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1. 天津大学 精密仪器与光电子工程学院, 天津 300072
2. 南开大学 电子信息与光学工程学院, 天津 300071
收稿日期:2014-06-26,
修回日期:2014-07-11,
网络出版日期:2014-07-30,
纸质出版日期:2014-12-05
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孙雷, 张毅, 胡兴凯, 田浩. LED用KZn<sub>4</sub>(BO<sub>3</sub>)<sub>3</sub>:Eu<sup>3+</sup>荧光粉的合成与发光性能研究[J]. 液晶与显示, 2014,29(6): 893-900
SUN Lei, ZHANG Yi, HU Xing-kai, TIAN Hao. Synthesis and photoluminescence properties of KZn<sub>4</sub>(BO<sub>3</sub>)<sub>3</sub>:Eu<sup>3+</sup>red-emitting phosphor[J]. , 2014,29(6): 893-900
孙雷, 张毅, 胡兴凯, 田浩. LED用KZn<sub>4</sub>(BO<sub>3</sub>)<sub>3</sub>:Eu<sup>3+</sup>荧光粉的合成与发光性能研究[J]. 液晶与显示, 2014,29(6): 893-900 DOI: 10.3788/YJYXS20142906.0893.
SUN Lei, ZHANG Yi, HU Xing-kai, TIAN Hao. Synthesis and photoluminescence properties of KZn<sub>4</sub>(BO<sub>3</sub>)<sub>3</sub>:Eu<sup>3+</sup>red-emitting phosphor[J]. , 2014,29(6): 893-900 DOI: 10.3788/YJYXS20142906.0893.
荧光粉转化法是目前制备白光LED的主流技术。但是商业化的荧光粉由于缺少红色部分或红色不稳定,使得制备出的LED灯泡颜色偏冷,因此研制低成本、性能稳定的红色荧光粉具有重要的意义。本项目以化学性质稳定、合成工艺温和的硼酸盐KZn
4
(BO
3
)
3
为基质,掺杂稀土离子来研究荧光粉的发光性能。通过高温固相法合成了一系列不同掺杂浓度的KZn
4
(BO
3
)
3
:Eu
3+
,并测试了XRD衍射图谱,发射和激发光谱。研究表明Eu
3+
离子倾向于占据Zn
2+
格位。同时,KZn
4
(BO
3
)
3
:Eu
3+
的最佳激发波长(393 nm)位于近紫外波段,适于用近紫外LED芯片激发来制备LED。 KZn
4
(BO
3
)
3
:Eu
3+
的最强发射峰位于590 nm,属于
5
D
0
-
7
F
1
跃迁。当发生浓度猝灭时,Eu
3+
-Eu
3+
离子间的临界距离为3 nm。该荧光粉的色坐标为(0.629 7,0.369 9),色饱和较高。该物质是一种潜在的可被用于LED照明用的红色荧光粉。
Phosphor transformation is the main method of producing white-light LEDs. However
most phosphors in the market are lack of red component or color stability
because most commercial LEDs produce cool white light. Thus it is realistic to search for new red phosphors with high stability and low cost. In this regard
borates
chemical stable and easily productive
have attracted our attention.The structure and photoluminescence properties of KZn
4
(BO
3
)
3
doped with Eu
3+
are analyzed.We have synthesized a series of KZn
4
(BO
3
)
3
:Eu
3+
with different doping concentration by solid state reactions. From the X-ray diffraction data
it is concluded that Eu
3+
ions are inclined to occupy Zn
2+
site in the structure of KZn
4
(BO
3
)
3
. And the PLE indicates that the best exciting wavelength(393 nm) of KZn
4
(BO
3
)
3
:Eu
3+
is near ultraviolet
which makes it suitable for near-UV LEDs. According to the PL
the strongest peak locates at 590 nm which is ascribed to the transition of
5
D
0
-
7
F
1
.In addition
the quenching concentration of Eu
3+
is about 1.5%
and the critical distance is about 3 nm.Finally
the CIE coordinates of KZn
4
(BO
3
)
3
:Eu
3+
is(0.629 7
0.369 9)
which has high color saturation.The material is a potential red phosphor used for LEDs.
Yousuke U, Shinji O, Hajime Y.Photoluminescence properties of Ba3MgSi2O8:Eu2+ blue phosphor and Ba3MgSi2O8:Eu2+,Mn2+blue-red phosphor under near-ultraviolet-light excitation[J].J. Electrochem. Soc,2008,155(7): J193-J197.[2] Yao S S, Li Y Y, Xue L H, et al.Luminescent properties of Ba2(Mg,Zn)Si2O7:Eu2+ particles as potential blue-green phosphors for ultraviolet light-emitting diodes[J].J. Am. Ceram. Soc.,2010,93(11): 3793-3797.[3] Zhang J Y, Zhang Z T, Tang Z L, et al.Luminescent properties of the BaMgAl10O17:Eu2+,M3+(M=Nd, Er) phosphor in the VUV region[J].Chem. Mater,2002,14(7): 3005-3008.[4] Dhanaraj J, Jagannathan R, Trivedi D C. Y2O2S:Eu3+ nanocrystals-synthesis and luminescent properties[J].J. Mater. Chem,2003,13: 1778-1782.[5] Chartier C, Barthou C, Benalloul P, et al.Bandgap energy of SrGa2S4:Eu2+and SrS:Eu2+[J].Electrochem. Solid-State Lett,2006,9(2): G53-G55.[6] Xie R J, Naoto H, Takayuki S, et al.A simple efficient synthetic route to Sr2Si5N8:Eu2+-based red phosphors for white light-emitting diodes[J].Chem.Mater,2006,18(23): 5578-5583.[7] Song X F, He H, Fu R L, et al.Photoluminescent properties of SrSi2O2N2:Eu2+ phosphor:concentration related quenching and red shift behavior[J].J. Phys. D: Appl. Phys,2009,42(6):1-6.[8] Robert W S, Jeanne L L. Framework alkali metal zinc orthoborates:AZn4(B03)3(A=K, Rb, Cs)[J].Inorg. Chem,1992,31: 4679-4682.[9] Zhang Y, Wang B, Wu L, et al.Structure and photoluminescence properties of KSr4(BO3)3:Eu3+ red-emitting phosphor[J].Opt. Express,2012,2(1): 92-102.[10] Ji M Y.The synthesis and properties of multicolored phosphors based on the same host[D]. Tianjin:Nankai University, 2010.[11] 张中太, 张俊英.无机光致发光材料及应用[M]. 2版.北京:化学工业出版社,2011. Zhang Z T, Zhang J Y.Inorganic Photoluminescent Materials and Applications[M]. 2nd ed. Beijing:Chemical Industry Press, 2011.(in Chinese)[12] 王琦,马东阁. 白光有机发光二极管的制备方法[J]. 液晶与显示, 2009,24(5): 617-629. Wang Q, Ma D G. Fabrication methods of white organic light-emitting diodes[J].Chin J of Liquid Crystals and Displays,2009,24(5): 617-629.(in Chinese)[13] 于晶杰,肖志国,宁桂玲. Ba10(PO4)4(SiO4)2:Eu2+荧光体的光谱特性[J]. 发光学报, 2013,34(12): 1561-1566. Yu J J, Xiao Z G, Ning G L. Spectra properties of Ba10(PO4)4(SiO4)2:Eu2+Phosphor[J].Chin J of Luminescence,2013,34(12): 1561-1566.(in Chinese)[14] 吕少哲,张家骅,张继森,等. Eu3+掺杂的含氧磷酸盐发光性质[J]. 发光学报, 2013,34(11): 1435-1439. Lv S Z, Zhang J H, Zhang J S,et al.Luminescent properties of Eu3+-doped oxyphosphates[J].Chin J of Luminescence,2013,34(11): 1435-1439.(in Chinese)
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