Influence of PbF2 and MoO3 on properties of PbWO4 crystals

The influence of doping (with F, Gd and Mo ions) and co-doping (with F, Gd or F, Gd, Mo ions) of PbWO₄ crystals was investigated. It is shown that even a small amount of specific impurities (especially F ions) causes an important redistribution of the point defects and changes the physical properties of the crystals. The cell parameters were refined from X-ray powder diffraction data. It was found that the cell parameters of F-doped PbWO₄ samples are larger than those of undoped samples. Photoluminescence and optical transmission spectra of pure and doped PbWO₄ were investigated.     

Effects of Ce3+ energy level structure on absorption and luminescence properties of Ce-doped YAlO3,Y3Al5O12,and LaAlO3 single crystals

We investigate the spectra and scintillation properties of Ce:YA103,Ce:Y₃Al₅O₁₂,and Ce:LaA103.For Ce:YAlO₃,the excitation spectrum is very similar with the absorption spectrum;for Ce:Y₃Al₅O₁₂ and Ce:LaAlO₃,the excitation spectra are different from the absorption spectra.Further,Ce:YAlO₃ has better scintillation performance than Ce:Y₃Al₅O₁₂ whereas Ce:LaAlO₃ has not demonstrated scintillation performance to date.We also provide reasonable explanations for these experimental phenomena from the viewpoint of energy level structure.     

Time-resolved optical absorption in YAlO3 crystals

The present work is devoted to the investigation of transient absorption (TA) induced by a pulsed electron beam (E=250 keV) in pure and doped YAlO₃ (YAP) single crystals. The nature of centers responsible for TA is discussed.     

Red emission of PbWO4 crystals

Luminescence characteristics of a large number of undoped and doped PbWO₄ crystals, grown by the Czochralski or Bridgman method, as-grown or annealed in the nitrogen atmosphere or in air, were studied in the 4.2–300 K temperature range. Two types of red emission centres were found. The centres with the emission band, peaking at 4.2 K at 1.57 eV, were observed in most of the crystals studied. The centres with the emission band, peaking at 4.2 K at 1.48 eV, were observed only in the PbWO₄ : Mo⁶⁺, Y³⁺ crystal. It is suggested that incompletely compensated lead vacancies are responsible for the appearance of the red emission.     

Perturbed Al photon echo ENDOR double resonance in Pr:YAlO3 and Eu:YAlO3

Aluminum pure quadrupole spectra measured by photon echo ENDOR double resonance (PENDOR) are reported for crystals of YAlO₃ doped with Pr³⁺ and for crystals doped with Eu³⁺. These spectra, which correspond to aluminum nuclei adjacent to a rare earth impurity, are compared to the results of a conventional NMR study of ²⁷ Al in YAlO₃.     

Electron spin resonance study of Mo centers in YAlO3

Electron spin resonance measurements of Ce-doped YAlO₃ single crystals (40–50 ppm of Ce) grown by Czochralski method from Molybdenum crucibles evidenced two kinds of Mo³⁺ centers. The ESR spectra of both centers were described by spin Hamiltonian with orthorhombic symmetry and an effective electron spin . The experimental g-factors as well as four magnetically nonequivalent positions found for each center support a hypothesis that Mo impurity ion is located at Al site. Under high-temperature annealing and UV irradiation the Mo centers show the change of charge state, indicating, that they are probably involved in the charge carrier capture in the energy transfer and storage processes in this scintillator material.     

Radiation-stimulated defects into LaB3O6 and Li6Gd(BO3)3:Ce single crystals

The radiation-induced defect types in LaB₃O₆ and Li₆Gd(BO₃)₃:Ce single crystals have been determined taking into account crystal-lattice features, absorption characteristics, photo- and thermostimulated luminescence data. The possible activator center models in Li₆Gd(BO₃)₃:Ce crystals are proposed.     

Scintillation properties of PbWO4 crystals doped with the rare-earth ions

In PbWO₄(PWO) crystals grown by Czochralski method the influence of atmosphere of the growth (O₂, air) and doping with the rare-earth ions of different types (A³⁺=Lu³⁺, Gd³⁺,Tb³⁺,Eu³⁺ as well as doubly doped A³⁺–Li⁺) on light yield and luminescence decay were analyzed. PWO scintillator with the ultra-fast (τ=0.5 ns) main component of luminescence decay (87% of total light yield) was obtained using the O₂-growth atmosphere and doping by Eu₂O₃ at a concentration of 5000 ppm. It is concluded that the decrease of decay constant of the main scintillation component is the result of the resonant energy transfer between the centers of “blue” PWO luminescence (λ_max=420 nm) and the 4f–4f-transitions of Eu³⁺ ions in this spectral region.     

YAlO3晶体中pr3+的4f2能级

YAlO3∶pr3+是一种受到广泛关注的发光体系,本文根据文献中给出的YAlO3∶pr3+晶体中Pr3+的晶体场能级,从Nd3+离子的晶体场参数和Pr3+的准自由离子参数出发,采用f-shell计算软件包对pr3+的能级参数进行了研究,并对获得的参数进行了讨论.用拟合获得的参数计算了pr3+的4f2电子构型的所有能级.     

Scintillation properties of the Yb-doped YAlO3 crystals

Yb³⁺-doped YAlO₃ single crystals were grown by the Czochralski method with a radio frequency heating system. The starting melt compositions of Y_1−xYb_xAlO₃ were varied as x=0.02, 0.1, 0.2, 0.3 and 0.45. Photo- and thermo-luminescence characteristics including emission decays were measured within 4–300 K. Very fast charge transfer luminescence of Yb³⁺ was found, with the typical double peak spectrum at 345 and 525 nm. At room temperature the photoluminescence and scintillation decay curves show a leading subnanosecond decay component without any additional slower processes. The high density of Yb-rich YAlO₃ makes this material a promising candidate for fast scintillators.     

X-ray damage characterization in BaLiF3,KMgF3 and LiCaAlF6 complex fluorides

Two-inch sized KMgF₃,BaLiF₃ and LiCaAlF₆ (LiCAF) single crystals were grown by the Czochralski method under a CF₄ atmosphere. X-ray irradiation was used to carry out a comparative study of induced optical absorption phenomena and colour centre creation in the ultra-violet and visible spectral regions. The integral of the induced absorption spectra is significantly lower in LiCAF with respect to the other studied materials. It is found that the amplitude of the F-absorption band is suppressed more than a factor of 3 by Mg-doping. For Mg-doped crystals, the optimum doping concentration is about 0.2 mol% of Mg²⁺.     

Scintillation properties of K2LaCl5 with Ce doping

In this work we present the scintillation properties of K₂LaCl₅ doped with Ce³⁺ concentrations of 0, 0.1, 1 and 10%. Under X-ray excitation the crystals show the efficient Ce³⁺ (5d–4f) luminescence between 340 and 400 nm. Depending on the Ce concentration, the light yields vary between 24,000 and 50,000 photons/MeV (ph/MeV). Experiments with 662 KeV gamma ray excitation show light yields varying between 13,000 and 30,000 ph/MeV. For Ce luminescence a single exponential decay time of approximately 40 ns is expected. However, for K₂LaCl₅:10%Ce, the decay is not single exponential. As a function of the time t, it can be described by a 1/t^1.63 behaviour for large t. With a crystal of K₂LaCl₅:10%Ce we obtained an energy resolution of 5.1% for 662 KeV gamma ray excitation of ¹³⁷Cs.     

Decay kinetics of the green emission in tungstates and molybdates

Luminescence characteristics of a number of undoped and variously doped PbWO₄ crystals were studied at 0.4–400 K by the time-resolved spectroscopy and compared with those of ZnWO₄,CdWO₄ and PbMoO₄ crystals. Two types of green emission centres are detected in PbWO₄ crystals. The centres of the first type are responsible for the low-temperature 2.3–2.4 eV emission observed under excitation around 3.90–3.95 eV. The structure and parameters of their relaxed excited states were determined. It was concluded that the origin of defects responsible for the green emission of the first type could vary for different crystals. The centres of the second type with the emission around 2.5 eV appear in crystals containing oxygen vacancies after the thermal destruction of Pb⁺-WO₃ centres at T>180 K. Decomposition of the exciton and various defect-related states was also studied, and activation energies of this process were calculated.     

Luminescence study of pure and Fe- or Mo-doped ZnWO4 crystals

ZnWO₄, ZnWO₄:Fe and ZnWO₄:Mo crystals were investigated by the methods of time-resolved spectroscopy in the temperature range of 4.2–300 K. It is shown that the Mo and Fe impurities significantly reduce the light yield of ZnWO₄. The main 2.5 eV emission of ZnWO₄ and the 1.77 eV emission band of ZnWO₄:Mo are shown to originate from the triplet excited state of the WO₆ and MoO₆ complex, respectively. In ZnWO₄:Fe,Mo the MoO₆ emission band is shifted to lower energies due to the perturbing influence of the iron impurity. No perturbing effect of Fe or Mo ions was observed for the main emission of ZnWO₄:Fe and ZnWO₄:Mo. The creation spectrum of self-trapped holes was measured for ZnWO₄, ZnWO₄:Fe and ZnWO₄:Mo crystals in the energy region of 4–30 eV.     

稀土(La/Ce/Pr/Nd)掺杂锐钛矿相TiO_2磁性及光催化活性的第一性原理研究

采用密度泛函理论下的平面波赝势方法,建立了未掺杂锐钛矿TiO_2和La/Ce/Pr/Nd单掺杂的锐钛矿TiO_2模型.几何优化后,通过计算形成能分析了掺杂结构的稳定性;通过自旋电子态密度的计算分析了各个掺杂模型的磁性状态,并采用比较磁性基态能量的方法对分析结果加以验证;讨论了各稀土元素掺杂对锐钛矿能带结构和吸收光谱的影响.结果表明:La/Pr掺杂的锐钛矿TiO_2具有亚铁磁性,Nd掺杂的锐钛矿具有反铁磁性,Ce掺杂锐钛矿为顺磁体;Ce掺杂对锐钛矿能带结构影响较小,吸收光谱红移不明显,而La/Nd掺杂则能有效提升锐钛矿对可见光的吸收系数,Pr掺杂能使锐钛矿TiO_2在红外光区出现吸收峰.     

Ce和O空位共掺杂TiO_2的电子结构与光学性质

采用基于密度泛函理论加U的计算方法,研究了Ce和O空位单(共)掺杂锐钛矿相TiO_2的电子结构和光吸收性质.计算结果表明,Ce和O空位共掺杂TiO_2的带隙中出现了杂质能级,且带隙窄化为2.67 eV,明显比纯TiO_2和Ce,O空位单掺杂TiO_2的要小,因而可提高TiO_2对可见光的响应能力,使TiO_2的光吸收范围增加.光吸收谱显示,掺杂后TiO_2的光吸收边发生了显著红移;在400.0—677.1 nm的可见光区,共掺杂体系的光吸收强度显著高于纯TiO_2和Ce单掺杂TiO_2,而略低于O空位单掺杂TiO_2.此外,Ce掺杂TiO_2中引入O空位后,TiO_2的导带边从-0.27 eV变化为-0.32 eV,这表明TiO_2的导带边的还原能力得到了加强.计算结果为Ce和O空位共掺杂TiO_2在可见光光解水方面的进一步研究提供了有力的理论依据.     

Radioluminescence of Lu2O3:Eu nanocrystalline powder and vacuum-sintered ceramic

Nanocrystalline powders of Lu₂O₃:Eu with the activator content varying in the range of 0.2–10% were prepared through a combustion technique. The powders were only slightly agglomerated and the size of crystallites were about 30 nm. Some of the powders were co-doped with Mg, Ca, Sr, Ba, La of various concentrations. Such powders were cold-pressed and sintered at 1750°C for 5 h in vacuum. X-ray-excited luminescence spectra of both the powders and the sintered ceramics were recorded and the efficiency was compared to the commercial standard Gd₂O₂S:Pr,Ce,F X-ray phosphor. It was found that the nanocrystalline powders of Lu₂O₃:Eu,Ca emit photons four-times less than the commercial micron-sized Gd₂O₂S:Pr,Ce,F powder. In the case of sintered materials the emission efficiency from our Lu₂O₃:Eu5%, Ca was roughly equal to the efficiency of the commercial-sintered Gd₂O₂S:Pr,Ce,F. The co-doping ions were shown to have various effects on the transparency of the sintered Lu₂O₃:Eu. Mg hindered the sintering process producing completely opaque pellets. Other ions facilitated the sintering course and the best results were obtained by co-doping the samples with 0.5% of Ba. Sr and La also significantly stimulated the sintering and the final pellets were only slightly cloudy.     

Optical absorption of isotopically enriched Li2B4O7 single crystals irradiated by thermal neutrons

Induced absorption spectra in the range 200–900 nm at 77 and 290 K for Li₂B₄O₇ single crystals, isotopically Li and B enriched are presented after irradiation of these crystals by thermal neutrons with fluence 1.8×10¹⁶ cm⁻². The dependence of induced absorption spectra on the isotope composition was revealed: for ⁶Li₂¹⁰B₄O₇ and ⁷Li₂¹⁰B₄O₇ crystals intensive band in the region of 280–294 nm was observed. Under substitution of ⁷Li isotope by ⁶Li in the lithium tetraborate lattice no changes in the absorption spectra were observed. The nuclear reaction ¹⁰B(n,)⁷Li is proposed to be the main mechanism of formation of the radiation defects.     

第一性原理方法研究N-Pr共掺杂ZnO的电子结构和光学性质

作为一种稳定性好、抗辐射能力强、原材料丰富的宽禁带半导体, ZnO在光催化的研究领域中成为热点材料,但是其仅能吸收可见光中的紫光,因此如何扩大ZnO对可见光的响应范围是一个值得研究的问题.掺杂改性是解决这个问题的常用方法.基于以上考量,本文应用第一性原理计算方法研究了N与Pr掺杂对ZnO的电子结构和光学性质的影响.研究结果表明:共掺体系比单掺体系更容易形成,且共掺体系的稳定性随Pr浓度的增加先增强后变弱;同一体系的最短Zn—O键与最长Zn—O键的布居数比例随杂质浓度的增大先增大后减小,说明杂质的掺入对体系的晶格畸变有很大的影响,有利于光生空穴-电子对的分离,从而提高材料的光催化活性. N 2p态与Pr 4f态发生杂化对晶体的完整性产生了破坏,在杂质原子周围形成晶场,造成能级劈裂,带隙减小;介电函数虚部的主峰位均向低能区域移动,吸收光谱中各掺杂体系发生红移,各共掺体系随着杂质原子Pr浓度的增加,在可见光区的响应范围依次扩大,吸收能力也依次增加,说明N与Pr的共掺杂对提高ZnO的光催化性是有利的.     

Recombination luminescence in lead tungstate scintillating crystals

Room temperature radioluminescence and photoluminescence decay kinetics measurements of Ba-doped PbWO₄ crystals were compared with those of undoped and Mo-doped samples. Photoluminescence decay measurements focus on the coexistence of the immediate (fast) decay having a decay time of a few nanoseconds with slower delayed recombination decay processes. The radioluminescence emission peaking at 500 nm in Ba-doped crystals is similar to that observed in Mo-doped samples. However, photoluminescence of the Ba-doped crystals shows much faster decay kinetics with respect to that of PbWO₄:Mo. Wavelength-resolved thermally stimulated luminescence data (10–300 K) provides complementary information about trapping states and is correlated to photoluminescence decay kinetics.