Optical spectroscopy of Ce 3+ ions in BaY 2 F 8 single crystals

In the present work we report on the spectroscopic properties of the Ce 3+ ion in BaY 2 F 8 single crystals. The absorption and excitation spectra of the emission centered at 340 v nm have been measured in the temperature range 15-300 v K. The 340 v nm emission consists of two broad partially overlapping bands, peaking at 324 and 347 v nm (at 15 v K), respectively. The full width at half maximum is about 0.5 v eV at room temperature. The absorption spectrum of the lowest in energy component of the f M d transition of Ce 3+ reveals at low temperature a marked vibronic structure. High resolution (0.02 v cm m 1 ) Fourier transform infrared spectroscopy in the wave number range 500-5000 v cm m 1 and in the temperature range 9-300 v K has been exploited to monitor the f level splitting. The absorption transitions from the three Stark components of the 2 F 5/2 manifold to the four of the 2 F 7/2 one, have been monitored in the wave number range 2000-3400 v cm m 1 . The wave number separation at 9 v K between the lowest level of the ground 2 F 5/2 manifold and lowest one of the 2 F 7/2 manifold is found to be 2197.47 v cm m 1 in good agreement with the splitting detected between the two components of the d M f emission.     

MO-Y2O3-B2O3:Re(M=Mg,Sr;Re=Eu,Tb)的真空紫外光谱特性

采用高温固相反应法合成了掺杂Eu3 及Tb3 的17MO-7.88Y2O3-75B2O3样品,研究了它们的光谱特性,结果表明,MO-T2O3-B2O3基质在真空紫外(VUV)区有很强的吸收,MgO-Y2O3-B2O3:Eu在147nm真空紫外光激发下产生对应于Eu3 的5D0→7FJ(J=1,2,3,4)跃迁的590和613 nm强发射峰;MgO-Y2O3-B2O3:Eu中Sr的引入使材料体系在147 nm附近的吸收和在613 nm附近的发射获得明显增强;MgO-Y2O3-B2O3:Tb的真空紫外激发谱除在147 nm附近的基质吸收外,还有对应于Tb3 的4f75d→4f8跃迁位于170,178,195,204,225 nm左右的一组谱峰,两者相互叠加使得材料在真空紫外区(120～220 nm)内都有很好的吸收.     

The colouration of CaF 2 crystals by keV AND GeV ions

CaF 2 crystals have been implanted with a variety of ions of widely different energies and mass. Effects have been monitored using optical absorption in the range 120-750 v nm. This includes the vacuum UV region. For 100 v keV ions (Al, Mg, Kr) we observe extrinsic colloid bands in the case of implanted metal ions at high fluences (10 17 v ions v cm 2 ) but no colour centres (F, F 2 etc). For GeV ions (U, Ni) we observe prominent absorption bands in the visible region at fluences of 10 12 v ions v cm m 2 attributed to extrinsic calcium colloids. New optical features are discussed including an absorption band near 185 v nm in the VUV and bands at 604 v nm and 672 v nm in the visible region.     

CaMgSi2O6:Eu的真空紫外光谱特性

采用高温固相反应利用原料CaCO3,MgO,SiO2和Eu2O3合成CaMgSi2O6:Eu3 样品,并研究了其结构特性、光谱特性.CaMgSi2O6:Eu3 属于单科晶系,基质掺入Eu离子后结构没有明显变化.CaMgSi2O6:Eu3 在147 nm真空紫外光激发下呈红色发射,发射主峰位于611 nm,是Eu3 的5D0→7F2跃迁的典型发射.当Eu3 的相对摩尔浓度在0.02到0.10 mol之间变化时,由相关数据可以发现有浓度猝灭现象发生.CaMgsi2O6:Eu2 在172 nm真空紫外光激发下呈蓝色发射,发射主峰位于452 nm,是Eu2 的5d→4f跃迁的典型发射.添加不同浓度的H3BO3后可大大提高样品的发光强度.     

Optical activity and damage recovery of erbium implanted strontium titanate

Single crystalline SrTiO 3 samples were implanted with Er ions of 150 v keV at room temperature with fluences of 5 ‐ 10 14 and 5 ‐ 10 15 . Annealing treatments were carried out both in reducing and oxidising atmospheres to recover the implantation damage. Infrared 1.54 v m Er 3+ luminescence between the two lowest spin-orbit levels 4 I 13/2 M 4 I 15/2 as well as emission from higher excited states 4 S 3/2 M 4 I 15/2 , 4 F 9/2 M 4 I 15/2 and 4 S 3/2 M 4 I 13/2 were observed in the implanted samples with highest fluence, annealed either in air or in vacuum. Multiple site location of Er 3+ ion is discussed and compared with RBS/C and emission channelling results that indicate that Er goes to Sr and Ti sites.     

977nm抽运下掺铒碲酸盐基氧卤玻璃的光谱特性

研究了掺铒TeO2-ZnO-PbCl2碲酸盐基氧卤玻璃在977nm激光二极管抽运下的发光和上转换发光特性，结果发现除红外153μm4I13/2→４I15/2发光外（荧光半高宽高达69nm），该玻璃还存在很强的２Ｈ11/2→４I15/2（527nm），４Ｓ3/2→４I15/2（549nm）和４Ｆ９／２→４Ｉ１５／２（666nm）可见上转换发光.应用Judd-Ofelt理论计算得到玻璃强度参数Ωt（t=2，4，6）分别为Ω2=587×10-20cm2，Ω4=208×10-20cm2，Ω6=116×10-20cm2，计算了铒离子跃迁振子强度、自发辐射概率、荧光分支比、荧光寿命等光谱参量.应用McCumber理论计算得153μm处的玻璃受激发射截面可达875×10-21cm2实验结果表明，与硅酸盐玻璃、磷酸盐玻璃、氟化物玻璃等比较，掺铒碲酸盐基氧卤玻璃在宽带掺铒光纤放大器和上转换激光器中有着极大的研究和应用潜力. 关键词： 掺Er3+ 碲酸盐玻璃 氧卤玻璃 Judd-Ofelt理论 光谱性质     

Upconverted VUV luminescence of Nd and Er doped into LiYF4 crystals under XeF-laser excitation

The upconverted VUV (185 nm) and UV (230 and 260 nm) luminescence due to 5d-4f radiative transitions in Nd³⁺ ions doped into a LiYF₄ crystal has been obtained under excitation by 351/353 nm radiation from a XeF excimer laser. The maximum upconversion efficiency, defined as the ratio of intensity for 5d-4f luminescence to overall intensity for 5d-4f and 4f-4f luminescence from the ⁴D_3/2 Nd³⁺ level, has been estimated to be about 70% under optimal focusing conditions for XeF laser radiation. A redistribution of intensity between three main components of 5d-4f Nd³⁺ luminescence is observed under changing the excitation power density, which favors the most long-wavelength band (260 nm) at higher excitation density level. The effect is interpreted as being due to excited state absorption of radiation emitted. The upconverted VUV and UV luminescence from the high-lying ²F(2)_7/2 4f level of Er³⁺ doped into a LiYF₄ crystal has also been obtained under XeF-laser excitation the most intense line being at 280 nm from the spin-allowed transition to the ²H(2)_11/2 4f level of Er³⁺, but the efficiency of upconversion for Er³⁺ emission is low, less than 5%.     

ZnS:TbF3,ErF3,HoF3ACTFEL的亮度与跃迁几率的关系

测量了低浓度下ZnS:TbF3,ErF3和ZnS:TbF3,HoF3交流电致发光薄膜(ACTFEL)中的Tb3+,Er3+,HO3+主要发射峰的相对积分强度,并与Tb3+,Er3+,Ho3+主要发射能级的辐射跃迁几率及高浓度时的发光特性进行了比较,发现稀土氟化物掺杂的ZnS薄膜电致发光(ACTFEL)的最大亮度,不完全取决于稀土离予本身的辐射跃迁几率,而主要取决于稀土离子主要发射能级激发态的运动。本文首次给出了Tb3+离子在ZnS中的强度参数Ω2=3.2×10-19cm2,Ω4=1.6×10-19cm2,Ω6=2.6×10-19cm2,并应用这组Ωλ参数估算了Tb3+离子的交叉弛豫(cross-relaxation)几率。     

LnZr(BO3)2:Eu3+(Ln=Ba,Sr)的真空紫外光谱特性的研究

采用高温固相法合成了Ba(1-x)SrxZr(BO3)2:Eu3 系列样品,样品Ba(1-x)SrxZr(BO3)2:Eu3 激发谱在130～170nm和230 nm区域有两个很强的吸收带,位于130～170nm的吸收带主要是硼酸盐基质的吸收;位于230nm附近的吸收主要是Eu3 电荷转移态的吸收.当在样品中以Al部分取代Zr时,电荷转移态的吸收明显增强,并且Ba(1-x)SrxZr(BO3)2:Eu3 发射强度也会明显增强;随着x的增大,硼酸盐基质的吸收强度减弱,基质吸收带的主峰值向低能方向移动了大约30 nm.样品Ba(1-x)SrxZr(BO3)2:Eu3 在147nm激发下,发射出主峰值位于616nm的强红光,对应Eu3 电偶极(5D0→7F2)跃迁发射.     

Sr3Gd(PO4)3:Tm3+的真空紫外光谱特性

研究了Sr3Gd(PO4)3 : Tm3 和GdPO4 : Tm3 样品的结构特性、光谱特性.GdPO4 : Tm3 为单斜晶系,基质掺入铥离子后结构没有明显变化.GdPO4:Tm3 在164和210 nm附近有强烈的吸收峰.位于164 nm附近的强烈的吸收峰是归因于基质的吸收引起,210 nm附近的吸收峰则归因于Gd 的8S7/2-6GJ的能级跃迁.在164 nm真空紫外光激发下,样品于453及363 nm处有较强的发射峰,发射主峰位于453nm,属于Tm3 的1D2→3H4(22,123 cm-1)跃迁的典型发射.由于阳离子质量的不同,Sr3Gd(PO4)3:Tm3 在166 nm附近的激发峰高于GdPO4: Tm3 的同位置的激发峰,其在363 nm处的发射有明显减弱,而在453 nm处的蓝色发射有显著的增强.     

EPR study of monomeric and dimeric vanadyl ions in SbVO 5

A new compound, SbVO 5 , formed in the V-Sb-O system, has been synthesized and investigated using the electron paramagnetic resonance (EPR) technique. SbVO 5 has been prepared by two methods: by heating equimolar mixtures of V 2 O 5 and f -Sb 2 O 4 in air and by oxidation of the known phase (SbVO 4.5 ) of rutile type obtained in pure argon at temperatures between 550 v C and 650 v C. At room temperature only a weak EPR signal from the powder sample of SbVO 5 was detected corroborating the absence of bulk V(IV) ions in the structure. Comparison with the CuSO 4 reference sample revealed that only 0.02% vanadium ions are EPR active. Intense EPR spectra obtained in the low temperature range, below 100 v K, showed a well resolved hyperfine structure typical of isolated vanadium ions in axial symmetry, present as VO 2+ species, and a broad line attributed to V 4+ -O-V 5+ bonds. The hyperfine structure lines could be analyzed by an axial spin Hamiltonian with g =1.9311, g =1.9425 and A =181 ‐ 10 m 4 v cm m 1 , A =54 ‐ 10 m 4 v cm m 1 . The spectrum recorded at the lowest obtainable temperature T=3.65 v K contains yet another component which is typical of a triplet state indicating the presence of two interacting VO 2+ nuclei with spin 1/2 giving a singlet S=0 and a triplet S=1 state. The appearance of a low-field line (B～1600 v Gs at g , 4) is another diagnostic for the presence of dimeric species and is attributed to the forbidden j M S = - 2 transition.     

The VUV‐VIS Spectroscopic Properties of Dy3+ Ion in Phosphors M5‐2XDyXNaX(PO4)3F (M=Ca,Sr, Ba) and Their Potential Applications in Mercury‐Free Lamps

The phosphors, fluorapatites M₅(PO₄)₃F (M=Ca, Sr, Ba) activated with Dy³⁺ ions, were prepared by a high‐temperature solid‐state reaction technique. The VUV‐UV excitation spectra and emission spectra under VUV/UV excitation were measured. The phosphors show broad and strong absorption near 172 nm and intensive emission with the chromaticity coordinates entering the white light region. Hence, the phosphors may be considered as suitable candidates for Hg‐free lamps.     

LaOBr中Ce—Tb、Tm—Er间能量传递的光声光谱和光致发光研究

本文首次报导了发光材料中两个不同稀土离子间能量传递的光声光谱研究。测量了LaOBr:Tb,Ce和LaOBr:Er,Tm体系的光声光谱,结合它们的光致发光特性,讨论了Ce³⁺对Tb³⁺的敏化、Tm³⁺对Er³⁺的猝灭。基质中掺入两种不同稀土离子后光声光谱的变化进一步证实了它们间的能量传递都伴随着多声子过程。分析LaOBr:Er,Tm的光声光谱,对Er³⁺r的红光猝灭的机制提出了新的解释。     

Er3+掺杂Ge-Ga-S-KBr硫卤玻璃的中红外发光和多声子弛豫的研究

用熔融急冷法制备了系列不同Er3+离子掺杂浓度的Ge-Ga-S-KBr硫卤玻璃,测试了样品折射率、吸收光谱、中红外荧光光谱。通过吸收光谱计算了Er3+离子吸收谱线的振子强度,应用Judd-Ofelt理论计算分析了Er3+离子在Ge-Ga-S-KBr硫卤玻璃中的强度参数Ωi ( i = 2 , 4 , 6) 、自发辐射跃迁几率A、荧光分支比?和辐射寿命?rad等光谱参数。研究了808nm激光泵浦下样品中红外荧光特性与掺杂浓度之间变化关系,并用Futchbauer-Ladenburg公式分别计算了2.8?m处的受激发射截面。结果表明,在808nm 激光泵浦下观察到了2.8?m中红外荧光,分别对应于Er3+： 4I11/2?4I13/2跃迁,当Er3+离子掺杂浓度从0.4wt%增加到1.0wt%时,中红外荧光强度都随相应增加,计算的Er3+:4I11/2?4I13/2跃迁多声子驰豫速率分别为37 s-1。     

Er^3＋／Yb^3＋共掺杂ZnO粉末的上转换发光特性

采用高温氧化法制备了Er3 /Yb3 共掺杂ZnO粉。通过X射线衍射和扫描电镜对其进行了成分和组织结构分析,发现样品主要由ZnO和YbF3组成。在ZnO中测量到少量Er3 和Yb3 ,而YbF3中无Er3 ,故发光主要是由ZnO产生的。在980nm半导体激光器的激发下,观察到由处于激发态能级4F9/2,4S3/2,2H11/2和2H9/2的Er3 离子向基态4I15/2跃迁时发出的波长依次为658,538,522和409nm的上转换发光。在488nmAr 激光器的激发下,观察到了较强的409nm的紫光,466和450nm的弱蓝光以及379nm的紫外光,分别对应于Er3 离子的2H9/2→4I15/2,2P3/2→4I11/2,4F3/2/4F5/2→4I15/2,4G11/2→4I15/2等跃迁。上转换发光强度随激发功率的变化关系表明,488nm激发下紫色上转换荧光为双光子过程,主要是通过Er3 /Yb3 离子间正向和反向的能量传递来实现的。     

YVO_4∶Yb~(3+),Er~(3+)纳米粒子颜色可控的高色纯度上转换发光

采用共沉淀法制备了四方相锆石型结构YVO_4∶Yb~(3+),Er~(3+)纳米粒子。粒子表面光滑,结晶良好,呈类球状,粒径~80 nm。在980 nm和1 550 nm红外激发下,粒子呈现类似的特征发射,峰位位于634~706 nm的红光和513~573 nm的绿色分别归因于Er~(3+)离子~4F_(9/2)→~4I_(15/2)和~2H_(11/2),~4S_(3/2)→~4I_(15/2)能级间的辐射跃迁。通过激发光波长控制,在同组分粒子中实现了颜色可控的高色纯度绿、红色发光,对应的绿红光和红绿光分支比分别高达29.5和37.97。借助能级跃迁模型,详细讨论了不同激发条件下的纳米粒子上转换发光的跃迁和变化机制。     

LaOBr:Ce,Tb中Ce3+对Tb3+发光的影响

近年来人们对LaOBr:Tb的合成及其发光特性的研究日益增多。LaOBr:Tb不仅是良好的X光增感屏材料,也是较好的阴极射线发光材料。为了进一步提高它的亮度,降低了b的含量(因Tb很贵),寻求LaOBr中Tb3+发光的敏化剂是很重要的。     

在NaGdF4：Tm3+, Dy3+中Gd3+间的能量迁移及Gd3+-Dy3+能量传递量子效率

基于量子剪裁基本原理,通过光谱技术研究NaGdF₄:Tm³⁺,Dy³⁺在一个真空紫外光子激发下获得两个蓝色光子的可能性。在这种化合物中,量子剪裁通过下转换,即通过应用不同镧系离子间的能量传递进行。通过对Tm 4f¹²-4f¹¹5d激发,部分能量从Tm³⁺离子5d态直接传递给Gd³⁺,然后在Gd³⁺-Tm³⁺之间发生交叉弛豫,剩余能量从Gd³⁺传递给Dy³⁺,产生两个可见光子发射,一个来自Tm³⁺的¹G₄-³H₆跃迁,另一个来自Dy³⁺的⁴F_9/2-⁶H_15/2跃迁。主要研究获得以NaGdF₄:Tm³⁺,Dy³⁺为基础的新型具有更高效率,更高稳定性和更强真空紫外(VUV)吸收量子剪裁发光粉的可能性。各种光谱技术,如光致发光、激发和衰减等被用来表征不同Dy³⁺浓度掺杂NaGdF₄中Gd³⁺晶格间能量迁移引起的施主Gd³⁺和受主Dy³⁺之间的能量传递。结果表明Gd³⁺离子之间存在能量迁移,随之交换相互作用引起施主与受主(Gd³⁺-Dy³⁺)之间的能量传递。通过Bursh-tein等人关于激发态的弛豫理论,施主-受主能量传递参数k_DS可以从Gd³⁺的⁶P_7/2发射的衰减计算出。Gd³⁺-Dy³⁺能量传递量子效率也可以得到。NaGdF₄:Tm³⁺和NaGdF₄:Tm³⁺,Dy³⁺是由水热法制备的,NaGdF₄:Dy³⁺是由文献[4]方法制备的。发射光谱和激发光谱通过自制的VUV光谱仪和F-4500测量。衰减曲线由OPO激光器激发获得Gd³⁺-Dy³⁺之间能量传递量子效率在受主浓度大约在N_A=0.6%时达到最佳值,并且明显地观测到浓度猝灭效应。     

Optical spectroscopy of Ca3Sc2Si3O12, Ca3Y2Si3O12 and Ca3Lu2Si3O12 doped with Pr

The silicates Ca₃Sc₂Si₃O₁₂, Ca₃Y₂Si₃O₁₂ and Ca₃Lu₂Si₃O₁₂, both undoped and doped with Pr³⁺ ions, have been synthesized by solid-state reaction at high temperature. The luminescence spectroscopy and the excited state dynamics of the materials have been studied upon VUV and X-ray excitation using synchrotron radiation. All doped samples have shown efficient 5d-4f emission upon direct VUV excitation of 5d levels, but only Ca₃Sc₂Si₃O₁₂:Pr³⁺ shows luminescence upon interband VUV or X-ray excitation. The VUV excited emission spectra of Ca₃Y₂Si₃O₁₂:Pr³⁺ and Ca₃Lu₂Si₃O₁₂:Pr³⁺ show features attributed to emission from two distinct sites accommodating the Pr³⁺ dopant. The decay kinetics of the Pr³⁺ 5d-4f emission in Ca₃Sc₂Si₃O₁₂:Pr³⁺ upon VUV excitation across the band gap are characterized by decay times in the range 25-28 ns with no significant rise after the excitation pulse. They appear to be faster upon X-ray irradiation than for VUV excitation. Weak afterglow components are attributed to defect luminescence.     

Er离子注入GaP,GaAs, InP的二次离子质谱(SIMS)的研究

近年来掺稀土元素的Ⅲ—Ⅴ族化合物研究在基础物理和器件应用方面都越来越引起人们的关注,[1,2]其中又由于Er3+的4I13/2—4I15/2的特征发光波长为1.54μm,恰好对应于石英光纤的低损耗区,且离子注入技术简单易行,因而倍受重视.国际上已报道了不少有关Er注入Ⅲ—Ⅴ族化合物的研究,大多选用较低的注入剂量(约1012～1014Er/cm2),而对较高剂量的注入有待于进一步研究.