In2O3:H03+,Yb3+纳米晶的制备与上转换发光

以乙二醇为溶剂,采用低温溶剂热法制备了H03+/Yb3+共掺杂In2O3纳米晶.利用X射线晶体衍射 (XRD)、透射电子显微镜(TEM)对粒子的结构和形貌进行表征,结果表明,合成的样品为纯的立方相In2O3,颗粒尺寸约为30nm.通过上转换发光(UCL)光谱研究了粒子的上转换发光性质,在980nm半导体激光激 发下...     

UPCONVERSION FLUORESCENCE DYNAMICS OF Tm3+ IONS IN LiYF4 CRYSTAL

According to Judd-Ofelt parameter calculation and energy transfer theory, the cross-relaxation process of the Tm³⁺ ions is investigated. A four-level system of coupled rate equations is established to study the fluorescence dynamics of Tm³⁺ in LiYF₄ crystal. Attentions are focused on the upconversion luminescence ¹G₄→³H₆ (483.0 nm) in Tm³⁺:LiYF₄. The relationship between the avalanche properties (critical pump rate, fluorescence intensity and buildup time) originated by resonant excited state absorption and the doped Tm³⁺ concentration is discussed, and some useful conclusions are drawn.     

Effect of WO3 on the spectroscopic properties in Er/Yb co-doped bismuth–borate glasses

The spectroscopic properties of Er³⁺/Yb³⁺ co-doped Bi₂O₃–B₂O₃–WO₃ (BBW) glasses were analyzed and discussed. The effect of WO₃ content on the absorption spectra, the Judd–Ofelt parameters Ω_t (t=2, 4, 6), emission spectra and the lifetime of the ⁴I_13/2 level and the quantum efficiency of Er³⁺:⁴I_13/2→⁴I_15/2 transition were also investigated. With the substitution of WO₃ for B₂O₃, the measured lifetime of the ⁴I_13/2 level and the quantum efficiency of Er³⁺:⁴I_13/2→⁴I_15/2 transition increase from 0.98 to 1.31 ms and from 38.2% to 49.2%, respectively. The effective width of emission band and the emission cross-section both decrease slightly. And the emission spectra is analyzed via the different curve (σ_e−σ_a) of BBW glasses, the influence of OH⁻is also discussed.     

Ho3+掺杂的Ba0.8Sr0.2TiO3厚膜的发光特性

用丝网印刷法在氧化铝衬底上制备了Ho3+掺杂的Ba0.8Sr0.2TiO3(BST)厚膜.XRD谱表明,随着Ho3+掺杂摩尔分数从0.5%增加到2.0%,BST厚膜的晶格尺寸先增大后减小.在514 nm的氩离子激光激发下,样品均出现了中心波长为549,650,753 nm的发光带,分别对应于Ho3+离子的(5F4,5S...     

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。     

Effect of Yb on red to blue conversion fluorescence of Tm in fluorozirconate glass

The mechanisms governing the upconversion fluorescence from the ¹G₄ level of Tm³⁺ ions have been investigated in fluorozirconate glass doped with Tm³⁺ only and codoped with Tm³⁺ and Yb³⁺ ions, under 649 (³H₄→¹G₄) and 684 nm (³H₆→³F₃) excitation wavelengths. The emission intensity depends on the excitation power quadratically in both samples, showing the two-photon absorption nature of the processes. An enhancement of the ¹G₄→³H₆ emission was observed in the codoped sample under 684 nm excitation. The upconversion emission in the single doped sample is mainly due to the E.S.A. process upon both excitations. The dominant mechanism was found to be the energy transfer processes between Tm³⁺ and Yb³⁺ ions in the codoped sample when the excitation was tuned at 684 nm. The upconverted emission intensity shows a different temperature dependence under the two excitations in the codoped sample. However, for the 649 nm excitation the dependence is the same in both samples. This confirms the dominance of the E.S.A. process under 649 nm excitation in both, singly and doubly doped samples.     

Er3+/Yb3+共掺NaYF4/LiYF4微米晶体的上转换荧光特性

采用水热法成功制备了Er³⁺/Yb³⁺共掺杂的NaYF₄和LiYF₄微米晶体. 通过X射线衍射仪和环境扫描电子显微镜对样品的晶体结构及形貌进行表征. 实验结果表明: 六方相NaYF₄微米晶体为棒状结构, 而四方相LiYF₄微米晶体则为八面体结构. 在近红外光980 nm激发下, NaYF₄:Yb³⁺/Er³⁺和LiYF₄:Yb³⁺/Er³⁺ 微米晶体均展现出很强上转换荧光发射. 且NaYF₄:Yb³⁺/Er³⁺微米晶体的荧光发射强度大约是LiYF₄:Yb³⁺/Er³⁺微米晶体的2倍, 但红绿比明显较低. 根据荧光光谱, 并借助激光光谱学及发光动力学深入探讨基质变化及表面修饰剂乙二胺四乙二酸(EDTA)对荧光特性的影响. 实验结果发现: 影响荧光强度的主要因素是基质环境的局域对称性, 而导致不同红绿比则是由于样品表面较多的EDTA分子所引起. Er³⁺掺杂的NaYF₄和LiYF₄ 微米晶体呈现出很强的绿光发射可被应用于全色显示, 荧光粉和微光电子器件中.     

共掺杂Ce~(3+)调控β-NaLuF_4:Yb~(3+)/Ho~(3+)纳米晶体的上转换荧光发射

在980 nm近红外光激发下,通过共掺杂Ce~(3+)离子调控六方相NaLuF_4:Yb~(3+)/Ho~(3+)纳米晶体的上转换荧光发射.实验结果表明,当掺杂Ce~(3+)离子浓度从0增加到12.0%时,Ho~(3+)离子的上转换荧光发射实现了由绿光向红光的转变,其红绿比提高了近24倍.根据Ho~(3+)离子的能级结构发现,Ho~(3+)离子的红光发射源自~5F_5能级到5I8能级的辐射跃迁,因此要增强红光发射,必须提高该能级粒子数布居.Ho~(3+)与Ce~(3+)离子之间相近的能级差促使它们之间产生了共振交叉弛豫,从而有效地提高了Ho~(3+)离子~5F_5能级的粒子数布居,增强了红光发射.同时对Ho~(3+)离子的上转换调控机理进行讨论,并借助不同的激发策略,进一步证实了Ho~(3+)与Ce~(3+)离子之间相互作用的发生.     

Investigation of 1.3 μm emission in Nd-doped bismuth-based oxide glasses

Nd₂O₃-doped 43Bi₂O₃–xB₂O₃–(57−x)SiO₂–1.0Nd₂O₃ (x=57, 47, 39, 28.5, 19.5, 10, 0 mol%) bismuth glasses were prepared by the conventional melt-quenching method, and the Nd³⁺: ⁴F_3/2→⁴I_13/2 fluorescence properties had been studied in an oxide system Bi₂O₃–B₂O₃–SiO₂. The Judd–Ofelt analysis for Nd³⁺ ions in bismuth boron silicate glasses was also performed on the basis of absorption spectrum, and the transition probabilities, excited-state lifetimes, the fluorescence branching ratios, quantum efficiency and the stimulated emission cross-sections of ⁴F_3/2→⁴I_13/2 transition were calculated and discussed. The stimulated emission cross-sections of 1.3 μm were quite large due to a large refractive index of the host. Although the effective bandwidths decreased with increasing SiO₂ content, quantum efficiencies and stimulated emission cross-sections enhanced largely with increasing SiO₂ content.     

Er3+/Tm3+共掺杂Ga5Ge20Sb10S65玻璃的发光特性及能量传递

采用高温熔融急冷法制备了系列Er3+/Tm3+共掺杂的Ga5Ge20Sb10S65玻璃,测试了样品的吸收光谱,以及分别在980 nm和800nm LD激发下样品的荧光光谱.运用Judd-Ofelt理论计算了Er3+离子在Ga5Ge20Sb1oS65玻璃中的强度参数Ω(i=2,4,6)、自发辐射跃迁几率A和辐射寿命τ等光...     

在BaYF5中Eu2+和Ho3+的荧光和能量传递

在脉冲N₂分子激光激发下,研究了在BaYF,中Eu²⁺和Ho³⁺的发射光谱,激发光谱和荧光寿命,以及Ho³⁺的超灵敏跃迁(⁵I₈→⁵G₆)。在Ho³⁺发射光谱中,⁵S₂→⁵I₈跃迁占主导地位。从Eu²⁺ 关键词：     

NaGdF4:Yb3+,H03+与GdF3:Yb3+,H03+纳米材料的合成、形貌控制与发光性质

采用水热法通过调控n(F-):n(Ln3+),pH值以及n(Citrate):n(Ln)等一系列反应条件,合成了六方相的NaGdF4:Yb3,ho3+与GdF3:yb3+,Ho3+纳米上转换材料,实现了形貌的可控合成.利用X射线粉末衍射(XRD),场扫描电子显微镜(SEM)以及发光光谱等手段对产物的物相结构、形貌和荧光...     

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。     

Electronic and vibronic spectra of Pr in LiYF4

The polarized absorption and fluorescence spectra of Pr³⁺ in single crystals of LiYF₄ having the scheelite structure have been investigated and assignments made on the basis of S₄ site symmetry. Strong vibronic coupling associated with the ³H₄→³H₅, ¹D₂ transitions in absorption and the ³P₀→³H_4,6 transitions in fluorescence was observed. Using selection rules for vibronic coupling and the known k = 0 phonons, these “extra” features of the spectrum can be accounted for in polarization and frequency.     

Visible quantum cutting via downconversion in LiGdF4 : Er, Tb upon Er 4f→4f5d excitation

Visible quantum cutting (the emission of two photons of visible light per absorbed photon) is reported for LiGdF₄ codoped with Er³⁺ and Tb³⁺. In this compound visible quantum cutting is achieved through downconversion, i.e., by making use of energy transfer between different lanthanide ions. Upon VUV excitation in the 4f¹⁰5d levels of Er³⁺, part of the excitation energy can be transferred to Gd³⁺ by cross-relaxation, yielding both Er³⁺ and Gd³⁺ in an excited state. This is followed by the emission of two visible photons: one from Er³⁺ due to the ⁴S_3/2→⁴I_15/2 transition, and, after energy transfer from Gd³⁺ to Tb³⁺, one from Tb³⁺ due to the ⁵D_J→⁷F_J transition. It is shown that this process occurs, next to other energy transfer processes from the Er³⁺ 4f¹⁰5d states to Gd³⁺ yielding only one visible photon.     

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.     

Green and red up-conversion emissions of Er–Yb Co-doped TiO2 nanocrystals prepared by sol–gel method

In this paper, green and red up-conversion emissions of Er³⁺–Yb³⁺ co-doped TiO₂ nanocrystals were reported. The phase structure, particle size and optical properties of Er³⁺–Yb³⁺ co-doped TiO₂ nanocrystals samples were characterized by using X-ray diffraction (XRD), transmission electron microscopy (TEM), UV–vis–NIR absorption spectra and photoluminescence (PL) spectra. Green and red up-conversion emissions in the range of 520–570 nm (²H_11/2, ⁴S_3/2→⁴I_15/2) and 640–690 nm (⁴F_9/2→⁴I_15/2) were observed for the Er³⁺–Yb³⁺ co-doped TiO₂ nanocrystals. The visible up-conversion mechanism and temperature dependence of up-conversion emission for Er³⁺ in TiO₂ nanocrystals were discussed in detail.     

Ho,Yb: Tb3Ga5O12纳米粉体制备及发光性能研究

以Tb₄O₇和Ga₂O₃(化学计量比为3: 5)、Ho₂O₃、Yb₂O₃为原料,其中Yb³⁺的掺杂浓度为8at.%,Ho³⁺的掺杂浓度分别为0.5at.%、1at.%、1.5at.%、2.0at.%,以碳酸氢铵为沉淀剂,在1 200 ℃下烧结10 h得到了Ho,Yb: Tb₃Ga₅O₁₂(Ho,Yb: TGG)纳米粉体。对样品进行了XRD物相分析、热重-差热分析、红外光谱分析以及扫描电镜分析、上转换发射光谱分析。实验结果表明,温度为1 200 ℃下样品平均晶粒尺寸为38.10 nm。在泵浦源为980 nm激发下,Ho³⁺掺杂浓度为1.5at.%,Yb³⁺掺杂浓度为8at.%时,在红、绿、蓝波段范围内出现了明显的上转换发光现象,并对其形成机理进行了讨论。分析认为,Ho³⁺由激发态⁵S₂,⁵F₄向基态⁵I₈跃迁,实现了绿光输出,而Ho³⁺由激发态⁵F₅和⁵F₃向基态⁵I₈跃迁,分别实现了红光和蓝光输出。     

Intensities and spectral features of the ~4I_(13/2)-~4I_(15/2) potential laser transition of Er~(3+) centers in CaF_2-CeF_3 disordered crystal

A CaF_2-CeF_3 disordered crystal containing 1.06% of Er~(3+) ions was grown by the temperature gradient technique.Optical absorption and emission spectra recorded at room temperature and at 10 K, luminescence decay curve recorded at room temperature, and extended x-ray-absorption fine structure spectra were analyzed with an intention to assess the laser potential related to the ~4I_(13/2)→~4I_(15/2) transition of Er~(3+). In addition, the thermal diffusivity of the crystal was measured at room temperature. The analysis of room-temperature spectra revealed that the ~4I_(13/2) emission is long-lived with a radiative lifetime value of 5.5 ms, peak emission cross section of 0.73 × 10~(-20) cm~2, and large spectral width pointing at the tunability of the emission wavelength in the region stretching from approximately 1480 nm to 1630 nm. The energies of the crystal field components for the ground and excited multiplets determined from low-temperature absorption and emission spectra made it possible to predict successfully the spectral position and shape of the room-temperature ~4I_(13/2)→~4I_(15/2) emission band. Based on the correlation of the optical spectra and dynamics of the luminescence decay, it was concluded that in contrast to Yb~(3+) ions in heavily doped CaF_2 erbium ions in the CaF_2-CeF_3 crystal reside in numerous sites with dissimilar relaxation rates.