Sm2+-Ce3+共掺CLLB闪烁晶体生长及发光性能研究

doi:10.16553/j.cnki.issn1000-985x.2025.0192

摘要/Abstract

摘要： 二价钐离子（Sm²⁺）掺杂卤化物闪烁体表现出优异的近红外闪烁性能。本文采用垂直布里奇曼法成功生长出不同浓度Sm²⁺共掺杂的Cs₂LiLaBr₆∶Ce³⁺，Sm²⁺闪烁晶体，详细研究了它们的发光性能、能量传递及缺陷情况。通过ICP-MS方式估算出Sm²⁺在CLLB基质中的分凝系数约为2.0。紫外-可见荧光光谱发现Ce³⁺、Sm²⁺共掺的Cs₂LiLaBr₆晶体呈现390、420和770 nm三个发射峰，分别归属于Ce³⁺和Sm²⁺的5d-4f电子跃迁发射，通过Sm²⁺的共掺成功获得近红外发光。荧光量子效率测试结果表明，随Sm²⁺掺杂浓度的增加，晶体的荧光量子效率呈现先增加后下降的趋势，掺杂浓度（原子数分数）为3%Sm²⁺时，荧光量子效率达到最高98.5%。Sm²⁺和Ce³⁺的光谱重叠及衰减时间结果表明Ce³⁺-Sm²⁺之间存在能量传递，且在传递过程中存在较多的能量损失。最后，基于不同离子掺杂浓度晶体样品的热释光（TL）曲线和X射线激发发射（XEL）结果研究了Sm²⁺掺杂对基质缺陷的影响，并讨论了其发光机理。

关键词: Sm²⁺掺杂; Cs₂LiLaBr₆∶Ce³⁺; Sm²⁺; 垂直布里奇曼法; 能量传递; 闪烁晶体; 发光性能

Abstract: Due to the better matched with the spectral response of silicon-based photodetectors，offering a promising route toward compact，highly sensitive radiation detection，the near infrared scintillators have attracted much interest. The Sm²⁺ activated halide scintillators with emission wavelength of 700 nm to 900 nm have been developed. However，the strategy of single Sm²⁺ doping have some disadvantage of low light out and worse energy resolution. Usually，the co-doping is an effect method to improve the scintillation properties by adjusting the energy transfer efficiency，defect structure and quantity.In this work，the Cs₂LiLaBr₆∶Ce³⁺ with excellent scintillation properties is chosen as a host，and the Sm²⁺ is introduced as a near infrared emitting center to construct an energy transfer route from Ce³⁺ to Sm²⁺. Cs₂LiLaBr₆∶Ce³⁺，Sm²⁺ single crystals with varied Sm²⁺ concentrations were successfully grown by the vertical Bridgman method. The axial distribution and segregation behavior of Sm²⁺ were quantitatively evaluated using ICP-MS，yielding an effective segregation coefficient of about 2.0，which indicates a pronounced tendency of Sm enrichment during crystal growth. Optical properties and energy transfer were investigated by steady state photoluminescence，time resolved decay measurements，and photoluminescence quantum yield. In addition，X-ray excited luminescence and thermoluminescence were employed to probe defect related trapping and radiative processes.The co-doped crystals exhibit three characteristic emission bands centered at approximately 390，420 and 770 nm. The two visible bands originate from Ce³⁺ 5d to 4f transitions，while the near infrared band is assigned to Sm²⁺ 5d-4f emission，demonstrating successful introduction of near infrared luminescence for the Cs₂LiLaBr₆ matrix. The spectral overlap between Ce³⁺ emission and Sm²⁺ excitation is observed，together with the evolution of decay dynamics，provide strong evidence for energy transfer from Ce³⁺ to Sm²⁺. Notably，a number of energies are loss during the energy transfer pathway of Ce-Sm，implying the presence of competing nonradiative channels and trap assisted dissipation. The photoluminescence quantum yield increased firstly and then decreased as Sm²⁺ concentration raised. It reaches a maximum value of about 98.5% when the Sm²⁺ concentration is 3%. The concentration quenching is happened for the higher doping concentration. Thermoluminescence and X-ray excited luminescence further reveal that the Sm²⁺ co-doping reconstructs the defect energy of the host，altering the trap depth and recombination pathways.Overall，this study establishes a systematic design and characterization framework for Ce³⁺ sensitized Sm²⁺ near infrared emission in the Cs₂LiLaBr₆ host，provides quantitative insight into dopant segregation，and clarifies the coupled roles of energy transfer losses and defect evolution. These findings offer practical guidance for optimizing near infrared halide scintillators intended for silicon-based readout and advanced radiation detection applications.

Key words: Sm²⁺ doping; Cs₂LiLaBr₆∶Ce³⁺; Sm²⁺; vertical Bridgman method; energy transfer; scintillation crystal; luminescence property

中图分类号:

O782

王浩涵, 魏钦华, 舒昶, 尹航, 唐高, 张素银, 秦来顺. Sm²⁺-Ce³⁺共掺CLLB闪烁晶体生长及发光性能研究[J]. 人工晶体学报, 2026, 55(2): 201-210.

WANG Haohan, WEI Qinhua, SHU Chang, YIN Hang, TANG Gao, ZHANG Suyin, QIN Laishun. Growth and Luminescence Properties of Sm²⁺-Ce³⁺ Co-Doped CLLB Scintillation Crystals[J]. Journal of Synthetic Crystals, 2026, 55(2): 201-210.

图/表 9

图1 CLLB∶2%Ce3+，x%Sm2+晶体的照片（a）及其XRD图谱（b）

Fig.1 Crystal diagram of CLLB∶2%Ce3+，x%Sm2+ （a） and its XRD patterns （b）

图2 （a）CLLB∶2%Ce3+，x%Sm2+晶体XPS总图谱；（b）CLLB∶2%Ce3+，3%Sm2+中Cs+、La3+、Br-精细谱；（c）CLLB∶2%Ce3+，x%Sm2+晶体Sm2+精细谱；（d）CLLB∶2%Ce3+，x%Sm2+晶体Ce3+精细谱

Fig.2 （a） Survey XPS of CLLB∶2%Ce3+，x%Sm2+ crystal；（b） high-resolution XPS of Cs+，La3+，and Br- in CLLB∶2%Ce3+，3%Sm2+；（c） high-resolution XPS of Sm2+ in CLLB∶2%Ce3+，x%Sm2+ crystal；（d） high-resolution XPS of Ce3+ in CLLB∶2%Ce3+，x%Sm2+ crystal

图3 （a）晶体图片与所取位置；（b）Sm2+在晶体中的分凝

Fig.3 （a） Crystal image and selected sampling positions；（b） segregation of Sm2+ in crystal

表1 Sm2+在晶体中不同位置的浓度

Table 1 Concentrations of Sm2+ at different positions in crystal

Sample ID/cm	Sm²⁺ concentration in crystal/%	Relative solidification position （Z/L）
1 （0.00）	4.00	0
2 （0.08）	2.49	0.016
3 （0.33）	2.06	0.066
4 （0.50）	1.83	0.100
5 （0.67）	1.49	0.134
6 （1.17）	1.32	0.234
7 （1.67）	1.23	0.334
8 （2.17）	1.16	0.434
9 （2.67）	0.86	0.534
10 （3.67）	0.48	0.734

图4 （a）不同Sm2+浓度晶体的发射光谱（λex=360 nm）；（b）晶体的激发光谱，监测波长分别为390、420和770 nm；（c）CLLB∶2%Ce3+，3%Sm2+晶体的激发光谱（λem=770 nm）和发射光谱（λex=360 nm）；（d）晶体发射光谱（λex=420、390 nm）

Fig.4 （a） Emission spectra of crystals with different Sm2+ concentrations （λ??=360 nm）；（b） excitation spectra of crystals，monitored at wavelengths of 390，420，and 770 nm respectively；（c） excitation spectrum （λ?? = 770 nm） and emission spectrum （λ?? = 360 nm） of CLLB∶2%Ce3+，3%Sm2+ crystal；（d） emission spectra of crystal （λ??=420，390 nm）

图5 CLLB∶2%Ce3+，x%Sm2+晶体荧光衰减曲线

Fig.5 Fluorescence decay curves of CLLB∶2%Ce3+，x%Sm2+ crystals

图6 CLLB∶2%Ce3+，x%Sm2+晶体的PLQY测试结果

Fig.6 PLQY results of CLLB∶2%Ce3+，x%Sm2+ crystals

图7 CLLB∶2%Ce3+，x%Sm2+晶体的XEL结果，插图分别是Ce3+和Sm2+相关的发光峰的强度积分值占比

Fig.7 XEL results of CLLB∶2%Ce3+，x%Sm2+ crystals，insets is proportion of integrated intensity of Ce3+ and Sm2+ related emission peaks

图8 （a）CLLB∶2%Ce3+、CLLB∶2%Ce3+，1%Sm2+、CLLB∶2%Ce3+，3%Sm2+从100~400 K TL图谱；（b）CLLB∶Ce3+，Sm2+发光机理图

Fig.8 （a） TL spectra of CLLB∶2%Ce3+，CLLB∶2%Ce3+，1%Sm2+，and CLLB∶2%Ce3+，3%Sm2+ in temperature range from 100 K to 400 K；（b） luminescence mechanism diagram of CLLB∶Ce3+，Sm2+

参考文献 30

[1]	刘　波，陈　鸿，顾　牡，等. 闪烁体与光子人工微结构［J］. 物理，2014，43（4）：254-262.
	LIU B，CHEN H，GU M，et al. Scintillators boosted by nanophotonics［J］. Physics，2014，43（4）：254-262 （in Chinese）.
[2]	LIANG F，SMITH J. Characterization of CLLBC coupled to silicon photomultipliers［J］. IEEE Transactions on Nuclear Science，2020，67（6）：927-932.
[3]	MAO R H，ZHANG L Y，ZHU R Y. Optical and scintillation properties of inorganic scintillators in high energy physics［C］//2007 IEEE Nuclear Science Symposium Conference Record. October 26 - November 3，2007，Honolulu，HI，USA. IEEE，2007：2285-2291.
[4]	WANG Z H，DUJARDIN C，FREEMAN M S，et al. Needs，trends，and advances in scintillators for radiographic imaging and tomography［J］. IEEE Transactions on Nuclear Science，2023，70（7）：1244-1280.
[5]	侯玉欣，陈　明，杨春雷. X射线探测器的研究现状与展望［J］. 物理，2021，50（8）：526-533.
	HOU Y X，CHEN M，YANG C L. Present status and prospects of X-ray detectors［J］. Physics，2021，50（8）：526-533 （in Chinese）.
[6]	王晓莉，杨　蕾，侯越云. 中子/伽马双探测用稀土卤化物闪烁晶体的研究进展［J］. 人工晶体学报，2023，52（4）：671-677.
	WANG X L，YANG L，HOU Y Y. Research progress of rare earth halide scintillation crystals for neutron/gamma dual detection［J］. Journal of Synthetic Crystals，2023，52（4）：671-677 （in Chinese）.
[7]	岳　珂，徐瑚珊，梁晋洁，等. 基于GEANT4的CsI（Tl）闪烁体探测器的Monte Carlo模拟［J］. 原子核物理评论，2010，27（4）：445-449.
	YUE K，XU H S，LIANG J J，et al. Monte Carlo simulation of CsI（Tl） scintillator detector with GEANT4 ToolKit［J］. Nuclear Physics Review，2010，27（4）：445-449 （in Chinese）.
[8]	TONG Y F，WEI Q H，SONG R Q，et al. Achieving superior n/γ discrimination and luminescent thermal stability in Cs₂LiLaBr₆ single crystals by high concentration Ce³⁺ doping［J］. Crystal Growth & Design，2024，24（1）：514-521.
[9]	王京康，王承二，孙希磊，等. Li掺杂浓度对NaI∶Tl，Li晶体光学和闪烁性能的影响［J］. 人工晶体学报，2023，52（9）：1582-1588.
	WANG J K，WANG C E，SUN X L，et al. Influence of Li doping concentration on the optical and scintillation properties of NaI∶Tl，Li crystals［J］. Journal of Synthetic Crystals，2023，52（9）：1582-1588 （in Chinese）.
[10]	何君雨，李　雯，魏钦华，等. 1英寸Cs₂LiLaBr₆∶Ce闪烁晶体的生长及性能研究［J］. 人工晶体学报，2021，50（10）：1879-1882.
	HE J Y，LI W，WEI Q H，et al. Growth and properties of 1-inch Cs₂LiLaBr₆∶Ce scintillation crystal［J］. Journal of Synthetic Crystals，2021，50（10）：1879-1882 （in Chinese）.
[11]	LI Y D，GE L Q，Kun-Sun，et al. Energy spectrum response of a CsI（Tl） detector read out by an APD［J］. Journal of Instrumentation，2020，15（5）：T05005.
[12]	SCAFÈ R，PANI R，PELLEGRINI R，et al. Si-APD readout for LaBr₃∶Ce scintillator［J］. Nuclear Instruments and Methods in Physics Research Section A：Accelerators，Spectrometers，Detectors and Associated Equipment，2007，571（1/2）：355-357.
[13]	胡　浪，张开琪，曾国强，等. CsI（Tl）晶体的APD前端读出特性研究［J］. 核技术，2016，39（10）：45-49.
	HU L，ZHANG K Q，ZENG G Q，et al. Characteristics study on the APD-based front-end readout for CsI（Tl） detector［J］. Nuclear Techniques，2016，39（10）：45-49 （in Chinese）.
[14]	VAN LOEF E V D，DORENBOS P，VAN EIJK C W E，et al. High-energy-resolution scintillator∶Ce³⁺ activated LaCl₃ ［J］. Applied Physics Letters，2000，77（10）：1467-1468.
[15]	AWATER R H P，ALEKHIN M S，BINER D A，et al. Converting SrI₂∶Eu²⁺ into a near infrared scintillator by Sm²⁺ co-doping［J］. Journal of Luminescence，2019，212：1-4.
[16]	WOLSZCZAK W，KRÄMER K W，DORENBOS P. CsBa₂I₅∶Eu²⁺，Sm²⁺：the first high-energy resolution black scintillator for γ-ray spectroscopy［J］. Physica Status Solidi （RRL）-Rapid Research Letters，2019，13（9）：1900158.
[17]	RUSAKOV A I，SHALAEV A A，SHENDRIK R Y，et al. Growth and spectroscopy of BaBrI crystals activated by Eu²⁺ ions［C］//Xvi International Conference on Luminescence and Laser Physics Devoted to the 100th Anniversary of Irkutsk State University，Arshan，Russia. Author（s），2019：020002.
[18]	SHALAEV A A，SHENDRIK R Y，RUSAKOV A I，et al. Growth and study of scintillation properties of BaBrI crystals activated by samarium ions［J］. Physics of the Solid State，2019，61（12）：2403-2406.
[19]	WOLSZCZAK W，KRÄMER K W，DORENBOS P. Engineering near-infrared emitting scintillators with efficient Eu²⁺→Sm²⁺ energy transfer［J］. Journal of Luminescence，2020，222：117101.
[20]	VAN AARLE C，ROTURIER N，BINER D A，et al. Light yield and thermal quenching of Ce³⁺ and Pr³⁺ co-doped LaBr₃∶Sm²⁺ near-infrared scintillators［J］. Optical Materials，2023，145：114375.
[21]	王晴晴，任国浩. 中子探测用钾冰晶石型闪烁晶体研究进展［J］. 硅酸盐学报，2016，44（3）：457-463.
	WANG Q Q，REN G H. Recent development on elpasolite scintillation crystals for neutron detection［J］. Journal of the Chinese Ceramic Society，2016，44（3）：457-463 （in Chinese）.
[22]	SHANNON R D. Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides［J］. Acta Crystallographica Section A，1976，32（5）：751-767.
[23]	LI T，WANG Z J，LI P L，et al. A novel red emitting phosphor LiBaB₉O₁₅∶Sm²⁺/Sm³⁺，Li⁺ with broad excitation band for white LEDs［J］. Luminescence，2018，33（2）：438-442.
[24]	CHEN Q L，MA Q H. Mixed samarium valences effect in Faraday rotation glasses：structure，optical，magnetic and magneto-optical properties［J］. Journal of Non-Crystalline Solids，2020，530：119803.
[25]	HUA J J，ZHANG M H，LI X，et al. The effect of Sb₂O₃ on optical，scintillation and service performance of Ce³⁺-ion doped gadolinium aluminosilicate glasses［J］. Optical Materials，2024，157：116153.
[26]	TONG Y F，WEI Q H，LI W，et al. Effects of Ce³⁺ substitution on the local structure of cerium and scintillation properties of CLLBC∶Ce crystals［J］. Journal of Crystal Growth，2022，600：126940.
[27]	ZHANG X G，KANG Z，CAI Z C，et al. Study on the segregation behavior of Ce in CLYC crystals［J］. Journal of Crystal Growth，2021，573：126308.
[28]	SHIRWADKAR U，GLODO J，VAN LOEF E V，et al. Scintillation properties of Cs₂LiLaBr₆ （CLLB） crystals with varying Ce³⁺ concentration［J］. Nuclear Instruments and Methods in Physics Research Section A：Accelerators，Spectrometers，Detectors and Associated Equipment，2011，652（1）：268-270.
[29]	LI B Y，HUANG Z，CAI P Q，et al. Enhanced VIS-NIR emission of Re⁴⁺ doped Cs₂ZrCl₆ for optical thermometry and near-infrared illumination applications［J］. Inorganic Chemistry Frontiers，2024，11（16）：5157-5171.
[30]	LIN J，WEI Q H，ZHANG D，et al. Crystal growth and scintillation properties of non-stoichiometric Cs₂LiLaBr₆∶Ce［J］. Crystal Research and Technology，2019，54（10）：1900047.

Sm²⁺-Ce³⁺共掺CLLB闪烁晶体生长及发光性能研究

Growth and Luminescence Properties of Sm²⁺-Ce³⁺ Co-Doped CLLB Scintillation Crystals

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 9

参考文献 30

相关文章 15

编辑推荐

Metrics

本文评价

[1]	赵美丽, 宗蕾, 王谦, 李云云, 张春生, 吴云涛. Cu⁺或Ag⁺共掺杂LaBr₃∶Ce晶体的生长及性能研究[J]. 人工晶体学报, 2026, 55(1): 58-67.
[2]	贾宇桢, 李政隆, 颜欣龙, 王瑞辰, 彭晨, 段韦恒, 杨伟虎, 何伟民, 宋柏君, 程瑶, 范潇宇, 杨帆. 0维钙钛矿Cs₃CdBr₅的晶体生长与闪烁性能研究[J]. 人工晶体学报, 2025, 54(7): 1221-1228.
[3]	孟晓燕, 甘欣, 王春洋, 朱瑶贤, 杨流赛, 吴丽丹, 董洪霞. CaMoO₄：Dy³⁺/Sm³⁺白光荧光粉的设计、合成及发光性能研究[J]. 人工晶体学报, 2025, 54(4): 663-673.
[4]	王元娥, 王晶, 葛彩霞, 傅国娟, 宋明君. Tb³⁺, Sm³⁺掺杂的可变色KSrGd(WO₄)₃荧光粉的制备及发光性能研究[J]. 人工晶体学报, 2025, 54(4): 674-683.
[5]	黄东阳, 黄浩天, 潘明艳, 徐子骞, 贾宁, 齐红基. 垂直布里奇曼法生长氧化镓单晶及其性能表征[J]. 人工晶体学报, 2025, 54(2): 190-196.
[6]	詹畯伟, 阮勇奇, 陈志强, 温磊, 彭思艳, 杨流赛. Li⁺掺杂YPO₄∶Dy³⁺荧光粉的诱导相变与发光性能优化[J]. 人工晶体学报, 2025, 54(12): 2146-2155.
[7]	殷洁, 张小强, 陈灿, 潘建国. Eu²⁺掺杂Cs₂BaBr₄晶体的生长和闪烁性能研究[J]. 人工晶体学报, 2025, 54(11): 1931-1936.
[8]	黄渠, 姜洪喜, 周波. CaLa₂(WO₄)₄∶Eu³⁺,Sm³⁺新型白光LED用红色荧光粉的发光性能研究[J]. 人工晶体学报, 2025, 54(1): 69-76.
[9]	刘云云, 黄传鑫, 王猛, 王燕. Dy³⁺/Eu³⁺双掺杂CaLaGa₃O₇颜色可调荧光粉的制备与发光性能[J]. 人工晶体学报, 2024, 53(9): 1560-1567.
[10]	张守超, 高森单, 刘洪飞, 姜荣云, 王翠红, 聂晓菊, 张丽文, 覃冰. Tb³⁺掺杂钒磷酸盐蓝绿发光调控及发光机理研究[J]. 人工晶体学报, 2024, 53(8): 1422-1433.
[11]	伍仕停, 余春燕, 方佳庆, 徐阳, 翟光美. ZnSe基蓝光量子点的中间壳层结构调控及其发光性能研究[J]. 人工晶体学报, 2024, 53(7): 1160-1169.
[12]	杨江浩, 黄欣帅, 蓝陈慧, 魏钦华, 秦来顺. Cs₄EuI₆∶Sm近红外闪烁晶体的生长及发光性能研究[J]. 人工晶体学报, 2024, 53(4): 627-633.
[13]	万前银, 王强, 刘双全, 黄先超, 肖雄, 宋宝林, 蒋赟睿, 陶祖才, 丁雨憧. GAGG:Ce闪烁晶体光输出的温度特性研究[J]. 人工晶体学报, 2024, 53(12): 2073-2078.
[14]	陈金润, 陈梦玉, 李子璇, 李微, 楚楚, 曹秀哲, 翟永清. NaCa₂Mg₂(VO₄)₃∶Eu³⁺颜色可调荧光粉的熔盐法合成及其发光性能研究[J]. 人工晶体学报, 2024, 53(1): 90-96.
[15]	孟晓燕, 廖云, 张丽蓉, 张雨蒙, 吴丽丹, 杨流赛. GdPO₄∶Tb³⁺荧光粉的制备及发光性能研究[J]. 人工晶体学报, 2024, 53(1): 107-114.