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.     

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.     

Narrow-band emitters in LED backlights for liquid-crystal displays

Over the last decade, narrow-band emitters have been recognized as key enablers for light emitting diodes (LEDs) backlights in liquid-crystal displays (LCDs) by competing with other display technologies. Today, efforts have been devoted to the exploration of narrow-band green/red luminescent materials with high quantum efficiency and excellent stability to optimize the performance of LED backlights. This review first presents an overview of the significant progress made in the development of narrow-band emitters used in LED backlights for LCDs with the emphasis on the versatile materials databases from doped phosphors to luminescent II–VI, III-V semiconductor quantum dots, and the recent halide perovskites nanocrystals and bulk metal halides. Subsequently, the correlation of structure-luminescence properties, and the device performance optimization of these emitters have been analyzed. The focus is placed on summarizing and comparing the remarkable examples of outdated and new narrow-band luminescent materials as potential candidates in LED backlights. Finally, the outlooks and challenges in discovering new narrow-band emitters have been proposed.     

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.     

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.     

白光LED用单一基质白光荧光粉的研究进展

白光LED以其独特优势被称为第四代光源,具有广阔的应用前景。单一基质白光荧光粉(SMWP)因颜色稳定、色彩还原性好,成为白光LED用光转换材料的研究热点。概述了由近紫外LED芯片激发的白光荧光粉的研究现状,指出了该荧光粉存在的问题并对其发展趋势做了展望。     

白光LED荧光粉的性能表征与测量

芯片与荧光粉的匹配优劣是影响白光LED性能的重要因素,针对这一问题,本文提出了LED荧光粉的性能表征与测量方法.采用了一种双分光式荧光粉测量系统,分析了荧光粉的光谱特性,得到了其三维光谱分布.并用发光效率,量子效率和能量效率来评价荧光粉特性.通过评价具有不同峰值波长的LED与荧光粉的匹配,得到了其最优匹配.结果表明此种系统和评价方法不仅可以得到荧光粉的特性,对于研究高效率白光LED有重要的意义.     

Epitaxial growth of three-dimensionally architectured optoelectronic devices

Optoelectronic devices have long benefited from structuring in multiple dimensions on microscopic length scales. However, preserving crystal epitaxy, a general necessity for good optoelectronic properties, while imparting a complex three-dimensional structure remains a significant challenge. Three-dimensional (3D) photonic crystals are one class of materials where epitaxy of 3D structures would enable new functionalities. Many 3D photonic crystal devices have been proposed, including zero-threshold lasers, low-loss waveguides, high-efficiency light-emitting diodes (LEDs) and solar cells, but have generally not been realized because of material limitations. Exciting concepts in metamaterials, including negative refraction and cloaking, could be made practical using 3D structures that incorporate electrically pumped gain elements to balance the inherent optical loss of such devices. Here we demonstrate the 3D-template-directed epitaxy of group III-V materials, which enables formation of 3D structured optoelectronic devices. We illustrate the power of this technique by fabricating an electrically driven 3D photonic crystal LED.     

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。     

Nanocrystal-based light-emitting diodes utilizing high-efficiency nonradiative energy transfer for color conversion

We report a practical implementation of high-efficiency color conversion in an electrically pumped light-emitting diode (LED) using nonradiative energy transfer. On the basis of a new LED design that offers both strong energy-transfer coupling and efficient carrier injection, we show that a hybrid structure comprising a single monolayer of CdSe nanocrystals assembled on top of an InGaN/GaN quantum well provides nearly 10% color conversion efficiency. This value is significantly higher than that for a traditional absorption-re-emission color-conversion scheme in a similar device structure. Furthermore, these hybrid devices can also provide improved efficiencies, compared not only to phosphor-based structures but also to stand-alone LEDs.     

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.     

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.     

Performance enhancement by different sidewall structures for InGaN-based light-emitting diodes

We demonstrate high-performance GaN-based light-emitting diodes (LEDs) using different sidewall structure. The patterned pyramidal sidewall (PPS) structure in LED is fabricated by crystallographic etching process, which is applying hot phosphoric acid wet etching at the GaN/Al₂O₃ interface after normal front-side laser scribing. To obtain continuous, regular and bigger pyramidal sidewalls we applied higher temperature and longer time on the LEDs. However, there might be negative effect on the reliability of the PPS-LED by the higher experimental conditions. On the other hand, we applied the new stealth dicing process to form the clean and non-destructive sidewalls. The three times stealth dicing process can get a better well-distributed and shipshape sidewall than one time stealth dicing. The light output power of the PPS-LED had a 39.6 % enhancement compared to the standard LED owing to the larger light-scattering when measured in LED chip form. But the LED with stealth dicing is more reliable than PPS-LED regardless of the crystal quality of the LED.     

Efficient and Tunable Electroluminescence from In Situ Synthesized Perovskite Quantum Dots

Semiconductor quantum dots (QDs) are among the most promising next‐generation optoelectronic materials. QDs are generally obtained through either epitaxial or colloidal growth and carry the promise for solution‐processed high‐performance optoelectronic devices such as light‐emitting diodes (LEDs), solar cells, etc. Herein, a straightforward approach to synthesize perovskite QDs and demonstrate their applications in efficient LEDs is reported. The perovskite QDs with controllable crystal sizes and properties are in situ synthesized through one‐step spin‐coating from perovskite precursor solutions followed by thermal annealing. These perovskite QDs feature size‐dependent quantum confinement effect (with readily tunable emissions) and radiative monomolecular recombination. Despite the substantial structural inhomogeneity, the in situ generated perovskite QDs films emit narrow‐bandwidth emission and high color stability due to efficient energy transfer between nanostructures that sweeps away the unfavorable disorder effects. Based on these materials, efficient LEDs with external quantum efficiencies up to 11.0% are realized. This makes the technologically appealing in situ approach promising for further development of state‐of‐the‐art LED systems and other optoelectronic devices.     

Enhanced light extraction from GaN-based LEDs with a bottom-up assembled photonic crystal

Photonic crystal (PhC) structure is an efficient tool for light extraction from light-emitting diodes (LEDs). The fabrication of a large area PhC structure on the light output surface of LEDs often involves sophisticated equipments such as nanoimprint lithography machine. In this study a monolayer of polystyrene (PS) microspheres was employed as a template to fabricate a noninvasive photonic crystal of indium tin oxide (ITO) on the surface of GaN-based LED. PS spheres can help to form periodic arrangement of bowl-like holes, a photonic crystal with gradually changed fill factors. Importantly, the electroluminescence intensity of LED with a photonic crystal was significantly enhanced by 1.5 times compared to that of the conventional one under various forward injection currents.     

LED用绿色荧光粉的研究进展

白光LED被誉为第四代照明光源,有着显著的节能前景和庞大的应用市场。荧光粉光转换型是未来白光LED发展的主流方向。(近)紫外激发三基色荧光粉的研制具有十分重要的意义。综述了近年来半导体白色发光二极管(WLED)用绿色荧光粉的研究进展,重点推介了性能较好的绿色荧光粉,并展望了LED用绿色荧光粉发展趋势。     

Interface and Defect Engineering for Metal Halide Perovskite Optoelectronic Devices

Metal halide perovskites have been in the limelight in recent years due to their enormous potential for use in optoelectronic devices, owing to their unique combination of properties, such as high absorption coefficient, long charge‐carrier diffusion lengths, and high defect tolerance. Perovskite‐based solar cells and light‐emitting diodes (LEDs) have achieved remarkable breakthroughs in a comparatively short amount of time. As of writing, a certified power conversion efficiency of 22.7% and an external quantum efficiency of over 10% have been achieved for perovskite solar cells and LEDs, respectively. Interfaces and defects have a critical influence on the properties and operational stability of metal halide perovskite optoelectronic devices. Therefore, interface and defect engineering are crucial to control the behavior of the charge carriers and to grow high quality, defect‐free perovskite crystals. Herein, a comprehensive review of various strategies that attempt to modify the interfacial characteristics, control the crystal growth, and understand the defect physics in metal halide perovskites, for both solar cell and LED applications, is presented. Lastly, based on the latest advances and breakthroughs, perspectives and possible directions forward in a bid to transcend what has already been achieved in this vast field of metal halide perovskite optoelectronic devices are discussed.     

Temperature estimation of high-power light emitting diode street lamp by a multi-chip analytical solution

Light emitting diodes (LEDs) are now widely used in many fields including traffic lights, vehicle backlights and liquid crystal display (LCD) displays because of their long life, good illumination efficiency and low energy consumption. At present, LEDs are increasingly replacing the traditional lighting and are being used in general illumination such as the street lamp. For the high-power LED street lamps, good light extraction is the most important thing, but low junction temperature of the LED modules is also critical for achieving a long lifetime and a high optical efficiency. Actually, there have been many reports about early failures of street lamps, called dead lamps that have been regarded as a barrier in the public and administration acceptance of LED street lamps. Therefore temperature estimation is always a crucial issue for LED product development. A multi-chip spreading thermal resistance model was applied to estimate the temperature distribution of LED street lamp. The experiment was first done to obtain temperatures of several locations in a prototype LED street lamp. Then the multi-chip spreading resistance model was established to calculate the full temperature distribution. Comparison between the model calculation and experimental measurement showed a good agreement, which demonstrates that the present model can be used in engineering design to estimate the temperature distribution of high-power LED street lamps.     

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.     

Polarisation fields in III-nitrides: effects and control

III-Nitrides are materials that have revolutionised the lighting industry allowing for the development of high brightness and efficiency white light emitting diodes (LEDs), enabling cost and energy savings at an unprecedented scale. However, there remain several obstacles to the further enhancement of the efficiency of LEDs, particularly for emission at longer wavelengths. The existence of polarisation fields as an inherent property of wurtzite III-nitride materials severely hampers LED performance. The origin of these fields due to the deviation from an ideal tetrahedral bonding structure and their relation to strain has been addressed in this review. The effect of the polarisation fields on the band structure of heterostructure quantum wells, known as the quantum confined stark effect, and its implications for the efficiency and spectral stability of LEDs have also been reviewed. Finally, the effectiveness and viability of several proposed methods of mitigating the harmful effects of the polarisation fields, such as the growth of III-nitrides on alternative planes, doping, strain engineering and growth of cubic GaN, have been addressed.