Experimental study on a nonlinear photonics process of Er(0.5)Yb(3): FOV oxyfluoride nanophase vitroceramics

We study the nonlinear photonics of rare-earth-doped oxyfluoride nanophase vitroceramics (FOV), oxyfluoride glass (FOG), and ZBLAN fluoride glass. We found that an interesting fluorescence intensity inversion phenomenon between red and green fluorescence occurs from Er(0.5)Yb(3):FOV The dynamic range Sigma of the intensity inversion between red and green fluorescence of Er(0.5)Yb(3):FOV is about 5.753 x 10(2), which is 100 to 1000 times larger than those of other materials. One of the applications of this phenomenon is double-wavelength fluorescence falsification-preventing technology, which is proved to possess the novel antifriction loss and antiscribble properties. (c) 2007 Optical Society of America.

Effect of bismuth oxide on the thermal stability and Judd-Ofelt parameters of Er 3(+)/Yb3(+) co-doped aluminophosphate glasses

The Er3+/Yb3+ co-doped glasses with compositions of xBi(2)O(3)-(65-x)P2O5-4Yb(2)O(3)-11Al(2)O(3)-5BaO-15Na(2)O (where x = 0, 2.5, 5, 7.5 and 10 mol%) were prepared using the normal melt quench technique. The optical absorption spectra of the glasses were recorded in the wavelength range 300-1700 nm. The effect of Bi2O3 content on the thermal stability and absorption spectra of glasses was investigated. In addition, the Judd-Ofelt parameters and oscillator strengths were calculated by employing Judd-Ofelt theory. It was observed that the positions of the fundamental absorption edge and cut-off wavelength shifted towards red as the content of Bi2O3 increased. However, there were no red shifts found both in the peak wavelength and in the center of mass wavelength of all absorption bands with Bi2O3 content increasing. The results of Judd-Ofelt theory analysis showed that Judd-Ofelt parameters Omega(t), (t = 2, 4, 6) changed sharply when Bi2O3 concentration exceeded 5 mol%. The variation trends of experimental oscillator strength were similar with those of Judd-Ofelt parameters as function of Bi2O3 concentrations. Moreover, differential scanning calorimetry experiments showed that the increases of Bi2O3 content weakened the network structure and then lowered the thermal stability of the glasses. The spontaneous emission probability A(rad), branching ratio beta and the radiative lifetime tau(rad) were also calculated and analyzed. The stimulated emission cross-section of Er3+ was calculated according to the McCumber theory. It was found that the stimulated emission cross-section of Er3+ was monotonically increases with Bi2O3 content increasing. (C) 2006 Elsevier B.V. All rights reserved.

碱金属和碱土金属氟化物对掺Er^3＋氟磷酸盐玻璃光谱性质的影响

研究了碱金属和碱土金属离子修饰的掺Er^3＋氟磷酸盐玻璃的光谱性质，讨论了碱金属和碱土金属对铒氟磷玻璃的吸收和发射截面、荧光半高宽，Judd-Ofelt强度参数和上转换发光强度等光谱性质的影响，并与一些传统氧化物玻璃系统进行了比较．研究表明碱金属K^＋和碱土金属Sr^2＋掺杂高的玻璃更适宜用作光放大器基质．含12mol％K^＋的氟磷玻璃展现出7．83×10^-21cm^2的高发射截面和最小的荧光上转换强度；含23mol％Sr^2＋的氟磷玻璃则有7．58×10^-21cm^2的高发射截面、65nm的荧光半高

Co^2＋，Er^3＋：Y3Al5O12晶体的生长及其吸收特性

应用中频感应提拉法成功生长出新型的Co^2＋，Er^3＋：Y3Al5O12晶体。研究了室温下晶体的吸收光谱性能。结合Er^3＋：Y3Al5O12晶体的光谱，并利用调Q判据对Co^2＋，Er^3＋：Y3Al5O12晶体调Q特性进行了简单的分析。结果表明Co^2＋，Er^3＋：YAG晶体是一种很有潜力的白调Q激光晶体。

高浓度掺Er^3＋铌酸锂晶体的光谱参数计算

用提拉法成功地生长了6mol％的高浓度掺铒铌酸锂晶体。测量了晶体的两个非偏振方向（X和Z）以及两个偏振方向（π和δ）的吸收光谱。高浓度掺铒铌酸锂晶体的吸收系数高，有利于提高泵浦效率。根据所测的吸收光谱用Judd-Ofelt理论拟合出了Er^3＋离子的强度参数Ωλ。所得的均方差结果显示偏振拟合的误差要小于非偏振拟合。利用偏振吸收数据计算了各能级跃迁的自发辐射跃迁几率（AJJ’）、辐射寿命（τ）、荧光分支比（β）和积分发射截面（σp）等参数，对计算结果进行了讨论并与其他文献的报道结果进行了比较。

Er^3＋掺杂钨酸铅晶体的发光和光谱特征

本试验测试了Er^3＋掺杂钨酸铅晶体（PbWO4：Er^3＋）的吸收光谱，依据J-O理论，首次计算报道了光谱项特征：J-O强度参数、量子荧光效率、荧光分支比等，Ω2=3．75×10^-20cm^2，Ω4=0．67×10^-20cm^2，Ω6=0．41×10^-20cm^2。计算证实，PWO：Er^3＋中几乎有80％的激发能量非辐射跃迁转移致^4I13／2能级，^4I13／2的计算寿命是5200μs，J-O计算显示，在PWO中产生^4I13/2→^4I15/2和发射1．53μm．有高的几率。讨论了不同浓度E

Er^3＋／Yb^3＋共掺的氧化镧钇透明陶瓷的光谱性能研究

采用传统无压烧结工艺制备了Er^3＋／Yb^3＋共掺的氧化镧钇透明陶瓷并对其光谱性能进行了研究．样品具有较大的吸收和发射截面．La2O3的添加使样品的荧光寿命（τs）与玻璃接近，当Yb^3＋和Er^3＋的掺杂量分别为5at％和0．5at％时，测得τs=9．65ms．这种荧光寿命长、发射截面大和线宽窄的特性有利于微型、可集成化和大功率激光输出的实现．

M_2RSbO_6:R~(3+)复合氧化物的合成组成结构和性能的研究(M = Ba、Sr、Ca, R = La、Gd、Y、Bi, R' = Sm、Eu、Dy、Ho、Er、Tm)

对于稀土与非稀土所组成的二元复合氧化物的研究国外已有较多的报导。但是，对于稀土和锑的复合氧化物只是近年来才开始有些研究工作。含锑与稀土的多元复合氧化物的报导就更少。本文在我们实验室张静筠等人三元复合氧化物研究的基础上，开展Mo—Sb_2O_5—R_2O_3—R'_2O_3—Bi_2O_3多元体系的研究工作，这对于我国丰产元素稀土和锑的应用以及利用Bi~(3+)的激活与敏化将是有益的。本文按Thornton等人的方法合成了Ba_2BiSbO_6，Ba_2GdSbO_6，按EγΦECEHKO等人的方法合成了M_2RSbO_6 (M = Ba、Sr、Ca, R = La Y)。并以M_2RSbO_6为基质，掺Sm~(3+)、Eu~(3+)、Dy~(3+)、Ho~(3+)、Er~(3+)、Tm~(3+)和Bi~(3+)，研究它们的化学组成，晶体结构与发光性能的关系及规律，Bi~(3+)的荧光和敏作用。同时研究了它们的磁学和热学性能。化学组成的分析结果表明，计算的含量与实验测得的含量符合较好，说明化学反应是按化学计量比进行的。通过X-射线粉沫物相分析和晶胞参数的理论计算确定M_2RSbO_6(M = Ba、Sr、R = La、Y、Gd、Bi)复合氧化物是属于立方钙钛太型化合物。空间群为Fm3m，点群为Oh。用计算机计算了Ca_2YSbO_6的晶胞参数并结合荧光光谱分析确定它属于畸变的单斜钙钛矿，空间群为P_(21)。用磁天平测量了样品M_2RSbO_6 (M = Ba、Sr、Ca; R = Gd、Y、Bi)的磁化率。除Ba_2GdSbO_6是顺磁性物质外共余的都是反磁性的物质。按所用原料Sb_2O_5计算的磁化率与测量值符合较好，表明在所研究的M_2RSbO_6化合物中锑是正五价的。用热重热差分析仪测量了样品在反应中的热性能，观察到在化合物形成的过程中所用原料Sb_2O_3大约在520 ℃左右氧化变为Sb_2O_5。除所用原料碳酸盐分解外没有挥发性的物质，这就进一步证明化学组成分析和磁化率测量的结果是正确的。光学测量的结果表明，所有的磷光体随着激活离子浓度的不同其光谱都发生规律性的变化。对于不同Eu~(3+)浓度的Ba_2YSbO_6:Eu~(3+)和Br_2YSbO_6:Eu~(3+), Bi~(3+)体系用254nm激发时均能观察到Eu~(3+)于595nm的尖峰发射。用基质和Bi~(3+)的激发峰325nm激发时，明显地看到敏化剂Bi~(3+)到Eu~(3+)的能量传递，使Eu~(3+)于595nm的发射大大增强，我们认为Bi~(3+)对Eu~(3+)的敏化作用是由于基质和Bi~(3+)的~1S。→ 3P_1的跃迁吸收了激发的能量，然后无辐射弛豫到Eu~(3+)的激发态~5D_0，产生~5D_0 → 7F_1的磁偶极跃迁。对于不同Eu~(3+)浓度的Sr_2YSbO_6:Eu~(3+)和Sr_2YSbO_6:Eu~(3+), Bi~(3+)体系用245nm激发时均能观察到Eu~(3+)于595nm的尖峰发射。用基质和Bi~(3+)的激发峰335nm激发时，观察到基质和Bi~(3+)对Eu~(3+)具有某种能量传递。敏化作用机理与上述的Ba_2YSbO_6:Eu~(3+)和Ba_2YSbO_6:Eu~(3+), Bi~(3+)体系相同。对于不同Eu~(3+)浓度的Ca_2YSbO_6:Eu~(3+)和Ca_2YSbO_6:Eu~(3+), Bi~(3+)体系用396nm激发时，均能观察到Eu~(3+)于613nm很强的尖峰发射。用基质和Bi~(3+)的激发峰313nm激发时，见到Bi~(3+)和基质对Eu~(3+)具有某种能量传递，这种敏化作用主要是由于基质和Bi~(3+)的3P_1 → ~1S_0的400nm的宽带发射和Eu~(3+)的~7F_0 → ~5L_6的396nm的吸收相匹配产生~5L_6→~5D_0→~7F_2的跃迁。通过对激发光谱和荧光光谱的分析给出了Ca_2Y_(0.96)Eu_(0.04)SbO_6的能级图，从实验上可见，Eu~(3+)的发光强烈地依赖于钙钛矿的结构，当Eu~(3+)在空间群为Fm3m 的Ba_2YSbO_6和Sr_2YSbO_6中处于Oh点对称性时，主要是~5D_0 → ~7F_1的磁偶极跃迁。当Eu~(3+)在空间群为P_(21)的单斜钙钛矿中时，主要是~5D_0 → ~7F_2的电偶极跃迁。对于不同掺杂浓度M_2YSbO_6:R~(13+)(M = Ba、Ca; R' = Sm、Dy、Ho、Er、Tm)体系，通过激发和荧光光谱的研究，合理地确定了谱项。发现基质对Sm~(3+)、Dy~(3+)、Ho~(3+)具有敏化作用。对不同Bi~(3+)浓度的Ca_2YSbO_6:Bi~(3+)，由激发和荧光光谱可见Bi~(3+)具有二个激发带，第一激发带位于240nm处相当于~1S_0 → ~1P_1的跃迁，第二激发带位于315nm处相当于~1S_0 → ~3P_1的跃迁。有一个很强的兰紫色发射位于400nm处相当于~3P_1 →~1S_0的跃迁。

掺铒nc-Si/SiO_2薄膜中nc-Si和Er~(3+)与非辐射复合缺陷间相互作用对薄膜发光特性的影响

对nc-Si/SiO_2薄膜中纳米硅(nc-Si)、Er~(3+)和非辐射复合缺陷三者间的关系作了研究.在514.5 nm光激发下,nc-Si/SiO_2薄膜在750nm和1.54μm处存在较强的发光,前者与薄膜中的nc-Si有关,后者对应于Er~(3+)从第一激发态4I13/2到基态4I15/2的辐射跃迁.随薄膜中Er3+含量的提高,1.54μm处的发光强度明显增强,750 nm处的发光强度却降低.H处理可以明显增强薄膜的发光强度,但是对不同退火温度样品,处理效果却有所不同.根据以上实验结果,可得如下结论:在nc-Si颗粒附近的Er~(3+)和其他的缺陷组成了nc-Si颗粒内产生的束缚激子的非辐射复合中心,束缚激子通过Er~(3+)的非辐射复合,激发Er~(3+)产生1.54μm处的发光,同时降低了750nm处的发光强度.nc-Si颗粒附近其他非辐射复合中心的存在会降低Er~(3+)被激发的概率,引起1.54μm处的发光强度降低.

注铒a-SiO_x:H中Er~(3+)发光与薄膜微观结构的关系

采用光致发光（PL）谱和傅里叶变换红外（FTIR）谱研究了掺铒a-SiO_x:H(a-SiO_x:H)薄膜在不同退火温度下光学性质和微观结构的变化。PL谱的测量结果表明：薄膜在1.54μm的Er~(3+)发光和750nm处的可风发光随退火温度有相同的变化趋势，这种变化和薄膜在退火过程中微观结构的变化有着密切关系。FTIR谱的分析表明：a-SiO_x:H薄膜是一种两相结构，富硅相镶嵌在富氧相中。两者的成分可近似用a-SiO_(x≈0.3):H和a-SiO_(x≈1.5):H表示，前者性质接近于氢化非晶硅（a-Si:H），后者性质接近于a-SiO_2。富硅相在退火中的变化对Er~(3+)的发光强度有重要影响。

Synthesis and characterization of monodisperse spherical SiO2@RE2O3 (RE = rare earth elements) and SiO2@Gd2O3:Ln(3+) (Ln = Eu, Tb, Dy, Sm, Er, Ho) particles with core-shell structure

Spherical SiO2 particles have been coated with rare earth oxide layers by a Pechini sol-gel process, leading to the formation of core-shell structured SiO2@RE2O3 (RE = rare earth elements) and SiO2@Gd2O3:Ln(3+) (Ln = Eu, Tb, Dy, Sm, Er, Ho) particles. X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), photoluminescence (PL), and cathodoluminescence spectra as well as lifetimes were used to characterize the resulting SiO2@RE2O3 (RE = rare earth elements) and SiO2@Gd2O3:Ln(3+) (Eu3+, Tb3+, Dy3+, Sm3+, Er3+, Ho3+) samples. The obtained core-shell phosphors have perfect spherical shape with narrow size distribution (average size ca. 380 nm), smooth surface and non-agglomeration. The thickness of shells could be easily controlled by changing the number of deposition cycles (40 nm for two deposition cycles).

Self-assembled 3D flowerlike Lu2O3 and Lu2O3 : Ln(3+) (Ln = Eu, Tb, Dy, Pr, Sm, Er, Ho, Tm) microarchitectures: Ethylene glycol-mediated hydrothermal synthesis and luminescent properties

Three-dimensional flowerlike Lu2O3 and Lu2O3:Ln(3+) (Ln = Eu, Th, Dy, Pr, Sm, Er, Ho, Tm) microarchitectures have been successfully synthesized via ethylene glycol (EG)-mediated hydrothermal method followed by a subsequent heat treatment process. X-ray diffraction, Fourier transform infrared spectroscopy, energy-dispersive X-ray spectra, thermogravimetric and differential thermal analysis, elemental analysis, inductively coupled plasma atomic absorption spectrometric analysis, ion chromatogram analysis, X-ray photoelectron spectra, scanning electron microscopy, transmission electron microscopy, photoluminescence spectra as well kinetic decays, and cathodoluminescence spectra were used to characterize the samples. Hydrothermal temperature, EG, and CH3COONa play critical roles in the formation of the lutetium oxide precursor microflowers. The reaction mechanism and the self-assembly evolution process have been proposed. The as-formed lutetium oxide precursor could transform to Lu2O3 With their original flowerlike morphology and slight shrinkage in the size after postannealing process.

Highly uniform and monodisperse beta-NaYF4 : Ln(3+) (Ln = Eu, Tb, Yb/Er, and Yb/Tm) hexagonal microprism crystals: Hydrothermal synthesis and luminescent properties

beta-NaYF4:Ln(3+) (Ln = Eu, Tb, Yb/Er, and Yb/Tm) hexagonal microprisms with remarkably uniform morphology and size have been synthesized via a facile hydrothermal route. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), and photoluminescence (PL) spectra as well as kinetic decays were used to characterize the samples. It is found that sodium citrate as a shape modifier introduced into the reaction system plays a critical role in the shape evolution of the final products. Furthermore, the shape and size of the products can be further manipulated by adjusting the molar ratio of citrate/RE3+ (RE represents the total amount of Y3+ and the doped rare earth elements such as Eu3+, Tb3+, Yb3+/Er3+, or Yb3+/Tm3+). Under the excitation of 397 nm ultraviolet light, NaYF4:xEu(3+) (x = 1.5, 5%) shows the emission lines of Eu3+ corresponding to D-5(0-3) -> F-7(J) (J = 0-4) transitions from 400 to 700 nm (whole visible spectral region) with different intensity, resulting in yellow and red down-conversion (DC) light emissions, respectively.

水热微乳液法合成BaLiF_3:Er~(3+)纳米微粒及表征

采用水/CTAB/正丁醇/正辛烷体系微乳液法及水热技术制备了BaLiF3∶Er3+纳米微粒。利用X射线衍射(XRD)、环境扫描电镜(ESEM)和红外荧光光谱等手段对所制备产物进行了表征。X射线衍射数据表明,所制备微粒与JCPDS标准卡片18-715吻合很好,利用谢乐公式计算所制备产物平均粒径在98.45 nm左右,与环境扫描电镜观察结果基本相同。BaLiF3∶Er3+纳米微粒的红外发射图谱由4个峰构成,最强峰位于1540 nm处,属于Er3+的f→f跃迁。