Crystal field parameters for Yb ions at orthorhombic centers in garnets—Revisited

The major purpose of this paper is to clarify the deficiencies identified in the recent paper by Liu et al. (J. Lumin. 130 (2010) 103) as well as to reanalyze the available data and provide corrected results for the orthorhombic crystal field parameters (CFPs) for selected rare-earth ions in garnets. It appears that Liu et al., when utilizing the computer package for standardization of CFPs, have inadvertently confused the properties of CFPs expressed in the Wybourne notation with those in the extended Stevens operator notation. This confusion has led to misinterpretations concerning the orthorhombic standardization transformations and incorrect labeling of the CFP sets as supposedly ‘standardized’ for Yb³⁺, Pr³⁺, Nd³⁺, and Er³⁺ ions in various garnets. These deficiencies have prompted us to reconsider the CFP sets determined earlier by matching the experimental data, i.e. the orthorhombic spin Hamiltonian parameters (g factors, g_i, and hyperfine structure constants, A_i; i=x, y, z) and available optical spectral band positions, with the theoretical data calculated using the complete diagonalization method. To further verify the correctness of the present results the CFPs for orthorhombic Yb³⁺ centers in Yb₃Al₅O₁₂ and Yb₃Ga₅O₁₂ garnets are calculated using the superposition model (SPM), which requires adoption of a well-defined symmetry-adapted axis system (SAAS). Hence, the SPM calculations enable reanalysis of available CFP sets based on the correct standardization procedure and establishing the correspondence between the SAAS and the ‘nominal’ axis systems assigned to fitted CFP sets. Using the proper SAAS and general transformations of the axis systems, the relations between the calculated g_i and/or A_i values and the respective principal values determined by EPR experiments can be established. The consistent methodology utilized here may be helpful for proper reanalysis of spectroscopic data for rare-earth and transition-metal ions at orthorhombic symmetry sites in various crystals.     

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.     

Growth and optical properties of Yb and Tb codoped BaB2O4 crystals

Optical absorption and luminescence spectra of ytterbium and terbium codoped BaB₂O₄ (β-BBO and α-BBO) crystals grown in different conditions have been studied. Low-temperature absorption peaks were observed in all samples. Features related to rare earth ions were observed in absorption and luminescence spectra. Absorption and emission in the range 860-1000 nm are caused by ²F_5/2↔²F_7/2 transitions in Yb³⁺ ions. Emission peaks at 500, 550, 590 and 630 nm correspond to ⁵D₄→⁷F₆, ⁷F₅, ⁷F₄, and ⁷F₃ transitions of Tb³⁺ ions, respectively. The probable reasons of variations in spectroscopic features related to Yb in BBO host are discussed. It has been shown that the replacement of Ва²⁺ by Yb³⁺ in the lattice of ВаВ₂О₄ results in the decrease in the symmetry of oxygen surrounding of Yb³⁺.     

Effect of Yb3+ concentration on photoluminescence properties of cubic Gd2O3 phosphor

Yb³⁺ doped phosphor of Gd₂O₃ (Gd₂O₃:Yb³⁺) have been prepared by solid state reaction method. The structure and the particle size have been determined by X-ray powder diffraction measurements. The average particle size of the phosphor is in between 35 and 50 nm. The particle size and structure of the phosphor was further confirmed by TEM analysis. The visible and NIR luminescence spectra were recorded under the 980 nm laser excitation. The visible upconversion luminescence of Yb³⁺ ion was due to cooperative luminescence and the presence of rare earth impurity ions. The cooperative upconversion and NIR luminescence spectra as a function of Yb³⁺ ion concentration were measured and the emission intensity variation with Yb³⁺ ion concentration was discussed. Yb³⁺ energy migration quenched the cooperative luminescence of Gd₂O₃:Yb³⁺ phosphor with doping level over 5%, while the NIR emission luminescence continuously increases with increasing Yb³⁺ ion concentration.     

Investigations of the optical spectra and spin-Hamiltonian parameters for the rhombic Yb centers in garnets

Two complete diagonalization (of energy matrix) methods (CDM-I and CDM-II) are used to calculate the six optical spectral band positions and nine spin-Hamiltonian (SH) parameters (g factors g_i and hyperfine structure constants ¹⁷¹A_i, ¹⁷³A_i, where i=x, y, z) for Yb³⁺ ions in the rhombic dodecahedral sites of garnets Y₃Al₅O₁₂, Lu₃Al₅O₁₂ and Y₃Ga₅O₁₂. In CDM-I, the Hamiltonian concerning energy matrix does not contain the Zeeman and hyperfine interaction terms, whereas in CDM-II, it does. So, in CDM-I, the SH parameters are obtained by first-order perturbation method or the equivalence between SH and Zeeman term (or hyperfine interaction term) and in CDM-II, the SH parameters and optical spectral band positions are calculated together. The results obtained from both methods are not only close to each other, but also in reasonable agreement with the observed values. So the second-order perturbation formulas of SH parameters developed recently are incorrect and unnecessary.     

Variation in luminescence behavior of Yb3+ doped GdAlO3 phosphor with gradual increase in Yb3+ concentration

The present paper reports the combustion synthesis of Yb³⁺ doped GdAlO₃ phosphors. The structural characterization and luminescence spectra of Yb³⁺ doped GdAlO₃ phosphors have been discussed. The effects of variable concentration of Yb³⁺ on Photoluminescence (PL) behavior were studied. The structural characterization was done by X-ray diffraction (XRD) and Transmission electron microscope technique (TEM). The good connectivity with grains and the semi-sphere line structure was found by TEM. The functional group analysis was carried out by Fourier transform infrared (FTIR) spectroscopic techniques. The prepared phosphor gives emission spectra in visible as well as NIR region. Both emissions were studied as a function of Yb³⁺ concentration. The emission intensity variation with Yb³⁺ ion concentration for visible and NIR region were discussed separately. The NIR emission luminescence of GdAlO₃:Yb³⁺ phosphor luminescence continuously increases with increasing Yb³⁺ ion concentration.     

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.     

Observation of stimulated Raman scattering in Y3Al5O12 single crystals and nanocrystalline ceramics and in these materials activated with laser ions Nd3+ and Yb3+

High-order Raman parametric generation was excited in the visible and near-IR regions on the Stokes and anti-Stokes lines of Y₃Al₅O₁₂ single crystals and nanocrystalline ceramics. All generation components, as well as the χ⁽³⁾-active vibrational modes of these materials, were identified. In connection with the extensive use of the Nd³⁺-and Yb³⁺-doped Y₃Al₅O₁₂ crystals and, in recent years, nanocrystalline Y₃Al₅O₁₂: Nd³⁺ ceramics in laser physics and quantum electronics, the applied aspect of the observed nonlinear properties of these materials is outlined.     

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.     

Er/Yb共掺体系的光致荧光行为及相关物理过程研究

采用固相反应方法，制备了Er₂O₃浓度固定为0.5mol%，Yb₂O₃浓度范围为0.0mol%—5.5mol%的Er/Yb共掺激光玻璃.通过吸收光谱、光致荧光光谱和上转换荧光光谱，研究了Yb₂O₃浓度对Er³⁺荧光特性的影响，并探讨了相关的物理机制.研究结果表明：Yb³⁺共掺对Er³⁺的⁴ 关键词： Er/Yb共掺 光致荧光 能量传递 合作上转换     

Er,Yb:YAG微晶玻璃发光特性的研究

高温熔制Er³⁺，Yb³⁺离子掺杂CaO-Y₂O₃-Al₂O₃-SiO₂系统玻璃，并进行微晶化处理，研究了微晶玻璃中Er³⁺离子的发光及上转换发光特性，分析了微晶玻璃上转换发光机理.结果表明：原始玻璃经热处理得到了Er,Yb:YAG微晶玻璃，微晶玻璃中Er³⁺离子在室温下⁴I_13/2→⁴I_15/2跃迁产生横盖1450—1650nm区间的超宽带荧光，荧光半高宽达180nm，这可能由于YAG微晶相中Er³⁺离子与玻璃相中残留Er³⁺离子的共同发光；Er³⁺与Yb³⁺离子局域基质声子能量的降低使微晶玻璃Er³⁺离子上转换发光强度与原始玻璃相比显著提高，绿光、红光上转换荧光强度比玻璃样品分别增强约7和3倍；微晶化后Er³⁺，Yb³⁺离子局域环境发生变化也导致微晶玻璃中Er³⁺离子绿光、红光上转换发光相对强度发生变化. 关键词： 铒 镱:钇铝石榴石 微晶玻璃 荧光光谱     

Infrared-to-visible up-conversion luminescence and energy transfer of RE3+/Yb3+(RE = Ho,Tm) co-doped SrIn2O4

Near-infrared excited up-conversion phosphors of RE³⁺/Yb³⁺(RE = Ho, Tm) co-doped SrIn₂O₄ were synthesized by a solid-state reaction method. X-ray diffraction analysis revealed the phase composition of those samples, and the up-conversion spectroscopic properties were studied in terms of up-conversion emission spectra. Under 980 nm near-infrared laser excitation, strong green emission with the peak at 546 nm was observed in SrIn₂O₄: Ho³⁺/Yb³⁺, which can be assigned to the characteristic ⁵S₂(⁵F₄) → ⁵I₈ transition of Ho³⁺. Furthermore, SrIn₂O₄: Tm³⁺/Yb³⁺ showed bright blue emission with the peak at 486 nm, which is associated with the ¹G₄ → ³H₆ transition of Tm³⁺. The UC power studies indicated that the luminescence of SrIn₂O₄: Ho³⁺/Yb³⁺ and SrIn₂O₄: Tm³⁺/Yb³⁺ are attributed to two-photon and three-photon process, respectively. The possible UC luminescence mechanism and energy transfer in SrIn₂O₄: RE³⁺/Yb³⁺ were discussed.     

Facile synthesis of well-dispersed SrF2:Yb/Er upconversion nanocrystals in oleate complex systems

Well oil-dispersible SrF₂:Yb³⁺/Er³⁺ upconversion (UC) nanocrystals (NCs) were easily synthesized in the water-ethanol-oleic acid-sodium oleate complex systems. The as-prepared NCs all show size-uniformity, and their sizes, morphologies can be controlled by varying the solvent and reaction time, and rectangular SrF₂:Yb³⁺/Er³⁺ nanosheets with the sizes of 5-25 nm can be obtained. The possible mechanism on the nucleation and growth of nanocrystals occurred at the oleic acid/sodium oleate interface was also discussed. The size and morphology dependent UC luminescence behaviors have been observed in SrF₂:Yb³⁺/Er³⁺ NCs, and their UC luminescence transitions were proposed. The as-prepared UC nanocrystals are expected to fulfill the demand for biological applications.     

The phase transition, hygroscopicity, and thermal expansion properties of Yb2-xAlxMo3O12

Materials with the formula Yb2-xAlxMo3O12 （x = 0.1, 0.2, 0.3, 0.4, 0.5, 0.7, 0.9, 1.0, 1.1, 1.3, 1.5, and 1.8） were synthesized and their structures, phase transitions, and hygroscopicity investigated using X-ray powder diffraction, Raman spectroscopy, and thermal analysis. It is shown that Yb2-xAlxMo3012 solid solutions crystallize in a single monoclinic phase for 1.7 〈 x 〈 2.0 and in a single orthorhombic phase for 0.0 〈 x 〈 0,4, and exhibit the characteristics of both monoclinic and orthorhombic structures outside these compositional ranges. The monoclinic to orthorhonlbic phase transition temperature of A12Mo3012 can be reduced by partial substitution of A13＋ by Yb3＋, and the Yb2-zAlxMo3012 （0.0 〈 x 〈 2.0） materials are hydrated at room temperature and contain two kinds of water species. One of these interacts strongly with and hinders the motions of the polyhedra, while the other does not. The partial substitution of A13＋ for Yb3＋ in Yb2Mo3012 decreases its hygroscopicity, and the linear thermal expansion coefficients after complete removal of water species are measured to be -9.1 x 10-6/K, -5.5 x 10-6/K, 5.74 x 10-6/K, and 9.5 x 10 6/K for Ybl.sAlo.2（MoO4）3, Yb1.6Alo.4（MoO4）3, Ybo.4All.6（Mo04）3, and Ybo.2Al1.8（MoO4）3, respectively.     

Enhanced superhyperfine interaction on Ru3+ in Tm3Al5O12 and on Ru3+ and Yb3+ in Tm3Ga5O12

Measurements of the enhanced superhyperfine interaction linking the electron spin of an impurity EPR ion and the nuclear moments of Van Vleck host lattice ions are reported for Ru³⁺ in Tm₃Al₅O₁₂ and for Ru³⁺ and Yb³⁺ in Tm₃Ga₅O₁₂. The Ru³⁺ results appear to be the first reported where this interaction is large enough to give rise to a well resolved superhyperfine structure. For Yb³⁺ the observed temperature dependent line narrowing evidences the role of Tm spin fluctuations.     

Growth and luminescence properties of Pr3+-doped single crystalline films of garnets and perovskites

Peculiarities of growth of single crystalline films (SCF) of Pr³⁺ doped Y₃Al₅O₁₂ and Lu₃Al₅O₁₂ garnets and YAlO₃ and LuAlO₃ perovskites by the liquid phase epitaxy method from melt-solutions based on PbO–B₂O₃ flux as well as luminescent and scintillation properties of these SCFs were studied in this work. Dependence the intensity of the Pr³⁺ d-f and f-f-luminescence on the activator concentration and influence of Pb²⁺ flux dopant on the light yield of SCFs of the mentioned garnets and perovskites were analyzed.     

A study of energy transfer phenomenon leading to photon up-conversion in Ho3+:Yb3+:CaF2 crystalline powders and its temperature sensing properties

When Ho³⁺:Yb³⁺:CaF₂ crystalline powders prepared by combustion synthesis were exposed to near-infrared (λ ～ 975 nm) radiation, intense photon up-conversion (UC) was observed at the visible with emission bands peaked at ～ 545, ～650 and ～750 nm identified as 4f-4f transitions from higher levels (⁵F₄, ⁵S₂) and ⁵F₅ to lower levels ⁵I₈ and ⁵I₇ of Ho³⁺. The emission bands at the green and red, in particular, have been demonstrated to be useful for temperature sensing based on luminescence intensity ratio technique. However, no model is available in literature to explain the change of the electronic populations of states (⁵F₄, ⁵S₂) and ⁵F₅ with temperature. The UC phenomenon was studied from both theoretical and experimental points of view. A rate equation model with temperature dependent parameters for Ho³⁺ and Yb³⁺ electronic populations considering a high sensitization of Ho³⁺ ions by Yb³⁺ ions was used. High Yb³⁺ → Ho³⁺ energy transfer efficiency was found (～88% at room temperature). The change with temperature predicted by the model for the luminescence intensity ratio of the UC green and red emission lines agrees well with the experimental data.     

Investigation of luminescence spectra of the Y<Subscript>3</Subscript>Al<Subscript>5</Subscript>O<Subscript>12</Subscript> and Y<Subscript>3</Subscript>Al<Subscript>5</Subscript>O<Subscript>12</Subscript>:Ce single-crystal films

The luminescence spectra of single-crystal films and bulk crystals of yttrium-aluminum garnet Y₃Al₅O₁₂ and Ce³⁺-activated Y₃Al₅O₁₂ were investigated. It was shown that the room-temperature luminescence intensity of the Ce³⁺-free single-crystal Y₃Al₅O₁₂ film was considerably lower than that of the bulk crystals, while the luminescence intensity of the Ce³⁺ ions in the Y₃Al₅O₁₂:Ce films was considerably higher than that one for the corresponding bulk crystal.     

Temporal dynamics of upconversion luminescence in Er3+, Yb3+ co-doped crystalline KY(WO4)2 thin films

Crystalline Er³⁺ and Yb³⁺ singly and doubly doped KY(WO₄)₂ thin films were grown by low-temperature liquid-phase epitaxy. Absorption, luminescence, excitation and temporal evolution measurements were carried out for both Er³⁺ and Yb³⁺ transitions from 10 K to room temperature. Green Er³⁺ upconversion luminescence was observed after Yb³⁺ and Er³⁺ excitation. The mechanisms responsible for the upconversion phenomena detected in each case were identified.     

Enhanced upconverted photoluminescence in Er and Yb codoped ZnO nanocrystals with and without Li ions

The upconversion luminescence spectral intensity of Er³⁺ in Er³⁺ and Yb³⁺ codoped ZnO nanocrystals with and without Li⁺ are investigated. Yb³⁺ ions as a tradition sensibilizer have efficient energy transfer processes from Yb³⁺ (²F_5/2) to Er³⁺ (⁴I_13/2, ⁴I_11/2, ⁴F_9/2), which lead to the increment of upconversion luminescence intensity. Following by adding Li⁺ to the Er³⁺ and Yb³⁺ codoped ZnO nanocrystals, the upconversion intensity emitted by Er³⁺ ions is found greatly enhanced. The enhancement is attributed to the distortion of the local field symmetry of Er³⁺ ions, so increases various intra-4f transitions of Er³⁺ ions. Both Yb³⁺ and Li⁺ can disperse Er³⁺ ions in specimen, so reduced the interaction between neighboring Er³⁺ ions.