白光LED用光转换无机荧光粉

本文综述了近年来白色发光二极管用光转换无机荧光粉的国内外研究进展.分别从能被蓝光LED芯片激发的黄色、绿色与红色荧光粉,和能被近紫外LED芯片激发的蓝色、绿色与红色荧光粉以及单一基质白光荧光粉进行了综述,对性能较好的荧光粉进行了重点推介;对相应的铝酸盐、硅酸盐、氮(氧)化物、钼酸盐等荧光粉的光致发光光谱及其调控原理进行...     

Sr3SiO5:Eu2+荧光粉的微波合成及性能研究

0 引 言 白光LED是一种具有广阔前景的节能照明灯具,被誉为人类的第四代照明用灯具.白光LED实现主要有两种方案,其中在蓝光LED芯片上涂覆黄色荧光粉,蓝光芯片发出的蓝光与荧光粉发出的黄光复合而获得白光,受到人们的重点关注[1-5].     

Li+,Eu3+共掺杂La2MoO6红色荧光粉的Pechini法合成及近紫外/蓝光激发下的发光特征

采用Pechini法合成了白光LED用红色荧光粉La_1.9-xMoO₆:0.10Eu³⁺,xLi⁺(x=0,0.10,0.20,0.25),并对样品分别进行了X射线衍射(XRD)、扫描电子显微镜(SEM)、电子能谱(EDX)以及荧光光谱(PL)等技术手段分析。 PL光谱显示该荧光粉可被近紫外光(395 nm)和蓝光(466 nm)有效激发,产生616和623 nm强的红光发射,归属于Eu³⁺的⁵D₀→⁷F₂电偶极跃迁。该荧光粉与近紫外LED芯片(370~410 nm)和蓝光LED芯片(450~470 nm)均匹配良好,具有潜在的商业应用价值。 共掺Li⁺离子作为敏化剂能显著提高荧光粉的发光强度,且最优掺杂量为x=0.20。     

白光LED用黄色荧光粉Ba(Y1-0.5x-yAly)2S4:xHo3+的合成和发光特性

采用高温固相法合成了Ba(Y1-0.5x-yAly)2S4:xHo3+系列荧光粉。在465 nm蓝光激发下,荧光粉的发射光谱呈多谱带发射,主峰位于492、543和661 nm处,分别对应于Ho3+的5F3→5I8,(5S2,5F4)→5I8和5F5→5I8跃迁发射。研究了Ho3+和Al3+掺杂量对BaY2S4:Ho3+发光性能的影响。结果表明,随着Ho3+掺杂量的逐渐增大,荧光粉的发光颜色由绿色逐渐向红色转变;适量Al3+取代Y3+可以提高BaY2S4:Ho3+荧光粉的发光强度。荧光粉Ba(Y0.665Al0.3)2S4:0.07Ho3+在蓝光(465 nm)激发下发射黄光,是一种潜在的白光LED用黄色荧光粉。     

黄光类水滑石的制备、表面改性及应用

采用共沉淀法合成了荧光类水滑石材料,该材料在470 nm蓝光激发下可发出黄色荧光(557 nm),采用硅烷偶联剂对其进行表面改性,探讨了表面改性对黄光类水滑石的发光性能、结构及热稳定性的影响。将改性黄光类水滑石与GaN基蓝光芯片封装后制得了白光LED。研究结果表明,改性的黄光类水滑石是制作白光LED可供选用的黄色发光材料。本文成功地将低温一步法制备得到的金属有机配合物/无机纳米杂化材料应用于LED,拓展了LED用荧光粉的选用范围。     

黄光类水滑石的制备、表面改性及应用

采用共沉淀法合成了荧光类水滑石材料,该材料在470 nm蓝光激发下可发出黄色荧光(557 nm),采用硅烷偶联剂对其进行表面改性,探讨了表面改性对黄光类水滑石的发光性能、结构及热稳定性的影响。将改性黄光类水滑石与GaN基蓝光芯片封装后制得了白光LED。研究结果表明,改性的黄光类水滑石是制作白光LED可供选用的黄色发光材料。本文成功地将低温一步法制备得到的金属有机配合物/无机纳米杂化材料应用于LED,拓展了LED用荧光粉的选用范围。     

全光谱白光发光二极管用Eu3+掺杂Ca2KZn2(VO4)3黄色荧光粉的制备及光学性能

基于蓝光芯片激发黄色荧光粉或近紫外芯片激发三基色荧光粉构建的白光发光二极管(WLED)在青光区域呈现明显的凹口,导致白光的色彩性能不够理想。为了弥补这一缺陷,实现全光谱白光,我们设计了Eu³⁺掺杂Ca₂KZn₂(VO₄)₃黄色荧光粉,其发射波长范围为400~750 nm。在387 nm激发下,在所制荧光粉中可同时获得来自VO₄^3-基团和Eu³⁺的发射光。Eu³⁺在Ca₂KZn₂(VO₄)₃基质中的最佳掺杂浓度(物质的量分数)为0.05,且VO₄^3-基团向Eu³⁺的能量传递效率达到64.9%。基于变温的发射光谱,揭示了所制荧光粉的热稳定性并发现VO₄^3-基团和Eu³⁺的激活能分别为0.538和0.510 eV。此外,将所制黄色荧光粉与商用蓝色荧光粉和近紫外芯片进行封装整合,得到可发射暖白光的WLED器件,其色温和显色指数分别为3843 K和85.8。     

基于能量传递可调光色荧光粉Ca2LaTaO6∶ Dy3+, Sm3+的发光性质及其发光二极管器件应用

通过固相反应法设计了Dy³⁺, Sm³⁺共掺杂双钙钛矿结构Ca₂LaTaO₆(CLTO)光色可调的白光发光二极管(LED)荧光粉. 通过Rietveld精修计算, 确定了Ca₂LaTaO₆的晶体结构参数和Dy³⁺, Sm³⁺离子的晶格占位, 并用密度泛函理论(DFT)计算了禁带宽度. 激发/发射光谱和荧光衰减行为证实了共掺杂体系中Dy³⁺到Sm³⁺的能量传递. Dy³⁺→Sm³⁺的能量传递机制为电偶极-电偶极相互作用, 离子间的临界距离为1.176 nm. 基于Dy³⁺→Sm³⁺的能量传递, 可通过调节Dy³⁺/Sm³⁺离子的掺杂浓度比, 使发光颜色从黄色转变为黄红色, 并实现白光发射. 利用该荧光粉与紫外芯片结合制作成白光发光二极管器件, 并确定了这些LED器件的发光效率、 CIE色度坐标、 相关色温(CCT)和显色指数(CRI)等. 结果表明, 这些荧光粉在紫外激发的白光LED中具有潜在的应用价值.     

白光LED用Eu掺杂红色荧光粉

白光LED因亮度高、体积小、寿命长、高效节能、绿色环保等优点而引起人们的广泛关注,但是目前大部分白光LED用荧光粉的不足之处在于其发光效率较低,显色指数较差,色温较高,成本较高等等。红色荧光粉可明显改善白光LED的色温和显色指数,因此红色荧光粉在调制白光LED和改善其显色指数方面具有至关重要的作用。近年来红色荧光粉得到了深入研究,并有不少文献报道了新型的红色荧光粉。本文介绍了Eu³⁺掺杂的线状红光发射荧光粉、Eu²⁺掺杂的带状红光发射荧光粉并着重介绍了Eu²⁺掺杂的新型窄带红光发射荧光粉,以及目前Eu掺杂红色荧光粉发展的不足及其改善方法。     

白光LED用新型红色荧光粉KCaY(MoO4)3:Eu3+的制备及发光性能

采用高温固相法制备了新型KCaY1-x(Mo04)3:Eux红色荧光粉.利用X射线衍射(XRD)、扫描电镜(SEM)和荧光光谱技术对粉体进行了结构、表面形貌和发光性能表征.结果表明:该系列荧光粉均为四方晶系的白钨矿结构,能够被近紫外光(394 nm)和蓝光(465 nm)有效激发,产生Eu3的5 D0→7 F2特征跃迁红光发射(613 nm).对这种荧光粉作后处理,可改善其表面形貌,并提高其发光强度.该系列荧光粉在394,465 nm的吸收与目前广泛应用的近紫外和蓝光LED芯片的输出波长相匹配.因此这种荧光粉是一种可能应用在白光LED上的红色荧光粉材料.     

New Phosphors for White LEDs

White light-emitting diodes (WLEDs) have matched the emission efficiency of florescent lights and will rapidly spread as light source for homes and offices in the next 5 to 10 years. WLEDs provide a light element having a semiconductor light emitting layer (blue or UV LEDs) and photoluminescence phosphors. GaN-based highly efficient blue InGaN LEDs combined with phosphors can produce white light. These solid-state LED lamps have a number of advantages over conventional incandescent bulbs and halogen lamps, such as high efficiency to convert electrical energy into light, reliability, and long operating lifetime (about 100,000 hours). For the purpose of development of high energy-efficient white light sources, we need to produce highly efficient new phosphors, which can absorb excitation energy from blue or UV LEDs and generate emissions.In this paper, we investigate the development of blue or UV LEDs by the appropriate combination of new phosphors which can lead us to obtain high brightness white light. The criteria of choosing the best phosphors, for blue (380-450 nm) and UV (360-400 nm) LEDs, strongly depends on the absorption and emission of the phosphors. Moreover, the balance light between the light emission from blue LEDs and the yellow YAG:Ce,Gd phosphor is important to obtain white light with high color temperature. The phosphors with high efficiency which can be excited by UV LEDs are important to obtain the white light with high color rendering index.     

蓝色有机电致发光材料及器件的研究进展

有机电致发光器件因在全彩平板显示和固态照明领域中具有广阔的应用前景, 而受到人们的广泛关注。 时至今日, 与现有的红色和绿色有机电致发光材料和器件相比, 具有优越综合性能的蓝色有机电致发光材料和器件却始终匮乏。 相对而言, 蓝光材料具有较宽的能隙, 因而很难获得低电压、高效率和良好稳定性的深蓝光器件。 通常, 白色有机电致发光器件可以通过混合三基色或者两种颜色的方法获得。 但是无论哪种方法, 蓝光材料均是必不可少的。 另外, 还可以通过能量传递将蓝光转化为红光和绿光。 因此, 研发出具有优越综合性能的蓝光材料对有机电致发光器件的推广及应用十分关键。 本文综述了近年来蓝色荧光材料、蓝色磷光材料的研究进展以及蓝光材料在蓝色和白色有机电致发光器件中的应用, 并结合现有工作, 对蓝色有机电致发光材料的研究和应用前景进行展望。     

Strong f‐f Excitation and Bright Red Emission in Cd4Gd1‐xEuxO(BO3)3 (0≤x≤1): Near‐UV LED Pumped Red Phosphor with Low Thermal Quenching

Searching efficient red phosphors under near‐UV or blue light excitation is practically important to improve the current white light‐emitting diodes (WLEDs). Eu²⁺‐ and Mn⁴⁺‐based red phosphors have been extensively studied. Here we proposed that Eu³⁺ is also a promising activator when it resides on a noncentrosymmetric coordination site. We proved that Cd₄GdO(BO₃)₃ is a good host, which has a significantly distorted coordination for Eu³⁺. A careful crystallographic study was performed on the solid solutions of Cd₄Gd_1‐xEu_xO(BO₃)₃ (0≤x≤1) by Rietveld refinements. The as‐doped Eu³⁺ cations locate at the Gd³⁺ site and are well separated by CdO₈, CdO₆ and BO₃ groups; thus, only a slight concentration quenching was observed at ≈80 atom % Eu³⁺. Most importantly, the parity‐forbidden law of 4f‐4f transitions for Eu³⁺ are severely depressed, thus the absorptions at ≈393 and ≈465 nm are remarkable. Cd₄Gd_0.2Eu_0.8O(BO₃)₃ can be pumped by a 395 nm LED chip to give a bright red emission, and when mixed with other commercial blue and green phosphors, it can emit the proper white light (0.3657, 0.3613) with a suitable R_a≈87 and correlated colour temperature ≈4326 K. In‐situ photoluminescence study indicated the low thermal quenching of these borate phosphors, especially under 465 nm excitation. Our case proves the practicability to develop near‐UV excited red phosphors in rare‐earth‐containing borates.     

Li2SrSiO4:Ce3+,Tb3+荧光粉的发光特性及Ce3+→Tb3+的能量传递

用固相反应法合成了具有单相的Li2EuSiO4结构的Li2Sr1-x-ySiO4:xCe3+,yTb3+系列样品。荧光光谱研究表明,Li2SrSiO4:Ce3+发射很强的蓝光,最强的激发峰位于360 nm;而Li2SrSiO4:Tb3+发射很强的绿光,最强的激发激发峰位于243 nm,但在350～410 nm的激发非常微弱。在Ce3+,Tb3+共掺杂的样品Li2Sr0.99-ySiO4:0.01Ce3+,yTb3+中,观察到Ce3+对Tb3+的共振能量传递。由于Ce3+对Tb3+能量传递,Tb3+的激发光谱中出现360 nm附近的宽激发峰。控制Tb3+/Ce3+掺杂浓度比可以实现绿蓝双基色的调制。这种双基色的荧光粉有望在紫外激发的白光LED中获得应用。     

硅、氮共掺杂碳点荧光粉的制备及发光性能

采用N-苯基对苯二胺和3-氨基丙基三甲氧基硅烷为原料,通过光化学催化法合成了高荧光强度的硅、氮共掺杂碳点（Si/N-CDs）。通过透射电子显微镜（TEM）、X射线光电子能谱（XPS）、荧光光谱、X射线衍射（XRD）和红外光谱（FT-IR）等对Si/N-CDs进行了表征。制备的Si/N-CDs形貌呈球形,平均直径约6.45 nm,在365 nm紫外光照射下发明亮的蓝绿色荧光,量子产率可达30.8%,连续30 d测试Si/N-CDs均保持高的荧光强度。用Si/N-CDs替代传统的红/绿/蓝三基色稀土荧光粉中的蓝/绿稀土荧光粉,并与红色荧光粉（Sr,Ca）AlSiN3∶Eu2+复合制备白光二极管（White Light Emitting Diode,WLED）。在60 mA电流下运行WLED,可实现86.9的高显色指数和7.76 lm/W的发光效率,色坐标是（0.3773,0.3734）,色温为4062 K,并且色点位于黑体普朗克轨迹上,表明制备的WLED可以产生高质量的照明效果。硅、氮共掺杂碳点具有简便的制备方法和优异的光学性质,并能够代替蓝/绿色稀土荧光粉与红光荧光粉复合制备高质量照明的...     

SrSi2O2N2∶Eu2+荧光粉的制备及性能研究

以SrCO3,Si3N4,Eu2O3为原料,在N2气氛下,采用自还原高温固相法制备了SrSi2O2N2:Eu2+荧光粉。研究了该荧光粉的物相结构、发光性能和晶体形貌,同时对比在不同气氛下合成的荧光粉。结果表明,在N2气氛与N2/H2气氛下分别合成的SrSi2O2N2:Eu2+荧光粉物相结构和光谱特性基本一致。显示出合成了主晶相SrSi2O2N2,但还含有少量未知的中间项。Eu2+浓度的变化不影响激发状态,而发射光谱的波长在Eu2+浓度为1mol%-20mol%之间,从530 nm的绿光红移至550 nm的黄绿光区域。同时,激发光谱覆盖的范围宽,均能有效的被UV或蓝光激发,这意味着该类荧光粉在白光LED方面有可能得到广泛的应用。     

Photoluminescence characterization of Ca10Na(PO4)7:Eu3+ red-emitting phosphor

Eu3+-doped Ca10Na(PO4)7 phosphors were successfully synthesized by solid-state reaction techniques. Their structures and photoluminescence characteristics were carefully studied. An efficient red emission under near-ultraviolet excitation is observed. The maximum intensity of luminescence was observed at the Eu3+ concentration around 9 mol%. The quadrupole-quadrupole interaction between Eu3+ ions is the dominant mechanism for concentration quenching of fluorescence emission from Eu3+ ions in Ca10-xNa(PO4)7:xEu3+. Due to the excitation spectrum is well coupled with near UV light, Ca10-xNa(PO4)7:xEu3+ phosphors have potential application as red phosphors in near UV chip-based white light emitting diodes.     

Combinatorial search for green and blue phosphors of high thermal stabilities under UV excitation based on the K(Sr1-x-y)PO4:Tb3+ xEu2+y system

The present investigation aims at the synthesis of KSr 1-x-y PO 4:Tb(3+) x Eu(2+) y phosphors using the combinatorial chemistry method. We have developed square-type arrays consisting of 121 compositions to investigate the optimum composition and luminescence properties of KSrPO 4 host matrix under 365 nm ultraviolet (UV) light. The optimized compositions of phosphors were found to be KSr 0.93PO 4:Tb(3+) 0.07 (green) and KSr 0.995PO 4:Eu(2+) 0.005 (blue). These phosphors showed good thermal luminescence stability better than commercially available YAG:Ce at temperature above 200 degrees C. The result indicates that the KSr 1-x-y PO 4:Tb(3+) x Eu (2+)y can be potentially useful as a UV radiation-converting phosphor for light-emitting diodes.     

Synthesis, characterization, photophysics and electrophosphorescent applications of phosphorescent platinum cyclometalated complexes with 9-arylcarbazole moieties

A series of cyclometalating platinum(II) complexes with substituted 9-arylcarbazolyl chromophores have been synthesized and characterized. These complexes are thermally stable and most of them have been characterized by X-ray crystallography. The phosphorescence emissions of the complexes are dominated by ³MLCT excited states. The excited state properties of these complexes can be modulated by varying the electronic characteristics of the cyclometalating ligands via substituent effects, thus allowing the emission to be tuned from bright green to yellow, orange and red light. The correlation between the functional properties of these metallophosphors and the results of density functional theory calculations was made. Because of the propensity of the electron-rich carbazolyl group to facilitate hole injection/transport, the presence of such moiety can increase the highest occupied molecular orbital levels and improve the charge balance in the resulting complexes relative to the parent platinum(II) phosphor with 2-phenylpyridine ligand. The solution-processed electrophosphorescent organic light-emitting diodes doped with these platinum-based phosphors have been fabricated which showed a maximum external quantum efficiency of 2.77% for the best device, corresponding to a power efficiency of 3.48 lm/W and a luminance efficiency of 8.49 cd/A. The present work enables the rational design of platinum-carbazolyl electrophosphors by synthetically tailoring the structure of carbazolylpyridine ring that can permit good color-tuning versatility suitable for multi-color display technology.