硅酸盐学报2024，Vol.52Issue(3)：755-764,10.DOI:10.14062/j.issn.0454-5648.20230675
Ce掺杂浓度对Ce,Ca∶Lu3Al5O12陶瓷闪烁性能的影响
Effect of Ce Doping Concentration on Scintillation Performance of Ce,Ca∶Lu3Al5O12 Ceramics
摘要
Abstract
Introduction Lutetium aluminum garnet(Lu3Al5O12,LuAG)is investigated as a classical scintillation material.LuAG can be fabricated in the form of single crystals,optical ceramics,thin films and other morphologies to meet different scintillation application demands.Cerium-doped LuAG(Ce∶LuAG)ceramics can be used as a promising candidate for detection material in shashlik calorimeter for high-energy physics(HEP)experiments due to their high density,fast decay,efficient scintillation and relatively low cost.For HEP experiments with a high event rate,however,a slow scintillation component of Ce∶LuAG ceramics leads to a pileup effect that needs to be diminished as much as possible.Divalent,optically inactive,Ca2+co-doping is an effective strategy for suppressing slow scintillation component according to the defect engineering theory.In addition,the coprecipitated nano-powder can be also used as a raw material of ceramics,and improving the consistency of structure,composition and luminescence within the ceramics is also an important strategy to optimize the performance of Ce∶LuAG scintillation ceramics.In this paper,Ce,Ca∶LuAG ceramics with different Ce concentrations were prepared with the coprecipitation nano-powders.The effect of activator ion concentration on the decay behavior,light yield(LY)at different shaping times and afterglow intensity of Ce,Ca∶LuAG ceramics were investigated. Methods A series of Ce,Ca∶LuAG ceramics with the chemical composition of(CexCa0.001 5Lu0.998 5-x％)3Al5O12;x=0.1,0.2,0.3,0.4,0.5 were prepared with coprecipitated nano-powders through vacuum pre-sintering and hot isostatic pressed(HIP)post-treatment.In the process of nano-powder preparation,high purity Lu2O3(99.995％),CeO2(99.999％),and CaCO3 powders were dissolved in nitric acid solution,and Al(NO3)3·9H2O(AR)powders were dissolved in deionized water to obtain various nitrate solutions.The metal nitrate solutions were mixed and further diluted to a specific concentration.Ammonium hydrogen carbonate(AHC,99％)was dissolved in de-ionized water as a precipitant solution,and ammonium sulfate(99％)was added into the precipitant solution as a dispersant.The mixed metal nitrate solution was dripped into the AHC solution under mild agitation at room temperature(RT).The resulting suspension was aged for 1 h and then washed with deionized water and ethanol.The precursor was dried,sieved and calcined to obtain Ce,Ca∶LuAG nano-powders with a pure garnet phase.The powders were uniaxially dry-pressed into pellets at 20 MPa and then cold-isostatically pressed at 250 MPa.The green bodies were vacuum pre-sintered at 1 825 ℃ for 10 h,and then HIP in argon atmosphere under 176 MPa at 1 600 ℃ for 3 h.The fabricated Ce,Ca∶LuAG ceramics were annealed in air at 1 450 ℃ for 10h to remove oxygen vacancies introduced via sintering in a reducing atmosphere.The final Ce,Ca∶LuAG ceramics were polished on the both sides to the thickness of 1 mm for the coming characterization. Results and discussion The XRD patterns of all the ceramic samples are in reasonable agreement with the standard XRD patterns of LuAG(PDF 73-1368),indicating that the main phase of the prepared ceramics is a LuAG garnet phase.The lattice parameters of Ce,Ca∶LuAG ceramics with different Ce concentrations increase gradually with increasing doping concentration.The presence of Ce3+can act as a sintering aid to accelerate the migration of grain boundaries during sintering of garnet ceramics and increase the average grain size.The absorption spectra of Ce,Ca∶LuAG ceramics indicate that the amplitudes of 4f→5d1 transition at 447 nm and the 4f→5d2 transition at 345 nm of Ce3+increase with the starting content of Ce3+that evidences its entering into the garnet lattice.An intense absorption below 350 nm is due to the charge transfer absorption band induced by Ce4+in the garnet lattice.The photoluminescence decay curves of the 5d1→4f emission of Ce3+(510 nm)under the 452 nm excitation show that the fast component intensity I1 of all Ce,Ca∶LuAG ceramics is＞95％.The main decay time shows an acceleration at the Ce concentration of＞0.3％because the formation of closely spaced(Ce4+-Ca2+)pairs can increase with the increase of Ce concentration.The scintillation decay under y-excitation slightly slows down with increasing Ce concentration,since the proportion of induced Ce4+decreases with increasing total Ce concentration,and the competition in accelerating scintillation process becomes progressively weaker.The X-ray excited luminescence(XEL)intensity of the Ce,Ca∶LuAG ceramics firstly increases and then decreases with the Ce concentration,reaching the maximum value as x=0.3.The integral scintillation efficiency of Ce,Ca∶LuAG ceramics is 146％-190％of a BGO crystal.The variation of the LY and the integral scintillation efficiency obtained from XEL have a similar pattern,i.e.,increasing and then decreasing with the increase of Ce concentration.The optimum energy resolution(ER)is obtained as x=0.3.The normalized afterglow intensity after continuous X-ray irradiation monotonically decreases with the Ce concentration due to the more intense competition ability of cerium centers for charge carrier capture. Conclusions Ce,Ca∶LuAG scintillation ceramics with different Ce concentrations were prepared with coprecipitation nano-powders via vacuum pre-sintering and HIP post-treatment.A small amount of Al-rich secondary phase existed in the ceramics due to the loss of lutetium during coprecipitation and washing,which could be avoided by component design in the future ceramic preparation.At the Ce concentration of 0.3％,Ce,Ca∶LuAG ceramic had the optimum XEL integral efficiency,LY and ER.This study demonstrated that Ce doping concentration had a certain effect on the PL decay,scintillation decay and afterglow of Ce,Ca∶LuAG ceramics,providing a guidance for the subsequent selection of doping concentration in practical applications.关键词
铈/钙/镥铝石榴石陶瓷/闪烁性能/共沉淀法Key words
cerium/calcium/lutetium aluminum garnet ceramics/scintillation performance/coprecipitation method分类
通用工业技术引用本文复制引用
朱丹阳,蔡金伶,BEITLEROVA Alena,KUCERKOVA Romana,CHEWPRADITKUL Weerapong,NIKL Martin,李江..Ce掺杂浓度对Ce,Ca∶Lu3Al5O12陶瓷闪烁性能的影响[J].硅酸盐学报,2024,52(3):755-764,10.基金项目
中国科学院国际合作计划项目(121631KYSB20200039). （121631KYSB20200039）
