Ca1−<italic style="font-style: italic">x</italic>Li<italic style="font-style: italic">x</italic>Al1−<italic style="font-style: italic">x</italic>Si1+<italic style="font-style: italic">x</italic>N3: Eu2+ solid solutions as broadband, color-tunable and thermally robust red phosphors for superior color rendition white light-emitting diodes

Le Wang; Rong-Jun Xie; Yuanqiang Li; Xiaojun Wang; Chong-Geng Ma; Dong Luo; Takashi Takeda; Yi-Ting Tsai; Ru-Shi Liu; Naoto Hirosaki

doi:10.1038/lsa.2016.155

Go to Nature Website

Your Location：

Home >

Browse articles >

Ca₁_−xLi_xAl₁₋_xSi_1+xN₃: Eu²⁺ solid solutions as broadband, color-tunable and thermally robust red phosphors for superior color rendition white light-emitting diodes

Original Articles

- Ca₁_−xLi_xAl₁₋_xSi_1+xN₃: Eu²⁺ solid solutions as broadband, color-tunable and thermally robust red phosphors for superior color rendition white light-emitting diodes
- Ca₁_−xLi_xAl₁₋_xSi_1+xN₃: Eu²⁺ solid solutions as broadband, color-tunable and thermally robust red phosphors for superior color rendition white light-emitting diodes
- LSA 2016年5卷第4期
- Affiliations：
  
  1.College of Optics and Electronic Science and Technology, China Jiliang University, Hangzhou, Zhejiang 310018, China
  2.College of Materials, Xiamen University, Xiamen, Fujian 361005, China
  3.Sialon Group, National Institute for Materials Science (NIMS), Tsukuba, Ibaraki 305-0044, Japan
  4.Intematix Corporation, Fremont, CA 94538, USA
  5.College of Sciences, Chongqing University of Posts and Telecommunications, Chongqing 400065, China
  6.Department of Chemistry, Taiwan University
  7.Department of Mechanical Engineering and Graduate Institute of Manufacturing Technology, Taipei University of Technology
- Author bio：
  
  L Wang, Email: calla@cjlu.edu.cn
  RJ Xie, Email: rjxie@xmu.edu.cn
- Funds：
- DOI：10.1038/lsa.2016.155
  中图分类号：
- 纸质出版日期：2016-12，
  
  网络出版日期：2016-04-15，
  
  收稿日期：2016-02-26，
  
  修回日期：2016-04-07，
  
  录用日期：2016-04-11
- Accepted：
Scan QR Code
Ca₁_−xLi_xAl₁₋_xSi_1+xN₃: Eu²⁺ solid solutions as broadband, color-tunable and thermally robust red phosphors for superior color rendition white light-emitting diodes[J]. LSA, 2016,5(4).

Wang, L. et al. Ca₁_−xLi_xAl₁₋_xSi_1+xN₃: Eu²⁺ solid solutions as broadband, color-tunable and thermally robust red phosphors for superior color rendition white light-emitting diodes. Light: Science & Applications, 5, e16155 (2016).
Ca₁_−xLi_xAl₁₋_xSi_1+xN₃: Eu²⁺ solid solutions as broadband, color-tunable and thermally robust red phosphors for superior color rendition white light-emitting diodes[J]. LSA, 2016,5(4). DOI： 10.1038/lsa.2016.155.

Wang, L. et al. Ca₁_−xLi_xAl₁₋_xSi_1+xN₃: Eu²⁺ solid solutions as broadband, color-tunable and thermally robust red phosphors for superior color rendition white light-emitting diodes. Light: Science & Applications, 5, e16155 (2016). DOI： 10.1038/lsa.2016.155.

摘要

Abstract

Color rendition

luminous efficacy and reliability are three key technical parameters for white light-emitting diodes (wLEDs) that are dominantly determined by down-conversion phosphors. However

there is usually an inevitable trade-off between color rendition and luminescence efficacy because the spectrum of red phosphor (that is

spectral broadness and position) cannot satisfy them simultaneously. In this work

we report a very promising red phosphor that can minimize the aforementioned trade-off via structure and band-gap engineering

achieved by introducing isostructural LiSi

into CaAlSiN

: Eu

. The solid solution phosphors show both substantial spectra broadening (88→117 nm) and blueshift (652→642 nm)

along with a significant improvement in thermal quenching (only a 6% reduction at 150 ℃)

which are strongly associated with electronic and crystal structure evolutions. The broadband and robust red phosphor thus enables fabrication of super-high color rendering wLEDs (Ra=95 and R9=96) concurrently with the maintenance of a high-luminous efficacy (101 lm W

−1

)

validating its superiority in high-performance solid state lightings over currently used red phosphors.

关键词

Keywords

color renderingLEDsnitridephosphorstructure disorder

references

Schubert EF, Kim JK. Solid-state light sources getting smart.Science2005;308: 1274–1278..

Pimputkar S, Speck JS, DenBaars SP, Nakamura S. Prospects for LED lighting.Nat Photonics2009;3: 180–182..

Xie RJ, Li YQ, Yamamoto H, Hirosaki N.Nitride Phosphors and Solid State Lighting. Boca Raton: CRC Press. 2011.

Dai PP, Li C, Zhang XT, Xu J, Chen Xet al. A single Eu2+-activated high-color-rendering oxychloride white-light phosphor for white-light-emitting diodes.Light Sci Appl2016;5: e16024, doi:10.1038/lsa.2016.24..

Li XF, Budai JD, Liu F, Howe JY, Zhang JHet al. New yellow Ba0.93Eu0.07Al2O4 phosphor for warm-white light-emitting diodes through single-emitting-center conversion.Light Sci Appl2013;2: e50, doi:10.1038/lsa.2013.6..

Mueller-Mach R, Mueller G, Krames MR, Hopper HA, Stadler Fet al. Highly efficient all-nitride phosphor-converted white light emitting diode.Phy Stat Sol A2005;202: 1727–1732..

Kimura N, Sakuma K, Hirafune S, Asano K, Hirosaki Net al. Extrahigh color rendering white light-emitting diode lamps using oxynitride and nitride phosphors excited by blue light-emitting diode.Appl Phys Lett2007;90: 051109..

Setlur AA, Radkow EV, Henderson CS, Her JH, Srivastava AMet al. Energy-efficient, high-color-rendering LED lamps using oxyfluoride and fluoride phosphors.Chem Mater2010;22: 4076–4082..

Li YQ, van Steen JEJ, van Krevel JWH, Botty G, Delsing ACAet al. Luminescence properties of red-emitting M2Si5N8: Eu2+(M=Ca, Sr, Ba) LED conversion phosphors.J Alloy Compds2006;417: 273–279..

Uheda K, Hirosaki N, Yamamoto Y, Naito A, Nakajima Tet al. Luminescence properties of a red phosphor, CaAlSiN3: Eu2+, for white light-emitting diodes.Electrochem Solid-State Lett2006;9: H22–H25..

Watanabe H, Kijima N. Crystal structure and luminescence properties of SrxCa1-xAlSiN3: Eu2+mixed nitride phosphors.J Alloys Compds2009;475: 434–439..

Pust P, Weiler V, Hecht C, Tucks A, Wochnik ASet al. Narrow-band red-emitting Sr[LiAl3N4]: Eu2+as a next-generation LED-phosphor material.Nat Mater2014;13: 891–896..

Zhu HM, Lin CC, Luo WQ, Shu ST, Liu ZGet al. Highly efficient non-rare-earth red emitting phosphor for warm white light-emitting diodes.Nat Commun2014;5: 4312..

Mirhosseini R, Schubert MF, Chhajed S, Cho J, Kim JKet al. Improved color rendering and luminous efficacy in phosphor-converted white light-emitting diodes by use of dual-blue emitting active regions.Opt Express2009;17: 10806–10813..

Brinkley SE, Pfaff N, Denault KA, Zhang Z, Hintzen HTet al. Robust thermal performance of Sr2Si5N8: Eu2+: an efficient red emitting phosphor for light emitting diode based white lighting.Appl Phys Lett2011;99: 241106..

Zhang CN, Uchikoshi T, Xie RJ, Liu LH, Cho Yet al. Reduced thermal degradation of the red-emitting Sr2Si5N8: Eu2+phosphorviathermal treatment in nitrogen.J Mater Chem C2015;3: 7642–7651..

Nguyen HD, Lin CC, Liu RS. Waterproof alkyl phosphate coated fluoride phosphors for optoelectronic materials.Angew Chem Int Ed2015;54: 10862–10866..

Watanabe H, Yamane H, Kijima N. Crystal structure and luminescence of Sr0.99Eu0.01AlSiN3.J Solid State Chem2008;181: 1848–1852..

Huang WY, Yoshimura F, Ueda K, Pang WK, Su BJet al. Domination of second-sphere shrinkage effect to improve photoluminescence of red nitride phosphors.Inorg Chem2014;53: 12822–12831..

Yamamoto S, Takamura K. Highly enhanced visible luminescence in Zn1 −xMgxO nanocrystals.Jpn J Appl Phys2014;53: 035001..

Mocatta D, Cohen G, Schattner J, Millo O, Rabani Eet al. Heavily doped semiconductor nanocrystal quantum dots.Science2011;332: 77–81..

Mikami M, Uheda K, Kijima N. First-principles study of nitridoaluminosilicate CaAlSiN3.Phys Stat Sol A2006;203: 2705–2711..

Ohkubo K, Shigeta T. Absolute fluorescent quantum efficiency of NBS phosphor standard samples.J Illum Eng Inst Jpn1999;83: 87–93..

Kanaya K, Okayama S. Penetration and energy-loss theory of electrons in solid targets.J Phys D Appl Phys1972;5: 43–58..

10.1107/S0567739476001551Shannon RD. Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides. Acta Crystallogr A 1976; A32: 751–761..

Kresse G, Hafner J. Ab initio molecular dynamics for liquid metals.Phys Rev B1993;47: 558–561..

Kress G, Furthmuller J. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set.Comput Mat Sci1996;6: 15–50..

Blasse G, Sabbatini N. A comparison between 'second-sphere effects' in the excited state properties of coordination compounds and nonmolecular solids.J Solid State Chem1987;70: 93–100..

Carduner KR, Blackwell CS, Hammond WB, Reidinger F, Hatfield GR.29Si NMR characterization of α- and β-silicon nitride.J Am Chem Soc1990;112: 4676–4679..

Kempgens P, Harris RK, Thompson DP.6Li and7Li solid-state NMR spectroscopy of nitrogen ceramic phases.Solid State Nucl Magn Reson1999;15: 109–118..

Takeda T, Hirosaki N, Xie RJ, Kimoto K, Saito M. Anomalous Eu layer doping in Eu, Si co-doped aluminum nitride based phosphor and its direct observation.J Mater Chem2010;20: 9948–9953..

Yeh CW, Chen WT, Liu RS, Hu SF, Sheu HSet al. Origin of thermal degradation of Sr2-xSi5N8: Eux phosphors in air for light-emitting diodes.J Am Chem Soc2012;134: 14108–14117..

Li YQ, Hirosaki N, Xie RJ, Takeda T, Miomo M. Crystal, electronic structures and photoluminescence properties of rare-earth doped LiSi2N3.J Solid State Chem2009;182: 301–311..

Piao X, Machida K, Horikawa T, Hanzawa H, Shimomura Yet al. Preparation of CaAlSiN3: Eu2+phosphors by the self-propagating high-temperature synthesis and their luminescent properties.Chem Mater2007;19: 4592–4599..

Hirosaki N, Xie RJ, Kimoto K, Sekiguchi T, Yamamoto Yet al. Characterization and properties of green-emitting β-SiAlON: Eu2+powder phosphors for white light-emitting diodes.Appl Phys Lett2005;86: 211905..

Bhushan S, Chukichev MV. Temperature dependent studies of cathodoluminescence of green band of ZnO crystals.J Mater Sci Lett1988;7: 319–321..

Wang SS, Chen WT, Li Y, Wang J, Sheu HSet al. Neighboring-cation substitution tuning of photoluminescence by remote-controlled activators in phosphor lattice.J Am Chem Soc2013;135: 12504–12507..

浏览量

Downloads

CSCD

文章被引用时，请邮件提醒。

Submit

工具集

关联资源

UV/VUV switch-driven color-reversal effect for Tb-activated phosphors

Ca1−xLixAl1−xSi1+xN3: Eu2+ solid solutions as broadband, color-tunable and thermally robust red phosphors for superior color rendition white light-emitting diodes

Ca1−xLixAl1−xSi1+xN3: Eu2+ solid solutions as broadband, color-tunable and thermally robust red phosphors for superior color rendition white light-emitting diodes

DOI：10.1038/lsa.2016.155

摘要

Abstract

关键词

Keywords

references

Ca₁_−xLi_xAl₁₋_xSi_1+xN₃: Eu²⁺ solid solutions as broadband, color-tunable and thermally robust red phosphors for superior color rendition white light-emitting diodes

Ca₁_−xLi_xAl₁₋_xSi_1+xN₃: Eu²⁺ solid solutions as broadband, color-tunable and thermally robust red phosphors for superior color rendition white light-emitting diodes