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.     

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用硅酸盐基质发光粉的制备及其封装特性

在还原气氛下采用高温固相法合成了Eu²⁺激活的硅酸盐基质白光LED用发光粉,运用扫描电子显微镜和荧光分光光度计分别对发光粉的形貌和激发、发射光谱进行了表征,并对其与YAG发光粉的封装特性进行了对比研究。结果表明,合成的硅酸盐基质白光LED用发光粉其激发光谱覆盖范围宽。采用不同波段的LED芯片进行封装时,和YAG发光粉相比,其色坐标、显色指数和流明效率波动不大,尤其是流明效率波动仅在8%左右,而且其老化性能也和YAG发光粉差别不大。对其和YAG LED的相对发射光谱研究表明,硅酸盐更适合暖白光LED的封装,硅酸盐发光粉粒径与封装流明效率规律变化的研究结果表明,较大粒径的硅酸盐发光粉有可能在大功率LED上有潜在的应用前景。     

White light emission from blue and near ultraviolet light-emitting diodes precoated with a Sr3SiO5:Ce3+,Li+ phosphor

White-light-emitting diodes (WLEDs) were fabricated by combining a yellow Sr3SiO5:Ce3+, Li+ phosphor with a blue light-emitting diode (LED) (460 nm chip) or a near ultraviolet (n-UV) LED (405 nm chip), respectively. Color temperature (Tc) of Sr3SiO5:Ce3+, Li+-based WLEDs could be tuned from 6500 to 100,000 K (blue LED pumping) and from 4900 to 50,000 K (n-UV LED pumping) without mixing with other phosphors. The blue LED-pumped WLED showed excellent white light (luminous efficiency=31.7 lm/W, Tc=6857 K) at 20 mA. This WLED showed a stable color coordinates property against an increase of the forward current. An n-UV LED-pumped WLED also showed bright white light (25.0 lm/W, 5784 K) at 20 mA.     

基于Ce:YAG单晶的白光发光二极管性能研究

以Ce:YAG单晶取代传统Ce:YAG荧光粉用于制备白光发光二极管(LED),研究了Ce:YAG单晶厚度及驱动电压的变化对其发射光谱、色坐标、亮度、光视效能和色温的影响。研究结果表明,在基于Ce:YAG单晶的白光LED中,发射光的色坐标以及蓝光与黄绿光之间的相对强度可通过对Ce:YAG单晶片厚度的改变进行调整。在恒定电压驱动下,白光LED样品的亮度、光视效能和色温均随单晶片厚度的减小而增加。当Ce:YAG单晶厚度为0.6mm时,可获得较纯的白发射光,并且其色坐标具有较高的可靠性和稳定性,基本不受驱动电压变化的影响。研究结果表明Ce:YAG单晶是一种可用于新型白光LED的理想荧光材料。     

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.     

Fabrication of red-emitting CaAlSiN3: Eu2+ through phosphor-in-glass approach for application in rear combination lamp

In this study, the red-emitting phosphor-in-glass (PiG) using the CaAlSiN₃: Eu²⁺ (CASN) phosphor is reported for the first time. The CASN: Eu²⁺ PiG samples with a maximum luminous flux of 25.1–29.4 for l minute at laser power of 1 W/mm² was obtained using a low-temperature glass frit and GPS furnace. Despite the increase in the phosphor from 15 to 25 wt%, the PiG produced at low temperature of 380 °C showed robust properties. Finally, the red PiG module designed for rear lamp applications maintains over 90% lumens for a minute at 350 mA and achieves an intense red light having a color temperature of 4589 K.     

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.     

Phosphor in glasses with Pb-free silicate glass powders as robust color-converting materials for white LED applications

Phosphor-in-glass (PiG) typed robust color converters were fabricated using Pb-free silicate glasses for high-power white LED applications. SiO₂-B₂O₃-RO(R=Ba,Zn) glass powder showed good sintering behavior and high visible transparency under the sintering condition of 750?°C for 30?min without noticeable interaction with phosphors. By simply changing the thickness of the PiG plate or mixing ratio of glass to Y₃Al₅O₁₂:Ce³⁺ phosphor, CIE chromaticity coordinates of the LED can be easily controlled. Enhanced thermal quenching property of PiG compared to phosphor with conventional silicone resin suggests its prominent feasibility for high-power/high-brightness white LEDs.     

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。     

Tailored photoluminescence of YAG:Ce phosphor through various methods

Trivalent cerium Ce³⁺ (Ce) activated yttrium aluminum garnet Y₃Al₅O₁₂ (YAG) phosphor was synthesized by two methods: solid state reaction (SS), and combustion (CB) with urea, respectively. The crystallization and luminescent properties of the phosphors were studied. Factors influencing on the intensity of luminescence and the location of emission band of YAG:Ce, such as the type of flux used in SS, the reaction atmosphere, the concentration of activator, were investigated in detail. We accomplished red or blue shift of Ce emission band by a number of techniques in order to match with the variable emission wavelength of blue light emitting diodes. The change of emission in color coordinates was illustrated by chromaticity. Co-doping other rare earth ions with Ce³⁺ ions into YAG was attempted to increase the color rendering index.     

白光LED荧光粉涂敷工艺及光学性质

在20mA电流下,对自行设计的白光LED进行测试,发现荧光粉远离芯片封装方法与传统封装方法相比,流明效率提高了20.3%。效率的提高主要是因为减小了LED芯片对荧光粉散射的吸收。同时测得随着正向电流的增加,色坐标x,y的值逐渐减小,色温升高,而光通量呈非线性增加,流明效率逐渐下降。     

高显色白光LED的制备及其变温特性

分别用黄色、红色荧光粉和黄色、红色、绿色荧光粉制备了两种高显色指数白光发光二极管(LED),调整荧光粉的比例使显色指数达到最高。对两种样品进行光学测试,发现加绿粉的样品光通量比较大,这是因为加绿粉后绿光成分较多,而绿光的视效函数比红光的大得多。对两种样品进行10℃～90℃的变温测试,发现发光效率都降低,显色指数反而升高。发光效率降低一方面是由芯片的内量子效率降低引起的,另一方面是芯片的发射波长红移使其与荧光粉的激发波长不匹配,并且荧光粉在升温时激发效率会降低。显色指数升高是因为高温时芯片发出的蓝光光谱变宽,使得整个光谱相对于室温时的光谱更平滑,更接近太阳光谱。     

结温对DCJTB混合YAG∶Ce3+白光LED光谱特性的影响

研究了结温变化对DCJTB混合YAG∶Ce3+荧光粉的白光LED光谱特性的影响。采用分层点粉的方法,在LED芯片上分层涂覆YAG荧光粉和有机材料DCJTB,可以使器件的显色指数高达90。利用实验室自行研发的一体化LED散热支架可方便准确测量出结温。实验表明：结温升高使蓝光芯片辐射幅值不断下降,YAG荧光粉被激发所辐射的黄光辐射幅值先增大后减小,红光光谱发生蓝移,器件的显色指数呈线性下降,色温先增大后减小。     

Study of UV excited white light‐emitting diodes for optimization of luminous efficiency and color rendering index

Wavelength down‐converted white‐light sources excited by near ultraviolet light‐emitting diodes require specific phosphor properties in order to generate high‐quality white light (namely, light with good color rendition and stability of color coordinate). Simulation and experimental results are discussed, with particular emphasis on the spectral distribution property of red phosphor required to realize high values of luminous efficiency and color rendition. A peak wavelength of 610 nm and an FWHM of 80 nm for the spectral power distribution were proposed, and co‐doped phosphate materials were synthesized successfully. This can contribute to a white‐light source with a luminous efficiency of 45 lm/W and color rendering index greater than 90 at a color temperature of 5600 K and an operational current of 20 mA. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

All-in-one-type organic light-emitting diodes for color tuning using phosphor in glasses with Pb-free silicate powders

We demonstrate all-in-one-type organic light-emitting diodes (OLEDs) that are fabricated using a color converting plate as a substrate. The color converting plate is Pb-free phosphor-in-glass (PiG), which is prepared by mixing Y₃Al₅O₁₂:Ce³⁺ (YAG:Ce³⁺) and SiO₂–B₂O₃–RO (R = Ba, Zn) glass frit by sintering at 750 °C for 30 min. The maximum luminance, luminance efficiency, and power efficiency of blue OLEDs fabricated on commercial glass are measured as 10500 cd/m², 10.18 cd/A, and 2.95 lm/W, respectively. The Commission Internationale de l'Eclairge (CIE) coordinates of blue OLEDs is (0.167, 0.325). Our obtained results show that the luminance value decreased as the PiG thickness increased, and the glass to phosphor (GTP) ratio decreased. The OLED devices fabricated on the PiG substrate (GTP ratio = 9:1, thickness: 150 μm) showed a maximum luminance, luminance efficiency, and power efficiency of 7600 cd/m², 8.76 cd/A, and 2.85 lm/W, respectively. The CIE color coordinates changed to (0.286, 0.504) at 200 mA/cm². These results proved that color coordination can be easily adjusted by varying the GTP ratio and the thickness of the PiG.     

功率型白光LED光学特性退化分析

将GaN基蓝光芯片涂敷YAG荧光粉和透明硅胶制成额定功率为1 W的白光发光二极管(LED),对其施加900mA的电流应力,在老化过程中测量白光LED的主要光学参数,考察其光学特性的退化情况。经过4 200 h的老化,样品光通量退化为初始值的15%~18% 。样品的漏电流明显增大,表明芯片有源区缺陷密度提高,但光谱分布图中蓝光部分的辐射量未减少,仅观察到黄光部分辐射量的减少,推断出YAG荧光粉的转换效率降低。同时,从原理上分析了样品色温逐渐增大,显色指数基本不变的原因,对大功率白光LED在照明领域的应用有一定的借鉴意义。     

Superior color rendering with a phosphor‐converted blue‐cyan monolithic light‐emitting diode

The future generation of modern illumination should not only be cheap and highly efficient, but also demonstrate high quality of light, light which allows better color differentiation and fidelity. Here we are presenting a novel approach to create a white solid‐state light source providing ultimate color rendition necessary for a number of applications. The proposed semi‐hybrid device combines a monolithic blue‐cyan light emitting diode (MBC LED) with a green‐red phosphor mixture. It has shown a superior color rendering index (CRI), 98.6, at correlated color temperature of around 3400 K. The MBC LED epi‐structure did not suffer from the efficiency reduction typical for monolithic multi‐color emitters and was implemented in the two most popular chip designs: “epi‐up” and “flip‐chip”. Redistribution of the blue and cyan band amplitudes in the white‐light emission spectrum, using the operating current, is found to be an effective tool for fine tuning the color characteristics.

     

Warm-white light-emitting diode with yellowish orange SiALON ceramic phosphor

A warm-white light-emitting diode (LED) without blending of different kinds of phosphors is demonstrated. An approach that consists of a blue LED chip and a wavelength-conversion phosphor is carried out. The phosphor is a newly developed yellowish orange CaEuSiAlON ceramic phosphor with high efficiency. The CIE1931 chromaticity coordinates (x, y) are (0.458, 0.414), the color temperature is 2750 K, and the luminous efficacy of this LED is 25.9 lm/W at room temperature and with a forward-bias current of 20 mA. The chromaticity of the assembled LED is more thermally stable than that of a LED with a conventional oxide phosphor (YAG:Ce) because of the better thermal stability of the oxynitride phosphor.