长余辉材料SrAl2O4 ∶ Eu,Dy中Eu的价态变化及对发光性能的影响

陈雪花; 胡义华; 王银海; 柳 成; 陈 仁; 廖 峰

doi:null

您当前的位置：

首页 >

文章列表页 >

长余辉材料SrAl₂O₄ ∶ Eu,Dy中Eu的价态变化及对发光性能的影响

论文 | 更新时间：2020-08-12

- 长余辉材料SrAl₂O₄ ∶ Eu,Dy中Eu的价态变化及对发光性能的影响
- Valence-change of Eu and Its Effect on the Luminescent Properties of Long Afterglow Phosphor SrAl2O4∶Eu,Dy
- 发光学报 2009年30卷第1期页码：40-46
- 作者机构：
 
 广东工业大学物理与光电工程学院,广东广州,510006
- 作者简介：
- 基金信息：
- DOI：
 中图分类号： O482.31;O614.33
- 纸质出版日期：2009-02-20，
 
 网络出版日期：2009-02-20，
 
 收稿日期：2008-05-22，
 
 修回日期：1900-01-02，
- 稿件说明：
移动端阅览
陈雪花, 胡义华, 王银海, 等. 长余辉材料SrAl₂O₄ ∶ Eu,Dy中Eu的价态变化及对发光性能的影响[J]. 发光学报, 2009,30(1):40-46.

CHEN XUE-HUA, HU YI-HUA, WANG YIN-HAI, et al. Valence-change of Eu and Its Effect on the Luminescent Properties of Long Afterglow Phosphor SrAl2O4∶Eu,Dy. [J]. Chinese journal of luminescence, 2009, 30(1): 40-46.
陈雪花, 胡义华, 王银海, 等. 长余辉材料SrAl₂O₄ ∶ Eu,Dy中Eu的价态变化及对发光性能的影响[J]. 发光学报, 2009,30(1):40-46. DOI：

CHEN XUE-HUA, HU YI-HUA, WANG YIN-HAI, et al. Valence-change of Eu and Its Effect on the Luminescent Properties of Long Afterglow Phosphor SrAl2O4∶Eu,Dy. [J]. Chinese journal of luminescence, 2009, 30(1): 40-46. DOI：

摘要

采用高温固相法

先在空气气氛下制备了SrAl

∶ Eu

后对其进行还原→氧化→还原处理。X射线衍射结果表明

经过还原→氧化→还原处理后样品的晶体结构没有改变。样品的发射光谱测试表明

在高温空气气氛下有少量的Eu

还原成Eu

。Eu

和Eu

有不同的发光特性

产生的是线状特征光谱

发射峰值在592

616 nm。Eu

产生的是带状光谱

带的中心位置在513 nm。经过还原处理的样品和经过氧化处理的样品相比

的浓度得到显著提高

而Eu

的浓度则急剧下降。对Eu

的氧化、Eu

的还原的机理进行了细致地讨论。另外

样品的热释光谱测试表明

经过氧化气氛处理和经过还原气氛处理过的样品的热释光峰值有很大的变化

但陷阱能级深度基本不变

在0.65 eV左右。这表明

对长余辉材料SrAl

∶ Eu

Dy进行还原→氧化→还原处理

Eu离子价态和发光强度会产生变化

并不影响其中Dy离子的陷阱能级。

Abstract

As novel functional materials

long afterglow phosphors have drawn more and more attention in recent years because of a constantly growing market for their applications in traffic signs

emergency signage

watches and clocks

textile printing

among others. Amid the newly developed long afterglow materials which have already found commercial use

green-emitting SrAl2O4∶Eu2+

Dy3+ is of special interest because of its high quantum efficiency

good stability and excellent persistent luminescence combined with an easy proces-sability. However the mechanism of afterglow phosphors is still unclear

even the effect of the reductive using on the producing process on the luminescence is not well studied. In this paper

compounds of SrAl2O4∶Eu

Dy were prepared in air atmosphere by high temperature solid state reaction firstly

and then were treated in weak reductive atmosphere (95%N2+5%H2).Thirdly

in air atmosphere again

and finally

in weak reductive atmosphere (95%N2+5%H2). The effect of this process on the structure

luminescent properties

and themoluminescent spectra of the samples were studied by X-ray diffraction (XRD)

fluorescent spectrophoto-meter and thermoluminescence dosimeter (TLD) respectively. The monoclinic structure remains the same irrespective of the process

and is in good agreement with that of the powder diffraction file (JCPDS) 34-0379 (SrAl2O4). The reduction of Eu3+→Eu2+ was firstly observed in the aluminate phosphor of SrAl2O4∶Eu

Dy synthesized in air condition and the reductive mechanism was also discussed in this paper. Eu3+ shows completely different luminescent properties with Eu2+ in SrAl2O4. Eu3+ has two narrow

intense spectra peaking at 592 nm and 612 nm

which resulted from the 5D0→7F1 transition and 5D0→7F4 transition respectively

implied that the Eu3+ may occupy two different lattice sites in the host crystal lattice; while Eu2+ has only one broad band spectra peaking at 513 nm

which resulted from the 4f65d→4f7 transition. The emission of Dy3+ was not found in all the four samples

indicated that the Dy3+ ions play a roll as trap centre in the phosphor

but not the luminescence centre. The concentration of Eu2+ in the samples treated in weak reductive atmosphere greatly increased whereas the concentration of Eu3+greatly decreased when compared to the samples treated in air atmosphere. The samples treated in weak reductive atmosphere have much higher thermoluminescent peak than that of the samples treated in air atmosphere. But all the samples

irrespective being treated in air atmosphere or reductive atmosphere

have the same trap depth (about 0.65 eV)

which derived from Dy3+. All these phenomena indicated that

for the long after-glow phosphor material of SrAl2O4∶Eu

Dy prepared in air atmosphere

the process of being treated in weak reductive atmosphere

air atmosphere and weak reductive atmosphere orderly

changes the valence of Eu ion and luminescence intensity

but doesnt change the trap depth in the material.

关键词

长余辉铝酸盐铕价态变化

Keywords

long afterglowstrontium aluminateeuropiumvalence-change

references

. Mao Xianghui, Wu Baoguo, Lian Shixun. Study on the effect of Eu ion in the photoconversion material [J]. Acta. Sci. Nat. Univ. Norm. Hunan (湖南工业大学学报), 1994, 17 (2):56-58 (in Chinese).

. Shi Chunshan, Ye Zeren. Spectral structure and valence stability of europium (Ⅱ) in systems ARF4(A=Na, K; R=Gd, Lu, and Y) [J]. Chin. J. Lumin.(发光学报), 1987, 8 (3):245-251 (in Chinese).

. Shi Chunshan, Ye Zeren, Hu Haining, et al. Spectral structure and site substitution of europium (Ⅱ) in systems ARF3 [J]. Chin. Science Bulletin (科学通报), 1988, 33 (6):433-436 (in Chinese).

. Sun Jiayue, Shi Chunshan, Li Youmo. Spectral characteristic and its regularity of low valency rare earth ions [J]. J. Chin. Rare Earth Soc.(中国稀土学报), 1988, 6 (2):35-39 (in Chinese).

. Liu Yingliang, Shi Chunshan, Li Youmo. Spectral characteristic and variation low of Eu (Ⅱ) in xMF2-yMF3 [J]. Chin. J. Lumin.(发光学报), 1990, 11 (1):22-28 (in Chinese).

. Palilla F C, Levine A K, Tocks M R. Fluorescent properties of alkaline earth aluminates of the type MAl2O4: activated by divalent europium [J]. J. Electrochem. Soc:Solid State Science, 1968, 115 (6):642-644.

. Tuomas Aitasalo, Jorma Holsa, Hogne Jungner, et al. Effect of temperature on the luminescence processes of SrAl2O4 ∶ Eu2+ [J]. Radiation Measurements, 2004, 38 (4-6):727-730.

. Lu Yiqing, Li Yongxiang, Xiong Yuhong, et al. SrAl2O4 ∶ Eu2+, Dy3+ phosphors derived from a new sol-gel route [J]. Microelectronics Journal, 2004, 35 (4):379-382.

. Lu Xingdong, Shu Wangen, Huang Kelong. Effect of SrO/Al2O3 ration on phosphorescence of SrAl2O4 ∶ Eu, Dy [J]. Chin. J. Lumin.(发光学报), 2004, 25 (6):672-678 (in Chinese).

. Wang Wenjie, Yang Zhiping, Guo Zhi, et al. Effect of different hosts and rare earth content on the after-glow characteristics of material SrAl2O4 ∶ Eu2+, Dy3+ [J]. J. Hebei University (Natural Science Edition) (河北大学学报,自然科学版), 2004, 24 (2):138-142 (in Chinese).

. Meng Yanshuang, Wang Dajian, Li Lan, et al. Effect of Sr/Al ration on phase and luminescent properties of strontium aluminate doped with rare earths [J]. J. Chin. Rare Earth Soc.(中国稀土学报), 2005, 23 (3):277-280 (in Chinese).

. Shen Yi, Zhang Ping, Zheng Zhentai, et al. Influence of different additives on the luminescence properties of SrAl2O4 ∶ (Eu, Dy) phosphors [J]. J. Chin. Ceramic Soc.(硅酸盐学报), 2006, 34 (10):1187-1190 (in Chinese).

. Niittykoski J, Aitasalo T, Hls J, et al. Effect of boron substitution on the preparation and luminescence of Eu2+ doped strontium aluminates [J]. J. Alloys and Compounds, 2004, 374 (1-2):108-111.

. Morito Akiyama, Xu Chaonan, Liu Yun, et al. Influence of Eu, Dy co-doped strontium aluminate composition on mechanoluminescence intensity [J]. J. Lumin., 2002, 97 (1):13-18.

. Geng Xiuju, Chen Yongjie, Xiao Linjiu, et al. Luminescence properties of long afterglow luminescent materials SrAl2O4 ∶ Eu2+, Dy3+ [J]. J. Shenyang Institute of Chemical Technology (沈阳化工学院学报), 2005, 19 (3):167-171 (in Chinese).

. Guo Chongfeng, Luan Lin, Huang Dexiu, et al. Study on the stability of phosphor SrAl2O4 ∶ Eu2+, Dy3+ in water and method to improve its moisture resistance [J]. Materials Chem. and Phys., 2007, 106 (2-3):268-272.

. Han Sang-Do, Singh Krishan C, Cho Tai-Yeon, et al. Preparation and characterization of long persistence strontium aluminate phosphor [J]. J. Lumin., 2008, 128 (3):301-305.

. Jia Dongdong. Charging curves and excitation spectrum of long persistent phosphor SrAl2O4 ∶ Eu2+, Dy3+ [J]. Opt. Materials, 2003, 22 (1):65-69.

. Zhang Linli, Guo Changxin, Zhang Junjing, et al. Synthesis of ZnO ∶ Dy nanopowder and photoluminescence of Dy3+ in ZnO [J]. J. Rare Earths, 2005, 23 (5):607-610.

. Peng Mingying, Pei Zhiwu, Hong Guangyan, et al. Study on the reduction of Eu3+→ Eu2+ in Sr4Al14O25 ∶ Eu prepared in air atmosphere [J]. Chem. Phys. Lett., 2003, 371 (1-2):1-6.

. Peng Mingying, Hong Guangyan. Reduction from Eu3+ to Eu2+ in BaAl2O4 ∶ Eu phosphor prepared in an oxidizing atmosphere and luminescent properties of BaAl2O4 ∶ Eu [J]. J. Lumin., 2007, 127 (2):735-740.

. Zeng Qinghua, Pei Zhiwu, Wang Shubing, et al. The reduction of Eu3+ in SrB6O10 prepared in air and the luminescence of SrB6O10 ∶ Eu [J]. J. Alloys and Compounds, 1998, 275 (24):238-241.

. Su Qiang, Li Chengyu, Wang Jing, et al. Electron trapping materials doped with rare earth ions [J]. Chin. J. Lumin.(发光学报), 2005, 26 (3):143-148 (in Chinese).

. Koichiro Fukuda, Kentaro Fukushima. Crystal structure of hexagonal SrA12O4 at 1 073 K [J]. J. Solid State Chem., 2005, 178 (9):2709-2714.

. Kaiya K, Takahashi N, Nakamura T, et al. EPR studies of europium (II)-doped strontium aluminate phosphors [J]. J. Lumin., 2000, 87-89 :1073-1079.

. Pei Zhiwu, Su Qiang, Zhang Jiyu. The Valence change from RE3+ to RE2+ (RE=Eu, Sm, Yb) in SrB4O7 ∶ RE prepared in air and the spectral properties of RE2+ [J]. J. Alloys and Compounds, 1993, 198 (1-2):51-53.

. Wang Dong, Yin Qingrui, Li Yongxiang, et al. Concentration quenching of Eu2+ in SrO/Al2O3 ∶ Eu2+ phosphor [J]. J. Lumin., 2002, 97 (1):1-6.

. Li Zhonghe. Crystallography Chemistry [M]. First Edition. Hangzhou: Zhejiang University Press, 1989, 91 (in Chinese).

. Aitasalo T, Dere P, Hls J, et al. Persistent luminescence phenomena in materials doped with rare earth ions[J]. J. Solid State Chem., 2003, 171 (1-2):114-122..

. Zhang Xiyan, Lu Liping. Luminescence Materials of Rare Earth [M]. First Edition. Beijing: Industry of National Defense Press, 2005,118 (in Chinese).

. Matsuzawa T, Aoki Y, Takeuehi N, et al. A new long phosphorscent phosphors with high brightness, SrAl2O4 ∶ Eu2+, Dy3+ [J]. J. Electrochem Soc., 1996, 143 (8):2670-673.

. Hajime Yamamoto, Takashi Matsuzawa. Mechanism of long phosphorescence of SrAl2O4 ∶ Eu2+, Dy3+ and CaAl2O4 ∶ Eu2+, Nd3+ [J]. J. Lumin., 1997, 72-73 :287-289.

. Yuan Zhaoxin, Chang Chengkang, Mao Dali, et al. Effect of composition on the luminescent properties of Sr4Al14O25 ∶ Eu2+, Dy3+ phosphors [J]. J. Alloys and Compounds, 2004, 377 (1-2):268-271.

. Abanti Nag, Kutty T R N. Role of B2O3 on the phase stability and long phosphorescence of SrAl2O4 ∶ Eu, Dy [J]. J. Alloys and Compd., 2003, 354 (1-2):221-231.

浏览量

下载量

CSCD

文章被引用时，请邮件提醒。

提交

工具集

关联资源

SrAl₂O₄∶Eu²⁺,Dy³⁺,Tm³⁺荧光材料的光激励诱导长余辉特性及其防伪应用

Sr₃(BN₂)₂荧光粉的合成与发光性能

Zn₂GeO₄:Mn²⁺绿色磷光粉的制备和长余辉性能

Eu掺杂GaN薄膜的阴极荧光特性

CdTe:Eu量子点的合成及其光学性能研究