掺Yb3+闪烁晶体的研究进展

掺Yb3+闪烁晶体是新近发展起来的一类闪烁体,有可能用于探测太阳中微子.本文简要介绍了掺Yb3+闪烁晶体的电荷迁移发光的机理以及基质晶体对温度猝灭与浓度猝灭的影响.综述了具有石榴石结构和钙钛矿结构的两类掺Yb3+闪烁晶体的研究进展,特别是YbYAG和YbYAP晶体的生长、闪烁性能以及应用前景.最后,对掺Yb3+闪烁晶体的未来研究方向做了展望.     

激光非线性复合功能晶体的研究和发展

简要回顾了激光非线性复合功能晶体(即自倍频晶体)的发展过程,从结构、生长和性能等方面对现已研制发展的Nd:Mg:LiNbO₃(NMLN)、Nd_xY_1-xAl₃(BO₃)₄(NYAB)、Cr:KTP、LaBGe_^O5:Nd³⁺、β’-Gd₂(MoO₄)₃:Nd³⁺(GMO:Nd³⁺)、掺Nd³⁺或Yb³⁺的ReCa₄O(BO₃)₃(ReCOB;Re=Gd、Y)(即 Nd:GdCOB、Yb:GdCOB、Nd:YCOB、Yb:YCOB)、Yb:BaCaBO₃F 等几种主要类型的自倍频晶体的研究现状进行了总结,并对该类晶体的发展做了展望.     

不同掺杂对Ba3Y(BO3)3晶体的生长和相变的影响

结合X射线粉末衍射和差示扫描量热法,系统研究了不同格位上的掺杂对Ba₃Y(BO₃)₃晶体的生长和相变的影响. 研究发现,相同掺杂浓度10at%时,掺Nd³⁺的α-Ba₃Y(BO₃)₃晶体的相变温度（1099.6℃）比掺Yb³⁺的晶体的相变温度（1145.3℃）低;且随着掺Nd³⁺浓度的降低,晶体的相变温度升高,晶体在降温过程中更容易发生相变. 在晶体中掺入Sr²⁺离子,可以有效提高Yb³⁺∶α-Ba₃Y(BO₃)₃晶体的稳定性. 随着Sr²⁺掺入浓度的增加,晶体的熔点升高,相变温度降低. 当Sr²⁺掺杂浓度为16at%时,晶体的相变峰消失;当Sr²⁺掺杂浓度分别为5at%、10at%时,晶体仍然发生相变.     

Cr,Yb:YAG晶体的光谱性质

采用提拉法生长了原子分数为10％的Yb和不同掺杂浓度Cr的Cr,Yb:YAG激光晶体.测试了室温下晶体的吸收光谱、荧光光谱和荧光寿命.随着晶体中Cr离子掺杂浓度的增加,晶体在1.03μm处的吸收系数增大、荧光强度和荧光寿命下降,同时Yb³⁺→Cr⁴⁺能量转移效率增加、量子效率降低.确定了Cr,Yb:YAG晶体中Cr的最佳浓度值.     

Yb3+掺杂SiO2-Bi2O3-B2O3玻璃的物理性质及光谱性质

选取玻璃组分60SiO₂-xBi₂O₃-(30-x)B₂O₃-2K₂O-7Na₂O-1Yb₂O₃(以mol％记,x=0,5,10,15,20,25,30)为研究对象。通过测试试样的物理性质和光谱性质,应用倒易法(reciprocity method)计算Yb³⁺离子的受激发射截面(σ_emi),并且计算了Yb³⁺的自发辐射几率(A_rad),²F_5/2能级的辐射寿命(T_rad)。讨论了玻璃中Bi₂O₃和B₂O₃的组成变化对其物理性质、Yb³⁺离子的吸收特性、发光特性以及OH^-离子对实测Yb³⁺荧光寿命(T_f)的影响。结果表明:Yb³⁺掺杂的Si₂-Bi₂O₃-B₂O₃具有较好的光谱性能,是一种新型的Yb³⁺掺杂双包层光纤候选基质材料。     

镱离子敏化与温度对铒离子掺杂碲酸盐玻璃上转换光谱的影响

用熔融-淬冷法制备了玻璃样品系列75TeO₂-20ZnO-(4.6-x)La₂O₃-0.4Er₂O_3-xYb₂O₃ (x=0, 0.4, 0.8, 2.0, 3.2, 4.0), 研究了镱离子的掺入及温度的变化对该玻璃系统上转化光谱的影响, 结果表明: 在常温下, 当Yb³⁺离子浓度达到2mol%时, 上转换红光和545nm绿光都达到了最大值, 此时545nm绿光强度是未掺Yb³⁺时的6倍左右, 红光强度为未掺Yb³⁺时的4倍左右; 当温度在8～300K变化时, 530nm绿光强度随着温度的升高而增大, 545nm绿光与657nm红光强度随着温度的升高首先增大, 在80K达到最大值, 然后随着温度的升高而下降. 通过速率方程, 分析了镱离子的敏化及温度对该玻璃系统上转换光谱的影响.     

Gd3+为敏化剂的掺Tb3+硅酸盐闪烁玻璃

实验制备了以Tb³⁺为激活剂、Gd³⁺为敏化剂的硅酸盐闪烁玻璃, 研究了Tb₂O₃和Gd₂O₃含量对玻璃密度和玻璃折射率, 以及对玻璃在紫外光激发和X射线激发条件下的光学光谱特性的影响. 通过研究Tb³⁺/Gd³⁺共掺闪烁玻璃的激发与发光特性、荧光寿命, 结合稀土离子能级结构, 分析了Gd³⁺→Tb³⁺离子之间的能量转移与传递机制. 结果表明：在紫外激发条件下, 大量引入Tb₂O₃和Gd₂O₃可提高Gd³⁺→Tb³⁺离子之间的能量传递效率, 有利于Tb³⁺离子的绿色发光; 但是在X射线激发条件下大量引入Tb³⁺离子, 由于缺陷数增加而弱化Tb³⁺离子荧光.     

熔体组成与PbWO4:Y3+晶体闪烁性能稳定性的关系

部分PWO:Y³⁺晶体辐照后光产额升高,并且辐照硬度对退火温度较敏感.本文选取未掺杂及Sb、La³⁺、Y³⁺单掺和La³⁺/Sb、Y³⁺/Sb双掺的PWO样品进行对照实验,同时选取代表性晶体的顶部急冷料做了X射线荧光主量分析.结果发现:低剂量辐照后光产额升高现象只存在于含Y³⁺离子的PWO晶体中,并且这类晶体往往存在420nm吸收带;在改进Bridgeman法生长PWO晶体的后期,使熔体保持一定程度的负电性将有利于抑制该现象,即可有效地抑制同样是负电性的间隙氧进入晶体.结合测试数据,本文讨论了该现象的起因和机理,提出了掺杂剂的选择原则.     

Si4+离子对Y3+:PbWO4晶体闪烁性能及辐照硬度的影响

Y³⁺离子掺杂钨酸铅晶体特殊的低剂量率辐照行为一般在晶体顶端表现更为明显,以往研究认为该现象起因于晶体中有效分凝系数<1的Na⁺、K⁺和Si⁴⁺等杂质在顶端的富集.本文研究了Si⁴⁺掺杂的Y³⁺:PWO晶体,对晶体顶端和晶种端的分段晶体测试了退火温度对晶体透过率和辐照硬度的影响,结果发现:在实验所涉及的掺杂浓度范围内,Si⁴⁺离子杂质对Y³⁺:PWO晶体的辐照硬度及透过率无影响,可以认为Y³⁺:PWO晶体特殊的低剂量率辐照行为和晶体中的Si⁴⁺离子含量无关.     

CaF2:20Yb2Er/Na@CaF2:Ce纳米材料近红外二区发光性能研究

利用热分解法制备了CaF₂:20Yb2Er/Na@CaF₂:Ce纳米颗粒，并对其NIR-Ⅱ发光性能和荧光寿命进行了探讨。研究结果表明，在980 nm光源激发下，其NIR-Ⅱ发光性能强度约为CaF₂:20Yb2Er的68倍，且位于1 525 nm处的荧光寿命为2.29 ms。该体系Yb³⁺作为敏化剂，Er³⁺作为激活剂，Na⁺共掺杂使晶体场的局部对称性改变，核壳结构的构建使发光中心的荧光猝灭最小化，壳层结构引入Ce³⁺可以使得Er³⁺与Ce³⁺在界面处产生交叉弛豫。由此可见，将离子共掺杂和构建核壳结构两种策略结合起来更有利于NIR-Ⅱ发光性能的提升。综上，CaF₂:20Yb2Er/Na@CaF₂:Ce纳米颗粒在生物成像领域具有潜在的应用价值。     

Scintillation properties of SrF2 and SrF2-Ce3+ crystals

This Letter presents the results of measuring scintillation properties of pure SrF₂ crystals and crystals activated by various concentrations of Ce³⁺ ions. The light yield of these materials is compared to that of the known scintillators NaI-Tl and CaF₂-Eu²⁺. Strontium fluoride crystals activated with Ce³⁺ ions are found to be characterized by high light yield and to be promising materials for use in scintillation detectors employed for γ-ray well logging.     

陶瓷闪烁材料最新研究进展

概述了透明陶瓷的研究现状及闪烁体的一些重要性能。讨论了新型陶瓷闪烁体相比闪烁单晶在成像应用中的优势 ,介绍了几种重要的陶瓷闪烁体 ,如 (Y ,Gd) 2 O3:Eu ,Pr;Gd2 O2 S :Pr ,Ce ,F ;Gd3Ga5O1 2 :Cr,Ce ;Lu2 O3:Eu ,Tb。并陶瓷闪烁体在先进医学和工业X 射线探测器CT成像中的应用和趋向进行了展望。     

核医学成像技术对无机闪烁材料的需求

介绍了目前正在使用的X－射线成像屏、X－CT和PET等核医学成像技术的原理及其探头对无机闪烁体的性能要求，展示了几种最有发展前景的无机闪烁晶体－－硅酸镥（LSO）、铝酸镥（LuAP）和钨酸铅晶体的研究现状和存在的问题。指出透明陶瓷闪烁体的出现是对传统闪烁晶体的一个挑战。     

Scintillation properties of YAG:Yb crystals

We report on measurements of the light yield, emission spectrum, and time response of YAG:Yb crystals. The temperature dependence of light yield was investigated. Data show that YAG:Yb crystals are good scintillators, suitable for applications to neutrino detection and spectroscopy.     

稀土离子掺杂Gd2O2S闪烁陶瓷的研究进展

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。     

Growth and characterization of polycrystalline lanthanide halide scintillators

We are exploring a novel time- and cost-efficient approach to produce robust, large-volume polycrystalline lanthanide halide scintillators using a hot wall evaporation (HWE) technique. To date, we have fabricated LaBr₃:Ce and LaCl₃:Ce films (slabs) measuring up to 7 cm in diameter and 7+ mm in thickness (20–25 cm³ in volume) on quartz substrates. These polycrystalline scintillators exhibit very bright emissions approaching those exhibited by their melt-grown crystal counterparts. Scanning electron micrographs (SEMs) and X-ray diffraction analysis confirm polycrystalline growth with columnar structures, both of which help in light piping, thereby contributing to the observed high light yields. The new scintillators also exhibit good energy resolution for γ-rays over the tested range of 60 keV (²⁴¹Am) to 662 keV (¹³⁷Cs), although they have not yet reached that of the corresponding crystals. The measured response linearity over the same energy range is comparable for both our HWE synthesized films and melt-grown commercially-available reference crystals. Similar consistency in response is also observed in terms of their decay time and afterglow behaviors. The data collected so far demonstrate that our HWE technique permits the rapid creation of scintillators with desired structural and compositional characteristics, without the introduction of appreciable defects, and yields material performance equivalent to or approaching that of crystals. Consequently, the deposition parameters may be manipulated to tailor the physical and scintillation performance of the resulting structures, while achieving a cost per unit volume that is substantially lower than that of crystals. In turn, this promises to allow the use of these novel scintillation materials in such applications as SPECT, PET, room-temperature radioisotope identification and homeland security, where large volumes of materials in a wide variety of shapes and sizes are needed. This paper describes our growth and testing of polycrystalline LaBr₃:Ce scintillators and provides comparative characterizations of their performance with crystals.     

Characterization of Yb:YAG and Yb:YAP scintillators by means of LAAPD at temperature around 100 K

A new class of scintillators based on charge-transfer luminescence of the Yb³⁺ ion is being investigated for the last few years. The main prospect for these scintillators is in neutrino physics. The crystals manifest maximum light output at temperatures 100 K<T<150 K. In this range Large Area Avalanche Photodiodes (LAAPD) are the best photodetectors. In this work Yb(25%):YAG and Yb(5%):YAP scintillators were characterized by means of a 16 mm diameter API LAAPD at temperatures around 100 K. Light yield and energy resolution were determined. Light yield non-proportionality was detected for all the crystals comparing light output at 661.6 and 59.6 keV peaks.     

快速闪烁晶体在未来高能物理实验中的应用

简要综述了快速闪烁晶体在未来高能物理实验中的应用和目前研究进展.在未来高亮度强子对撞机（HL LHC）上通过采用高亮度、快速和高抗辐照强度的LYSO晶体为CMS的量能器升级,可以建成具有良好E/γ能量分辨率的稳定的精密电磁量能器.通过读取PbF2,PbFCl和BSO晶体中的切伦科夫光和闪烁光,可以为未来的轻子对撞机建立具有良好的喷注能量分辨率的均匀强子量能器.有亚纳秒衰变时间的BaF2晶体将为未来的高能物理强度前沿实验建立在速率及时间分辨率提高超过10倍的晶体量热器.对新型快闪烁晶体如PbFCl,YAP:Yb,ZnO:Ga和CuI的研究可能为今后高能物理实验发挥重要作用.     

Growth and characterization of strontium metaborate scintillators

The undoped and 0.5% Ce³⁺-doped strontium metaborate SrB₂O₄ single crystals has been grown successfully by micro-pulling down method with radio frequency (RF) heating system, and scintillation characteristics including optical properties and radiation response were studied for these crystals. The Ce³⁺-doped SrB₂O₄ crystal showed absorption band around 240–320 nm, which is corresponding to the 4f-5d transition of Ce³⁺. Intense emission band at 375 nm due to the Ce³⁺ 5d–4f transition was observed under ²⁴¹Am 5.5 MeV α-ray excitation. The scintillation decay time showed fast (50 ns) and slow (1430 ns) components ascribed to the Ce³⁺ 5d–4f transition and lattice defect in the crystal, respectively. The scintillation light yield of Ce³⁺-doped SrB₂O₄ was calculated to be about 1000 ph/n under ²⁵²Cf irradiation.