不同波长响应的Y2O2S:Er3+,Yb3+上转换发光材料的光谱特性

以Y2O2S为基质材料、Er2O3为激活剂、Yb2O3为敏化剂,采用固相反应法制备Y2O2S:Er3+,Yb3+上转换发光材料.采用X射线粉末衍射分析和荧光光谱分析表征样品的结构和发光性能,并分析上转换发光机理.结果表明:在980 nm和1 550 nm红外光激发下,样品发出源于Er3+的2H11/2→4I15/2、4...     

Er3+:Yb3+:Y3Al5O12单晶中Er3+离子光谱参数的计算

采用提拉法生长出光学质量的Er3 :Yb3 :Y3Al5O12(YAG)单晶,测定了晶体的吸收光谱和上转换荧光光谱,根据Judd-Ofelt理论,计算出Er3 在YAG晶体中的强度参数Ω2=1.074 1×10-20cm2,Ω4=1.295 3×1020cm2,Ω6=0.923 8×1020cm2.由此得到部分波段跃迁的荧光分支比、辐射寿命和积分发射截面积.提出将679 nm波段的4F9/2→4I15/2跃迁作为激光输出进一步研究的新通道.     

柠檬酸凝胶法制备Er,Tm∶Yb3Al5O12纳米粉体及发光性能

以柠檬酸为燃烧剂,采用柠檬酸凝胶法制备了Er,Tm∶Yb3Al5O12(Er,Tm:YbAG)纳米粉体,其最佳的制备工艺条件:Er3+和Tm3+掺杂的摩尔分数分别为2%和1%,柠檬酸与金属硝酸盐原子总数的摩尔比为1.7∶1,煅烧温度和时间分别为950℃和2h。制备的粉体颗粒为规则球形,粒径均匀、分散性好,平均粒径约为45nm。研究了样品的发光性能,结果表明:2%Er,1%Tm∶YbAG样品的发光性能最好,在1 587、1 658和1 711nm处有较强发射峰,分别对应Er3+的4 I13/2→4 I15/2跃迁和Tm3+的3 F4→3 H6跃迁。样品的上转换光谱表明,上转换荧光峰包括了蓝光、绿光和红光。     

Directionally solidified Al2O3-ME3Al5O12 (ME: Y,Er and Yb) eutectic coatings for thermophotovoltaic systems

Selective emitters for thermophotovoltaic systems consisting of directionally solidified Al₂O₃-ME₃Al₅O₁₂ (ME: Y, Er and Yb) eutectic coatings on Al₂O₃ substrates were produced and characterizated. Coatings were deposited by dip-coating on cylindrical substrates. After sintering, a continuous-wave CO₂ laser was used to produce the surface resolidification. The optimization of the processing parameters yielded dense eutectic coatings with good adhesion to the substrate and with 90–200 µm in thickness. All coatings were free of voids and showed a eutectic microstructure consisting of a three dimensional interpenetrated network of Al₂O₃ and ME₃Al₅O₁₂. The mechanical properties of the coatings (hardness and fracture toughness) were evaluated by indentation techniques. Thermal emission was studied by heating the rods with a CO₂ laser at temperatures between 1000 and 1400 °C. Selective emission was observed in Er³⁺ and Yb³⁺ based coatings and attributed to the electronic transitions of the rare earth ions. Er³⁺-coatings showed the best emission properties as selective emitters for thermophotovoltaic converters.     

Kinetic effects of substitution Er3+ for Y3+ in (Y1-xErx)3Al5O12 garnet

The crystallization kinetics of erbium-substituted yttrium aluminum garnet (Er:YAG) from the amorphous phase was studied depending on the degree of substitution of yttrium by erbium: (Y_1-xEr_x)₃Al₅O₁₂, x = 0 – 0.9. The corresponding series of nanopowders were synthesized using the sol-gel method with binary sols as the starting materials. Crystallized single-phase Er:YAG powders were obtained at temperatures as low as 1370 K through the formation of intermediate phases. The crystallization kinetics of the Er:YAG precursors was analyzed using non-isothermal differential scanning calorimetry and X-ray diffraction analysis. The proposed unified crystallization model, based on which the kinetic parameters of the crystallization process of the Er:YAG from the amorphous phase were determined, depending on the content of erbium oxide. Time-temperature-transformation curves were developed from the obtained data to determine the optimal modes in the heat treatment and sintering of optical ceramics. Er:YAG transparent ceramics were obtained by vacuum sintering of sol-gel powders.     

A broadband-sensitive upconverter: Garnet-type Ca3Ga2Ge3O12 codoped with Er3+, Y3+, Li+, Ni2+, and Nb5+

We have developed a new broadband-sensitive photon upconversion (UC) material that can be used for transparent ceramic plates mounted on the rear faces of crystalline silicon solar cells. We selected the host material of a cubic crystal structure codoped with Er³⁺ and Ni²⁺ so that the Ni²⁺ dopants were fully activated to sensitize the Er³⁺ emitters. In garnet-type Ca₃Ga₂Ge₃O₁₂ with additional codopants of Nb⁵⁺ and Li⁺ for charge compensation, all the Ni²⁺ dopants occupied the six-coordinated Ga³⁺ sites, leading to highly efficient energy transfer from the Ni²⁺ to the Er³⁺. Formation of four-coordinated Ni²⁺ that quenches the UC emission of the Er³⁺ was prevented, because Ni²⁺ cannot substitute the four-coordinated Ge⁴⁺ much smaller than Ni²⁺. Consequently, energy dissipation from the Er³⁺ to the Ni²⁺ was well reduced compared with the previously developed Gd₃Ga₅O₁₂:Er,Ni,Nb in which the Ni²⁺ dopants partially occupied the four-coordinated Ga³⁺ sites. Additional introduction of Y³⁺ and Li⁺ enhanced optical transitions and improved the UC performance, owing to more enhanced lattice distortion, along with eliminating different phases. The optimal composition (Ca_0.6Er_0.1Y_0.1Li_0.2)₃(Ga_0.98Ni_0.01Nb_0.01)₂Ge₃O₁₂ exhibited a broadband sensitivity ranging from 1.1 μm (the absorption edge of silicon) to 1.6 μm for the UC emission at 0.98 μm.     

氯化物助熔剂对Y3Al5O12:Ce3+荧光粉性能的影响

选用卤化物LiCl、NaCl、KCl和SrCl2等作为助熔剂,合成了一系列YAG∶Ce粉体,并研究了助熔剂对YAG∶Ce荧光粉晶相、形貌和发光性能的影响.结果表明适量助熔剂有利于YAG∶Ce荧光粉的晶化,合成的荧光粉具有石榴石的结构,规则的形貌和窄的粒度分布.添加适量助熔剂可以提高YAG∶Ce荧光粉的发光强度.最适宜的添加量分别是:LiCl 10%,NaCl 7%,KCl 7%,SrCl,4%.     

Color-tunable up-conversion emission in Y2O3:Yb3+, Er3+ nanoparticles prepared by polymer complex solution method

Abstract

Powders of Y₂O₃ co-doped with Yb³⁺ and Er³⁺ composed of well-crystallized nanoparticles (30 to 50 nm in diameter) with no adsorbed ligand species on their surface are prepared by polymer complex solution method. These powders exhibit up-conversion emission upon 978-nm excitation with a color that can be tuned from green to red by changing the Yb³⁺/Er³⁺ concentration ratio. The mechanism underlying up-conversion color changes is presented along with material structural and optical properties.

PACS

42.70.-a, 78.55.Hx, 78.60.-b     

铒镱共掺钆镓石榴石激光晶体生长及荧光光谱分析

采用提拉法生长了掺10%(摩尔分数,下同)Yb3+、掺Er3+分别为3%,5%和10%的Er3+:Yb3+:Gd3Ga5O12(Er:Yb:GGG)晶体。分析了Er:Yb:GGG晶体的结构和荧光光谱。结果表明:所生长的晶体属于立方晶系,Ia3d空间群。在980nm激光激发下,晶体样品在1000～1600nm范围内存在3个较强的发射带,相应的发射峰分别位于1030,1471nm和1534nm附近。由于Yb3+对Er3+的敏化作用,随着Er3+掺量的递增,1030nm处的发射峰强度逐渐减弱,1471nm和1534nm处的发射峰强度逐渐增强。计算了各个发射峰的受激发射截面积,铒和镱离子掺量为10%的晶体(10%Er:10%Yb:GGG)的受激发射截面高达2.0073×10–18cm2,可以产生较强的1534nm人眼安全波段的激光。     

Yb3Al5O12激光晶体的生长

采用中频感应提拉法成功生长出Yb3Al5O12(YbAG)激光晶体.通过X射线粉末衍射分析,得出了YbAG晶体的晶胞参数a=1.193799nm,β=90°,V=1.70135nm3;密度为6.62g/cm3.测量了室温下YbAG晶体的吸收光谱和发射光谱特性.研究表明在938nm和968nm处存在Yb3+离子的2个吸收带,能与InGaAs激光二极管(LD)有效耦合,适合激光二极管泵浦;其荧光主峰位于1036nm附近,YbAG晶体的荧光寿命为270μs.     

Deep red upconversion photoluminescence in Er3+-doped Yb3Ga5O12 nanocrystalline garnet

The nanocrystalline single-phase Er³⁺-doped Yb₃Ga₅O₁₂ garnets have been prepared by the sol-gel combustion technique with a crystallite size of ≈30 nm. The presence of Yb³⁺ in garnet hosts allows their efficient excitation at the ≈977 nm wavelength. The Er³⁺ doping of Yb₃Ga₅O₁₂ garnet host results in deep red Er³⁺: ⁴F_9/2 → ⁴I_15/2 upconversion photoluminescence (UCPL) emission. The dominance of the red UCPL emission over the green Er³⁺: ⁴F_7/2/²H_11/2/⁴S_3/2 → ⁴I_15/2 component was investigated using the measurement of the steady-state and time-dependent Er³⁺ and Yb³⁺ emission spectra in combination with the power-dependent UCPL emission intensity. The proposed upconversion mechanism is discussed in terms of the Er³⁺ → Yb³⁺ energy back transfer process as well as Yb³⁺(Er³⁺) → Er³⁺ energy transfer and Er³⁺ ↔ Er³⁺ cross-relaxation processes. The studied Er³⁺-doped Yb₃Ga₅O₁₂ garnet may be utilized as a red upconversion emitting phosphor.     

Thermal enhancement of up-conversion luminescence in Lu2W2.5Mo0.5O12: Er3+, Yb3+ phosphors

Lu₂W_2.5Mo_0.5O₁₂: Er³⁺/Yb³⁺ phosphors were synthesized through high temperature solid state method. Under 980 nm laser excitation, the Lu₂W_2.5Mo_0.5O₁₂: Er³⁺/Yb³⁺ compounds show thermal enhancement of up-conversion luminescence (UCL), which is attributed to the lattice contraction and distortion from negative thermal expansion (NTE) of Lu₂W_2.5Mo_0.5O₁₂ host enhancing the energy transfer of Yb³⁺ to Er³⁺, eliminating the energy transfer of Er³⁺ to Er³⁺ through Er³⁺ single-doped Lu₂W_2.5Mo_0.5O₁₂ phosphors without thermal enhancement of UCL. The green luminescence intensities at 693 K of the Lu_1.98-xW_2.5Mo_0.5O₁₂: 0.02Er³⁺, xYb³⁺ (x = 0.2, 0.3, 0.4) samples are 4.6, 4.3 and 7.0 times as that of 302 K, respectively. And through fluorescence intensity ratio (FIR) technique, the corresponding maximum absolute sensitivities are 0.00741, 0.00744 and 0.00723, respectively. The green monochromaticity of UCL spectra in Er³⁺/Yb³⁺ co-doped samples increase with the increasing of temperature, and the possible UCL mechanism with temperature was discussed. The results indicate that the Lu₂W_2.5Mo_0.5O₁₂: Er³⁺/Yb³⁺ phosphors can be applied at a high temperature as optical thermometer with a good green monochromaticity.     

Photoluminescence and energy transfer of Lu3Al5O12:Ce3+, Pr3+ phosphors

Ce³⁺ and Pr³⁺ co?doped Lu₃Al₅O₁₂ phosphors were synthesized by the sol–gel process, and their crystal structure, photoluminescence (PL) properties, and energy transfer (ET) from the Ce³⁺ to Pr³⁺ were studied. The Lu_2.94?yAl₅O₁₂:0.06Ce³⁺, yPr³⁺ phosphors (0.002 ≤ y ≤ 0.008) showed the green?yellow emission from the ²D_3/2 → ²F_{5/2, 7/2} transition of Ce³⁺ and the red emission at 610 and 637 nm, which were caused by the ¹D₂→³H₄ and ³P₀→³H₅ transitions of Pr³⁺, respectively. The optimal concentration of Pr³⁺ for efficient ET was found to be x = 0.006. The electric quadrupole?quadrupole interaction was responsible for the concentration quenching in the Lu_2.94?yAl₅O₁₂:0.06Ce³⁺, yPr³⁺ phosphors, based on Dexter's theory. The incorporation of Pr³⁺ for Lu³⁺ enhanced the red PL intensity in the Lu_2.94Al₅O₁₂:0.06Ce³⁺ phosphor.     

Y3Al5O12:Tb3+粉体的制备及其发光特性

以AlF3和H3BO3作助熔剂,经过固相反应,在1 350℃保温4 h成功制备出结晶较好、粒度分布均匀且粒径为0.5～2.0μm的Y3Al5O12:Tb3 (YAG:Tb)单相粉末样品.通过对样品的紫外光和真空紫外光激发下的发光特性研究,发现在147 nm真空紫外光的激发下,YAG:Tb样品的真空紫外激发光谱(λem=543nm)由位于140～190nm之间的铝酸根基团吸收、O2-→Y3 电荷迁移带吸收以及Tb3 的特征吸收组成,其发射光谱由激活离子的特征发射峰构成,发光强度有明显提高.     

Yb3+和Er3+共掺杂的NaY（WO4）2纳米晶的制备与发光性能

采用水热法制备出NaY(WO4):Yb3+,Er3+纳米发光粉。通过X射线衍射、扫描电子显微镜表征了制备的发光粉样品;研究了不同Yb/Er摩尔比对发光强度的影响。结果表明:Yb3+和Er3+共掺杂的NaY(WO4)2属于四方晶系,其粒径在30 nm左右,且分散均匀。当Yb/Er摩尔比为4:1时,NaY(WO4):Yb3+,Er3+发光粉样品的发射峰强度达到了最大值。用980nm激光对其进行激发,在室温下观察到了410、524、553和656nm的发射峰,分别对应于2H9/2→4I15/2,2H11/2→4I15/2,4S3/2→4I15/2和4F9/2→4I15/2的跃迁。根据激发功率与发光强度的关系得出410、524、553和656 nm发射峰均为双光子过程。     

Thermal emission properties of Al2O3/Er3Al5O12 eutectic ceramics

The mechanical properties and thermal stability of the Al₂O₃/Er₃Al₅O₁₂ (EAG) eutectic ceramics have been investigated at very high temperature. The emissive properties of this eutectic ceramics have also been measured and its possibilities of application to an emitter have been discussed. The present eutectic ceramic has excellent high-temperature strength characteristics, showing that tensile yielding stress is approximately 300 MPa at 1650 °C and superior thermal stability at 1700 °C in an air atmosphere. The present material shows strong selective emission bands at wavelength 1.5 μm due to Er³⁺ ion. The emission bands of this material are nearly coincident with the sensitive region of GaSb PV cell, therefore, the Al₂O₃/EAG eutectic ceramic can be regarded as one of the promising emitter materials in TPV systems.     

Er3+和Yb3+共掺锗硅酸盐玻璃的上转换发光性能

采用熔融-淬火法制备了基体为30SiO2-20GeO2-15Al2O3-5B2O3-30CaF2的Er3+和Yb3+共掺锗硅酸盐玻璃.采用X射线衍射仪、荧光光谱仪和热分析仪对样品进行了表征.结果表明:Er2O3含量从0.5％(摩尔分数,下同)增加到2.0％时,玻璃转变温度Tg和Tx-Tg(Tx为第一析晶温度)数值均有明显下降.Yb2O3含量从1.5％增加到4.5％时,玻璃上转换红光发光强度数量级由103提高到105,对其中1个样品在740℃热处理12h后发现,微晶化处理并未对Er的上转换发光产生有益影响.     

Luminescence and self-referenced optical temperature sensing performance in Ca2YZr2Al3O12:Bi3+,Eu3+ phosphors

Ca₂YZr₂Al₃O₁₂:Bi³⁺,Eu³⁺ phosphors were elaborated by a traditional solid-state reaction method. The luminescence of Ca₂YZr₂Al₃O₁₂:Bi³⁺ samples, energy transfer from Bi³⁺ to Eu³⁺, and the temperature sensing properties of Ca₂YZr₂Al₃O₁₂:Bi³⁺,Eu³⁺ samples have been systematically researched. Under the excitation of ultraviolet light, Bi³⁺ single doped phosphors give 313 and 392 nm emission bands, which origin from the substitutions of Bi³⁺ instead of Ca²⁺ and Y³⁺ sites, respectively. And the color-adjustable emission from blue to red were observed by increasing Eu³⁺ content in Ca₂YZr₂Al₃O₁₂:Bi³⁺,Eu³⁺ samples. Relying on different temperature dependent variation tendency, the fluorescence intensity ratio (FIR) values present outstanding temperature sensing properties. The absolute and relative sensitivity can be up to 0.826 %K^-1 and 0.664 %K^-1, respectively. All above results suggest that Ca₂YZr₂Al₃O₁₂:Bi³⁺,Eu³⁺ phosphor is a potential alternative for optical thermometer.     

Preparation,Structure, and Up‐Conversion Luminescence of Yb3+/Er3+ Codoped SrIn2O4 Phosphors

SrIn₂O₄, which shows lower phonon energy than CaIn₂O₄, is not only a good photocatalyst but also can be an excellent up‐conversion (UC) host to exhibits UC luminescence. In this work, Yb³⁺ and/or Er³⁺ doped SrIn₂O₄ phosphors were synthesized, and their UC luminescence properties were studied and compared with those in the CaIn₂O₄ host. The structure of SrIn₂O₄: 0.01Er³⁺ and SrIn₂O₄: 0.1Yb³⁺/0.01Er³⁺ samples were refined by the Rietveld method and found to that SrIn₂O₄: 0.1Yb³⁺/0.01Er³⁺ showed increasing unit cell parameters and cell volume, indicating In³⁺ sites were substituted successfully by Yb³⁺ and/or Er³⁺ ions. From the UC luminescence spectra and diffuse reflection spectra, Er³⁺‐doped SrIn₂O₄ showed very weak luminescence due to ground state absorption of Er³⁺; Yb³⁺/Er³⁺ codoped SrIn₂O₄ presented strong green (550 nm) and red (663 nm) UC emissions which were assigned to energy transfer from Yb³⁺ transition ²F_7/2→²F_5/2 to the Er³⁺ transition ⁴S_3/2 → ⁴I_15/2 and ⁴F_9/2 → ⁴I_15/2. Comparing with CaIn₂O₄, Yb³⁺/Er³⁺ codoped SrIn₂O₄ showed obvious advantages with higher UC luminescent intensity. The pumping powers study showed that UC emissions in Yb³⁺/Er³⁺ codoped SrIn₂O₄ were attributed to energy transfer of Yb³⁺→Er³⁺ with a two‐photon process. The possible UC luminescent mechanism of Yb³⁺/Er³⁺‐doped SrIn₂O₄ was discussed.