白光LED用钨/钼酸盐红色发光材料研究进展

摘要/Abstract

摘要： 红色发光材料的性能对白光LED的显色指数和色温有着极其重要的影响,本文主要介绍了白钨矿型钨/钼酸盐、双钙钛矿型钨/钼酸盐以及复合型钨/钼酸盐等几大体系红色发光材料的结构组成、发光性能以及研究成果,并对钨/钼酸盐红色发光材料的未来前景进行展望。

关键词: 白光LED, 红色荧光粉, 钨/钼酸盐, 白钨矿型, 双钙钛矿型, 发光材料

Abstract: The performance of red luminescent materials has an extremely important influence on the color rendering index and color temperature of white LEDs. This article mainly introduces the structural composition, luminescence properties and research results of several major systems of red luminescent materials such as scheelite type tungsten/molybdate, double perovskite type tungsten/molybdate and composite tungsten/molybdate, the future prospects of tungsten/molybdate red luminescent materials is prospected.

Key words: white LED, red phosphor, tungsten/molybdate, scheelite type, double perovskite type, luminescent material

中图分类号:

阮文科, 谢木标. 白光LED用钨/钼酸盐红色发光材料研究进展[J]. 人工晶体学报, 2021, 50(1): 167-178.

RUAN Wenke, XIE Mubiao. Recent Research Progress on Tungsten and Molybdate Red Luminescent Material for White LED[J]. JOURNAL OF SYNTHETIC CRYSTALS, 2021, 50(1): 167-178.

参考文献

[1] 翟永清,王恒刚,李天姿,等.ZnWO₄∶Eu³⁺,Dy³⁺白色荧光粉的微波水热合成及其发光性能[J].人工晶体学报,2019,48(11):2105-2110.
ZHAI Y Q, WANG H G, LI T Z, et al. Microwave hydrothermal synthesis and luminescent properties of ZnWO₄∶Eu³⁺, Dy³⁺ white light-emitting phosphors[J]. Journal of Synthetic Crystals, 2019, 48(11): 2105-2110(in Chinese).
[2] LI G G, TIAN Y, ZHAO Y, et al. Recent progress in luminescence tuning of Ce³⁺ and Eu²⁺-activated phosphors for pc-WLEDs[J]. Chemical Society Reviews, 2015, 44(23): 8688-8713.
[3] NAKAMURA S, SENOH M, MUKAI T. High-power InGaN/GaN double-heterostructure violet light emitting diodes[J]. Applied Physics Letters, 1993, 62(19): 2390-2392.
[4] NAKAMURA S, MUKAI T, SENOH M. Candela-class high-brightness InGaN/AlGaN double-heterostructure blue-light-emitting diodes[J]. Applied Physics Letters, 1994, 64(13): 1687-1689.
[5] 王春浩.Eu³⁺掺杂钼钨酸盐荧光材料发光热猝灭行为的研究[D].广州:华南理工大学,2018.
WANG C H. Study of Eu³⁺ luminescence thermal quenching behaviours in molybdate-tungstate materials[D]. Guangzhou: South China University of Technology, 2018(in Chinese).
[6] AVCI N, CIMIERI I, SMET P F, et al. Stability improvement of moisture sensitive CaS∶Eu²⁺ micro-particles by coating with sol-gel alumina[J]. Optical Materials, 2011, 33(7): 1032-1035.
[7] CHEN C C, CHEN W J, RAINWATER B, et al. M₂Si₅N₈∶Eu²⁺-based (M=Ca, Sr) red-emitting phosphors fabricated by nitrate reduction process[J]. Optical Materials, 2011, 33(11): 1585-1590.
[8] YANG R, TANG H D. Synthesis and luminescence properties of red-emitting K₂MgSiO₄∶Eu³⁺ phosphors[J]. International Journal of Modern Physics B, 2017, 31(16/17/18/19): 1744058.
[9] GUPTA S K, GHOSH P S, SAHU M, et al. Intense red emitting monoclinic LaPO₄∶Eu³⁺ nanoparticles: host-dopant energy transfer dynamics and photoluminescence properties[J]. RSC Advances, 2015, 5(72): 58832-58842.
[10] GOLYEVA E V, TOLSTIKOVA D V, KOLESNIKOV I E, et al. Effect of synthesis conditions and surrounding medium on luminescence properties of YVO₄∶Eu³⁺ nanopowders[J]. Journal of Rare Earths, 2015, 33(2): 129-134.
[11] RAJENDRAN M, VAIDYANATHAN S. New red emitting phosphors NaSrLa(MO₄)₃∶Eu³⁺ [M=Mo and W] for white LEDs: synthesis, structural and optical study[J]. Journal of Alloys and Compounds, 2019, 789: 919-931.
[12] 鞠小霞,王海波,向枫,等.钼酸盐荧光粉的研究进展[J].稀土,2019,40(6):105-116.
JU X X, WANG H B, XIANG F, et al. Recent advances of molybdate phosphors[J]. Chinese Rare Earths, 2019, 40(6): 105-116(in Chinese).
[13] 耿秀娟,田彦文,陈永杰,等.白光LED用钨/钼酸盐红色荧光粉的研究进展[J].材料导报,2010,24(13):54-57.
GENG X J, TIAN Y W, CHEN Y J, et al. Progress in studies on tungstate and molybdate red emitting phosphor used for white-LED[J]. Materials Review, 2010, 24(13): 54-57(in Chinese).
[14] RASU K K, BALAJI D, BABU S M. Spectroscopic properties of Eu³⁺∶KLa(WO₄)₂ novel red phosphors[J]. Journal of Luminescence, 2016, 170: 547-555.
[15] 李桂芳,杨倩,卫云鸽.复合钙钛矿型NaLaMgWO₆∶Eu³⁺红色荧光材料的制备及发光性能研究[J].无机材料学报,2017,32(9):936-942.
LI G F, YANG Q, WEI Y G. Synthesis and photoluminescence properties of double perovskite NaLaMgWO₆∶Eu³⁺ red phosphors[J]. Journal of Inorganic Materials, 2017, 32(9): 936-942(in Chinese).
[16] WU H Y, YANG J F, WANG X X, et al. Tune color of single-phase LiGd(MoO₄)_2-x(WO₄)_x∶Sm³⁺, Tb³⁺ via adjusting the proportion of matrix and energy transfer to create white-light phosphor[J]. Solid State Sciences, 2018, 77: 20-26.
[17] SU J Y, ZHANG X Y, LI X, et al. Synthesis and luminescence properties of Yb³⁺, Tm³⁺ and Ho³⁺ co-doped SrGd₂(WO₄)₂(MoO₄)₂ nano-crystal[J]. Advanced Powder Technology, 2020, 31(3): 1051-1059.
[18] KIM D W, CHO I S, SHIN S S, et al. Electronic band structures and photovoltaic properties of MWO₄(M=Zn, Mg, Ca, Sr) compounds[J]. Journal of Solid State Chemistry, 2011, 184(8): 2103-2107.
[19] 王林香.Na⁺,Li⁺,Bi³⁺掺杂CaWO₄∶Eu³⁺荧光粉的制备及发光特性[J].高等学校化学学报,2018,39(1):25-31.
WANG L X. Preparation and luminescence properties of Na⁺, Li⁺, Bi³⁺ doped CaWO₄∶Eu³⁺ phosphors[J]. Chemical Journal of Chinese Universities, 2018, 39(1): 25-31(in Chinese).
[20] 孔丽,乔露,魏奇业,等.助熔剂对白光LED用红色荧光粉SrMoO₄∶Eu³⁺的光谱性能影响[J].人工晶体学报,2019,48(4):616-620+626.
KONG L, QIAO L, WEI Q Y, et al. Effect of flux on the luminescence of red phosphor SrMoO₄∶Eu³⁺ for white LED[J]. Journal of Synthetic Crystals, 2019, 48(4): 616-620+626(in Chinese).
[21] 翟永清,马健,胡志春,等.微波辅助溶胶-凝胶法合成红色发光材料NaLa(MoO₄)₂∶Eu³⁺及其发光性能研究[J].人工晶体学报,2013,42(7):1323-1329.
ZHAI Y Q, MA J, HU Z C, et al. Synthesis and luminescent properties of red-emitting phosphors NaLa(MoO₄)₂∶Eu³⁺ by microwave-assisted Sol-gel method[J]. Journal of Synthetic Crystals, 2013, 42(7): 1323-1329(in Chinese).
[22] SHI P L, XIA Z G, MOLOKEEV M S, et al. Crystal chemistry and luminescence properties of red-emitting CsGd_1-xEu_x(MoO₄)₂ solid-solution phosphors[J]. Dalton Transactions (Cambridge, England), 2014, 43(25): 9669-9676.
[23] LI L L, ZHANG J J, ZI W W, et al. Synthesis and luminescent properties of high brightness MRE(MoO₄)₂∶Eu³⁺(M=Li, Na, K; RE=Gd, Y, Lu) red phosphors for white LEDs[J]. Solid State Sciences, 2014, 29: 58-65.
[24] 张振乾,马晶,赵婉男,等.NaGd(MoO₄)₂∶Eu³⁺发光粉的水热合成与发光性质[J].硅酸盐通报,2016,35(11):3541-3545.
ZHANG Z Q, MA J, ZHAO W N, et al. Hydrothermal synthesis and luminescence properties of NaGd(MoO₄)₂∶Eu³⁺ phosphors[J]. Bulletin of the Chinese Ceramic Society, 2016, 35(11): 3541-3545(in Chinese).
[25] REN Q, LIN F, WU X L, et al. Synthesis and luminescent properties of KGd(MoO₄)₂∶Sm³⁺ red phosphor for white light emitting diodes[J]. Materials Research Bulletin, 2017, 90: 66-72.
[26] BAI L, MENG Q Y, HUO M X, et al. Optical properties of NaY(MoO₄)₂∶Eu³⁺ nanophosphors prepared by molten salt method[J]. Journal of Rare Earths, 2019, 37(12): 1261-1268.
[27] 翟永清,赵鑫,杨帅,等.Bi³⁺或Sm³⁺掺杂对NaGd(WO₄)₂∶Eu³⁺荧光粉结构和发光性质的影响[J].发光学报,2017,38(8):987-994.
ZHAI Y Q, ZHAO X, YANG S, et al. Influence of Bi³⁺ or Sm³⁺ doping on structure and luminescence properties of NaGd(WO₄)₂∶Eu³⁺ phosphors[J]. Chinese Journal of Luminescence, 2017, 38(8): 987-994(in Chinese).
[28] WU J X, LI M, WANG M T, et al. Preparation and luminescence properties of NaLa(WO₄)₂∶Sm³⁺ orange-red phosphor[J]. Journal of Luminescence, 2018, 197: 219-227.
[29] SHRUTHI D L, REDDY A J, KUMAR G N A, et al. Judd Ofelt theoretical analysis, photoluminescence properties of Eu³⁺ activated LiGd(WO₄)₂ phosphors[J]. Journal of Luminescence, 2020, 222: 117167.
[30] MENG X M, LIN Z B, ZHANG L Z, et al. Structure and spectral properties of Nd³⁺-doped KBaGd(MoO₄)₃ crystal with a disorder structure[J]. Cryst Eng Comm, 2011, 13(12): 4069-4073.
[31] YU Y, HUANG Y, ZHANG L, et al. Growth and spectral assessment of Yb³⁺-doped KBaGd(MoO₄)₃ crystal: a candidate for ultrashort pulse and tunable lasers[J]. PLoS One, 2013, 8(1): e54450.
[32] SONG M J, ZHAO W, RAN W G, et al. Multicolor tunable luminescence and energy transfer mechanism in a novel single-phase KBaGd(WO₄)₃∶Tb³⁺, Eu³⁺ phosphor for NUV WLEDs[J]. Journal of Alloys and Compounds, 2019, 803: 1063-1074.
[33] 宋明君,台夕市,张娜娜,等.KMGd(MoO₄)₃∶Eu³⁺(M=Ca,Sr)红色荧光粉的制备、光谱及封装性能研究[J].功能材料,2019,50(6):6109-6115.
SONG M J, TAI X S, ZHANG N N, et al. Preparation, spectral and packaging performance of KMGd(MoO₄)₃∶Eu³⁺(M=Ca, Sr) phosphors[J]. Journal of Functional Materials, 2019, 50(6): 6109-6115(in Chinese).
[34] ZHU H K, FANG M H, HUANG Z H, et al. Photoluminescence properties of Li₂Mg₂(WO₄)₃∶Eu³⁺ red phosphor with high color purity for white LEDs applications[J]. Journal of Luminescence, 2016, 172: 180-184.
[35] 孙继强,张振乾,马晶,等.不同晶体结构Gd₂(MoO₄)₃∶Eu³⁺荧光粉的合成及其发光性能研究[J].人工晶体学报,2020,49(2):222-228.
SUN J Q, ZHANG Z Q, MA J, et al. Synthesis and luminescence properties of Gd₂(MoO₄)₃∶Eu³⁺ phosphors with the different crystalline structures[J]. Journal of Synthetic Crystals, 2020, 49(2): 222-228(in Chinese).
[36] ZHOU W W, SONG M J, ZHANG Y, et al. Color tunable luminescence and optical temperature sensing performance in a single-phased KBaGd(WO₄)₃∶Dy³⁺, Eu³⁺ phosphor[J]. Optical Materials, 2020, 109: 110271.
[37] BALAKIREVA T P, BRISKINA C M, VAKULYUK V V, et al. Luminescence and stimulated emission from BaGd_2-xNd_x(MoO₄)₄ single crystals[J]. Soviet Journal of Quantum Electronics, 1981, 11(3): 398-400.
[38] 赵旺,周薇薇,刘淑河,等.BaGd₂(MoO₄)₄∶Tb³⁺,Eu³⁺荧光粉的发光特性与能量传递机理[J].发光学报,2019,40(5):581-588.
ZHAO W, ZHOU W W, LIU S H, et al. Luminescent characters and energy transfer mechanisms of BaGd₂(MoO₄)₄∶Tb³⁺,Eu³⁺ phosphors[J]. Chinese Journal of Luminescence, 2019, 40(5): 581-588(in Chinese).
[39] 蒲勇,赵聪,敬小龙,等.CaGd₂(MoO₄)₄∶Eu³⁺,Bi³⁺红色荧光粉的制备及发光性能[J].发光学报,2018,39(8):1045-1050.
PU Y, ZHAO C, JING X L, et al. Synthesis and luminescence properties of CaGd₂(MoO₄)₄∶Eu³⁺, Bi³⁺ red phosphors[J]. Chinese Journal of Luminescence, 2018, 39(8): 1045-1050(in Chinese).
[40] LI G F, WEI Y G, LONG W X, et al. Photoluminescence properties, energy transfer and thermal stability of the novel red-emitting CaGd₂(WO₄)₄∶Eu³⁺, Sm³⁺ phosphors[J]. Materials Research Bulletin, 2017, 95: 86-94.
[41] YANG Q, LI G F, WEI Y G, et al. Synthesis and photoluminescence properties of red-emitting NaLaMgWO₆∶Sm³⁺, Eu³⁺ phosphors for white LED applications[J]. Journal of Luminescence, 2018, 199: 323-330.
[42] LI G F, WANG Y, WEI Y G, et al. Structure, energy transfer, and luminescence properties of NaLaMgWO₆∶Tb³⁺, Eu³⁺ phosphors for solid-state lighting[J]. Journal of Materials Science: Materials in Electronics, 2020, 31(5): 3835-3844.
[43] SIVAKUMAR V, VARADARAJU U V. A promising orange-red phosphor under near UV excitation[J]. Electrochemical and Solid-State Letters, 2006, 9(6): H35.
[44] 林金填,邱镇民,蔡金兰,等.Gd₂MoO₆∶Sm³⁺荧光粉的制备及其发光性能研究[J].中国照明电器,2018(8):5-8.
LIN J T, QIU Z M, CAI J L, et al. Preparation and photoluminescence properties of Gd₂MoO₆∶Sm³⁺ phosphors[J]. China Light & Lighting, 2018(8): 5-8(in Chinese).
[45] 王梅芳,周立群,李玲,等.Li⁺,Eu³⁺共掺杂La₂MoO₆红色荧光粉的Pechini法合成及近紫外/蓝光激发下的发光特征[J].应用化学,2015,32(4):447-452.
WANG M F, ZHOU L Q, LI L, et al. Synthesis of Li⁺ and Eu³⁺ co-doped La₂MoO₆ red phosphors by pechini methods and its photoluminescence properties under near-ultraviolet and blue light[J]. Chinese Journal of Applied Chemistry, 2015, 32(4): 447-452(in Chinese).
[46] NEERAJ S, KIJIMA N, CHEETHAM A K. Novel red phosphors for solid-state lighting: the system NaM(WO₄)_2-x(MoO₄)_x∶Eu³⁺ (M=Gd, Y, Bi)[J]. Chemical Physics Letters, 2004, 387(1/2/3): 2-6.
[47] 谢安,袁曦明,王娟娟,等.红色荧光粉KY_yEu_1-y(WO₄)_x(MoO₄)_2-x的制备及其发光性能研究[J].中国稀土学报,2009,27(4):501-505.
XIE A, YUAN X M, WANG J J, et al. Synthesis and photoluminescence property of red phosphor KY_yEu_1-y(WO₄)_x(MoO₄)_2-x for white LED[J]. Journal of the Chinese Rare Earth Society, 2009, 27(4): 501-505(in Chinese).
[48] RU J J, GUO F Y, CHEN J Z. Synthesis and luminescence characteristics of Li₂Y_4-xEu_x(WO₄)_7-y(MoO₄)_y red-emitting phosphor for white LED[J]. Journal of Rare Earths, 2013, 31(11): 1059-1062.
[49] YAN Y, CAO F B, TIAN Y W, et al. Improved luminescent properties of red-emitting Ca_0.54Sr_0.16Eu_0.08Gd_0.12(MoO₄)_0.2(WO₄)_0.8 phosphor for LED application by charge compensation[J]. Journal of Luminescence, 2011, 131(6): 1140-1143.
[50] FAN G D, WANG X J, QIU X Y, et al. Luminescent properties of orange-red emitting phosphors NaGd(MoO₄)(WO₄)∶Sm³⁺ for white LED[J]. Optical Materials, 2019, 91: 363-370.
[51] 武超,李峰,范伟,等.Mg²⁺或Zn²⁺掺杂的Ca(WO₄)_1-x(MoO₄)_x∶Eu³⁺荧光粉的制备及发光性能研究[J].化工新型材料,2019,47(11):87-93.
WU C, LI F, FAN W, et al. Preparation and luminescent properties of Mg²⁺/Zn²⁺ doped Ca(WO₄)_1-x(MoO₄)x∶Eu³⁺[J]. New Chemical Materials, 2019, 47(11): 87-93(in Chinese).
[52] DONG S L, YE S, WANG L L, et al. Gd₃B(W, Mo)O₉∶Eu³⁺ red phosphor: from structure design to photoluminescence behavior and near-UV white-LEDs performance[J]. Journal of Alloys and Compounds, 2014, 610: 402-408.
[53] JING L D, LIU X H, LI Y T. Synthesis and optical properties of novel red phosphors Sr₃MoO₆∶Eu³⁺ with highly enhanced emission by W⁶⁺ doping[J]. Journal of Luminescence, 2015, 158: 351-355.
[54] SLETNES M, LINDGREN M, VALMALETTE J C, et al. Photoluminescence of A-and B-site Eu³⁺-substituted (Sr_xBa_1-x)₂CaW_yMo_1-yO₆ phosphors[J]. Journal of Solid State Chemistry, 2016, 237:72-80.