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.     

BaMgF_4:Er~(3+),Yb~(3+)上转换纳米晶的合成及其发光性能研究

采用反向共沉淀法制备了形貌呈棒状的BaMgF4:Er3+,Yb3+上转换纳米晶.样品在980 nm半导体激光器激发下发射绿色和红色上转换荧光,其发射的绿、红发射带归因于Er3+离子的2H11/2—4I15/2,4S3/2—4I15/2和4F9/2—4I15/2跃迁.当Er3+的掺杂浓度为3%,Yb3+离子掺杂浓度为10%时,荧光粉的上转换发光强度最强;随着Yb3+离子浓度的增加样品的红光发射增强,绿光发射减弱.通过上转换发光强度与抽运电流关系曲线的拟合,得出BaMgF4:Er3+,Yb3+上转换材料的绿光与红光的上转换过程均为双光子吸收过程.     

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.     

Ln2Sn2O7：Er3+纳米晶的制备及发光性能研究

采用溶胶-凝胶法合成Ln₂Sn₂O₇:Er³⁺(Ln=La,Gd,Y)纳米晶。通过X射线衍射和场发射扫描电子显微镜测试了样品的晶体结构和形貌,同时对样品的上转换发光性能进行了测试。结果表明:在980 nm连续激发光的激发下,样品主要表现为绿光发射。发射中心在528,549 nm的绿光和672 nm处的红光发射分别对应Er³⁺离子的⁴S_3/2→⁴I_15/2、²H_11/2→⁴I_15/2和 ⁴F_9/2→⁴I_15/2跃迁。以La₂Sn₂O₇:Er³⁺纳米晶为例,Er³⁺离子的摩尔分数为7%、退火温度为1 150℃是其制备的最佳条件,此时其各个发射峰的强度最高。对La₂Sn₂O₇:Er³⁺的发光强度与激发功率关系的研究表明,其绿光和红光发射均为双光子过程。激发光吸收和能量转移是La₂Sn₂O₇:Er³⁺纳米晶上转换发光的主要机制。     

Er3+单掺和Er3+/Yb3+共掺碲酸盐玻璃的光谱性质及能量传递

采用高温熔融法制备了新型Er3+单掺和Er3 +/Yb3+共掺的TeO2-Bi2O3-SiO2-B2O3玻璃,测试并分析了样品的吸收光谱、发射光谱以及Er3 +/Yb3共掺杂样品的发射光谱和荧光寿命.计算出了玻璃的J-O强度系数Ωt(t=2,4,6);系统讨论了Er3+/Yb3+共掺杂样品在808 nm激光激发下,Yb...     

Er3+,Yb3+共掺杂SrTiO3超细粉末的可见上转换发光

钛酸锶(SrTiO₃)具有高介电常数、良好的绝缘性质、优良的物理化学稳定性和在可见光范围内的优异的透明度等优点,是一种重要的无机功能材料。近年来,Al³⁺,Ga³⁺等离子共掺杂的SrTiO₃:Pr³⁺做为一种优异的红色场发射显示(FED)荧光粉引起了人们的兴趣。另外,SrTiO₃具有相对较小的声子频率,因而它可以作为一种有利于上转换发光的基质材料。以NaCl为助熔剂制备了Er³⁺,Yb³⁺共掺杂的SrTiO₃超细粉末。在980nm激发下,样品发出很强的来自于Er³⁺离子的²H_11/2→⁴I_15/2,⁴S_3/2→⁴I_15/2(绿光)和⁴F_9/2→⁴I_15/2(红光)跃迁的上转换发光。Yb³⁺离子的共掺杂对Er³⁺离子的上转换发光起明显的增强作用。研究了上转换发光强度与稀土离子浓度以及激发光强度之间的依赖关系,表明在Er³⁺单掺杂和Er³⁺,Yb³⁺共掺杂的样品中,绿光和红光都是被双光子激发过程激发的。还对上转换发光的机理做了初步分析。     

试验优化设计Er3+/Yb3+共掺BaGd2ZnO5荧光粉及其上转换发光性质

为得到绿光和红光最大发光强度的Er³⁺/Yb³⁺共掺BaGd₂ZnO₅上转换材料荧光粉, 首先采用试验优化设计中的均匀设计初步寻找Er³⁺/Yb³⁺合理的掺杂浓度; 其次通过二次通用旋转组合设计进一步优化实验, 建立起Er³⁺/Yb³⁺掺杂浓度与绿光和红光发光强度的回归方程; 最后通过遗传算法计算出方程的最优解, 即绿光和红光最大发光强度时对应的Er³⁺/Yb³⁺掺杂浓度. 利用传统的高温固相法分别制备出最优样品. 采用X 射线衍射对得到荧光粉的晶体结构进行了分析, 证明了所有产物均为纯相BaGd₂ZnO₅. 采用980 nm抽运激光作为激发源, 在同样的条件下测量了样品的上转换荧光发射光谱, 从中可见样品有较强的红光发射和绿光发射, 发光中心位于662, 551和527 nm, 分别对应于⁴F_9/2→⁴I_15/2, ⁴S_3/2→⁴I_15/2 及²H_11/2→⁴I_15/2能级跃迁. 研究了绿光和红光最优样品的上转换发光强度与激光器工作电流之间的关系, 通过分析发现红色和绿色上转换发光均为双光子过程. 由归一化的绿色上转换发射光谱可以看出, 激光器工作电流导致的样品温度变化可以忽略不计. 由于能级²H_11/2和⁴S_3/2之间存在热平衡, 并满足玻尔兹曼分布, 由此探讨了绿光最优样品上转换发射光谱中的绿色发射与温度的关系, 计算出²H_11/2和⁴S_3/2之间的能级差为ΔE=926.11 cm^-1. 研究了绿光最优样品的温度效应, 随着温度的升高, 发射强度逐渐变小, 出现了温度猝灭现象. 并计算了样品的激活能, 分别为总体激活能ΔE_总=0.45 eV, 绿光激活能ΔE_绿=0.45 eV, 红光激活能ΔE_红=0.46 eV.     

Ba5SiO4Cl6: Yb3+, Er3+, Li+荧光粉的制备及上转换发光性质研究

本文采用高温固相反应法制备了Ba₅SiO₄Cl₆: Yb³⁺, Er³⁺, Li⁺ 荧光粉, 并对其上转换发光性质及其发光机理进行了研究. 在980 nm 激光的激发下, Ba₅SiO₄Cl₆: Yb³⁺, Er³⁺ 荧光粉呈现较强的红色(662 nm) 和较弱的绿色(550 nm) 的上转换发光, 红色和绿色的上转换发光分别对应于Er³⁺ 离子的⁴S_3/2/²H_11/2→⁴I_15/2 和⁴F_9/2→⁴I_15/2 跃迁, 且随着掺杂的Er³⁺ 和Yb³⁺ 离子浓度增加, 样品的上转换发光强度增加, 这是因为Yb³⁺ 离子和Er³⁺ 离子之间的能量传递效率增加引起的. 在0.5—0.8 W 功率激发下,样品属于双光子发射, 而在0.9—1.2 W 功率激发下样品具有新的上转换发光机理——光子雪崩效应. 探讨了Li⁺ 掺杂对Ba₅SiO₄Cl₆: Yb³⁺, Er³⁺ 样品的上转换发光性质的影响, Li⁺ 离子的掺杂引起Ba₅SiO₄Cl₆:Yb³⁺, Er³⁺ 上转换发光强度增加, 这是由于Li⁺ 离子的掺入降低了晶体场的对称性引起的.     

Er~(3+)/Yb~(3+)共掺杂氧氟硼硅酸盐微晶玻璃绿色上转换发光的温度特性

采用高温熔融法和热处理工艺制备得到透明的Er3+/Yb3+共掺杂氧氟微晶玻璃。XRD结果证实析出的纳米晶相为Ba YF5。在980 nm激发下,观察到强的绿光发射,源于Er3+的2H11/2→4I15/2和4S3/2→4I15/2跃迁的上转换发光。根据荧光强度比(FIR)的方法研究了微晶玻璃上转换荧光的温度传感特性,其最大灵敏度在523 K时为0.003 4 K-1,表明Er3+/Yb3+共掺氧氟硼硅酸盐微晶玻璃上转换发光在高精度温度传感器方面具有一定的应用前景。     

Er3+单掺、Er3+/Yb3+共掺杂Ca12Al14O32F2的 制备及上转换发光性质

利用高温固相法成功制备了Er~(3+)单掺、Er~(3+)/Yb~(3+)共掺杂Ca_(12)Al_(14)O_(32)F_2上转换发光样品。在980 nm激光激发下,Er~(3+)单掺和Er~(3+)/Yb~(3+)共掺杂样品均呈现出较强的绿光(528,549 nm)和较弱的红光(655 nm)发射,分别归因于Er~(3+)离子的~2H_(11/2),~4S_(3/2)→~4I_(15/2)和~4F_(9/2)→~4I_(15/2)能级跃迁。随着Er离子浓度的增加,单掺杂样品上转换发光强度先增大后减小,最佳掺杂浓度为0.8%。共掺杂Yb~(3+)后,Er~(3+)的发光强度明显增大。还原气氛下合成的样品上转换发光强度增大约两倍,可能和笼中阴离子基团变化有关。发光强度和激发光功率的关系表明所得上转换发射为双光子吸收过程,借助Er~(3+)-Yb~(3+)体系能级结构详细讨论了上转换发射的跃迁机制。     

水溶性β-NaY(Gd)F4:Yb3+/Er3+纳米棒的水热合成及生物偶联

以聚乙烯亚胺(PEI)为表面活性剂,采用水热合成法,制得了表面氨基修饰的水溶性β-NaY(Gd)F₄:Yb³⁺/Er³⁺纳米棒,并对β-NaY(Gd)F₄:Yb³⁺/Er³⁺上转换纳米棒的制备方法、条件等进行了考察.结果表明,当Gd³⁺的引入摩尔分数为40%时,200 ℃下反应8 h即可获得纯β-NaY(Gd)F₄:Yb³⁺/Er³⁺纳米棒.利用X射线粉末衍射仪(XRD)、扫描电子显微镜 (SEM)、透射电子显微镜(TEM)、荧光光谱(PL)对样品的结构、形貌及光谱特性进行了表征.结构和形貌分析结果表明,制得的样品为单相β-NaY(Gd)F₄:Yb³⁺/Er³⁺纳米棒,纳米棒的截面粒径约为40 nm,平均长度约为210 nm.在980 nm波长激发下,样品的上转换发光光谱中出现了4个发射中心位于407,529,546,660 nm的发射带,分别对应于Er³⁺离子的²H_9/2→⁴I_15/2、²H_11/2→⁴I_15/2、⁴S_3/2→⁴I_15/2和⁴F_9/2→⁴I_15/2跃迁.采用戊二醛法,使β-NaY(Gd)F₄:Yb³⁺/Er³⁺上转换纳米棒表面的氨基与牛血清蛋白(BSA)分子中的氨基成功偶连在一起.利用紫外光谱分析(UV)和考马斯亮蓝法,对二者的偶联进行了证明.     

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。     

氨基磷酸辅助的水热合成NaYF4:Yb3+,Er3+纳米晶及其上转换发光

以氨基磷酸为螯合剂,通过共沉淀与水热法相结合,成功地制备出NaYF4:Yb3+,Er3+纳米晶.研究结果表明:水热前后NaYF4:Yb3+,Er3+纳米晶均为立方相结构,其颗粒大小约为80nm.在980 nm近红外光激发下,实现了样品的上转换发光.样品的上转换绿红光发射带归因于Er3+的2H11/2,4S3/2→4 I...     

Er,Yb：(LaLu)2O3透明陶瓷制备及上转换发光性能

采用柠檬酸燃烧法制备Er,Yb：（LaLu）₂O₃陶瓷粉体,用X射线衍射对其进行了物相鉴定,研究表明1 000℃时已经得到纯相的（LaLu）₂O₃。采用冷等静压-真空烧结法制备了Er,Yb：（LaLu）₂O₃和Er：（LaLu）₂O₃陶瓷,对陶瓷的结构和光谱性能进行了详细的研究,研究发现掺杂5% Yb³⁺和10% La³⁺样品的上转换发光强度与未掺Yb³⁺、La³⁺样品相比明显增大,根据上转换光谱显示较强发射峰位于564 nm和661 nm处,对应Er³⁺的⁴S_3/2（²H_11/2）→⁴I_15/2能级跃迁和⁴F_9/2→⁴I_15/2能级跃迁,并讨论了Er³⁺-Yb³⁺的能量传递过程及其上转换发光机制。     

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.     

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...     

Yb3+/Er3+共掺BaGd2O4荧光粉的制备及其上转换发光性质

采用溶胶-凝胶法制备了Yb³⁺/Er³⁺共掺杂BaGd₂O₄上转换荧光粉。研究了退火温度对BaGd₂O₄晶体结构的影响,以及Yb³⁺/Er³⁺共掺杂的BaGd₂O₄荧光粉在971 nm LED激发下,激发密度与上转换发射光功率及效率的关系。研究结果表明,尽管BaGd₂O₄与目前报道效率最高的Yb³⁺/Er³⁺共掺杂BaGd₂ZnO₅基质的最高声子能量相同,但光-光转换效率却相差82倍,极值量子效率相差7.8倍。结论认为,在声子能量不是很高的情况下,材料结构是影响上转换效率的主要因素。     

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.     

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.     

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...