An efficient blue-emitting phosphor LiCaPO4:Eu2+ for white LEDs

A new blue-emitting phosphor LiCaPO₄: Eu²⁺ was synthesized by solid state reaction at a relatively low temperature of 900 °C. It gives a single intense emission band centering at 470 nm, which corresponds to the 4f⁶5d¹→4f⁷ transition of Eu²⁺. The dependence of luminescence intensities on Eu²⁺ concentration was investigated. The phosphor, with a single excitation band extending from 250 to 400 nm, could be efficiently excited by near-ultraviolet light-emitting diodes and is believed to be a promising blue-emitting phosphor for white light-emitting diodes.     

High-brightness red-emitting double-perovskite phosphor Sr_2LaTaO_6:Eu~(3+) with high color purity and thermal stability [Invited]

Bright Eu~(3+)-activated double-perovskite Sr_2LaTaO_6 red-emitting phosphors were successfully synthesized by a high-temperature solid-state method. Under near-ultraviolet excitation at 394 nm, optimal Sr_2LaTaO_6∶0.2 Eu~(3+)phosphors emitted high-brightness red light around 613 nm with the International Commission on Illumination chromaticity coordinates(0.650,0.349). Notably, the color purity can reach 92%. Impressively, the favorable thermal stability of the Sr_2LaTaO_6∶0.2 Eu~(3+)phosphors was characterized by temperature-dependent emission spectra at different temperatures from 303 to 463 K, and the emission intensity at 423 K remained 73% of its value at 303 K. All of the results suggested that the as-prepared Sr_2LaTaO_6∶0.2 Eu~(3+)phosphors can be used in near-ultraviolet-excitable white light-emitting diodes as a red-emitting color converter.     

Spectroscopic characteristics of Tm3+ in Tm and Tm,Nd, Yb:Sc2O3 ceramic

The spectroscopic investigation of Tm³⁺ or (Nd, Yb, Tm)-doped Sc₂O₃ transparent ceramics, as laser-active media for visible and IR emission, was performed. The spectra are dominated by Tm³⁺ ions in sites of C₂ symmetry and an energy level scheme and other spectral parameters were determined. The strong concentration quenching of ³H₄ level emission in Tm:Sc₂O₃ at 300 K is discussed by considering the resonant cross-relaxation (³H₄→³F₄)?(³H₆→³F₄) process and multipolar interactions of various orders. The main energy-transfer processes leading to the blue upconversion emission from the ¹G₄ Tm³⁺ level in (Tm, Nd, Yb):Sc₂O₃ ceramic, under pulsed pumping at 808.3 nm were evidenced.     

Critical separation for efficient Tm3+ -Tm3+ energy transfer evidenced in nanostructured Tm3+: Al2O3 thin films

Nanostructured amorphous Al oxide (a-Al2O3) thin films doped with Tm3+ were synthesized by alternate pulsed laser deposition. The Tm3+ ions have been deposited in layers with in-depth separation ranging from 0.75 to 6 nm. The films show two broad emission bands originated from the Tm3+ 3H4-->3F4 and 3F4-->3H6 transitions. Their intensity increases at a similar rate and the lifetimes are not modified as the layer separation decreases down to 1.5 nm, suggesting that there is no concentration quenching. At the critical value of 1.5 nm the onset of Tm3+ -Tm3+ energy transfer is evidenced by a sharp decrease of the emission intensity and lifetime. Below this critical value, the rate at which the intensity increases for the 3F4-->3H6 transition is much higher than that for the 3H4-->3F4 transition, evidencing quenching of the 3H4-->3F4 transition through a cross-relaxation mechanism. The control of the Tm3+ ions in the nanometer scale allows evidencing the onset of energy transfer processes among ions and offers a route to optimize compact photonic gain integrated devices.     

SrAl4O7:Tm3+/Yb3+ nanocrystalline blue phosphor: structural, thermal and optical properties

Strontium aluminate (SrAl₄O₇) nanophosphor codoped with Tm³⁺–Yb³⁺ has been synthesized through the combustion route using urea as the reducing agent. Structural, thermal and optical characterizations have been carried out. Heat treatment of the samples shows a change in the crystallite phases and the relative luminescence intensities for the different bands. The nanocrystalline particles in the as-synthesized sample seem to arrange in rod like shapes of submicrometer length on annealing. A broad (350–550 nm) emission in the UV–green region is observed when 266 nm radiation is used for excitation. Intense upconversion (UC) emissions in blue, red and infrared are seen with excitation by 976 nm radiation. An emission at 364 nm not observed earlier and attributed to ¹D₂→³H₆ transition in Tm³⁺ is also seen. The blue emission from SrAl₄O₇:Tm³⁺/Yb³⁺ codoped nanophosphor (annealed at 1200°C) exhibits high color purity (89%) and is comparable to phosphors used commercially. The energy transfer mechanisms, responsible for these UC emissions, are proposed and discussed.     

Spectroscopic characterization of a Tm3+:SrGdGa3O7 crystal

3 O₇ crystal have been recorded at room temperature and at approximately 8 K. Room-temperature luminescence lifetimes of ¹D₂, ¹G₄, ³H₄, and ³F₄ states have been measured for Tm concentration ranging from [%at.]0.5 to [%at.]9. Based upon these data the crystal field splitting of luminescent states has been derived and radiative transitions rates have been evaluated. Strong self-quenching of luminescence originating in the ¹G₄ and ³H₄ states has been found in this activator–host combination. Peak emission cross section of the potential laser transition at 1800 nm was determined to be 3.9×10^-21 cm² and the gain coefficient versus wavelength was estimated and discussed. Received: 14 April 1998/Revised version: 10 August 1998     

Luminescence and energy transfer in phosphor LiAl5O8: Ce3+, Dy3+

Ce³⁺ and Dy³⁺-doped LiAl₅O₈ were synthesized in the present study. The luminescence properties of Ce³⁺ and Dy³⁺, and the energy transfer from Ce³⁺ to Dy³⁺ were investigated. The Ce³⁺ species in LiAl₅O₈ emit one broad band that peaks at 351 nm under the excitation of ultraviolet light, which is attributed to the 5d–4f transitions of Ce³⁺. The luminescence of Dy³⁺ in singly doped LiAl₅O₈ can not be detected due to its low oscillator strength. However, Dy³⁺ emit intense blue (477 nm) and yellow (569 nm) light after the introduction of Ce³⁺. This phenomenon demonstrates that there exists effective energy transfer from Ce³⁺ to Dy³⁺, which occurs because the emission spectrum of Ce³⁺ perfectly overlays the excitation spectrum of Dy³⁺. The energy transfer from Ce³⁺ to Dy³⁺ is performed through dipole–dipole interactions. The experimental results show that LiAl₅O₈ co-doped with Ce³⁺ and Dy³⁺ can be a potential two-band (blue and yellow) phosphor.     

Improved color purity in nano-size Eu-doped YBO3 red phosphor

Nano-size YBO₃:Eu³⁺ phosphor has been synthesized by the co-precipitation method. X-ray diffraction (XRD) pattern confirmed the formation of hexagonal vaterite-type structures of YBO₃:Eu³⁺ nanoparticles. The transmission electron microscopy (TEM) study revealed the formation of spherical YBO₃:Eu³⁺ nanoparticles with size 20-40 nm. The photoluminescence spectra revealed that the ratio of the red emission (⁵D₀-⁷F₂) to the orange emission (⁵D₀-⁷F₁) was much higher in the synthesized nano-size YBO₃:Eu³⁺ phosphor. The improved relative intensity, i.e., higher R/O value of emission peaks, is due to a lower symmetry of crystal field around Eu³⁺ ions.     

Upconversion enhancement in Yb3+,Tm3+:BaY2F8 quasi-nanoparticles

Yb³⁺Tm³⁺:BaY₂F₈ single crystals have been milled to quasi-nanometric size. A complete characterization of the quasi-nanoparticles has been compared with that of a bulk crystal with the same composition. The emission spectra did not show any difference as for the shape and relative intensity of the various peaks within each band, but the infrared lifetime of the quasi-nanoparticles is significantly longer than that of the bulk crystal. In agreement with other literature results we observed a strong increase of the upconverted luminescence intensity in the quasi-nanoparticles. An explanation is given as the effect of radiation trapping of the pumping radiation that increases the effective pump intensity in the volume of the quasi-nanoparticles with respect to the bulk crystal.     

H3BO3对BaAl2Si2O8：Eu2+蓝色荧光粉物相组成和发光特性的影响

采用化学共沉淀法一次煅烧工艺合成了BaAl₂Si₂O₈：Eu²⁺蓝色荧光粉.用X射线衍射仪、荧光分光光度计和扫描电镜测试了助熔剂H₃BO₃对BaAl₂Si₂O₈：Eu²⁺蓝色荧光粉物相结构、发光性能、形貌等的影响.研究表明：化学共沉淀法一次煅烧工艺合成的BaAl₂Si₂O₈：Eu²⁺蓝色荧光粉为单相,H₃BO₃的加入使基质结构由六方相转变成单斜相,并引起发射主峰位置和发射强度的变化;BaAl₂Si₂O₈：Eu²⁺蓝色荧光粉的发光强度随着H₃BO₃加入量的增加先增强,后减弱,当加入H₃BO₃的质量分数为1.5%时,发光强度最大;H₃BO₃的加入使合成BaAl₂Si₂O₈：Eu²⁺蓝色荧光粉的颗粒呈类球形,分布更加均匀,粒度更小. 关键词： 3BO₃')" href="#">H₃BO₃ 2Si₂O₈：Eu²⁺')" href="#">BaAl₂Si₂O₈：Eu²⁺ 发光特性 化学共沉淀法     

Relaxation dynamics of excited states of Tm3+ in SrGdGa3O7 crystals activated with Tm3+ and Tb3+

3 H₄ and ³F₄ states of Tm in SrGdGa₃O₇ single crystal was evaluated. Tm-Tb energy transfer reduces effectively the lifetime of terminal level in a potential ³H₄-³F₄ laser transition but gives rise to parasitic nonradiative relaxation of the initial ³H₄ level. SrGdGa₃O₇ crystal single doped with thulium possesses combination of properties advantageous for laser oscillations near 1.9 μm, namely high rate of cross relaxation process leading to population buildup on the initial ³F₄ level and relatively high crystal field splitting of the ground ³H₆ level. Received: 25 April 1996/Revised version: 10 October 1996     

Luminescent properties of Mg3Ca3(PO4)4: Eu2+ blue-emitting phosphor for white light emitting diodes

A blue-emitting phosphor, Eu²⁺-activated Mg₃Ca₃(PO₄)₄ phosphor was synthesized by conventional solid-state reaction. X-ray powder diffraction (XRD) analysis confirmed the phase formation. Photoluminescence (PL) results showed that Mg₃Ca₃(PO₄)₄: Eu²⁺ could be efficiently excited by UV–visible light from 250 to 430 nm, which matched well with the emission wavelengths of near-UV and UV LED chips. The effects of the doped-Eu²⁺ concentration in Mg₃Ca₃(PO₄)₄: Eu²⁺ on the PL were also investigated. The result reveals that Mg₃Ca₃(PO₄)₄: Eu²⁺ is a potential blue-emitting phosphor for white LEDs.     

One color,pulsed excited-state upconversion in YAG:Tm3+

One color red laser pumping of YAG:Tm³⁺ crystals results in a strong upconverted near ultraviolet and blue fluorescence from the excited¹ D ₂ and¹ G ₄ multiplets. It is found that under pulsed-pumping conditions the quasi-resonant excited-state absorption from the³ H ₄ multiplet is the responsible process. Analysis of the upconverted emission confirmed previous results on³ H ₄ level assignments as well as on inhomogeneous line broadening in the YAG structure.     

Ba2B2P2O10:Eu3+材料的光谱特性

采用高温固相法合成了Ba2B2P2O10:Eu3+材料,并研究了材料的光谱特性。在400nm近紫外光激发下,材料的发射光谱由4组线状峰组成,峰值分别为600,618,627和660nm,分别对应Eu3+的5D0→7F1,7F2,7F3和7F4跃迁。研究了Eu3+掺杂浓度及电荷补偿剂对材料发射强度的影响,结果显示,随Eu3+掺杂浓度的增大,材料的发射强度增大,并未出现浓度猝灭效应,同时,添加电荷补偿剂可增强材料的发射强度。     

Preparation and luminescence of blue-emitting phosphor Ca2PO4Cl:Eu2+ for n-UV white LEDs

A series of blue-emitting Ca_2 ? xEu_xPO₄Cl phosphors were synthesized by a solid state method in a reducing atmosphere. The factors those affect the structure and the photoluminescence (PL) intensities of phosphors, including the dosage of chlorine source CaCl₂, reaction time and annealing temperature, have been investigated in detail. X-ray diffraction (XRD) and photoluminescence measurements were performed to testify the crystal structure and luminescent properties. The optimal Eu²⁺ concentration was determined, and the mechanism of the concentration quenching was predominated by dipole–dipole interaction. The present phosphor exhibits a strong absorption in the near-UV region, emits an intense blue emission centered at 451 nm and presents excellent thermal stability, suggesting that the phosphor is competitive as a promising blue-emitting phosphor for near ultraviolet (n-UV) light-emitting diodes (LEDs).     

A novel blue-emitting phosphor: BaAl2B2O7: Pb

Pb²⁺ doped BaAl₂B₂O₇ materials were prepared by a solution combustion synthesis. The phase of the synthesized materials was determined using the powder X-ray diffraction. The photoluminescent properties of Pb²⁺ doped BaAl₂B₂O₇ materials were investigated using spectrofluorometer at room temperature. The emission and excitation bands of BaAl₂B₂O₇: Pb²⁺ were observed at 423 and 266 nm, respectively. The dependence of the emission intensity on the Pb²⁺ concentration for BaAl₂B₂O₇: Pb²⁺ was investigated. The Stokes shifts of BaAl₂B₂O₇: Pb²⁺ was calculated to be 13 953 cm⁻¹.     

Co-doped Y2O3:Tb3+/Tm3+ multicolor emitting phosphors for thermometry

In this study, the new temperature-dependent phosphor, Y2O3:Tb3+/Tm3+, was investigated for high-temperature thermometry. The photoluminescence intensity at 456?nm emitted from Tm3+ was strong at temperatures higher than 1100?K, whereas the peak intensities emitted from Tb3+ decreased due to the thermal quenching effect. Thus, the intensity ratio between those emissions showed an appropriate variation for thermometry over a wide temperature range. In addition, the phosphors showed a distinct change of visible emission colors from green to blue with increasing temperature. These findings suggest the applicability of these phosphors in visual thermo-sensors.     

Tm3+掺杂SrAl2O4:Eu2+的光激励和热释光性能

通过高温固相法制备出Sr_{0.98-xAl2O4:0.02Eu²⁺,xTm³⁺(x=0,0.01,0.02,0.03,0.04,0.05)系列样品,并对其光激励和热释光性能进行了研究。在SrAl2O4:Eu²⁺原有陷阱能级结构的基础上,通过Tm³⁺的掺杂引入了更深的陷阱TB,并增加原有陷阱TA浓度,进而优化了材料的光存储容量及光激励特性。对比研究了系列样品的初始光激励发光强度和热释光强度随着Tm³⁺掺杂量的变化规律,证实陷阱TB为光激励发光提供了有效俘获中心。当Tm³⁺的掺杂摩尔分数x=0.03时,材料中的陷阱TB的浓度达到最高值,同时光激励发光强度最大。对比Tm³⁺共掺前后热释光图谱,通过Chen's半宽法计算出了引入陷阱TB的陷阱深度。实验结果证实材料中TB的浓度对其光激励发光性能起着决定性的作用。在980 nm激发下,由深陷阱TB释放出来的电子可以再次被浅陷阱TA俘获,这种浅陷阱TA的再俘获效应在光激励发光过程中表现为光激励余辉现象。}