Yb3+,Tb3+共掺杂Sr2B2O5荧光粉的制备及其下转换发光性能的研究

doi:10.15541/jim20160122

摘要/Abstract

摘要：

采用高温固相法合成了Tb³⁺, Yb³⁺共掺杂的Sr₂B₂O₅荧光粉。通过X射线衍射(XRD)和荧光光谱(PL)对样品的物相结构和发光性质进行了表征。XRD结果表明, 合成样品为单斜结构的Sr₂B₂O₅相。分别使用543 nm和980 nm的监测波长, 得到的激发光谱均在354 nm、374 nm处有较强的激发峰, 其中374 nm处最强, 说明Sr₂B₂O₅荧光材料在近紫外光区对太阳光有很强的吸收; 在374 nm( Tb³⁺:⁷F₆→⁵D₃) 紫外光激发下, 观察到Tb³⁺:⁵D₄→⁷F_J ( J = 6, 5, 4, 3) 可见光区发射光, 并检测到Yb³⁺: ²F_5/2→²F_7/2的近红外发射光。通过研究激发光谱和发射光谱与Yb³⁺掺杂浓度的关系, 发现在单斜晶体Sr₂B₂O₅中, Yb³⁺具有很高的猝灭浓度。

关键词: Sr₂B₂O₅, Tb³⁺, Yb³⁺, 下转换, 发光材料

Abstract:

Tb³⁺ and Yb³⁺ co-doped Sr₂B₂O₅ phosphors were synthesized by conventional solid-state reactions. The obtained Sr₂B₂O₅: Tb³⁺, Yb³⁺ phosphors were characterized by X-ray diffraction (XRD) and photoluminescence (PL) spectra. XRD results show that all prepared phosphors can be readily indexed to pure monoclinic phase of Sr₂B₂O₅. The dominant excitation at 374 nm was observed among three strong excitation peaks located at 354, 374 and 487 nm monitored at 543 nm and 980 nm, by which Sr₂B₂O₅ phosphors could be considered as having a strong absorption in the near ultraviolet region of sunlight. Under the ultraviolet light excitation at 374 nm, the strong intensity of visible emission from Tb³⁺:⁵D₄→⁷F_J ( J = 6, 5, 4, 3), and near-infrared (NIR) emission from Yb³⁺ (²F_5/2→²F_7/2) were detected. The relationship between the luminescence spectra and Yb³⁺ doping content demonstrated the monoclinic Sr₂B₂O₅ exhibited the excellent quenching concentration.

Key words: Sr₂B₂O₅, Yb³⁺, Tb³⁺, down-conversion, luminescent material

中图分类号:

O614

戴智刚, 李友芬, 李刚, 杨儒. Yb³⁺,Tb³⁺共掺杂Sr₂B₂O₅荧光粉的制备及其下转换发光性能的研究[J]. 无机材料学报, 2016, 31(10): 1081-1086.

DAI Zhi-Gang, LI You-Fen, LI Gang, YANG Ru. Preparation and Down-conversion Luminescent Properties of Tb³⁺, Yb³⁺ Co-doped Sr₂B₂O₅[J]. Journal of Inorganic Materials, 2016, 31(10): 1081-1086.

图/表 11

图1 不同k值合成样品的XRD图谱(a) k=1; (b) k=1.03

Fig. 1 XRD patterns of the samples prepared with (a) k=1 and (b) k=1.03

图2 不同温度下制备的Sr2B2O5:Tb3+, Yb3+的XRD图谱

Fig. 2 XRD patterns of Sr2B2O5:Tb3+, Yb3+ prepared at different temperatures

图3 Sr2B2O5:Tb3+, Yb3+的XRD衍射精修图

Fig. 3 Rietveld refinement of X-ray diffraction pattern for Sr2B2O5:Tb3+, Yb3+

图4 Sr2B2O5:Tb3+, Yb3+的晶体结构

Fig. 4 Crystal structure of Sr2B2O5:Tb3+, Yb3+

表1 部分原子坐标和等效各向同性位移参数

Table 1 Fractional atomic coordinates and equivalent isotropic displacement parameters (nm)

Atom	x	y	z	x'	y'	z'
Sr(1)	0.062319(9)	0.04098(1)	0.034069(5)	0.062064	0.041266	0.034105
Sr(2)	0.111767(9)	0.04502(1)	0.036749(5)	0.011638	0.04475	0.036887
O(1)	0.035710(7)	0.01510(1)	0.035170(4)	0.036784	0.013452	0.034672
O(2)	0.060710(7)	0.02120(1)	0.014040(4)	0.061327	0.022331	0.012791
O(3)	0.090130(7)	0.00920(1)	0.033130(4)	0.089034	0.007279	0.033207
O(4)	0.085370(7)	0.06980(1)	0.042790(4)	0.084245	0.074122	0.041785
O(5)	0.074630(7)	0.01010(1)	0.049270(4)	0.073834	0.006773	0.048866
B(1)	0.066000(1)	0.00680(2)	0.059500(6)	0.070546	0.003887	0.058088
B(2)	0.083900(1)	-0.0047(2)	0.041590(6)	0.089177	-0.001638	0.037818

图5 样品Sr2B2O5:4%Tb3+-x%Yb3+(x=0,14)(a)激发光谱和(b)发射光谱

Fig. 5 (a) Excitation spectra and (b) emission spectra of Sr2B2O5:4%Tb3+-x%Yb3+(x=0,14)

表2 不同锶硼酸盐的荧光性质

Table 2 Fluorescence properties of different strontium borate

System	Crystal structure	Excitation/nm	Emission/nm
Sr₂B₂O₅:Tb³⁺, Yb³⁺	Monoclinic	354, 374, 487	487, 543, 582, 620
Sr₂B₂O₅:Tb^3+[14]	Monoclinic	245, 300-400	488, 545, 586, 623
SrB₂O₄:Tb^3+[16]	Orthorhombic	319, 353,370, 378	490, 544, 584, 622
SrB₄O₇:Tb^3+[17]	Orthorhombic	170, 205, 225	488, 544, 585, 620

图6 样品Sr2B2O5: y%Tb3+, 10%Yb3+(a)激发光谱和(b)可见光区发射光谱图

Fig. 6 (a) Excitation spectra and (b) emission spectra of sample Sr2B2O5: y%Tb3+, 10%Yb3+ recorded in visible spectral range 450-650 nm

图7 Sr2B2O5:4%Tb3+, x% Yb3+(x=6,10,14,20,24)样品在980 nm近红外光监测下的激发光谱图

Fig. 7 Excitation spectra recorded at 980 nm of sample Sr2B2O5:4%Tb3+, x% Yb3+(x=6,10,14,20,24)

图8 不同Yb3+掺杂浓度的样品在374 nm紫外光激发下的发射光谱图

Fig. 8 Visible emission spectra and near-infrared (NIR) emission spectra excited at 374 nm of the sample doped with different Yb3+ concentrations Inset show change of the emission intensity with Yb3+ concentrations

图9 在Sr2B2O5晶体中Tb3+与Yb3+之间的能量传递机理

Fig. 9 Energy transfer mechanisms of Tb3+ and Yb3+ in Sr2B2O5

参考文献 26

[1]	BI Y, WANG G S, TIAN Y W.Research progress of rare earth borate luminescent materials.Materials Review A, 2013, 27(1): 34-37.
[2]	ZHANG Q Y, YANG C H, PAN Y X.Cooperative quantum cutting in one-dimensional (YbxGd1-x)Al3(BO3)4:Tb3+ nanorods.Applied Physics Letters, 2007, 90(2): 021107.
[3]	HUANG X Y, YU D C, ZHANG Q Y.Enhanced near-infrared quantum cutting in GdBO3:Tb3+,Yb3+ phosphors by Ce3+ codoping.Journal of Applied Physics, 2009, 106(11): 113521.
[4]	JIA H Z, HUANG P, CUI C E, et al.Down-conversion luminescence of Tb3+,Yb3+ co-doped LuBO3 phosohors.Journal of Synthetic Crystals, 2014, 43(12): 3093-3097.
[5]	ZHENG J, YING L, CHENG Q, et al.Blue-emitting SrB2O4:Eu2+ phosphor with high color purity for near-UV white light-emitting diodes.Materials Research Bulletin, 2015, 64: 51-54.
[6]	GAWANDE A B, INGLE J T, SONEKAR R P, et al.Photoluminescence in Pb2+ activated SrB4O7 and SrB2O4 phosphors.Journal of Luminescence, 2014, 149(5): 236-239.
[7]	ZHANG Y, LI Y D.Red photoluminescence and crystal structure of Sr3Y2(BO3)4.Journal of Alloys and Compounds, 2004, 384(1): 88-92.
[8]	DESMOULINS H, MALO S, PEREZ O, et al.Stability of the Sr2B3O6.5-δ phases (B = Fe, Co, Ga): existence range, structural and physical properties.Chemistry of Materials, 2011, 23(11): 2786-2794.
[9]	WANG R, XU J, CHEN C.Luminescent characteristics of Sr2B2O5: Tb3+, Li+ green phosphor.Materials Letters, 2012, 68(1): 307-309.
[10]	WEI Z F, CHEN X L, WANG F M, et al.Phase relations in the ternary system SrO-TiO2-B2O3.Journal of Alloys and Compounds, 2001, 327(1): L10-L13.
[11]	PAN F, WANG R J, SHEN G Q, et al.The crystal structure and NLO property of strontium tetraborate SrB4O7.Chemical Journal of Chinese Universities, 2001, 22(z1): 154-158.
[12]	BALE C W, BELISLE E. Fact-web suite of interactive programs [CP/OL], .
[13]	LIN Q S, CHENG W D, CHEN J T, et al.Crystal and electronic structures and linear optics of strontium pyroborate.Journal of Solid State Chemistry, 1999, 144(1): 30-40.
[14]	SUN J, LAI J, ZHU J, et al.Luminescence properties and energy transfer investigations of Sr2B2O5:Ce3+, Tb3+ phosphors.Ceramics International, 2012, 38(7): 5341-5345.
[15]	HUANG X, HAN S, HUANG W, et al.Enhancing solar cell efficiency: the search for luminescent materials as spectral converters.Chemical Society reviews, 2013, 42(1): 173-201.
[16]	Wu Z C, WANG P, LIU J, et al.Improved photoluminescence properties of a new green SrB2O4:Tb3+ phosphor by charge compensation.Materials Research Bulletin, 2012, 47(11): 3413-3416.
[17]	LIANG H B, WANG J, YE X, et al.The VUV-Vis luminescent properties of Ln3+ (Ln = Ce, Pr, Tb) in Sr0.96Na0.02Ln0.02B4O7.Journal of Alloys and Compounds, 2006, 425(1): 307-313.
[18]	JIANG G C, WEI X T, WANG L X, et al. Preparation and luminescence of down-conversion material β-NaYF4: Tb3+, Yb3+. Spectroscopy and Spectral Analysis, 2011, (31)2: 331-334.
[19]	LIN H, ZHOU S M, HOU X R, et al. Preparation and investigation on down-conversion near infrared emission of Tb3+, Yb3+ co-doped Y2O3 transparent ceramics. Acta Optica Sinica, 2010, (30)12: 3547-3551.
[20]	VERGEER P, VLUGT T J H., KOX M H F, et al. Quantum cutting by cooperative energy transfer in YbxY1-xPO4: Tb3+.Physical Review B, 2005, 71(1): 014119.
[21]	TERRA I A A, GONZALEZ L J B, NUNES L A O, et al. Analysis of energy transfer processes in Yb3+-Tb3+ co-doped, low-silica calcium aluminosilicate glasses.Journal of Applied Physics, 2011, 110(8): 083108.
[22]	LIU T C, ZHANG G, QIAO X, et al.Near-infrared quantum cutting platform in thermally stable phosphate phosphors for solar cells.Inorganic Chemistry, 2013, 52(13): 7352-7357.
[23]	WEI X T, JIANG G C, DENG K M, et al. Rare-earth doped optical spectral conversion materials with their applications. Scientia Sinica: Physica, Mechanica & Astronomica, 2012, (42)11: 1112-1123.
[24]	黄小勇. 稀土掺杂发光材料下转换发光特性研究. 广州: 华南理工大学博士学位论文, 2011.
[25]	LI L, WEI X, CHEN Y, et al.Energy transfer in Tb3+,Yb3+ co-doped Lu2O3 near-infrared down-conversion nanophosphors.Journal of Rare Earths, 2012, 30(3): 197-201.
[26]	YANG Y M, LIU L L, CAI S Z, et al.Synthesis and near-infrared quantum cutting of Tb3+, Yb3+ co-doped BaGd2ZnO5 phosohors.Chinese Journal of Luminescence, 2013, 34(9): 1173-1177.

Yb³⁺,Tb³⁺共掺杂Sr₂B₂O₅荧光粉的制备及其下转换发光性能的研究

Preparation and Down-conversion Luminescent Properties of Tb³⁺, Yb³⁺ Co-doped Sr₂B₂O₅

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