稀土离子掺杂Gd2O2S闪烁陶瓷的研究进展

doi:10.15541/jim20200544

摘要/Abstract

摘要：

稀土离子掺杂Gd₂O₂S闪烁陶瓷是20世纪80年代以后发展的硫氧化物闪烁体。高密度和高热中子吸收截面的Gd₂O₂S基质具有高的X射线和热中子阻止能力, 稀土离子(Pr³⁺、Tb³⁺等)的掺杂使其表现出快衰减或高光产额等特性, 在闪烁领域的应用中占据着重要地位。硫氧化合物的组分控制一直是其合成过程中需要解决的关键问题, Gd₂O₂S材料的高熔点和S元素挥发严重的问题, 限制了高光学质量和优良闪烁性能单晶的制备, 因此陶瓷是Gd₂O₂S闪烁体的主要应用形式。颗粒小、粒径分布窄且低团聚的纯相Gd₂O₂S粉体是高质量闪烁陶瓷烧结的关键, 单纯提高烧结温度制备的Gd₂O₂S闪烁陶瓷会产生大量的硫空位和氧空位, 降低材料的闪烁性能。制备Gd₂O₂S闪烁陶瓷通常需要压力辅助烧结, 这种苛刻的制备条件提高了生产成本。本文介绍了闪烁体的闪烁机理及研究概况, 着重综述了Gd₂O₂S闪烁陶瓷的制备工艺、缺陷的解决方法以及在中子成像和医学X-CT上的研究现状及应用情况, 最后对全文进行总结并对Gd₂O₂S闪烁陶瓷发展前景进行了展望。

关键词: Gd₂O₂S闪烁陶瓷, 可控制备, 缺陷控制, 中子成像, 医学X-CT, 综述

Abstract:

Rare earth ions doped Gd₂O₂S scintillators are new type of oxysulfide scintillators, which have been developed since 1980s. The Gd₂O₂S matrix with cross section of high density and high thermal neutron absorption has high X ray and thermal neutron stopping capacity. The doping of different rare earth ions (Pr³⁺, Tb³⁺, etc.) shows fast decay or high light yield, which plays a very important role in application of scintillation. Composition control of oxysulfide is always a key problem to be solved in the synthesis process. However, the high melting point of Gd₂O₂S material and the serious volatilization of sulfur restrict the preparation of Gd₂O₂S single crystals, with high optical quality and excellent scintillation performance. Ceramic is the main application form of Gd₂O₂S scintillation material. Its pure phase Gd ₂O₂S phosphors with small particle size, narrow particle size distribution and low agglomeration is the key to sintering high quality scintillation ceramics. These ceramics prepared by simply increasing the sintering temperature produce a large number of sulfur vacancies and oxygen vacancies, decreasing the scintillation properties. Therefore, preparation of Gd₂O₂S scintillation ceramics usually need pressure assistance to increase the production cost. In this paper, their scintillation mechanism and research situation are introduced firstly. Then, their fabrication process, solution of defects removal, research status and applications in neutron imaging and medical X-CT fields are overviewed. Finally, we summarized the previous and prospected the future development of Gd₂O₂S scintillation ceramics.

Key words: Gd₂O₂S scintillation ceramics, controllable fabrication, defects control, neutron imaging, medical X-CT, review

中图分类号:

TQ174

李江, 丁继扬, 黄新友. 稀土离子掺杂Gd₂O₂S闪烁陶瓷的研究进展[J]. 无机材料学报, 2021, 36(8): 789-806.

LI Jiang, DING Jiyang, HUANG Xinyou. Rare Earth Doped Gd₂O₂S Scintillation Ceramics[J]. Journal of Inorganic Materials, 2021, 36(8): 789-806.

图/表 24

图1 稀土掺杂无机闪烁体中闪烁物理过程示意图[14]

Fig. 1 Scintillation mechanism of activator doped inorganic scintillators in terms of energy band structure[14]

图2 首次发表光产额大于20000 ph/MeV的闪烁体的发展史(1940~2017年)[18]

Fig. 2 History (1940-2017) of first publication of scintillators with light output of >20000 ph/MeV, representing scintillators published in peer-reviewed articles [18] Blue bars: new compounds; Yellow bars: known compounds with new activator or codoped; Red letters: commercial products; Green letters: under development

表1 部分典型闪烁体的光学和闪烁性能

Table 1 Optical and scintillation properties of selected scintillators

Scintillator	Density/(g·cm^-3)	Z_eff/cm	Decay time/ns	λ_em/nm	Light yield/(×10³, ph/MeV)	Ref.
NaI:Tl	3.67	50.8	230	415	43	[23]
LaI:Ce	5.6	54.2	1-2	452, 502	0.2-0.3	[24]
SrI₂:Eu	4.55	49.85	1200	435	115	[25]
BaBrI:Eu	5.21	51.1	331-714	413	89	[26]
Bi₄Ge₃O₁₂	7.13	75.2	300	505	8.2	[27]
PbWO₄	8.28	75.6	6	420	0.1	[28]
CaWO₄	6.1	63.8	600	430	20	[22]
Gd₂O₂S:Pr,Ce,F	7.34	61.1	4000	510	35	[16]
YAlO₃:Ce	5.5	33.6	30	350	21	[29]
Y₃Al₅O₁₂:Pr	4.56	32.6	23.4	310, 380	9.25	[16]
Gd₂SiO₅:Ce	6.71	59.4	60-600	430	12.5	[16]
Y₂SiO₅:Pr	4.45	35	6.5-33	270, 35	4.58	[30]
Gd₃A_l2Ga₃O₁₂:Ce	6.67	50.6	80-800	520	46	[31]
(Gd,Y)₃(Al,Ga)₅O₁₂:Ce	5.8	45	100-600	560	60	[32]

图3 Gd2O2S的结构示意图[41]

Fig. 3 Schematic of Gd2O2S structure[41]

表2 Gd2O2S的基本物化性质[41,42]

Table 2 Basic physical and chemical property of Gd2O2S[41,42]

Property	Feature
Molecular formula	Gd₂O₂S
Relative molecular mass	378
Crystal structure	Hexagonal crystal system
Cell parameters	a=0.38514 nm, c/a=1.73
Melting point	2070 ℃
Density	7.34 g/cm³
Z_eff	61.1
Index of refraction	2.2
Band gap	4.6-4.8 eV
Phonon energy	520 cm^-1
Color	Colorless
Technical aspects	Chemical stability

图4 不同粉体的FE-SEM照片[52]

Fig. 4 FE-SEM images of different powder[52] (a) Commercial Gd2O3 powder; (b) Gd2O3 powder synthesized by coprecipitation; (c) Synthesis by commercial powder; (d) Synthesis by coprecipitation powder

图5 助熔剂法合成的GOS:Tb粉体的SEM照片[53]

Fig. 5 SEM images of GOS:Tb phosphors synthesized by the flux method[53] (a) Without Na4P2O7 flux; (b) With Na4P2O7 flux

图6 前驱体La2(OH)4SO4·nH2O和不同气氛下煅烧产物的结构图[63]

Fig. 6 Structure diagrams of precursor La2(OH) 4SO4·nH2O and calcined products in different atmospheres[63]

图7 GOS:Tb粉体在不同加速电压和电流下的荧光光谱[70]

Fig. 7 Fluorescence spectra of GOS:Tb powders under different accelerating voltages and electron beam currents[70] (A) Different accelerating voltages; (B) Different beam currents; (C) Variation of luminous intensity with voltage and current; (D) Calculated incident electron depth varied with voltage Colorful figures are available on website

图8 热压烧结制备的Gd2O2S陶瓷(厚度1.6 mm)的总透过率曲线[72]

Fig. 8 Total transmittance curves of GOS ceramics (thickness 1.6 mm) prepared by hot pressing[72] 1-GOS:F ceramics; 2-GOS:Pr,Ce ceramics

图9 烧结后GOS:Tb陶瓷断口的FESEM形貌图和EDS分析[58]

Fig. 9 FESEM images of the fracture surfaces and EDS analysis[58] (a) Green body; (b) Pre-sintered body; (c) After hot isotatic pressing; (d) EDS analysis of the selected area in (c)

图10 GOS陶瓷在不同条件下无压烧结后的微观结构[78]

Fig. 10 Microstructures of GOS ceramics prepared by pressureless sintering under different conditions[78] (a) 1380 ℃×6 h, 1.0 K/min; (b) 1300 ℃×3 h, 2.8 K/min

图11 无压烧结制备的不同厚度的GOS:Pr,Ce,F陶瓷和商业GOS陶瓷的脉冲高度谱(a)以及无压烧结制备的GOS:Pr,Ce,F陶瓷和商业陶瓷的余辉曲线(b)[79]

Fig. 11 Pulse height spectra (a) of GOS:Pr, Ce, F ceramics with different thicknesses prepared by pressureless sintering and commercial GOS ceramics, and afterglow curve (b) of GOS:Pr,Ce,F ceramics by pressureless sintering and commercial ceramics[79] (a) Sample thickness is 0.5 mm, 1.0 mm, and 1.5 mm, respectively; (b) Commercial ceramic thickness is 0.5 mm Colorful figures are available on website

图12 退火温度对GOS:Pr陶瓷余辉性能的影响[75]

Fig. 12 Influence of annealing temperature on the afterglow performance of GOS: Pr ceramics[75]

表3 不同稀土离子掺杂GOS陶瓷的闪烁性能

Table 3 Scintillation property of GOS ceramics doped with different rare earth ions

Scintillators	λ_em/nm	Decay time/μs	Afterglow/(%, after 3 ms/100 ms)	Light yield/(ph·MeV^-1)	Ref.
Gd₂O₂S:Pr,Ce,F	510	4	<0.1/<0.01	35000	[29,85]
Gd₂O₂S:Tb	545	1×10³	-	60000	[29]
Gd₂O₂S:Eu	625	1×10³	0.14%@3 ms	60000	[73,85-86]
Gd₂O₂S:Eu,Tb,Ce,Ca	600	-	0.18%@30 ms	62000	[87]

图13 中子成像原理示意图[95]

Fig. 13 Schematic diagram of neutron imaging[95]

表4 常用中子成像闪烁屏核素的性质对比

Table 4 Property of commonly used neutron imaging scintillation screen nuclides

Isotope	Reaction	Cross-section of thermal neutron adsorption/m²	Natural abundance/%	Ref.
⁶Li	³H, ⁴He	9.1×10^-26	7.5	[96-97]
¹⁰B	α, γ, ⁷Li	3.83×10^-25	19.9	[97]
¹¹³Cd	γ, e^-	2.1×10^-24	12.2	[98]
¹⁵⁵Gd	γ, e^-	6.09×10^-24	14.7	[96-97]
¹⁵⁷Gd	γ, e^-	2.55×10^-23	15.7	[96-97]

表5 中子成像用的无机闪烁体及其性质

Table 5 Inorganic scintillators used in neutron imaging and their properties

Scintillator	Density/ (g·cm^-3)	λ_em/nm	Light yield		α/β ratio	τ/ns		Ref.
Scintillator	Density/ (g·cm^-3)	λ_em/nm	Neutron/(×10³, ph·neu.^-1)	γ/(×10³, ph·MeV^-1)	α/β ratio	Neutron	γ	Ref.
⁶Li-glass:Ce	2.5	395	6	4	0.3	70	70	[99]
⁶LiI:Eu	4.1	470	50	12	0.87	1.4×10³	1.4×10³	[6,100]
⁶LiF/ZnS:Ag	2.6	450	160	75	0.44	8×10⁴	100	[99,101]
LiYSiO₄:Ce	3.8	410	10	10	-	-	3.8×10⁴	[102]
⁶Li₆Gd(¹¹BO₃)₃:Ce	3.5	385, 415	40	25	0.32	-	200,800	[103]
Cs₂⁶LiYCl₆:Ce	3.3	380	70	22	0.66	100,10³	100,10³	[6,99]

图14 X-CT成像系统原理图[29]

Fig. 14 Principle diagram of X-CT imaging system[29]

表6 医学成像用无机闪烁体及其性能

Table 6 Inorganic scintillators for medical imaging and their properties

Scintillator	Density/(g·cm^-3)	Thickness to stop 99%*/mm	λ_em/nm	Light yield/ (ph·MeV^-1)	Decay time/μs	Afterglow/(% after 3 ms/100 ms)	Ref.
CsI:Tl	4.51	6.8	550	66000	1.22	>2/0.3	[16]
Bi₄Ge₃O₁₂	7.13	-	480	9000	0.30	0.005%@3 ms	[29]
CdWO₄	7.9	2.4	495	20000	5.00	<0.1/0.02	[16,29]
(Y,Gd)₂O₃:Eu,Pr	5.9	6.1	610	42000	1000	4.9/<0.01	[114]
Gd₂O₂S:Pr,Ce,F	7.3	2.9	510	35000	4	<0.1/<0.01	[29,85,115]
Gd₃(Ga,Al)₂O₁₂:Ce	6.2	-	540	58000	0.09-0.17	<0.01%@20 ms	[40]

图15 宝石闪烁体材料和用于Discovery CT750 HD的检测器模块[114]

Fig. 15 Gemstone scintillator material and detector module for Discovery CT750 HD[114]

图16 日本东芝公司制备的GOS:Pr,Ce,F闪烁陶瓷实物图[116]

Fig. 16 Photo of GOS:Pr,Ce,F scintillation ceramics prepared in Toshiba[116]

图17 德国西门子GOS(UFC)闪烁陶瓷的余辉曲线(a)和X射线吸收效率曲线(b)[117]

Fig. 17 Afterglow (a) and X-ray absorption efficiency (b) curves of German Siemens GOS (UFC ) scintillation ceramics[117] Colorful figures are available on website

表7 国内外各大公司制备的GOS:Pr,Ce(F)闪烁陶瓷的性能

Table 7 Performance of GOS:Pr,Ce(F) scintillation ceramics prepared in the major companies abroad and at home

Manufacturer	λ_em/nm	Light yield/(ph·MeV^-1)	Decay time/μs	Afterglow	Ref.
Siemens (Germany)	512	50000	3	0.01%@2.5-4 ms	[29,117]
Philips (Netherlands)	514	40000	3	0.02%@3 ms	[118]
Toshiba (Japan)	512	36000	3	0.08%@10 ms	[116]
Hitachi (Japan)	512	42000	3	0.001%@300 ms	[119]
Iray (China)	510	27000	3	0.1%@3 ms	[120]

参考文献 120

[1]	GLODO J, WANG Y, SHAWGO R, et al. New developments in scintillators for security applications. Physics Procedia , 2017, 90:285-290. DOI URL
[2]	LECOQ P. Development of new scintillators for medical applications. Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment , 2016, 809:130-139.
[3]	MARTIN T, KOCH A, NIKL M. Scintillator materials for X-ray detectors and beam monitors. MRS Bulletin , 2017, 42(6):451-457. DOI URL
[4]	NIKL M, YOSHIKAWA A. Recent R&D trends in inorganic single-crystal scintillator materials for radiation detection. Advanced Optical Materials , 2015, 3(4):463-481. DOI URL
[5]	WEBER M J. Inorganic scintillators: today and tomorrow. Journal of Luminescence , 2002, 100(1-4):35-45. DOI URL
[6]	VAN EIJK C W E. Inorganic-scintillator development. Nuclear Instruments and Methods in Physics Research Section A: Accelerators,Spectrometers,Detectors and Associated Equipment , 2001, 460(1):1-14.
[7]	LEMPICKI A, BRECHER C, LINGERTAT H, et al. A ceramic version of the LSO scintillator. IEEE Transactions on Nuclear Science , 2008, 55(3):1148-1151. DOI URL
[8]	潘裕柏, 李江, 姜本学. 先进光功能透明陶瓷. 北京: 科学出版社, 2013: 24-28.
[9]	MURRAY R B, MEYER A. Scintillation response of activated inorganic crystals to various charged particles. Physical Review , 1961, 122(3):815-826. DOI URL
[10]	PAYNE S A, CHEREPY N J, HULL G, et al. Nonproportionality of scintillator detectors: theory and experiment. IEEE Transactions on Nuclear Science , 2009, 56(4):2506-2512. DOI URL
[11]	KIRKIN R, MIKHAILIB V V, VASILEV A N. Recombination of correlated electron-hole pairs with account of hot capture with emission of optical phonons. IEEE Transactions on Nuclear Science , 2012, 59(5):2057-2064. DOI URL
[12]	VASILEV A N, GEKTIN A V. Multiscale approach to estimation of scintillation characteristics. IEEE Transactions on Nuclear Science , 2013, 61(1):235-245. DOI URL
[13]	NIKL M, LAGUTA V V, VEDDA A. Complex oxide scintillators: material defects and scintillation performance. Physica Status Solidi B , 2008, 245(9):1701-1722. DOI URL
[14]	LECOQ P, GEKTIN A, KORZHIK M. Scintillation Mechanisms in Inorganic Scintillators. Berlin: Springer , 2017: 125-174.
[15]	NIKL M, PEJCHAL J, MIHOKOVA E, et al. Antisite defect-free Lu₃(Ga_xAl₁-_x)₅O₁₂:Pr scintillator. Applied Physics Letters , 2006, 88(14):141916. DOI URL
[16]	GEKTIN A, KORZHIK M. Inorganic Scintillators for Detector Systems. Berlin: Springer, 2017: 20-77.
[17]	COLTMAN J W, MARSHALL F H. Some characteristics of the photo-multiplier radiation detector. Physical Review , 1947, 72:528.
[18]	DUJARDIN C, AUFFRAY E, BOURRET-COURCHESNE E, et al. Needs, trends, and advances in inorganic scintillators. IEEE Transactions on Nuclear Science , 2018, 65(8):1977-1997. DOI URL
[19]	HOFSTADTER R. The detection of gamma-rays with thallium- activated sodium iodide crystals. Physical Review , 1949, 75(5):796-810. DOI URL
[20]	VANSCIVER W, HOFSTADTER R. Scintillations in thallium- activated CaI₂ and CsI. Physical Review , 1951, 84(5):1062-1063.
[21]	WEBER M J, MONCHAMP R R. Luminescence of Bi₄Ge₃O₁₂: spectral and decay properties. Journal of Applied Physics , 1973, 44(12):5495-5499. DOI URL
[22]	ERSHOV N N, ZAKHAROV N G, RODNYI P A. Spectral- kinetic study of the intrinsic-luminescence characteristics of a fluorite-type crystal. Optics and Spectroscopy , 1982, 53:51-54.
[23]	SAKAI E. Recent measurements on scintillator-photodetector systems. IEEE Transactions on Nuclear Science , 1987, 34(1):418-422. DOI URL
[24]	BESSIERE A, DORENBOS P, VAN EIJK C W E, et al. Luminescence and scintillation properties of the small band gap compound LaI₃:Ce³⁺. Nuclear Instruments and Methods in Physics Research Section A: Accelerators,Spectrometers,Detectors and Associated Equipment , 2005, 537(1/2):22-26.
[25]	CHEREPY N J, PAYNE S A, ASZTALOS S J, et al. Scintillators with potential to supersede lanthanum bromide. IEEE Transactions on Nuclear Science , 2009, 56(3):873-880. DOI URL
[26]	GUNDIAH G, BIZARRI G, HANRAHAN S M, et al. Structure and scintillation of Eu²⁺-activated solid solutions in the BaBr₂-BaI₂ system. Nuclear Instruments and Methods in Physics Research Section A: Accelerators,Spectrometers,Detectors and Associated Equipment , 2011, 652(1):234-237.
[27]	HOLL I, LORENZ E, MAGERAS G. A measurement of the light yield of common inorganic scintillators. IEEE Transactions on Nuclear Science , 1988, 35(1):105-109. DOI URL
[28]	ANNENKOV A A, KORZHIK M V, LECOQ P. Lead tungstate scintillation material. Nuclear Instruments and Methods in Physics Research Section A: Accelerators,Spectrometers, Detectors and Associated Equipment , 2002, 490(1/2):30-50.
[29]	VAN EIJK C W E. Inorganic scintillators in medical imaging. Physics in Medicine & Biology , 2002, 47(8):R85.
[30]	DORENBOS P, MAISMAN M, VAN EIJK C W E et al. Scintillation properties of Y₂SiO₅: Pr crystals. Radiation Effects and Defects in Solids , 1995, 135(1-4):325-328. DOI URL
[31]	KAMADA K, YANAGIDA T, ENDO T, et al. 2 inch diameter single crystal growth and scintillation properties of Ce:Gd₃Al₂Ga₃O₁₂. Journal of Crystal Growth , 2012, 352(1):88-90. DOI URL
[32]	CHEREPY N J, SEELEY Z M, PAYNE S A, et al. Development of transparent ceramic Ce-doped gadolinium garnet gamma spectrometers. IEEE Transactions on Nuclear Science , 2013, 60(3):2330-2335. DOI URL
[33]	CONTL M. State of the art and challenges of time-of-flight PET. Phys. Med.-Eur. J. Med. Phys. , 2009, 25(1):1-11.
[34]	NIKL M. Wide band gap scintillation materials: progress in the technology and material understanding. Physica Status Solidi A , 2000, 178(2):595-620. DOI URL
[35]	WANG C, REN G H. Research progress of garnet series scintillation crystals. Journal of the Chinese Ceramic Society , 2015, 43(7):882-891.
[36]	MOSZYNSKI M, LUDZIEJEWSKI T, WOLSKI D, et al. Properties of the YAG:Ce scintillator. Nuclear Instruments and Methods Physical Research Section A , 1994, 345(3):461-467. DOI URL
[37]	LI J, CHEN X P, KOU H M, et al. Recent development on garnet single crystal and ceramic scintillators. Journal of the Chinese Ceramic Society , 2018, 46(1):116-127.
[38]	刘书萍. LuAG:Ce透明闪烁陶瓷的制备及其性能优化研究. 上海: 中国科学院上海硅酸盐研究所博士学位论文, 2016.
[39]	陈肖朴. 高光输出快衰减铈掺杂石榴石闪烁陶瓷的制备与性能研究. 上海: 中国科学院上海硅酸盐研究所博士学位论文, 2020.
[40]	KAMADA K, KUROSAWA S, PRUSA P, et al. Cz grown 2-in. size Ce:Gd₃(Al,Ga)₅O₁₂ single crystal; relationship between Al, Ga site occupancy and scintillation properties. Optical Materials , 2014, 36(12):1942-1945. DOI URL
[41]	潘宏明. 中子成像用Gd₂O₂S:Tb闪烁陶瓷的制备与性能研究. 江苏: 江苏大学硕士学位论文, 2019.
[42]	DANIEL J H, SAWANT A, TEEPE M, et al. Fabrication of high aspect-ratio polymer microstructures for large-area electronic portal X-ray images. Sensors and Actuators A: Physical , 2007, 140(2):185-193. DOI URL
[43]	LIAN J B. First-principles study on the electronic structure and optical properties of Gd₂O₂S. Bulletin of the Chinese Ceramic Society , 2011, 30(05):1029-1033.
[44]	WU G Q, QIN H M, FENG S W, et al. Ultrafine Gd₂O₂S:Pr powders preparedvia urea precipitation method using SO₂/SO₄²- as sulfuration agent-a comparative study. Powder Technology , 2017, 305:382-388. DOI URL
[45]	HE C, XIA Z G, LIU Q L. Microwave solid state synthesis and luminescence properties of green-emitting Gd₂O₂S:Tb³⁺ phosphor. Optical Materials , 2015, 42:11-16. DOI URL
[46]	ZHAN Y H, AI F R, CHEN F, et al. Intrinsically zirconium-89 labeled Gd₂O₂S:Eu nanoprobes for in vivo positron emission tomography and gamma-ray-induced radioluminescence imaging. Small , 2016, 12(21):2872-2876. DOI URL
[47]	POPOVICI E J, MURESAN L, HRISTEA-SIMOC A, et al. Synthesis and characterisation of rare earth oxysulphide phosphors. I. Studies on the preparation of Gd₂O₂S:Tb phosphor by the flux method. Optical Materials , 2004, 27(3):559-565. DOI URL
[48]	GRESKOVICH C, DUCLOS S. Ceramic scintillator. Annual Review of Materials Science , 1997, 27(3):69-88. DOI URL
[49]	PEARSON, RALPH G. Hard and soft acids and bases. Journal of the American Chemical society , 1963: 3533-3539.
[50]	HAN P D, ZHANG L, WANG L X, et al. Investigation on the amounts of Na₂CO₃ and sulphur to obtain pure Y₂O₂S and up-conversion luminescence of Y₂O₂S:Er. Journal of Rare Earths , 2011, 29(9):849-854. DOI URL
[51]	DING Y J, YANG W M, ZHANG Q T, et al. Influence of alkali metal compound fluxes on Gd₂O₂S:Tb particle and luminescence. Journal of Materials Science: Materials in Electronics , 2015, 26(3):1982-1986. DOI URL
[52]	DING Y J, HAN P D, WANG L X, et al. Preparation, morphology and luminescence properties of Gd₂O₂S:Tb with different Gd₂O₃ raw materials. Rare Metals , 2019, 38(3):221-226. DOI URL
[53]	USTABAEV P S, BAKHMETYEV V V. Synthesis and properties study of the X-ray phosphors Gd2O2S:Tb. Journal of Physics: Conference Series. IOP Publishing , 2020, 1560(1):012022.
[54]	TIAN Y, CAO W H, LUO X X, et al. Preparation and luminescence property of Gd₂O₂S:Tb X-ray nano-phosphors using the complex precipitation method. Journal of Alloys and Compounds , 2007, 433(1/2):313-317. DOI URL
[55]	THIRUMALAI J, CHANDRAMOHAN R, DIVAKAR R, et al. Eu³⁺ doped gadolinium oxysulfide (Gd₂O₂S) nanostructures- synthesis and optical and electronic properties. Nanotechnology , 2008, 19(39):395703. DOI URL
[56]	SONG Y H, YOU H P, HUANG Y J, et al. Highly uniform and monodisperse Gd₂O₂S:Ln³⁺ (Ln=Eu,Tb) submicrospheres: solvothermal synthesis and luminescence properties. Inorganic Chemistry , 2010, 49(24):11499-11504. DOI URL
[57]	LEPPERT J. Method for Producing Rare Earth Oxysulfide Powder. United States, C01F17/00, US6296824. 2001.10.02.
[58]	LIU Q, PAN H M, CHEN X P, et al. Gd₂O₂S:Tb scintillation ceramics fabricated from high sinterability nanopowders via hydrogen reduction. Optical Materials , 2019, 94:299-304. DOI URL
[59]	LIU Q, WU F, CHEN X P, et al. Fabrication of Gd₂O₂S:Pr scintillation ceramics from water-bath synthesized nanopowders. Optical Materials , 2020, 104:109946. DOI URL
[60]	TERAZAWA S, NITTA H. Production Method of Rare Earth Oxysulfide, Ceramic Scintillator and Its Production Method, Scintillator Array, and Radiation Detector. United States, CO1F17/0093, US9896623. 2018.2.20.
[61]	LIANG J B, MA R Z, GENG F X, et al. OLn₂(H)₄SO₄·nH₂O (Ln=Pr to Tb; n~2): a new family of layered rare-earth hydroxides rigidly pillared by sulfate ions. Chemistry of Materials , 2010, 22(21):6001-6007. DOI URL
[62]	WANG X J, MOLOKEEV M S, ZHU Q, et al. Controlled hydrothermal crystallization of anhydrous Ln₂(OH)₄SO₄ (Ln= Eu-Lu,Y) as a new family of layered rare earth metal hydroxides. Chemistry-A European Journal , 2017, 23(63):16034-16043. DOI URL
[63]	WANG X J, LI J G, MOLOKEEV M S, et al. Layered hydroxyl sulfate: controlled crystallization, structure analysis, and green derivation of multi-color luminescent (La,RE)₂O₂SO₄ and (La,RE)₂O₂S phosphors (RE=Pr,Sm,Eu,Tb and Dy). Chemical Engineering Journal , 2016, 302:577-586. DOI URL
[64]	WANG X J, LI J G, ZHU Q, et al. Facile and green synthesis of (La_0.95Eu_0.05) ₂O₂S red phosphors with sulfate-ion pillared layered hydroxides as a new type of precursor: controlled hydrothermal processing, phase evolution and photoluminescence. Science and Technology of Advanced Materials , 2013, 15(1):014204. DOI URL
[65]	WANG X J, WANG X J, WANG Z H, et al. Photo/cathodoluminescence and stability of Gd₂O₂S:Tb,Pr green phosphor hexagons calcined from layered hydroxide sulfate. Journal of the American Ceramic Society , 2018, 101(12):5477-5486. DOI URL
[66]	RIZKALLA E N, CHOPPIN G R. Hydration of lanthanides and actinides in solution. Journal of Alloys and Compounds , 1992, 180(1/2):325-336. DOI URL
[67]	LIAN J B, LIU F, WANG X J, et al. Hydrothermal synthesis and photoluminescence properties of Gd₂O₂SO₄:Eu³⁺ spherical phosphor. Powder Technology , 2014, 253:187-192. DOI URL
[68]	LIAN J B, QIN H, LIANG P, et al. Controllable synthesis and photoluminescence properties of Gd₂O₂S:x%Pr³⁺ microspheres using an urea-ammonium sulfate (UAS) system. Ceramics International , 2015, 41(2):2990-2998. DOI URL
[69]	SANG X T, LIAN J B, WU N C, et al. Synthesis, characterization and formation mechanism of Gd₂O₂S:Pr³⁺,Ce³⁺ phosphors by sealed triple-crucible method. Journal of Asian Ceramic Societies , 2020, 8(3):733-744. DOI URL
[70]	WANG X J, MENG Q H, LI M T, et al. A low temperature approach for photo/cathodoluminescent Gd₂O₂S:Tb (GOS:Tb) nanophosphors. Journal of the American Ceramic Society , 2019, 102(6):3296-3306. DOI URL
[71]	BOLYASNIKOVA L, DEMIDENKO V, GOROKHOVA E, et al. Fluorescent Ceramic and Fabrication Method Thereof. United States, C09K11/17, US8025817. 2011.09.27.
[72]	GOROKHOVA E I, DEMIDENKO V A, MIKHRIN S B, et al. Luminescence and scintillation properties of Gd₂O₂S:Tb,Ce ceramics. IEEE Transactions on Nuclear Science , 2005, 52(6):3129-3132. DOI URL
[73]	GOROKHOVA E I, DEMIDENKO V A, ERONKO S B, et al. Luminescence and scintillation properties of Gd₂O₂S:Eu optical ceramic. Journal of Optical Technology , 2010, 77(1):50-58. DOI URL
[74]	ZEITLER G, SCHREINEMACHER H, RONDA C. Hot Axial Pressing Method. United States, B29C47/76, US8221664. 2012.07.17.
[75]	ITO Y, YAMADA H, YOSHIDA M, et al. Hot isostatic pressed Gd₂O₂S:Pr,Ce,F translucent scintillator ceramics for X-ray computed tomography detectors. Japanese Journal of Applied Physics , 1988, 27(8A):L1371. DOI URL
[76]	LACOURSE B C, ZANDI M. Rare Earth Oxysulfide Scintillator and Methods for Producing Same. United states, C09K II/84. US8460578. 2013.06.11.
[77]	WANG Y C, ZHANG Q J, LI Y J, et al. Process for the Preparation of Gadolinium Oxysulfide Scintillation Ceramics. United States, C09K11/77, US9771515. 2017.09.26.
[78]	KOBUSCH M, ROSSNER W. Method for Producing a Scintillator Ceramic. United States, C04B33/32, US7303699. 2007.12.04.
[79]	WANG W, LI Y S, KOU H M, et al. Fabrication of Gd₂O₂S:Pr,Ce,F scintillation ceramics by pressureless sintering in nitrogen atmosphere. International Journal of Applied Ceramic Technology , 2015, 12:E249-E255. DOI URL
[80]	BLASSE G. Scintillator materials. Chemistry of Materials , 1994, 6(9):1465-1475. DOI URL
[81]	王伟. 面向医用CT 闪烁陶瓷 Gd₂O₂S: Pr,Ce的制备和性能表征. 上海: 华东理工大学博士学位论文, 2015.
[82]	WANG W, KOU H M, LIU S P, et al. Optical and scintillation properties of Gd₂O₂S:Pr,Ce,F ceramics fabricated by spark plasma sintering. Ceramics International , 2015, 41(2):2576-2581. DOI URL
[83]	PAN H M, LIU Q, CHEN X P, et al. Fabrication and properties of Gd₂O₂S:Tb scintillation ceramics for the high-resolution neutron imaging. Optical Materials , 2020, 105:109909. DOI URL
[84]	KANDARAKIS I, CAVOURAS D. Role of the activator in the performance of scintillators used in X-ray imaging. Applied Radiation and Isotopes , 2001, 54(5):821-831. DOI URL
[85]	MICHAIL C, VALAIS I, SEFERIS I, et al. Measurement of the luminescence properties of Gd₂O₂S:Pr,Ce,F powder scintillators under X-ray radiation. Radiation measurements , 2014, 70:59-64. DOI URL
[86]	TAKAHASHI M, YUMURA T, YODA I, et al. Visualization of bubbles behavior in lead-bismuth eutectic by gamma-ray. International Conference on Nuclear Engineering , 2010, 49323:533-539.
[87]	YAMADA H, MIURA I, DOI M, et al. Phosphor, and Radiation Detector and X-ray CT Unit Each Equipped Therewith. United States, C09K11/86, US6340436. 2002.01.22.
[88]	DA SILVA A A, CEBIM M A, DAVOLOS M R. Excitation mechanisms and effects of dopant concentration in Gd ₂O₂S:Tb³⁺ phosphor. Journal of Luminescence , 2008, 128(7):1165-1168. DOI URL
[89]	GRABMAIER C, BOEDINGER H, LEPPERT J. Phosphor with an Additive for Reducing Afterglow: United States, C09K11/08, US5560867. 1996.10.01.
[90]	NAKAMURA R, YAMADA N, ISHII M. Effects of halogen ions on the X-ray characteristics of Gd₂O₂S:Pr ceramic scintillator. Japanese Journal of Applied Physics , 1999, 38(12R):6923. DOI URL
[91]	ROSSNER W, OSTERTAG M, JERMANN F. Properties and applications of gadolinium oxysulfide based ceramic scintillators. Electrochemical Society Proceedings , 1999, 98(24):187-194.
[92]	ZHANG J W, LIU Y L, MAN S Q. Afterglow phenomenon in erbium and titanium codoped Gd₂O₂S phosphors. Journal of Luminescence , 2006, 117(2):141-146. DOI URL
[93]	KHARIEKY A A, SARAEE K R E. Synthesis and characterization of radio and thermoluminescence properties of Sm doped Gd₂O₃, Gd₂O₂S and Gd₂O₂SO₄ nanocrystalline phosphors. Journal of Luminescence , 2020, 220:116979. DOI URL
[94]	KARDJILOV N, MANKE I, WORACEK R, et al. Advances in neutron imaging. Materials Today , 2018, 21(6):652-672. DOI URL
[95]	KARDJILOV N, DAWSON M, HILGER A, et al. A highly adaptive detector system for high resolution neutron imaging. Nuclear Instruments and Methods in Physics Research Section A: Accelerators,Spectrometers,Detectors and Associated Equipment , 2011, 651(1):95-99.
[96]	ANDERSON I S, MCGREEVY R L, BILHRUX H Z. Neutron imaging and applications. Springer Science Business Media , 2009, 200(2209):47-63.
[97]	GALUNOV N Z, GRINYOV B V, KARAVAEVA N L, et al. Gd-bearing composite scintillators as the new thermal neutron detectors. IEEE Transactions on Nuclear Science , 2011, 58(1):339-346. DOI URL
[98]	BACKLIN A, HOLMBERG N E, BACKSTROM G. Internal conversion study of ¹¹³Cd (n, γ)¹¹⁴Cd. Nuclear Physics , 1966, 80(1):154-176. DOI URL
[99]	VAN EIJK C W E. Inorganic scintillators for thermal neutron detection. IEEE Transactions on Nuclear Science , 2012, 59(5):2242-2247. DOI URL
[100]	SUN R K S. Photo-energy calibration of ⁶LiI (Eu) crystals in mixed radiation fields using ²⁴Na. Health Physics , 1987, 53(2):191-196.
[101]	DORENBOS P, DE HAAS J T M, VAN EIJK C. Non-proportionality in the scintillation response and the energy resolution obtainable with scintillation crystals. IEEE Transactions on Nuclear Science , 1995, 42(6):2190-2202. DOI URL
[102]	KNITEL M J, DORENBOS P, COMBES C M, et al. Luminescence and storage properties of LiYSiO₄: Ce. Journal of Luminescence , 1996, 69(5/6):325-334. DOI URL
[103]	VAN EIJK C W E, BESSIER A, DORENBOS P. Inorganic thermal-neutron scintillators. Nuclear Instruments and Methods in Physics Research Section A: Accelerators,Spectrometers, Detectors and Associated Equipment , 2004, 529(1/2/3):260-267.
[104]	VAN EIJK C W E. Inorganic scintillators for thermal neutron detection. Radiation Measurements , 2004, 38(4/5/6):337-342. DOI URL
[105]	YASUDA R, KATAGIRI M, MATSUBAYASHI M. Influence of powder particle size and scintillator layer thickness on the performance of Gd₂O₂S:Tb scintillators for neutron imaging. Nuclear Instruments and Methods in Physics Research Section A: Accelerators,Spectrometers,Detectors and Associated Equipment , 2012, 680:139-144.
[106]	TRTIK P, HOVIND J, GRUNZWEIG C, et al. Improving the spatial resolution of neutron imaging at Paul Scherrer Institute- the neutron microscope project. Physics Procedia , 2015, 69:169-176. DOI URL
[107]	TRTIK P, LEHMANN E H. Isotopically-enriched gadolinium-157 oxysulfide scintillator screens for the high-resolution neutron imaging. Nuclear Instruments and Methods in Physics Research Section A: Accelerators,Spectrometers,Detectors and Associated Equipment , 2015, 788:67-70.
[108]	ROSSNER W, GRABMAIER B C. Phosphors for X-ray detectors in computed tomography. Journal of Luminescence , 1991, 48:29-36.
[109]	ISHII M, KOBAYASHI M. Single crystals for radiation detectors. Progress in Crystal Growth and Characterization of Materials , 1992, 23:245-311. DOI URL
[110]	LECOQ P. Development of new scintillators for medical applications. Nuclear Instruments and Methods in Physics Research Section A: Accelerators,Spectrometers,Detectors and Associated Equipment , 2016, 809:130-139.
[111]	BUZUG T M. Computed tomography: from photon statistics to modern cone-beam CT. Springer Science & Business Media , 2009, 36:3858.
[112]	CHEN J Y, SHI Y, FENG T, et al. Scintillation ceramics and their application on medical X-CT. Journal of the Chinese Ceramic Society , 2004, 32(7):868-872.
[113]	WU Y T, REN G H, NIKL M, et al. CsI: Ti^+, Yb²⁺: ultra-high light yield scintillator with reduced afterglow. CrystEngComm , 2014, 16(16):3312-3317. DOI URL
[114]	JIANG H C, VARTULI J, VESS C. Gemstone-the Ultimate Scintillator for Computed Tomography. GE White Paper CT-0376-1108-EN-US, 2008:1-8.
[115]	NAKAMURA R. Improvements in the X-ray characteristics of Gd₂O₂S:Pr ceramic scintillators. Journal of the American Ceramic Society , 1999, 82(9):2407-2410. DOI URL
[116]	https://www.toshiba-tmat.co.jp/en/product/sc_cera.htm. [2020-09-17]
[117]	https://www.siemens-healthineers.com/computed-tomography/technologies-innovations/ufc-ultra-fast-ceramic. [2020-09-17]
[118]	http://www.umich.edu/~ners580/ners-bioe_481/lectures/pdfs/2013-AAPM_Altman-CTdetectors.pdf. [2020-09-17]
[119]	http://www.hitachi-metals.co.jp/e/products/elec/md/p05_14.html.
[120]	http://www.irayam.com/pdf/4200007A0_Datasheet%20GOS%20Ceramic-CN.pdf. [2020-09-17]

稀土离子掺杂Gd₂O₂S闪烁陶瓷的研究进展

Rare Earth Doped Gd₂O₂S Scintillation Ceramics

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