PMN-PT:Er3+铁电晶体的光谱特性与J-O理论分析

为了探索Er3+在Pb(Mg1/3Nb2/3)-PbTiO3弛豫铁电晶体场中的发光特性,采用高温溶液法生长了PMN-32PT:Er3+弛豫铁电单晶,测试并分析了该晶体的微观形貌、相结构、吸收光谱与上转换发射光谱,利用Judd-Ofelt理论计算了Er3+在PMN-32PT晶体场中的J-O振子强度参数.该晶体四方相晶胞参数为a=0.4023 nm,c=0.4033 nm,V=0.06523 nm3,单斜相晶胞参数为a=0.4035 nm,b=0.4032 nm,c=0.4031 nm,V=0.06557 nm3.振子强度参数Ω2=1.77×10-20 cm2,Ω4=1.50×10-20 cm2,Ω6=0.79×10-20 cm2,δrms=0.18×10-6;4 I11/2的理论能级寿命τ=1.75 ms.样品晶体在980 nm光源激发下,发射出了很强的绿光(552 nm).研究结果表明PMN-PT:Er3+单晶是一种性能优异的新型发光晶体.     

PSN-PMN-PT∶Er3+晶体Judd-Ofelt理论分析

为了探索Er3+在铁电晶体场中的发光特性,采用高温溶液法生长了Er3+掺杂Pb(Sc1/2Nb1/2)O3-Pb(Mg1/3Nb2/3)O3-PbTiO3弛豫铁电单晶.该晶体在紫外-可见-近红外吸收光谱380～1800 nm波段出现了7个吸收峰;在980 nm泵浦光源照射下,该晶体的发射光谱出现了强绿光和强红光上转换发射带,分别对应于Er3+的4S3/2→4I15/2和4F9/2→4I15/2跃迁;利用Judd-Ofelt理论计算了晶体的振子强度三参数(Ω2＝2.54×10-20 cm2,Ω4＝1.36×10-20 cm2,Ω6 ＝2.38× 10-20 cm2)以及Er3+在PSN-PMN-PT晶体场中的跃迁几率、能级寿命和荧光分支比.研究结果表明 PSN-PMN-PT∶Er3+弛豫铁电晶体是一种新型发光晶体.     

双掺Er~(3+)/Yb~(3+)∶Sr_3La_2(BO_3)_4晶体的生长与光谱特性

采用提拉法生长了尺寸为20mm×30mm的Er3+/Yb3+∶Sr3La2(BO3)4晶体,研究了Er3+/Yb3+∶Sr3La2(BO3)4晶体的吸收光谱和荧光光谱。根据Judd-Ofelt理论分析并计算了辐射跃迁几率、辐射寿命、荧光分支比等光谱参数,获得的唯象参数为:Ω2=15.59×10-20cm2,Ω4=2.25×10-20cm2,Ω6=1.49×10-20cm2。在Er3+/Yb3+∶Sr3La2(BO3)4晶体中Er3+在1533nm处发射跃迁截面为7.88×10-21cm2,Er3+的4I13/2→4I15/2能级跃迁的荧光寿命和辐射寿命分别为0.728ms和4.24ms,结果表明Yb3+对Er3+有敏化作用,提高了对泵浦光的吸收能力,Er3+/Yb3+∶Sr3La2(BO3)4晶体可望作为1.55μm波段的一种有潜力的激光材料。     

掺钬铌酸锂晶体光谱性能研究

采用提拉法得到了纯LiNbO3和掺杂量为2mol;的Ho:LiNbO3晶体.测试了Ho:LiNbO3晶体的吸收光谱、光致发光光谱,采用620nm激发波长得到了523nm的上转换荧光.利用Judd-Ofelt理论计算出在LiNbO3中的强度参数Ω2=27.4×10-20 cm2、Ω4=7.45×10-20 cm2、Ω6=27.1×10-20 cm2,并由此计算了5G4→5I8、5S2→5I7、5F3→5I8处的自发辐射跃迁几率和积分发射截面.     

上转换激光晶体Er:BaY2F8的生长与光谱分析

报道了上转换激光晶体Er:BaY2F8以及Er,Yb:BaY2F8的温度梯度法生长及其光谱参数分析.所得到的Er:BaY2F8晶体的直径为13 mm,长度达40 mm,是目前国内最大的此种晶体.测试了晶体的吸收光谱,吸收光谱中Er离子的特征吸收峰清晰可辨.根据J-O理论的计算,得到了唯象的晶场参数Ωi( i=2,4,6),其数值分别为1.43×10-20 cm2,0.49×10-20 cm2和1.36×10-20 cm2.重点分析了Er:BaY2F8晶体的各能级的荧光寿命,较之氧化物有很大的提高,其中4I11/2能级的寿命约为5 ms,这样大的荧光寿命对于上转换激光的形成极为有利.     

Er3+,Yb3+:YAl3(BO3)4晶体的光谱性质研究

采用助熔剂法生长了Er3+,Yb3+共掺的YAl3(BO3)4晶体,测量了晶体的室温吸收谱.由此吸收谱,根据JuddOfelt理论计算了Er3+在Er3+,Yb3+:YAl3(BO3)4晶体中的强度参数、自发辐射几率、积分发射截面等参数.强度参数为Ω2=2.44×10-20cm2、Ω4=2.00×10-20cm2、Ω6=6.10×10-20cm2.研究了晶体的荧光特性,并在976nm激光泵浦下得到了上转换绿色荧光.     

Nd:YbVO4晶体的拉曼光谱和荧光光谱研究

用群论的方法计算了Nd:YbVO4晶体的拉曼活性振动模数目,在室温下测得了其极化拉曼谱线,并指认了在不同几何配置下,各振动模式所对应的频率.同时,测得了室温下晶体的吸收谱,得到了中心波长为808 nm吸收峰的半高宽为12 nm,并在J-O理论的基础上计算了晶体的光学参数,其三个晶场参数分别为Ω2=6.88945×10-20 cm2、Ω4=4.13394×10-20 cm2、Ω6= 4.54503×10-20 cm2,并由此得到4F3/2能级的荧光寿命为178.69 μs,1062 nm处的荧光分支比为48.85;,积分发射截面为2.7867 10-18 cm2.分别在808 nm、940 nm激发下测得晶体室温发射谱,观察到了Nd→Yb以及Nd←Yb间的能量传递现象.     

掺铒硼酸钙氧钆(GdCOB:Er)晶体的光谱分析

生长并测量了新型激光晶体GdCa4O(BO3)3:Er(简称GdCOB:Er)的透过谱,计算了Er3+离子在晶体中的吸收截面.由积分吸收截面的公式拟合出唯象强度参量Ω2＝2.531×10-20cm2,Ω4＝2.716×10-20cm2,Ω6＝1.891×10-20cm2,并应用Judd-Ofelt理论计算出振子强度fJ,J、辐射跃迁几率AJ,J、荧光辐射寿命τ及积分发射截面σ.并根据这些光学参量,讨论了GdCa4O(BO3)3:Er晶体用作激光晶体的可能性.     

Nd~(3+)掺杂的Sr_3Y_2(BO_3)_4晶体光谱特性研究

采用提拉法生长出25mm×40mm的Nd3+∶Sr3Y2(BO3)4晶体,测试了该晶体的吸收光谱、荧光光谱及荧光寿命。结果表明:Nd3+∶Sr3Y2(BO3)4晶体在807nm附近有最强的吸收峰,其半峰宽(FWHM)为16nm,宽的吸收半峰宽适合于LD泵浦;从荧光光谱得到发射波长分别为910.8nm、1065.2nm和1399nm的荧光峰。根据吸收和荧光光谱,计算了晶体的吸收截面和发射截面。采用J-O理论计算了Nd3+在Sr3Y2(BO3)4中的强度参数、各能级的振子强度、自发辐射几率、荧光分支比等参数。计算结果表明,其强度参数Ω2=3.816×10-20cm2,Ω4=10.895×10-20cm2,Ω6=12.44×10-20cm2,辐射寿命为104μs,量子效率η=49.7%,荧光分支比β1(0.88μm)=0.429,β2(1.06μm)=0.461,β3(1.35μm)=0.107,β4(1.88μm)=0.003。     

Er~(3 ),Yb~(3 )∶YAl_3(BO_3)_4晶体的光谱性质研究

采用助熔剂法生长了Er3 ,Yb3 共掺的YAl3 (BO3 ) 4 晶体 ,测量了晶体的室温吸收谱。由此吸收谱 ,根据Judd Ofelt理论计算了Er3 在Er3 ,Yb3 ∶YAl3 (BO3 ) 4 晶体中的强度参数、自发辐射几率、积分发射截面等参数。强度参数为Ω2 =2 .4 4× 10 -2 0 cm2 、Ω4=2 .0 0× 10 -2 0 cm2 、Ω6=6 .10× 10 -2 0 cm2 。研究了晶体的荧光特性 ,并在 976nm激光泵浦下得到了上转换绿色荧光。     

Au／CdS-核／壳结构纳米复合颗粒的制备与表征

本文制备并表征了Au/CdS几何结构的纳米簇复合物.TEM和尺寸分布图显示,Au颗粒和CdS颗粒的平均粒径分别为6 nm和8 nm,Au/CdS粒径分布较窄且分散性较好,平均粒径19 nm.这种核壳结构纳米复合颗粒和单CdS颗粒一样,在485 nm和543 nm有两处发射峰.从UV-Vis上观察到,CdS的吸收边在470 nm,Au/CdS的吸收谱线上Au的吸收峰消失,吸收边相对于单CdS出现蓝移.     

Up‐conversion luminescence of ytterbium and thulium codoped potassium yttrium double tungstate crystal

Thulium and ytterbium co‐doped double tungstate Yb³⁺,Tm³⁺: NaY(WO₄)₂ single crystals were prepared by using RF‐heating Czochralski (CZ) pulling method. Its polarized transmittance spectra have been recorded in the region of 290‐2000 nm at room temperature. The energy levels transitions were assigned to the corresponding absorption line. The up‐conversion luminescences at 793 nm and 475 nm were measured when the sample were pumped by 972 nm LD and the energy transfer mechanism between Yb³⁺ and Tm³⁺ ions was analyzed.     

Czochralski法生长Lu2SiO5：Ce晶体的发光特性

本文使用铱坩埚感应加热Czochralski法成功地生长出了无色透明且尺寸达5 0mm× 6 0mm的Lu2 SiO5:Ce晶体。XRD结构分析表明 ,该晶体为单斜结构。在室温下分别以X射线和紫外光为激发源测量了该晶体的发射光谱 ,获得的发射波长分别为 4 0 3nm和 4 2 0nm ,光衰减时间为 4 1ns,光产额达 32 0 0 0p/MeV。发射光谱的双峰结构以及晶体的发光特性证明其发光源于Ce3 离子的 5d1→5F5/ 2 和 5d1→5F7/ 2 跃迁。     

On the crystallochemical origin of the disordered form of Ba7(EuII)F12Cl2 and the structural changes induced at high temperature

The crystal structure of the disordered modification of Ba₇F₁₂Cl₂ has been carefully re‐examined on several new crystals prepared under different conditions of synthesis. All single crystal structure refinements reveal a residual electron density of ∼3 e^–/ų in the 0,0,0 position which is explained by the introduction of a small amount of sodium ions in the crystal. The title compound transforms from a disordered to an ordered modification at ∼800 °C. New structural data show a change in space group from P6₃/m to P6. During this process, a slight chemical change and the formation of nano‐channels in the crystals is observed by electron microscopy. These changes were further studied by electron microprobe analysis, by spectroscopic methods and thermal analysis. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Czochralski法生长Lu2SiO5:e晶体的发光特性

本文使用铱坩埚感应加热Czochralski法成功地生长出了无色透明且尺寸达φ50mm×60mm 的Lu2SiO5:e晶体.XRD结构分析表明, 该晶体为单斜结构.在室温下分别以X射线和紫外光为激发源测量了该晶体的发射光谱,获得的发射波长分别为403nm和420nm,光衰减时间为41ns,光产额达32000p/MeV.发射光谱的双峰结构以及晶体的发光特性证明其发光源于Ce3+离子的5d1→5F5/2 和 5d1→5F7/2跃迁.     

前驱液pH值对2ZnO·2.2B2O3·3H2O∶Eu3+荧光粉发光性能的影响

采用水热法,通过氨水调节前驱液的pH值,制备了一系列2ZnO.2.2B2O3.3H2O∶Eu3+样品。对所制备的样品进行X射线衍射和荧光光谱分析。研究结果表明:前驱液的pH值影响2ZnO.2.2B2O3.3H2O的结晶程度,在中性条件下制备的样品结晶度最好。当前驱液的pH=5.7时,激发光谱中的Eu-O电荷迁移带的峰位波长最大(262 nm),这可能是由于在此条件下合成的样品中Eu-O键长最长。发射光谱表明:当前驱液的pH>5.7时,Eu3+的发射光谱中的红橙比(I614/I589)随pH值的增大而增大,且当前驱液的pH值在5.7～6.9区间,红橙比(I614/I589)随pH值的增大的速率要比pH值在6.9～9.3之间增加的速率要快。另外,随着pH值的增大,样品的发光强度呈先增大后减小的变化趋势。当前驱溶液pH=8.1时,样品的发光强度最大。     

Luminescence characteristics of undoped and Eu‐doped GdCa4O(BO3)3 single crystals and nanopowders

Single crystals of GdCa₄O(BO₃)₃ (GdCOB) pure and doped with Eu concentration of 1 and 4 at% were grown by the Czochralski and micropulling‐down methods. The distribution of Eu ions in GdCOB crystals was uniform. The substitutions of Eu³⁺ in Gd, Ca(1) and Ca(2) cation sites and eventually formation Eu²⁺ have been investigated. The spectroscopic properties of crystals are compared with the properties of nanopowders obtained by sol‐gel method. Radioluminescence spectra of undoped GdCOB crystal show the characteristic emission of Gd³⁺ at about 312 nm, whereas this emission dramatically decreases in Eu‐doped crystals upon X‐ray excitation, as well as in Eu‐doped nanopowders excited in vacuum ultraviolet (VUV) region. The VUV excitation in the range 125‐333 nm for Eu‐doped samples leads to strong emission in red coming from the ⁵D₀ multiplet of Eu³⁺, only. In the photoluminescence decay kinetics of 312 nm emissions substantial shortening and departure for single exponential decay in Eu‐doped samples is clearly observed. Higher Eu doping results in further acceleration of the decay. In undoped GdCOB crystal, the lifetime of the Gd^{3+ 6}P_7/2 multiplet is 2.79 ms. The Eu^{3+ 5}D₀ decay kinetics monitored at 613 nm are rather constant. Numerical fitting of fully exponential curves, reveals lifetimes 2.7 ms for nanopowder and 2.5 ms for single crystal. The results suggest that this material may be used as a red phosphor in plasma display panels in nanopowder form because of strong excitation band of Eu³⁺ luminescence in the 160‐200 nm regions. Contrary to nanopowder sample, such an excitation band, attributed to the Gd³⁺–O^2– charge transfer was not observed in crystal obtained by the micropulling‐down method. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Luminescent properties of CsI single crystals grown from the melt treated with EuI2

CsI single crystals treated with EuI₂ as a scavenger are grown and their radioluminescence spectra and scintillation light decay curves are obtained. Addition of the quantities of the scavenger comparable with the total concentration of the oxygen‐containing admixtures in the melt results in complete destruction of the latter. In its turn, this causes the disappearance of the band with a maximum at 2.8 eV in the radioluminescence spectrum and decreases the fraction of the slow 2 µs‐component to 0.01. The addition of larger quantities of EuI₂ leads to the appearance of a wide band with the maximum at 2.8 eV characterized by a decay constant of 2 µs; its intensity increases with the EuI₂ concentration. The maximum ratio of two faster components with the decay constants equal to 7 and 30 ns approaches 0.58:0.41 at EuI₂ concentration in CsI melt equal to 0.01 mol·kg⁻¹.     

Growth and photoluminescence properties of CdS solid solution semiconductor

Photoluminescence (PL) emitted from Cd_1‐xZn_xS and CdS_1‐ySe_y solid solution semiconductor was significantly stronger than PL from the pure CdS and CdSe semiconductor. The samples were prepared using an improved Se‐S‐Na₂S flux route. Photoluminescence in Cd_1‐xZn_xS crystal was brightly yellow at the room temperature under VU radiation. The phase and composition of the solid solution was measured by the XRD and was confirmed by UV‐NIS spectrum as x of 0.3 and y of 0.2. The enhanced photoluminescence was presumably due to the introduction of extra defect (vacancies) by solid solution action and consequently the increasing of luminescence center concentration. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

焦硅酸镥(Lu2Si2O7:Ce)闪烁晶体的生长与发光性能研究

铈掺杂的焦硅酸镥晶体(简写为LPS:Ce)是新近发现的一种具有潜在应用价值的无机闪烁晶体.本文用提拉法成功地生长出尺寸为φ15mm×40mm的LPS:Ce晶体.XRD结构测试表明,该晶体属于单斜晶系,C2/m空间群,晶体中分布有少量的LPS和石英颗粒包裹体.对从毛坯中切割出的无色透明晶体样品在室温下分别进行了透射光谱、紫外激发、X射线激发发射光谱和衰减时间测试.结果表明,铈(Ce3+)离子掺杂使LPS晶体的紫外吸收边从175nm红移到350nm,紫外和X射线激发的荧光光谱中都可以分解出384nm和412nm两个发射峰,它们分别对应于电子从铈(Ce3+)离子的5d轨道向4f轨道的两个能级(2F5/2和2F7/2)的辐射跃迁,从衰减曲线中可以拟合出一个38.75ns的时间常数.这些发光特征与该晶体独特的晶体结构密切相关.