Infrared emissions, visible up-conversion, thermoluminescence and defect centres in Er3Al5O12 phosphor obtained by solution combustion reaction

The Er₃Al₅O₁₂ phosphor powders were prepared using the solution combustion method. Formation and homogeneity of the Er₃Al₅O₁₂ phosphor powders have been verified by X-ray diffraction and energy-dispersive X-ray analysis respectively. The frequency up-conversion from Er₃Al₅O₁₂ phosphor powder corresponding to the ²H_9/2 → ⁴I_15/2, ²H_11/2 → ⁴I_15/2, ⁴S_3/2 → ⁴I_15/2, ⁴F_9/2 → ⁴I_15/2 and the infrared emission (IR) due to the ⁴I_13/2 → ⁴I_15/2 transitions lying at ∼410, ∼524, ∼556, 645–680 nm and at ∼1.53 μm respectively upon excitation with a Ti-Sapphire pulsed/CW laser have been reported. The mechanism responsible for the frequency up-conversion and IR emission is discussed in detail. Defect centres induced by radiation were studied using the techniques of thermoluminescence and electron spin resonance. A single glow peak at 430°C is observed and the thermoluminescence results show the presence of a defect center which decays at high temperature. Electron spin resonance studies indicate a center characterized by a g-factor equal to 2.0056 and it is observed that this center is not related to the thermoluminescence peak. A negligibly small concentration of cation and anion vacancies appears to be present in the phosphor in accordance with the earlier theoretical predictions.     

Yb:Y3Al5O12/Y3Al5O12复合晶体的制作和光谱性能

采用热键合技术,制作中运用不同的工艺参量制作出12片Yb:Y3Al5O12/Y3Al5O12(Yb:YAG/YAG)复合.晶体.利用偏光显微镜对其键合界面进行了观察,研究了样品的透射光谱,从而确定出复合晶体合适的制作工艺.通过透射光谱的形状和透射率来表征复合晶体键合界面的质量.研究表明Yb:YAG/YAG复合晶体键合质量较好,可实现一体化.     

Yb:Y3Al5O12晶体晶格振动光谱的研究

采用提拉法生长Y3Al5O12(YAG)晶体和Yb3 掺杂原子数分数分别为5%,10%,15%,20%,25%,50%和100%的Yb:Y3Al5O12(Yb:YAG)晶体.系统表征和分析了Yb3 掺杂浓度对拉曼光谱的影响.随着Yb3 掺杂浓度的增加,晶体的振动模式没有明显的变化,晶体结构没有改变;在370 cm-1和785 cm-1附近,振动吸收峰的半峰全宽逐渐增大.分析得出,Yb3 掺杂浓度对晶体的晶格、对称性、荧光寿命均有影响,从而可能影响到晶体的光谱和激光性能.     

Synthesis, characterization, optical absorption, luminescence and defect centres in Er3+ and Yb3+ co-doped MgAl2O4 phosphors

The Er³⁺–Yb³⁺ co-doped MgAl₂O₄ phosphor powders have been prepared by the combustion method. The phosphor powders are well characterized by X-ray diffraction (XRD) and energy dispersive (EDX) techniques. The absorption spectrum of Er³⁺/Er³⁺–Yb³⁺ doped/co-doped phosphor powder has been recorded in the UV–Vis–NIR region of the electro-magnetic spectrum. The evidence for indirect pumping under 980 nm excitation of Er³⁺ from Yb³⁺ was observed in the MgAl₂O₄ matrix material. Electron spin resonance (ESR) studies were carried out to identify the defect centres responsible for the thermally stimulated luminescence (TSL) process in MgAl₂O₄:Er³⁺ phosphor. Three defect centres were identified in irradiated phosphor by ESR measurements which were carried out at room temperature and these were assigned to an O^? ion and F⁺ centres. O^? ion (hole centre) appears to correlate with the low temperature TSL peak at 210 °C and one of the F⁺ centres (electron centre) is related to the high temperature peak at 460 °C.     

不同Yb掺杂量的Yb:Y3Al5O12晶体的光谱分析

采用提拉法生长了Yb3+掺杂量分别为5.4at%, 16.3at%, 27.1at%, 53.6at%和100at%的Yb:Y3Al5O12晶体.系统地表征和分析了Yb3+掺杂量对晶体吸收光谱和荧光光谱的影响.随着Yb3+掺杂量的增加,各峰值吸收系数呈线性增加的趋势.应用Smakula公式计算了各吸收峰对应的振荡强度,并分析了Yb3+掺杂量对振荡强度的影响.当Yb3+掺杂量增加到27.1at%时观察到了荧光猝灭现象;当Yb3+掺杂量增加到53.6at%时,荧光光谱的线形发生了很大的变化.     

Magnetic-field-controlled polarized luminescence of Y3Al5O12-Tb and Y3Al5O12-Ho garnets

The circularly polarized luminescence spectra of Y₃Al₅O₁₂-Tb and Y₃Al₅O₁₂-Ho garnets are analyzed in the wavelength ranges of the ⁵ D ₄ → ⁷ F ₅ transition in the Tb³⁺ ion and the ⁵ S ₂ → ⁵ I ₈ transition in the Ho³⁺ ion. It is found that the intensities of the orthogonal circularly polarized components of the series of luminescence lines attributed to the studied garnets differ substantially. The results obtained are interpreted in terms of the mixing of the Tb³⁺ and Ho³⁺ electronic states in an external magnetic field.     

Infrared spectroscopy and lattice dynamical calculations of Gd3Al5O12, Tb3Al5O12 and Lu3Al5O12 single crystals

The infrared (IR) reflectance spectra of Gd₃Al₅O₁₂, Tb₃Al₅O₁₂ and Lu₃Al₅O₁₂ single crystals are studied for the first time. At room temperature, 15 infrared active modes for Lu₃Al₅O₁₂ and 14 for Gd₃Al₅O₁₂, Tb₃Al₅O₁₂, out of the 17 theoretically predicted, have been experimentally recorded. The complex dielectric function the refractive index, the absorption coefficient as well as the longitudinal (ω_LO) and transverse (ω_TO) frequencies of the long-wavelength T_1u modes are determined by the Kramers-Kronig transformation of the reflectance spectra. The experimental data are compared and discussed with the theoretical results obtained by the rigid ion model. Our theoretical analysis reveals that the bonds in the tetrahedra exhibit a covalent character while those in the dodecahedra almost ionic character, which is in accordance with the results for other materials of this crystal family.     

Multiphoton excitation of visible emission in Y2O2S: Er,Yb phosphors by 810 nm excitation

During investigations of anti-Stokes effects in erbium—ytterbium doped yttrium oxysulphide phosphors we have found an excitation of the erbium green emission due to 810 nm radiation (⁴I$\text{15}\text{2}$ → ⁴I$\text{9}\text{2}$ transition), the effect being of a two-photon type. There is also a two-photon excited blue emission (²H$\text{9}\text{2}$ → ⁴I$\text{15}\text{2}$ transition) due to the same radiation. Introduction of ytterbium impurity has a deleterious effect on the above 810 nm excitation, in contrast to its sensitization of the 1000 nm anti-Stokes excitation. To distinguish between various excitation schemes a two-beam excitation technique has been used. Results show that ytterbium inclusions lead to loss of energy from the 810 nm excitation by increasing the probability of downward transitions from the ⁴F$\text{9}\text{2}$ level to ⁴I$\text{11}\text{2}$ and ⁴I$\text{13}\text{2}$ states, reached after onephoton absorption. This effect is indicated by an increase in 1500 nm emission (⁴I_{$\text{13}\text{2}$} → ⁴I_{$\text{15}\text{2}$} with ytterbium concentration.     

Luminous and tunable white-light upconversion for YAG (Yb3Al5O12) and (Yb,Y)2O3 nanopowders

We report on multiphoton white-light upconversion in vacuum for Pechini synthesis Yb(3)Al(5)O(12) (YbAG) and combustion synthesis (Yb,Y(2))O(3) nanopowders under IR excitation. Their intense white-light upconversion is attributed to charge transfer luminescence superimposed upon a broadband emission. Unlike common nanoscale phosphors, which show low luminescence efficiency, the intensity of white-light upconversion for nanopowders is similar to that of their bulk counterparts. The luminary efficacy of the upconversion is estimated to be 10-15 lm W(-1), and the Commission Internationale d'Eclairage (CIE) coordinates can be widely tuned by the excitation power, pressure, and codoping ratio. The nano-YbAG sample exhibits a longer buildup time for emission, a higher excitation threshold, and a wider CIE range than the oxide nanopowders.     

Studies of the spin-Hamiltonian parameters and defect structures for the trigonal Mo 3+ centers in Y 3Al 5O 12 and Lu 3Al 5O 12 crystals

The complete diagonalization (of energy matrix) method (CDM) and the perturbation theory method (PTM) are applied to calculate the spin-Hamiltonian (SH) parameters (electron paramagnetic resonance g factors g _//, g _⊥ and zero-field splitting D) of the trigonal Mo ³⁺ centers in Y ₃Al ₅O ₁₂ and Lu ₃Al ₅O ₁₂ crystals. Both methods are based on the cluster approach in which the covalence effect due to the admixture between the d orbitals of central d ⁿ ion and p orbitals of ligands is considered. The g factors calculated by both methods are close to each other and agree with the experimental values. However, the calculated zero-field splittings D from PTM for both crystals are about 84% those from CDM. The reasons that the CDM is preferable to the PTM in the calculations of SH parameters are discussed. The angular distortions of Mo ³⁺ centers in both garnet crystals are predicted.     

Effect of different doped elements on visible light absorption and ultraviolet light emission on Er3+:Y3Al5O12

In this progress report, seven kinds of novel carefully designed and fabricated up-conversion luminescence agents, Er³⁺:Y₃Al₅O₁₂, Er³⁺:Yb_nY_3?nAl₅O₁₂, Er³⁺:Y₃B_aAl_5?aO₁₂, Er³⁺:Y₃Ga_bAl_5?bO₁₂, Er³⁺:Y₃Al₅N_xO_12?x, Er³⁺:Y₃Al₅F_yO_12?y and Er³⁺:Yb_nY_3?nB_aGa_bAl_5?a?bN_xF_yO_12?x?y, are successfully synthesized using sol–gel methods. After that, their corresponding photocatalysts, Er³⁺:Y₃Al₅O₁₂/TiO₂, Er³⁺:Yb_nY_3?nAl₅O₁₂/TiO₂, Er³⁺:Y₃B_aAl_5?aO₁₂/TiO₂, Er³⁺:Y₃Ga_bAl_5?bO₁₂/TiO₂, Er³⁺:Y₃Al₅N_xO_12?x/TiO₂, Er³⁺:Y₃Al₅F_yO_12?y/TiO₂ and Er³⁺:Yb_nY_3?nB_aGa_bAl_5?a?bN_xF_yO_12?x?y/TiO₂, are also prepared by sol–gel coating process. The obtained up-conversion luminescence agents and photocatalysts were characterized by using XRD, XPS, SEM, UV–vis and fluorescence spectrophotometer. Synchronously, several kinds of organic dyes are used to test their photocatalytic degradation using prepared photocatalysts. It indicates that the up-conversion luminescence ability of Er³⁺:Y₃Al₅O₁₂ can be improved obviously through doping of some elements. And then, the photocatalytic activity of TiO₂ is markedly enhanced by modified up-conversion luminescence agents which can transform much visible light into ultraviolet light.     

Spectroscopic properties of Yb3+-doped Y3Al5O12 nano-ceramics obtained under different sintering pressures

Yb³⁺:YAG nano-ceramics have been obtained by a low temperature/high pressure sintering process. Structural properties have been studied by X-ray diffraction (XRD). Grain sizes and R.M.S micro-strains have been calculated based on the XRD patterns by Rietveld analysis method. Emission spectra and decay curves have been recorded and analyzed. It has been observed that the decay time decreases with the increase of sintering pressure. Presence of Yb³⁺–Yb³⁺ pairs have been detected by cooperative emission spectroscopy.     

Photoluminescence of Lu3Al5O12:Bi and Y3Al5O12:Bi single crystalline films

Single crystalline films of Lu₃Al₅O₁₂:Bi and Y₃Al₅O₁₂:Bi have been studied at 4.2–450 K by the time-resolved luminescence spectroscopy method. Their emission spectrum consists of two types of bands with strongly different characteristics. The ultraviolet band consists of two components, arising from the electronic transitions which correspond to the ³P₁ → ¹S₀ and ³P₀ → ¹S₀ transitions in a free Bi³⁺ ion. At T < 80 K, mainly the lower-energy component with the decay time ～10^?3 s is observed, arising from the metastable ³P₀ level. At T > 150 K, the higher-energy component prevails, arising from the thermally populated emitting ³P₁ level. The visible emission spectrum consists of two dominant strongly overlapped broad bands with large Stokes shifts. At 4.2 K, their decay times are ～10^?5 s and ～10^?4 s and decrease with increasing temperature. Both of the visible emission bands are assumed to be of an exciton origin. The lower-energy band is ascribed to an exciton, localized near a single Bi³⁺ ion. The higher-energy band, showing a stronger intensity dependence on the Bi³⁺ content, is assumed to arise from an exciton, localized near a dimer Bi³⁺ center. The structure of the corresponding excited states is considered, and the processes, taking place in these states, are discussed.     

Kinetic studies of electronically conducting Yb3Al5O12 garnet

Upon reduction, originally fully transparent and insulating ytterbium alumina garnet single crystals, Yb₃Al₅O₁₂, become deeply colored and electrically conducting with a conductivity of the order of 10^− 3 Ω^− 1 cm^− 1 in the temperature range of 550 °C to 1000 °C. The redox kinetics of the material is studied by means of conductivity relaxation experiments performed at oxidising and reducing conditions. Good agreement is obtained with an optical study into the redox kinetics of Yb₃Al₅O₁₂.     

Distortion of the Ligand Environment of Gd3+ and Eu2+ Ions in Garnets: Y3Al5O12, Lu3Al5O12, and Y3Ga5O12

Physics of the Solid State - Using experimental second-rank&nbsp;parameters of the spin Hamiltonian of the rhombic centers Gd3+ and Eu2+ in three garnets and the superposition approximation...     

Er~(3+),Yb~(3+)共掺杂Y_2O_3纳米晶体粉末中1.5μm近红外发光增强现象的研究

用燃烧法制备了平均粒径为10和40nm的(Y0.96Er0.02Yb0.02)O3纳米晶体样品,并通过1200℃高温退火获得了同样组分的体材料样品。利用X射线衍射谱(XRD),傅里叶变换红外吸收光谱(FTIR),透射电镜(TEM)和透射电镜(SEM)照片对样品的晶体结构和形貌进行了表征。测量了不同样品980nm激发下的上转换发射光谱和近红外发射光谱。对实验结果的分析发现,随着粒径的减小,样品发射光谱中红光和近红外发射的成分增加。产生这一现象的原因是由于纳米材料具有比表面积大的特点,能够吸附更多的OH-(振动能量3200～3800cm-1),OH-数量的增加使电子从Er3+的4I11/2→4I13/2能级(能量差3600cm-1)的无辐射弛豫速率增大,这一无辐射弛豫过程减少了4I11/2上的电子布居数,使绿光发射减弱;同时增加了4I13/2上的电子布居数,使红光和近红外发射增强。40nm样品的1.5μm发射主峰强度是体材料的1.6倍,这一结果对纳米发光材料的实际应用是很有意义的。     

Improvement of sonocatalytic activity of TiO2 by using Yb,N and F-doped Er3+:Y3Al5O12 for degradation of organic dyes

In this study, several up-conversion luminescence agents (Er³⁺:Y₃Al₅O₁₂, Er³⁺:Yb_0.2Y_2.79Al₅O₁₂, Er³⁺:Yb_0.2Y_2.79Al₅N_0.01O_11.99, Er³⁺:Yb_0.2Y_2.79Al₅F_0.01O_11.99 and Er³⁺:Yb_0.2Y_2.79Al₅N_0.01F_0.01O_11.98) were synthesized using sol–gel method. And then, the corresponding sonocatalyst (Er³⁺:Y₃Al₅O₁₂/TiO₂, Er³⁺:Yb_0.2Y_2.79Al₅O₁₂/TiO₂, Er³⁺:Yb_0.2Y_2.79Al₅N_0.01O_11.99/TiO₂, Er³⁺:Yb_0.2Y_2.79Al₅F_0.01O_11.99/TiO₂ and Er³⁺:Yb_0.2Y_2.79Al₅N_0.01F_0.01O_11.98/TiO₂ coated composites) were prepared by sol–gel coating process. The synthesized up-conversion luminescence agents and their coated composites were characterized by X-ray diffraction (XRD) and scanning electron microscope (SEM). And that, the sonocatalytic activities were detected through the degradation of Azo Fuchsine (AF) dye in aqueous solution by UV–vis spectroscopy. Some key influences such as heat-treated temperature and heat-treated time on the sonocatalytic activity of Er³⁺:Yb_aY_2.99−aN_xF_yAl₅O_12−x−y/TiO₂ coated composite, as well as ultrasonic irradiation time and initial dye concentration on the sonocatalytic degradation were studied. The results showed that the doping of Yb, N and F into Er³⁺:Y₃Al₅O₁₂/TiO₂ significantly enhanced the sonocatalytic activity of Er³⁺:Y₃Al₅O₁₂/TiO₂ coated composite in the degradation of organic dyes. Particularly, Er³⁺:Yb_0.2Y_2.79Al₅N_0.01F_0.01O_11.98/TiO₂ coated composites with 3:7 M ratio heat-treated at 550 °C for 60 min showed the highest sonocatalytic activity. At last, the experiments also indicated that the Er³⁺:Yb_0.2Y_2.79Al₅N_0.01F_0.01O_11.98/TiO₂ coated composites has a good sonocatalytic activity to degrade other organic dyes under ultrasonic irradiation.     

Absorption and luminescence of Nd3+:Y3Al5O12

In this paper there are briefly summarized the results of our experimental measurements of the fluorescence spectra, originating in levels of the⁴ F _3/2 term and terminating on the first two terms of the⁴I multipet, and the results of the absorption spectra at room temperature (RT) and at liquid-nitrogen temperature (NT) from which Nd³⁺: Y₃Al₅O₁₂ energy-level diagram was determined. Further, using the splitting of the⁴F_3/2,⁴F_5/2 and⁴F_7/2 terms the crystal-field parameters were calculated.