. However, existing commercially available thermal neutron detection materials currently still face many developmental challenges in terms of detection performance and manufacturing costs. In this study, a series of organic-inorganic composite scintillators sensitive to thermal neutrons was prepared via solid-state reaction by uniformly dispersing 0-20% (in mass) of LiF-CaF₂:Eu eutectic powder in organic polystyrene matrixes. X-ray diffraction patterns, scanning electron microscope morphologies, and elemental distributions of the synthesized LiF-CaF₂:Eu eutectic powder were analyzed. The radioluminescence and optical transmittance of the prepared composite scintillators were evaluated, and comparisons were made between LiF-CaF₂:Eu eutectic powder and LiF-CaF₂:Eu mixed powder as inorganic additives. Using cadmium difference method and pulse shape discrimination technologies, the thermal neutron detection performance of composite scintillators loaded with LiF-CaF₂:Eu (natural Li abundance) and ⁶LiF-CaF₂:Eu (95% enriched ⁶Li) eutectic powder was systematically investigated. Compared to composites filled with LiF-CaF₂:Eu mixed powder, those filled with LiF-CaF₂:Eu eutectic powder exhibited better optical transmittance and higher radioluminescence intensity, which increased with the addition of more eutectic powder. Increasing the abundance of ⁶Li can effectively improve thermal neutron detection efficiency, and figure of merit for thermal neutron/gamma discrimination in composite scintillators can reach 2.64. As a promising novel scintillator for thermal neutron detection, the composite scintillators loaded with LiF-CaF₂:Eu eutectic powder show excellent thermal neutron detection and thermal neutron/gamma discrimination.

Key words: composite scintillator, thermal neutron detection, LiF-CaF₂:Eu, eutectic, discrimination

中图分类号:

TL812

周琦, 李翔, 张开辉, 王泽亮, 邓明雪, 贾文宝, 王珂, 陈俊锋. 填充LiF-CaF₂:Eu共晶粉体的有机-无机复合闪烁体制备与表征[J]. 无机材料学报, 2026, 41(2): 201-207.

ZHOU Qi, LI Xiang, ZHANG Kaihui, WANG Zeliang, DENG Mingxue, JIA Wenbao, WANG Ke, CHEN Junfeng. Organic-Inorganic Composite Scintillators Loaded with LiF-CaF₂:Eu Eutectic Powder: Preparation and Characterization[J]. Journal of Inorganic Materials, 2026, 41(2): 201-207.

图/表 6

图1 热中子探测装置示意图

Fig. 1 Schematic diagram of thermal neutron response measurement setup

图2 (a) LiF-CaF2:Eu和6LiF-CaF2:Eu共晶粉体的XRD图谱; (b) LiF-CaF2复合闪烁体的拉曼光谱

Fig. 2 (a) XRD patterns of LiF-CaF2:Eu and 6LiF-CaF2:Eu eutectic powders; (b) Raman spectra of LiF-CaF2 composite scintillators

图3 LiF/CaF2:Eu混合粉体和LiF-CaF2:Eu共晶粉体的SEM照片和元素分布图

Fig. 3 SEM images and elemental mappings of the synthesized LiF/CaF2:Eu mixed powder and LiF-CaF2:Eu eutectic powder (a) SEM image and (b-d) EDS analyses of LiF/CaF2:Eu mixed powder; (e) Schematic diagram of neutron detection using LiF/CaF2:Eu mixed powder; (f) SEM image and (g-i) EDS analyses of LiF-CaF2:Eu eutectic powder;(j) Schematic diagram of neutron detection using LiF-CaF2:Eu eutectic powder. Colorful figures are available on website

图4 (a~e) 20%(质量分数)LiF-CaF2:Eu共晶粉体与(f~j) 20%(质量分数)LiF/CaF2:Eu混合粉体填充的复合闪烁体的SEM-EDS分析

Fig. 4 SEM-EDS analyses of composite scintillators loaded with (a-e) 20% (in mass) LiF-CaF2:Eu eutectic powder and (f-j) 20% (in mass) LiF/CaF2:Eu mixed powder Colorful figures are available on website

图5 LiF-CaF2和LiF/CaF2复合闪烁体的光学透过谱图和XEL光谱图

Fig. 5 Optical transmittance spectra and XEL spectra of LiF-CaF2 and LiF/CaF2 composite scintillators (a) Optical transmittance spectra of 20% (in mass) LiF-CaF2 and LiF/CaF2 composite scintillators; (b) XEL spectra of 20% (in mass) LiF-CaF2 and LiF/CaF2 composite scintillators; (c) Optical transmittance spectra of 0-20% (in mass) LiF-CaF2 composite scintillators; (d) XEL spectra of 5%-20% LiF-CaF2 composite scintillators. Colorful figures are available on website

图6 LiF-CaF2:Eu共晶粉体填充的复合闪烁体的热中子响应和热中子/伽马甄别性能

Fig. 6 Thermal neutron response and thermal neutron/gamma discrimination properties of composite scintillator loaded with LiF-CaF2:Eu eutectic powder (a) Schematic diagram of neutron detection process in LiF-CaF2:Eu eutectic powder; (b) Pulse height spectra under irradiation of 241Am-Be source; (c, d) 1D PSD histograms with and without Cd shielding; (e, f) 2D PSD scatter plots

参考文献 21

[1]	VAN DER ENDE B M, LI L, GODIN D, et al. Stand-off nuclear reactor monitoring with neutron detectors for safeguards and non- proliferation applications. Nature Communications, 2019, 10: 1959. DOI
[2]	SOLTES J, VIERERBL L, LAHODOVA Z, et al. Thermal neutron filter design for the neutron radiography facility at the LVR-15 reactor. IEEE Transactions on Nuclear Science, 2016, 63(3): 1640. DOI URL
[3]	CIEŚLAK M, GAMAGE K, GLOVER R. Critical review of scintillating crystals for neutron detection. Crystals, 2019, 9(9): 480. DOI URL
[4]	PIETROPAOLO A, ANGELONE M, BEDOGNI R, et al. Neutron detection techniques from μeV to GeV. Physics Reports, 2020, 875: 1. DOI URL
[5]	KOUZES R T. The ³He supply problem. Pacific Northwest National Lab, 2009, 18388: 1.
[6]	KAMADA K, CHIBA H, YOSHINO M, et al. Growth and scintillation properties of Eu doped LiSrI₃/LiI eutectics. Optical Materials, 2017, 68: 70. DOI URL
[7]	HOU Y Y, GUI Q, ZHANG C S, et al. Scintillation properties of Cs₂LiYCl₆:Ce crystal for neutron and gamma dual detection. Journal of Synthetic Crystals, 2021, 50(10): 1933.
[8]	ZHANG X, KANG Z, CAI Z, et al. Study on the segregation behavior of Ce in CLYC crystals. Journal of Crystal Growth, 2021, 573: 126308.
[9]	HE J Y, LI W, WEI Q H, et al. Growth and properties of 1-inch Cs₂LiLaBr₆:Ce scintillation crystal. Journal of Synthetic Crystals, 2021, 50(10): 1879.
[10]	WOOLF R S, PHLIPS B F, WULF E A. Characterization of the internal background for thermal and fast neutron detection with CLLB. Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, 2016, 838: 147.
[11]	WU C, TANG B, SUN Z J, et al. A study of ZnS(Ag)/⁶LiF with different mass ratios. Radiation Measurements, 2013, 58: 128. DOI URL
[12]	STAVE S, BLISS M, KOUZES R, et al. LiF/ZnS neutron multiplicity counter. Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, 2015, 784: 208. DOI URL
[13]	BEDOGNI R, LEGA A, MENZIO L, et al. A numerical model to predict pulse height distribution of alpha particles in thin ZnS(Ag) scintillators. Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, 2021, 990: 164991. DOI URL
[14]	WATANABE K, MITSUBOSHI N, ISHIKAWA A, et al. Basic study on a LiF-Eu:CaF₂ mixed powder neutron scintillator. Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, 2020, 954: 161244. DOI URL
[15]	KAWAGUCHI N, KIMURA H, TAKEBUCHI Y, et al. Dosimetric properties of non-doped LiF/CaF₂ eutectic. Radiation Measurements, 2020, 132: 106254. DOI URL
[16]	KAWAGUCHI N, FUKUDA K, YANAGIDA T, et al. Fabrication and characterization of large size ⁶LiF/CaF₂:Eu eutectic composites with the ordered lamellar structure. Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, 2011, 652: 209. DOI URL
[17]	KAWANO N, KAWAGUCHI N, FUKUDA K, et al. Scintillation and dosimeter properties of ⁶LiF/CaF₂:Eu eutectic composites. Journal of Materials Science: Materials in Electronics, 2018, 29(11): 8964. DOI
[18]	LI X, DENG M, SHI Y, et al. Bulk polystyrene-BaF₂ composite scintillators for highly efficient radiation detection. Crystals, 2023, 13(9): 13. DOI URL
[19]	LI P, CHENG W, ZHOU Y, et al. Large scale BN‐perovskite nanocomposite aerogel scintillator for thermal neutron detection. Advanced Materials, 2023, 35(25): 2209452. DOI URL
[20]	TAUDUL B, TIELENS F, CALATAYUD M. Raman characterization of plastics: a DFT study of polystyrene. The Journal of Physical Chemistry B, 2024, 128(17): 4243.
[21]	TROJAN-PIEGZA J, GLODO J, SARIN V K. CaF₂(Eu²⁺):LiF-structural and spectroscopic properties of a new system for neutron detection. Radiation Measurements, 2010, 45(2): 163. DOI URL

填充LiF-CaF₂:Eu共晶粉体的有机-无机复合闪烁体制备与表征

Organic-Inorganic Composite Scintillators Loaded with LiF-CaF₂:Eu Eutectic Powder: Preparation and Characterization

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 6

参考文献 21

相关文章 9

编辑推荐

Metrics

本文评价

[1]	郑中秋, 魏钦华, 童宇枫, 唐高, 尹航, 秦来顺. Zr⁴⁺共掺对Cs₂LaLiBr₆:Ce晶体的中子/伽马甄别性能的影响[J]. 无机材料学报, 2024, 39(5): 539-546.
[2]	刘海方, 苏海军, 申仲琳, 姜浩, 赵迪, 刘园, 张军, 刘林, 傅恒志. 激光增材制造超高温氧化物共晶陶瓷研究进展[J]. 无机材料学报, 2022, 37(3): 255-266.
[3]	孙鲁超, 周翠, 杜铁锋, 吴贞, 雷一明, 李家麟, 苏海军, 王京阳. 光悬浮区熔定向凝固Al₂O₃/Er₃Al₅O₁₂和Al₂O₃/Yb₃Al₅O₁₂共晶陶瓷的制备与性能研究[J]. 无机材料学报, 2021, 36(6): 652-658.
[4]	于建政, 张军, 苏海军, 宋衎, 刘林, 傅恒志. 激光双面区熔Al₂O₃/Y₃Al₅O₁₂共晶自生复合陶瓷的制备与表征[J]. 无机材料学报, 2012, 27(8): 843-848.
[5]	邓杨芳, 张军, 苏海军, 宋衎, 刘林, 傅恒志. 激光区熔Al₂O₃/Er₃Al₅O₁₂共晶自生复合陶瓷的组织与断裂韧性[J]. 无机材料学报, 2011, 26(8): 841-846.
[6]	李家科,刘磊,刘意春,张文龙,胡文彬. Ti-Si共晶钎料的制备及其对SiC陶瓷可焊性[J]. 无机材料学报, 2009, 24(1): 204-208.
[7]	崔春娟,张军,苏海军,王红,刘林,傅恒志. Si-TaSi₂共晶自生复合场发射材料的定向凝固组织特征[J]. 无机材料学报, 2007, 22(5): 1019-1023.
[8]	白玉霞,王淑兰,厉英. NaOH-KOH熔盐中合成BaTiO₃反应过程电导率的变化[J]. 无机材料学报, 2002, 17(3): 609-612.
[9]	潘振甦,张惠丰,郭景坤. 定向凝固共晶多相复合陶瓷的研究现状[J]. 无机材料学报, 1999, 14(4): 513-519.