Emission color variation of M2SiO4:Eu (M=Ba, Sr, Ca) phosphors for light-emitting diode

The luminescent properties of alkaline earth orthosilicates M₂SiO₄ (M=Ba, Sr, Ca) doped with Eu²⁺ ions are investigated. Two emission bands are assigned to the f-d transitions of Eu²⁺ ions doped into two different cation sites in host lattices confirmed by electron paramagnetic resonance signal. Two emission bands show the different emission color variation with substituting M²⁺ cations with smaller cations. This behavior is discussed in terms of two competing factors of the crystal field strength and covalence. Also the decay times are in order of 600-1000 ns. These phosphors with maximum excitation of around 370 nm can be applied as a color-tunable phosphor for light-emitting diode based on ultraviolet chip/phosphor technology.     

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).     

Spherical Zn2SiO4:Eu@SiO2 phosphor particles in core-shell structure: Synthesis and characterization

Spherical SiO₂ particles have been coated with Zn₂SiO₄:Eu³⁺ phosphor layers by a Pechini sol-gel process. The microstructure and luminescent properties of the obtained Zn₂SiO₄:Eu³⁺@SiO₂ particles were well characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), transmission electron microscopy (TEM), photoluminescence (PL) spectra, and lifetime. The results demonstrate that the Zn₂SiO₄:Eu³⁺@SiO₂ particles, which have regular and uniform spherical morphology, emitted an intensive red light emission at 613 nm under excitation at 395 nm. Besides, the effects of the Eu³⁺ concentration, annealing temperature and charge compensators of Li⁺ ions on the PL emission intensities were investigated in detail.     

A white light emitting phosphor Sr1.5Ca0.5SiO4:Eu, Tb, Eu for LED-based near-UV chip: Preparation, characterization and luminescent mechanism

In this work, we report preparation, characterization and luminescent mechanism of a phosphor Sr_1.5Ca_0.5SiO₄:Eu³⁺,Tb³⁺,Eu²⁺ (SCS:ETE) for white-light emitting diode (W-LED)-based near-UV chip. Co-doped rare earth cations Eu³⁺, Tb³⁺ and Eu²⁺ as aggregated luminescent centers within the orthosilicate host in a controlled manner resulted in the white-light phosphors with tunable emission properties. Under the excitation of near-UV light (394 nm), the emission spectra of these phosphors exhibited three emission bands: one broad band in the blue area, a second band with sharp lines peaked in green (about 548 nm) and the third band in the orange-red region (588-720 nm). These bands originated from Eu²⁺ 5d→4f, Tb³⁺⁵D₄→⁷F_J and Eu³⁺⁵D₀→⁷F_J transitions, respectively, with comparable intensities, which in return resulted in white light emission. With anincrease of Tb³⁺ content, both broad Eu²⁺ emission and sharp Eu³⁺ emission increase. The former may be understood by the reduction mechanism due to the charge transfer process from Eu³⁺ to Tb³⁺, whereas the latter is attributed to the energy transfer process from Eu²⁺ to Tb³⁺. Tunable white-light emission resulted from the system of SCS:ETE as a result of the competition between these two processes when the Tb³⁺ concentration varies. It was found that the nominal composition Sr_1.5Ca_0.5SiO₄:1.0%Eu³⁺, 0.07%Tb³⁺ is the optimal composition for single-phased white-light phosphor. The CIE chromaticity calculation demonstrated its potential as white LED-based near-UV chip.     

The improvement of moisture resistance and thermal stability of Ca3SiO4Cl2:Eu phosphor coated with SiO2

Green-emitting phosphors Ca₃SiO₄Cl₂:Eu²⁺ were prepared by the high temperature solid-state method. Sol-gel process was adopted to encapsulate the as-prepared phosphors with tetraethylorthosilicate (TEOS) as silicon coating reagent. Fluorescence spectrometer, scanning electron microscopy (SEM) and powder X-ray diffraction (XRD) patterns were employed to characterize the emission spectra, the surface morphologies and the phase structures, respectively. The chemical stability testing was operated by the method of soaking the phosphors in deionized water and roasting them at different temperatures. The results indicated that the surfaces of the green phosphors were evenly coated by SiO₂ and the phase structure of the coated phosphors remained the same as the uncoated samples. The luminance centre of Eu²⁺ did not shift after surface treatment and the luminance intensity of coated phosphors was lower than that of the uncoated samples. The results demonstrated that the water-resistance stability of the coated phosphor was improved to some degree because the pH value and the luminance intensity variation were both smaller than the uncoated phosphor after steeping within the same time. Moreover, the thermal stability of coated phosphors was enhanced obviously compared to the original samples based on the temperature dependent emission spectra measurement.     

Photoluminescence investigations of Zn2SiO4 co-doped with Eu and Tb ions

Zinc silicate phosphors co-doped with Eu³⁺ ions and also with both Eu³⁺ and Tb³⁺ ions were prepared by high temperature solid state reaction in air or reducing atmosphere. The luminescence characteristics of the prepared phosphors were investigated. While in the samples prepared in air, Eu³⁺ emission was found to be dominant over Tb³⁺ emission, in the samples prepared in reducing atmosphere, intense Eu²⁺ emission at 448 nm was found to be predominant over narrow Tb³⁺ emission. Luminescence studies showed that Eu³⁺ ions occupy asymmetric sites in Zn₂SiO₄ lattice. The intense f-f absorption peak of Eu³⁺ at 395 nm observed in these phosphors suggests their potential as red emitting phosphors for near ultra-violet light emitting diodes.     

Influence of Ba-doping on structural and luminescence properties of Sr2SiO4:Eu phosphors

Ba²⁺-doped Sr₂SiO₄:Eu²⁺ phosphors were synthesized with the high-temperature solid-state reaction technique. The experimental results, summarized in the successful production of a single-phase powder with fine microstructure of spherical particles with smooth surface, suggest that Ba²⁺-doping favors the stabilization of α′-Sr₂SiO₄. Rietveld refinement of X-ray diffractograms suggests that Ba²⁺ and Eu²⁺ ions occupy the sites of Sr²⁺ in the lattice of α′-Sr₂SiO₄. The produced phosphors show two intense emission bands at green and yellow regions of spectrum, originated from Eu²⁺ ions accommodated at two different sites in the host crystal, whose peaks depend on the concentrations of Ba²⁺ and Eu²⁺. Intense and broad excitation spectra extend from ultraviolet to the blue region.     

Energy transfer between activators at different crystallographic sites in Sr3SiO5:Eu

A yellow phosphor, Sr₃SiO₅:Eu²⁺, was synthesized by a high temperature solid-state method. Sr₃SiO₅:Eu²⁺ exhibits a single yellow emission under the blue radiation excitation. However, Sr₃SiO₅:Eu²⁺ shows a two-peak emission under the ultraviolet radiation excitation when Eu²⁺ doping content is less than 0.01 mol. Moreover, the blue emission disappears and the yellow emission reaches the peak value when Eu²⁺ doping content is 0.01 mol. Namely, the energy transfer takes place between the Eu²⁺ activators, which is located at two different crystallographic sites in the Sr₃SiO₅. And the energy transfer mechanism is the dipole-dipole interaction.     

Ca2SiO4:Dy3+材料的制备及其发光特性

采用高温固相法制备了Ca₂SiO₄:Dy³⁺发光材料.在365nm紫外光激发下,测得Ca₂SiO₄:Dy³⁺材料的发射光谱为一多峰宽谱,主峰分别位于486nm,575nm和665nm处;监测575nm发射峰,测得材料的激发光谱为一多峰宽谱,主峰分别位于331nm,361nm,371nm,397nm,435nm,461nm和478nm处.研究了Dy³⁺掺杂浓度对Ca₂SiO₄:Dy³⁺材料发射光谱及发光强度的影响,结果显示,随Dy³⁺浓度的增大,黄、蓝发射峰强度比(Y/B)逐渐增大,利用Judd-Ofelt理论解释了其原因;随Dy³⁺浓度的增大,Ca₂SiO₄:Dy³⁺材料发光强度先增大,在Dy³⁺浓度为4 mol%时到达峰值,而后减小,根据Dexter理论其浓度猝灭机理为电偶极-电偶极相互作用.研究了电荷补偿剂Li⁺,Na⁺和K⁺对Ca₂SiO₄:Dy³⁺材料发射光谱的影响,结果显示,不同电荷补偿剂下,随电荷补偿剂掺杂浓度的增大,Ca₂SiO₄:Dy³⁺材料发射光谱强度的演化趋势相同,即Ca₂SiO₄:Dy³⁺材料发射峰强度先增大后减小,但不同电荷补偿剂下,材料发射峰强度最大处对应的补偿剂浓度不同,对应Li⁺,Na⁺和K⁺时,浓度分别为4mol%,4mol%和3mol%. 关键词： 白光LED 2SiO₄:Dy³⁺')" href="#">Ca₂SiO₄:Dy³⁺ 发光特性 电荷补偿     

Eu2+激活的Ca3SiO5绿色荧光粉的制备和发光特性研究

研究了Eu²⁺激活的绿色发光材料Ca₃SiO₅的制备条件和发光性质. Eu²⁺中心形成主峰值为501 nm和次峰值为570 nm的特征宽带，两峰值叠加形成发射峰值为502nm的绿色发射光谱带. 利用这些光谱结果和Van Uitert 经验公式，确认Ca₃SiO₅:Eu²⁺中存在两种性质有差异的Eu²⁺发光中心，它们分别占据基质中八配位的Ca²⁺(Ⅰ)格位和四配位的Ca²⁺(Ⅱ)格位. 其激发光谱分布在250—450 nm的波长范围，峰值位于375 nm处，可以被InGaN管芯产生的350—410 nm辐射有效激发. 关键词： 发光 荧光粉 绿色荧光粉 3SiO₅')" href="#">Ca₃SiO₅ 2+')" href="#">Eu²⁺     

Intense green/yellow emission in Ca8Zn(SiO4)4Cl2:Eu, Mn through energy transfer for blue-LED lighting

Eu²⁺ and Mn²⁺ co-doped Ca₈Zn(SiO₄)₄Cl₂ phosphors have been synthesized by a high temperature solid state reaction. Energy transfer from Eu²⁺ to Mn²⁺ is observed. The emission spectra of the phosphors show a green band at 505 nm of Eu²⁺ and a yellow band at 550 nm of Mn²⁺. The excitation spectra corresponding to 4f⁷-4f⁶5d transition of Eu²⁺ cover the spectral range of 370-470 nm, well matching UV and/or blue LEDs. The shortening of fluorescent lifetimes of Eu²⁺ followed by simultaneous increase of fluorescent intensity of Mn²⁺ with increasing Mn²⁺ concentrations is studied based on energy transfer. Upon blue light excitation the present phosphor can emit intense green/yellow in comparison with other chlorosilicate phosphors such as Eu²⁺ and Mn²⁺ co-doped Ca₈Mg(SiO₄)₄Cl₂ and Ca₃SiO₄Cl₂, demonstrating a potential application in phosphor converted white LEDs.     

Temperature-dependent emission spectra of M2SiO4:Eu (M=Ca, Sr, Ba) phosphors for green and greenish white LEDs

The temperature dependence of emission spectra of alkaline earth ortho-silicates M₂SiO₄ (M=Ca, Sr, Ba) doped with Eu²⁺ ions is investigated. Two emission bands of Sr₂SiO₄:Eu²⁺ show the normal redshift with broadening bandwidth and decreasing emission intensity as an increase in temperature. On the other hand, emission bands of Ca₂SiO₄:Eu²⁺ and Ba₂SiO₄:Eu²⁺ show the anomalous blueshift with increasing temperature. For Ca₂SiO₄:Eu²⁺ and Ba₂SiO₄:Eu²⁺, the temperature dependence of the emission color can be described in terms of back tunneling from the excited state of low-energy emission band to the excited state of high-energy emission band in the configuration coordinate diagram. Our phosphors have a promising potential as phosphors for green or greenish white-light-emitting diode pumped by ultraviolet chip.     

Photoluminescence of Eu single doped and Eu/Dy codoped Sr2Al2SiO7 phosphors with long persistence

This paper reports the preparation of long persistent Sr₂Al₂SiO₇:Eu²⁺ and Sr₂Al₂SiO₇:Eu²⁺, Dy³⁺ phosphors and the comparison of their photoluminescent properties. The silicate phosphors prepared by solid-state reaction routine showed a broad blue emission peaking at 484 nm when activated by UV illumination. Such a bluish-green emission can be attributed to the intrinsic 4f-5d transitions of Eu²⁺. After the UV source was switched off, long persistent phosphorescence could be observed by naked eyes for both samples in darkness. Afterglow measurements revealed that Eu/Dy codoped phosphor possesses better afterglow properties than the Eu single doped one, since the maximum lifetime (τ_max=99 s) of the photons calculated from the decay profile is much larger than that of the Eu single doped phosphor (τ_max=82 s). TSL results suggested that the difference in afterglow properties was caused by the difference in the electron traps within the crystal lattice. For Eu/Dy codoped phosphor, the doping of Dy ions produced electron traps with trap depth of 0.52 eV, which is suitable and therefore leads to good persistence. However, in the case of Eu single doped phosphor, the trap depth is 0.88 eV, which is really too deep an energy barrier to overcome, and therefore a poor persistence was observed in the experiment.     

用于白光LED的单一基质白光荧光粉Ca2SiO3Cl2:Eu2+，Mn2+的发光性质

用高温固相法合成了Eu²⁺，Mn²⁺共激活的Ca₂SiO₃Cl₂高亮度白色发光材料，并对其发光性质进行了研究. 该荧光粉在近紫外光激发下发出强的白色荧光，Eu^{2+中心形成峰值为419 nm和498 nm的特征宽带，通过Eu2+中心向Mn2+中心的能量传递导致了峰值为578 nm的发射，三个谱带叠加从而在单一基质中得到了白光. 激发光谱均分布在250—415 nm的波长范围，红绿蓝三个发射带的激发谱峰值分别位于385 nm，412 nm，370 nm和396 nm处，可以被InGaN管芯产生的紫外辐射有效激发. Ca₂SiO₃Cl₂:Eu2+，Mn2+是一种很有前途的单一基质白光LED荧光粉.}     

Judd-Ofelt analysis of luminescence emission from Zn2SiO4:Eu nanoparticles obtained by a polymer-assisted sol-gel method

In this research we prepared Zn₂SiO₄:Eu³⁺ phosphor nanopowders using a combination of sol-gel and combustion synthesis with the aim to examine the influence of synthesis conditions on the optical properties of the phosphor. As combustion fuels we used polyethylene glycol (PEG) with different average molecular weights, and the combustion was performed in two ways—in a microwave oven and a conventional furnace. Optical properties were examined by photoluminescence spectroscopy and spectra of all samples showed intense red emission, typical for f-f electronic transitions of the Eu³⁺ ions. Emission decays exhibited classical one exponential behavior at longer times and nonlinear nature at short times, with average lifetimes varied from 0.49 to 0.71 ms between samples. Judd-Ofelt theory was applied to experimental data for the quantitative determination of optical parameters such as Ω_2,4 Judd-Ofelt parameters, radiative and nonradiative transition rates and emission quantum efficiency. Calculated parameters vary moderately between samples prepared with different PEGs and combusted in different manner.     

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.     

A potential red-emitting phosphor CaSrAl2SiO7:Eu for near-ultraviolet light-emitting diodes

A novel red-emitting phosphor CaSrAl₂SiO₇:Eu³⁺ was firstly synthesized through the high temperature solid state reaction at 1300 °C. The structure, diffuse reflection spectra, photoluminescence spectra, color-coordinate parameters and quantum efficiencies (QE) of phosphors were investigated. The obtained CaSrAl₂SiO₇:Eu³⁺ phosphors have the same structure with that of the Ca₂Al₂SiO₇ and Sr₂Al₂SiO₇ phosphor, which have the melilite structure. Optical properties were studied as a function of Eu³⁺ concentration x, when x>0.14, the intensity of absorption of the f–f transitions of Eu³⁺ at 393 nm is stronger than that of the broad charge transfer transition band (CTB) around 254 nm, and which matches well with the output lights of NUV–LEDs, whereas, the concentration of Eu³⁺x≤0.14, the absorption of 393 nm is weaker than that of CTB. The underlying reason of Eu³⁺ concentration on their luminescent properties was investigated and discussed in detail. As a result, comparing with the commercial red phosphor Y₂O₂S:Eu³⁺, the CaSrAl₂SiO₇:xEu³⁺ (x>0.14) phosphor exhibited excellent color purity and much higher brightness and could be considered as promising red phosphors for NUV–LEDs.     

Electronic energy relaxation and luminescence decay dynamics of Eu in Zn2SiO4:Eu phosphors

Electronic energy relaxation and decay dynamics of Eu³⁺ in Zn₂SiO₄:Eu³⁺ phosphors display evidence of intra-ion energy transfer from the ⁵D₁ to the ⁵D₀ manifold. The energy transfer timescale does not depend on Eu³⁺ concentration, or the addition of Mn²⁺ as a co-dopant and is estimated to be about 11 μs in Zn₂SiO₄. Evidence for intra-ion Eu³⁺ electronic energy transfer has also been observed in Eu-doped MgS as well as Eu³⁺ encapsulated in zeolite-Y. The energy transfer timescale in these other materials is shorter than in Zn₂SiO₄, most likely due to differences in Eu³⁺ surroundings or site symmetry.     

Thermally stable deep-blue Ba1.2Ca0.8SiO4:Ce phosphor for white-light-emitting diode

A novel deep-blue phosphor, Ba_1.2Ca_0.8SiO₄:Ce³⁺, has been developed for white-light-emitting diodes. The phosphor exhibits two absorption bands at 280 and 325 nm, and an intense deep-blue emission peaking at 400 nm. With increasing Ce/Li concentrations, the lattice expands, and the emission peak is blueshifted. This correlation is explained in terms of the crystal field effect and the configurational coordinate diagram. This phosphor shows much higher thermal quenching temperature (225 °C) due to a weak electron-phonon interaction. Thus, it can be used as a sensitizer phosphor to excite other green or red phosphors, or a promising deep-blue phosphor for white-light-emitting diodes.     

Photoluminescence and gamma-ray irradiation of SrAl2O4:Euand Y2O3:Eu phosphors

Y₂O₃:Eu³⁺ phosphor is a very attractive material for use as a red phosphor in many fields. SrAl₂O₄:Eu²⁺ belongs to long lasting phosphor (LLP) and it is a useful bluish-green luminescence material, which can also be a promising candidate as a simple and easy-to-use radiation detection element for visual display of two dimensional radiation distributions. In the present study, both these two kinds of phosphors were synthesized using high temperature solid state reactions. In our work, the influence of gamma-ray irradiation on the properties of these two kinds of phosphors was studied by comparing photoluminescence, brightness and the decay curve of unirradiated and gamma-ray-irradiated samples. Conclusions from the present work can be briefly summarized as follows. In irradiated samples, the brightness is decreased without sensible change in the wavelength distribution of the luminescence spectrum and in the decay kinetic upon gamma exposure. Moreover, the emission due to Eu³⁺→Eu²⁺ conversion in Y₂O₃:Eu³⁺ phosphors was not observed in our sample after irradiation to high exposure. Also the brightness of SrAl₂O₄:Eu²⁺ phosphor turned out to decrease after the exposition to ionizing radiation while the luminescence wavelength distribution remained unchanged. The reason for the effect of gamma-ray irradiation on the properties of phosphors is also discussed in the paper.