Gd3(Al,Ga)5O12:Ce闪烁晶体扭曲生长、组分偏析与性能研究

doi:10.15541/jim20200268

无机材料学报 ›› 2021, Vol. 36 ›› Issue (2): 188-196.DOI: 10.15541/jim20200268

所属专题：【虚拟专辑】透明陶瓷与光学晶体；【信息功能】透明陶瓷与光学晶体

Gd₃(Al,Ga)₅O₁₂:Ce闪烁晶体扭曲生长、组分偏析与性能研究

孟猛¹^,²^,³(), 祁强¹^,⁴, 丁栋舟¹^,⁵(), 赫崇君²^,³(), 赵书文¹, 万博¹, 陈露¹, 施俊杰¹^,⁵, 任国浩¹^,⁵

1.中国科学院上海硅酸盐研究所, 上海 201899
2.南京航空航天大学工业和信息化部重点实验室, 空间光电探测与感知实验室, 南京 210016
3.南京航空航天大学航天学院, 南京 210016
4.上海理工大学材料科学与工程学院, 上海 200093
5.中国科学院海西创新研究院, 福建 350002

收稿日期:2020-05-15 修回日期:2020-08-03 出版日期:2021-02-20 网络出版日期:2020-09-09
通讯作者: 赫崇君, 副教授. E-mail: hechongjun@nuaa.edu.cn;
作者简介:孟猛(1994-), 男, 硕士研究生. E-mail: 865770183@qq.com
基金资助:
国家自然科学基金(61675095);“中国科学院关键技术人才”项目(Y74YQ3130G);中科院上海硅酸盐研究所科技创新重点项目(Y74ZC5152G);海西研究院自主部署项目(FJCXY18040202)

Twisted Growth, Component Segregation and Characteristics of Gd₃(Al,Ga)₅O₁₂:Ce Scintillation Crystal

MENG Meng¹^,²^,³(), QI Qiang¹^,⁴, DING Dongzhou¹^,⁵(), HE Chongjun²^,³(), ZHAO Shuwen¹, WAN Bo¹, CHEN Lu¹, SHI Junjie¹^,⁵, REN Guohao¹^,⁵

1. Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 201899, China
2. Key Laboratory of Space Photoelectric Detection and Perception, Ministry of Industry and Information Technology, Nanjing University of Aeronautics and Astronautics, Nanjing 210016, China
3. College of Astronautics, Nanjing University of Aeronautics and Astronautics, Nanjing 210016, China
4. School of Materials Science and Engineering, University of Shanghai for Science and Technology, Shanghai 200093, China
5. Fujian Institute of Innovation, Chinese Academy of Sciences, Fujian 350002, China

Received:2020-05-15 Revised:2020-08-03 Published:2021-02-20 Online:2020-09-09
About author:MENG Meng(1994-), male, Master candidate. E-mail: 865770183@qq.com
Supported by:
National Natural Science Foundation of China(61675095);Project of “Key Technical Talents of the Chinese Academy of Sciences”(Y74YQ3130G);Key Project of Science and Technology Innovation of Shanghai Institute of Ceramics of Chinese Academy of Sciences(Y74ZC5152G);Independent Deployment Project of Hercynian Research Institute(FJCXY18040202)

摘要/Abstract

摘要：

新型闪烁晶体Gd₃(Al,Ga)₅O₁₂:Ce(简写为GAGG:Ce)在制备过程中易出现多晶扭曲生长、组分偏析等问题, 严重影响晶体的性能。为了得到大尺寸高质量的GAGG:Ce晶体, 采用X射线衍射(XRD)、电感耦合等离子体发射光谱(ICP-OES)和X射线激发发射谱(XEL)等手段, 结合熔体特性分析了GAGG:Ce晶体多晶扭曲生长、组分偏析的形成机制。通过调整温场、抑制组分挥发等方法生长出φ50 mm×120 mm的GAGG:Ce晶体, 并重点研究了GAGG:Ce晶体的光谱特性与闪烁性能。结果表明: GAGG:Ce晶体的光输出达58000 ph./MeV, 能量分辨率为6.4%@662 keV, 在550~800 nm波长区间的透过率约为82%。晶体闪烁衰减快分量为126 ns (83%), 慢分量为469 ns (17%)。晶体的发射峰中心波长在550 nm左右, 与硅光电倍增管的接收波长匹配, 且发光峰值处的透过率EWLT(Emission Weighted Longitudinal Transmittance)值高达79.8%。GAGG:Ce晶体兼具高光输出与高能量分辨率, 在中子和伽马射线探测领域具有广阔的应用前景。

关键词: 多晶扭曲生长, 温度梯度, 组分偏析, 衰减时间

Abstract:

There are many problems such as polycrystal twisted growth and component segregation during the preparation of the new scintillation crystal Gd₃(Al,Ga)₅O₁₂:Ce (abbreviated as GAGG:Ce) by the Czochralski method. In order to solve these problems to obtain large-size and high-quality GAGG:Ce crystals, with a combination of melt characteristics, formation mechanism of twisted growth, component segregation, spectral characteristics and scintillation performance of GAGG:Ce crystals were studied. A complete GAGG:Ce crystal with size of ?50 mm× 120 mm was successfully grown by adjusting the temperature field and inhibiting the volatilization of the components. The results show that light output of the GAGG:Ce crystal sample (10 mm×10 mm×2 mm) is 58000 ph./MeV, while energy resolution is 6.4%@662 keV with transmittance at 550 nm of 82%, decay time of 126 ns (83%), and the slow component is 469 ns (17%). The peak position of emission wavelength of the crystal is about 550 nm, which matches well with the silicon photomultiplier. Meanwhile, the emission weighted longitudinal transmittance is as high as 79.8%. GAGG:Ce crystal has an excellent combination of high light output and energy resolution, and all of these properties show that GAGG:Ce crystal is a promising scintillator for neutron and gamma detection applications.

Key words: polycrystal twisted growth, temperature gradient, component segregation, decay time

中图分类号:

O734

孟猛, 祁强, 丁栋舟, 赫崇君, 赵书文, 万博, 陈露, 施俊杰, 任国浩. Gd₃(Al,Ga)₅O₁₂:Ce闪烁晶体扭曲生长、组分偏析与性能研究[J]. 无机材料学报, 2021, 36(2): 188-196.

MENG Meng, QI Qiang, DING Dongzhou, HE Chongjun, ZHAO Shuwen, WAN Bo, CHEN Lu, SHI Junjie, REN Guohao. Twisted Growth, Component Segregation and Characteristics of Gd₃(Al,Ga)₅O₁₂:Ce Scintillation Crystal[J]. Journal of Inorganic Materials, 2021, 36(2): 188-196.

图/表 17

图1 多晶扭曲生长的GAGG:Ce晶体照片

Fig. 1 Photo of polycrystal twisted growth GAGG:Ce crystal

图2 GAGG:Ce晶体生长挥发物照片(a)及其XRD图谱(b)

Fig. 2 Photo and XRD pattern of volatiles during crystal growth of GAGG:Ce: (a) volatiles photo; (b) XRD pattern

图3 Gd2O3-Ga2O3相图[11]

Fig. 3 Gd2O3-Ga2O3 phase diagram[11] (a) Phase region of stable phase; (b) Phase region of metastable phase

表1 多晶扭曲生长样品的电感耦合等离子体发射光谱(ICP-OES)成分分析结果

Table 1 Component analysis data by Inductively Coupled Plasma Optical Emission Spectrum (ICP-OES) of polycrystal twisted growth samples

Sample	n_Gd : n_Al : n_Ga
Melt	3.0 : 2.3 : 2.7
Twisted growth crystal	3.00 : 3.57 : 0.83

图4 多晶扭曲生长晶体样品的粉末XRD图谱

Fig. 4 XRD patterns of polycrystal twisted growth crystal powder

图5 GAGG:Ce晶体的随机突起、缩进与铱金附着物

Fig. 5 Random protrusions, indentations and iridium attachments of GAGG:Ce crystal

图6 组分偏析的GAGG:Ce晶体照片

Fig. 6 Photo of GAGG:Ce Crystal with partial component

表2 晶体头、尾部样品的电感耦合等离子体发射光谱(ICP-OES)成分分析数据

Table 2 Component analysis data by Inductively Coupled Plasma Optical Emission Spectrum (ICP-OES) of crystal head and tail samples

Sample	n_Gd : n_A : n_Ga
Melt	3.0 : 2.3 : 2.7
Crystal head	3.00 : 3.56 : 1.57
Crystal tail	3.0 : 2.3 : 2.7

图7 晶体头、尾部样品的粉末XRD图谱

Fig. 7 XRD patterns of crystal head and tail powder

表3 GAGG:Ce晶体的X射线能谱分析(EDS)成分分析数据

Table 3 Component analysis data by Electronic Differential System (EDS) of GAGG:Ce crystal

Spectrum	Mole fraction/mol%				Ratio of ions
Spectrum	Gd	Ce	Al+Ga	O	Gd:(Al+Ga):O
1 (inclusion)	20.61	-	19.39	60	1 : 1 : 3
2 (matrix)	14.97	-	25.03	60	3 : 5 : 12

图8 GAGG:Ce晶体的扫描电镜照片

Fig. 8 SEM image of GAGG:Ce crystal

图9 室温下组分偏析晶体及陶瓷样品的X射线激发发射谱

Fig. 9 X-ray excited spectra of partial crystal and ceramics (a) Head and tail of partial crystal; (b) GdAl0.5Ga0.5O3:Ce (GAGP:Ce), Gd3Al2.5Ga2.5O3:Ce (GAGG:Ce), and Gd4Al2O9:Ce (GAM:Ce)

图10 提拉法生长GAGG:1%Ce晶体的毛坯照片

Fig. 10 Photo of GAGG:1%Ce crystal grown by Czochralski method

图11 室温下GAGG:1%Ce晶体样品的透过光谱及X射线激发发射谱

Fig. 11 Transmission and X-ray excited spectra of GAGG:1% crystal at room temperature Black solid line representing the transmittance; Red solid line representing the X-ray excited spectra; Blue solid dots representing the theoretical limit of transmittance calculated from the measured refractive indices N

表4 GAGG:1%Ce晶体的折射率及理论透过率

Table 4 Refractive index and theoretical transmittance of GAGG:1%Ce crystal

Parameter	λ/nm
Parameter	400	475	520	575	625	700
n	1.951	1.919	1.91	1.904	1.9	1.898
T/%	81.17	81.97	82.18	82.34	82.43	82.48

图12 室温下GAGG:1%Ce样品在137Cs源激发下的多道能谱

Fig. 12 Multi-channel energy spectra of GAGG:1%Ce crystal excited by 137Cs

图13 GAGG:1%Ce晶体样品的时间特性

Fig. 13 GAGG:1%Ce crystal time behavior (a) Light output curve at different time Gates and its fitted line; (b) Scintillation decay curve and its fitted line

参考文献 22

[1]	MENG MENG, QI QIANG, DING DONG-ZHOU, et al. Research progress on novel scintillation crystal Gd₃(Al,Ga)₅O₁₂:Ce³⁺. Journal of Synthetic Crystals, 2019,48(8):1386-1394.
[2]	VAN EIJK C. Inorganic Scintillators in Positron Emission Tomography. Radiation Detectors for Medical Applications. Netherland: Springer Netherlands, 2006: 259-274.
[3]	KAMADA K, TAKAYUKI A, YANAGIDA T, et al. 2 inch diameter single crystal growth and scintillation properties of Ce:Gd₃Al₂Ga₃O₁₂. Journal of Crystal Growth, 2012,352(1):88-90.
[4]	TAMAGAWA Y, INUKAI Y, OGAWA I, et al. Alpha-gamma pulse-shape discrimination in Gd₃Al₂Ga₃O₁₂:Ce³+ crystal scintillator using shape indicator. Nuclear Instruments and Methods in Physics Research, 2015,795(21):192-195.
[5]	KOCHURIKHIN V, KAMADA K, IVANOV M, et al. Czochralski growth of 4-inch diameter Ce:Gd₃Al₂Ga₃O₁₂single crystals for scintillator applications. Journal of Crystal Growth, 2020,531:1.
[6]	FENG DA-JIAN. Study on the growth and scintillation properties of Ce:GAGG crystal. Piezoelectrics and Acoustooptics, 2016,38(3):430-432.
[7]	WANG CHAO, WU YUN-TAO, DING DONG-ZHOU, et al. Optical and scintillation properties of ce-doped (Gd₂Y₁)Ga_2.7Al_2.3O₁₂, single crystal grown by Czochralski method. Nuclear Instruments and Methods in Physics Research A, 2016,820:8-13.
[8]	YUAN HANG, CHEN YU-XIAO, WANG YING-JIE, et al. Inorganic scintillator gadolinium gallium aluminum garnet (GAGG)’s performance research and application. Modern Industrial Economy and Informationization, 2018,8(11):24-26.
[9]	SHISHIDO T, OKAMURA K, YAJIMA S. Gd₃Al₅O₁₂ phase obtained by crystallization of amorphous Gd₂O₃·5/3Al₂O₃. J. Am. Ceram. Soc., 1978,61(7/8):37-375.
[10]	ASADIAN M, HAJIESMAEILBAIGI F, MIRZAEI N, et al. Composition and dissociation processes analysis in crystal growth of Nd:GGG by the Czochralski method. Journal of Crystal Growth, 2010,312(9):1645-1650.
[11]	DIGIUSEPPE A, SOLED L, WENNER M, et al. Phase diagram relationships of the garnet-perovskite transformation in the Gd₂O₃-Ga₂O₃ and Sm₂O₃-Ga₂O₃ systems. Progress in Crystal Growth and Characterization of Materials, 1980,49(4):746-748.
[12]	DING DONG-ZHOU, LI HUAN-YING, QIN LAI-SHUN, et al. Research on the defects in Lu_xY₁-_xAlO₃:Ce crystals. Journal of Inorganic Materials, 2010,25(10):1021-1024.
[13]	KAMADA K, NIKL M, KUROSAWA S, et al. Alkali earth co-doping effects on luminescence and scintillation properties of Ce-doped Gd₃Al₂Ga₃O₁₂ scintillator. Optical Materials, 2015,41(13):63-66.
[14]	ZHANG YE, CHEN XIAN-QIANG, QIN HAI-MING, et al. Fabrication of Ce-doped Gd₃(Al,Ga)₅O₁₂ powders using Co-precipitation Method. Journal of Inorganic Materials, 2016,31(10):1151-1156.
[15]	KUCERA M, HANUS M, ONDERISINOVA Z, et al. Energy transfer and scintillation properties of Ce³⁺ doped (Lu,Y,Gd)₃(Al,Ga)₅O₁₂multicomponent garnets. IEEE Transactions on Nuclear Science, 2014,61(1):282-289.
[16]	VERWEIJ J, COHEN M, BOUTTET D, et al. Luminescence properties of GdAlO₃:Ce powders. Chemical Physics Letters, 1995,239(1/2/3):51-55.
[17]	SINHA A, SHARMA B, GOPALAN P, et al. Study on phase evolution of GdAl₁-_xGa_xO₃ system. Journal of Alloys and Compounds, 2009,492(2010):325-330.
[18]	ETIENNETTE A, RAMUNAS A, ANDREI F, et al. Excitation transfer engineering in Ce-doped oxide crystalline scintillators by codoping with alkali-earth ions. Physica Status Solidi A, 2018,215(7):1700798.
[19]	KOZLOVA N S, BUSANOV O A, ZABELINA E V, et al. Optical properties and refractive indices of Gd₃Al₂Ga₃O₁₂:Ce³+ crystals. Crystal Lography Reports, 2016,61(3):474-478.
[20]	ZELMON D E, SMALL D L, PAGE R. Refractive-index measurements of undoped yttrium aluminum garnet from 0.4- 5.0 μm. Applied Optics, 1998,37(21):4933-4935. URL PMID
[21]	ZHANG GUO-QING, YANG FAN, WU YUN-TAO, et al. Influence of F/Cl ratio on the crystal growth and luminescence properties of PbFCl crystals. Journal of Inorganic Materials, 2014,29(2):162-166.
[22]	YOSHIHO M, KAMADA K, SHOJI Y, et al. Effect of Mg co-doping on scintillation properties of Ce:Gd₃(Ga,Al)₅O₁₂single crystals with various Ga/Al ratios. Journal of Crystal Growth, 2017,468:420-423.

Gd₃(Al,Ga)₅O₁₂:Ce闪烁晶体扭曲生长、组分偏析与性能研究

Twisted Growth, Component Segregation and Characteristics of Gd₃(Al,Ga)₅O₁₂:Ce Scintillation Crystal

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