Preparation and Upconversion Luminescence of Y3Al5O12∶Yb3+, Er3+ Transparent Ceramics

YAG:1% (atom fraction) Yb3 , 0.5% (atom fraction) Er3 transparent ceramics were fabricated by the solid state reaction method using high-purity Y2O3, Al2O3, Yb2O3, and Er2O3 powders as starting materials. The mixed powder compact was sintered at 1760 ℃ for 6 h in vacuum and annealed at 1500 ℃ for 10 h in an air atmosphere. The ceramics consisted of about 10 μm grains and exhibited a pore-free structure. The optical transmittance of the ceramics at 1064 nm was nearly 80%. Upconversion emissions were investigated on the ceramics pumped by a 980 nm continuous wave diode laser, and strong green emission centered at 523 and 559 nm and red emission centered at 669 nm were observed, which originated from the radiative transitions of 2H11/2→4I15/2, 4S3/2→4I15/2, and 4F9/2→4I15/2 of Er3 ions, respectively.     

Influence of B2O3 on Spectroscopic Properties of Er^3＋/Yb^3＋ Co-Doped Tungsten-Tellurite Glasses

A series of novel Er^3＋/Yb^3＋ co-doped （85- x ） TeO2-15WO3-xB2O3 （TWB;x=2%,5%,8%（mole fraction） ） glasses were prepared. Influence of B203 on the spectroscopic properties of Er^3＋/Yb^3＋ co-doped tungsten-tellurite glasses were investigated. It is found that the intensity of 1.5μm fluorescence, lifetime of the ^4I13/2 level and upconversion fluorescence all decrease with the increase of B2O3 content. The product of full width at half maximum （FWHM） and stimulated emission cross-section （σe^peak） of Er^3＋ ：^4I13/2→^4I15/2 transition has an optimum when B203 is 5% （mole fraction）. The emission spectra of Er^3＋ ： ^4I13/2→^4I15/2 transition was analyzed using peak-fit routine, and an equivalent four-level system was proposed to estimate the stark splitting for the 411512 and ^4I13/2 levels of Er^3＋ ions in TWB glasses at room temperature.     

Upconversion luminescence of Y2O3：Er^3＋ ,Yb^3＋ nanoparticles prepared by a homogeneous precipitation method

Y2O3： Er^3＋, Yb^3＋ nanoparticles were synthesized by a homogeneous precipitation method without and with different concentrations of EDTA 2Na. Upconversion luminescence spectra of the samples were studied under 980 nm laser excitation. The results of XRD showed that the obtained Y2O3：Er^3＋,Yb^3＋ nanoparticles were of a cubic structure. The average crystallite sizes calculated were in the range of 28-40 nm. Green and red upconversion emission were observed, and attributed to ^2H11/2,^4S3/2→^4I15/2 and ^4F9/2→^4I15/2 transitions of the ion, respectively. The ratio of the intensity of green emission to that of red emission drastically changed with a change in the EDTA 2Na concentration. In the sample synthesized without EDTA, the relative intensity of the green emission was weaker than that of the red emission. The relative intensities of green emission increased with the increased amount of EDTA 2Na used. The possible upconversion luminescence mechanisms were discussed.     

Upconversion emission of SrYbF5：Er3＋nanosheets modified by Tm3＋ions

Through a hydrothermal route, the Er3＋and Tm3＋co-doped SrYbF5 nanosheets were synthesized. The resulting samples were characterized by X-ray diffraction, scanning electron microscopy, energy dispersive X-ray spectroscopy and luminescence spec-tra. Under the excitation of 980 nm laser irradiation, the upconversion emissions of Tm3＋ions centered at 474 nm （1G4→3H6）, 679 nm （3F2→3H6）, 699 nm （3F3→3H6）, 803 nm （3H4→3H6） and emissions of Er3＋ions centered at 522 nm （2H11/2→4I15/2）, 543 nm （4S3/2→4I15/2）, 654 nm （4F9/2→4I15/2） were observed. The upconversion emissions of Er3＋ions were adjusted by the concentration of Tm3＋ions. The energy transfer mechanisms among Er3＋-Yb3＋-Tm3＋in SrYbF5 nanosheets were discussed.     

Luminescence of Er^3＋ in Oxyfluoride Transparent Glass-Ceramics

Erbium doped silicate, germanate, and tellurium-germanate oxyfluoride glasses were prepared in a bulk form. Through appropriate heat treatment of the as-prepared glasses, transparent glass-ceramics (TGCs) were obtained with the formation of β-PbF2∶Er3 nanocrystals in the glass matrix were confirmed by X-ray diffraction. Well-defined diffraction peaks were observed in the samples after heat-treatment. The average crystal diameter of these precipitated crystals from full-width at half-maximum (FWHM) of the diffraction peak was estimated to be between 8 and 13 nm. Optical absorption, photoluminescence, and upconversion luminescence were measured on as-prepared glass and glass-ceramics. Luminescence spectra in the TGC samples revealed well-resolved, sharp stark-splitting peaks, which indicates that a majority of Er3 ions has been incorporated into the crystalline phase of the nanocrystals. The intensity of the visible and near infrared luminescence mostly increases in TSG compared to that in the as-prepared glass. In 1.53 μm absorption and emission bands, the maximum absorption peak is blue-shifted from 1531 to 1507 nm, whereas the maximum emission peak is red-shifted from 1535 to 1543 nm in TGC, as compared with that in glass. The bandwidth at half-maximum (BWHM) of the emission band is significantly broader in TGC than in glass, which is beneficial to the erbium-doped fiber amplifier (EDFA). Upconversion luminescence was measured using 800 nm near-infrared light excitation. Drastically increased upconversion luminescence was observed from the TGC as compared to that from their corresponding as-prepared glasses. In addition to a strong green emission centered at 545 nm because of 4S3/2→4I15/2 transition and a weaker red emission centered at 662 nm because of 4F9/2→4I15/2 transition, generally seen from the Er3 doped glasses, two violet emissions centered at 410 nm because of 2H9/2→4I15/2 transition and centered at 379 nm because of 4G11/2→4I15/2 transition were also observed from the TGC. The increased luminescence was attributed to the decreased effective phonon energy and the increased energy transfer between the excited ions when Er3 ions were incorporated into the precipitated β-PbF2 nanocrystals. The results indicated two attractive spectroscopic properties of the Er3 doped TGC samples, compared to glass samples, namely a reduced multiphonon decay rate and a reduced inhomogeneous broadening. In addition, these oxyfluoride TGC materials were robust, easy and flexibile to process, and possible to be fabricated in the fiber form for device applications.     

Energy transfer and frequency upconversion in Er~（3＋）-Yb~（3＋） codoped oxy-fluoro-tungstosilicate glasses

Er3+-Yb3+ codoped oxy-fluoro-tungstosilicate glasses with infrared-to-visible frequency upconversion luminescence were prepared by melting quenching in air.The effects of Er3+ doping on the optical properties of the samples were measured by means of techniques such as optical absorption spectra and photoluminescence spectra.The results showed that intense green and red signals centered at 546 and 665 nm,corresponding to the 4S3/2 → 4I15/2 and 4F9/2 → 4I15/2 transitions of Er3+ by a multiphoton stepwise phonon-assisted excited-state absorption process,respectively,were simultaneously observed by exciting the samples with a diode laser operating at 980 nm at room temperature.The upconversion process was found very sensitive to Er3+ content at a constant Yb2O3 content of 5 mol.%.With the increase of Er3+ content from 0.5% to 1.5%,the upconversion intensity increased gradually.Further increasing of Er3+ content to 3.0% resulted in a significant fluorescence quenching.Moreover,the possible upconversion mechanisms were discussed based on the energy-matching conditions and the quadratic dependence on excitation power.     

A novel synthesis method and up-conversion properties of hexagonal-phase NaYF4:Er nano-crystals

A novel synthesis method for hexagonal(β)-phase NaYF4:Er nano-crystals(NCs)which showed up-conversion(UC)from infrared to visible spectral region was developed.The NaYF4:Er NCs were synthesized in oleic acid(OA)and 1-octadecene(ODE)with Y2(CO3)3· xH2O,Er2(CO3)3· xH2O,Na2CO3 and NH4F as precursors.This proposed method was simple and less toxic compared with generally used method so far.The XRD results showed that the molar ratio of OA/ODE and the temperature were key factors for phase control of NaYF4:Er NCs.The UC emission spectra were obtained with the emission wavelength at about 980 nm(4I11/2→4I15/2),800 nm(4I9/2→4I15/2),660 nm(4F9/2→4I15/2)and 540 nm(4S3/2→4I15/2)from Er3+ ions,by excitation wavelength of 1550 nm.The slope values,n,in the pump-power dependence,showed that the emission at 980 and 800 nm were generated by 2-step UC and at 660 nm and 540 nm were 3-step UC.The optical process for the UC excitation was discussed.     

Synthesis and Spectral Properties of Nd^3＋： Gd3Ga5O12 Nanopowder for Transparent Laser Ceramics

Nd^3＋： Gd3Ga5O12（Nd ： GGG） nanopowder for transparent laser ceramics was synthesized using sol-gel method. XRD, SEM, and fluorescence spectrum were used to study the properties of Nd^3＋ ：Gd3Ga5O12 nanopowder. XRD patterns of samples show that it has a cubic structure. Meanwhile, pure Nd：GGG crystals were obtained at 1000 ℃ for 12 h. SEM photographs show that dispersed, uniform, ball-like Nd：GGG nanopowder is obtained. Both XRD and SEM results show that the crystallization degree and the grain size increase with the increase in calcining temperature. Analysis of fluorescence spectrum shows that fluorescence emission occurs at 1062.7 nm, which is the result of Nd^3＋ （^4F3/2→^4I11/2） transition. Homogenous Nd ： GGG nanopewder with a small grain size synthesized using the sol-gel method is favorable for sintering the transparent ceramic, which proves that the nanopewder obtained is suitable as a precursor for preparing GGG transparent ceramics.     

Local microstructure and photoluminescence of Er-doped 12CaO·7Al2O3 powder

Er-doped 12Ca0.7Al2O3 （C12A7：Er） powders were prepared using the sol-gel method followed by annealing inorganic precursors. X-ray diffraction （XRD）, Raman and absorption spectra revealed that Er ions existed and substituted Ca^2＋ lattice site in C12A7. The photoluminescence of C12A7：Er at room temperature was observed in the visible and infrared region using 488 nm （2.54 eV） Ar^＋ line as excitation source, respectively. The sharp and intense green emission bands with multi-peaks around 520 nm and 550 nm correspond to the transitions from the excited states ^2H11/2 and ^4S3/2 tO the ground state ^4I15/2, respectively. Furthermore, red emission band around 650 nm was also observed. It was attributed to the electronic transition from excited states ^4F9/2 to the ground state ^4I15/2 inside 4f-shell of Er^3＋ ions. The intensive infrared emission at 1.54 μm was attributed to the transition from the fast excited states of ^4I13/2 to the ground state （^4I15/2）. The temperature dependent photoluminescence of infrared emission showed that the integrated intensity reached a maximum value at near room temperature. The forbidden transitions of intra-4f shell electrons in free Er^3＋ ions were allowed in C12A7 owing to lack of the inversion symmetry in the Er^3＋ position in C12A7 crystal field. Our results suggested that C12A7：Er was a candidate for applications in Er-doped laser materials, and full color display.     

Spectroscopic Properties and Effect of Radiation Trapping of a New Er^3＋/Yb^3＋ Co-Doped Tellurite-Silicate Glasses

A new serials of Er^3＋/Yb^3＋ co-doped tellurite-silicate glasses were prepared by the technique of high-temperature mehing. The thermal stability, absorption spectra, emission spectra and upconversion spectra were measured and investigated. It is found that these kinds of glasses have good thermal stability, broad FWHM and large stimulated emission cross-section. The three upconversion emission at 525, 546, 658 nm, corresponding to the ^2H11/2→^4Ⅰ15/2, ^4S3/2→4^Ⅰ15/2 and ^F9/2→^4Ⅰ15/2 transitions of Dr^3＋ ions,     

Influence of Molten Salt on Luminescent Intensity and Particle Size of Y2O3 ：Eu^3＋ Phosphor

The Y-Eu oxalate precursor was prepared with a homogeneous precipitation method. And the additives, Na2CO3, S, NaCl or their combination, were introduced into the precursor to prepare Y2O3 ：Eu^3＋ red phosphors at 1000 1300 ℃ for 2 h. The effect of molten salts on particle size and luminescent intensity was studied. The experimental results showed that the complex molten salt （Na：CO3 ＋ S ＋ NaCl） was conductive to enhance the luminescent intensity of Y2O3 ：Eu^3＋. The emission intensity of the phosphor prepared with these additives at 1300 ℃ was about 45% higher than that of the one prepared without molten salt, and about 11% higher than that of the corresponding commercial phosphor. Meanwhile, the particle size of Y2O3 ：Eu^3＋ phosphor was controlled effectively with the molten salt.     

Synthesis of Spherical （Y, Gd） BO3 ： Eu^3＋ Phosphor Using W/O Emulsion System

Spherical （Y, Gd）BO3：Eu^3＋ phosphor particles with a narrow size distribution（2 -4 μm） was obtained by firing the Y-Gd-Eu-BO3 precursor prepared in a W/O style emulsion system. In the W/O emulsion system, kerosene, used as oil phase, was mixed with Span 80 and Tween 80 compounds which were employed as the emulsifier with an HLB （hydrophile-lipophile balance） value of 5.2- 5.3. Both rare earths （Y, Gd and Eu） nitrate and boric acid solution or ammonia solution were used as aqueous phase. The synthesis conditions, such as emulsion composition, emulsifying style, precipitation reaction process, reaction temperature, morphology control, and so on, were investigated, and the optimum synthesis conditions for preparing spherical （Y, Gd）BO3：Eu^3＋ phosphor was obtained. The phosphor was characterized by XRD, SEM, laser particle size analysis, emission and excitation spectrum under vacuum ultraviolet （VUV）, and so on. The phosphor synthesized using the water-in-oil emulsion method with median diameter （D50） of 2 - 4 μm shows agreeable photoluminescence （PL） property and sphericity. The main emission peak appears at about 593 nm, which corresponds to ^5D0→^7F1 transition （magnetic-dipole transition） of the Eu^3＋ ion. The cell parameters and powder diffraction data were indexed. The structure of the phosphor belongs to the hexagonal system with space group P63/m.     

Upconversion of Er^3＋ Ions in LiKGdF5 ： Er^3＋ , Dy^3＋ Single Crystal Produced by Infrared and Green Laser

The upconversion fluorescence of Er^3＋ ions in LiKGdF5 ： Er^3＋, Dy^3＋ single crystal was studied under 785, 514.5, and 980 nm laser excitation. With the laser excitation set at 785 nm, strong green （centered at 543 nm） upconversion emissions, as well as weak red （651 nm）, violet （406 nm）, and blue （470 nm） upconversion emissions were obtained. With 514.5 nm laser excitation, violet （406 nm） and blue （470 nm） upconversion emissions were observed. Under 980 nm laser excitation, strong green （543 nm） and weak red （651） emissions were also obtained. The laser power dependence of the upconverted emissions was investigated to understand the upconversion mechanism. The excited state absorption （ESA） and the energy transfer （ET） processes were discussed as the possible mechanisms for all upconversion emissions.     

Luminescent Properties of SrGa2S4 :Eu and Its Application in Green-LEDs

Phosphor SrGa2S4Eu2 was synthesized with a high temperature solid state reaction.Its absorption spectrum, photoluminescence spectra, and fluorescence lifetime were studied in details.The excitation spectrum extended from UV to visible light region, and matched the emission of GaN chip.(Sr1-xEux)Ga2S4 emits strong green light and the concentration quenching did not occur; while the thermal quenching was evident.The emission peak shifted to long wavelength with increasing Eu2 concentration because of the changing of the crystal field strength.The lifetime of Eu2 ion was in the order of microsecond, which was reasonable for d→f transition.The electroluminescence spectrum of as-fabricated PC-LED at IF=20 mA was measured and most of the blue light of blue-LED chip at 460 nm was absorbed by the phosphor and simultaneously down-converted into an intensive green light at 540 nm.The color coordinate was (0.32, 0.63).SrGa2S4Eu2 was a promising phosphor for GaN-based green LEDs.     

Syntheses of Alkaline Earth and Lanthanide Cryptates with Pyridine-Based Group

New alkaline earth metal cryptates [ML]（NO3）2 ·2H2O （M=Ca^2＋, Sr^2＋, Ba^2＋; L = 1, 4,12,15,18, 26, 31, 39, 42, 43, 44-undecaazapentacyclo- [ 13.13.13.1^6,10 .1^20,24 .1^33,37 ]-tetratetraconta -4, 6, 8, 10（44）, 11, 18, 20, 22, 24（43）, 25, 31, 33, 35, 37（42）, 38-pentadecaene） were synthesized by [2 ＋ 3 ] template condensation of tris（2-aminoethyl） amine with 2, 6-diformylpyridine, and then by transmetallation reactions of the calcium cryptate [CaL] （NO3）2·2H2O with corresponding lanthanide ions; three lanthanide cryptates [ LnL] （NO）3·3H2O （Ln = Eu, Gd, Tb） were synthesized and characterized by physical methods. The crystal structure of the terbium cryptate [TbL] （NO）3·3H2O was studied by X-ray analysis. The central atom was coordinated by three pyridyl and six imino nitrogen atoms and exhibited a distorted tricapped trigonal prismatic coordination geometry.     

Al2O3含量对放电等离子烧结Al2O3/Cu复合材料组织与性能的影响

以微米级Cu粉为基体相,纳米Al₂O₃颗粒为绝缘相,采用机械球磨和放电等离子烧结工艺相结合的方法制备Al₂O₃/Cu复合材料,研究Al₂O₃含量对复合材料微观结构、电阻率和热导率的影响。结果表明,Al₂O₃/Cu复合材料为核?壳结构,随Al₂O₃含量增加,Al₂O₃包覆层对Cu基体的包覆效果逐渐提升;当w(Al₂O₃)为5%时,Al₂O₃/Cu复合材料的热导率较高,为85.92 W/(m·K),但电阻率偏低,仅为12.6 mΩ·cm。当w(Al₂O₃)增加至15%时,虽然Al₂O₃/Cu复合材料的密度降至6.69 g/cm³,孔隙率较高,但电阻率显著提高至2.09×10⁸ mΩ·cm,约为Cu电阻率的10¹¹倍,且热导率为7.6 W/(m·K),明显高于传统金属基板的热导率。     

Influence of Composition on Properties of Medium Temperature Sintering （Ba, Sr）TiO3 Series Capacitor Ceramics

The influence of the composition (Yb2O3, MgO, CeO2, Li2CO3) on the dielectric properties of medium temperature sintering (Ba,Sr)TiO3(BST) series capacitor ceramics was investigated by means of conventional technology process and orthogonal design experiments. The major secondary influencing factors and the influencing tendency of various factor′s levels for the dielectric properties of BST ceramics were obtained. The optimum formula for maximum dielectric constant (ε) and for minimum dielectric loss (tanδ) was obtained under the experimental conditions. The BST ceramics with optimum comprehensive properties was obtained by means of orthogonal design experiments, with the sintering temperature at 1200 ℃, the dielectric constant 5239, the dielectric loss 0.0097, withstand electric voltage over 6 MV·m-1, capacitance temperature changing rate (ΔC/C) -75.67%, and suited for Y5V character. The mechanism of the influence of various components on the dielectric properties of medium temperature sintering BST ceramics was studied, thus providing the basis for preparation of multilayer capacitor ceramics and single-chip capacitor ceramics.     

钠离子对KNa4B2P3O13: Sm荧光粉发光性能的增强作用研究

通过高温固相法在硼磷酸盐KNa₄B₂P₃O₁₃基质中掺杂稀土Sm3+离子获得橘红色发光性能,研究了电荷补偿剂Na+对该荧光粉发光性能的影响,开展了粉末X射线衍射、红外光谱、紫外可见漫反射、荧光光谱、荧光寿命及量子效率等测试对材料的物相、形貌和发光性能进行了表征。研究结果表明,该荧光粉的荧光发射源于Sm3+的4G_5/2→6H_5/2（562 nm）、4G_5/2→6H_7/2（598 nm）和4G_5/2→6H_9/2（645 nm）跃迁,Na+的掺杂没有改变Sm3+特征发射峰的形状和位置,增强了其发光强度。Na+浓度为1%时,可使发光积分强度提高48%。此外,掺杂Na+对荧光粉的寿命和色坐标无明显影响,其色坐标均位于橘红色区域。      

溶胶-凝胶法制备La2Ce2O7:Eu3+及其发光性能

采用溶胶-凝胶法（Sol-gel）合成La₂Ce₂O₇:Eu3+系列红色荧光粉,并研究煅烧温度、Eu3+掺杂浓度以及不同种类电荷补偿剂对样品发光性能的影响.通过XRD、SEM、荧光光谱对样品的晶体结构、形貌以及发光性能进行测量和表征.结果表明:实验所得样品主晶相为La₂Ce₂O₇,属于萤石结构. Eu3+及电荷补偿剂的掺杂没有改变其晶体结构.合成的样品在467 nm蓝光激发下发出612 nm的红光.样品的发光强度随煅烧温度以及Eu3+掺杂浓度的提高先增强后减弱,样品的较优的煅烧温度为1 100 ℃,Eu3+较优的掺杂浓度为10 %（摩尔百分比）.掺入电荷补偿剂可以有效增强样品的发光强度,其中掺入Li+后发光增强的效果最显著.