全范围掺杂调制强黄色发光Gd0.5-yTb1.5REyW3O12 (RE=Eu, Sm)荧光粉的研究

doi:10.15541/jim20180522

摘要/Abstract

摘要：

黄光荧光材料在近紫外(NUV)芯片激发的白光发光二极管(W-LED)的制造中起重要作用。在本研究中, 通过在Gd₂W₃O₁₂基质中共掺Tb ³⁺/Eu ³⁺或Tb ³⁺/Sm ³⁺, 从而获得较强的黄光发射。由于Gd ³⁺的有效激发通常在深紫外区, 在Gd₂W₃O₁₂中并不会被382 nm的紫外光激发, 因此Gd ³⁺对Tb ³⁺/Eu ³⁺、Tb ³⁺/Sm ³⁺共掺杂的黄光发射并无影响。而Tb ³⁺与Gd ³⁺具有相似的离子半径, Tb ³⁺在全浓度范围内可以对Gd ³⁺进行取代。当Tb ³⁺离子掺杂浓度为75mol%时, 该体系绿光的发射强度达到最强, 对应的内量子产率(IQE)为37.6%。在最佳Tb ³⁺掺杂浓度下, 通过引入可以被近紫外光有效激发的Eu ³⁺或Sm ³⁺, 在Gd₂W₃O₁₂基质中实现Tb ³⁺/Eu ³⁺或Tb ³⁺/ Sm ³⁺共同掺杂, 得到了高亮度的黄色发光, IQE分别达到39.6%和47.8%。利用制备的Gd_0.494Tb_1.5Eu_0.006W₃O₁₂和Gd_0.494Tb_1.5Sm_0.006W₃O₁₂黄光荧光粉与NUV-蓝色芯片成功组装了W-LED器件。由此可见, Gd_0.5-_yTb_1.5RE_yW₃O₁₂(RE=Eu, Sm)荧光粉有望用于组装W-LED器件。此外, 全范围掺杂法可用于其他体系以获得高效的荧光粉。

关键词: 固相合成, 荧光, 钨酸盐, 稀土, 内量子效率

Abstract:

Yellow emission phosphors play an important role in fabrication of near ultraviolet (NUV) chip pumped white light emitting diodes (W-LEDs). In this study, doping of Gd₂W₃O₁₂ host with Tb ³⁺ and Eu ³⁺/Sm ³⁺ were used for obtaining yellow light emission. The excitation of Gd ³⁺ typically is in deep ultraviolet region, but Gd ³⁺ in Gd₂W₃O₁₂ does not emit under the excitation of 382 nm, thus Gd ³⁺ does not interfere with the emission from Tb ³⁺ and Eu ³⁺/Sm ³⁺ for obtaining yellow emission. Due to the similar ionic radii, the doping of Gd ³⁺ by Tb ³⁺ can be achieved in the full concentration range, and at the optimal concentration of 75mol% Tb ³⁺, green emission with reasonably high internal quantum efficiency of 37.6% was obtained. With the optimal doping concentration of Tb ³⁺, Eu ³⁺/Sm ³⁺ was co-doped in the Gd₂W₃O₁₂ host, and bright yellow emission with IQE of 39.6% and 47.8% were obtained. The yellow phosphors of Gd_0.494Tb_1.5Eu_0.006W₃O₁₂ and Gd_0.494Tb_1.5Sm_0.006W₃O₁₂ were used to fabricate W-LED devices with NUV-blue chips. Thus, Gd_0.5-_yTb_1.5RE_yW₃O₁₂ (RE=Eu, Sm) phosphors are candidates as the yellow phosphors for fabricating W-LED devices. Additionally, the full-range doping strategy can be used in other systems for obtaining efficient phosphors.

Key words: solid state synthesis, photoluminescence, tungstate, rare earth, internal quantum efficiency

中图分类号:

TQ174

代艳南, 杨帅, 沈阳, 单永奎, 杨帆, 赵庆彪. 全范围掺杂调制强黄色发光Gd_0.5-_yTb_1.5RE_yW₃O₁₂ (RE=Eu, Sm)荧光粉的研究[J]. 无机材料学报, 2019, 34(11): 1210-1216.

DAI Yan-Nan, YANG Shuai, SHEN Yang, SHAN Yong-Kui, YANG Fan, ZHAO Qing-Biao. Intense Yellow Emission from Gd_0.5-_yTb_1.5RE_yW₃O₁₂ (RE=Eu, Sm) Phosphors Tuned through Full Range Doping[J]. Journal of Inorganic Materials, 2019, 34(11): 1210-1216.

图/表 8

Fig. 1 (a) The polyhedron models of the crystal structure of Gd2W3O12 from perspectives of x axis, (b) the one-dimensional chain structure of [GdO8] polyhedrons

Fig. 2 XRD patterns of Gd2W3O12, TbGdW3O12 and Tb2W3O12

Fig. 3 (a) The excitation spectra of Gd2-xW3O12: xTb3+ (x= 0.25, 0.75, 1.0, 1.25, 1.5, 1.75, 2.00) monitored with 549 nm emission; (b) The concentration dependent excitation intensity of 7F6→5D4 transition of Tb3+ at 382 nm in Gd2-xW3O12: x Tb3+ (a) Coloful spectra are available on website

Fig. 4 (a) The emission spectra of Gd2-xW3O12: xTb3+ (x=0.25, 0.75, 1.00, 1.25, 1.50, 1.75, 2.00) phosphors under 382 nm ultraviolet excitation; (b) The concentration dependent 549 nm emission intensity of Gd2-xW3O12: xTb3+ (where x=0.25, 0.75, 1.00, 1.25, 1.50, 1.75, 2.00) phosphors

Fig. 5 (a, b) The excitation spectra of Gd0.5-yTb1.5REyW3O12 (RE=Eu, Sm), (c, d) the emission spectra of Gd0.5-yTb1.5REyW3O12 (RE=Eu, Sm) with 382 nm excitation Colourful spectra are available on website

Table 1 Comparison of the IQE and CIE coordinates of Gd0.5-yTb1.5REyW3O12 (RE=Eu, Sm) with other yellow phosphors

Sample	λ_ex/nm	IQE	CIE coordinates (x, y)
YAG: Ce³⁺ (Nichia, Japan)	430	~90%	Yellow
Sr₃AlO₄F: Ce^3+[28]	430	84%	Yellow
Gd₃Al₂Ga₃O₁₂: Ce^3+[29]	435	81.9%	Yellow
La₃Si₆N₁₁: Ce^3+[30]	450	78.6%	(0.422, 0.553)
LuVO₄: Bi^3+[31]	305	68%	Yellow
Tb_2.82Ce_0.09Eu_0.09Al₅O₁₂^[32]	460	40%	Yellow
Sr₃Lu_0.95Ce_0.05Al₂O_7.5^[33]	450	41%	(0.454, 0.533)
Ca_1.5Mn_0.5Gd_7.6Ce_0.4(SiO₄)₆O₂^[34]	330	33.9%	(0.552, 0.423)
NaSc_0.75Mn_0.20Eu_0.05Si₂O₆^[35]	365	33%	(0.431, 0.465)
La_0.90Tb_0.08Eu_0.02NbO₄^[36]	261	30%	(0.473, 0.500)
Gd_0.86Eu_0.12Tb_0.02NbO₄^[37]	260	21.1%	Yellow
Gd_0.494Tb_1.5Sm_0.006W₃O₁₂(This work)	382	47.8%	(0.510, 0.456)
Gd_0.494Tb_1.5Eu_0.006W₃O₁₂(This work)	382	39.6%	(0.491, 0.472)

Fig. 6 The 1931 CIE coordinates diagram of (a) Gd2-xTbxW3O12 (x=0, 0.25, 0.75, 1.00, 1.25, 1.50, 1.75, and 2.00), (b) Gd0.5-yTb1.5EuyW3O12 (y=0, 0.002, 0.004, 0.006, 0.008, 0.010, and 0.020) and (c) Gd0.5-yTb1.5SmyW3O12 (y=0, 0.002, 0.004, 0.006, 0.008, 0.010, and 0.020). The inserts in (b) and (c) are W-LED (1W), which was fabricated by Gd0.494Tb1.5Eu0.006W3O12 or Gd0.494Tb1.5Sm0.006W3O12 phosphors and NUV-blue chip, respectively

Table 2 The CIE coordinates of Gd0.5-yTb1.5REyW3O12 (RE=Eu, Sm)

Samples	y (Eu³⁺)	CIE coordinates (x, y)	y (Sm³⁺)	CIE coordinates (x, y)
1	0	(0.140, 0.562)	0	(0.140, 0.562)
2	0.002	(0.416, 0.529)	0.002	(0.430, 0.516)
3	0.004	(0.468, 0.490)	0.004	(0.476, 0.480)
4	0.006	(0.491, 0.472)	0.006	(0.510, 0.456)
5	0.008	(0.501, 0.459)	0.008	(0.497, 0.460)
6	0.010	(0.518, 0.444)	0.010	(0.508, 0.450)
7	0.020	(0.572, 0.400)	0.020	(0.528, 0.423)

参考文献 37

[1]	CRAWFORD M H . LEDs for solid-state lighting: Performance challenges and recent advances. IEEE Journal of Selected Topics in Quantum Electronics, 2009,15(4):1028-1040.
[2]	SHANG M, LI C, LIN J . How to produce white light in a single- phase host? Chemical Society Reviews, 2014,43(5):1372-1386.
[3]	ZHOU J, XIA Z . Luminescence color tuning of Ce ³+, Tb ³+ and Eu ³+ codoped and tri-doped BaY₂Si₃O₁₀ phosphors via energy transfer. Journal of Materials Chemistry C, 2015,3(29):7552-7560.
[4]	YANG P K, CHEN J C, CHUANG Y H . Improvement on reflective color measurement using a tri-color LED by multi-point calibration. Optics Communications, 2007,272(2):320-324.
[5]	PARK J K, KIM C H, PARK S H , et al. Application of strontium silicate yellow phosphor for white light-emitting diodes. Applied Physics Letters, 2004,84(10):1647-1649.
[6]	SONG G, MIAO J, JIANG B , et al. White LED based on near UV LED chip precoated with tri-color phosphors. Semiconductor Technology, 2011,36(8):586-590.
[7]	YE S, XIAO F, PAN Y X , et al. Phosphors in phosphor-converted white light-emitting diodes: recent advances in materials, techniques and properties. Materials Science and Engineering: R: Reports, 2010,71(1):1-34.
[8]	LIU Y, SILVER J, XIE R J , et al. An excellent cyan-emitting orthosilicate phosphor for NUV-pumped white LED application. Journal of Materials Chemistry C, 2017,5(2):12365-12377.
[9]	LIU Y, ZHANG J, ZHANG C , et al. Ba₉Lu₂Si₆O₂₄:Ce ³+: an efficient green phosphor with high thermal and radiation stability for solid-state lighting. Advanced Optical Materials, 2015,3(8):1096-1101.
[10]	LIN C C, TANG Y S, HU S F , et al. KBaPO₄: Ln (Ln=Eu, Tb, Sm) phosphors for UV excitable white light-emitting diodes. Journal of Luminescence, 2009,129(12):1682-1684.
[11]	LI P, WANG Z, YANG Z , et al. Luminescent characteristics of LiCaBO₃: M (M=Eu ³+, Sm ³+, Tb ³+, Ce ³+, Dy ³+) phosphor for white LED. Journal of Luminescence, 2010,130(2):222-225.
[12]	TIAN Y, CHEN B, HUA R , et al. Co-precipitation synthesis and characterization of Bi ³+, Eu ³+ co-doped nanocrystal Gd₂WO₆ phosphors. J. Nanosci Nanotechnol, 2010,10(3):1943-1946.
[13]	ZOU Z, WU T, LU H , et al. Structure, luminescence and temperature sensing in rare earth doped glass ceramics containing NaY(WO₄)₂ nanocrystals. RSC Advances, 2018,8(14):7679-7686.
[14]	LI J, LI J G, LIU S , et al. Greatly enhanced Dy ³+ emission via efficient energy transfer in gadolinium aluminate garnet (Gd₃Al₅O₁₂) stabilized with Lu ³+. Journal of Materials Chemistry C, 2013,1(45):7614-7622.
[15]	SHANNON R D . Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides. Acta Crystallographica, Section A: Crystal Physics, Diffraction, Theoretical and General Crystallography, 1976,32(5):751-767.
[16]	LEI, BINGFU, SHI -QING, , et al. Luminescence properties of Sm³+-doped Sr₃Sn₂O₇ phosphor. Materials Chemistry & Physics, 2010,124(2):912-915.
[17]	YU R, NOH H M, MOON B K , et al. Photoluminescence characteristics of Sm³+-doped Ba₂CaWO₆ as new orange-red emitting phosphors. Journal of Luminescence, 2014,152(5):133-137.
[18]	JAIN A, SHYUE PING O, HAUTIER G , et al. Commentary: The Materials Project: a materials genome approach to accelerating materials innovation. APL Materials, 2013,1(1):011002.
[19]	HOU Z, CHENG Z, LI G , et al. Electrospinning-derived Tb₂(WO₄)₃: Eu³+ nanowires: energy transfer and tunable luminescence properties. Nanoscale, 2011,3(4):1568-1574.
[20]	RAI V K, RAI S B, RAI D K . Optical properties of Tb ³+ doped tellurite glass . Journal of Materials Science Letter, 2004,39(15):4971-4975.
[21]	FOUASSIER C, SAUBAT B, HAGENMULLER P . Self-quenching of Eu ³+ and Tb ³+ luminescence in LaMgB₅O₁₀: a host structure allowing essentially one-dimensional interactions . Journal of Luminescence, 1981,23(3):405-412.
[22]	DU Z, LIU Q, HOU T , et al. The effects of Tb³+ doping concentration on luminescence properties and crystal structure of BaF₂ phosphor. Bulletin of Materials Science, 2015,38(3):1-5.
[23]	LIU Y, ZHANG J, ZHANG C , et al. High efficiency green phosphor Ba₉Lu₂Si₆O₂₄:Tb³+: visible quantum cutting via cross-relaxation energy transfers. Journal of Physical Chemistry C, 2016,120(4):2362-2370.
[24]	BLASSE G . Energy transfer in oxidic phosphors. Physics Letters A, 1968,28(6):444-445.
[25]	VAN UITERT L G, JOHNSON L F . Energy transfer between rare-earth ions. The Journal of Chemical Physics, 1966,44(9):3514-3522.
[26]	DEXTER D L, SCHULMAN J H . Theory of concentration quenching in inorganic phosphors. Journal of Chemical Physics, 1954,22(6):1063-1070.
[27]	QIANG S . Influence of environment on the luminescence of rare earths. Journal of Luminescence, 1988, 40-41:113-114.
[28]	ZHENG X, LUO H, LIU J , et al. Sr₃AlO₄F: Ce³+-based yellow phosphors: structural tuning of optical properties, and use in solid-state white lighting. Journal of Materials Chemistry C, 2013,1(45):7598-7607.
[29]	LIU Y F, LIU P, WANG L , et al. A two-step solid-state reaction to synthesize the yellow persistent Gd₃Al₂Ga₃O₁₂: Ce ³+ phosphor with an enhanced optical performance for AC-LEDs. Chemical Communications, 2017,53(53):10636-10639.
[30]	DU F, ZHUANG W, LIU R , et al. Synthesis, structure and luminescent properties of yellow phosphor La₃Si₆N₁₁: Ce ³+ for high power white-LEDs. Journal of Rare Earths, 2017,35(11):1059-1064.
[31]	FENGWEN K, MINGYING P, QINYUAN Z , et al. Abnormal anti-quenching and controllable multi-transitions of Bi³+ luminescence by temperature in a yellow-emitting LuVO₄ :Bi³+ phosphor for UV-converted white LEDs. Chemistry-A European Journal, 2015,20(36):11522-11530.
[32]	NAZAROV M, NOH D Y, SOHN J , et al. Quantum efficiency of double activated Tb₃Al₅O₁₂: Ce³+, Eu³+. Journal of Solid State Chemistry, 2007,180(9):2493-2499.
[33]	TAO Z, ZHANG W, QIN L , et al. A yellow-emitting nanophosphor of Ce³+-activated aluminate Sr₃LuAl₂O_7.5. Journal of Alloys & Compounds, 2014,588(5):540-545.
[34]	LI G, GENG D, SHANG M , et al. Tunable luminescence of Ce³+/Mn²+-coactivated Ca₂Gd₈(SiO₄)₆O₂ through energy transfer and modulation of excitation: potential single-phase white/yellow- emitting phosphors. Journal of Materials Chemistry, 2011,21(35):13334-13344.
[35]	XIA Z, ZHANG Y, MOLOKEEV M S , et al. Structural and luminescence properties of yellow-emitting NaScSi₂O₆: Eu ²+ phosphors: Eu ²+ site preference analysis and generation of red emission by codoping Mn ²+ for white-light-emitting diode applications. Journal of Physical Chemistry C, 2013,117(40):20847-20854.
[36]	LI K, ZHANG Y, LI X , et al. Host-sensitized luminescence in LaNbO₄: Ln ³+(Ln ³+ = Eu ³+/Tb ³+/Dy ³+) with different emission colors. Physical Chemistry Chemical Physics, 2015,17(6):4283-4292.
[37]	LIU X, CHEN C, LI S , et al. Host-sensitized and tunable luminescence of GdNbO₄: Ln ³+(Ln ³+ = Eu ³+/Tb ³+/Tm ³+) nanocrystalline phosphors with abundant color. Inorganic Chemistry, 2016,55(20):10383-10396.

全范围掺杂调制强黄色发光Gd_0.5-_yTb_1.5RE_yW₃O₁₂ (RE=Eu, Sm)荧光粉的研究

Intense Yellow Emission from Gd_0.5-_yTb_1.5RE_yW₃O₁₂ (RE=Eu, Sm) Phosphors Tuned through Full Range Doping

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