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.     

The effect of zinc ions on the fluorescence spectra of (La, Zn)OF:Sm powder phosphors

This paper reports the fluorescence properties of a new series of (La, Zn) OF:Sm³⁺ powder phosphors. The measured fluorescence spectra were analyzed by computing the color coordinates and relative fluorescence intensity ratios (ED/MD). A bright yellowish-orange color was observed from these powder phosphors under a UV-source due to the confirmation of the transitions ⁴G_5/2→⁶H_5/2, ⁴G_5/2→⁶H_7/2, and ⁴G_5/2→⁶H_9/2. Scanning electron microscopic studies were performed to understand the average grain size of the synthesized powder phosphors.     

Optical properties and local structure of Eu-doped synthetic analogue of the microporous titanosilicate mineral sitinakite

The synthetic analogue of the microporous titanosilicate mineral sitinakite has been hydrothermally synthesized and used as a host in the preparation of a new photoluminescent material. The inclusion of Eu³⁺ in the pores of the sitinakite doubles the unit cell volume and changes the symmetry of the initial sodium phase. The Eu³⁺-doped material displays a stable room temperature emission ascribed to the Eu³⁺ intra-4f^{6 5}D₀→⁷F₀₋₄ transitions, with a maximum external quantum yield of 6%. The observation of two components for the non-degenerated ⁵D₀→⁷F₀ transition, the local field splitting of the ⁵D₀→⁷F₁₋₂ transitions, and the ⁵D₀ emission decay curves point out the presence of two optically active Eu³⁺ sites. Possible structural distribution of the detected Eu³⁺ cations is discussed.     

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.     

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。     

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.     

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.     

近紫外激发具有颜色可调的Er3+/Eu3+共掺BiOCl荧光粉

本文采用固相法在500℃合成了Er³⁺/Eu³⁺共掺BiOCl 荧光粉, 并通过XRD, SEM, 吸收, 激发和发射光谱研究了其结构、形貌和发光特性. XRD 和SEM结果表明在500℃下即可成功合成纯四方相片层结构的Er³⁺/Eu³⁺共掺BiOCl荧光粉. 吸收光谱表明掺杂Er³⁺/Eu³⁺离子使BiOCl形成杂质能级; 激发光谱显示该荧光粉具有来自于基质BiOCl价带(VB)到导带(CB)跃迁的优异宽带近紫外激发特性. 在380 nm近紫外光激发下, 同时获得了Er³⁺离子和Eu³⁺离子的特征发射峰, 其中发光中心位于410 nm (²H_9/2→⁴I_15/2), 525 nm (²H_11/2→⁴I_15/2), 554 nm (⁴S_3/2→⁴I_15/2), 673 nm (⁴F_9/2→⁴I_15/2)的发射峰来自于Er³⁺离子的跃迁, 而581 nm(⁵D₀→⁷F₀), 594 nm (⁵D₀→⁷F₁), 622 nm (⁵D₀→⁷F₂), 653 nm (⁵D₀→⁷F₃), 699 nm (⁵D₀→⁷F₄)的发射峰则来自于Eu³⁺离子的跃迁. 值得注意的是, 与传统Er³⁺/Eu³⁺掺杂的材料不同, 该荧光粉还具有独特高效的紫光(Er³⁺)和长波红光(Eu³⁺)发射特性, 分析表明这与BiOCl的结构有关; 并且通过改变掺杂浓度, 实现了发光颜色由黄绿光→黄光→橙红光的调节. 研究结果表明Er³⁺/Eu³⁺共掺BiOCl荧光粉有望成为一种潜在的近紫外激发白光LED荧光粉.     

Radiative and non radiative spectroscopic properties of Er ion in tellurite glass

We have investigated in detail the mechanism of infrared emission and upconversion emission of Er³⁺ in tellurite glass as a function of the dopant concentration. Both the infrared and upconversion emissions are competing processes and the efficiency of infrared emission at 1534 nm is 100% at the lowest Er content (0.5 mol%) and reduces to 50% at higher dopant concentration (>2 mol%). The green upconversion emission at 548 nm is mainly due to the excited state absorption (ESA) from ⁴I_11/2, which populate the ⁴F_7/2 level. In addition to this, the possible energy transfer (ET) through Er³⁺(⁴I_11/2) + Er³⁺(⁴I_11/2) → Er³⁺(⁴F_7/2) + Er³⁺(⁴I_15/2) can also results in the green emission as is noticed from the concentration dependent efficiency change of the green emission. The fluorescence quenching of green emission with Er concentration may be related with the cross relaxation (CR) process ²H_11/2 + ⁴I_15/2 → ⁴I_9/2 + ⁴I_13/2. The red emission is due to the combined effect of the ESA from level ⁴I_13/2 to ⁴F_9/2, the energy transfer process described by Er³⁺(⁴I_13/2) + Er³⁺(⁴I_11/2) → Er³⁺(⁴F_9/2) + Er³⁺(⁴I_15/2) and the cross relaxation process.     

上转换纳米粒子CaF2:Er3+,Yb3+的合成及其温敏特性

采用水热合成法制备了CaF₂：Yb³⁺,Er³⁺上转换纳米粒子。在980 nm激发下,研究了来源于Er³⁺的²H_11/2/⁴S_3/2→⁴I_15/2跃迁的绿光发射和来源于⁴F_9/2→⁴I_15/2跃迁的红光发射。由于Er³⁺具有一对热耦合能级（²H_11/2/⁴S_3/2）,所合成的样品在293~573 K温度范围内有良好的温敏特性。利用荧光强度比（FIR）技术,测得样品在483 K时具有最大灵敏度0.002 85 K^-1。     

近紫外光激发黄色荧光粉Ba3Y4O9：Dy3+的制备及发光特性

通过高温固相法合成了一系列Ba₃Y_4-xO₉：xDy³⁺荧光粉材料。利用X射线粉末衍射、荧光光谱和荧光寿命对样品进行了表征。实验表明,样品的激发光谱由一系列线状峰组成,峰值分别位于328,355,368,386,427,456,471 nm。在355 nm激发下,荧光粉在490 nm（⁴F_9/2→⁶H_15/2）和580 nm（⁴F_9/2→⁶H_13/2）处有很强的发射,发射光谱的色坐标位于黄光区域。研究了不同Dy³⁺掺杂浓度对样品发光性质的影响,发现样品的发光随着Dy³⁺浓度的增大而增强,但光谱形状基本保持不变,表明Dy³⁺占据了基质中低对称性的Y³⁺格位。当Dy³⁺摩尔分数x=0.08时出现发光强度猝灭现象,浓度猝灭机理为电偶极-电偶极相互作用。样品的发光寿命随着Dy³⁺浓度的增大逐渐减小,进一步证明了Dy³⁺离子之间存在着能量传递现象。Ba₃Y₄O₉：Dy³⁺荧光粉的发光位于黄光区域,有较好的热稳定性,是潜在的白光LED用荧光粉材料。     

Tm-to-Ho resonant and nonresonant energy transfer in LiYF4

Absorption and luminescence measurements of Tm³⁺ and Ho³⁺ ions in LiYF₄:Tm³⁺, LiYF₄:Ho³⁺ and LiYF₄:Tm³⁺, Ho³⁺ crystals were carried out. The data collected were used to determine the Ho³⁺ absorption coefficient integral for ⁵I₈→⁵I₇ transition, and the overlap integral between the normalized Tm³⁺ luminescence spectrum due to the ³F₄→³H₆ transition and the Ho³⁺ absorption band due to ⁵I₈→⁵I₇ transition. The relevant critical transfer distance (R_o), that gives a measure of the Tm³⁺–Ho³⁺ coupling, was determined considering the Förster type interaction between the ions. It was found to be 22.5 Å and 28.8 Å at 300 and 78 K, respectively.     

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。     

Spectroscopy, laser operation at 1.3 μm and self-frequency doubling in GdAl3(BO3)4: Nd

We report for the first time the spectroscopy and the laser operation of GdAl₃(BO₃)₄: Nd³⁺ (NGAB) near 1338 nm corresponding to the ⁴F_3/2→⁴I_13/2 channel. Their features have been found favorable for self-frequency doubling in order to generate a red radiation at 669 nm and more generally for self-frequency conversions. The emission cross-section in σ-polarization was estimated to be 5.5×10⁻²⁰ cm². We demonstrated self-frequency doubling despite of non-optimal experimental conditions.     

Splitting of the near infrared absorption bands of Sm in POCl3:SnCl4, POCl3:ZrCl4 and POCl3:TiCl4

The near infrared absorption spectra of Sm³⁺ in POCl₃:SnCl₄, POCl₃:ZrCl₄ and POCl₃:TiCl₄ consist of a series of bands, attributed to the ⁶H_5/2 → ⁶F_J transitions. Each one of these absorption bands is split into three components. The extent of splitting differs slightly from state to state. For each component of the ⁶F-multiplet the splitting decreases gradually from POCl₃:SnCl₄ to POCl₃:ZrCl₄ and POCl₃:TiCl₄. Energy differences between adjacent components of the near infrared absorption bands vary from a maximum of 166 cm⁻¹ to a minimum of 123 cm⁻¹. The band half-widths of the corresponding components vary from 86 to 120 cm⁻¹. At lower temperatures the intensity of the high energy component increases whereas the intensity of the entire absorption band envelope, associated with each component of the ⁶F-multiplet, remains almost constant. The splitting observed is attributed to the Stark splitting of the ⁶H_5/2-state of Sm³⁺ into three components, in conjunction with appropriate Stark splitting of the states of the ⁶F-multiplet.     

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.     

ErP5O14非晶玻璃的红外量子剪裁

研究了Er_1.0P₅O₁₄铒非晶玻璃的红外量子剪裁现象. 从吸收谱和激发光谱的计算比较中肯定了Er_1.0P₅O₁₄非晶 玻璃的1537.0 nm红外荧光为多光子量子剪裁荧光. 从Er_1.0P₅O₁₄非晶玻璃的可见和红外荧光发射光谱中发现激发²H_11/2, ⁴G_11/2和⁴G_9/2能级所导致的⁴I_13/2→⁴I_15/2量子剪裁红外荧光很强;基于自发辐射速率、无辐射弛豫速率和能量传递速率等参数的计算,对其量子剪裁机理进行了分析.发现起源于基态的强下转换能量传递{²H_11/2→⁴I_9/2,⁴I_15/2→⁴I_13/2},{⁴G_11/2→⁴I_13/2, ⁴I_15/2→²H_11/2},{⁴G_9/2→⁴F_7/2,⁴I_15/2→⁴I_13/2}和{⁴G_9/2→⁴I_13/2, ⁴I_15/2→²H_11/2}是导致Er_1.0P₅O₁₄非晶玻璃具有强的三光子和四光子量子剪裁红外荧光的原因.研究结果对改善太阳能电池效率有一定意义.     

Structural and electrical properties of crystalline (1−x)Ta2O5−xTiO2 thin films fabricated by metalorganic decomposition

Polycrystalline (1−x)Ta₂O₅−xTiO₂ thin films were formed on Si by metalorganic decomposition (MOD) and annealed at various temperatures. As-deposited films were in the amorphous state and were completely transformed to crystalline after annealing above 600 °C. During crystallization, a thin interfacial SiO₂ layer was formed at the (1−x)Ta₂O₅−xTiO₂/Si interface. Thin films with 0.92Ta₂O₅–0.08TiO₂ composition exhibited superior insulating properties. The measured dielectric constant and dissipation factor at 1 MHz were 9 and 0.015, respectively, for films annealed at 900 °C. The interface trap density was 2.5×10¹¹ cm⁻² eV⁻¹, and flatband voltage was −0.38 V. A charge storage density of 22.8 fC/μm² was obtained at an applied electric field of 3 MV/cm. The leakage current density was lower than 4×10⁻⁹ A/cm² up to an applied electric field of 6 MV/cm.     

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.     

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。