Spectroscopic Properties of Ce：YAP Scintillation Crystal Grown by Temperature Gradient Technique

Spectroscopic properties of Ce-doped yttrium orthoaluminate （Ce：YA1O3 or Ce：YAP） crystals gown by temperature gradient technique （TGT） were investigated, and the effects of the growth conditions on the properties were analyzed. Methods of optical absorption （OA）, photoluminescence （PL）, photoluminescence decay （PLD）, X-my excited luminescence （XL） and cathodeluminescence （CL） were used in these investigations. The results showed that the absorption band peak at 202,394 and 532 nm originated from F and F^＋ color center induced by the weak reducing growth atmosphere, green emission band near 500 nm derived from Ce3^＋ -Ce^3＋ pairs and band at 650 - 850 nm from some unintentional impurity in crystals.     

Effects of Annealing Treatments on Luminescence and Scintillation Properties of Ce：Lu3 Al5 O12 Crystal Grown by Czochralski Method

Lu3Al5O12 single crystals grown in pure N2 atmosphere by Czochralski method were annealed in oxidizing atmosphere （air）and reducing atmosphere （H2 ＋ N2）, respectively. Effects of annealing treatments on luminescence and scintillation properties of the crystals were investigated. The crystal annealed in air showed the highest luminescence intensity under blue light or vacuum ultraviolet excitation in comparison with that annealed in reducing flux or the as-grown crystal. Under X-ray excitation, crystal annealed in reducing atmosphere had the lowest light yield, and crystal annealed in air had the fastest decay time under ^137Cs 662 keV γ-ray excitation. Different annealing treatments resulted in different luminescence and scintillation properties, which might related with oxygen vacancies or defect existing in the crystals.     

YAG: Ce Phosphors for WLED via Nano-Pesudoboehmite Sol-Gel Route

The sub-micron sized YAG: Ce phosphors were synthesized via a modified sol-gel method by peptizing nano-pesudoboehmite particulate. It is found that YAG phase from the dried gel powders appears at 1000 ℃ then the pure YAG phase exists at a relatively lower sintering temperature of 1400 ℃. The smaller sizes of phosphors in the ranges of 1 ～ 3 μm are obtained due to the contribution of seeding effects of nano-sized alumina particles to strengthen each step of the processes. Both the excitation and emission spectra of photoluminescence of the phosphor obtained at 1400 ℃ meet well with the spectroscopic requirements of the WLED phosphors.     

Ab Initio Calculation of 4f→5d Transition Energy and Electronic Structure of Ce3+ Doped in LiYF4 Crystal

The electronic structures of LiYF4:Ce3 and LiYF4 crystals simulated by an embedded (in a microcrystal containing 1938 ions) cluster CeY4Li8F24, and Y5Li8F24 respectively, were computed by the ab initio self-consistent relativistic DV-Xa(discrete variational Xa) method. The ground-state calculation showed that only the lowest 5d level Ed of Ce3 ion lies around the BCB (bottom of the conduction band) while the lowest 4f levels is 2.5 eV lower than BCB. The CB states consist of 4p of Y mixed with 5d of Ce, even for the wavefunctions (WFS) of Ed under BCB there are still 24% of Y-4p and 9% of F-2p as components. Furthermore, transition state (TS) calculation was performed in this work to obtain the 4f→5d transition energies Efd, to improve the calculation of Ref.[6] in which a small CeF8 cluster embedded in an array of point charge was used and the results of ground-state calculation were roughly used to compare directly with the observed 4f→5d transition energies. The ionic radius of Ce3 is larger than that of Y3 , for modeling approximately the lattice relaxation, we simply let the eight fluorine ions of the nearest-neighbor and next-nearest-neighbor move out radially and simultaneously. As results, the CeY4Li8F24 cluster with 4.56% outward relaxation of the eight fluorines has the lowest total energy and gave satisfactory 4f→5d energies Efd, but the calculated ground-state Ed is 0.68 eV higher than BCB. For another cluster with 7.36% outward relaxation the Ed is 0.43 eV lower than BCB, which makes the observation of fine structure (including zero-phonon line) of the lowest 5d band understandable easier, but the splits between the transition energies Efd were not as good as the former. Therefore, we consider the relaxation is somehow around 4.56%～7.36% outward, not as large as 10%.     

Hydroxyl groups in nonmetamict chevkinite-(Ce):a crystal chemical discussion

The minerals of chevkinite group were commonly considered to be anhydrous minerals. The infrared absorption spectrum of natural nonmetamict chevkinite-(Ce) from the aegirine-alkali granite, Mianning, Sichuan Province, China, exhibited two broad peaks in the 3600-2800 cm-1 region owing to the OH stretching. The corresponding H2O content required for the charge balance in formula was 1.27%. The O-H ··· O bond lengths maight cover from 0.2658 to 0.2794 nm by the correlated OH stretching energies. An electrostatic charge balance for chevkinite-(Ce) based on the assigned site-population from chemical data was calculated without the hydrogen contribution. The resulting empirical bond-valence sum on O6, O8, O2, O3, O5, and O4 ranged from 1.73 to 1.95 vu. The partial substitution of O by OH may occur in four atom sites: O6, O2, O4, and O5. The small differences in the bond-valence sums between the supposed donors and acceptors may mean a mixed donor/acceptor role of the involved oxygen atoms. The IR spectral features between 3394 and 3035 cm-1 consisted of various hydrous species at different structural sites and orientations. The OH groups in the chevkinite-(Ce) appeared to be involved in local charge imbalance in the structure and to be present when the mineral crystallized hydrothermally.     

Photorefractive Properties of Potassium Lithium Niobate Crystals with CeO2 and Nd2O3

KLN and Ce：Nd：KLN crystals were gown by Czochralski method and polarized into single ferroelectrics domain along c-axis. The properties of KLN and Ce：Nd：KLN crystals, such as Curie temperature, Raman spectra, exponential gain coefficient （Г） and thin crystal sheet effect, were measured. The results showed that the two spectra resembling Ce：Nd：KLN crystal were of tetragonal tungsten bronze structure, the exponential gain coefficient of Ce：Nd：KLN crystal was higher than that of KLN crystals and Ce：Nd：KLN crystal had thin crystal sheet effect, for its exponential gain coefficient increasing with crystal sheet thinning. The thin crystal sheet effect of Ce：Nd：KLN crystal was also discussed.     

Preparation of SiO2 coated Ce2S3 red pigment with improved thermal stability

SiO2 coated Ce2 S3 red pigment was prepared in ethanol/H2 O system via sol-gel method and TEOS were used as silica sources.X-ray diffraction(XRD),scanning electron microscopy(SEM),energy dispersive spectroscopy(EDX),UV-visible spectrophotometer and automatic colorimeter were used to investigate the properties of the samples.The results showed that the compact SiO2 film formed on the surface of Ce2 S3 pigment at a cerium silicon molar ratio of 2.The thermal stability temperature of Ce2 S3 pigment was improved to 450 oC after SiO2 coating.In addition,the color of Ce2 S3 pigment was not affected significantly through coating colorless and transparent SiO2 and it could be used as safe red pigment in higher temperature fields.     

Theoretical study of the VUV spectroscopy of Ce3+ and Tb3+ in BaBPO5 crystal using an empirical-ab initio hybrid method

The f-d transition of Ce3+and Tb3+in BaBPO5 was studied theoretically using the parametric Hamiltonian model.In order to overcome the difficulty in determining many of the parameter values,we adopted the model-space effective Hamiltonian method to determine the crystal-field parameters and spin-orbit parameters values.The method made use of the energies and eigenvectors,which were obtained from an ab initio calculation using the relativistic self-consistent discrete variational Slater software package(DV-Xα).Other parameters,which were less dependent on host crystals,were taken from published data.The calculated values of parameters were reasonable,and the energy-levels and f-d transition spectra agreed reasonably well with the measured excitation spectra of 5d-4f emission.     

Synthesis of YAG:Ce3+ Phosphor by Polyacrylamide Gel Method and Promoting Action of α-Al2O3 Seed Crystal on Phase Formation

YAG:Ce3 phosphor particles were prepared using polyacrylamide gel method. The structure evolution of powders during annealing process was followed by X-ray diffraction determination. It is found that some intermediate phases, including θ-Al2O3, YAM and YAP, are formed when calcining polyacrylamide gel, however, the pure YAG phase can be formed directly when calcining polyacrylamide gel with α-Al2O3 as seed crystal. These facts show that the existence of α-Al2O3 seed crystal can block the formation of θ-Al2O3, YAM and YAP, and accelerate its reaction with Y2O3 to form YAG phase directly at lower temperature. The emission peak of prepared YAG:Ce3 phosphor is wide with maximum at 550 nm and the exitation band has two peaks, the major one is around at 460 nm, which matches the blue emission of GaN LED and is suitable for the assemble of white LED. Some fluxes can enhance the photoluminescence intensity of phosphor particles, that can be attributed both to the improvement of crystallization processes of YAG and to the stabilization of trivalence cerium ion in YAG:Ce3 .     

Optical characteristics of Ce,Eu:YAG single crystal grown by Czochralski method

Eu-doped Ce:YAG single crystal (SC) was fabricated by the Czochralski method. The crystal structure, optical and photoelectric property of the constructed w-LED was investigated. The XRD and HRTEM results show that YAG crystal structure has little change when Eu³⁺, Ce³⁺ are doped. Absorption spectra and photoluminescence spectra show that the Ce,Eu:YAG single crystal can effectively absorb the 460 nm blue light to form a broadband emission center at 530 nm, decay curves of the crystal show that the energy transfer between Ce³⁺ and Eu³⁺ is highly suppressed. Compared with commercial Ce:YAG phosphor, Ce,Eu:YAG exhibits better thermal stability.     

Robust YAG:Ce single crystal for ultra-high efficiency laser lighting

At present, solid-state laser-driven lighting fabricated with blue laser diode (LD) and phosphor has been greatly developed in high-power lighting applications. The major obstacle is the luminescence saturation threshold of the fluorescence conversion material (YAG:Ce). In this work, we successfully prepared a series of high-quality and robust YAG:Ce single crystals. With high quantum efficiency (QE = 92%), regular crystal structure and high thermal conductivity, the single-crystal has excellent ability to deal with high radiation flux and thermal accumulation generated by high power. Matching the single-crystal with the laser, the luminous efficiency up to 274 lm/W and saturation threshold of 12 W/mm² were obtained. In addition, the influence of Ce doping concentration and sample processing conditions on the indicators in laser-driven white lighting was systematically studied. The results are of great significance and are believed to promote the development of solid-state laser-driven lighting.     

Citrate sol-gel combustion preparation and photoluminescence properties of YAG:Ce phosphors

Yellow-emitting YAG:Ce3+ nanocrystalline phosphors were prepared by citrate sol-gel combustion method using citric acid as the fuel and chelating agent. The influence of mole ratio of citric acid to metallic ions (MRCM), pH value of the solution, calcination temperature and Ce-doped concentration on the structures and properties of as-prepared powders were investigated in detail. Higher crystallinity and better luminescence performance powders were obtained at MRCM=2, pH=3 and the calcination temperature of 1200 °C. The phosphors exhibited the characteristic broadband visible luminescence of YAG:Ce. The optimum concentration of Ce3+ was 1.0 mol.%, and the concentration quenching was derived from the reciprocity between electric dipole and electric quadrupole (d-q). Especially, the pH value of the solution was a key factor to obtain a stable sol-gel system and then obtain pure and homogeneous rare earth ions doped YAG phosphors at a lower tem-perature. The Y3Al5O12:Ce0.03 phosphor with optimized synthesis-condition and composition had a similar luminescence intensity with the commercial phosphor YAG:Ce.     

Synthesis of LaPO4:Ce, Terbium by Co-Precipitation Method

The synthesis of precursor of green phosphors, LaPO4:Ce, Tb, by means of co-precipitation with cocurrent flow feed was studied. The effects of the reaction temperature, the kind and concentration of the acid in the bottom water, and the charging rate on the physical properties, such as particle size, were investigated. It is found that the particle size of the powder is controllable by adjusting acidity in bottom water and charging rate. The powder with diameter size of 3 to 5 μm was obtained. Its XRD and SEM were analyzed. XRD patterns of the as-prepared green phosphor powders display the typical peaks of CePO4. SEM shows that the morphology of powders is ball-shaped.     

A New Promising X-Ray Storage Phosphor BaBrCl:Eu2+

Photostimulated luminescence was observed in X-ray irradiated BaBrCl doped with Eu2 . It shows an emission band that peak at 413 nm, and two difference absorption spectra (DAS) bands that peak at ～550 nm and 675 nm respectively. The stimulation energy is lower than that of BaFX:Eu2 (X=Cl, Br), and matches the cheaper, more portable, and more convenient semiconductor laser better. The results indicate that BaBrCl:Eu2 shows positive potential as a promising X-ray storage phosphor for practical utilization.     

Temperature effects on photoluminescence of YAG:Ce3+ phosphor and performance in white light-emitting diodes

The well crystalline YAG:Ce3 phosphor was synthesized by solid-state method, and the temperature dependence of excitation and emission spectra of YAG:Ce3 phosphor were investigated in the temperature range from room temperature to 573 K. With temperature increasing, it was noted that the emission intensity of as-prepared phosphors decreased considerably more rapidly when pumped by 460 nm than by 340 nm. The temperature-intensity curves under different excitation wavelengths were obtained using an Arrhenius function, and the corresponding activation energies were also obtained respectively. Thus, the experimental phenomenon was discussed in terms of nonradiative decay rate. The effects of as-prepared phosphors on the performance of the white LED with changing temperature were also studied.     

Synthesis and crystal structure of（C5Me4SiMe3）[（^iPrN）2CCH2SiMe3]2Y

Reaction of (C5Me4SiMe3)Y(CH2SiMe)2(THF) with two equivalents of iPrN=C=NiPr in hexane at room temperature afforded a mixed-ligand yttrium complex (C5Me4SiMe3)[(iPrN)2CCH2SiMe3]2Y. X-ray diffraction revealed that the center metal was nine-coordinated by one cyclopentadienyl ring and two amidinate ligands, and adopted a four-legged piano stool geometry.     

Influence of Rare Earth Elements on Luminescent Properties of Y2SiO5:Tb

Photoluminescent(PL) and cathodoluminescent(CL) properties of rare earths (Sc3 , La3 , Gd3 and Lu3 ) doped (Y0.97Tb0.03)2SiO5 were studied. Rare earth doping clearly influences PL and CL properties of Y2SiO5:Tb. For La3 doped system, PL intensity increases nearly 10% at x=0.05 whereas for Lu3 doped system, the intensity increases about 20% at x=0.20. Gd3 doping and Sc3 doping reduce the intensity; at x=0.3, it is reduced about 30% for Gd3 doped system and about 15% for Sc3 doped system, respectively. Quenching concentration of activator became higher in rare earth doped samples, which may be understood by that the rare earth dopants might dilute the concentration of the activator. Additionally, doping also influences the color saturation of Y2SiO5:Tb. Sc3 , La3 , and Gd3 doping improve the color saturation, whereas Lu3 doping decreases the color saturation. CL measurements show that CL intensity increases for all rare earths doped systems. The energy transfer from Gd3 to Tb3 was discussed.     

Relationship between Crystal Structure and Luminescence Properties of （Y0.96-x Lnx Ce0.04 ）3 Al5 O12 （LH=Gd,La, Lu） Phosphors

The doping effects of La^3＋, Gd^3＋ and Lu^3＋ on the crystal structure and luminescence properties of （Yo96-x LnxCe0.04）3Al5O12（Ln = Gd, La, Lu） phosphors were studied. The X-ray diffraction patterns presented that with the inerease of the doping concentrations of La^3＋ and Gd^3＋ ions, the d-value of （Y0.96-xLnxCe0.04）3Al5O12 （Ln = Gd, La） inereased and the larger the doping ion, the stronger the effect would be. The doping amount causing phase transition in （Y0.96-xLnxCe0.04）3Al5O12 decreased with the inerease of the ionic radii of the doping lanthanide ions （La^3＋： 0.106 nm, Gd^3＋： 0. 094 nm, Lu^3＋ ： 0.083 nm）. The bigger doping ion of Gd^3＋ made the emission of （Y0.96-xGdxCe0.04）3Al5O12 move to red spectral region, but the smaller one of Lu^3＋ made it blue.     

Long Lasting Phosphorescence in Eu2+ and Ce3+ Co-Doped Strontium Borate Glasses

Long lasting phosphorescence (LLP) was observed in Eu2+, Ce3+ co-doped strontium borate glasses prepared under the reducing atmosphere due to the emission of both Eu2+ and Ce3+. The methods of photoluminescence, thermoluminescence and phosphorescence were used to study the samples, and possible mechanism was suggested. The co-doping of Ce3+ ions poisoned the phosphorescence emission of Eu2+ because of the competition to obtain the trapped electron. The phosphorescence of Ce3+ in the sample decays more quickly than that of Eu2+, which is suggested for the reason that the emission energy of Ce3+ is higher or the distance between Ce3+ and electron traps of the glasses is longer.     

Radiation induced color centers in cerium-doped and cerium-free multicomponent silicate glasses

The effect of doped cerium on the radiation-resistance behavior of silicate glass was investigated in our work. The ultraviolet-visible absorption spectra and electron paramagnetic resonance（EPR） spectra were obtained after the cerium-rich and cerium-free multicomponent silicate glasses（K509 and K9） were irradiated by gamma rays with a dose range from 10 to 1000 kGy. The results showed that E’ center, oxygen deficient center（ODC） and non-bridging oxygen hole center（HC1 and HC2） were induced in K9 and K509 glasses after radiation. The concentrations of all color centers presented an exponential growth with the increase of the gamma dose. Moreover, the concentration of HC1 and HC2 in cerium-doped K509 glass was much lower than that in cerium-free K9 glass at the same dose of radiation, which could be attributed to the following mechanism： Ce3＋ ions capturing holes then forming Ce3＋＋ centers inhibited the formation of hole trapped color centers（HC1 and HC2） and Ce4＋ ions capturing electrons to form Ce3＋ centers suppressed the formation of electron trapped color centers like E’ center.