高光输出快衰减高温无机闪烁晶体的研究与发展

无机闪烁晶体在影像核医学诊断、工业在线无损检测、油井勘测以及高能离子探测等领域有着广阔的应用背景.尽管不同应用领域对闪烁晶体性能的要求各异,但是不同应用领域要求闪烁晶体具有高光输出、快响应速度以及优良的物化性质等特点却是一致的.因此,近年来,寻求具有高光输出快衰减等综合性能优良的无机闪烁晶体引起了人们的极大兴趣.本文综述了具有高光输出和快衰减无机闪烁晶体的研究与发展趋势,重点阐述了掺杂Ce3+离子的高温闪烁晶体的研究及发展情况.     

国产YAP:Ce闪烁晶体的相对探测能力测量

为适应在n、γ混合脉冲辐射场中对低强度快脉冲γ辐射测量的需要,近年国内新研制出实用型YAlO3:Ce(YAP:Ce)快响应无机闪烁晶体.我们使用脉冲线性电流大于1.5 A的光电倍增管,分别配置这种晶体以及CeF3、NaI等晶体构成闪烁探测器,在放射性标准源场中,对晶体的相对探测能力进行测量.测量结果表明:国产新型YAP:Ce无机晶体对这1.25 MeV 射线的探测能力比同体积的CeF3平均高一个量级,是同体积NaI的40;左右;当晶体厚度小于2 mm时,YAP:Ce与CeF3、NaI的输出比值分别大于16和44;,说明厚度越薄晶体的相对探测能力越强.     

温梯法Ce:YAG闪烁晶体的宏观缺陷观察

采用温度梯度法(TGT)成功生长了直径为76mm高光学质量的Ce:YAG高温闪烁晶体,采用偏光显微镜研究了Ce:YAG闪烁晶体中的主要宏观缺陷,观察到了生长条纹、侧心、气泡、包裹物以及应力双折射等宏观缺陷.实验结果表明,晶体中的气泡、包裹物以及应力双折射等宏观缺陷主要集中在晶体边缘部分,因此温梯法可以获得高质量的Ce:YAG闪烁晶体.     

Ce:YAP晶体生长和光谱性质

本文报道了用中频感应加热提拉法生长Ce:YAP晶体,晶体尺寸为35mm×80mm.在部分晶体中观察到了开裂、解理、孪晶、云层、核心和生长层等宏观缺陷,分析了缺陷与晶体生长温度梯度等因素的关系,对晶体样品进行了吸收光谱和荧光光谱分析.     

温梯法生长76mm Ce:YAG闪烁晶体的研究

首次采用温度梯度法(TGT)成功生长了直径为76mm高光学质量的Ce:YAG高温闪烁晶体,采用ICP-AES测试了Ce离子在Ce:YAG晶体中的分凝系数约为0.082.在室温下,测试了原生态Ce:YAG晶体的吸收光谱和X射线激发发射光谱(XEL).吸收光谱显示了Ce3+离子的3个特征吸收带,对应的中心波长分别为223nm,340nm及460nm;XEL发射谱表明Ce:YAG的发射峰为550nm,能与硅光二极管有效地耦合.     

Nanosized structural transformation and nonlinear optical properties of lithium niobium germanate glasses

Glass formation in Li₂O-Nb₂O₅-GeO₂ (LNG) system, the structure and crystallization behavior of glasses that have compositions near the ratio Li₂O/Nb₂O₅ ∼ 1 corresponding to stoichiometry of ferroelectric phase LiNbO₃ were examined by differential thermal analysis, X-ray diffraction, small-angle neutron scattering and second harmonic generation (SHG). LNG glasses were subjected to heat treatments at temperatures in the range between T_g and temperature of the first exothermic peak in order to initiate nonlinear optical activity by nanoheterogeneity formation. Transparent nanostructured glasses with second-order optical nonlinearity were obtained for compositions characterized by the Li₂O/Nb₂O₅ molar ratio ranging from 0.83 to 1.2 and GeO₂ 40-45 mol%. As prolonged heat treatments of nanostructured glasses result in crystallization of ferroelectric LiNbO₃ the origin of SHG in transparent LNG glasses is supposed to be connected predominantly with polarity of nanoheterogeneities formed at the initial stage of phase separation.     

YAG:Ce荧光粉体的柠檬酸盐分解法制备和表征

通过对柠檬酸盐分解法的改进,在800℃的低温下合成了YAG:Ce立方晶荧光粉体,用X-射线衍射法研究了YAG的成相过程.结果表明:Y2O3与Al2O3的摩尔比为33∶5时更易形成YAG相,成相过程是由无定型态直接转变为YAG相的.同时考察了样品的发光性质.     

Ce3+:YAG单晶闪烁体的激发和发光特性

铈激活钇铝石榴石(Ce3+∶YAG)单晶是综合性能优良的快衰减闪烁材料.本文以普通光源、激光、同步辐射以及阴极射线为激发源,对我们生长的Ce3+∶YAG闪烁晶体的激发和发光特性进行了系统的研究.结果表明:Ce3+∶YAG单晶的激发光谱(监测荧光波长为545nm)由五个激发峰组成.不同激发条件下的发射光谱均能用双高斯峰进行较好的拟合,拟合后得到的Ce3+的5d→2F5/2和5d→2F7/2发光带的中心波长分别约为520nm和570nm.但是,不同条件激发下5d→2F5/2和5d→2F7/2发光带的强度比有较大差异,这可能与不同的激发机制和激发能传输途径有关.     

退火温度对Ce:YAlO3单晶体的影响研究

将生长完成的Ce:YAlO2单晶体在1680℃的高温氢气气氛下退火,晶体颜色、吸收光谱和荧光光谱相对于未退火的样品均发生了变化.本文对此现象进行了分析.研究结果表明,1680℃高温氢气退火后,Ce:YAP晶体中同时包含YAP相和YAG相.     

非真空密闭条件下的Ce3+: LiYF4晶体生长

本文报道了氟化物激光晶体Ce3+: LiYF4的坩埚下降法生长工艺.以高纯氟化物LiF、YF3和CeF3为初始试剂,按照LiF: YF3: CeF3 = 51.5: 47.5: 1.0的物质的量比配料,经高温氟化处理合成严格无水的Ce3+: LiYF4多晶料.将Ce3+: LiYF4多晶料密封于铂坩埚中,添加少量聚四氟乙烯粉末,可避免氟化物熔体的氧化与挥发,从而在非真空条件下实现Ce3+: LiYF4晶体的坩埚下降法生长,成功生长出尺寸达28 mm×70 mm的无色透明完整单晶.采用XRD、差热/热重分析、透射光谱和荧光光谱对Ce3+: LiYF4单晶基本性质的进行表征.结果表明,该晶体在320~3000 nm区域内的光透过率达90;以上,晶体在297 nm处有一强吸收峰;荧光光谱显示晶体在紫外光区310 nm、325 nm处有两个强发射峰.     

影响LYSO∶ Ce晶体余辉强度的几个主要因素

探究了LYSO∶ Ce晶体的余辉现象,以及在不同曝光时间、光照强度下,余辉计数率随时间的变化规律.同时探究了温度对晶体余辉强度的影响,发现加热晶体可以快速缩短余辉持续时间,这一发现为日常的晶体检测和应用带来一定便利.     

Investigation of the crystallization process in oxyfluoride glass ceramics codoped with Er/Yb

The oxyfluoride glass ceramics are important up-conversion luminescent materials. Er³⁺/Yb³⁺-codoped transparent oxyfluoride glasses were prepared by melt-quenching and subsequently heat-treated at different times and temperatures, and the crystallization process of fluoride nanocrystals from the glass was investigated. X-ray diffraction (XRD) and fluorescence spectra investigations reveal that fluoride nanocrystals are distributed homogeneously among the glassy matrix for the sample doped with Er³⁺/Yb³⁺. The crystallization process indicates that heat-treatment temperature influences the size of fluoride nanocrystals, while heat-treatment time influences their concentration. Moreover, the red emission intensities increase due to the incorporation of Er³⁺/Yb³⁺ into the fluoride nanocrystals under different heat-treatment methods, which are studied by fluorescence spectra.     

掺铈硅酸钆闪烁晶体的研究进展与发展方向

本文综述了铈离子掺质硅酸钆(Ce:Gd2SiO5)闪烁晶体的结构、闪烁性能、闪烁机理及晶体生长的研究现状,重点讨论了Ce:GSO闪烁晶体生长的研究进展;提出了硅酸钆闪烁晶体未来研究发展的几个方向为:大尺寸晶体的生长、高光输出的研究、混合型硅酸钆晶体的研究等.     

Role of flux on synthesis of poly single crystals of Ce3+ doped yttrium aluminum garnet

Yttrium aluminum garnet powders of good morphology are composed of tiny single crystals of regular faces. However, the growth mechanism of those ploy single crystals remains unknown. This paper provides morphology images of particles uncrushed, and it is found that those tiny crystals grow from large clusters in a pomegranate‐like manner. The morphology change occurs after phase transition, and is driven by flux, which provides a semi‐liquid environment around the crystals. This paper is beneficial for understanding growth mechanism of poly tiny single crystals of yttrium aluminum garnet powders.     

国产无机闪烁晶体LaCl_3∶Ce的探测能力和时间响应测量

以国产的掺铈氯化镧(LaCl3:Ce)闪烁晶体与线性电流大于1.5 A的光电倍增管构成闪烁探测器,利用 60Co、137Cs放射性标准源场,实验测量这种探测器对γ辐射的探测能力,并与同情况NaI:Tl闪烁探测器进行比对;利用266 nm单色激光和ns级的γ脉冲辐射分别对这种闪烁体的光致激发、辐射激发的时间响应性能进行测量.测量结果表明:国产新型LaCl3:Ce无机闪烁晶体样品构成的探测器对1.25 MeV 、0.66 MeV γ射线的探测能力平均约为同情况NaI:Tl闪烁探测器的103%,高的已超过了同尺寸NaI:Tl构成的闪烁探测器;266 nm单色激光光致激发时间响应波形前沿、半高宽、后沿和衰减常数分别为1.05 ns、17.42 ns、54.30 ns和24.61 ns,ns级的γ脉冲辐射激发的时间响应波形前沿、半高宽、后沿和衰减常数分别为1.52 ns、21.99 ns、75.13 ns和34.19 ns.     

硅酸镥闪烁晶体的生长与缺陷研究

本文采用提拉法生长出了硅酸镥闪烁晶体,讨论了晶体生长中遇到的问题,所生长的硅酸镥晶体有开裂、解理、多晶、回熔现象等宏观生长缺陷和包裹物、位错等微观缺陷.开裂是由热应力和晶体解理两种因素引起的,其中热应力是导致开裂的主要因素,优化生长工艺条件可完全避免开裂.晶体中存在两种包裹物,成份分别为氧化镥和坩埚材料铱,氧化镥很可能是未参加反应的原料,也有可能是氧化硅挥发而导致氧化镥析出.     

Optical and structral properties of pure and Ce-doped nanocrystals of barium titanate

Nanocrystals barium titanate (nc-BT) and Ce-doped barium titanate were synthesized by an unusual hydrothermal process. X-ray diffraction and Raman spectroscopy were used to investigate their microstructures, as well as their lattice vibration and photoluminescence (PL) spectra. Particle sizes as small as 20 nm were measured by X-ray diffraction pattern via Scherer equation. The critical size relative to the cubic-tetragonal transition is about 48 nm in nc-BT below which ferroelectricity vanishes. The lattice parameter ratio c/a of is equal to 1.003, much smaller than 1.01 for that of the bulk crystal, leading to a weakening of ferroelectricity. Hydroxyl defects are observed in the Ce-doped nc-BT samples which show a vibrational band at 3300 em t. Good crystallization character and the lattice perfection were characterized by Raman spectra in the nanophase barium titanate. Strong PL spectra centered at 696 and 585 nm were observed in the pure and Ce-doped nc-BT, respectively. PL dependence on temperature and annealing time was examined. A molecule-like recombination and the charge transfer between Ce⁴⁺ and Ce ³⁺ are proposed to elucidate the luminescence process in the nc-BT and Cc-doped nc-BT system.     

Luminescence of GeO2 glass, rutile-like and α-quartz-like crystals

The luminescence of GeO₂ rutile-like crystals was studied. Crystals were grown from a melt of germanium dioxide and sodium bicarbonate mixture. Luminescence of the crystal was compared with that of sodium germanate glasses produced in reduced and oxidized conditions. A luminescence band at 2.3 eV was observed under N₂ laser (337 nm). At higher excitation photon energies and X-ray excitation an additional band at 3 eV appears in luminescence. The band at 2.3 eV possesses intra-center decay time constant about 100 μs at 290 K and about 200 μs at low temperature. Analogous luminescence was obtained in reduced sodium germanate glasses. No luminescence was observed in oxidized glasses under nitrogen laser, therefore the luminescence of rutile-like crystal and reduced sodium germanate glass was ascribed to oxygen-deficient luminescence center modified by sodium. The band at 2.3 eV could be ascribed to triplet-singlet transition of this center, whereas the band at 3 eV, possessing decay about 0.2 μs, could be ascribed to singlet-singlet transitions. Both bands could be excited in recombination process with decay kinetics determined by traps, when excitation realized by ArF laser or ionizing irradiation with X-ray or electron beam. Another luminescence band at 3.9 eV in GeO₂ rutile-like crystal was obtained under ArF laser in the range 100-15 K. Damaging e-beam irradiation of GeO₂ crystal with α-quartz structure induces similar luminescence band.     

Fabrication of heavy metal fluoride glass, optical planar waveguides by hot-spin casting

Hot-spin casting is further investigated using a customised rig for making optical planar waveguides from inorganic-compound-glasses. The rig enables a controlled mass of core-glass, held above its liquidus, to be gravity-cast onto the top surface of a spinning cladding-glass substrate that has been pre-heated to around its glass transformation temperature. Spinning encourages the cast liquid to spread as a film over the top surface of the glass substrate. The mass of liquid cast is controlled by the timed opening of an orifice in the base of the core-glass melt-crucible. The resulting step index, slab optical waveguides are annealed, then cooled to room temperature; they comprise a higher refractive index, glass film core, on top of a lower refractive index glass substrate cladding. The glass film core is air-clad. at its upper surface. The process is applied to two heavy metal fluoride core/clad. glass pairs, namely ZBLANPb/ZBLAN and ZBLALiYPb/HBLANY (where ZBLANLiYPb is ZrF₄-BaF₂-LaF₃-AlF₃-LiF-YF₃-PbF₂ and H is HfF₄) to give waveguides of small and large numerical aperture (NA) (e.g. at 643.8 nm wavelength, NA is 0.18 and 0.33, respectively). The Hot-Spin-Cast waveguides exhibit a guiding region whose top surface tends to be parallel to the upper surface of the underlying substrate. However, flatness of the top surface of the guiding region is limited by the flatness of the top surface of the underlying substrate. Multimode slab waveguiding is demonstrated for both NA waveguide types for glass film cores of depths ?10 μm.     

Ce掺杂六方相WO3光催化剂的制备及其光解水制氢性能

采用溶胶-凝胶工艺制备了Ce掺杂六方相WO3光催化剂,Ce掺杂的摩尔分数分别为0、1;、2;、3;和5;.采用XRD和SEM表征了催化剂的结构,研究了Ce掺杂、热处理温度对WO3催化剂结构和光解水制氢性能的影响.结果表明:Ce掺杂提高了WO3催化剂的光催化活性.Ce掺杂摩尔分数为2;、热处理温度为400℃、催化剂用量为0.2g时,Ce掺杂WO3催化剂的光催化活性最好,光解水制氢速率为6.5,μmol/h.