新型Sr3Y(PO4)3∶ Ce3+, Tb3+绿光荧光粉的制备与发光机理的研究

doi:10.3964/j.issn.1000-0593(2015)08-2189-05

摘要
参考文献
相关文章 (15)

全文: PDF (2708 KB)
输出: BibTeX | EndNote (RIS)

摘要：采用传统的高温固相法合成了一种新型的绿色荧光粉Sr₃Y(PO₄)₃∶Ce³⁺, Tb³⁺，利用X射线衍射（XRD）和荧光光谱（PL）对该材料的晶体结构和光学性能进行表征。结果分析表明，制得样品的XRD图谱不含Sr₃Y(PO₄)₃以外的杂峰，稀土掺杂并未改变基质的晶体结构，得到的样品为纯相的磷酸钇锶。从本文实验中明显观察到Sr₃Y(PO₄)₃∶Tb³⁺的激发光谱和Ce³⁺的发射光谱在320～390 nm有重叠，表明在Sr₃Y(PO₄)₃基质中可存在从Ce³⁺到Tb³⁺的能量传递。在紫外光（315 nm）激发下该荧光粉发射出了Ce³⁺的蓝光（320～420 nm）和Tb³⁺的黄绿光（480～500 nm）和（530～560 nm），当Ce³⁺的浓度为7%，Tb³⁺的浓度由1%增大到50%时，通过Ce³⁺的4f→5d电子跃迁将能量传递到Tb³⁺，然后发生⁵D₄→⁷F_j电子跃迁，该荧光粉发射光谱可由蓝光逐渐调节为黄绿光。本文绘制了Ce³⁺, Tb³⁺的能级和Sr₃Y(PO₄)₃∶Ce³⁺, Tb³⁺荧光粉中的能量转移过程示意图，并详细阐述了由Ce³⁺到Tb³⁺的能量传递过程。通过对比Ce³⁺和Tb³⁺的发光强度以及由Ce³⁺到Tb³⁺能量转移效率的相对变化，可以得出，随着掺入的Tb³⁺浓度不断增加，Tb³⁺的发射强度（⁵D₄→⁷F_j）和能量转移效率（Ce³⁺到Tb³⁺）也在增大，而Ce³⁺的发射强度却有了明显的下降。当Tb³⁺的浓度为50% 时能量转移效率可高达80%。通过CIE色度图也可以看出，当Tb³⁺浓度不断增大, 样品的色坐标从图中的蓝色区域移动到绿色区域。所以在紫外光激发下，Ce³⁺和Tb³⁺共掺Sr₃Y(PO₄)₃可作为一种绿光荧光粉应用在白光LED或LCD背光源上。

关键词：稀土;磷酸钇锶;能量传递

Abstract：A novel green light-emitting phosphor Sr₃Y(PO₄)₃Ce³⁺, Tb³⁺ was synthesized by the traditional high temperature solid state reaction method. Luminescence mechanism and crystal structure were investigated by X-Ray Diffraction (XRD) and photoluminescence spectra (PL). The XRD patterns demonstrate that the samples belong to the single phase of Sr₃Y(PO₄)₃ in experimental doping concentrations range. Obviously,the excitation band of Sr₃Y(PO₄)₃∶Tb³⁺ and the emission of Sr₃Y(PO₄)₃∶Ce³⁺ have a significant spectral overlap in the wavelength range of 330～380 nm, which implies the great possibility of an efficient ET from Ce³⁺ to Tb³⁺. Under the 315 nm ultraviolet excitation, a blue emission（320～420 nm）from Ce³⁺ and a yellowish-green emission（480～500, 530～560 nm）from Tb³⁺ were obtained from Sr₃Y(PO₄)₃∶Ce³⁺, Tb³⁺. When the Ce³⁺ concentration was 7%, the emission could be adjusted from blue to green region by tuning the Tb³⁺ doping concentrations from 1% to 50% through an energy transfer process. This text plot the schematic energy levels of Ce³⁺, and Tb³⁺ with electronic transitions and energy transfer processes in Sr₃Y(PO₄)₃∶Ce³⁺, Tb³⁺, which disclose the electron motion processes of Sr₃Y(PO₄)₃∶Ce³⁺, Tb³⁺. From the dependence of relative emission intensity of Ce³⁺, Tb³⁺ （⁵D₄→⁷F_j）and ET efficiency from Ce³⁺ to Tb³⁺ on the concentrations of Tb³⁺, It can be seen that the relative intensity of Tb³⁺ and the values of η_ET increase gradually with the increasing of Tb³⁺ as well as the relative intensity of Ce³⁺ decreases remarkably. The largest energy transfer efficiency reaches as high as 80% when the concentration of Tb³⁺ was 50%, demonstrating the efficient energy transfer from Ce³⁺ to Tb³⁺. The CIE chromaticity coordinate positions are plotted, as can be seen the emitting color of Ce³⁺ and Tb³⁺ singly doped Sr₃Y(PO₄)₃∶Ce³⁺, Tb³⁺ phosphor are blue and yellowish green, respectively.The emitting color of samples Sr₃Y(PO₄)₃∶Ce³⁺, Tb³⁺ changes from blue region to green region with the rising doping contents of Tb³⁺. Sr₃Y(PO₄)₃∶Ce³⁺ and Tb³⁺ phosphor can be used as a green light-emitting phosphor in white LED devices and LCD backlights.

Key words：Rare earth;Tunable emitting;Sr₃Y(PO₄)₃;Energy transfer

收稿日期: 2014-03-08 修订日期: 2014-07-14

中图分类号:

O482.3

通讯作者: 罗莉 E-mail: luoli@gdut.edu.cn

引用本文:

董国帅，刘海波，罗莉^*，王银海 . 新型Sr₃Y(PO₄)₃∶ Ce³⁺, Tb³⁺绿光荧光粉的制备与发光机理的研究 [J]. 光谱学与光谱分析, 2015, 35(08): 2189-2193.
DONG Guo-shuai, LIU Hai-bo, LUO Li^*, WANG Yin-hai . Study on Synthesis and Luminescence Mechanism of Novel Green Sr₃Y(PO₄)₃∶Ce³⁺, Tb³⁺ Phosphors. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2015, 35(08): 2189-2193.

链接本文:

https://www.gpxygpfx.com/CN/10.3964/j.issn.1000-0593(2015)08-2189-05 或 https://www.gpxygpfx.com/CN/Y2015/V35/I08/2189

[1] Yang P H, Yua X, Xu X H, et al. J. Solid State Chem., 2013, 202: 143.
[2] Jin Y H, Hu Y H, Chen L, et al. J. Lumin., 2013, 138: 83.
[3] Chen Y, Wang J, Liu C M, et al. Appl. Phys. Lett., 2011, 98: 081917.
[4] Jin Y H, Hu Y H, Chen L, et al. J. Am. Ceram. Soc., 2013, 96: 3821.
[5] Liu W R, Huang C H, Yeh C W, et al. R. Soc. Chem. Adv.，2013, 3: 9023.
[6] Liu W R, Huang C H, Yeh C W, et al. Inorg. Chem., 2012, 51: 9636.
[7] Huang C H, Liu W R, Chen T M. J. Phys. Chem. C, 2010, 114: 18698.
[8] Setlur A A, Heward W J, Gao Y, et al. Chem. Mater., 2006, 18: 3314.
[9] Li Y Q, Delsing A C A, de With G, et al. Chem. Mater., 2005, 17: 3242.
[10] Xia Z G, Liu R S. J. Phys. Chem. C, 2012, 116: 15604.
[11] Jin Y H, Hu Y H, Chen L, et al. Physica B, 2014, 436: 105.
[12] Roh H S, Hur S, Song H J, et al. Mater. Lett., 2012,70: 37.
[13] Zhao C C, Yin X, Wang Y M, et al. J. Lumin., 2012, 132: 617.
[14] Zhang J S, Chen B J, Liang Z Q, et al. J. Fluor. Chem., 2012, 144: 1.
[15] Mao Z Y, Zhu Y C, Zeng Y, et al. J. Lumin., 2013, 43∶ 587.
[16] Guo C F, Ding X, Seo H J, et al. Opt. Laser Technol., 2011, 43∶ 1351.
[17] Ogieglo J M, Zych A, Ivanovskikh K V, et al. J. Phys. Chem. A, 2012, 116: 8464.
[18] Han B, Zhang J, Lü Y H. J. Am. Ceram. Soc., 2013, 96: 179.
[19] Kuo T W, Chen T M. J. Electrochem. Soc., 2010, 157: J216.
[20] Tang Y S, Hu S F, Lin C C, et al. Appl. Phys. Lett., 2007, 90: 151108.
[21] Sun J Y, Sun Y N, Zeng J H, et al. J. Phys. Chem. Solids, 2013, 74: 1007.
[22] Sun J Y, Zeng J H, Sun Y N, et al. J. Alloys Compd., 2012, 540: 81.
[23] Guo N, Zheng Y H, Jia Y C, et al. New J. Chem., 2012, 36: 168.
[24] Yang B Z, Yang Z P, Liu Y F, et al. Ceram. Int., 2012, 8: 4895.
[25] Hou D, Liang H, Xie M, et al. Opt. Express, 2011, 19: 11071.
[26] Han B, Liang H B, Huang Y, et al. J. Phys. Chem. C, 2010, 114: 6770.
[27] Chang C K, Chen T M. Appl. Phys. Lett. 2007, 91: 081902.