Silicon-based oxynitride and nitride phosphors for white LEDs—A review

As a novel class of inorganic phosphors, oxynitride and nitride luminescent materials have received considerable attention because of their potential applications in solid-state lightings and displays. In this review we focus on recent developments in the preparation, crystal structure, luminescence and applications of silicon-based oxynitride and nitride phosphors for white light-emitting diodes (LEDs). The structures of silicon-based oxynitrides and nitrides (i.e., nitridosilicates, nitridoaluminosilicates, oxonitridosilicates, oxonitridoaluminosilicates, and sialons) are generally built up of networks of crosslinking SiN₄ tetrahedra. This is anticipated to significantly lower the excited state of the 5d electrons of doped rare-earth elements due to large crystal-field splitting and a strong nephelauxetic effect. This enables the silicon-based oxynitride and nitride phosphors to have a broad excitation band extending from the ultraviolet to visible-light range, and thus strongly absorb blue-to-green light. The structural versatility of oxynitride and nitride phosphors makes it possible to attain all the emission colors of blue, green, yellow, and red; thus, they are suitable for use in white LEDs. This novel class of phosphors has demonstrated its superior suitability for use in white LEDs and can be used in bichromatic or multichromatic LEDs with excellent properties of high luminous efficacy, high chromatic stability, a wide range of white light with adjustable correlated color temperatures (CCTs), and brilliant color-rendering properties.     

蓝光激发红色荧光粉的研究进展及其在白光LED中的应用

蓝光LED芯片激发黄色荧光粉是目前白光LED的主要实现方式,引入红色荧光粉对调整白光LED的显色指数及色温有重要意义。重点介绍和评述了可被蓝光激发且具有宽发射带的硫化物、氮化物、铝酸盐等几种体系红色荧光粉的发光性质、最新研究成果及在白光LED中的应用。对比发现,氮化物荧光粉可被从近紫外到可见绿光有效激发,随基质组成的不同,可发出峰值波长为600～650nm的红色荧光,且由于其优良的化学稳定性、热稳定性成为最有前途的一类红色荧光粉。采用两种以上的荧光粉代替单一黄色荧光粉,有利于调整白光LED的色温,提高显色指数。     

Dependence of luminescence properties on composition of rare-earth activated (oxy)nitrides phosphors for white-LEDs applications

Rare-earth-activated nitride and oxynitride phosphors are attractive converter materials for white-LEDs applications due to their efficient luminescent characteristics, high thermal and chemical stabilities because their basic crystal structure is built on rigid tetrahedral networks, either of the Si–(O,N) or Al–(O,N) type. Recent progress in fluorescence properties of silicon–aluminum–(oxy)nitride-based luminescent materials with broad excitation bands activated by Eu²⁺, Ce³⁺, and Yb²⁺ for phosphor-converted white-LEDs are reviewed in this article, with the emphasis on the dependence of luminescence properties on composition. We elaborate on these composition-dependent properties in three sections: (i) Eu²⁺-activated nitride and oxynitride phosphors; (ii) Ce³⁺-activated nitride and oxynitride phosphors; and (iii) Yb²⁺-doped α-SiAlON phosphor. Eu²⁺- or Ce³⁺-activated nitride and oxynitride phosphors are categorized into four parts following the structural and/or composition characteristics, i.e., α-SiAlON, β-SiAlON, oxonitridosilicates, nitridoalumosilicates, and nitridosilicates. Some involving aspects for designing and the trends of research and development of these phosphors are addressed at the end of this article.     

Luminescent properties of Eu3+ activated MLa2(MoO4)4 based (M = Ba,Sr and Ca) novel red-emitting phosphors

Eu³⁺-activated novel red phosphors, MLa₂(MoO₄)₄ (M = Ba, Sr and Ca) were synthesized by the conventional solid state method. The excitation and emission spectra indicate that these phosphors can be effectively excited by UV (395 nm) and blue (466 nm) light, and exhibit a satisfactory red performance at 614 nm. Upon excitation with a 466 nm light, our synthesized phosphors have stronger emission intensity than the sulfide red phosphors used in white LEDs. Due to high emission intensity and a good excitation profile, the Eu³⁺-doped CaLa₂(MoO₄)₄ phosphor may be a promising candidate in solid-state lighting applications.     

Ceramic materials and phosphors based on silicon nitride and sialon

This review covers some of the main trends in the field of synthesis and the applications of materials based on silicon nitride presented in publications over the past 10–15 years. Attention is paid to the technique for synthesizing nitride and oxynitride compounds and for the production of ceramic construction materials and phosphors in silicon nitride systems.     

BPO4@B2O3 and (BPO4@B2O3):Eu3+: The novel single-emitting-component phosphors for near UV-white LEDs

Nowadays much effort has been devoted to exploring novel luminescent materials with low-cost, high stability and excellent luminescent properties. In this paper, a new kind of luminescent material BPO₄@B₂O₃ was prepared by using a facile method. The as-obtained samples contain numerous BPO₄ nanoparticles enclosed by amorphous and crystalline B₂O₃ homogeneously, which exhibits a broad emission band ranging from 380 to 700 nm under near-UV irradiation. More importantly, it is worth noting that the BPO₄@B₂O₃ phosphor exhibits the excellent thermal quenching property, which endows it with a promising prospect as phosphors for high power white LEDs. To further promote its application as white light phosphors, Eu³⁺ ions were doped into the BPO₄@B₂O₃ samples and prepared the (BPO₄@B₂O₃):Eu³⁺ phosphors with chromaticity coordinates (0.3022, 0.3122). The corresponding packaging of LEDs indicates that both BPO₄@B₂O₃ and (BPO₄@B₂O₃):Eu³⁺ can be considered as the promising phosphors for WLEDs.     

Preparation and photoluminescence properties of γ-KCaPO4: Eu phosphors for near UV-based white LEDs

Novel whitish-blue phosphors based on a phosphate host matrix, γ-KCaPO₄: Eu²⁺, were prepared by a conventional solid-state reaction method using slightly phosphorus deficient conditions and their photoluminescence properties were investigated. The concentration quenching process, temperature dependence of the luminescence and decay curve were also investigated. The γ-KCaPO₄: Eu²⁺ phosphor was efficiently excited by UV-Visible light at wavelengths of 200-450 nm and exhibited a bright whitish-blue emission with a maximum peak wavelength of 473 nm. All of these characteristics suggest that the γ-KCaPO₄: Eu²⁺ phosphors combined with red phosphors could be applicable to near UV-based white LEDs, i.e., only two kinds of phosphor powders are needed for the formation of white light.     

Synthesis,structure and photoluminescence properties of (Sr,Ca)AlSiN<Subscript>3</Subscript>:Eu<Superscript>2+</Superscript> phosphor for white light emitting diodes with controllable optical performance

A series of Sr_yCa_1?x?yAlSiN₃:xEu²⁺ (x = 0–0.01, y = 0–0.8) phosphors have been successfully prepared by solid state reaction under atmospheric pressure. All the phosphors exhibit orthorhombic crystal structure similar with CaAlSiN₃ structure. It is found that the emission bands for all Ca_1?xAlSiN₃:xEu²⁺ phosphors are centered at ~650 nm and fluorescence quenching has been observed along with the increase of Eu²⁺ concentration in host materials. Through substitution of Ca²⁺ by Sr²⁺, an expected red emission peak (625 nm) and enhanced luminescent intensity can be achieved. The obtained Sr_0.8Ca_0.192AlSiN₃:0.008Eu²⁺ phosphor was further used as efficient red component to fabricate white light emitting diodes (LEDs). Under the optimized condition of LED packaging, the white LEDs own the excellent optical properties with luminous efficiency of 90.6 lm/W and an ideal color rendering index (Ra = 82). Furthermore, the color correlated temperature of white LEDs can be simply adjusted through changing the red phosphor concentration and dispensing package saves time.     

荧光粉Sr3-x-yAl2O6∶xCe3+,yEu2+的制备及其发光特性

采用高温固相反应法制备了Sr3-x-yAl2O6:xCe3+,yEu2+(x=0,y=0;x=0.04,y=0;x=0.04,y=0.02;x=0.04,y=0.04;x=0.04,y=0.06;x=0.04,y=0.08;x=0,y=0.04)荧光粉,研究其相组成与荧光特性,结果表明,样品具有单相Sr3Al2O6晶体结构。在360nm波长的紫外光激发下,Ce3+离子辐射出峰值在434nm附近的宽谱蓝光。通过能量传递作用,Eu2+离子辐射峰值为517nm左右的宽谱绿光。Ce3+和Eu2+的荧光组合获得了色坐标为(0.2611,0.3313)的近白光发射。样品的激发光谱分布在250～400nm的波长范围,这种荧光粉有望在紫外或近紫外激发的白光LED中获得应用。     

Controllable white light emission from Dy<Superscript>3+</Superscript>–Eu<Superscript>3+</Superscript> co-doped KCaBO<Subscript>3</Subscript> phosphor

Potassium calcium borate, KCaBO₃:Eu³⁺ phosphors with various Dy³⁺ concentrations (0–3 wt%) were synthesized by solid state reaction and studied for the first time. Under various UV–violet excitations, the obtained single monoclinic phased Dy³⁺–Eu³⁺ co-doped KCaBO₃ polycrystalline phosphors emit a combination of yellow–blue and red–orange wavelength giving intense white light, which can easily be controlled by varying the concentration of Dy³⁺. The increase in white light emission with the increase of Dy³⁺ concentration indicates the efficient energy inter-ion transfer from Dy³⁺ to Eu³⁺ ions. Furthermore, the observed emission lifetimes and the intense white light emission are suggestive exploration for the present phosphor for potential optoelectronic applications such as white light-emitting phosphor for blue LEDs chips.     

Up-converted ultraviolet luminescence of Er<Superscript>3+</Superscript>:BaGd<Subscript>2</Subscript>ZnO<Subscript>5</Subscript> phosphors for healthy illumination

Moderate level of exposure to the solar irradiation containing UV component is essential for health care. To incorporate the UV-emitting phosphors into the commercial YAG-based white light-emitting diode introduces the possibilities of healthy illumination to individuals’ daily lives. 1 mol.% Er³⁺-doped BaGd₂ZnO₅ (BGZ) particles were synthesized via sol-gel method and efficient up-converted luminescence peaked at 380 nm was detected under 480 nm excitation. The mixed phosphors with varied mass ratio of Er³⁺:BGZ and Ce³⁺:YAG particles were encapsulated to form LEDs. The study of the LEDs indicated that the introduction of BGZ component favored the enhancement of color-rendering index and the neutralization of the white light emitting. The WLED with the BGZ/YAG ratio of 8:2 was recommendable for its excellent overall white light luminous performances and UV intensity of 84.55 mW/cm². The UV illumination dose of the WLEDs with mixed YAG and BGZ was controllable by adjusting the ratio, the illumination distance and the illumination time. Er³⁺:BGZ phosphors are promising UVemitting phosphors for healthy indoor illumination.     

Improving radiative recombination efficiency of green light-emitting diodes

Although the solid-state lighting industry has achieved huge successes in both red and blue part of the visible spectrum during the last 40 years, light-emitting diodes (LEDs) that emit green light consistently exhibit inferior efficiencies. Thanks to the use of down-conversion phosphors, white LEDs have been commercialised without using green LEDs. However, the efficiency problem of green LEDs still hinders many potential applications of solid-state lighting and limits the overall system efficiency. This review first attempts to conclude and comment on the complex factors that limit the performance of green LEDs with recent research progresses. Then the article focuses on reviewing various strategies to improve green light LED radiative recombination efficiencies.

This review was chosen as a runner up of the 2018 Materials Literature Review Prize of the Institute of Materials, Minerals and Mining, run by the Editorial Board of MST. Sponsorship of the prize by TWI Ltd is gratefully acknowledged.     

Advances in sulfide phosphors for displays and lighting

For traditional applications such as cathode ray tubes and fluorescent lamps, many inorganic phosphors have been optimised during decades. For new applications in display and lighting technology, novel materials are being developed. After giving a short history of sulfide phosphors, the present paper will focus on Ca_1−x Sr _x S:Eu single crystal particle phosphors. The material is grown by solvothermal synthesis, process not needing toxic gases or high temperature processing steps. This phosphor combines a broad excitation spectrum and a broad—saturated red—emission spectrum, which makes it an ideal material for wavelength conversion in LEDs for general lighting.     

Photoluminescence properties of Eu doped Ba2ZnS3 phosphor for white light emitting diodes

The synthesis and photoluminescence properties of novel Eu²⁺ doped Ba₂ZnS₃ phosphors for white light emitting diodes (LEDs) are reported. Diffuse reflection spectra of Ba₂ZnS₃ host and synthesized phosphors have been measured. The excitation spectra of synthesized phosphors consist of three broad bands between 250 nm and 550 nm and are consistent with the diffuse reflectance spectra. The emission spectra show the characteristic 4f⁶5d¹ → 4f⁷ transition of Eu²⁺ ion and there exists efficient energy transfer from host to Eu²⁺ ions when excited by 350-nm light. The dependence of emission spectra on temperature is also measured; the possible reasons applied to explain the experimental results are also discussed. The fluorescence lifetime of Eu²⁺ in Ba_1.995ZnS₃:0.005Eu²⁺ is measured and the values are 1.49 and 23.4 μs.     

一种新颖的白光LED荧光粉测量系统和分析方法(英文)

为获得高效率的白光LED,得到荧光粉和芯片的最佳匹配,本文提出了一种新颖的白光LED荧光粉测量系统和分析方法.该方法根据荧光粉测量原理,采用单色光激发荧光粉,获得荧光粉的激发光谱特性.由单波长激发的光谱组合可以得到荧光粉的三维光谱特性,荧光粉光谱与LED芯片光谱匹配可以模拟白光LED光谱.分析了荧光粉在单波长及光谱激发条件下的效率.实验结果表明,该测量系统和分析方法可以确定荧光粉和兰光LED芯片的最佳匹配,从而为获得高效率白光LED奠定了良好的基础.     

Eu2+掺杂硅基氮氧化物荧光粉的制备与发光特性

为获得接近太阳光的自然发光效果,制备了Eu2+掺杂的硅基氮化物系列荧光粉,并对其发光特性及原理进行研究.采用碳热还原氮化法制备了Eu2+掺杂Sr Si O3-Sr2Si5N8-Sr Si2O2N2红色荧光粉.利用X射线衍射仪(XRD)、荧光分光光度计、MS-CASTEP对产物物相、发光光谱、电子结构进行了测试分析.结果发现:通过调节煅烧工艺参数,可同时获得2种主要物相或者单一物相的荧光粉;所制备的荧光粉,能够在350~400 nm范围内被UVLED很好地激发,根据主晶相的不同,产物的发射光谱可以在400~700 nm波段内调控.采用第一性原理分析了发射峰位于650 nm附近橙红色主晶相Sr2Si5N8∶Eu2+的电子结构和光物理性能,发现该物相为直接带隙半导体材料,Eu2+的4f轨道对费米面电子峰起主要作用.Eu2+掺杂Sr Si O3-Sr2Si5N8-Sr Si2O2N2是优良的、颜色可调控的红色荧光粉材料.     

Color tuning of Y3Al5O12:Ce phosphor and their blend for white LEDs

Gadolinium or lanthanum co-doped (0.5 mole) yttrium aluminum garnet doped with cerium phosphors were synthesized by a citric acid gel method and the effect of co-dopants on the structural and luminescent properties were studied. A significant peak shift in the photoluminescence spectra of yttrium aluminum garnet doped cerium was observed from 535 to 556 and 576 nm for gadolinium or lanthanum co-doped phosphors, respectively. The color tuned phosphor were blended with yttrium aluminum garnet doped cerium which showed a considerable improvement in the Commission International De Eclairage chromaticity co-ordinate values of gallium nitride based blue light emitting diode pumped white light. White light emitted from yttrium aluminum garnet doped cerium shows a Commission International De Eclairage value of (0.229, 0.182) whereas the yttrium aluminum garnet doped cerium phosphor blended with gadolinium or lanthanum co-doped phosphor shows (0.262, 0.243) and (0.295, 0.282), respectively. These results demonstrate the possibility to use these phosphor blends to enhance the white light generation in the field of white-light emitting diode solid-state lighting.     

Photoluminescence optimization of BCNO phosphors synthesized using citric acid as a carbon source

Citric acid was used as carbon source for the optimization of the photoluminescence (PL) performance of boron carbon oxynitride (BCNO) phosphor. Citric acid was chosen as an alternative carbon source because of its simple molecular structure, low decomposition temperature, relative inexpensiveness, and environmental friendliness. The prepared sample exhibited a single, homogeneous, and broad photoluminescence emission band whose peak varied from near-UV (400 nm) to yellow-visible (500 nm) upon excitation at 365 nm. The effects of varying the synthesis temperature, molar ratio of the carbon/boron and nitrogen/boron sources, and addition of SiO₂ nanoparticles on the PL properties were also studied. The optimized BCNO phosphors may find potential use in white LED applications.     

A novel blue emitting phosphor NaBa<Subscript>0.98</Subscript>Eu<Subscript>0.02</Subscript>PO<Subscript>4</Subscript> and the improvement of its luminescence properties

A novel blue-emitting phosphor NaBa_0.98Eu_0.02PO₄ was synthesized by conventional solid state reaction, and it exhibits efficient blue emission under near-ultraviolet (n-UV) excitation. The emission spectrum shows a single band centered at about 440 nm, which corresponds to the 4f⁶5d¹-4f⁷ transition of Eu²⁺. The excitation spectrum is a broad band in the wavelength range between 200 and 450 nm, which can match the emission of white light emitting diodes (LEDs) by the method of n-UV conversion. The Ca²⁺, Sr²⁺ and Mg²⁺ were co-doped into NaBa_0.98Eu_0.02PO₄ respectively. Special attention was paid to the sample co-doped with Ca²⁺ that could possess a higher luminous efficacy than the analogs co-doped with Sr²⁺ and Mg²⁺. With the co-doping of Ca²⁺, the enhanced intensity of the excitation and emission band appears. The optimum co-doping concentration of Ca²⁺ is 7 mol.%. The emission intensity of NaBa_0.91Ca_0.07Eu_0.02PO₄ phosphoris about 1.68 times than that of NaBa_0.98Eu_0.02PO₄ phosphor. The as-prepared phosphors are the potential blue phosphors for application in white LEDs.     

A novel blue emitting phosphor NaBa0.98Eu0.02PO4 and the improvement of its luminescence properties

A novel blue-emitting phosphor NaBa_0.98Eu_0.02PO₄ was synthesized by conventional solid state reaction, and it exhibits efficient blue emission under near-ultraviolet (n-UV) excitation. The emission spectrum shows a single band centered at about 440 nm, which corresponds to the 4f⁶5d¹-4f⁷ transition of Eu²⁺. The excitation spectrum is a broad band in the wavelength range between 200 and 450 nm, which can match the emission of white light emitting diodes (LEDs) by the method of n-UV conversion. The Ca²⁺, Sr²⁺ and Mg²⁺ were co-doped into NaBa_0.98Eu_0.02PO₄ respectively. Special attention was paid to the sample co-doped with Ca²⁺ that could possess a higher luminous efficacy than the analogs co-doped with Sr²⁺ and Mg²⁺. With the co-doping of Ca²⁺, the enhanced intensity of the excitation and emission band appears. The optimum co-doping concentration of Ca²⁺ is 7 mol.%. The emission intensity of NaBa_0.91Ca_0.07Eu_0.02PO₄ phosphoris about 1.68 times than that of NaBa_0.98Eu_0.02PO₄ phosphor. The as-prepared phosphors are the potential blue phosphors for application in white LEDs.