Sol-gel synthesis and photoluminescence of CaSiO3:Eu nanophosphors using novel silicate sources

In this paper, seven kinds of silane coupling reagents were employed as silicate sources to prepare CaSiO₃:Eu³⁺ phosphors by the sol-gel method. The different silicate precursors were used to adjust the microstructure and size of the resulting phosphors. The crystallite size of phosphors is in the range of 30-35 nm and some of them show regular microstructure after high-temperature thermolysis. The photoluminescence properties show that all of them exhibit the characteristic fluorescence ⁵D₀→⁷F_J (J=0, 1, 2, 3, 4) of the Eu³⁺ ion and the strongest one is the red emission at 610 nm. Furthermore, the emission quantum efficiency (η) of the ⁵D₀ Eu³⁺ excited state has been calculated to be around 33% from the emission spectrum and the lifetime of the Eu³⁺ first excited level (τ, ⁵D₀).     

Comparative structural and photoluminescent study of Eu-doped La2O3 and La(OH)3 nanocrystalline powders

Eu³⁺-doped La₂O₃ nanocrystalline powder was prepared by polymer complex solution method and further used for preparation of Eu³⁺-doped La(OH)₃. Structural and optical characterization was carried out by powder X-ray diffraction and photoluminescent spectroscopy. XRD measurements confirmed the formation of hexagonal La₂O₃ and its recrystallization into La(OH)₃ in a humid atmosphere. Excitation spectra show redshift of host lattice and charge transfer emission bands in La(OH)₃ while bands that correspond to Eu³⁺f–f transitions are placed at same wavelengths in both samples. Photoluminescence spectra recorded over the temperature range from 10 K to 300 K show that intensities of emission lines in Eu³⁺-doped La₂O₃ do not depend on temperature as much as in La(OH)₃ sample. Observed dominant ⁵D₀→⁷F₂ and markedly visible ⁵D₀→⁷F₀ emissions in doped La₂O₃ indicate that Eu³⁺ ion is located in a structural site without an inversion center. On the other hand, in Eu³⁺-doped La(OH)₃⁵D₀→⁷F₀ transition is barely visible while ⁵D₀→⁷F₂ is not prominent, and with temperature drop three ⁵D₀→⁷F_J (J=1, 2, 4) transitions become almost of the same intensity. In both La₂O₃ and La(OH)₃ structures Eu³⁺ ion replaces La³⁺ in non-centrosymmetric C_3v and C_3h crystallographic sites, respectively, and difference in symmetry of the crystal field around europium ion is explained by comparing shape and volume of these sites. Decay times of the ⁵D₀- level recorded over the temperature range 10−300 K revealed that emission lifetime values in La₂O₃ (~0.7 ms) are almost two times higher than in La(OH)₃ (~0.4 ms), and unlike in La₂O₃, lifetime in La(OH)₃ is temperature dependent.     

Spectroscopic and magnetic susceptibility analyses of the FJ and D4 energy levels of Tb(4f) in TbAlO3

Detailed analyses of spectroscopic and temperature-dependent magnetic susceptibility data are reported for the crystal-field split energy levels of the ⁷F_J and ⁵D₄ of Tb³⁺ in stoichiometric single crystals of ortho-aluminate TbAlO₃. The spectroscopic data include absorption spectra obtained between 2940 and 480 nm from 8 to 300 K. High resolution fluorescence spectra are reported, representing transitions from ⁵D₄ to ⁷F_6,5,4, at a sample temperature of 85 K. Using crystal-field modeling techniques recently adapted for low symmetry systems, we have assigned all 58 experimental Stark levels within the ⁷F_J and ⁵D₄ manifolds, with a fitting standard deviation of 4.5 cm⁻¹ (3.8 cm⁻¹ rms error). As a further test, the theoretical Stark levels and calculated wavefunctions were used to determine the temperature dependence of the magnetic susceptibility along the c-axis of the TbAlO₃ crystal. Good agreement is obtained between the calculated susceptibility and temperature-dependent magnetic data reported earlier, including a prediction of a 0.2 cm⁻¹ splitting of the ground-state quasi-doublet. The susceptibility calculation also confirms the predicted ordering of states within the ⁷F₆ multiplet manifold.     

Emission analysis of Tb:MgAl2O4 powder phosphor

This paper reports the emission analysis of green-emitting Tb³⁺-doped MgAl₂O₄ phosphors. Uniformity of the phase of the Tb³⁺-doped MgAl₂O₄ phosphor has been checked by X-ray diffraction (XRD) technique and show common bands existing in the results of Fourier transform infrared (FT-IR). This phosphor exhibits weak blue, orange emissions and a strong emission at λ_exci=350 nm. The blue and green-orange emissions are ascribed to ⁵D₃→⁷F_J and ⁵D₄→⁷F_J (where J=3-6) transitions of Tb³⁺ ions, respectively. These phosphors have shown a strong, more prominent green emission from ⁵D₄→⁷F₅ at 543 nm. The results have indicated that MgAl₂O₄:Tb³⁺ could be a potential candidate as agreen-emitting powder phosphor.     

Luminescence properties of novel NaBa4(BO3)3:Ce, Eu phosphors

Novel Eu³⁺, Ce³⁺ activated NaBa₄(BO₃)₃ phosphors were synthesized by solid-state reactions. The excitation spectrum of NaBa₄(BO₃)₃:Ce³⁺ consists of an intense band peaking at 350 nm and a weak band in the higher energy side, and the emission spectrum exhibits a blue band with a maximum at about 420 nm. The Eu³⁺ emission in NaBa₄(BO₃)₃ consists of the transitions from ⁵D₀ to ⁷F_J, and the excitation spectrum consists of broad excitation band peaking at 270 nm and some intense narrow lines. The optimum doped concentration, the critical distance of the concentration quenching, and the fluorescence lifetime have also been investigated.     

Green emission from Tb-doped SrSi2O2N2 phosphors under ultraviolet light irradiation

Tb-doped SrSi₂O₂N₂ phosphors with promising luminescent properties were synthesized by the conventional solid-state reaction method, characterized by powder X-ray diffraction and studied by photoluminescence excitation and emission spectra. The synthesized materials exhibited a weak blue emission and a strong green emission in the region of 400-470 nm and 480-650 nm, which are attributed to ⁵D₃→⁷F_j (j=5, 4, 3) and ⁵D₄→⁷F_j (j=6, 5, 4, 3) transitions of Tb³⁺, respectively. The green emission from ⁵D₄→⁷F₅ at 543 nm showed the highest intensity under the optimized concentration of 0.1 mol, after which the quenching concentration became relevant. The quenching behavior of the emission of Tb³⁺ was explained by the cross-relaxation of its excited state.     

LnP5O14晶体中Tb3+和Eu3+的发光光谱特性

本工作测量了室温下TbP₃O₁₄和EuP₅O₁₄晶体的吸收和发射光谱。根据吸收光谱和Judd-Ofelt理论计算了Tb³⁺和Eu³⁺的实验和理论的振子强度。用最小二乘法拟合实验与理论的振子强度得到唯象强度参量Ω_λ。然后计算了Tb³⁺的⁵D₃→⁷F₅,⁵D₄→⁷F₄和⁵D₄→⁷F₆以及Eu³⁺的⁵D₀→⁷F₂,⁵D₀→⁷F₄的跃迁几率和寿命。同时用时间分辨光谱测量了不同温度下相应的荧光辐射寿命。计算与实验结果基本相符。理论和实验的结果表明Tb³⁺的⁵D₃态的寿命主要取决于⁵D₃→⁵D₄和⁷F₆→⁷F₀两能级对之间的电偶极-电偶极交叉弛豫。 关键词：     

Synthesis and luminescence investigation of RE (Eu, Tb and Ce)-doped lithium silicate (Li2SiO3)

Synthesis and photoluminescence (PL) investigations of lithium metasilicate doped with Eu³⁺, Tb³⁺ and Ce³⁺ were carried out. PL spectra of Eu-doped sample showed peaks corresponding to the ⁵D₀→⁷F_j (j=1, 2, 3 and 4) transitions under ultraviolet excitation. Strong red emission coming from the hypersensitive ⁵D₀→⁷F₂ transition of Eu³⁺ ion suggested the presence of the dopant ion in structurally disordered environment. Tb³⁺-doped silicate sample showed blue-green emission corresponding to the ⁵D₄→⁷F_j (j=6, 5 and 4) transitions. Ce-doped sample under excitation from UV, showed a broad emission band in the region 350-370 nm with shoulders around 410 nm. The fluorescence lifetimes of Eu³⁺ and Tb³⁺ ions were found out to be 790 and 600 μs, respectively. For Ce³⁺, the lifetime was of the order of 45 ns. PL spectra of the europium- and terbium-doped samples were compared with commercial red (Y₂O₃:Eu³⁺) and green (LaPO₄:Tb³⁺) phosphors, respectively. It was found that the emission from the doped silicate sample was 37% of the commercial phosphor in case of the Tb-doped sample and 8% of the commercial phosphor in case of the Eu-doped sample.     

Spectra, energy levels, and symmetry assignments for Stark components of Eu(4f) in gadolinium gallium garnet (Gd3Ga5O12)

Absorption and fluorescence spectra observed between 450 and 750 nm at 85 K and room temperature (300 K) are reported for Eu³⁺(4f⁶) in single-crystal Czochralski-grown garnet, Gd₃Ga₅O₁₂ (GGG). The spectra represent transitions between the ^2S+1L_J multiplets of the 4f⁶ electronic configuration of Eu³⁺ split by the crystal field of the garnet. In absorption, Eu³⁺ transitions are observed from the ground state, ⁷F₀, and the first excited multiplet, ⁷F₁, to multiplet manifolds ⁵D₀, ⁵D₁, and ⁵D₂. The Stark splitting of the ⁷F_J multiplets (J=0-6) was determined by analyzing the fluorescence transitions from ⁵D₀, ⁵D₁, and ⁵D₂ to ⁷F_J. The Eu³⁺ ions replace Gd³⁺ ions in sites of D₂ symmetry in the lattice during crystal growth. Associated with each multiplet manifold are 2J+1 non-degenerate Stark levels characterized by one of four possible irreducible representations (irreps) assigned by an algorithm based on the selection rules for electric-dipole (ED) and magnetic-dipole (MD) transitions between Stark levels in D₂ symmetry. The quasi-doublet in ⁵D₁ was characterized by an analysis of the magneto-optical spectra obtained from the transitions observed between ⁵D₁ and ⁷F₁. A parameterized Hamiltonian defined to operate within the entire 4f⁶ electronic configuration of Eu³⁺ was used to model the experimental Stark levels and their irreps. The crystal-field parameters were determined through use of a Monte-Carlo method in which nine independent crystal-field parameters, were given random starting values and optimized using standard least-squares fitting between calculated and experimental levels. The final fitting standard deviation between 57 calculated-to-experimental Stark levels is 5.9 cm⁻¹. The choice of coordinate system, in which the nine are real and the crystal-field z-axis is parallel to the [0 0 1] crystal axis and perpendicular to the xy plane, is identical to the choice we used previously in analyzing the spectra of Er³⁺ and Ho³⁺ garnets.     

Optical properties of Eu:CsGd2F7 downconversion phosphor

Luminescence spectra and excitation spectra in 150-420 nm spectral region have been recorded at room temperature for polycrystalline sample of (0.5%)Eu³⁺:CsGd₂F₇. The relatively intense emission has been observed from ⁵D₃, ⁵D₂ and ⁵D₁ levels. Emission and excitation spectra prove that the excitation energy is efficiently transferred from the ⁶G_J and ⁶I_J levels of Gd³⁺ ions to Eu³⁺ ions. The visible quantum cutting via downconversion has been detected, with efficiency of the cross-relaxation step of ∼50%.     

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.     

Dependence of photoluminescent properties of cubic Y2O3:Tb nanocrystals on particle size and temperature

Temperature-dependent spectral properties in the cubic Y₂O₃:Tb³⁺ nanocrystals (NCs, 10-70 nm) under 488 nm excitation were studied and compared to that in the bulk. In NCs, emission lines assigned to the ⁵D₄-⁷F_J (J=1-6) transitions of Tb³⁺ ions and a broad band originated from oxygen defects were observed. As a function of temperature, two intensity maximums of the ⁵D₄-Σ⁷F_J transitions appeared in the NCs, at ∼250 and ∼500 K, while in the bulk only one maximum appeared at ∼250 K. The relative intensity of the maximum at ∼500 K to that at ∼250 K increased with decreasing particle size. The intensity maximum of the band emissions that came from the oxygen defects appeared in the range of 500-600 K. The appearance of intensity maximum as a function of temperature was attributed to the rivalry between thermal quenching process and phonon-assisted excitation. The appearance of two maxima in the NCs was attributed to the luminescence contributed by different Tb³⁺ centers, the internal and the surface. The emission for the surface Eu³⁺ centers has higher quenching temperature in contrast to that for the internal centers.     

Fast and efficient VUV/UV emissions from (Ba,La)F2:Er crystals

We report observation of fast and efficient VUV/UV luminescence from the mixed (Ba,La)F₂:Er crystals. The broad bands, peaking at 162.5, 181.9, 194.2, 202.8, 216.1, 233.5 and 281.5 nm and decaying, at 10 and 293 K, with time constants of 46 and 35 ns respectively, are due to spin-allowed transitions from the low-spin (LS) state of the 4f¹⁰5d configuration.We also observed a weak and slow broad band emission peaking at 170 nm due to the spin-forbidden transition from the high-spin (HS) state of the 4f¹⁰5d configuration.While at room temperature the excitation into any of the three identified LS bands (J=8, 7 and 6) dominating the excitation spectrum yields fast VUV and UV emissions, at 10 K the excitation into higher lying J=7 and 6 bands generates slow and sharp line emissions. The positions of these lines fit energies of transitions originating from the ²G_7/2 multiplet at 66140 cm⁻¹. The emission from the ²G_7/2 multiplet has been never, to the best of our knowledge, observed before.The efficient and fast VUV and UV emissions from the higher (LS, J=8) with almost no contribution from the lower (HS, J=8) level of the 4f¹⁰5d configuration are possible because the modified crystal field in (Ba,La)F₂ shifts the level of the (LS, J=8) state below the ²F_5/2 multiplet which, therefore, does not contribute to nonradiative relaxation between the LS and HS levels.We conclude that the ²G_7/2 and ²F_5/2 levels have major impact on VUV and UV emissions from the Er³⁺ ion in (Ba,La)F₂ contributing to complex emission pattern described in this report Their key role, elucidated by the VUV and UV luminescence spectroscopy, is consistent with predictions from a simple configuration coordinate model based on experimental results and calculations of the 4f¹¹ energy levels.     

Sol-gel preparation and photoluminescence property of YBO3:Eu/Tb nanocrystalline thin films

YBO₃:Eu³⁺/Tb³⁺ nanocrystalline thin films were successfully deposited onto quartz glass substrates by Pechini sol-gel dip-coating method, using rare-earth nitrates and boric acid as starting materials. The crystal structure, morphology, chemical composition and photoluminescence property of the films were investigated by X-ray diffraction (XRD), atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared (FTIR) spectroscopy and fluorescence spectrophotometer. The results of XRD, AFM, XPS and FTIR revealed that the films were composed of spherical YBO₃:Eu³⁺/Tb³⁺ nanocrystals with average grain size of 80 nm. The YBO₃:Eu³⁺ film exhibited strong orange emission at 595 nm and red emission at 615 nm, which were, respectively ascribed to the (⁵D₀→⁷F₁) and (⁵D₀→⁷F₂) transitions of Eu³⁺. The YBO₃:Tb³⁺ film showed dominant green emission at 545 nm due to the ⁵D₄-⁷F₅ transition of Tb³⁺.     

Effect of temperature and activator concentration on relaxation of excited states of Eu in K5Li2La1−xEuxF10 crystals

Single crystals of K₅Li₂La_1−xEu_xF₁₀ (where x=0.01,0.03,0.1,0.25,0.50,1) have been obtained from anhydrous fluorides by solid state reaction and then by the Bridgman crystal growth process. Optical properties of crystals were investigated at various temperatures between 5 and 300 K. Energy level scheme for Eu³⁺ has been constructed based on absorption and emission spectra recorded at 5 K. Emission from ⁵D₃, ⁵D₂, ⁵D₁ and ⁵D₀ levels has been studied in detail. It has been found that emission originating from the ⁵D₀ and ⁵D₁ levels is efficient and long lived for all Eu³⁺ concentrations. Estimated selfquenching rate of the ⁵D₁ luminescence is as small as about 10³ s⁻¹ in K₅Li₂EuF₁₀. Temperature dependence of this selfquenching is found to be consistent with a cross-relaxation process in which a donor ion makes the ⁵D₁-⁵D₀ transition and an acceptor ion makes the ⁷F₁-⁷F₃ transition. The ⁵D₂ luminescence is considerably strongly influenced by activator-activator interaction but it is still easily detectable. The ⁵D₃ luminescence is completely quenched in K₅Li₂EuF₁₀.     

Effects of Tb doping on the photoluminescence of Y2O3:Tb nanophosphors

The effects of Tb doping on the photoluminescence (PL) of Y₂O₃:Tb nanophosphors have been investigated. Nanophosphors were prepared by the glycine-nitrate solution combustion technique using yttria and terbia powders as precursors. PL excitation spectra at room temperature consist of two overlapping bands centered at 277 and 304 nm, whereas emission spectra comprise several groups of lines corresponding to the ⁵D₄→⁷F_J (J=1-6) 4f electronic transitions of the Tb⁺³ ions. A direct comparison of nanophosphor and bulk concentration-quenching curves was obtained by annealing the nanophosphor powder and converting it to bulk material without altering the Tb concentration. The peak in the nanophosphor concentration-quenching curve occurs at a concentration ∼3 times higher than that of the bulk.     

Tm3+离子掺杂的钨酸钇钠晶体中浓度猝灭效应的研究

测量了Tm³⁺离子不同浓度(0.5at.%, 3 at.%, 5 at.%)掺杂的NaY(WO₄)₂晶体在800nm激光二极管激发下的上转换发射光谱.结合吸收谱、荧光谱和由Judd-Ofelt理论计算的光谱参数，详细分析了Tm³⁺:NaY(WO₄)₂晶体中上转换能量传递机理和离子浓度对上转换发射的影响.讨论了四种影响上转换发光效率的离子间相互作用机理：³H₅+¹G₄→³H₆+¹D₂，³H₅+³H₅→³H₆+³F₃，¹G₄+³H₆→³F₄+³F₃，¹G₄+³H₆→³F₃+³F₄，并根据Miyakawa-Dexter理论定量计算了各过程的发生概率.论证了交叉弛豫和共协上转换等浓度猝灭效应是影响Tm³⁺离子蓝色上转换荧光发射效率的主要因素. 关键词： 3+离子')" href="#">Tm³⁺离子 4)₂晶体')" href="#">NaY(WO₄)₂晶体 上转换 浓度猝灭     

Spectroscopic properties of Yb ions in La2(WO4)3 crystal

Yb³⁺-doped La₂(WO₄)₃ single crystals were grown by the Czochralski technique. Absorption and fluorescence spectra of the crystal were recorded at the room temperature. The stimulated emission cross-sections of Yb³⁺ ions were calculated using the reciprocity method and Fuchtbauer-Ladenburg formula, respectively. The fluorescence decay curves of ²F_5/2 manifold of Yb³⁺ ions were recorded at room temperature for both crystal and powder samples. The effect of radiation trapping on the spectroscopic properties is discussed. Comparison with other Yb³⁺-doped laser crystals is made. The results show that Yb³⁺:La₂(WO₄)₃ crystal is a promising laser material.     

Luminescence of Tb3+ ions in silicate glasses

The optical absorption and photoluminescence emission spectra of terbium doped sodium and lithium aluminium silicate glasses have been measured as a function of terbium concentration. Optical absorption has been measured over the wavelength range from 250 nm to 40 μm and the absorption bands attributed to Tb³⁺ ions have been identified. Luminescence emission occurs in two groups of bands in the blue and in the green. The green ⁵D₄ → ⁷F_J emission is more intense than the blue ⁵D₃ → ⁷F_J. The green luminescence is enhanced at the expense of the blue when the Tb³⁺ ion concentration reaches 0.5 molar%, which corresponds to an ion separation of 20 Å. The green emission is quenched when the Tb³⁺ ion concentration exceeds 5 molar%, corresponding to an ion separation of 9.5 Å. It is concluded that energy transfer from ⁵D₃ to ⁵D₄ levels begins at Tb³⁺ ion separations of 20 Å, and that the process is multipolar. Exchange dipole processes set in at 9.5 Å and quench the green emission. The ion separations at which the two processes occur in silicate glasses are much larger than those at which similar processes set in crystalline material. This enhancement of energy transfer processes in silicate glass is attributed to inhomogeneous broadening of the absorption and emission bands. The detailed structure of the emission bands, particularly that of the ⁵D₄ → ⁷F_6,5,4 doublets, is used to suggest that the Tb³⁺ ions occupy two different sites with rhombohedral and cubic symmetries.     

Investigation of crystallographic sites of Eu in La2BaZnO5 by site-selective laser-excitation spectroscopy

La₂BaZnO₅:Eu³⁺ (0.05 mol%) was prepared by a solid-state reaction at high temperature. X-ray powder diffraction analysis confirmed the formation of single phase La₂BaZnO₅. Luminescence properties of La₂BaZnO₅:Eu³⁺ are investigated by site-selective laser-excitation and emission spectroscopy at 18 K. Two different crystallographic sites for Eu³⁺ corresponding to the La³⁺ and Ba²⁺ sites are identified from the ⁷F₀→⁵D₀ excitation spectra obtained by monitoring the ⁵D₀→⁷F_J (J=1, 2, …, 6) emissions. It is found that Eu³⁺ substituted for the Ba²⁺ ion experiences stronger crystal-field strength than Eu³⁺ substituted for the La³⁺ ion. Energy transfer between the two crystallographic Eu³⁺ centers is investigated by luminescence decay curves at 18 K.