共沉淀法制备Y2SiO5∶Er3+ ,Yb3+ ,Tm3+及其上转换发光性能研究

采用化学共沉淀法制备了系列Y_1.98-2xYb_2x Er_0.02SiO₅(0.00≤x≤0.15)以及Y_1.736Yb_0.24Er_0.02Tm_0.004SiO₅上转换发光材料,比较了室温下Y_1.98-2xYb_2x Er_0.02 SiO₅ (x=0.00,0.08)样品在400—1600 nm范围内的吸收光谱,测量了所有样品在976 nm OPO激光器激发下的上转换发射光谱,以及Er³⁺离子⁴S_3/2(⁴F_9/2)→⁴I_15/2,Tm³⁺离子¹G₄→³H₆荧光衰减曲线和不同激发功率下的上转换蓝光发射强度,从而分析讨论了Er³⁺,Tm³⁺在Y₂SiO₅中的上转换发光机理.研究结果表明:在1250 ℃相对较低的温度下合成了X2型单斜晶系Y₂SiO₅ ∶Ln³⁺(Ln³⁺=Er³⁺,Yb³⁺,Tm³⁺),Yb³⁺的敏化显著增强了样品在976 nm附近的吸收能力,并大幅度加宽了该处的吸收带.分析上转换发射光谱发现:上转换绿光和红光强度都随着Yb³⁺浓度的增加先增强后减弱,但红光的猝灭浓度较高,归因于Er³⁺→Yb³⁺反向能量传递ETU4和Yb³⁺→Er³⁺正向能量传递ETU3过程的发生;上转换蓝光发射是三光子吸收过程,是通过Yb³⁺,Tm³⁺之间三次声子辅助的能量转移方式实现的. 关键词： 上转换 共沉淀 2SiO₅∶Er³⁺')" href="#">Y₂SiO₅∶Er³⁺ 3+')" href="#">Yb³⁺ 3+')" href="#">Tm³⁺     

Photoluminescence of sol–gel-derived Y<Subscript>2</Subscript>O<Subscript>3</Subscript>:Eu<Superscript>3+</Superscript> thin-film phosphors with Mg<Superscript>2+</Superscript> and Al<Superscript>3+</Superscript> co-doping

Red-light-emitting Y₂O₃:Eu³⁺ thin-film phosphors were synthesized using a sol–gel process. The effect of Mg²⁺ and Al³⁺ co-dopants on the Y₂O₃:Eu³⁺ thin-film phosphor photoluminescence (PL) property was investigated. At a certain concentration, both Mg²⁺ and Al³⁺ co-dopants were found to further enhance the PL emission intensity of Y₂O₃:Eu³⁺ thin-film phosphors. The optimum PL emission intensity was observed in Y₂O₃:12%Eu³⁺, 7%Mg²⁺ and Y₂O₃:12%Eu³⁺, 2%Al³⁺ phosphor films. From our results, the enhancement of the emission intensity by the Mg²⁺ and Al³⁺ co-dopants is explained in terms of the creation of defect states near the Y(4d+5s) conduction band, which overlap with the Eu³⁺ charge-transfer state (CTS). The overlapping leads to CTS broadening and consequently induces higher absorption and hence an increase of the emission intensity. From X-ray diffraction results, we have found that there is no additional phase formed in the co-doped phosphor films. PACS 68.55.Ln; 78.55.-m; 81.20.Fw     

Optical study of single crystals grown by the Czochralski method from Yb3+-doped (Gd1−x Y x )2SiO5 solid solution

Yb³⁺-doped crystals were grown by the Czochralski method from (Gd_0.5Y_0.5)₂SiO₅ melt employing seeds cut out from single crystals of Yb:Gd₂SiO₅ and Yb:Y₂SiO₅. XRD analysis revealed that the structure of the solid solution crystals grown is consistent with the structure of the seed, namely C2/c for the Yb:Y₂SiO₅ seed and P2₁/c for the Yb:Gd₂SiO₅ seed. Optical absorption spectra, emission spectra and luminescence decay curves were recorded at 10 K and 300 K. Analysis of gathered spectroscopic data made it possible to evaluate radiative transition rates for the ²F_5/2 multiplet of Yb³⁺ in the two structures and to assess crystal field splitting of multiplets involved in radiative transitions. It has been concluded that transition intensities and relaxation dynamics of Yb³⁺ in the systems studied are similar but the intensity distribution of emission and absorption bands depends significantly on the system structure. This feature, combined with inhomogeneous broadening of spectral lines, may be advantageous for the tailoring of lasers employing ytterbium-doped crystals for specific applications.     

UV excitable Y2? x ? y Gd y SiO5:Ce x phosphors for cool white light emission

Cool white light was realized in Y_2−x−y Gd _x SiO₅: Ce _y phosphor under near UV excitation, due to the occupation Ce³⁺ in Y³⁺ 1st and 2nd site, synthesized using solid state carbothermal reduction route. SEM with elemental analysis show the existence of Gd in Y₂SiO₅:Ce enhances the particles size in comparison to Y₂SiO₅:Ce phosphors alone. Gd³⁺ (0.00≤x≤0.75) and Ce³⁺ (0.02≤y≤0.10) concentration was optimized to 0.50 and 0.08 in Y₂SiO₅, respectively. The CIE chromaticity color coordinates (0.24, 0.20) are close to cool white light value which could be useful for the fabrication of cool white LED.     

Ionic conductivity of Li4−2xMgxSiO4

Solid solutions Li_4−2xMg_xSiO₄ in the system Li₄SiO₄Mg₂SiO₄ were prepared at 1000°C. The single phase region extended up to x=0.5. The conductivity is much higher than that of the end member Li₄SiO₄, and passes through a maximum at Li_3.2Mg_0.4SiO₄ with values of 2.3 × 10⁻⁵ S cm⁻¹ at 200°C, rising to 1.5 × 10⁻² S cm⁻¹ at 400°C. The solid solutions are easy to prepare, are stable in air, and retain their conductivity over a long period of time.     

Excited state absorption and stimulated emission of Nd3+ in crystals. Part I: Y3Al5O12, YAlO3, and Y2O3

4 F_3/2 excited state of the Nd³⁺ ion in Y₃Al₅O₁₂, YAlO₃, and Y₂O₃ were measured in a continuous wave pump- and probe experiment in a wide spectral range from 850 nm (780 nm for Y₃Al₅O₁₂) to 1500 nm. The cross sections were determined from a comparison with the emission spectra and the simultaneously measured ground state absorption bleaching. The strongest excited state absorption transitions were found in the 1220–1400 nm spectral region due to transitions to the ²G_9/2 and ⁴G_7/2 levels. The spectral positions of the measured transitions are in good agreement with the theoretically expected transitions calculated from the known Stark-level splittings. Received: 4 December 1997/Revised version: 8 May 1998     

The nature of activation centers in Y2SiO5:Pr3+, Gd2SiO5:Pr3+, and Lu2SiO5:Pr3+ crystals

A complex study of the energy spectra and relaxation channels for the excitation energy of activation centers in Y₂SiO₅:Pr³⁺, Lu₂SiO₅:Pr³⁺, and Gd₂SiO₅:Pr³⁺ was performed. An analysis of the low-temperature optical spectra showed that the energy parameters and the character of field splitting of the ¹ D ₂ and ³ H ₄ activator ion terms were substantially different in crystals of different crystallographic types. The pseudosymmetry effect was observed in splitting of the ¹ D ₂ and ³ H ₄ terms of Pr³⁺ ions situated in nonequivalent crystal lattice cation sites of Y₂SiO₅ and Lu₂SiO₅. Activator ions nonuniformly populated nonequivalent cation sites of the Y₂SiO₅ crystal lattice. At high activator ion concentrations (>1 at %), luminescence decay in Y₂SiO₅ could not be described by a simple exponential time dependence. The complex luminescence decay law was caused by activator ion excitation energy migration and capture by acceptors. The role of energy acceptors was played by activator ion dimers.     

Ultraviolet upconversion in Pr3+:Y2SiO5 crystal by Ar+ laser (488 nm) excitation

Ultraviolet upconversion fluorescence band (260–350 nm) has been observed from Pr³⁺:Y₂SiO₅ pumped by Ar⁺ ion laser (488 nm). Power dependence of the fluorescence emitted from 4f5d, ³P₀ and ¹D₂ were measured. The upconversion mechanism was analyzed using the rate equations with a simplified three level model. It appears that excited state absorption (ESA) is the dominant upconversion process for lower Pr³⁺ concentration and energy transfer upconversion (ETU) is dominant for higher Pr³⁺ concentration.     

Luminescence centers in yttrium silicate and germanate

Luminescence spectra for isostructural Y₂SiO₅ and Y₂GeO₅ are investigated. The spectra are resolved into elementary components by the Alentsev—Fock method. Bands with maxima in regions of 2.6, 2.3, and 2.05 eV in the spectra of Y₂SiO₅ luminescence and in regions of 2.55, 2.25, and 2.0 eV in the spectra of Y₂GeO₅ luminescence are considered as radiative recombination of excited associative donor-acceptor Y³⁺−O²⁻ pairs. The indicated bands are related to certain distances between yttrium (the donor) and oxygen (the acceptor). A band with a maximum of 2.95 eV in Y₂SiO₅ and 3.0 eV in Y₂GeO₅ occurs in recombination of electrons with holes trapped by an anionic sublattice. I. Franko L’vov State University, 50, Dragomanov St., L’vov, 290005, Ukraine. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 65, No. 4, pp. 528–531, July–August, 1998.     

White light-emitting Mg0.1Sr1.9SiO4:Eu phosphors

Divalent europium-activated strontium orthosilicate Sr₂SiO₄:Eu²⁺ and Mg_0.1Sr_1.9SiO₄:Eu²⁺ phosphors were synthesized through the solid-state reaction technique. Their luminescent properties under ultraviolet excitation were investigated. The X-ray diffraction (XRD) results show that these phosphors are of α′-Sr₂SiO₄ phase with a trace of β-Sr₂SiO₄. Doping of Eu²⁺ ion into the crystal lattice results in the lattice constant being expended, while Mg²⁺ makes the lattice constant shrinking. A solid solution with the same crystal structure is formed when Eu²⁺ or Mg²⁺ substitutes part of Sr²⁺ ions and occupies the same lattice sites. The Sr₂SiO₄:Eu²⁺ phosphors show two emission spectra peaked at 535 and 473 nm originated from the 5d-4f transition of Eu²⁺ ion doped in two different Sr²⁺ sites in the host lattice. By substitution of 0.1 mol of Sr²⁺ with Mg²⁺, these two emission bands are tuned to be in the blue and yellow region (459 and 564 nm for Mg_0.1Sr_1.88SiO₄:Eu_0.02), respectively. The tuning effect is discussed. With a combination of the blue and yellow emission bands the phosphors show white color, indicating that these phosphors may become promising phosphor candidates for white light-emitting diodes (LEDs).     

Effect of high-energy electron irradiation on forsterite laser crystals

The effect of 21-MeV electron irradiation on the optical absorption characteristics of Czochralski-grown forsterite (Mg₂SiO₄) single crystals (both undoped and chromium-doped) has been investigated. The irradiation is found to induce additional optical absorption (AOA) in the crystals in the range of 225–1200 nm due to the formation of color centers based on intrinsic host point defects and the change in the oxidation state of chromium ions. The AOA spectra have been decomposed into elementary bands. The influence of the chromium concentration in crystals, the oxygen content in the growth atmosphere, and additional doping with lithium on the behavior of these bands has been analyzed. A possible structure of the color centers responsible for the AOA is discussed. It is shown that the electron irradiation somewhat decreases the intensity of the characteristic absorption bands of tri- and tetravalent chromium ions and gives rise to a new absorption band in Mg₂SiO₄:Cr and Mg₂SiO₄:Cr,Li crystals heavily doped with chromium.     

Synthesis and photoluminescence of Eu- or Tb-doped Mg2SiO4 nanoparticles prepared by a combined novel approach

Tb³⁺- or Eu³⁺-doped magnesium silicate phosphors were prepared for the first time by using a novel approach, combined sol-gel-microwave heating. X-ray diffraction (XRD), transmission electron microscope (TEM), thermogravimetric analysis (TGA) and photoluminescence analyses were used to characterize the phosphors. XRD confirmed a forsterite lattice of Mg₂SiO₄ for the phosphors. TEM observation indicated that the phosphors have a spherical-like shape with little aggregation and the particle size is about 50 nm, and the small size is favorable to the potential application in field emission displays. The luminescent colors of Mg₂SiO₄:Tb³⁺ and Mg₂SiO₄:Eu³⁺ phosphors are green and red respectively, furthermore the luminescent intensities of them are relatively higher than the traditional Zn₂SiO₄:Tb³⁺ and Zn₂SiO₄:Eu³⁺ phosphors. In addition, Eu³⁺ ion emissions as a structural probe suggest that the rare earth ions replace the Mg²⁺ ions in the site of M2 (C_s) in the forsterite lattice of Mg₂SiO₄.     

Photoluminescence and excited state structure in Bi3+-doped Y2SiO5 single crystalline films

Single crystalline films of Bi-doped Y₂SiO₅ are studied at 4.2–350 K by the time-resolved luminescence methods under excitation in the 3.8–6.2 eV energy range. Ultraviolet luminescence of Y₂SiO₅:Bi (≈3.6 eV) is shown to arise from the radiative decay of the metastable and radiative minima of the triplet relaxed excited state (RES) of Bi³⁺ centers which are related to the ³P₀ and ³P₁ levels of a free Bi³⁺ ion, respectively. The lowest-energy excitation band of this emission, located at ≈4.5 eV, is assigned to the ¹S₀ → ³P₁ transitions of a free Bi³⁺ ion. The phenomenological model is proposed to describe the excited-state dynamics of Bi³⁺ centers in Y₂SiO₅:Bi, and parameters of the triplet RES are determined.     

Effect of Mg and Ti doping on the luminescence of Y2O3:Eu

The Y₂O₃:Eu³⁺,Mg²⁺,Ti^IV materials (x_Eu: 0.02, x_Mg: 0.08, x_Ti: 0.04) were prepared by solid state reaction. The purity and crystal structure of the material was studied with the X-ray powder diffraction. Luminescence properties were studied in the UV-VUV range with the aid of synchrotron radiation. The emission of Y₂O₃:Eu³⁺,Mg²⁺,Ti^IV had a maximum at 612 nm (λ_exc: 250 nm) due to the ⁵D₀→⁷F₂ transition of Eu³⁺. The excitation spectra (λ_em: 612 nm) showed a broad band at 233 nm, due to the charge transfer transition between O²⁻ and Eu³⁺, and at 297 nm due to the Ti→Eu³⁺ energy transfer. Only very weak persistent luminescence was discovered. In the room and 10 K temperature excitation spectra, the line at 208 nm is due to the formation of a free exciton (FE) and a broad band at 199 nm was related to the valence-to-conduction band absorption of the Y₂O₃ host lattice. The absorption edge was ca. 205 nm giving 6.1 eV as the energy gap of Y₂O₃.     

Raman spectroscopic investigation of pure and ytterbium‐doped rare earth silicate crystals

Raman spectroscopy was used to study the molecular structure of a series of selected rare earth (RE) silicate crystals including Y₂SiO₅ (YSO), Lu₂SiO₅ (LSO), (Lu_0.5Y_0.5)₂SiO₅ (LYSO) and their ytterbium‐doped samples. Raman spectra show resolved bands below 500 cm⁻¹ region assigned to the modes of SiO₄ and oxygen vibrations. Multiple bands indicate the nonequivalence of the RE O bonds and the lifting of the degeneracy of the RE ion vibration. Low intensity bands below 500 cm⁻¹ are an indication of impurities. The (SiO₄)⁴⁻ tetrahedra are characterized by bands near 200 cm⁻¹ which show a separation of the components of ν₄ and ν₂, in the 500–700 cm⁻¹ region which are attributed to the distorting bending vibration and in the 880–1000 cm⁻¹ region which are attributed to the symmetric and antisymmetric stretching vibrational modes. The majority of the bands in the 300–610 cm⁻¹ region of Re₂SiO₅ were found to arise from vibrations involving both Si and RE ions, indicating that there is considerable mixing of Si displacements with Si O bending modes and RE O stretching modes. The Raman spectra of RE silicate crystals were analyzed in terms of the molecular structure of the crystals, which enabled separation of the bands attributed to distinct vibrational units. Copyright © 2007 John Wiley & Sons, Ltd.     

Rescaling of 2D ESEEM Data as a Tool for Inverse Problem Solving

A rescaling procedure is proposed for electron spin echo envelope modulation spectra observed at several electron paramagnetic resonance transitions. Analytical expressions describing the relations between the rescaled frequencies and hyperfine and quadrupole parameters of the remote nucleus are obtained. The dependences of the rescaled data on the external magnetic field and spin projections of the ion nucleus and the remote nuclei are used to derive the parameters of the nuclear state in the crystals Y₂SiO₅ and YVO₄ doped by ion Nd³⁺.     

Synthesis, microstructure and photoluminescence of Eu/Tb activated Y2SiO5 nanophosphors by new silicate sources

Y_2−xTb_xSiO₅ and Y_2−xEu_xSiO₅ nanophosphors with seven different kinds of silicate sources were synthesized by sol-gel method. The structures have been investigated to be composed of nanometer-size grains of 30-60 nm through X-ray diffraction (XRD) and scanning electron microscopy (SEM) was used to compare the different morphology of patterns from seven different silicon sources. The photoluminescence of Y_2−xTb_xSiO₅ was investigated as a function of silicate sources and the results revealed that these nanometer materials showed the characteristic emission ⁵D₄ → ⁷F_J (J = 6, 5, 4, 3) of Tb ions. The characteristic emission ⁵D₀ → ⁷F_J (J = 1, 2, 4) of Eu ions was also found in the materials of Y_2−xEu_xSiO₅.     

Strong segregation of doped ions in Y2SiO5:Pr3+ nanocrystals

Strong temperature controlled segregation of doped ions in Y₂SiO₅:Pr³⁺ nanocrystals detected by spectroscopic techniques is reported. The elastic interactions stimulate Pr³⁺ segregation thus leading to non-uniform distribution of doped ions, pair formation and, as a consequence, to abnormal low threshold of luminescence concentration quenching for Y₂SiO₅:Pr³⁺ nanocrystals.     

Interaction of impurity and intrinsic defects in forsterite and its role in the formation of spectral and luminescence properties

This paper reports on the results of investigations of the coefficients of chromium distribution between a crystal and a melt of forsterite, the absorption and luminescence spectra, and the electron paramagnetic resonance spectra of chromium centers in Mg₂SiO₄: Cr, Mg₂SiO₄: Cr: Sc, and Mg₂SiO₄: Cr: Li crystals. It has been established that the concentration dependences of these properties vary upon changing over from the range of trace concentrations of chromium, scandium, or lithium impurities in the melt to the range of higher concentrations of these impurities. The observed phenomenon is explained by the interaction of impurities with intrinsic defects of the crystal, which is called as the microimpurity trapping effect. According to the performed estimations, the concentration of predominant intrinsic defects (magnesium Frenkel defects) in the forsterite crystals grown from the melt is equal to (7.5 ± 0.3) × 10⁻⁶ atomic fractions. The energy of the formation of magnesium Frenkel defects can be estimated as 4.2 ± 0.2 eV.     

Enhanced photoluminescence properties of Zn2SiO4:Mn co-activated with Y/Li under VUV excitation

A series of green phosphors Zn_1.92−2xY_xLi_xSiO₄:0.08Mn²⁺ (0≤x≤0.03) were prepared by solid-state synthesis method. Phase and lattice parameters of the synthesized phosphors were characterized by powder X-ray diffractometer (XRD) and the co-doped effects of Y³⁺/Li⁺ upon emission intensity and decay time were investigated under 147 nm excitation. The results indicate that the co-doping of Y³⁺/Li⁺ has favorable influence on the photoluminescence properties of Zn₂SiO₄:Mn²⁺, and the optimal photoluminescence intensity of Zn_1.90Y_0.01Li_0.01SiO₄:0.08Mn²⁺ is 103% of that of commercial phosphor when the doping concentration of Y³⁺/Li⁺ is 0.01 mol. Additionally, the decay time of phosphor is much shortened and the decay time of Zn_1.90Y_0.01Li_0.01SiO₄:0.08Mn²⁺ is 3.39 ms, shorter by 1.83 ms than that of commercial product after Y³⁺/Li⁺ co-doping.