Ba3Gd(PO4)3:Eu3+荧光粉的合成及发光性质

doi:10.15541/jim20150151

摘要/Abstract

摘要：

采用高温固相反应法合成了不同Eu³⁺掺杂浓度的Ba₃Gd(PO₄)₃荧光粉。利用X射线衍射对产生的晶体结构进行了分析, 证实产物为纯相, Eu³⁺的引入没有导致晶体结构的改变。利用Van Uitert模型对⁵D₀能级荧光的浓度猝灭行为进行了研究, 发现浓度猝灭是由于Eu³⁺间交换相互作用所导致。分析了⁵D₀荧光发射的温度依赖, 给出了荧光温度猝灭行为符合横向穿越模型, 并通过非线性拟合获得了激活能。利用Eu³⁺的发射光谱和荧光衰减数据, 计算了⁵D₀→⁷F_J辐射跃迁速率及荧光分支比, 同时得到了光学跃迁强度参数。

关键词: 高温固相法, 浓度猝灭, 热猝灭, 光学跃迁

Abstract:

A series of Ba₃Gd(PO₄)₃ phosphors with different Eu³⁺ concentrations were synthesized by a high-temperature solid-state method. The crystal structure of the products was examined by means of X-ray diffraction, and it was confirmed that the final products existed in a pure phase and the Eu³⁺ introduction did not change the crystal structure. The luminescence spectra and decay curves were analyzed as a function of Eu³⁺ concentration and temperature. It was found that the luminescent color of the phosphor can be adjusted from white to red with the increase of Eu³⁺ concentration. Concentration quenching for the prepared phosphors was studied based on the Van Uitert model and Dexter theory, which confirmed that the exchange interaction was responsible for energy transfer between Eu³⁺ ions resulting in the concentration quenching. The temperature dependence of ⁵D₀ fluorescence emissions was analyzed, and it was deduced that the thermal quenching behavior of ⁵D₀ fluorescence followed well the crossover model. The activation energy was obtained from the nonlinear fitting on the temperature quenching of luminescence intensity. Finally, Judd-Ofelt parameters of Eu³⁺ in the Ba₃Gd(PO₄)₃ phosphors were calculated by a facile method in the framework of the J-O theory, in which the refractive index of Ba₃Gd(PO₄)₃ was deduced to be about 1.55. Meanwhile, the radiative transition rates, fluorescence branching ratios and the J-O parameters were calculated by using the emission spectra and fluorescence decay.

Key words: high-temperature solid-state method, concentration quenching, thermal quenching, optical transition

中图分类号:

O482

李雪莹, 程丽红, 吴中立, 陈宝玖. Ba₃Gd(PO₄)₃:Eu³⁺荧光粉的合成及发光性质[J]. 无机材料学报, 2015, 30(11): 1201-1207.

LI Xue-Ying, CHENG Li-Hong, WU Zhong-Li, CHEN Bao-Jiu. Synthesis and Luminescence Properties of Ba₃Gd(PO₄)₃:Eu³⁺ Phosphors[J]. Journal of Inorganic Materials, 2015, 30(11): 1201-1207.

图/表 8

图1 掺杂不同浓度Eu3+的Ba3Gd(PO4)3及Ba3Gd(PO4)3标准XRD图谱(JCPDS 29-0163)

Fig. 1 XRD patterns for Ba3Gd(PO4)3 with various Eu3+ concentrations, and the standard XRD pattern of Ba3Gd(PO4)3 (JCPDS 29-0163)

图2 掺杂不同浓度Eu3+的Ba3Gd(PO4)3荧光粉的激发光谱, 监测波长为614 nm

Fig. 2 Excitation spectra for Ba3Gd(PO4)3 phosphors doped with various Eu3+ concentrations measured by monitoring 614 nm

图3 掺杂不同浓度Eu3+的Ba3Gd(PO4)3荧光粉在394 nm激发下的发射光谱

Fig. 3 Emission spectra for Ba3Gd(PO4)3 phosphors with different Eu3+ concentrations measured under 394 nm excitation The insert shows the emission spectrum for the sample doped with 70% Eu3+

图4 在394 nm激发波长下5D0→7FJ的发射强度随Eu3+掺杂浓度的变化趋势

Fig. 4 Dependence of integrated emission intensities of 5D0→ 7FJ transitions on Eu3+ concentration (λ ex= 394 nm) The solid curve shows the fitting curve

图5 不同温度下Ba3Gd(PO4)3: 20mol% Eu3+样品的发射光谱, 激发波长394 nm

Fig. 5 Emission spectra for Ba3Gd(PO4)3:20mol% Eu3+ upon 394 nm excitations measured at different temperatures

图6 不同温度下Ba3Gd(PO4)3: 5mol% Eu3+样品614 nm荧光的归一化衰减曲线

Fig. 6 Normalized 614 nm fluorescence decay curves for 5 mol% Eu3+ doped samples measured at different temperatures

图7 不同掺杂浓度样品的积分发射强度对温度的依赖关系

Fig. 7 Dependence of integrated luminescence intensity on temperature for Ba3Gd(PO4)3 phosphors doped with various Eu3+ concentrations

表1 Ba3Gd(PO4)3: Eu3+样品5D0→7FJ (J = 1、2、3、4、5、6)的辐射跃迁速率和分支比

Table 1 Transition rates and branch ratios for 5D0→7FJ (J = 1, 2, 3, 4, 5 and 6) of Eu3+ in Ba3Gd(PO4)3

Transition	I /(a.u.)	Wavenumber /cm^-1	Transition rate /s^-1	β/%
⁵D₀→⁷F₀	132.63	17310.92	2.32388	0.57
⁵D₀→⁷F₁	6040.82	16892.19	108.51386	27.08
⁵D₀→⁷F₂	13905.84	16241.48	244.46084	61.00
⁵D₀→⁷F₃	867.76	15296.04	15.24692	3.80
⁵D₀→⁷F₄	1600.65	14182.18	28.11328	7.01
⁵D₀→⁷F₅	39.64	13376.14	0.68016	0.16
⁵D₀→⁷F₆	78.25	12100.68	1.36032	0.33
J-O parameters: Ω₂=8.45×10^-20 cm^-2 Ω₄= 2.04×10^-20 cm^-2 Ω₆=1.81×10^-20 cm^-2

参考文献 30

[1]	SHANG M M, LI C X, LIN J, How to produce white light in a sngle-phase host?Chem. Soc. Rev., 2014, 43(5): 1372-1386.
[2]	LI G G, GENG D L, SHANG M 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.J. Mater. Chem., 2011, 21(35): 13334.
[3]	GAI S L, LI C X, YANG P P, et al.Recent progress in rare earth micro/nanocrystals: soft chemical synthesis, luminescent properties, and biomedical applications.Chem. Rev., 2014, 114(4): 2343-2389.
[4]	YAN S X, ZHANG J H, ZHANG X, et al.Enhanced red emission in CaMoO4:Bi3+,Eu3+.J. Phys. Chem., C, 2007,111(35): 13256-13260.
[5]	SUN X Y, ZHANG J H, ZHANG X, et al.A white light phosphor suitable for near ultraviolet excitation.J. Lumin., 2006, 122: 955-957.
[6]	EKAMBARAM S, MAAZA M.Combustion synthesis and luminescent properties of Eu3+-activated cheap red phosphors.J. Alloys Compd., 2005, 395(1/2): 132-134.
[7]	TIAN Y. CHEN B J, HUA R N, et al.Synthesis and characterization of novel red emitting nanocrystal Gd6WO12:Eu3+ phosphors.Physica B: Conden. Matter. 2009, 404(20): 3598-3601.
[8]	JEONG J H, YANG H K, SHIM K S, et al.Li doping effect on the luminescent chanracteristics of YVO4:Eu3+ thin films grown by pulsed laser deposition.Appl. Surf. Sci., 2007, 253(19): 8273-8277.
[9]	LIN X. FENG A, ZHANG Z J, et al.VUV spectroscopic properties of rare-earth (RE=Eu, Tb and Dy)-doped A2Zr(PO4)2 (A=Li, Na and K) phosphates. J. Rare Earths, 2014, 32(10): 946-951.
[10]	ZHONG J M, ZHAO W R, LAN L C, et al.Hydrothermal synthesis and luminescence properties of Eu3+ and Sm3+ codoped BiPO4.J. Rare Earths, 2014, 32(1): 5-11.
[11]	DI Q M, XU Q G, HAN L, et al. Synthesis and luminescence properties of Eu3+-doped Ba3Gd(PO4)3 phosphors for light-emitting diodes. Opt. Eng., 2015, 54(3): 035104-1-5.
[12]	SAHU N K, SINGH N S, NINGTHOUJAM R S, et al.Ce3+-sensitized GdPO4 :Tb3+ nanorods : an investigation on energy transfer, luminescence switching, and quantum yield.ACS Photonics, 2014, 1(4): 337-346.
[13]	LUDOVIC M, GERALDINE D, VINCENT J, et al.Dual light-emitting nanoparticles:second harmonic generation combined with rare-earth photoluminescence.J. Mater. Chem. C, 2014, 2(36): 7681-7686.
[14]	ZHANG L, FU L L, YANG X X, et al.Controlled synthesis and tunable luminescence of uniform YPO4 center dot 0.8H2O and YPO4 center dot 0.8H2O :Tb3+/Eu3+ nanocrystals by a facile approach.J. Mater. Chem. C, 2014, 2(43): 9149-9158.
[15]	TIAN Y, CHEN B J, HUA R N, et al. Optical transition, electron-phonon coupling and fluorescent quenching of La2(MoO4)3: Eu3+ phosphor. J. Appl. Phys., 2011, 109(5): 053511-1-6.
[16]	VAN UITERT L G. Characterization of energy transfer interactions between rare earth ions.J. Electrochem. Soc., 1967, 114(10): 1048-1053.
[17]	LI X P, CHEN B J, SHEN R S, et al.Fluorescence quenching of 5DJ (J = 1, 2 and 3) levels and Judd-Ofelt analysis of Eu3+ in NaGdTiO4 phosphors.J. Phys. D: Appl. Phys., 2011, 44(33): 335403-335409.
[18]	DEXTER D L.A theory of sensitized luminescence in solids.J. Chem. Phys., 1953, 21: 836-850.
[19]	BLASSE G.Energy transfer in oxidic phosphors.Phys. Lett., 1968, 28A(6): 444-445.
[20]	ABHILASH R G, HATA S, IKEDA K I, et al.Luminescence dynamics and concentration quenching in Gd2-xEuxO3 nanophosphor.Ceram. Int., 2015, 41(4): 6037-6050.
[21]	TIAN Y, CHEN B J, HUA R N, et al.Self-assembled 3D flower-shaped NaY(WO4)2:Eu3+ microarchitectures: microwave-assisted hydrothermal synthesis, growth mechanism and luminescent properties.CrystEngComm, 2012, 14(5): 1760-1769.
[22]	TIAN B N, CHEN B J, TIAN Y, et al.Excitation pathway and temperature dependent luminescence in color tunable Ba5Gd8 Zn4O21:Eu3+ phosphors.J. Mater. Chem. C, 2013, 1(12): 2338-2344.
[23]	FONGER W H, STRUCK C W.Eu3+ 5D resonance quenching to the charge transfer states in Y2O2S, La2O2S, and LaOCl.J. Chem. Phys., 1970, 52: 6364-6372.
[24]	CHAMBERS M D, ROUSSEVE P A, CLARKE D R.Decay pathway and high-temperature luminescence of Eu3+ in Ca2Gd8Si6O26.J. Lumin., 2009, 129(3): 263-269.
[25]	BERRY M T, MAY P S, XU H.Temperature dependence of the Eu3+ 5D0 lifetime in europium tris (2,2,6,6-tetramethyl-3,5- heptanedionato).J. Chem. Phys., 1996, 100(22): 9216-9222.
[26]	LIANG C H, CHANG Y C, CHANG Y S. Synthesis and photoluminescence characteristics of color-tunable BaY2ZnO5: Eu3+ phosphors. Appl. Phys. Lett., 2008, 93(21): 211902-1-4.
[27]	JUDD B R.Optical absorption intensities of rare-earth ions.Phys. Rev., 1962, 127: 750-761.
[28]	OFELT G S.Intensities of crystal spectra of rare-earth ions.J. Chem. Phys., 1962, 37: 511-520.
[29]	WANG B, CHENG L H, ZHONG H Y, et al.Excited state absorption cross sections of 4I13/2 of Er3+ in ZBLAN. Opt. Mater., 2009, 31(11): 1658-1662.
[30]	HUANG L B, CHENG L H, YU H Q, et al.Optical transition properties of Eu3+ in Eu(DBM)3phen mono-dispersed microspheres for microcavity laser application.Physica B: Conden. Matter., 2011, 406(14): 2745-2749.

Ba₃Gd(PO₄)₃:Eu³⁺荧光粉的合成及发光性质

Synthesis and Luminescence Properties of Ba₃Gd(PO₄)₃:Eu³⁺ Phosphors

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 8

参考文献 30

相关文章 7

编辑推荐

Metrics

本文评价

[1]	关旭峰, 李桂芳, 卫云鸽. Na_1-_xM_xCaEu(WO₄)₃ (M=Li, K)红色荧光粉的微观结构与热猝灭特性研究[J]. 无机材料学报, 2022, 37(6): 676-682.
[2]	于春凤,张翔清,韩文燕,张金苏,李香萍,徐赛,陈宝玖. Lu₂O₃:Er³⁺荧光粉的Judd-Ofelt参数计算[J]. 无机材料学报, 2019, 34(2): 213-218.
[3]	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[J]. 无机材料学报, 2017, 32(9): 936-942.
[4]	闫绍峰, 吴中立, 吴红梅, 廖国进, 李煜, 刘通, 赵莘彬. Eu³⁺掺杂硼酸盐玻璃的发光性质及其热稳定性研究[J]. 无机材料学报, 2017, 32(7): 765-769.
[5]	陈艳平, 罗德礼, 徐钦英, 杨锁龙, 唐涛, 王小英. Ce³⁺掺杂Li₂O-MgO-Al₂O₃-SiO₂玻璃的结构与荧光猝灭现象[J]. 无机材料学报, 2014, 29(9): 967-971.
[6]	周亚训,黄尚廉,周灵,徐铁峰,聂秋华. 不同铒离子掺杂浓度下碲酸盐玻璃荧光特性研究[J]. 无机材料学报, 2007, 22(4): 671-676.
[7]	张巍巍,谢平波,张慰萍,尹民,楼立人,夏上达. PDP荧光粉GdBO₃:Eu格位选择激发下的光致发光及其相变研究[J]. 无机材料学报, 2001, 16(3): 470-474.