一种近紫外激发的钼钨硼酸盐红色荧光粉及其制备方法

正专利申请号:CN201310461167.3公开号:CN103497768A申请日:2013.09.29公开日:2014.01.08申请人:华南理工大学本发明公开了一种近紫外激发的钼钨硼酸盐红色荧光粉及其制备方法。该近紫外激发的钼钨硼酸盐红色荧光粉以Gd3BW1-xMoxO9为基质,以稀土离     

白光LED用LaF_3:Eu~(3+)红色荧光粉的制备与表征

采用水热法制备具有单一相六方晶系的LaF_3:Eu~(3+)纳米荧光粉.通过X射线粉末衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)、光致发光光谱(PL)和荧光衰减曲线对LaF_3:Eu~(3+)纳米荧光粉进行表征. LaF_3:Eu~(3+)荧光粉的激发光谱主要由250 nm处的宽带(O2-→Eu3+的电荷转移跃迁)和一些尖峰(Eu3+f-f跃迁)构成,其中位于近紫外区396 nm处有一较强的激发峰.通过发射光谱探测Eu3+在LaF3晶体中的局部晶场环境.在298 K下激发光谱和发射光谱可知,在六方晶系的LaF3纳米晶体中的Eu3+晶格位置从D4h降至到C2v,这是由于晶格变化所造成的.在396 nm激发下,观测到较优掺杂浓度为10%的LaF_3:Eu~(3+)荧光粉在591 nm(5D0→7F1跃迁)处有强烈的红色发射峰.其发光性能表明,LaF_3:Eu~(3+)红色荧光粉在近紫外发光二极管领域具有潜在的应用价值.     

绿色荧光粉Na_(1-x)Li_xCaPO_4:0.02Eu~(2+)的制备及其性能的研究

采用高温固相反应法制备了稀土掺杂荧光粉NaCa0.98PO4:Eu2+0.02,在波长360nm激发光激发下,荧光粉发射波长在500nm左右的绿光。采用Li+为掺杂离子取代基质晶格中的Na+位,通过杂质离子掺杂量对发光性能影响的研究,获得Li+的最佳掺杂量为5mol%。在波长为360mm近紫外光激发下,Na0.95Li0.05Ca0.98PO4:0.02Eu2+的发射强度是NaCa0.98PO4:Eu0.022+的2.5倍,该荧光粉为适用于近紫外激发的白光LED的绿色荧光粉。     

蓝色荧光粉NaBa0.98PO4:Eu2+0.02的制备和发光性能研究

采用高温固相反应法合成了蓝色荧光粉NaBa0.98P04:Eu2+0.02.利用射线衍射(XRD)、扫描电镜(SEM)和荧光光谱等实验技术,研究了掺杂离子和掺杂浓度对荧光粉的晶体结构和发光性能的影响.结果表明:制备的粉末为单斜晶系NaBaP04,能被从紫外到蓝光波长范围的激发光有效激发,在波长360nm激发光激发下,发射光为波长在430nm左右的蓝光.同时,研究表明最佳掺杂离子为Ca2+,最佳掺杂浓度为7％ mol,荧光粉NaBa0.91Ca0.07PO4:Eu2+0.02的发光强度是NaBa0.98PO4:Eu2+0.02的1.68倍,该方法制备的荧光粉是一种很好的白光LED的蓝色荧光粉材料.     

作为白光LED用铕掺杂氟化镧红色荧光粉的制备与光谱性能研究

采用水热法制备具有单一相六方晶系的LaF₃:Eu3+纳米荧光粉.通过X射线粉末衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)、光致发光光谱(PL)和荧光衰减曲线对LaF₃:Eu3+纳米荧光粉进行表征.LaF₃:Eu3+荧光粉的激发光谱主要由250 nm处的宽带(O2-→Eu3+的电荷转移跃迁)和一些尖峰(Eu3+ f-f跃迁)构成,其中位于近紫外区396 nm处有一较强的激发峰.通过发射光谱探测Eu3+在LaF₃晶体中的局部晶场环境.在298 K下激发光谱和发射光谱可知,在六方晶系的LaF₃纳米晶体中的Eu3+晶格位置从D_4h降至到C_2v,这是由于晶格变化所造成的.在396 nm激发下,观测到较优掺杂浓度为10%的LaF₃:Eu3+荧光粉在591 nm(5D₀→7F₁跃迁)处有强烈的红色发射峰.其发光性能表明,LaF₃:Eu3+红色荧光粉在近紫外发光二极管领域具有潜在的应用价值.      

溶胶-凝胶法制备Ca3Al2O6：Eu3+红色荧光粉及其发光性能

采用溶胶-凝胶法合成Ca3Al2O6：Eu3+红色荧光粉,通过XRD、SEM、荧光光谱分别对样品的结构、形貌以及发光性能进行表征,讨论煅烧温度、Eu3+掺杂浓度以及电荷补偿剂对样品发光性能的影响.结果表明：实验所得样品的结构与Ca3Al2O6相同,Eu3+掺杂并没有改变其晶体结构.合成的荧光粉在394 nm近紫外光激发下发出615 nm明亮的红光.样品的红光强度随着煅烧温度的升高先增加后减弱,最佳烧结温度为1200℃.同样红光强度也随着Eu3+掺杂浓度的增加先增加后减弱,最佳Eu3+掺杂浓度为4%（摩尔分数）.加入电荷补偿剂后样品的发光强度均增强,其中加入K+后发光增强的效果最显著.该铝酸盐红色荧光粉性质稳定,在白光LED近紫外芯片激发中具有潜在的应用.     

外场辅助液相法制备红色球形Y_2O_3:Eu~(3+)荧光粉

研究了以尿素为沉淀剂,通过改变加热方式、溶液pH、Eu~(3+)掺杂量及煅烧温度等条件,采用微波辅助液相法制备Y_2O_3:Eu~(3+)红色荧光粉,并对所得荧光粉进行检测分析。结果表明:试验所制备的荧光粉为规整的球形,涂敷性好,可以被近紫外激发光有效激发,发射主峰位于614nm处,归属于Eu~(3+)的~5 D_0→~7 F_2跃迁;该红色荧光粉可应用在白光LED。     

溶胶-凝胶法制备的BaMgAl10O17:Eu2+荧光性能研究

研究了柠檬酸为络合剂的溶胶-凝胶法制备的BaMgAl10O17Eu2+蓝色荧光粉的荧光性能,考察了Eu 2+掺杂量和晶化温度等因素对荧光粉的紫外和真空紫外波段激发的荧光性能的影响,并通过X射线衍射分析,探讨了Eu2+掺杂量引起的晶胞参数和荧光粉发射波长的变化.结果表明BaMgAl10O17Eu2+随着Eu2+掺杂量的增加,除荧光强度发生变化外,发射光谱的波长发生红移;真空紫外波段激发,Eu2+的最佳添加量为0.1,紫外波段激发下为0.12,发射峰波长均为450 nm;晶化时间2小时,温度在1300℃以上更好.     

一种铕离子Eu~(3+)激活的钼酸盐红色荧光粉制备方法及应用

<正>专利申请号:CN201310577821.7公开号:CN103571481A申请日:2013.11.15公开日:2014.02.12申请人:苏州大学本发明公开了一种铕离子Eu3+激活的钼酸盐红色荧光粉、制备方法及应用,荧光粉的分子式为Na2A5-5xEu5xMo6O24:Eu3+[A=Zn,Mg],x为Eu3+替换A的摩尔比系数,0.000 1≤x≤0.2。该荧光粉在近紫外光和蓝光区间均具有高水平的激发平台,发射峰值位于612 nm左右的红光,与近紫外LED     

熔盐法合成红色荧光粉CaWO_4∶Eu~(3+)及其发光性能的研究

采用熔盐法在800℃条件下合成了红色荧光粉CaWO4:Eu3+。通过多种手段对样品进行了表征,并与固相法样品进行了对比。XRD结果表明所合成的荧光粉衍射峰位置和标准卡77-2233一致,为单一四方晶系的白钨矿结构;SEM结果表明荧光粉形貌规则,粒度分布均匀,分散性较好;光谱结果显示荧光粉的发射主峰位于614 nm处,激发主峰位于393 nm处,为近紫外激发,色坐标为(0.661,0.343),且色纯度与商品粉相当。由于CaWO4∶Eu3+用熔盐法合成具有工艺简单、能耗低、周期短等特点,合成样品粉体形貌好、粒度分布均匀、结晶度高,样品质量不低于固相法样品,因此,该方法值得研究者关注。     

Photoluminescent properties of Sr2SiO4:Eu3+ and Sr2SiO4:Eu2+ phosphors prepared by solid-state reaction method

Eu2+ and (or) Eu3+ doped Sr2SiO4 phosphors particles were synthesized by a conventional solid-state reaction technique, and their structural and optical properties were investigated. The X-ray diffraction (XRD) results showed that the obtained phosphors were composed of orthorhombic α'-Sr2SiO4 and monoclinic β-Sr2SiO4 phase. When excited under 256 nm, Sr2SiO4:Eu3+ phosphors showed intense emission in the red region. Sr2SiO4:Eu3+ phosphors exhibited white emissions (x=0.30, y=0.40, TC=6500 K) ranging from 425 to 650 nm when it was excited by near-ultraviolet (near-UV) light, indicating that Sr2SiO4:Eu2+ was a good light-conversion phosphor candidate for near-UV chip.     

Recent advances in solid-state LED phosphors with thermally stable luminescence

Phosphor-converted white light-emitting diode(LED) lighting has gained tremendous achievements since the invention of the InGaN blue LED by Nakamura et al., who won the Nobel Physics Prize in 2014.By far, a significant challenge comes from the thermal quenching(TQ) behavior of the present LED phosphors during the high-power LED operation or the updated laser lighting. But systematic research or review on the luminescence quenching character and/or how to realize thermally stable luminescence are lacking. Since TQ is an inherent property of phosphors, it can be diminished by different approaches.This review proceeds from the mechanism of TQ, summarizes previous researches on improving the thermal stability of LED phosphors and also discusses future research opportunities in this field. The developments of the phosphors with properties of high luminance and thermal stability, as well as the improved strategies involved,will benefit the basic researches and applications in high power lighting or high-luminance laser lighting.     

Rare earth double activated phosphors for different applications

For the purpose of development of highly energy-efficient light sources,one needs to design highly efficient green,red and yellow phosphors,which are able to absorb excitation energy and generate emissions.In this contribution,we present our results on producing some efficient phosphors with improved luminescence properties.Using double activation,energy could be transferred from one luminescent activator to the other one,resulting in more efficient or brighter device operation.Co-activators could be added to a host material to change the color of the emitted light.The incorporation of Eu3+ or Tb3+ ions into the CaWO4 crystal lattice modified the luminescence spectrum due to the formation of the emission centers that generated the specific red and green light.Very efficient new red phosphors based on YNbO4 and doped by Eu3+,Ga3+,Al3+ allowed recommending these materials as good candidates for different applications including LED and X-ray intensifying screens.For double activated TAG with Ce3+ and Eu3+ and for different mole ratios of Ce/Eu,the color temperature changed from 5500 K(0.331,0.322) up to 4200 K(0.370,0.381) and the light became "warmer".Application of TAG:Ce,Eu in the light emitting device showed better chromaticity coordinates of luminescence and color rendering index of LEDs.     

Rare earth double activated phosphors for different applications

For the purpose of development of highly energy-efficient light sources, one needs to design highly efficient green, red and yellow phosphors, which are able to absorb excitation energy and generate emissions. In this contribution, we present our results on producing some efficient phosphors with improved luminescence properties. Using double activation, energy could be transferred from one luminescent activator to the other one, resulting in more efficient or brighter device operation. Co-activators could be added to a host material to change the color of the emitted light. The incorporation of Eu³⁺ or Tb³⁺ ions into the CaWO₄ crystal lattice modified the luminescence spectrum due to the formation of the emission centers that generated the specific red and green light. Very efficient new red phosphors based on YNbO₄ and doped by Eu³⁺, Ga³⁺, Al³⁺ allowed recommending these materials as good candidates for different applications including LED and X-ray intensifying screens. For double activated TAG with Ce³⁺ and Eu³⁺ and for different mole ratios of Ce/Eu, the color temperature changed from 5500 K (0.331, 0.322) up to 4200 K (0.370, 0.381) and the light became “warmer”. Application of TAG: Ce, Eu in the light emitting device showed better chromaticity coordinates of luminescence and color rendering index of LEDs.     

Luminescent properties and application of Eu3+ -activated Gd2(MoO4)3 red-emitting phosphor with pseudo-pompon shape for solid-state lighting

Eu3+ -activated Gd2(MoO4)3 pseudo-pompon-like red-emitting phosphors were prepared by solid-state method.The structure,morphology,and luminescent properties of these powder samples were investigated by X-ray diffraction (XRD),scanning electron microscopy(SEM),and fluorescent spectrophotometry,respectively.The as-obtained phosphors were single crystalline phase with orthorhombic unit cell.The particles of the powder samples had the length of 5-12 μm and width of 3-7 μm with flake shape and large surface area,which is suitable for manufacture of white LEDs.The phosphor could be efficiently excited by the incident light of 348-425 nm,well matched with the output wavelength of near-UV (In,Ga)N chip,and re-emitted an intense red light peaking at 615 nm.By combing this phosphor with a～395 nmemitting (In,Ga)N chip,a red LED was fabricated,so that the applicability of this novel phosphor to white LEDs was confirmed.It is considered to be an efficient red-emitting conversion phosphor for solid-state lighting based on (In,Ga)N LEDs.     

Luminescence properties of Eu~(3+):NaGd(WO_4_)2 nanoparticles and nanorods

The NaGd(WO_4)_2:Eu~(3+) phosphors were prepared by the microemulsion mediated hydrothermal method. The morphology and size of the samples could be dependent on the p H in the initial solution. These phosphors obtained had a strong absorption at 395 nm matching with the popular emission of near-UV LED chips, and could emit intense red light at 616 nm. The small ellipsoid-like particles or short rods were provided with large parameters of oscillator strength ?_2 and asymmetry ratio. Compared to the ellipsoid-like phosphors, the rod-like phosphors took on stronger emission, longer lifetime and larger quantum efficiency. This work demonstrated that the one-dimension Na Gd(WO_4)_2:Eu~(3+) phosphors might be a more favorable device than zero-dimension ones for photoluminescence.     

Luminescence and energy transfer of color-tunable Lu_2MgAl_4SiO_(12):Eu~(2+),Ce~(3+),Mn~(2+) phosphors

Energy transfer among the co-doped activators is an efficient route to achieve color-tunable emission in inorganic phosphors.Herein,photoluminescence tuning from blue to cyan has been achieved in the Lu_2MgAl_4 SiO_(12);Eu~(2+),Ce~(3+)phosphors by varying the Ce~(3+) concentration with a fixed Eu~(2+)content.With the further introduction of a Mn~(2+)-Si4+couple into the host lattice,the emission color can be tuned to red through the energy transfer of Eu~(2+)and Mn~(2+).The luminescence properties and the energy transfer mechanism were studied in detail.The energy transfer from Eu~(2+)to Ce~(3+)is certified as a dipolequadrupole interaction with the energy transfer efficiency of 41.4% and Eu~(2+)to Mn~(2+)belongs to a dipole-dipole interaction with the energy transfer efficiency of 94.3%.The results imply that this singlephased Lu_2MgAl4 SiO_(12):Eu~(2+),Ce~(3+),Mn~(2+)phosphor has a potential prospect for application in near-UV chip pumped white light emitting diodes.     

Fabrication and luminescent properties of red phosphor M3BO6:Eu3+（M=La,Y）

A series of red phosphors M3BO6:Eu3+(M=La,Y) were synthesized at 1150 oC by conventional solid state reaction method and their luminescent properties were investigated.Structural characterization of the luminescent materials was carried out with X-ray powder diffraction(XRD) analysis.Photoluminescence measurements indicated that the La3BO6:Eu3+ phosphor exhibited bright red emission centered at about 612 nm 626 nm under UV excited.La3BO6:Eu3+ phosphor had better luminescent intensity than Y3BO6:Eu3+ phosphors under the same excitation and measuring conditions.It was shown that the 0.08 mol.% Eu3+ ions in La3BO6:Eu3+ phosphors was optimal.The color parameter indicated that La3BO6:Eu3+ phosphor was a preferable red phosphor for white LED.     

Photoluminescent properties of SreSiO4：Eu^3＋ and Sr2SiO4：Eu^2＋ phosphors prepared by solid-state reaction method

Eu²⁺ and (or) Eu³⁺ doped Sr₂SiO₄ phosphors particles were synthesized by a conventional solid-state reaction technique, and their structural and optical properties were investigated. The X-ray diffraction (XRD) results showed that the obtained phosphors were composed of orthorhombic α'-Sr₂SiO₄ and monoclinic β-Sr₂SiO₄ phase. When excited under 256 nm, Sr₂SiO₄:Eu³⁺ phosphors showed intense emission in the red region. Sr₂SiO₄:Eu³⁺ phosphors exhibited white emissions (x=0.30, y=0.40, T_C=6500 K) ranging from 425 to 650 nm when it was excited by near-ultraviolet (near-UV) light, indicating that Sr₂SiO₄:Eu²⁺ was a good light-conversion phosphor candidate for near-UV chip.     

Emission tunable of Mg_(0.695)Si_(0.695)Al_(1.39)O_(3.65)N_(0.35):Eu~(2+),Mn~(2+) oxynitride phosphors via energy transfer for WLEDs

A series of Eu~(2+)doped and Eu~(2+)/Mn~(2+) co-doped Mg_(0.695)Si_(0.695)Al_(1.39)O_(3.65)N_(0.35)(MSAON) phosphors were synthesized by solid-state reaction at a lower temperature of 1500℃.The crystal morphology and structure of MSAON host were characterized by SEM,TEM and XRD.The quantum yield(QY) for Eu~(2+)doped MSAON phosphors was measured as high as 62%,indicating the excellent luminous efficiency.For the Eu~(2+)/Mn~(2+)co-doped MSAON phosphor,the photoluminescence spectrum and delay curves reveal the efficient energy transfer(ET) process from Eu2+to Mn~(2+)ions.Meanwhile,the corresponding energy transfer efficiency,critical distance and mechanism are discussed in detail.Temperature-dependent emission spectrum shows the thermal and color stabilities.The emission color of MSAON:Eu~(2+),Mn~(2+)phosphors could be tuned from blue through white to red via varying the concentration of Mn~(2+) ions.White-light-emitting diodes(WLEDs) were successfully fabricated by encapsulating the phosphors in nUV LED(365 nm) devices obtaining white light with color rendering index(CRI) as high as 87.7.The results reveal that the MSAON:Eu~(2+),Mn~(2+)phosphors could have potential application in the field of n-UV WLEDs.