白光LED用钼酸盐体系红色荧光粉的研究进展

详细介绍目前白光LED用钼酸盐体系红色荧光粉的研究现状,重点介绍近几年来钼酸盐荧光粉在制备合成方面的最新进展,最后展望了LED用钼酸盐红色荧光粉的发展前景.     

用于固态照明的红色荧光粉Lu_2MoO_6:Eu~(3+)的发光性质（英文）

采用高温固相法制得Eu~(3+)掺杂的Lu_2MoO_6荧光粉,通过X射线衍射(XRD)及激发、发射光谱和衰减寿命等手段对样品的结构和发光性质进行了表征。XRD结果表明:制备的荧光粉均为单斜结构。实验结果表明该样品在可见光谱范围内能够被近紫外光有效地吸收,该吸收来自Mo~(6+)–O~(2-)吸收带。在掺杂10% Eu~(3+)的情况下,发光最强。详细地研究最佳临界距离Rc和能量机制。Lu_2MoO_6:Eu~(3+)红色荧光粉是一种可应用于近紫外激发白光LED用的新型红色荧光粉。     

白光LED用Y3Al5O12:Mn4+红色荧光粉的发光性质（英文）

用高温固相反应法制备了Mn4+掺杂的Y3Al5O12荧光粉。研究了其发光性质。在467nm光激发下,这种荧光粉发出红光。主要的发射峰位于643和670nm,均属于Mn4+的5E→4A2跃迁。Mn4+的最佳掺杂浓度为1mol%。Y3Al5O12:0.01Mn4+荧光粉的色坐标值(0.701,0.299)位于红色区域。监测670nm发射得到的激发光谱由峰值分别位于410,450,468,474,482和494nm宽激发带组成,归属于Mn4+的4A2→2T2,4T2激发跃迁。测得了670nm荧光衰减曲线,得到了对应Mn4+浓度为0.001,0.005,0.01,0.03,0.05的样品相应的荧光寿命分别为1.35±0.07,1.14±0.06,1.09±0.05,0.87±0.04,和0.63±0.04ms。这些结果表明在制备白光LED过程中在Y3Al5O12:Ce3+荧光粉中能添加Y3Al5O12:Mn4+红色荧光粉而显著改善白光LED器件的显色指数。     

湿热环境下LED荧光粉的性能退化规律及机理研究

选用制备高品质白光LED所常用黄、红、橙3种荧光粉,研究其在高温高湿老化试验和浸水模拟饱和水环境实验中的发光性能、发热性能、晶体结构和微观颗粒形貌变化规律,分析不同荧光粉的性能退化机理。结果表明:(1)在湿热环境下荧光粉易与水发生反应产生OH-,提升湿环境pH值,引起主体晶体结构结晶度下降,晶格振动增强,光致发热能量增加,诱发热猝灭效应;同时荧光粉表面粗化效应增加蓝光散射,降低蓝光吸收和转化效率;(2)在浸水模拟实验的饱和水环境中,荧光粉的发光性能和发热性能变化规律与高温高湿长期老化试验结果一致,可以有效评估LED荧光粉在湿热环境下可靠性。     

黄色稀土铝酸盐荧光粉新型生产工艺的研究

本文通过对黄色稀土铝酸盐荧光粉的发光原理、晶体结构及不同浓度铈添加对荧光粉性能的影响等进行分析,提出一新型生产工艺:采用三基色蓝粉窑炉直接高温还原法,实现了能耗小、效率高、生产成本低的目的。     

一种新型全自动点荧光粉机的研制

开发了一种符合我国国情的LED封装设备,该设备采用模块化设计理念,由PLC控制,运用机电一体化技术,变繁琐的工人手动点荧光粉为自动点荧光粉,对LED自动化生产的推广与应用具有积极的作用,对于精微技术LED封装的发展同样具有积极作用.     

白光LED用宽激发带的稀土硅酸盐基质荧光粉材料

采用稀土复合溶胶的喷雾.热解两步法制备了化学计量为SrxM2-xSiO4:xEu2 (M=Ca、Mg、Ba,x=0～2)的用于白光LED的荧光粉.用Van Uitert公式对SrxCa2-xSiO4体系荧光粉中铕离子的激发态带边位置和微结构参数的关系进行了预测计算;对SrxCa2-xSiO4、SrxMg2-xSiO4、SrxBa2-xSio4碱土正硅酸盐基质荧光粉样品,实测的激发光谱峰值的典型波长在350～460 nm的较宽范围内,发射光谱的典型峰值为562 nm;在计算不同阳离子的配位数Eu2 的发射波长时,把发射波长的计算预测值与实测波长值对比,认为在Sr1.8Ca0.2SiO4:Eu0.04的发光中心中Eu2 取代Sr2 均位于六配位的Sr2 上;荧光颗粒由纳米颗粒(晶)-亚微米的梯次分级自组装结构组成.该稀土硅酸盐基质荧光粉可以作为一种功率型、高亮度和高显色指数的白光LED的重要候选荧光材料.     

超细钼粉制备技术的研究现状与进展

金属钼因低的热膨胀系数、高温强度、高弹性模量等特性,广泛用于航空航天、军工、石油化工以及核工业等尖端行业,是推动高科技领域发展不可或缺的材料。钼粉作为钼制品的基础原料,其物化性质与钼制品的性能密切相关。相比于普通钼粉,超细钼粉具有更大的比表面积、更高的活性以及更低的烧结温度。目前制备超细钼粉的方法主要有热还原法和热分解法,热还原法通过调整还原工艺达到阻止晶粒长大的目的;而热分解法的发展主要涉及到装备的升级改造与工艺的优化完善。本文着眼于超细钼粉的制备工艺、反应机理以及产物状态,重点分析了典型工艺的发展历程和技术特点,总结了超细钼粉制备技术的研究现状与进展,提出当前技术工艺所面临的问题以及未来的研究方向,以期为超细钼粉制备工艺的发展与工业化应用提供思路。     

溶剂热-溶胶凝胶两步法合成(Y,Gd)(P,V)O_4:Eu~(3+),Bi~(3+)荧光粉及其发光研究

采用溶剂热-溶胶凝胶两步法合成了(Y1-z,Gd z)1-x-y(P z,V1-z)O4:x Eu3+,yBi3+系列红色荧光粉。用XRD、SEM和荧光分光光度计,对试样的晶体结构、表面形貌及发光性能进行了表征。结果表明:样品为四方晶系,掺杂离子的加入对基质晶体结构影响不大;样品形貌均一,呈短杆状或椭圆状;激发光谱由位于250~400 nm的O2--V5+带和Eu3+-O2-带组成;最强发射峰位于619 nm,归属于Eu3+的5D0→7F2特征跃迁发射;Eu3+的最佳掺杂量为5 mol%(x=0.05);掺杂Bi3+、Gd3+、P5+后,样品发射强度得到显著提高,Bi3+的掺杂还会使激发带红移至400 nm。说明这类荧光粉是可用于近紫外芯片激发的白光LED用红色荧光粉。     

高导热涂层制备及其性能研究进展

随着高集成技术、微电子封装技术、大功率LED技术以及超级计算机的迅猛发展,小型化、微型化与轻薄化成为现代及未来电子设备、电子电路的发展潮流,因此对散热要求越来越高.目前电子器件及设备主要应用导热硅脂、导热硅胶及复合材料来实现散热.若在器件及设备上制备一层具有高热导率、耐腐蚀、结合强度良好的导热涂层,可以更好地实现散热.从高导热涂层的应用背景及导热涂层的特点出发,阐述了制备方法和材料体系不同的三大类高导热涂层,重点介绍了以喷涂技术、磁控溅射技术、涂料技术制备高导热涂层的研究进展.对比这几种导热涂层制备技术可以发现,因为空气是热的不良导体,基于冷喷涂技术制备的涂层孔隙率低的特点,加之对涂层进行热处理后会更加致密,所以冷喷涂技术制备的导热涂层具有较高的热导率.但目前的喷涂粉末具有导电性,因此喷涂在电路及电器设备上应用还不够成熟.基于冷喷涂技术制备绝缘、高导热涂层,提高器件设备的导热性能,还有待进一步探索.     

A novel red phosphor for white light emitting diodes

A novel red phosphor, CaMoO₄:Eu³⁺, has been developed for white light emitting diodes (LEDs). The phosphor was prepared by using oxides in air and its luminescent properties have been investigated. The excitation and emission spectra indicate that this phosphor can be effectively excited by ultraviolet (UV) (394 nm) and blue (464 nm) light, and exhibits a satisfactory red performance (616 nm), nicely fitting in with the widely applied UV or blue LED chips. The novel phosphor is much more stable and has stronger emission intensity than the sulfide red phosphors used in white LEDs.     

Near-ultraviolet light excited deep blue-emitting phosphor for solid-state lighting

BaMgAl₁₀O₁₇:Eu²⁺ (BAM) is one kind of commercial blue phosphor in fluorescent lamps, because of its efficient blue emission. A serial of phosphors BaMgAl₁₀O₁₇:0.1Eu²⁺ doped different H₃BO₃ concentration were prepared by solid-state reaction technique, and their photoluminescent properties were investigated. The introduction of H₃BO₃ broadens the excitation band of the phosphor BAM around 400 nm and enhances the emission intensity under 400 nm light excitation. The emission of the phosphor BAM doped with 6% H₃BO₃ has optimum blue emission, with good CIE (Commission Internationale de l’Eclairage, International Commission on Illumination) chromaticity coordinates x = 0.151, y = 0.058. Hence, the phosphor can be applied in fabrication of near-UV LED excited white light-emitting diode (LED).     

白光LED用Y3-xAl5O12：Ce3x＋材料发光性能的影响因素的研究

采用高温固相法,在氢氩混合气下还原制备了白光LED用荧光材料Y3-xAl5O12：Ce3x＋。研究了助熔剂用量、焙烧温度、保温时间等因素对材料发光性能的影响。研究表明,助熔剂用量、焙烧温度、保温时间对材料的发光性能影响较大,且均存在一个最佳值,当基质原料中Ce3＋掺杂量x为0.06,助熔剂用量为6%（质量）,焙烧温度为1300℃,保温时间为4 h时所得发光材料的性能最好。XRD测试表明,所制备的材料Y2.94Al5O12：Ce03.＋06属立方晶系。荧光光谱测试表明,在365 nm紫外光激发下,材料Y2.94Al5O12：Ce03.＋06呈现白光,其形成的宽带发射光谱的主发射峰波长分别约为427 nm和472 nm。     

白光LED用新型Eu或Gd共掺杂的Ce:YAG单晶荧光材料的光谱性能研究

开展了白光LED用新型YAG单晶荧光材料的制备和光谱性能研究,采用提拉法生长Eu,Ce:YAG及Gd,Ce:YAG晶体,并通过吸收光谱,激发、发射光谱及电光性能等对晶体材料的光谱特性进行表征。结果表明,Eu或Gd共掺杂的Ce:YAG单晶荧光材料均可以被波长460nm左右的蓝光芯片有效激发,产生一个范围为480～650nm的宽峰发射。Eu3+或Gd3+共掺杂会对Ce3+离子的发光产生影响:Eu3+离子的掺杂,会对Ce3+离子的发光产生淬灭效应;而Gd3+离子取代基质Y3+离子可以使Ce3+离子的发射峰发生红移。     

White light emission from blue InGaN LED precoated with conjugated copolymer/quantum dots as hybrid phosphor

In this work we fabricated white LEDs using a blue InGaN LED precoated conjugated copolymer/quantum dots (QDs) composite (green-emitting Poly {(9,9-dioctyl-2,7-divinylenefluorenylene)-alto-co-(2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylene)}/red-emitting CdSe quantum dots) as a hybrid phosphor. The emission peak wavelengths of the blue and red emissions in the spectra were 462 and 618 nm, respectively. The green-emitting polymer had two emission peaks at 515 and 543 nm. The subpeak of the copolymer (515 nm) was decreased by the absorption of QDs as the ratio of QDs increased, while the emission of the QD (618 nm) increased. Therefore, changes in the CIE-1931 coordinate, color temperature (Tc) and color-rendering index (Ra) were dependent on the QDs to copolymer ratios. The white LED of the hybrid phosphor containing 20 wt.% QDs had a luminous efficiency of 44.2 l m/W at 20 mA with a CIE-1931 coordinate, Tc and Ra of (0.3297, 0.3332), 5620 K and 75.3, respectively.     

Crystallization, morphology and luminescent properties of YAG：Ce^3＋ phosphor powder prepared by polyacrylamide gel method

A novel synthesis process, based on the polyacrylamide gel method, was used to prepare Ce-doped YAG phosphor powders. Effects of heat treatment parameters, temperature and holding time, the fluxes, and atmosphere on microstructure and particle morphology as well as luminescent properties of YAG：Ce^3＋ phosphor powders were studied by X-ray powder diffractometry, scanning electron microscopy, and fluorescence spectrophotometry. The results show that the formation temperature （1 000 ℃） of pure YAG phase is significant low when being synthesized by the polyacrylamide gel method, compared with solid-state reaction. For luminescent properties, the intensity of emission of YAG：Ce^3＋ phosphor increases steadily with increasing temperature from 900 ℃ to 1 300 ℃ and prolonging holding time from 100 min to 400 min. But blue shift phenomenon is observed for 400 min calcination Fluxes as BaF2 and H3BO3 can enhance the intensity of emission of phosphor due to the improvement of crystallization of YAG and the stabilization of trivalence cerium ion in YAG host lattice at high temperature. Weak reduction atmosphere can contribute to improvement of the emission intensity of YAG：Ce^3＋ phosphor powders.     

Trivalent europium-doped strontium molybdate red phosphors in white light-emitting diodes: Synthesis,photophysical properties and theoretical calculations

Eu³⁺-doped strontium molybdate red phosphors (Sr_1?xMoO₄:Eu_x (x = 0.01–0.2)) for white light-emitting diodes (LED) were synthesized by the solid-state reaction method. The fluorescent intensities of the as-prepared phosphors were remarkably improved. The excitation and emission spectra demonstrate that these phosphors can be effectively excited by the near-UV light (395 nm) and blue light (466 nm). Their emitted red light peaks are located at 613 nm, and the highest quantum yield value (η) of the as-grown red phosphor, which is 95.85%, is much higher than that of commercial red phosphor (77.53%). These red phosphors plus commercial yellow powers (1:10) were successfully packaged with the GaN-based blue chips on a piranha frame by epoxy resins. The encapsulated white LED lamps show high performance of the CIE chromaticity coordinates and color temperatures. Moreover, to explain the fluorescent spectra of these phosphors, a complete 3003 × 3003 energy matrix was successfully built by an effective operator Hamiltonian including free ion and crystal field interactions. For the first time, the fluorescent spectra for Eu³⁺ ion at the tetragonal (S₄) Sr²⁺ site of SrMoO₄ crystal were calculated from a complete diagonalization (of energy matrix) method. The fitting values are close to the experimental results.     

Citric based sol-gel synthesis and luminescence characteristics of CaLa2ZnO5:Euphosphors for blue LED excited white LEDs

A novel class of orange-red phosphors namely CaLa₂ZnO₅ (CLZ) doped with Eu³⁺ ions were prepared by adopting citrate based sol-gel method. Those were thoroughly characterized by means of XRD, SEM, Tg-DTA, photoluminescent (PL) spectral profiles. PL studies reveal that its emission intensity strongly depends on sintering temperature as well as the dopant ion (Eu³⁺) concentration. Eu³⁺ ion doped CaLa₂ZnO₅ phosphor has a strong excitation at 468 nm, which correspond to the popular emission line from a GaN based blue light-emitting diode (LED) chip. The influence of the preparation method on the luminescence property was studied by comparing the emission performance of phosphors prepared by sol-gel and solid-state reaction methods along with a commercial red phosphor Y₂O₂S:Eu³⁺. Thus, the intense red emission (⁵D₀ → ⁷F₂) of the Eu³⁺ doped CLZ phosphors under blue excitation suggests them to be a potential candidate for the production of white light by blue LEDs.