Calculating Hamiltonian parameters for Yb^3＋ in a low-symmetry lattice site, and fitting the structure and levels of Yb^3＋ ：RETaO4 （RE = Gd, Y, and Sc）

An iterative method is used to find the values of the Hamiltonian parameters for Yb^3＋ in a given low-symmetry crys- talline site. Samples of Yb^3＋ ：RETaO4 （RE = Gd, Y, and Sc） were prepared and their structures were determined. Based on the obtained structural data, their orbital-spin parameters and crystal field parameters were fitted by the superposition model （SM）. Using the crystal field parameters obtained by the SM fitting as the initial parameters, the Hamiltonian parameters were fitted iteratively. The calculated and experimental energy levels for Yb^3＋：RETaO4 are consistent, and the maximal mean-root-square deviation is only 2.84 cm^- 1, indicating that the method is effective to determine the Hamiltonian parameters of Yb^3＋ in low-symmetry crystalline sites.     

Full-profile fitting of emission spectrum to determine transition intensity parameters of Yb~(3+):GdTaO_4

The Judd-Ofelt theoretic transition intensity parameters A_(tp)~k of luminescence of rare-earth ions in solids are important for the quantitative analysis of luminescence.It is very difficult to determine them with emission or absorption spectra for a long time.A "full profile fitting" method to obtain A_(tp)~k in solids with its emission spectrum is proposed,in which the contribution of a radiative transition to the emission spectrum is expressed as the product of transition probability,line profile function,instrument measurement constant and transition center frequency or wavelength,and the whole experimental emission spectrum is the sum of all transitions.In this way,the emission spectrum is expressed as a function with the independent variables intensity parameters A_(tp)~k,full width at half maximum(FWHM) of profile functions,instrument measurement constant,wavelength,and the Huang-Rhys factor S if the lattice vibronic peaks in the emission spectrum should be considered.The ratios of the experimental to the calculated energy lifetimes are incorporated into the fitting function to remove the arbitrariness during fitting A_(tp)~k and other parameters.Employing this method obviates measurement of the absolute emission spectrum intensity.It also eliminates dependence upon the number of emission transition peaks.Every experiment point in emission spectra,which usually have at least hundreds of data points,is the function with variables A_(tp)~k and other parameters,so it is usually viable to determine A_(tp)~k and other parameters using a large number of experimental values.We applied this method to determine twenty-five A_(tp)~k of Yb~(3+) in GdTaO_4.The calculated and experiment energy lifetimes,experimental and calculated emission spectrum are very consistent,indicating that it is viable to obtain the transition intensity parameters of rare-earth ions in solids by a full profile fitting to the ions' emission spectrum.The calculated emission cross sections of Yb~(3+):GdTaO_4 also indicate that the F-L formula gives larger values in the wavelength range with reabsorption.     

镱掺杂钼酸铅的光谱和EPR谱的理论研究

该文表达了一个研究Yb³⁺掺杂PbMoO₄晶体的光谱和电子顺磁共振谱(EPR)的理论方法. 采用晶体场理论,推导了有关光谱和电子顺磁共振谱的公式. 基于这些理论公式,构建了4f¹³电子组态在D_2d晶体对称下包括Zeeman磁相互作用的14阶能量矩阵. 通过对角化这一能量矩阵,研究了Yb³⁺掺杂PbMoO₄晶体的光谱和电子顺磁共振谱. 所得的理论结果与实验值很好符合. 而且,相关的晶体场参量也在研究中确定.     

RE2O3 (RE = Lu, Y, Sc)的氧空位第一性原理计算研究

本研究选择三个电子结构类似的稀土倍半氧化物RE₂O₃(RE=Lu, Y,Sc),建立适当的模型通过第一性原理计算,研究氧空位对体系的电子结构的影响.本研究以密度泛函理论(DFT)为基础,利用PBE泛函加U值修正计算了纯稀土倍半氧化物的能带结构.计算结果表明三种基体材料RE₂O₃的能带结构相似.在引入氧空位后,其增加的缺陷能级数目不同,依次为:Sc₂O₃2O₃2O₃.     

Investigation of the Emission Cross-sections and the Spectra of (Cr~(4 ), Yb~(3 ) ): YAG Crystal

l introductionIn recent years, Cr4 --doped crystals have attracted a great deal of attention aspassive Q--,wit,h.,[l~4]. These Cr4 --dOPed crystals include Cr4 : YAG[l'21 ) Cr4 :GSGG[s], Cr4 : YSO['] etc. They have a large absorption cross section and lOwsaturable intensity at the laser wavelength. In comparison with previously usedsaturable absorbers such as dyes['] and LiF: FZ-- [6] cOlor center crystals, Cr4 -dopedcrystals are more photO--chemically and thermally stable and h…     

Photoluminescence studies of NaCaPO4:RE (RE=Dy, Mn or Gd)

The purpose of the present study is to develop an understanding of photoluminescence properties of Dy³⁺, Mn²⁺ or Gd³⁺doped NaCaPO₄ phosphors, which have served as efficient phosphors in many industrial applications. The phase formation was confirmed by the X-ray powder diffraction (XRD) measurement. Photoluminescence (PL) excitation spectrum measurement of NaCaPO₄:Dy³⁺ shows this phosphor can be efficiently excited by near-ultraviolet (UV) light from 300 to 400 nm and presents dominant luminescence band centered at 480 nm (blue) and 573 nm (yellow). The PL excitation of NaCaPO₄:Mn²⁺ and Gd³⁺ under UV wavelength shows the emissions at 520 and 313 nm, respectively. A scanning electron microscope (SEM) shows an average crystallite size in sub-micrometer range. The obtained results show that the phosphors have the potential for application in the lamp industry and medical applications.     

Tripolyphosphate as Precursor for REPO4:Eu3+ (RE = Y, La, Gd) by a Polymeric Method

A modification of the Pechini method was applied to obtain luminescent rare earth orthophosphates. The developed synthetic route is based on the ability of the tripolyphosphate anion () to act both as a complexing agent and as an orthophosphate precursor. Heating of aqueous solutions containing RE³⁺, Eu³⁺, , citric acid, and ethylene glycol led to polymeric resins. The ignition of these resins at different temperatures yielded luminescent orthophosphates. The produced nanosized phosphors (YPO₄:Eu³⁺, (Y,Gd)PO₄:Eu³⁺, and LaPO₄:Eu³⁺) were analyzed by infrared and luminescence spectroscopies, X-ray diffractometry, and scanning electron microscopy.     

Eu^3＋离子在晶体KY3F10,YPO4及YVO4中的角重迭晶场参数计算

本文运用角重迭模型首次对Eu~(3+)离子在KY_3F_(10)S、YPO_4及YVO_4晶体中的四个角重迭参数e_σ、e_π、e_δ、e_φ进行了计算。结果表明,所得规律与文献[1]基本相符,并且e_σ和e_φ两个参数对能级的劈裂和移动也有着不可忽略的作用。     

Nd~(3+):SrY_2O_4粉体的制备、结构与光谱性能研究

为探索新型激光晶体,采用固相法合成了(3 at.%)Nd~(3+):SrY_2O_4多晶,对其结构和发光性质进行了研究.对样品的X射线衍射谱进行Rietveld精修得到了样品的晶胞参数、原子位置等.在353 nm激发下,Nd~(3+):SrY_2O_4在可见波段的最强荧光峰位于419 nm,对应Nd3+的2D15/2→4I9/2跃迁.在824 nm激发下,Nd3+的4F3/2→4I11/2跃迁的荧光谱带宽约为90 nm,最强峰为1083 nm,荧光寿命为281.7μs.宽发射光谱和长的能级寿命表明,Nd~(3+):SrY_2O_4是一种很有希望的新波长激光二极管抽运超短脉冲激光材料.     

The temperature‐sensitive luminescence of (Y,Gd)VO4:Bi3+,Eu3+ and its application for stealth anti‐counterfeiting

Anti‐counterfeiting technologies are desired to protect products far away from the violation of dummy, fake and shoddy goods. The phosphor of (Y,Gd)VO₄:Bi³⁺,Eu³⁺ was synthesized for the application of this purpose. Its photoluminescence was investigated by exciting with different wavelengths at variant temperatures. Wide emission color ranged from green through yellow to orange was tuned up by tailor‐ing Bi³⁺ and Eu³⁺ concentrations. The temperature dependent luminescence and wavelength selective excitation of (Y,Gd)VO₄:Bi³⁺,Eu³⁺ were observed, which provide different encryptions in anti‐counterfeiting. To verify the feasibility in application, two anti‐counterfeiting patterns were fabricated practically and excellent performance was obtained. Moreover, the physical mechanisms for the different phenomena of luminescence were elucidated from excitation spectra combining with the configuration coordinate model. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Spectroscopy of YAl3(BO3)4:Cr3+ crystals following first principles and crystal field calculations

The CASTEP module of the Materials Studio package was used for calculations of the structural, electronic and optical properties of pure and Cr³⁺-doped YAl₃(BO₃)₄ (YAB). The exchange-correlation effects were treated within the generalized gradient approximation with the Perdew–Burke–Ernzerhof functional. The Monkhorst–Pack scheme k-points grid sampling was set at 3?×?3?×?4 for the Brillouin zone. The plane-wave basis set energy cutoff was set at 340?eV; ultrasoft pseudopotentials were used for all chemical elements. The convergence parameters were as follows: total energy tolerance 1?×?10^?5?eV/atom, maximum force tolerance 0.03?eV/nm, maximal stress component 0.05?GPa and maximal displacement 0.001?Å. The principal absorption peaks of the studied crystal were identified. The influence of 532?nm?cw, 300?mW laser radiation on the observed absorptions was studied.     

Yb3+掺杂KY(WO4)2激光晶体生长、结构与光谱分析

采用顶部籽晶提拉法(TSSG)生长出Yb:KY(WO₄)₂(Yb:KYW)激光晶体.对预烧后的原料及晶体进行了XRD分析，结果表明，分别在920℃和600℃预烧8h后的熔质和助熔剂基本上形成一相，抑止了实验中的挥发问题；所生长的晶体为β-Yb:KYW，计算其晶格常数为a=1.063nm，b=1.034nm，c=0.755nm，β=130.75°.测得不同厚度样品的吸收光谱，结果表明样品在933nm和981nm有较强的吸收峰，计算出主峰981nm的吸收截面σ关键词： Yb:KYW TSSG法 晶体结构 光谱参数     

Experimental optimum design and luminescence properties of NaY(Gd)(MoO_4)_2:Er~(3+)phosphors

Three-factor orthogonal design(OD) of Er~(3+)/Gd~(3+)/T(calcination temperature) is used to optimize the luminescent intensity of Na Y(Gd)(MoO_4)_2:Er~(3+)phosphor.Firstly,the uniform design(UD) is introduced to explore the doping concentration range of Er~(3+)/Gd~(3+).Then OD and range analysis are performed based on the results of UD to obtain the primary and secondary sequence and the best combination of Er~(3+),Gd~(3+),and T within the experimental range.The optimum sample is prepared by the high temperature solid state method.Photoluminescence excitation and emission spectra of the optimum sample are detected.The intense green emissions(530 nm and 550 nm) are observed which originate from Er~(3+)~2H_(11/2)→~4I_(15/2)and~4S_(3/2)→~4I_(15/2),respectively.Thermal effect is investigated in the optimum NaY(Gd~(3+))(MoO_4)_2:Er~(3+)phosphors,and the green emission intensity decreases as temperature increases.     

Passively Q-switched self-frequency doubling Nd~(3+):ReCa_4O(BO_3)_3(Re=Y,Gd) lasers with tin diselenide as a saturable absorber

With tin diselenide(SnSe_2) film as a saturable absorber(SA), the passively Q-switched self-frequency doubling(SFD) lasers were realized in Nd~(3+):ReCa_4O(BO_3)_3(Re = Y, Gd) crystals. For Nd:YCa_4O(BO_3)_3 crystal, the maximum average output power at 532 nm was 19.6 mW, and the corresponding pulse repetition frequency, pulse duration, single pulse energy, and peak power were 17.6 kHz, 91.9 ns, 1.1 μJ, and 12.1 W, respectively. For Nd:GdCa_4 O(BO_3)_3 crystal, these values were 14.5 mW, 22.1 kHz, 48.7 ns, 0.66 μJ, and 13.5 W.     

Shaped crystal growth and scintillating properties of Yb:(Gd,Lu)3Ga5O12 solid solutions

Shaped single crystals of (Lu_xGd_1−x)₃Ga₅O₁₂ (0.0x1.0) and (Yb_0.05Lu_xGd_0.95−x)₃Ga₅O₁₂ (0.0x0.9) were grown by the modified micro-pulling-down method. Continuous solid solutions with garnet structure and a linear compositional dependency of crystal lattice parameter in the system Yb:(Gd,Lu)₃Ga₅O₁₂ are formed. Measured optical absorption spectra of the samples show 4f–4f transitions related to Gd³⁺ ion at 275 and 310 nm, and also an onset of charge transfer transitions from oxygen ligands to Gd³⁺ or Yb³⁺ cations below 240 nm. A complete absence of Yb³⁺ charge transfer luminescence under X-ray excitation in any of the investigated samples was explained by the overlapping of charge transfer absorption of Yb³⁺ by that of Gd³⁺ ions. For specific composition of Lu_1.5Gd_1.5Ga₅O₁₂ an intense defect-host lattice-related emission, which achieve of about 40% integrated intensity compared with Bi₄Ge₃O₁₂, was found.     

Raman spectrum of decrespignyite [(Y,REE)4Cu(CO3)4Cl(OH)5·2H2O] and its relation with those of other halogenated carbonates including bastnasite,hydroxybastnasite, parisite and northupite

Raman spectroscopy complemented with infrared spectroscopy has been used to study the rare‐earth‐based mineral decrespignyite [(Y,REE)₄Cu(CO₃)₄Cl(OH)₅· 2H₂O] and the spectrum compared with the Raman spectra of a series of selected natural halogenated carbonates from different origins including bastnasite, parisite and northupite. The Raman spectrum of decrespignyite displays three bands at 1056, 1070 and 1088 cm⁻¹ attributed to the CO₃²⁻ symmetric stretching vibration. The observation of three symmetric stretching vibrations is very unusual. The position of the CO₃²⁻ symmetric stretching vibration varies with the mineral composition. The Raman spectrum of decrespignyite shows bands at 1391, 1414, 1489 and 1547 cm⁻¹, whereas the Raman spectra of bastnasite, parisite and northupite show a single band at 1433, 1420 and 1554 cm⁻¹, respectively, assigned to the ν₃ (CO₃)²⁻ antisymmetric stretching mode. The observation of additional Raman bands for the ν₃ modes for some halogenated carbonates is significant in that it shows distortion of the carbonate anion in the mineral structure. Four Raman bands are observed at 791, 815, 837 and 849 cm⁻¹, which are assigned to the (CO₃)²⁻ν₂ bending modes. Raman bands are observed for decrespignyite at 694, 718 and 746 cm⁻¹ and are assigned to the (CO₃)²⁻ν₄ bending modes. Raman bands are observed for the carbonate ν₄ in‐phase bending modes at 722 cm⁻¹ for bastnasite, 736 and 684 cm⁻¹ for parisite and 714 cm⁻¹ for northupite. Multiple bands are observed in the OH stretching region for decrespignyite, bastnasite and parisite, indicating the presence of water and OH units in the mineral structure. Copyright © 2011 John Wiley & Sons, Ltd.     

Synthesis,structural study and thermal behaviour of a new compound: trirubidium bis(hydrogen sulphate) dihydrogen arsenate Rb3(HSO4)2.5(H2AsO4)0.5

Mixed crystals Rb₃(HSO₄)_2.5(H₂AsO₄)_0.5 have been prepared by slow evaporation from aqueous solution at room temperature. The crystals were characterized by X-ray single analysis, which revealed that Rb₃(HSO₄)_2.5(H₂AsO₄)_0.5 crystallizes in the space group P with lattice parameters: a = 7.471(3) Å; b = 7.636(1) Å; c = 12.193(2) Å; α = 71.91(1)°; β = 73.04(6)° and γ = 88.77(2)°. In this structure, the ordered S(1)O₄ and the disordered S(3)/AsO₄ tetrahedra are connected by O–H..O hydrogen bonds, to a zigzag chains running in the b-direction. These chains are, in turn, bonded to one another by disordered hydrogen bridges O–H..H–O, to give a planar structure, with hydrogen-bonded sheets, laying parallel to (1 0 0). Each disordered tetrahedron is linked to a tetrahedron neighbouring S(2)O₄ by ordered hydrogen bonds. Broader peaks in IR spectrum of the title material support the assumption of disordered structure. Thermal analysis of the superprotonic transition in Rb₃(HSO₄)_2.5(H₂AsO₄)_0.5 showed that the transformation to the high-temperature phase occurs by one-step process at 404 K. Thermal decomposition of this compound takes place at much higher temperatures, with an onset of approximately 473 K.     

Method for fitting crystal field parameters and the energy level fitting for Yb3+ in crystal Sc2O3

<正>A method to compute the numerical derivative of eigenvalues of parameterized crystal field Hamiltonian matrix is given,based on the numerical derivatives the general iteration methods such as Levenberg-Marquardt,Newton method, and so on,can be used to solve crystal field parameters by fitting to experimental energy levels.With the numerical eigenvalue derivative,a detailed iteration algorithm to compute crystal field parameters by fitting experimental energy levels has also been described.This method is used to compute the crystal parameters of Yb~(3+) in Sc_2O_3 crystal, which is prepared by a co-precipitation method and whose structure was refined by Rietveld method.By fitting on the parameters of a simple overlap model of crystal field,the results show that the new method can fit the crystal field energy splitting with fast convergence and good stability.     

Two potassium rare-earth polyphosphates KLn(PO3)4 (Ln=Ce, Eu): Structural, optical, and electronic properties

Two potassium rare-earth polyphosphate single-crystals KLn(PO₃)₄ (Ln=Ce (1), Eu (2)) have been synthesized by the high-temperature solution reaction and characterized by single-crystal X-ray diffraction. The two isostructural compounds crystallize in the monoclinic system with space group P2₁, and all cell parameters shrink with the decrease of Ln³⁺ ion radius. The main structural feature is (PO₃)₄⁴⁻ wavy chains and infinite tunnels delimited by LnO₈ and KO₈ polyhedra. The energy band structures, density of states (DOS), and optical response functions for 1 have been calculated with the density functional theory (DFT) method, and the dielectric functions and refractive indices have been discussed. The measurements of the absorption and emission spectra show that 1 exhibits the ultraviolet emissions, and 2 displays the characteristic yellow-red emissions of Eu³⁺.