ZnS:Ho3+的辐射跃迁和无辐射过程

本工作研究了Ho³⁺离子在宽禁带半导体ZnS中的辐射跃迁和无辐射过程。用发射谱线的积分光强和激发态寿命获得ZnS:Ho³⁺的强度参数Ω_λ,同时计算了九个激发态的辐射跃迁几率和能级寿命。另外,通过在不同温度下测定Ho³⁺离子⁵G₆,³K₈,⁵F₂,⁵F₃和⁵S₂(⁵F₄)能级的发射光强和寿命的方法,研究了这几个激发态间的无辐射过程,其中⁵G₆,³K₈,⁵F₂和⁵F₃这四个能级是处于热平衡状态,而⁵F₃与⁵S₂(⁵F₄)能级间存在五个声子((1/n)ω_Lo=351cm^-1)参与的多声子弛豫过程。 关键词：     

YNbO4：Tm3+/Yb3+上转换发光特性研究

按照50Nb₂O₅-（46-x）Y₂O₃-4Yb₂O₃-xTm₂O₃（x=0.1,0.2,0.5,1,2）的配比方式,采用高温固相法制备出了掺杂Tm³⁺/Yb³⁺的YNbO₄晶体粉末。在980 nm红外光激发下,观测到波长为478,645,707 nm的上转换荧光,分别对应于Tm³⁺离子的¹G₄→³H₆、¹G₄→³F₄、³F₃→³H₆能级跃迁过程。利用上转换发射功率与980 nm激光器工作电流关系估算出跃迁过程吸收光子数目为2.72,2.69,2.01,从而确定出前两者为三光子吸收过程,最后一个对应于双光子吸收过程。运用Judd-Ofelt理论研究样品光谱特性,根据样品的吸收谱得到样品的谱线强度参数Ω_t（t=2,4,6）,进而得出理论振子强度及实验振子强度,二者均方根偏差δ_rms=1.299×10^-7。计算了Tm³⁺离子向下能级跃迁的跃迁几率、跃迁分支比等参数。最后得出结论：（1）³F₄能级寿命较长,适合作为上转换中间能级;（2）³H₅能级寿命较长,且³H₅→³H₆跃迁分支比（96.46%）接近100%,可用于产生1 216 nm激光。     

Tm3+-Yb3+共掺杂的碲酸盐玻璃和光纤的光谱特性

研究了Tm³⁺-Yb³⁺共掺杂的碲酸盐玻璃和光纤在980nm激光二极管激发下的可见与近红外光谱性质.室温下,Tm³⁺-Yb³⁺共掺杂的碲酸盐玻璃在480,800nm处观测到了很强的上转换发光,在650nm观测到一较弱的上转换发光,它们分别来自Tm³⁺离子的¹G₄^→3H₆,³H₄^{→ 3}H₆和¹G₄^{→ 3}F₄跃迁;在1020,1810nm处观测到近红外发射,它们分别属于Yb³⁺离子的²F_5/2^→2F_7/2跃迁和Tm³⁺离子的³F₄^→3H₆跃迁.研究了其发光特性与Tm³⁺及Yb³⁺的浓度的依赖关系.此外,在980nm激光激发下,还观测到Tm³⁺-Yb³⁺共掺杂的碲酸盐玻璃光纤在1060,1470,1910nm附近的近红外发射.详细讨论了其发光机制,该材料可望用于制作蓝色上转换光纤激光器、S-波段光纤放大器以及在医疗诊断和遥感中有着广泛的应用的1.9μm光纤激光器.     

PrxLa1-xP5O14的发光理论和浓度效应

本文利用Judd-Ofelt理论求得PrP₅O₁₄晶体的振子强度参数Q₂,比较了计算和实验的振子强度,计算了³P₁,³P₀,¹D₂和¹G₄能级的电偶极和磁偶极辐射跃迁几率及¹D₂→¹G₄和³H₄→³F₄能级对间的多极矩耦合的无辐射迁移几率。讨论了¹D₂能级发射强度的浓度效应。并且,给出¹D₂能级发射强度的表达式和强度随着浓度和单位时间内激发光引起的³H₄到¹D₂跃迁的诱导跃迁几率的变化图。 关键词：     

不同波长激发下YLiF4：Er3+,Tm3+,Yb3+的发光

水热法合成了YLiF₄:Er³⁺,Tm³⁺,Yb³⁺,其中Er³⁺、Yb³⁺和Tm³⁺的摩尔分数分别为1%、1.5%和2%。当用355nm光激发时,其发光为蓝色,峰值位于450nm,对应于Tm³⁺的¹D₂→³F₄跃迁。用378nm激发时,发光为绿色,主要发光峰位于552nm。980nm光激发时,发光为白色,发光峰分别位于665(651),552(543),484,450nm处,并在648nm处还观察到了一个发光峰,其中最强的发射为红光。YLiF₄:Er³⁺,Tm³⁺,Yb³⁺的蓝光来源于Tm³⁺的激发态¹G₄到基态³H₆的跃迁,绿光来源于Er³⁺的⁴S_3/2和²H_11/2到基态⁴I_15/2的跃迁,红光既来源于Tm³⁺的¹G₄→³F₄的跃迁,也来源于Er³⁺的⁴F_9/2→⁴I_15/2的跃迁。在上转换发光中,还探测到了紫外光359nm的发射。监测665nm得到的激发光谱不同于监测552nm的激发光谱,在665nm的激发光谱中出现了对应Tm³⁺的¹G₄能级的峰。在双对数曲线中,蓝光484nm、绿光552nm和红光665nm的斜率分别为2.25、2.28和2.21,紫外光359nm的斜率为2.85。因此在980nm激发下,蓝光484nm、绿光552nm和红光665nm都是双光子过程,紫外光359nm的发射是三光子过程。     

Tm3+离子掺杂的钨酸钇钠晶体中浓度猝灭效应的研究

测量了Tm³⁺离子不同浓度(0.5at.%, 3 at.%, 5 at.%)掺杂的NaY(WO₄)₂晶体在800nm激光二极管激发下的上转换发射光谱.结合吸收谱、荧光谱和由Judd-Ofelt理论计算的光谱参数，详细分析了Tm³⁺:NaY(WO₄)₂晶体中上转换能量传递机理和离子浓度对上转换发射的影响.讨论了四种影响上转换发光效率的离子间相互作用机理：³H₅+¹G₄→³H₆+¹D₂，³H₅+³H₅→³H₆+³F₃，¹G₄+³H₆→³F₄+³F₃，¹G₄+³H₆→³F₃+³F₄，并根据Miyakawa-Dexter理论定量计算了各过程的发生概率.论证了交叉弛豫和共协上转换等浓度猝灭效应是影响Tm³⁺离子蓝色上转换荧光发射效率的主要因素. 关键词： 3+离子')" href="#">Tm³⁺离子 4)₂晶体')" href="#">NaY(WO₄)₂晶体 上转换 浓度猝灭     

稀土掺杂的NaGdF4上转换发光材料的合成与发光特性研究

采用水热法制备了一系列不同掺杂浓度的NaGdF₄:Re(Re=Tm³⁺,Er³⁺,Yb³⁺)上转换发光粉。通过X射线衍射(XRD)、电子扫描电镜(SEM)和上转换发射光谱对样品进行了表征。XRD研究结果表明:合成的样品均为六方结构NaGdF₄。估算的平均晶粒尺寸为41~43 nm。在980 nm红外光激发下,Er³⁺和Yb³⁺共掺杂的NaGdF₄发光粉发出分别来自于Er³⁺离子²H_{11/ 2},⁴S_3/2→⁴I_15/2跃迁的绿光和⁴F_9/2→⁴I_15/2跃迁的红光发射,Tm³⁺和Yb³⁺共掺杂的NaGdF₄发光粉发出分别来自Tm³⁺离子的¹G₄→³H₆跃迁的蓝光、¹G₄→³F₄和³F_2,3→³H₆跃迁的红光和³H₄→³H₆跃迁的近红外光发射。Er³⁺,Tm³⁺和Yb³⁺共掺杂的NaGdF₄发光粉的发光强度及红、绿、蓝光发射的相对强度受Yb³⁺离子掺杂浓度的影响。对样品中可能的上转换发光机制进行了讨论。计算的色坐标显示:可通过改变掺杂离子浓度对上转换发光的颜色进行调控。     

Tm3+浓度对Y2（MoO4）3：Tm3+，Yb3+荧光粉上转换发光性质的影响

采用传统的高温固相反应法合成了Tm³⁺/Yb³⁺共掺杂Y₂（MoO₄）₃系列荧光粉。XRD结果表明合成的样品为相纯度好的Y₂（MoO₄）₃。在980 nm光激发下,样品具有较强的位于487 nm和800 nm的蓝色和近红外发射,同时伴有较弱的位于649 nm的红光发射。它们分别来自于Tm³⁺的¹G₄→³H₆、³H₄→³H₆和¹G₄→³F₄跃迁。根据功率相关的上转换发射和能级图分析了Tm³⁺的上转换发光机制。结果表明,¹G₄和³H₄能级的布居分别来自于三光子和两光子的能量传递上转换。此外,随着Tm³⁺浓度的增加,蓝色、红色和近红外发射带均呈先增加后降低的趋势,即发生了浓度猝灭。同时,蓝光发射和近红外发射的强度比随Tm³⁺掺杂浓度的增加而减小。     

绿色荧光粉NaCaPO4：Tb3+的制备与发光特性

采用高温固相法合成了适用于UVLED芯片激发的NaCaPO₄:Tb³⁺绿色荧光粉并对其发光性质进行了研究。该荧光粉的发射峰位于418,440,492,545,586,622nm,分别对应Tb³⁺的⁵D₃→⁷F₅、⁵D₃→⁷F₄、⁵D₄→⁷F₆、⁵D₄→⁷F₅、⁵D₄→⁷F₄、⁵D₄→⁷F₃能级跃迁。其中位于492,545nm的发射峰最强,样品发射很好的绿光。主要激发峰位于380~400nm之间,属于4f→4f电子跃迁吸收,与UVLED芯片的发射相匹配。考察了Tb³⁺掺杂浓度和Li⁺,Na⁺和K⁺作为电荷补偿剂对样品发光性能的影响:Tb³⁺的最佳掺杂浓度为10%,以Li⁺的补偿效果最好。NaCaPO₄:Tb³⁺是一种适用于白光LED的绿色荧光材料。     

LnP5O14晶体中Tb3+和Eu3+的发光光谱特性

本工作测量了室温下TbP₃O₁₄和EuP₅O₁₄晶体的吸收和发射光谱。根据吸收光谱和Judd-Ofelt理论计算了Tb³⁺和Eu³⁺的实验和理论的振子强度。用最小二乘法拟合实验与理论的振子强度得到唯象强度参量Ω_λ。然后计算了Tb³⁺的⁵D₃→⁷F₅,⁵D₄→⁷F₄和⁵D₄→⁷F₆以及Eu³⁺的⁵D₀→⁷F₂,⁵D₀→⁷F₄的跃迁几率和寿命。同时用时间分辨光谱测量了不同温度下相应的荧光辐射寿命。计算与实验结果基本相符。理论和实验的结果表明Tb³⁺的⁵D₃态的寿命主要取决于⁵D₃→⁵D₄和⁷F₆→⁷F₀两能级对之间的电偶极-电偶极交叉弛豫。 关键词：     

Study of absorption spectra of Er<Superscript>3+</Superscript> in KTaO<Subscript>3</Subscript> crystals

The first results of the study of optical absorption spectra of KTaO₃: Er³⁺ crystals are presented. In the 350–660-nm region, lines are observed deriving from intraconfigurational electronic transitions from the ⁴ I _15/2 ground state to levels of the ⁴ F _9/2, ⁴ S _3/2, ² H _11/2, ⁴ F _7/2, ⁴ F _5/2(⁴ F _3/2), ² G _9/2, and ⁴ G _11/2 excited states of the Er³⁺ ions. A comprehensive study of transitions to the ⁴ F _9/2, ⁴ S _3/2, ² H _11/2, and ⁴ F _7/2 levels at 77 K is carried out. The number of lines observed for the above transitions fits the theoretically possible number for ?-? electronic transitions in Er³⁺ ions in the cubic crystal field. In the case of a differently charged substituted ion, this situation occurs only under nonlocal impurity charge compensation. The energies of the excited state levels for the transitions under study are determined.     

Excited state absorption and stimulated emission of Nd3+ in crystals. Part I: Y3Al5O12, YAlO3, and Y2O3

4 F_3/2 excited state of the Nd³⁺ ion in Y₃Al₅O₁₂, YAlO₃, and Y₂O₃ were measured in a continuous wave pump- and probe experiment in a wide spectral range from 850 nm (780 nm for Y₃Al₅O₁₂) to 1500 nm. The cross sections were determined from a comparison with the emission spectra and the simultaneously measured ground state absorption bleaching. The strongest excited state absorption transitions were found in the 1220–1400 nm spectral region due to transitions to the ²G_9/2 and ⁴G_7/2 levels. The spectral positions of the measured transitions are in good agreement with the theoretically expected transitions calculated from the known Stark-level splittings. Received: 4 December 1997/Revised version: 8 May 1998     

Photoconductivity and photoluminescence in chemically deposited films of (Cd–Zn)S:CdCl2, Ho

Results of SEM, XRD, optical absorption/reflectance, photoconductivity (PC), and photoluminescence (PL) are presented for (Cd–Zn)S:CdCl₂, Ho films prepared by chemical deposition technique by direct dipping either at room temperature (RT) or at 60 °C in a water bath. SEM studies show the presence of non-uniform distribution of particles. XRD studies show lines of CdS, ZnS along with lines of CdCl₂ and Ho. PL is found to be pronounced in films of RT preparation and for those prepared at 60 °C, PC is higher. Optical absorption/reflectance studies show the presence of Ho corresponding to the transition ⁵I₈→⁵F₁/⁵G₆. Emissions corresponding to the transitions ⁵S₂/⁵ F₄→⁵ I₈, ⁵G₅→⁵I₇, and ³H₅→⁵I₈ are observed in PL emission spectra.     

Luminescence spectroscopy of rare earth-doped oxychloride lead borate glasses

Ln-doped oxychloride lead borate glasses were studied using luminescence spectroscopy. Rare earth ions were limited to trivalent Pr³⁺, Tm³⁺, Eu³⁺ and Er³⁺. Luminescence spectra were registered, which correspond to ³P₀-³H₄ and ¹D₂-³H₄ transitions of Pr³⁺, ¹G₄-³H₅ and ¹G₄-³F₄ transitions of Tm³⁺, ⁵D₀-⁷F_J (J=0, 1, 2, 3, 4) transitions of Eu³⁺ and ⁴S_3/2,²H_11/2-⁴I_15/2 and ⁴I_13/2-⁴I_15/2 transitions of Er³⁺. Luminescence decays from the excited states of Ln³⁺ ions were analyzed in detail. The experimental results indicate that relatively high phonon energy of the host gives important contribution to the excited state relaxation of rare earth ions.     

DIRECT UPCONVERSION SENSITIZATION LUMINESCENCE OF Ho(0.1)Yb(5):OXYFLUORIDE VITROCERAMICS

This paper studies the upconversion luminescence phenomenon of the Ho,Yb co-doped oxyfluoride vitroceramics. There is one group of strong upconversion luminescence lines positioned at 536.5nm, 18639cm^-1; 540.5nm, 18501cm^-1; 544.0nm, 18399cm^-1, which is easily identified as the transitions of ⁵S₂→⁵I₈. There are other splendid upconversion luminescence lines, which are ⁵S₂→⁵I₇,⁵F₅→⁵I₈,⁵G₆→⁵I₈, (⁵G³G)₅ →⁵I₈,(³F³H⁵G)₄→⁵I₇,⁵G₄→⁵I₈ and (⁵G³H)₅→⁵I₈. It is also found that an interesting kind of upconversion cooperative radiation fluorescence comes from a kind of coupling state of clusters consisting of two Yb³⁺ ions.     

Effect of composition on the spontaneous emission probabilities, stimulated emission cross-sections and local environment of Tm in TeO2-WO3 glass

Effect of composition on the structure, spontaneous and stimulated emission probabilities of various 1.0 mol% Tm₂O₃ doped (1−x)TeO₂+(x)WO₃ glasses were investigated using Raman spectroscopy, ultraviolet-visible-near-infrared (UV/VIS/NIR) absorption and luminescence measurements.Absorption measurements in the UV/VIS/NIR region were used to determine spontaneous emission probabilities for the 4f-4f transitions of Tm³⁺ ions. Six absorption bands corresponding to the absorption of the ¹G₄, ³F₂, ³F₃ and ³F₄, ³H₅ and ³H₄ levels from the ³H₆ ground level were observed. Integrated absorption cross-section of each band except that of ³H₅ level was found to vary with the glass composition. Luminescence spectra of the samples were measured upon 457.9 nm excitation. Three emission bands centered at 476 nm (¹G₄→³H₆ transition), 651 nm (¹G₄→³H₄ transition) and 800 nm (¹G₄→³H₅ transition) were observed. Spontaneous emission cross-sections together with the luminescence spectra measured upon 457.9 nm excitation were used to determine the stimulated emission cross-sections of these emissions.The effect of glass composition on the Judd-Ofelt parameters and therefore on the spontaneous and the stimulated emission cross-sections for the metastable levels of Tm³⁺ ions were discussed in detail. The effect of temperature on the stimulated emission cross-sections for the emissions observed upon 457.9 nm excitation was also discussed.     

Absorption Spectrum from Europium Ions in Europium Oxychloride,EuOCl

We have recorded part of the UV-visible region of the electronic spectrum of EuOCl at both 292 and 77 K by diffuse reflectance spectroscopy. Illumination of the sample and collection of the reflected light was accomplished through the use of an all-quartz fiberoptic probe. Several absorption maxima were observed which result from transitions from the ⁷F₀ ground state and ⁷F₁ excited state to the ⁵D₄ ⁵G_2,4,6 ⁵L₆, and ⁵D₃ excited states of the Eu³⁺ ion.     

Enhanced infrared to visible upconversion emission in Er3+ doped phosphate glass: Role of silver nanoparticles

Phosphate glasses with compositions (59.5–x)P₂O₅–MgO–xAgCl–0.5Er₂O₃ (0.0≤x≤1.5 mol%) containing fixed concentration of Er³⁺ ion with and without silver nanoparticles (NPs) are prepared using melt quenching technique. The amorphous nature of the glass is confirmed using the X-ray diffraction method. The homogeneous distribution of spherical Ag NPs (average size ～37 nm) in the glassy matrix is evidenced from the transmission electron microscopy (TEM) analyses. The UV–vis–NIR absorption spectra shows 10 bands corresponding to ⁴I_13/2, ⁴I_11/2, ⁴I_9/2, ⁴F_9/2, ⁴S_3/2, ²H_11/2, ⁴F_7/2, ⁴F_5/2, ²G_9/2, ⁴G_11/2 transitions in which the most intense bands are ²H_11/2 and ⁴G_11/2. The absorption spectrum of Er³⁺ ions free glass sample containing Ag NPs displays a prominent surface Plasmon resonance (SPR) band located at 528 nm. The infrared to visible frequency upconversion (UC) emission under 797 nm excitation shows two emission bands green (⁴S_3/2–⁴I_15/2) and red (⁴F_9/2–⁴I_15/2) centered at 540 nm and 634 nm, respectively, corresponding to Er³⁺ transitions. An enhancement in UC emission intensity of green band (⁴S_3/2–⁴I_15/2) is observed in the presence of silver NPs and the maximum enhancement occurred for 1.5 mol% AgCl. However, the enhancement of emission intensity of the red band (⁴F_9/2–⁴I_15/2) is smaller. The enhancement of UC emission is understood in terms of the intensified local field effect due to silver NPs.