Synthesis and densification of lutetium pyrosilicate from lutetia and silica

Cerium-doped lutetium pyrosilicate (Lu₂Si₂O₇:Ce) powder was synthesized by solid state reaction of Lu₂O₃ and SiO₂. Stoichiometric mixtures of the starting materials were heat treated at various different temperatures and their phase contents were measured by XRD technique. It was found that the first step in the formation of Lu₂Si₂O₇ (LPS) is the appearance of Lu₂SiO₅ (LSO). This takes place at 1100 °C, fully 300 °C below the first appearance of LPS. Between 1400 and 1500 °C both LSO and LPS coexist in the calcined batch, but by 1550 °C all LSO is completely converted to LPS. LPS formation temperature does not have appreciable effect on the density of the hot pressed samples. Hot pressed samples obtained from powder synthesized at 1650 °C are nearly transparent, although the particle size of the starting powder is higher than that of the powder formed at lower temperatures.     

Green photoluminescence of Tb3+ and Ce3+ doped mullite nanoparticles

Mullite have been actively surveyed, but as luminescent host materials, lanthanide doped mullite receive little attention. In this work, terbium and cerium co-doped mullite nanoparticles have been synthesized by co-precipitation process. These as-prepared mullite nanocrystals were characterized by transmission electron microscopy. The results showed that these nanoparticles are roughly spherical in shape and vary in size from 30 to 45 nm. The phase structures of these nanoparticles were investigated by X-ray diffraction. The results indicated that these nanoparticles crystallized well, and the peak positions and intensities agree well with the data for bulk mullite. Their fluorescence properties have been explored in detail and the resulting Al₆Si₂O₁₃: 8%Tb,0.1%Ce nanoparticles showed the typical emission bands centered at 490, 542 and 590 nm.     

The photoluminescence of Ce-doped Lu4Si2O7N2 green phosphors

Cerium-doped Lu₄Si₂O₇N₂ green phosphors were synthesized by a high-temperature solid-state reaction method under nitrogen atmosphere. Compared with Ce-doped Y₄Si₂O₇N₂ phosphors, Ce-doped Lu₄Si₂O₇N₂ phosphors showed longer wavelengths of both excitation and emission, lower Stokes shift, and much stronger emission intensity. Based on the first-principles calculations of the two phosphors, the strong emission intensity originates from the large density of states. At last, the effects of Ce³⁺ concentration on photoluminescence were also examined.     

Processing and mechanical properties of short fibers/Si3N4p reinforced BaO·Al2O3·2SiO2 ceramic matrix composites

Dense short silicon carbide (SiC_sf) and carbon fibers (C_sf) reinforced BaAl₂Si₂O₈ (BAS) glass-ceramic composites with silicon nitride were fabricated by hot-pressing technique. The phase characterization, microstructure, mechanical properties and fracture behavior of the composites were investigated by X-ray diffraction, scanning electron microscopy, transmission electron microscopy and three-point bending tests. The results showed that short silicon carbide and carbon fibers disperse homogeneously in BAS matrix, and had good chemical compatibility with the glass-ceramic matrix. The addition of Si₃N₄ could successfully eliminate the microcracks in the BAS matrix induced by the thermal mismatch between the fiber and matrix. Both the added short fibers could effectively reinforce the BAS glass-ceramic by the associated toughening mechanisms such as crack deflection, fiber bridging and pullout effects.     

Scintillation and luminescent properties of undoped and Ce3+ doped Y2SiO5 and Lu2SiO5 single crystalline films grown by LPE method

Single crystalline films (SCFs) of undoped and Ce³⁺ doped Y₂SiO₅ (YSO) and Lu₂SiO₅ (LSO) orthosilicates were crystallized for the first time by liquid phase epitaxy method onto undoped YSO substrates from melt-solution based on PbO–B₂O₃ flux. The scintillation and luminescent properties of YSO:Ce and LSO:Ce SCFs were compared with the properties of bulk single crystal counterparts. We show that the peculiarities of luminescent properties of YSO:Ce and LSO:Ce SCFs in comparison with the crystal analogues are caused by the different distribution of Ce³⁺ ions over Y1/Lu1 and Y2/Lu2 positions of YSO and LSO host and strong influence of Pb²⁺ flux-related impurity on luminescent properties of Ce³⁺ ions.     

5d-4f and 4f-4f emissions in Ln-doped sesquioxide ceramics

In this study, various lanthanide and mixed lanthanide oxides (Ln₂O₃ with Ln = La, Lu, Lu_0.5Gd_0.5) powders have been synthesized by a coprecipitation method. The luminescence properties and/or the quenching mechanisms of different dopants (europium, cerium, praseodymium) have been studied. Luminescence mechanisms of Ce:Ln₂O₃ and Pr:Ln₂O₃, are closely related to the 5d and 4f energy levels positions of the dopant versus materials bandgap and crossing effect between dopant energy levels. Energy level positions have been analyzed through optical spectroscopy and their effect on the luminescence is presented. Eu:Lu₂O₃ and Eu:LuGdO₃ have also been prepared as transparent ceramics and radioluminescence properties are presented.     

Molten salt synthesis and luminescence properties of Bi4Si3O12 powders

In this paper, Bismuth silicate (Bi₄Si₃O₁₂, BSO) powders were prepared by reaction in molten salts (NaCl and KCl) using Bi₂O₃ and SiO₂ powders as raw materials. The effects of salt contents and excessive contents of Bi₂O₃ and SiO₂ were characterized by X-ray diffraction and scanning electron microscopy. The properties of Bi₄Si₃O₁₂ powders were analyzed via fluorescence spectroscopy. Forming mechanism of platelets was discussed. The experimental results suggest that Bi₄Si₃O₁₂ powders are produced at 780 °C for 4 h with 40 wt% salts and 5 wt% excessive content of Bi₂O₃. The peaks of excitation spectrum and emission spectrum for BSO powders are separately located at 266 and 457.6 nm. Compared with crystal materials, the excitation spectrum and emission spectrum of Bi₄Si₃O₁₂ powders indicate blue shift. Interface reacting mechanism can be used to explain the coarsening process of bismuth silicate platelets produced in molten salt synthesis. In addition, dissolution–precipitation mechanism also plays an important role in the synthesis of bismuth silicate platelets.     

Formation of high-density scintillation ceramic from LuAG:Ce + Lu2O3 powders obtained by co-precipitation method

The results of formation of the high density effective scintillation ceramics consisting of two compounds of the cubic symmetry, LuAG:Ce and Lu₂O₃ (LuAG:Ce + Lu₂O₃), are described. Powders of a novel material LuAG:Ce + Lu₂O₃ were synthesized by co-precipitation method. The introduction of Lu₂O₃ into LuAG:Ce was shown to increase the density of the ceramics obtained and modify its scintillation properties.     

Green light-emitting Lu3Al5O12:Ce phosphor powders prepared by spray pyrolysis

Green light-emitting Lu_2.985Al₅O₁₂:Ce_0.015 (LuAG:Ce) phosphor powders are prepared by spray pyrolysis. The only crystallized phase in the precursor powders and post-treated powders at temperatures below 800 °C is Lu₂O₃ and the other components are amorphous. Phase pure cubic garnet LuAG:Ce phosphor powders are obtained by post-treatment at 1000 °C. Phosphor powders post-treated at temperatures below 1400 °C retain the spherical shape of the precursor powders. The mean crystallite sizes of phosphor powders post-treated at 1200, 1400, and 1500 °C are 30, 46, and 54 nm, respectively. The excitation spectra contain two bands: a weak band with the maximum peak at 345 nm and a strong broad band in the spectral range from 400 to 490 nm with the maximum peak at 455 nm. The LuAG:Ce phosphor powders have broad emission spectra between 480 and 600 nm, with the maximum peak intensity located at 507 nm. The photoluminescence intensity of the phosphor powders post-treated at 1400 °C is 84.2% of that of the powders post-treated at 1500 °C.     

Sol-Gel Synthesis and Photoluminescence of RE<Subscript>x</Subscript>Lu<Subscript>2-<Emphasis Type="Italic">x</Emphasis></Subscript>O<Subscript>3</Subscript>:Eu<Superscript>3+</Superscript> (RE = Y,Gd) Nanophosphors

RE_xLu_2-x O₃:Eu³⁺ (RE = Y, Gd) nanophosphors with x = 0.4, 1.0, and 1.6 were synthesized using rare-earth salicylate coordination polymers as precursors for the luminescent species RE_xLu_2-x O₃:Eu³⁺ (RE = Y, Gd) composed of polyethylene glycol both as a dispersing medium and fuel. Their particle sizes were around 100 nm as determined by scanning electron microscopy and x-ray diffraction.__________From Neorganicheskie Materialy, Vol. 41, No. 6, 2005, pp. 706–710.Original English Text Copyright © 2005 by Zhou, Yan.This article was submitted by the authors in English.     

A novel blue-emitting Ca2B5O9Br:Eu2+ phosphor prepared by a microwave calcination route

A blue-emitting Ca₂B₅O₉Br:Eu²⁺ phosphor for white light-emitting diodes was synthesized via a microwave calcination route. The phosphor powders were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and fluorescence spectrophotometer, respectively. The obtained results revealed that the Ca₂B₅O₉Br:Eu²⁺ phosphor prepared by the microwave calcination route possessed a rod-like morphology with the single phase orthorhombic structure. Based on the photoluminescence analysis, it was found that Ca₂B₅O₉Br:Eu²⁺ phosphor exhibited a broad excitation band chiefly in the near ultraviolet region (270–420 nm) and a blue broad emission band of main peak at 452 nm under the strongest excitation of 411 nm. Further investigation on concentration-dependent emission spectra indicated that Ca₂B₅O₉Br:0.03Eu²⁺ phosphor exhibited the strongest luminescent intensity, and the concentration quenching for the two Eu-site emission centers was caused by dipole–dipole interactions.     

Luminescent properties of Al2O3:Ce single crystalline films under synchrotron radiation excitation

The paper is dedicated to study the luminescent and scintillation properties of the Al₂O₃:Ce single crystalline films (SCF) grown by LPE method onto saphire substrates from PbO based flux. The structural quality of SCF samples was investigated by XRD method. For characterization of luminescent properties of Al₂O₃:Ce SCFs the cathodoluminescence spectra, scintillation light yield (LY) and decay kinetics under excitation by α-particles of Pu²³⁹ source were used. We have found that the scintillation LY of Al₂O₃:Ce SCF samples is relatively large and can reach up to 50% of the value realized in the reference YAG:Ce SCF. Using the synchrotron radiation excitation in the 3.7–25 eV range at 10 K we have also determined the basic parameters of the Ce³⁺ luminescence in Al₂O₃ host.     

浮区法生长Lu2Si2O7:Ce晶体的缺陷、光学和闪烁性能研究

通过浮区法制备得到LPS:0.5%Ce单晶样品, 并对其包裹体、开裂、闪烁和光学性能进行了研究,获得了晶体的电子探针谱、透过谱、77~500 K下的紫外激发发射谱、X射线激发发射谱和77~500 K下的衰减时间谱。研究发现晶体中存在解理开裂和热应力开裂, 同时存在两种类型的包裹体, 分别包含[Si₃O₉]^6-、阴离子团和过量的SiO₂。由于采用空气为生长气氛, 样品中部分Ce³⁺被氧化为Ce⁴⁺。浮区法LPS:0.5%Ce表现出较高的发光效率, 约为32000 ph/MeV。随着温度的升高, 样品的紫外激发发射谱逐渐向长波方向移动, 发射谱谱线随着温度的升高展宽, 导致自吸收的增加。衰减时间的温度转变点位于450 K, 表明LPS:Ce闪烁晶体适用于高温环境, 是一种性能优异的闪烁晶体。     

On the Ce3+ → Cr3+ energy transfer in Lu3Al5O12 garnets

Two series of Lu₃Al₅O₁₂:Cr³⁺ and Lu₃Al₅O₁₂:0.5% Ce³⁺,Cr³⁺ luminescent materials were prepared by a sol–gel combustion method. All samples were characterized by powder X-ray diffraction (XRD), infrared (IR) and photoluminescence (PL) measurements. Moreover, luminous efficacies (LE), CIE 1931 colour points, and quantum efficiencies (QE) were calculated and discussed. Luminescence measurements indicated that Ce³⁺ ions located at Lu³⁺ site transfers absorbed energy to Cr³⁺ ions located at Al³⁺ site. However, with increasing Cr³⁺ concentration the total light output of Lu₃Al₅O₁₂:0.5% Ce³⁺,Cr³⁺ phosphors decrease.     

Structural, morphological and optical investigations on BaMgAl10O17:Eu elaborated by a microwave induced solution combustion synthesis

Blue-emitting Eu²⁺-doped barium magnesium aluminate (BaMgAl₁₀O₁₇:Eu²⁺) for advanced displays and lighting devices was prepared by a microwave induced solution combustion synthesis using urea as combustion fuel and nitrates as oxidizer. Purity control of as-synthesized blue phosphor particles was undertaken by modifying the fuel to oxidizer molar ratio. X-ray diffraction, scanning electron microscopy and photoluminescence were used to investigate powders crystallinity, particles size, morphology and luminescent properties, respectively. Fuel-rich urea reactions preferentially lead to pure phases compared to the powders synthesized with a stoichiometric fuel to oxidizer ratio. In both cases, we produce a nearly pure well-crystallized and nanostructured BaMgAl₁₀O₁₇:Eu²⁺. Photoluminescence measurements exhibit the characteristic blue emission of Eu²⁺ under UV light excitation however a weak red emission associated to Eu³⁺ is also detected.     

Growth and luminescent properties of Lu2SiO5 and Lu2SiO5:Ce single crystalline films

Single crystalline films (SCF) of Lu₂SiO₅ (LSO) and Lu₂SiO₅:Ce (LSO:Ce) silicates with thickness of 2.5-15 μm were crystallized by liquid phase epitaxy method onto undoped LSO substrates from melt-solution based on PbO-B₂O₃ flux. The scintillation and luminescence properties of LSO:Ce SCF were compared with the properties of LSO:Ce single crystal. The peculiarities of luminescence properties of LSO:Ce SCF in comparison with crystal analog can be due to different distribution of Ce³⁺ over the Lu1 and Lu2 positions of LSO host and are further influenced by Pb²⁺ flux-originated contamination.     

Enhancement of thermal stability and reliability of green LuAG phosphors by appropriate Y substitution

Green Lu_2.94?xY_xAl₅O₁₂: 0.06Ce phosphors were prepared by conventional solid-state reaction. The influence of Y concentration on the photoluminescence (PL), thermal stability and reliability properties of the phosphors were studied. The PL emission bands of Lu_2.94?xY_xAl₅O₁₂: 0.06Ce showed red shift from 520 to 540 nm with increasing Y content (x value) under excited at 450 nm. As the temperature increases from 298 to 473 K, the PL intensity of Lu_2.94?xY_xAl₅O₁₂: 0.06Ce phosphor decreases by 21.72, 11.10, 5.45, 9.01 and 16.30% with x value is 0, 0.2, 0.4, 0.6 and 0.8, respectively. The thermal cycling testing results show that the relative PL intensity of Lu_2.94?xY_xAl₅O₁₂: 0.06Ce phosphor decrease to 86.97, 91.94, 97.22, 95.69 and 92.75% with x value is 0, 0.2, 0.4, 0.6 and 0.8 after storing the phosphors into an ambient condition of 120 °C for 1 h and ?40 °C for 1 h by turns for five times. Reliability test results show that the relative PL intensity of Lu_2.94?xY_xAl₅O₁₂: 0.06Ce phosphor decrease to 90.76, 95.17, 96.54, 93.37 and 91.12% with x value is 0, 0.2, 0.4, 0.6 and 0.8 after the ambient condition of 85 °C/RH 85% for the exposure time of 336 h; The relative PL intensity of Lu_2.94?xY_xAl₅O₁₂: 0.06Ce phosphor decrease to 88.63, 94.24, 95.74, 92.60 and 86.95% with x value is 0, 0.2, 0.4, 0.6 and 0.8 after soaking into boiled water for 3 h. It can be summarized that the appropriate addition of Y could enhance both the thermal stability and reliability of Lu_2.94?xY_xAl₅O₁₂: 0.06Ce phosphors remarkably.     

Effects of Zr/Ce molar ratio and water content on thermal stability and structure of ZrO2–CeO2 mixed oxides prepared via sol–gel process

ZrO₂–CeO₂ mixed oxides were synthesized via sol–gel process. Thermal stability, structure and morphology of samples were investigated by powder X-ray diffraction, FT-Raman spectroscopy, X-ray photoelectron spectroscopy and scanning electron microscopy. In this approach, the solvent composition and Zr/Ce molar ratio have great influences on the structure and morphology of final products. With decreasing water content in the mixed solvent, specific surface area of powders increased and the single tetragonal phase was obtained. Only when the volume ratio of water and ethanol and the Zr/Ce molar ratio were 1:1, tetragonal t″-Zr_0.5Ce_0.5O₂ could be stabilized in powders at temperature as high as 1000 °C. Meanwhile, tetragonal (t′) and (t″) phases coexisted in Zr_0.5Ce_0.5O₂ solid solution without peak splitting after calcination at 1100 °C, further transforming into cubic and tetragonal (t′) phases at 1200 °C. The effective activation energy for Zr_0.5Ce_0.5O₂ nanocrystallite growth during annealing is about 5.24 ± 0.15 kJ/mol.     

Enhanced red-emitting phosphor Na<Subscript>2</Subscript>Ca<Subscript>3</Subscript>Si<Subscript>2</Subscript>O<Subscript>8</Subscript>:Eu<Superscript>3+</Superscript> by charge compensation

A series of novel red-emitting Na₂Ca_3???x Si₂O₈:xEu³⁺ phosphors were synthesized by solid state reactions. The phosphors can strongly absorb 395 nm light, and show red emission with a good color purity. The excitation and emission spectra properties of Na₂Ca₃Si₂O₈:Eu³⁺ were characterized. Na₂Ca₃Si₂O₈:Eu³⁺ with self-compensated and alkali metal ions charge compensated approaches (2Ca²⁺→Eu³⁺ + M⁺, M?=?Li⁺, Na⁺, K⁺) have investigated, which found that the red emission of luminescent intensity can be greatly enhanced, and shows superior luminescent property to the commercial Y₂0₃S:Eu³⁺. The present work implies that the efficient charge compensated phosphors are promising candidates as red-emitting phosphor for w-LEDs.