Highly thermal conductive red-emitting AlN-CaAlSiN3:Eu2+ composite phosphor ceramics for high-power laser-driven lighting

Thermally robust red-emitting phosphor ceramics are urgently required for laser lighting and displays with high luminance and better color saturation. The most promising CaAlSiN₃:Eu ceramics have a low thermal conductivity of 4.2 W m^?1 K^?1 and a small luminance saturation of 0.5 W, making it hard to be used under high power laser irradiation. In this work, we incorporated AlN into the CaAlSiN₃:Eu ceramic to produce red-emitting AlN-CaAlSiN₃:Eu composite phosphor ceramics by spark plasma sintering. The fully densified phosphor ceramics have the highest thermal conductivity reported so far (53.5 W m^?1 K^?1), which is about 13 times higher than the reported one. The luminance saturation of the composite ceramics occurs at a high threshold of 4.2 W under blue laser excitation, enabling them to be used for high power laser lighting. This work provides an idea of tackling the microstructure of nitride phosphor ceramics and of preparing thermally robust red-emitting color converters.     

Suppression of phosphor‐glass reactions in YAG:Ce phosphor‐embedded glasses

For high‐power white LED applications, YAG:Ce‐based yellow phosphors were embedded in a low‐T_g Bi₂O₃–B₂O₅–ZnO–Sb₂O₅ glass (BiG) by sintering route. A high‐T_g silicate glass (SiG) was also used for comparison. Dense (porosity<2%) phosphor‐glass composites were obtained after sintered at 800°C (for SiG) and 325°C (for BiG). XRD quantitative analysis indicates that the loss of phosphor content is in the range of 2.5%‐22%, caused by partial dissolution of phosphor particles into the glass matrix during sintering. The element distribution across the interface and within the reaction zone between phosphor and glass was analyzed by TEM/SEM‐EDS. The intrinsic emission characteristic of YAG:Ce is nearly not altered, possibly resulted from the slight modification of the YAG phase during sintering. Thus the final emission intensity of the sintered body is mainly determined by the residual amount of the YAG:Ce phase. Replace the high‐T_g SiG glass by the low‐T_g BiG glass, prenitridize the YAG:Ce phosphor, and change the sintering atmosphere from air to N₂ suppress the loss of phosphor during sintering. Therefore, the resulting loss of emission intensity of the phosphor‐embedded glass material can be reduced to only about 1.8%.     

Anomalous enhancement of photoluminescence intensity of sintered YAG:Ce particles‐embedded glasses

For high‐power white LED applications, YAG:Ce‐based yellow phosphors were embedded in a low‐T_g Bi₂O₃–B₂O₅–ZnO–Sb₂O₅ glass by sintering route. Effects of sintering temperature (325‐390°C) on the microstructure and photoluminescence properties were investigated. X‐ray diffraction was used to measure the retained fraction of YAG:Ce phase after sintering. Scanning electron microscope and transmission electron microscope, equipped with energy‐dispersive X‐ray spectrometry, were used to examine the microstructure, including the element distribution across the phosphor–glass interface. Photoluminescence properties of the samples before and after sintering were compared. With the increasing sintering temperature, the retained fraction of YAG:Ce decreased from 83.3% to 82%. This effect tends to reduce the luminescence intensity of the samples after sintering. The increasing sintering temperature also enhances the diffusion of cations (esp. Bi) from glass matrix to YAG:Ce. This effect tends to increase the luminescence intensity of the YAG:Ce particles after sintering. When the sintering temperature was lower (325°C), the effect of YAG:Ce loss was dominant, thus the luminescence intensity was reduced after sintering. When the sintering temperature was higher (350‐390°C), the effect of solute dissolution was dominant, resulting in luminescence intensity anomalously higher than that before sintering. Similar result has not been reported in literatures. The maximum luminescence intensity of the sintered samples is 1.57 times as high as that of the samples before sintering.     

Effect of Laser Drilling on the Microstructure and Luminescence of YAG:Ce,Si Phosphor Ceramics

Y₃Al₅O₁₂:Ce,Si (YAG:Ce,Si) phosphor ceramics prepared by a solid‐state reaction method were drilled with an array of holes in a diameter of 100 μm. The laser‐induced heat‐affected zone surrounding the laser‐drilled holes with a ring width of about 150 μm was analyzed to consist of Y₄Al₂O₉, YAlO₃, and Al₂O₃ phases, induced by the phase transformations from the YAG melt during laser drilling. Photoluminescence study of the YAG:Ce,Si phosphor ceramic indicated variable blue light transmission and yellow emission, suggesting the potential of tuning blue/yellow intensity ratio as well as precise color control of light‐emitting diodes.     

Spectral dependency of Eu2+-activated silicate phosphors on the composition for LED application

An Sr₂SiO₄-Ba₂SiO₄ material system doped by Eu²⁺ was studied for light emitting diodes (LEDs) application. The main concern was the precise control of excitation and emission spectra for maximum light yield and color coordinate, which was carried out by changing the composition of the alkaline earth ions in host lattice. The Sr₂SiO₄ : Eu-Ba₂SiO₄ : Eu system was found to be excellent for white LED applications with excitation in the 380–465 nm region. Especially, the yellow light intensity from (Sr,Ba)SiO₄ : Eu phosphors was comparable to YAG : Ce phosphors in case of blue LED excitation.     

Al2O3-Ce:GdYAG composite ceramic phosphors for high-power white light-emitting-diode applications

In order to meet the increasing demand of high-power light-emitting-diode (LED) lighting, state-of-the-art white light-emitting diode technology needs phosphors with high thermal conductivity and high luminous efficacy as color converters. In this work, translucent Al₂O₃-Ce:GdYAG composite phosphors were prepared by solid-state reactive sintering. The microstructure shows that the Al₂O₃ particles are uniformly dispersed in the Ce:GdYAG matrix. These particles can not only improve the thermal conductivity of the ceramics, but also promote the extraction efficacy. The luminous characteristics of the Ce:GdYAG and Al₂O₃-Ce:GdYAG ceramics were analyzed after being packaged with blue LED. When the molar ratio of Al₂O₃/Ce:GdYAG is 0.8, a high luminous efficacy value of 112.6 lm/W is achieved by the Al₂O₃-Ce:GdYAG composite ceramic phosphor with the thickness of 0.4 mm, as well as the highest CRI valve of 71.4. The appropriate photoelectric properties of this kind of ceramic phosphor make it a promising candidate for high-power LED device.     

Tunable chromaticity and enhanced luminous efficacy of white LEDs with phosphor-in-glass coating via multilayer screen-printing

The phosphor-in-glass (PiG) coating was fabricated via multilayer screen-printing and low-temperature sintering. The PiG coating consisted of Eu₂O₃-doped P₂O₅-ZnO-B₂O₃ (PZB) glass, Y₃Al₅O₁₂:Ce³⁺ (YAG:Ce) yellow phosphor, and CaAlSiN₃:Eu²⁺ (CASN:Eu) red phosphor. Eu₂O₃ and CASN:Eu were used to provide red emission for tunable chromaticity of white light-emitting diodes (LEDs), and surprisingly, the luminous efficacy was also enhanced. The impact of the variation in the B₂O₃ content on the PZB glass and the effect of Eu₂O₃, YAG: Ce, and CASN:Eu on the luminescent properties of the PiG coating were investigated. The glass matrix with 8 mol% B₂O₃ showed the lowest transition temperature and a suitable coefficient of thermal expansion. The spectra showed that the coating can be excited by blue light and produce yellow light and red light. The spatial distribution of the PiG coating was inspected by scanning electron microscopy, and it was observed that only a low erosion of phosphor by the glass matrix occurred. Furthermore, the white LEDs devices were constructed with the PiG coating on the blue LED chips. This method showed a decreased correlated colour temperature of 5137, a increased colour rendering index of 82.8 and an improvement in the luminous efficacy. The PiG coating for tunable chromaticity and enhanced luminous efficacy of white LEDs shows potential for application.     

Particle Size Effect on the Packaging Performance of YAG:Ce Phosphors in White LEDs

The synthesis of cerium-doped yttrium aluminum garnet (YAG:Ce) phosphor of different sizes with uniform size distribution was carried out using solid-state reaction followed by grinding and sieving method. The effect of particle size distribution of YAG:Ce phosphors on the photoluminescence (PL) properties was investigated. The results demonstrate that the uniform size distribution and particle size affects the packaging performance in white light emitting diode (LED) applications. The YAG:Ce phosphors with different particle sizes were packaged in white LEDs using different amounts of each phosphors in order to get similar efficiency as that of commercially available YAG:Ce phosphors. It was observed that minimum amount of phosphor material is required for smaller particle size for getting the similar efficiency as that exhibited by commercially available YAG:Ce phosphors. The results are particularly interesting in view of reducing the cost of current LEDs by lowering the amount of phosphors without compromising the efficiencies of final LED package. A systematic study of YAG:Ce phosphors on the packing performance in white LEDs is reported.     

SPS烧结制备新型荧光玻璃材料

以实验室自制SiO2粉体和商用Ce∶YAG荧光粉为玻璃原料,采用放电等离子体烧结（SPS）技术,在1 200℃保温2 min烧结得到有望用于白光LED封装的Ce∶YAG荧光玻璃。用X射线衍射仪（XRD）、荧光光谱（PL）等方法对制备获得的荧光玻璃样品进行表征。结果显示,烧结并没有破坏Ce∶YAG荧光粉的晶体结构,且荧光玻璃主体相仍为玻璃体,该荧光玻璃在460nm具有强吸收峰,在此波长激发下发射出530 nm左右的黄光。研究结果表明,本实验制备的Ce∶YAG荧光玻璃是一种具有重要应用前景的LED封装用新型荧光材料。     

Color conversion properties of various thick-film phosphor-in-glasses depending on structural design for white LEDs

Thick-film phosphor-in-glasses (PiGs) were fabricated via a screen-printing method with various phosphor layer structures, to compose a white light emitting diode (LED). Green (Lu₃Al₅O₁₂:Ce³⁺) and red (CaAlSiN₃:Eu²⁺) phosphors were mixed, layered, and patterned on a glass substrate. The chromaticity of each structured PiG was tuned to achieve a white LED by varying phosphor content and thickness. The emission spectra and the related various color conversion properties, including color coordinates, correlated color temperature (CCT), color rendering index (CRI), luminous efficacy (LE) and the color gamut of the mounted PiGs with different phosphor layer structures were examined and compared. Time-resolved photoluminescence (TRPL) measurements of the white LEDs with various phosphor layer structural designs were also obtained and compared. It was observed that spectral variation depended on the PiG layer structure. A proper PiG layer structural design was discussed for practical applications.     

Tunable chromaticity and high color rendering index of WLEDs with CaAlSiN3:Eu2+ and YAG:Ce3+ dual phosphor-in-silica-glass

Phosphors-in-glass (PiG), which serves as a potential bi-replacement of both phosphors and organic encapsulants in high-power white light-emitting diodes (WLEDs), has captured much attention due to its high thermal stability and excellent luminescent properties. However, due to the high-temperature sensitivity and the chemical reactions between phosphors with glass matrix, a variety of phosphors, especially red phosphors could be hardly dispersed into the glass without thermal quenching and decomposition, which greatly limits the improvement of color rendering index and chromaticity tunability of the WLEDs. In this study, adopting the mesoporous silica (FDU-12) and commercial phosphors as raw materials, the phosphors-in-silica-glasses (PiSGs) embedded with red phosphor CaAlSiN₃:Eu²⁺ and yellow phosphor YAG:Ce³⁺ have been successfully prepared at low sintering temperature (950°C) and short preparation time (10 minutes) using spark plasma sintering. Owing to the well preservation of the originally emissive properties of the embedded phosphors, the warm WLEDs with tunable chromaticity and exhibited a superior performance with LE of 133 lm/W, CCT of 3970 K and CRI of 81 were fabricated by encapsulating the as-prepared PiSGs on the blue chips. Moreover, the PiSG composite exhibits a high thermal conductivity up to 1.6 W/m·K.     

Effect of Boron Nitride (BN) on Luminescent Properties of Y3Al5O12:Ce Phosphors and their White Light‐Emitting Diode Characteristics

This article reports a low‐cost yellow‐emitting Y₃Al_5‐xB_xO_12‐xN_x:Ce³⁺ phosphor with an enhanced luminescent intensity and excellent thermal stability for white light‐emitting diodes (LEDs). It was synthesized by a simple gas‐pressure sintering (GPS) process. The effect of B³⁺–N^3? incorporation on the optical properties of Y₃Al₅O₁₂:Ce³⁺ phosphor was investigated. The addition of appropriate amounts of boron nitride (BN) leads to a marked increase in photoluminescent intensity and a slight shift of its emission spectra toward the blue region, which is assigned to the improved crystallinity and increased particle size. Especially, the prepared oxynitride phosphor does not exhibit any thermal quenching under high temperature, and the emission intensity at 250°C even increases up to 175% of that measured at 20°C. Finally, the white LED flat lamp with luminous efficiency as high as 101 lm/W, color rendering index of 72, and correlated color temperature of about 6600 K is successfully realized by using YAG:Ce³⁺ phosphor doped with 0.5 molar ratio BN, which is acceptable and promising for general indoor illuminations to replace fluorescent or incandescent lamps.     

Enhanced red emission and improved thermal quenching of CaAlSiN3:Eu2+ phosphors via boron doping

The development of high-performance phosphors is required for phosphor-converted white light-emitting diodes. However, most approaches are unable to achieve optimum emission intensity and thermal quenching simultaneously. Here, a series of CaAlSiN₃:Eu²⁺ (CASN:Eu²⁺) red-emitting phosphors doped with B were synthesized using field-assisted sintering technology. Compared with CASN:Eu²⁺, the B-doped phosphor exhibited high external quantum efficiency (EQE) and good thermal quenching performance. With boron doping, the EQE of CaAlSiN₃:Eu²⁺ shows an obvious growth, increasing from 48.83% to 70.68%. Meanwhile, thermal quenching performance has also been greatly improved, which is strongly associated with the band structure of Eu²⁺ and the crystal structure of CASN. The location of B in the crystal lattice was studied and the mechanism of improving thermal quenching via B doping was discussed in detail. Finally, a white LED fabricated by the combination of a GaN blue chip (450 nm) with the as-synthesized red phosphors and Y₃(Al, Ga)₅O₁₂:Ce³⁺ green phosphors (531 nm), shows a high color rendering index (Ra =91.6). This study offers a novel method to improve luminescence properties of CASN:Eu²⁺ red-emitting phosphors, which may broaden their application in solid-state lighting devices.     

Enhancement of photoluminescence intensity of sintered CaAlSiN3:Eu2+ red phosphor-bismuthate glass composites

Wavelength converters in white light-emitting diodes are usually made by sintering of phosphor-glass powder compacts. An issue is that the sintering process usually results in the reduction of phosphor amount. In the present study, composites containing CaAlSiN₃:Eu²⁺ red phosphor and Bi₂O₃-B₂O₃-ZnO-Sb₂O₅ glass were fabricated by sintering method. Influences of CaAlSiN₃:Eu²⁺ phosphor content (10 vol%–30 vol%) and sintering temperature (410–430°C) on the residual amount of the phosphor phase and the resulting luminescence intensity of the composites were investigated. The change of CaAlSiN₃:Eu²⁺ content due to sintering was analyzed by X-ray diffraction. The interdiffusion between the CaAlSiN₃:Eu²⁺ and glass matrix was examine by scanning electron microscope equipped with energy dispersive X-ray spectrometry. This paper focuses on the change of luminescence intensity after sintering. It was found that although the content of phosphor CaAlSiN₃:Eu²⁺ reduces after sintering; the luminescent intensity of the composites anomalously increases. The optimum luminescence intensity is 14% higher than that of the as-mixed, unfired powder. It is proposed that the incorporation of Bi³⁺ ions from the glass matrix into the phosphor CaAlSiN₃:Eu²⁺ during sintering improves the luminescence ability of the phosphor particles.     

The effect of Lu3+ doping upon YAG:Ce phosphor ceramics for high-power white LEDs

Intense green emission is extremely significant to the color rendering index (CRI) of white LEDs. Various green-emitting YLuAG:Ce phosphor ceramics were successfully prepared by vacuum sintering. The effects of Lu³⁺ doping on structure and luminescence property were investigated in detail. In comparison with YAG:Ce, YLuAG:Ce ceramics own smaller grain size, better luminescence performance and higher thermal stability. The photoluminescence (PL) intensity of YLuAG:Ce ceramics increases by 23.6 % due to the “light scattering enhanced effect”. Furthermore, the Ce³⁺ emission is obviously blue-shifting from 533 nm to 519 nm, and the intensity of YLuAG:Ce ceramics reduces only about 8.9 % at 250 °C, showing better thermal stability (vs 11.1 % of YAG:Ce). The LE of LED packaged by YLuAG:Ce ceramic is up to 148.88 lm/W when the doping Lu³⁺ y is 2.1. The above results show that tailored YLuAG:Ce phosphor ceramic is a potential green-emitting color converter for high-power LEDs (hp-LEDs).     

Eu3+‐doped glass as a color rendering index enhancer in phosphor‐in‐glass

A new method for improving color rendering index (CRI) and low correlated color temperature (CCT) in high‐power white‐light‐emitting diodes (WLEDs) is proposed. We used a configuration of phosphor‐in‐glass (PIG) and studied light output changes with the increment in concentration of yellow‐emitting Y₃Al₅O₁₂:Ce³⁺ (YAG:Ce³⁺) phosphor. The PIG was coupled on the top of blue‐light‐emitting diodes (LED) chip (465 nm). To compensate the lack of red emission in the phosphor, Eu³⁺‐doped tellurium glass with different europium content was employed as a red emitter. The suitable contents of YAG:Ce³⁺ and Eu³⁺ were 7.5 weight percent (wt%) and 3 mol percent (mol%), respectively. The CRI value went from 72 to 82, whereas the CCT was reduced from 24 933 to 6434 K. The proposed structure can improve CCT as well as CRI of WLEDs just by placing a glass on top.     

Warm white light-emitting diodes using organic–inorganic halide perovskite materials coated YAG:Ce3+ phosphors

This work reports warm white light-emitting diodes (WLEDs) using organic–inorganic halide perovskite materials coated YAG:Ce³⁺ phosphors by a liquid phase synthesis method. The perovskite MAPbBr_3?xI_x-coated YAG:Ce³⁺ phosphors have more red light contribution than YAG:Ce³⁺ phosphors without the perovskite coating. The chromaticity coordinate of white LED with YAG:Ce³⁺ remote phosphor is (x = 0.3134, y = 0.3497) 6359. However, those of MAPbBr_2.5I_0.5 and MAPbBr_2.0I_1.0-coated YAG:Ce³⁺ remote phosphor shift to (x = 0.4220, y = 0.3725) 2908 and (x = 0.4067, y = 0.4028) 3525, respectively. The colors of perovskite-coated samples are more red and warm. Therefore, the perovskite-coated YAG:Ce³⁺ method is useful for warm WLED.     

Fabrication of Ce:YAG,Ce,Cr:YAG and Ce:YAG/Ce,Cr:YAG dual-layered composite phosphor ceramics for the application of white LEDs

(Ce_0.001Y_0.999)₃Al₅O₁₂ and (Ce_0.001Y_0.999)₃(Cr_xAl_1−x)₅O₁₂ (x=0.001−0.005) transparent ceramics were synthesized by the solid state reaction and vacuum sintering and their optical properties were measured. High quality white light was obtained when the Ce:YAG/Ce,Cr:YAG dual-layered composite ceramic was directly combined with commercial blue LED chip. A maximum luminous efficacy exceeding 76 lm/W at a low correlated color temperature of 4905 K was obtained. The color temperature can be controlled by variations of Cr³⁺ concentration and the ceramic thickness. Hence, the Ce:YAG/Ce,Cr:YAG dual-layered composite phosphor ceramic may be a promising candidate for white LEDs.     

A low sintering temperature glass based on SiO2–P2O5–ZnO–B2O3–R2O system for white LEDs with high color rendering index

A low sintering temperature glass based on the SiO₂–P₂O₅–ZnO–B₂O₃–R₂O (R=K and Na) system was studied as a matrix for embedding phosphors to fabricate color tunable white LEDs. The proposed system, which uses no heavy‐metal elements and can be sintered at 500°C, incorporates thermally weak commercial phosphors such as CaAlSiN₃:Eu²⁺ to produce phosphor‐in‐glasses (PiGs). Changing the mixing ratio of glass to phosphors affected the photo‐luminescence spectra and color coordinates of the PiGs when mounted on a blue LED. The color rendering index (CRI) and color correlated temperature (CCT) of the LEDs were also varied with the mixing ratio, providing color tunable white LEDs. A high CRI, up to 93, as well as highly improved thermal stability were obtained, along with a low sintering temperature compared to other glass systems, suggesting the practical feasibility of the proposed system.     

Effects of the surface area of phosphor powders on colour coordinate variance

In this study, the colour coordinate behaviours according to the surface area of phosphors were investigated to implement the colour coordinate of the desired zone in a random colour coordinate. For this purpose, the mixing ratio and dispensing amount of a green phosphor (Ce:YAG) and three red phosphors (CaAlSiN₃:Eu²⁺) with different specific surface areas were adjusted, and the corresponding colour coordinate behaviour was examined. As a result, the colour coordinate behaviour was found to be considerably influenced by the mixing ratio of red and green phosphors and the surface area of the phosphor powder particles. In conclusion, the colour coordinate of the desired zone can be more efficiently implemented by predicting the characteristics of different types of phosphors and their colour coordinate behaviours. The findings of this study are expected to greatly increase the yield of the light-emitting diode industry.