A red oxide phosphor, Sr2ScAlO5:Eu2+ with perovskite-type structure, for white light-emitting diodes

Sr2ScAlO5:Eu2+,a red oxide phosphor with a perovskite-type structure,has been synthesized through a solid-state reaction and its luminescence properties have been investigated.An absorption band centering at 450 nm is observed from the diffuse reflection spectra and the excitation spectra,indicating that the phosphor can match perfectly with the blue light of InGaN light-emitting diodes.A broad red emission band at 620 nm is found from the emission spectra,originating from the 4f 6 5d-4f 7 transition of the Eu 2+ ions.The best doping content of Eu in this material is about 5%.Sr2ScAlO5:Eu2+is a highly promising red phosphor for use in white light-emitting diodes.     

Luminescent properties of Eu-activated Sr3B2SiO8: A red-emitting phosphor for white light-emitting diodes

Single-phased Sr₃B₂SiO₈:Eu³⁺ phosphor was prepared by a solid-state method at 1020 °C. The luminescence spectra showed that Sr₃B₂SiO₈:Eu³⁺ phosphor can be effectively excited by near ultraviolet light (393 nm) and blue light (464 nm). When excited at 393 or 464 nm Sr₃B₂SiO₈:Eu³⁺ exhibited the main emission peaks at 611 and 620 nm, which resulted from the supersensitive ⁵D₀→⁷F₂ transition of Eu³⁺. The luminescence intensity of Sr₃B₂SiO₈:Eu³⁺ at 611 and 620 nm reached the maximum when the doping content of Eu³⁺ was 4.5 mol%. Its chromaticity coordinates (0.646, 0.354) were very close to the NTSC standard values (0.67, 0.33). Thus, Sr₃B₂SiO₈:Eu³⁺ is considered to be an efficient red-emitting phosphor for long-UV InGaN-based light-emitting diodes.     

Enhanced luminescent properties of long-persistent Sr2MgSi2O7:Eu, Dy phosphor prepared by the co-precipitation method

Sr₂MgSi₂O₇:Eu²⁺, Dy³⁺ phosphors were prepared by the (aminopropyl)-triethoxysilane (APTES) co-precipitation method. Effects of synthesis temperature on the crystal characteristics, luminescent properties and afterglow performance of Sr₂MgSi₂O₇:Eu²⁺, Dy³⁺ phosphors have been discussed in detail and compared with the corresponding commercial product. The experimental results indicated that the sample could be synthesized at a relatively lower temperature and had better performance on the above-mentioned properties using the co-precipitation method.     

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.     

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.     

Combustion synthesis of Sr3MgSi2O8:Eu and Sr2MgSi2O7:Eu phosphors

Sr₃MgSi₂O₈:Eu²⁺ and Sr₂MgSi₂O₇:Eu²⁺ phosphors find uses in applications such as plasma display panel (PDP), solid-state lighting, longafter glow. Preparation of these phosphors by a modified combustion synthesis is described in this paper. As-prepared samples did not show photoluminescence. After reducing the samples at 900 °C, characteristic Eu²⁺ emission was observed. Preparation of these phosphors by using similar methods helped clarifying various results obtained for Sr₃MgSi₂O₈:Eu²⁺ by different investigators.     

Luminescence properties of Tm co-doped Sr2Si5N8:Eu red phosphor

The Sr₂Si₅N₈:Eu²⁺ phosphors, both undoped and doped with Tm³⁺, were synthesized by high temperature solid-state method. The XRD pattern shows that only Sr₂Si₅N₈ phase is formed whatever Tm³⁺ was doped or not. The peak positions of both phosphors are centered at 612 nm which is assigned to the 4f⁶5d→4f⁷ transition of Eu²⁺. It implies that the crystal field, which affects the 5d electron states of Eu²⁺, is not changed dramatically after the phosphor is doped with Tm³⁺. The afterglow time is about 10 min after Tm³⁺ ion is introduced into the phosphor. The concentration of Tm³⁺ has little influence on the afterglow time of the phosphor. The depths of trap energy level of the two phosphors were calculated based on the TL spectra. The depths of Sr₂Si₅N₈:Eu²⁺ and Sr₂Si₅N₈:Eu²⁺, Tm³⁺ are 1.75 and 1.01 eV, respectively.     

Synthesis and luminescence properties of Eu, Ce and Tb-activated Sr3La2(BO3)4 under UV excitation

The spectroscopic properties in UV-excitable range for the phosphors of Sr₃La₂(BO₃)₄:RE³⁺ (RE³⁺=Eu³⁺, Ce³⁺, Tb³⁺) were investigated. The phosphors were synthesized by conventional solid-state reactions. The photoluminescence (PL) spectra and commission international de I'Eclairage (CIE) coordinates of Sr₃La₂(BO₃)₄:RE³⁺ were investigated. The f-d transitions of Eu³⁺, Ce³⁺ and Tb³⁺ in the host lattices are assumed and corroborated. The PL and PL excitation (PLE) spectra indicate that the main emission wavelength of Sr₃La₂(BO₃)₄:Eu³⁺ is 611 nm, and Sr₃La₂(BO₃)₄:Ce³⁺ shows dominating emission peak at 425 nm, while Sr₃La₂(BO₃)₄:Tb³⁺ displays green emission at 487, 542, 582 and 620 nm. These phosphors were prepared by simple solid-state reaction at 1000 °C. There are lower reactive temperature and more convenient than commercial phosphors. The Sr₃La₂(BO₃)₄:Tb³⁺ applied to cold cathode fluorescent lamp was found to emit green light and have a major peak wavelength at around 542 nm. These phosphors may provide a new kind of luminescent materials under ultraviolet excitation.     

Emission properties of Eu, Mn in MAl2Si2O8 (M=Sr, Ba)

The emission properties of Eu²⁺ and Mn²⁺ in monoclinic SrAl₂Si₂O₈ (M-SAS) and hexagonal BaAl₂Si₂O₈ (H-BAS), both of which have only one alkaline-earth site, were studied. The emission peaks of both Eu²⁺ (405 nm) and Mn²⁺ (564 nm) in SrAl₂Si₂O₈, are located at longer wavelengths, compared with those in H-BAS (373 nm for Eu²⁺ and 518 nm for Mn²⁺), because of the stronger crystal field strength at the Sr site. EPR spectra showed that the g values of Mn²⁺ are 4.5065 in M-SAS:Mn and 2.0247 in H-BAS:Mn. Magnetic measurements proved that Mn²⁺ was at high-spin state in both hosts. The large g value of Mn²⁺ in M-SAS was ascribed to the mixing of the first excitation state to the ground state, both of which have lower d orbital degeneracy due to the lower symmetry of Mn²⁺ site. The transfer efficiency from Eu²⁺ to Mn²⁺was about 10% in M-SAS, higher than that in H-BAS (5%). This was probably because Eu²⁺ emission overlaps the relatively low excitation level of Mn²⁺ in M-SAS. In order to obtain high transfer efficiency, it was necessary for the Eu²⁺ emission to overlap the lowest excitation level of Mn²⁺. The results obtained in this work may be helpful to design the new white or red phosphors for white-light emitting diode (w-LED) applications.     

Optical study of Sr2SnO4:Eu phosphor

This work presents the influence of europium dopant on optical properties of Sr₂SnO₄:Eu³⁺ powders fabricated by a facile low temperature method. Powders were obtained from the same amounts of Eu³⁺ doping into the different concentrations of Sr(NO₃)₂. Powders were examined by means of scanning electron microscopy (SEM), X-ray diffraction (XRD), and photoluminescence (PL). SEM measurements different Eu concentrations in fabricated powders was determined to found different morphologies. XRD analysis revealed the existence of crystalline Sr₂SnO₄ in the form of tetragonal and the diffraction intensity was remarkably changed. PL studies showed a red luminescence of Sr₂SnO₄:Eu³⁺ powders. The intensity of luminescence increased with better crystallinity. This approach provides economically viable route for large-scale synthesis of this kind of nanopowders.     

Synthesis and luminescence properties of nanocrystalline Gd2O3:Eu by combustion process

The nanocrystalline Gd₂O₃:Eu³⁺ powders with cubic phase were prepared by a combustion method in the presence of urea and glycol. The effects of the annealing temperature on the crystallization and luminescence properties were studied. The results of XRD show pure phase can be obtained, the average crystallite size could be calculated as 7, 8, 15, and 23 nm for the precursor and samples annealed at 600, 700 and 800 °C, respectively, which coincided with the results from TEM images. The emission intensity, host absorption and charge transfer band intensity increased with increasing the temperature. The slightly broad emission peak at 610 nm for smaller particles can be observed. The ratio of host absorption to O²⁻-Eu³⁺ charge transfer band of smaller nanoparticles is much stronger compared with that for larger nanoparticles, furthermore, the luminescence lifetimes of nanoparticles increased with increasing particles size. The effects of doping concentration of Eu³⁺ on luminescence lifetimes and intensities were also discussed. The samples exhibited a higher quenching concentration of Eu³⁺, and luminescence lifetimes of nanoparticles are related to annealing temperature of samples and the doping concentration of Eu³⁺ ions.     

Highly water resistant surface coating by fluoride on long persistent Sr4Al14O25:Eu/Dy phosphor

A novel and efficient method of providing moisture resistance of inorganic particles such as divalent europium activated strontium aluminate phosphors (Sr₄Al₁₄O₂₅:Eu²⁺/Dy³⁺) was developed by firing the phosphor in the presence of appropriate amount of ammonium fluoride at a temperature of 600-700 °C. Scanning electron microscopy, X-ray diffraction, FT-IR, EDAX and Photoluminescence measurements were carried out to characterize the uncoated and coated samples. The pH measurements were carried out for the water resistivity measurements. The phosphor particles became coated with a moisture-impervious thin coating that did not suppress the luminescence of the phosphor and can withstand complete immersion in water for long periods of time, showing very high water resistivity.     

Effects of dopant concentrations on phosphorescence properties of Eu/Dy-doped Sr3MgSi2O8

Long afterglow Sr₃MgSi₂O₈: Eu, Dy phosphor with high brightness was prepared by sintering at high temperature and weak reductive atmosphere. The luminescent properties of this photoluminescent pigment were studied systematically by investigating concentration effects. The analytical results indicated that the main emission peaks appear at 482 nm. The excitation and emission spectra of this phosphor show that both of them are broadband. This is ascribed to the 4f⁷→4f⁶5d¹ transition of Eu²⁺ in the pigment matrix, which is in good agreement with the calculated value of 470 nm, and implies that luminescent centers Eu²⁺ occupy the deca-coordinated Sr²⁺ sites with the host of Sr₃MgSi₂O₈.     

A new synthetic pathway of Sr2CeO4 phosphor and its characterization

A blue-white emitting Sr₂CeO₄ phosphor was synthesized via a simple sol-gel poly vinyl alcohol (PVA)-complexing process using strontium nitrate and cerium nitrate as raw materials. The samples were characterized by TG/DTA, XRD, FTIR, SEM and photoluminescence spectroscopy. The X-ray diffraction study confirms the structure of the system to be orthorhombic. The emission spectra when excited at 267 nm peaks at ∼470 nm. The emission band is assigned to the energy transfer between the molecular orbital of the ligand and charge transfer state of the Ce⁴⁺ ion. The Commission International de l'Eclairage (CIE) co-ordinates for the Sr₂CeO₄ sample were also calculated.     

新型电子俘获型光存储材料Sr2SnO4:Sb3+的发光性能研究

采用高温固相法在1300℃的温度获得了一种新型电子俘获型光存储材料 Sr₂SnO₄:Sb³⁺. 结果表明: 208 nm (Sb³⁺ 的¹S₀→¹P₁)和265 nm (¹S₀→³P₁)的紫外光是Sr₂SnO₄:Sb³⁺ 的最有效信息写入光源; 其发射是覆盖400---700 nm的宽带(³P_0,1→^XXS₀), 肉眼可看到淡黄色白光, 色坐标为(0.341, 0.395). 热释光谱研究结果表明: Sr₂SnO₄:Sb³⁺ 有分别位于39℃, 124℃, 193℃和310℃的四个热释峰. 其中, 39~℃的热释峰强度很低, 因而Sr₂SnO₄:Sb³⁺ 只具有不到140 s的微弱余辉. 而310℃的高温热释峰在空置1天后, 仍能保持约45.6%的初始强度, 并对980 nm的红外光有很好的红外上转换光激励响应. 因此, Sr₂SnO₄:Sb³⁺ 是一种具有一定的信息存储应用潜力的新型光存储发光材料.     

The structure and luminescence properties of a novel orange emitting phosphor Y3MnxAl5−2xSixO12

A series of phosphors with the composition Y₃Mn_xAl_5−2xSi_xO₁₂ (x=0, 0.05, 0.1, 0.15, 0.2, 0.3, 0.4, 0.5, 0.6) was prepared through solid state reactions. X-ray powder diffraction analysis of samples shows that when co-doping content does not exceed 16% of Al³⁺, equimolar co-doping of Mn²⁺ and Si⁴⁺ does not change the garnet structure of phosphors, but makes the interplanar distance to decrease a certain extent. However, if the co-doping content exceeds 16%, new phases will form in the samples. The excitation and emission spectra of samples show that Mn²⁺ in Y₃Mn_xAl_5−2xSi_xO₁₂ emits broadband orange light (peak wavelength varies from 586 to 593 nm). With an increment in co-doping content, the emission intensity of the phosphors increases when the value of x is lower than 0.1 while it decreases when it is higher than 0.1 and the emission peak moves to a longer wavelength.     

Preparation and luminescence characteristics of Eu^2＋ activated silicate phosphor

This paper synthesizes the Sr2SiO4：Eu^2＋ phosphor by high temperature solid-state reaction. The emission spectrum of Sr2SiO4 ： Eu^2＋ shows two bands centred at 480 and 547 nm, which agree well with the calculation values of emission spectrum, and the location of yellow emission of Sr2SiO4 ： Eu^2＋ is influenced by the Eu^2＋ concentration. The excitation spectrum for 547 nm emission has two bands at 363 and 402 nm. The emission spectrum of white light emitting diodes （w-LEDs） based on Sr2SiO4 ： Eu^2＋ phosphor ＋ InGaN LED was investigated.     

Synthesis and properties of submicron range CaSO4:Eu particles

CaSO₄:Eu with particle size in submicron range was synthesized. Radiation induced Eu³⁺↔Eu²⁺ conversion as well as thermal conversion was studied. The samples showed thermal conversion above 400 °C. However, no radiation induced conversion in submicron range particles was observed. Particles heated above 400 °C coalesce and when heated at 925 °C bigger particles of 20 μm size were formed. Optical microscopy of these particles reveals red inclusion of about 5 μm inside CaSO₄ particle. It is speculated that the red inclusion is CaS:Eu²⁺.     

Luminescent properties of green- or red-emitting Eu-doped Sr3Al2O6 for LED

Eu²⁺-doped Sr₃Al₂O₆ (Sr_3−xEu_xAl₂O₆) was synthesized by a solid-state reaction under either H₂ and N₂ atmosphere or CO atmosphere. When H₂ was used as the reducing agent, the phosphor exhibited green emission under near UV excitation, while CO was used as the reducing agent, the phosphor mainly showed red emission under blue light excitation. Both emissions belong to the d-f transition of Eu²⁺ ion. The relationship between the emission wavelengths and the occupation of Eu²⁺ at different crystallographic sites was studied. The preferential substitution of Eu²⁺ into different Sr²⁺ cites at different reaction periods and the substitution rates under different atmospheres were discussed. Finally, green-emitting and red-emitting LEDs were fabricated by coating the phosphor onto near UV- or blue-emitting InGaN chips.     

Sol-gel growth of Gd2MoO6:Eu nanocrystalline layers on SiO2 spheres (SiO2@Gd2MoO6:Eu) and their luminescent properties

SiO₂@Gd₂MoO₆:Eu³⁺ core-shell phosphors were prepared by the sol-gel process. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), field emission scanning electron microscopy (FESEM), energy-dispersive X-ray spectra (EDS), transmission electron microscopy (TEM), photoluminescence (PL) spectra as well as kinetic decays were used to characterize the resulting SiO₂@Gd₂MoO₆:Eu³⁺ core-shell phosphors. The XRD results demonstrate that the Gd₂MoO₆:Eu³⁺ layers on the SiO₂ spheres begin to crystallize after annealing at 600 °C and the crystallinity increases with raising the annealing temperature. The obtained core-shell phosphors have a near perfect spherical shape with narrow size distribution (average size ca. 600 nm), are not agglomerated, and have a smooth surface. The thickness of the Gd₂MoO₆:Eu³⁺ shells on the SiO₂ cores could be easily tailored by varying the number of deposition cycles (50 nm for four deposition cycles). The Eu³⁺ shows a strong PL luminescence (dominated by ⁵D₀-⁷F₂ red emission at 613 nm) under the excitation of 307 nm UV light. The PL intensity of Eu³⁺ increases with increasing the annealing temperature and the number of coating cycles.