Improvement of electroluminescent property of blue LED coated with highly luminescent yellow-emitting phosphors

White light-emitting diodes (WLEDs) were fabricated by combining InGaN-based blue light-emitting diodes (LEDs) with highly luminescent Tb₃Al₅O₁₂:Ce³⁺ (TAG:Ce), Y₃Al₅O₁₂:Ce³⁺ (YAG:Ce), and Sr₃SiO₅:Eu²⁺ (SS:Eu). The TAG:Ce-based WLED showed a color rendering index (R _a ) of 79 and a luminous efficiency (η _L ) of 34.1 lm/W at 20 mA. The YAG:Ce-based WLED and the SS:Eu-based WLED showed low R _a values of 75 and 57 but high luminous efficiency values of 38.9 and 41.3 lm/W at 20 mA, respectively. When a mixture of YAG:Ce and SS:Eu was coated on a blue LED and the resultant WLED operated at 20 mA, the WLED showed a highly bright white light similar to daylight (η _L =40.9 lm/W, color temperature T _c =5,716 K, and R _a =76). Moreover, the WLED showed stable color coordinates against a considerable variation of applied current.     

Cesium lead halide perovskite quantum dot-based warm white light-emitting diodes with high color rendering index

White light-emitting diodes (WLEDs) were fabricated by employing a combination of a commercial yellow emission Ce³⁺-doped Y₃Al₅O₁₂ (YAG:Ce)-based phosphor and all-inorganic perovskite quantum dots pumped with blue LED chip. Perovskite quantum dot solution was used as the color conversion layer with liquid-type structure. Red-emitting materials based on cesium lead halide (CsPb(X)₃) perovskite quantum dots were introduced to generate WLEDs with high efficacy and high color rendering index through compensating the red emission of the YAG:Ce phosphor-based commercialized WLEDs. The experimental results suggested that the luminous efficiency and color rendering index of the as-prepared WLED device could reach up to 84.7 lm/W and 89, respectively. The characteristics of those devices including correlated color temperature (CCT), color rendering index (CRI), and color coordinates were observed under different forward currents. The as-fabricated warm WLEDs showed excellent color stability against the increasing current, while the color coordinates shifted slightly from (0.3837, 0.3635) at 20 mA to (0.3772, 0.3592) at 120 mA and color temperature tuned from 3803 to 3953 K.     

植物照明用荧光粉转换白光二极管的研究

LED具有效率高、体积小、功耗低、寿命长等优点,并且因其具有可轻易实现宽幅光谱调控的特性,在植物照明领域崭露头角。植物照明用LED分为两大类,一类是单色光LED,另一类是白光LED,其中植物照明用白光LED可与单色LED混合或者单独使用从而实现植物补光照明。植物封装用白光LED大部分采用蓝光LED芯片或紫外LED芯片和荧光粉组合实现,即荧光粉转换型白光LED,但是光谱集中于可见光偏蓝,对植物进行光合作用的效率不明显。植物对于光的吸收不是全波段的而是有选择性的,基于植物光合作用吸收光谱的特殊性,将白光LED光谱的显色性能作为评判其光谱是否适合植物生长所需的光质的标准,其平均显色指数Ra,特殊显色指数R9(饱和红光),R12(饱和蓝光)被考虑选择为植物照明用白光LED的主要性能评价参数。为设计出植物进行生长发育所需要的、性能良好的能应用于植物照明领域的白光LED,选用常见商用YAGG为绿色颜色转换材料,选用(Sr, Ca)AlSiN₃为红色颜色转换材料,并用传统高温固相法制备了系列光谱可调的(Sr, Ca)AlSiN₃荧光粉,并进行了光谱性能分析。通过将搭建好的LED结构模型导入光学仿真软件并分别引入绿色荧光粉颗粒、红色荧光粉颗粒以及蓝光芯片的特性参数,在Lighttools中分别建立了单蓝光LED芯片(450 nm)和双蓝光LED芯片(450+470 nm)激发(Sr, Ca)AlSiN₃和YAGG荧光粉组合,实现了白光LED的光学仿真模型,研究了两种激发模式下仿真得到的不同色温白光LED的光谱功率分布及其显色性能。用蓝光LED芯片、(Sr, Ca)AlSiN₃以及YAGG荧光粉组合进行了单芯片和双芯片显色性能差异的封装验证。通过将Sr_0.8Ca_0.12AlSiN₃∶0.08Eu2+和YAGG荧光粉的混合物点涂在双蓝光LED芯片上进行了白光LED的封装制备,获得了Ra=91.2,R9=96.1,R12=78.9,光谱辐射光效LER=126 lm·W-1的高效高显色白光LED其含有植物生长所需要的蓝光和红光。     

A new‐generation color converter for high‐power white LED: transparent Ce3+:YAG phosphor‐in‐glass

Currently, the major commercial white light‐emitting diode (WLED) is the phosphor‐converted LED made of the InGaN blue‐emitting chip and the Ce³⁺:Y₃Al₅O₁₂ (Ce:YAG) yellow phosphor dispersed in organic epoxy resin or silicone. However, the organic binder in high‐power WLED may age easily and turn yellow due to the accumulated heat emitted from the chip, which adversely affects the WLED properties such as luminous efficacy and color coordination, and therefore reduces its long‐term reliability as well as lifetime. Herein, an innovative luminescent material: transparent Ce:YAG phosphor‐in‐glass (PiG) inorganic color converter, is developed to replace the conventional resin/silicone‐based phosphor converter for the construction of high‐power WLED. The PiG‐based WLED exhibits not only excellent heat‐resistance and humidity‐resistance characteristics, but also superior optical performances with a luminous efficacy of 124 lm/W, a correlated color temperature of 6674 K and a color rendering index of 70. This easy fabrication, low‐cost and long‐lifetime WLED is expected to be a new‐generation indoor/outdoor high‐power lighting source.     

TiO2微粒对远程荧光粉膜及白光发光二极管器件光色性能的影响

利用热压法将TiO₂微粒掺入至YAG:Ce荧光粉和硅树脂中制备出远程荧光粉膜并封装成白光发光二极管(LED)器件, 通过荧光粉相对亮度仪、双积分球测试系统和可见光光谱分析系统对样品的光色性能及机理进行了研究. 结果表明: TiO₂的散射效应能够显著提高蓝光的利用率和黄光的透射强度, 白光LED器件的光通量在TiO₂浓度为0.966 g/cm³ 时达到最高值415.28 lm(@300 mA, 9.3 V), 提高了8.15%, 相关色温从冷白6900 K逐渐变化至暖白3832 K. TiO₂的掺入不仅提高了远程荧光粉膜的发射强度和白光LED器件的光通量, 同时能调控其相关色温.     

白光LED用稀土荧光粉的制备和性质

在还原气氛保护下利用高温固相法合成了化学组分为(M₁,M₂)₁₀(PO₄)₆X₂(M₁=Ca,Sr,Ba;M₂=Eu,Mn;X=F,Cl,Br)的可被紫光激发的蓝光、绿光和红光荧光粉,制备了紫光LED芯片+蓝光荧光粉+YAG荧光粉的二基色白光LED;紫光LED芯片+蓝光荧光粉+红光荧光粉的二基色白光LED,以及紫光LED芯片+蓝光荧光粉+绿光荧光粉+红光荧光粉的三基色白光LED。测试了所有制备的白光LED在不同的直流电驱动下的色度坐标、相关色温和显色指数。     

白光LED极限流明效率的计算

对蓝光芯片加黄色荧光粉制备白光LED方法的流明效率进行了理论计算。根据光度学原理,我们考虑到视觉函数V(λ)的修正,以色坐标为x=0.325,y=0.332,显色指数为81.5,色温为5 914 K的白光LED发光光谱为依据,计算了白光LED流明效率的理论极限:得出每瓦白光LED辐射光功率产生的光通量为298.7 lm,白光LED发射的总光子数为2.7×10¹⁸。在理想情况下,注入一个电子-孔穴对产生一个蓝光光子,设荧光粉的量子效率为1,因此,注入的电子-孔穴对数亦等于白光光子数,进而计算出白光LED每辐射1 W的光功率所需的电功率为1.51 W,上述白光LED发光光谱对应的白光LED的电-光转换的理论极限流明效率为197.8 lm/W。     

光散射PC荧光树脂的制备及光学性能

以聚碳酸酯(PC)粉体、有机硅光扩散剂和YAG∶Ce荧光粉为原料,通过熔融共混法和高温压模法及减薄抛光工艺制备出不同有机硅光扩散剂质量分数的PC/YAG∶Ce光散射荧光树脂样品,通过SEM、XRD、透射光谱和PL的性能分析,表明：荧光树脂样品在500～800 nm光谱范围有较高的透光率,样品的主相都为Y₃Al₅O₁₂,在342和448 nm有两个激发波峰,发射光谱在532 nm有一宽峰,属于Ce3+的5d→4f特征跃迁发射,对应的荧光寿命在61.5 ns左右。把荧光树脂样品应用到白光LED器件的封装获得的光效为81.12 lm/W@100 mA, 说明PC/YAG∶Ce荧光树脂片适用于作白光LED封装的新型荧光材料。     

Origin of the discrepancy between photoluminescence brightness of TAG:Ce and electroluminescence brightness of TAG:Ce-based white LED expected from phosphor brightness

A yellow-emitting Tb(3)Al(5)O(12):Ce(3+) (TAG:Ce) phosphor was coated on blue light-emitting diodes (LEDs) to obtain white LEDs (WLEDs). Since TAG:Ce showed 90% of the brightness of Y(3)Al(5)O(12):Ce(3+) (YAG:Ce), it was expected that TAG:Ce-based WLEDs showed 90% of brightness of YAG:Ce-based ones. However, the TAG:Ce-based WLED showed 74% of the brightness of YAG:Ce-based one. Considering the density and size of the phosphors, the higher density and larger size of TAG:Ce induced a great deal of sedimentation of TAG:Ce particles in an epoxy resin. It is believed that this is one of main reasons for the reduced optical power of the TAG:Ce-based WLED compared to that of the WLED expected from the brightness of TAG:Ce.     

Warm-white light-emitting diodes integrated with colloidal quantum dots for high luminous efficacy and color rendering: comment

This is a comment on a previous Letter [Opt. Lett.35, 3372 (2010)]. The chromaticity coordinates of nanocrystal quantum dot (NQD)-integrated WLED1, WLED2, and WLED3 are out of the range of the chromaticity tolerance quadrangles of white light sources. So these NQD WLEDs do not satisfy the requirements recommended for general lighting with solid-state lighting products to ensure high-quality white light. Furthermore, correlated color temperatures of WLED2 and WLED3 should be 2682 and 2527 K, respectively, according to the chromaticity coordinates of WLED2 and WLED3 at 12 mA, not 2781 and 2390 K. The NQD-integrated WLED1 and WLED2 located in tolerance quadrangles are simulated by the changing spectral power of green-, yellow-, and orange-emitting NQDs. The simulation results are presented.     

中性色温下两基色、三基色荧光粉转换白光LED的光谱优化

针对中性色温4 870 K,考虑斯托克斯损失,研究了两基色、三基色的白光LED的光谱优化。结果表明:InGaN/GaN基蓝光LED激发YAG荧光粉合成的白光光视效能可高达483.5 lm/W,但显色性较差,计算的斯托克斯效率为83.9%。加入窄带红色荧光粉或红光LED,优化后的光视效能降低为343 lm/W,但显色指数升至94.7,同时计算得到该LED的斯托克斯效率为84.4%。对该优化的三基色LED光谱进行可调色温白光的特性分析,发现较高色温 (＞4 000 K)对应的显色指数普遍高于低色温(＜4 000 K)的显色指数。     

红、绿CdSe@ZnS量子点配比对三波段标准白光LED器件的影响

将一步法合成的具有梯度合金结构的红光、绿光CdSe@ZnS量子点与硅胶均匀混合后,作为光转换层涂覆到蓝色InGaN LED芯片上,制备了不含荧光材料的三波段白光LED器件。研究了峰值为650 nm和550 nm的高效率红、绿量子点在硅胶中的含量及配比对白光LED色坐标以及效率的影响。结果表明,当红、绿量子点配比为2：3时,可得到发射纯正白光的QDs-LED器件,色坐标为（0.322 8,0.335 9）、色温为5 725 K,功率效率为26.61 lm/W,显色指数为72.7。光谱中红、蓝、绿三色发光峰的半高宽分别为30,25,38 nm,表明器件具有很好的单色性和高色纯度。     

碳热还原法合成LaSi_3N_5∶Ce~(3+)蓝色荧光粉及其发光性能研究

利用碳热还原法制备了LaSi_3N_5∶Ce~(3+)蓝色荧光粉,重点研究了原料中掺C量和退火对样品纯度及发光性能的影响。通过X射线衍射仪和荧光光谱仪分别表征样品的晶体结构和发光性能。研究结果表明:1 600℃时能够合成主相为LaSi_3N_5∶Ce~(3+)的荧光粉。在360nm紫外光激发下样品可获得波段范围在380~600nm的单峰宽带发射谱,归结于Ce~(3+)的5d-4f的能级跃迁。当n_C/n_(La)=4/1时样品发光强度达到最大,并且光谱出现先红移后蓝移的现象。经过退火的样品的发光强度与退火前相比提高了60%~345%。将热处理后的n_C/n_(La)=4/1的样品与商用YAG混合涂覆在UV芯片上(λ_(em)=365nm)封装成WLED,证实了LaSi_3N_5∶Ce~(3+)在白光LED领域潜在的应用价值。     

Improved color rendering of phosphor-converted white light-emitting diodes with dual-blue active layers and n-type AlGaN layer

An InGaN/GaN blue light-emitting diode (LED) structure and an InGaN/GaN blue-violet LED structure were grown sequentially on the same sapphire substrate by metal-organic chemical vapor deposition. It was found that the insertion of an n-type AlGaN layer below the dual blue-emitting active layers showed better spectral stability at the different driving current relative to the traditional p-type AlGaN electron-blocking layer. In addition, color rendering index of a Y3Al5O12:Ce3+ phosphor-converted white LED based on a dual blue-emitting chip with n-type AlGaN reached 91 at 20 mA, and Commission Internationale de L'Eclairage coordinates almost remained at the same point from 5 to 60 mA.     

Synthesis and luminescence of Eu-doped alkaline-earth apatites for application in white LED

A series of Eu²⁺-doped alkaline-earth apatites (alkaline-earth=Ca, Sr and Ba) were synthesized by a solid state reaction method with excess chlorides, and the effect of the used excess chlorides on the luminescent property of the synthesized products was discussed. Photoluminescence measurements showed that Eu²⁺-doped calcium apatite exhibited intensely blue wide-band emission peaking at 457 nm under near UV excitation among the Eu²⁺-doped Ca, Sr and Ba apatites. Blue and white LEDs were successfully fabricated by pre-coating the calcium apatite phosphors onto ∼395 nm-emitting InGaN chips. The CIE coordinates, color temperature, luminous efficacy and rendering index value of the fabricated white LED are (0.3432, 0.3234), 4969 K, 8 lm/W and 80, respectively. The results indicate that the Eu²⁺-activated calcium apatite phosphor is a promising candidate as a blue component for fabrication of near UV-based white LEDs.     

MgO对Sr2SiO4:Eu2+荧光粉发光性质的影响

通过在Sr₂SiO₄:Eu²⁺荧光粉中加入MgO,提高了Sr₂SiO₄:Eu²⁺荧光粉的蓝光和黄光发射带的发射强度,研究了MgO浓度对Sr₂SiO₄:Eu²⁺荧光粉发光强度的影响。当Mg与Si的量比在1.0附近时,荧光粉的亮度较高,且发光颜色为白色。通过调节Sr₂SiO₄:yEu²⁺ ,MgO荧光粉中Eu²⁺的掺杂浓度,可以调节荧光粉的发光颜色。用Sr₂SiO₄:Eu²⁺ ,MgO和400 nm的InGaN管芯制备的白光LED,色坐标优于α'-Sr₂SiO₄:Eu²⁺和β-Sr₂SiO₄:Eu²⁺荧光粉制成的白光LED,显色指数和流明效率高于β-Sr₂SiO₄:Eu²⁺和α'-Sr₂SiO₄:Eu²⁺制成的白光LED。     

LiMBO3 : Dy3+材料的发光特性

采用固相法制备了LiM(M=Ca, Sr, Ba)BO₃ : Dy³⁺材料,并研究了材料的发光特性。LiM(M=Ca, Sr, Ba)BO₃ : Dy³⁺材料的发射光谱均呈多峰发射,对应于Ca,Sr,Ba,其主发射峰分别是Dy³⁺的⁴F_9/2→⁶H_15/2(484,486,486 nm),⁶H_13/2(577,578,578 nm)和⁶H_11/2(668,668,666 nm)跃迁。监测黄色发射峰时,所得激发光 谱峰值位置相同,主激发峰分别为331,368, 397,433,462,478 nm,对应Dy³⁺的⁶H_15/2→ ⁴D_7/2,⁶P_7/2,⁶M_21/2,⁴G_11/2,⁴I_15/2和⁶F_9/2跃迁。研究了敏化剂Ce³⁺及电荷补偿剂Li⁺、Na⁺和K⁺对LiM(M=Ca, Sr, Ba)BO₃ : Dy³⁺材料发光强度的影响。结果显示:加入敏化剂Ce³⁺提高了材料的发光强度,发光强度最大处对应的Ce³⁺浓度为3%;加入电荷补偿剂Li⁺、Na⁺和K⁺后,材料的发光强度也得到了明显提高,但发光强度最大处对应的Li⁺、Na⁺和K⁺浓度不同,依次为4%、4%和3%。     

Recent progress in single chip white light-emitting diodes with the InGaN underlying layer

Tremendous progress has been achieved in white light-emitting diodes (LEDs). To further improve the quality of white light and simplify the fabrication process, a single chip white-light LED with the InGaN underlying layer (UL) was studied and fabricated. The turn-on voltage of this type of LED was 2.7 V, and the spectrum at a forward bias current of 20 mA was comprised of blue (443 nm) and yellow (563 nm) lights. The intensity ratio of blue to yellow light was almost constant with the in- creasing injectio...     

Ce~(3+)、Tb~(3+)在SrZnP_2O_7材料中的发光及能量传递

采用高温固相法制备了Ce3+、Tb3+激活的SrZnP2O7材料,并研究了材料的发光性质。在290 nm紫外光激发下,SrZnP2O7∶Ce3+材料的发射光谱为双峰宽谱,主峰位于329 nm。SrZnP2O7∶Tb3+材料的发射光谱由420,443,491,545,587,625 nm六个峰组成,分别对应Tb3+的5D3→7F5、5D3→7F4、5D4→7F6、5D4→7F5、5D4→7F4和5D4→7F3特征发射;监测545 nm最强发射峰,所得激发光谱覆盖200~400 nm,主峰为380 nm。研究了Ce3+、Tb3+在SrZnP2O7材料中的能量传递过程,发现,Ce3+对Tb3+具有很强的敏化作用,提高了SrZnP2O7∶Tb3+材料的发射强度,当Ce3+摩尔分数为3%时,SrZnP2O7∶Tb3+材料的发射强度提高了近2倍。引入电荷补偿剂可提高SrZnP2O7∶Tb3+材料的发射强度,其中以掺入Li+和Cl-时效果最明显。     

LED白光源用Pr3+,Ce3+:YAG光纤制备与特性

采用激光加热基座法制备LED白光源用Pr3+,Ce3+:YAG单晶光纤荧光材料,对所制备材料的荧光光学特性进行了实验分析结果表明,在Pr3+和Ce3+共掺发光过程中,Pr3+离子的发光可以通过Ce3+敏化作用使得其610 nm谱线荧光强度得到有效增强|利用所制备Pr3+,Ce3+:YAG单晶光纤荧光材料与蓝色LED合成产生高效LED光纤白光源,光源的色坐标为(x＝0.322,y＝0.335),显色指数84.3,表明光源品质良好,有望用于未来高效大功率光纤白光源.