Zr4+共掺对Cs2LaLiBr6:Ce晶体的中子/伽马甄别性能的影响

doi:10.15541/jim20230543

无机材料学报 ›› 2024, Vol. 39 ›› Issue (5): 539-546.DOI: 10.15541/jim20230543 CSTR: 32189.14.10.15541/jim20230543

所属专题：【信息功能】透明与闪烁陶瓷（202506）；【结构材料】核用陶瓷（202506）

Zr⁴⁺共掺对Cs₂LaLiBr₆:Ce晶体的中子/伽马甄别性能的影响

郑中秋¹(), 魏钦华¹(), 童宇枫¹^,², 唐高¹, 尹航¹, 秦来顺¹

1.中国计量大学材料与化学学院, 杭州 310018
2.中国科学院上海硅酸盐研究所, 人工晶体研究中心, 上海 201899

收稿日期:2023-11-27 修回日期:2023-12-21 出版日期:2024-05-20 网络出版日期:2024-01-08
通讯作者: 魏钦华, 副教授. E-mail: weiqinhua@cjlu.edu.cn.
作者简介:郑中秋(1999-), 女, 硕士研究生. E-mail: 2668971946@qq.com
基金资助:
国家自然科学基金(12275262);国家重点研发计划项目(2022YFB3503600);浙江省自然科学基金(LGG22E020001);浙江省自然科学基金(Z23E020002)

Effect of Zr⁴⁺ Co-doping on Neutron/Gamma Discrimination of Cs₂LaLiBr₆:Ce Crystals

ZHENG Zhongqiu¹(), WEI Qinhua¹(), TONG Yufeng¹^,², TANG Gao¹, YIN Hang¹, QIN Laishun¹

1. College of Materials and Chemistry, China Jiliang University, Hangzhou 310018, China
2. Artificial Crystals Research Center, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 201899, China

Received:2023-11-27 Revised:2023-12-21 Published:2024-05-20 Online:2024-01-08
Contact: WEI Qinhua, associate professor. E-mail: weiqinhua@cjlu.edu.cn
About author:ZHENG Zhongqiu (1999-), female, Master candidate. E-mail: 2668971946@qq.com
Supported by:
National Natural Science Foundation of China(12275262);National Key R&D Program of China(2022YFB3503600);Natural Science Foundation of Zhejiang(LGG22E020001);Natural Science Foundation of Zhejiang(Z23E020002)

摘要/Abstract

摘要：

中子探测技术广泛用于国土安全、核材料安全检测以及高能物理等领域, 由于³He资源紧缺, 近年来急需开发出能够同时甄别中子/伽马的新型闪烁晶体, Cs₂LaLiBr₆:Ce(CLLB:Ce)晶体具有良好的中子/伽马甄别能力、优异的能量分辨率以及高的光输出, 但其中子/伽马甄别性能有待进一步提高。本研究采用垂直布里奇曼法成功生长了Zr⁴⁺共掺杂的CLLB:Ce晶体。通过不同表征手段研究了Zr⁴⁺共掺杂CLLB:Ce晶体的结构和组分, 结果表明Zr⁴⁺成功掺入基质材料且对基质晶体结构不产生明显的影响, Zr⁴⁺共掺杂后没有产生新的发光中心, 紫外衰减时间约为27.0 ns, 仍具有较快的荧光衰减。Zr⁴⁺共掺杂CLLB:Ce晶体的品质因子(Figure of Merit, FOM)从1.2提高到1.5, 表明其中子/伽马甄别能力得到改善。结合热稳定性和闪烁衰减时间, 探讨了衰减时间对FOM的影响机制, Zr⁴⁺共掺杂可以抑制浅电子陷阱和V_k中心, 减少电子捕获和脱陷过程, 使Ce³⁺直接捕获的概率大大增加, 从而表现出更快的衰减速率。本研究显示, Zr⁴⁺共掺杂CLLB:Ce晶体在中子/伽马探测领域具有潜在的应用前景。

关键词: 闪烁晶体, CLLB:Ce, 中子/伽马甄别, 钾冰晶石结构

Abstract:

Neutron detection technology is widely used in homeland security, nuclear material security detection, and high energy physics, etc. Due to the shortage of ³He resources, it is urgent to develop a novel scintillator that can discriminate neutron and gamma. The Cs₂LaLiBr₆:Ce (CLLB:Ce) crystal has good neutron/gamma discrimination capacity, excellent energy resolution and high light yield, but its neutron/gamma discrimination performance needs further improvement. Here, the CLLB:Ce crystals co-doped with Zr⁴⁺were grown successfully by the vertical Bridgman method. The results of different characterization methods prove that the Zr⁴⁺ was successfully doped into the matrix and did not effect on the structure of host. Meanwhile, no new luminescence center was generated after Zr⁴⁺ doping. The UV decay time is about 27 ns, presenting a fast fluorescence decay. Figure of merit (FOM) of CLLB:Ce crystal is enhanced from 1.2 to 1.5 by co-doping Zr⁴⁺, which means that the neutron/gamma discrimination performance of CLLB:Ce crystals is improved. Combined with the thermal stability and scintillation decay time, relationship between decay time and FOM was also analyzed. The co-doping of Zr⁴⁺ can inhibit shallow electron trap and V_K centers, reduce electron trapping-detrapping process, and greatly increase the probability of Ce³⁺ direct capturing electron, which results in a shorter decay time. Data from this study indicate that the CLLB:Ce crystals exhibit a huge application prospect in the field of neutron/gamma detection.

Key words: scintillation crystal, CLLB:Ce, neutron/gamma discrimination, elpasolite structure

中图分类号:

TQ174

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.

ZHENG Zhongqiu, WEI Qinhua, TONG Yufeng, TANG Gao, YIN Hang, QIN Laishun. Effect of Zr⁴⁺ Co-doping on Neutron/Gamma Discrimination of Cs₂LaLiBr₆:Ce Crystals[J]. Journal of Inorganic Materials, 2024, 39(5): 539-546.

图/表 10

图1 晶体样品的实物照片(a)和XRD图谱(b)

Fig.1 Pictures (a) and XRD patterns (b) of crystal samples (a) Grown crystal with a size of ϕ10 mm×50 mm and machined crystal sample with a size of ϕ10 mm×5 mm, and (b) XRD patterns of different samples

表1 ICP-MS结果与理论数据的掺杂浓度对比

Table 1 Doping concentration comparison of ICP-MS results and theoretical data

Sample	Co-doping element concentration/(mg·kg^-1)	Actual concentratio/% (in mole)	Raw concentration/% (in mole)
CLLB (Ce, Zr)	990.4075	0.101	0.1

图2 共掺杂晶体样品的XPS谱图

Fig. 2 XPS spectra of co-doped crystal samples (a) Total XPS spectrum of co-doped crystal sample; (b) Fine XPS spectrum of Zr4+

图3 PLE和PL光谱图、X射线激发发射光谱图和PL衰减时间曲线

Fig. 3 PLE and PL spectra, X-ray excitation emission spectra and PL decay time curves (a) PLE and PL spectra; (b) X-ray excitation emission spectra; (c, d) PL decay time curves (λex=375 nm, λem=388 nm) of CLLB:1%Ce and CLLB:1%Ce,0.1%Zr samples; Colorful figures are available on website

图4 CLLB:1%Ce,0.1%Zr的PL光谱图

Fig. 4 PL spectra of CLLB:1%Ce,0.1%Zr (a) PL spectra of CLLB:1%Ce,0.1%Zr at 80-450 K; (b) Normalized curves; (c) Relationship between comprehensive emission intensity and temperature; (d) Fitting line of activation energy; Colorful figures are available on website

图5 脉冲高度谱图和闪烁衰减时间曲线

Fig. 5 Pulse height spectra and scintillation decay time curves (a, b) Pulse height spectra of CLLB:1%Ce, CLLB:1%Ce,0.1%Zr and NaI:Tl standard sample; (c, d) Scintillation decay time curves of CLLB:1%Ce,0.1%Zr (c) and CLLB:1%Ce (d); Colorful figures are available on website

图6 脉冲形状甄别图谱(左)和能谱(右)

Fig. 6 PSD patterns (left) and energy spectra (right) (a) CLLB:1%Ce; (b) CLLB:1%Ce,0.1%Zr

图7 闪烁衰减时间曲线

Fig. 7 Scintillation decay time fitting curves (a) CLLB:1%Ce; (b) CLLB:1%Ce,0.1%Zr; Colorful figures are available on website

表2 CLLB晶体的衰减时间和成分比例

Table 2 Decay time and component proportion of CLLB crystal

Sample	Particle	Fast component/ns	Proportion of fast component photons/%	Slow component/ns	Proportion of slow component photons/%
CLLB:Ce	Neutron	127	94	747	6
CLLB:Ce	Gamma	136	94	789	6
CLLB (Ce, Zr)	Neutron	101	99	540	1
CLLB (Ce, Zr)	Gamma	105	99	570	1

图8 闪烁机理示意图

Fig. 8 Schematic representation of scintillation mechanism CB: Conduction band; VB: Valence band

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Zr⁴⁺共掺对Cs₂LaLiBr₆:Ce晶体的中子/伽马甄别性能的影响

Effect of Zr⁴⁺ Co-doping on Neutron/Gamma Discrimination of Cs₂LaLiBr₆:Ce Crystals

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