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中国科学院长春应用化学研究所稀土化学与物理开放实验室,吉林 长春,130022
收稿:2001-09-19,
修回:2002-3-11,
纸质出版:2002-05-20
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于敏, 林君, 周永慧. 柠檬酸-凝胶法合成ZnGa<sub>2</sub>O<sub>4</sub>:Mn<sup>2+</sup>/Eu<sup>3+</sup>及其发光性能的研究[J]. 发光学报, 2002,23(3): 287-290
YU Min, LIN Jun, ZHOU Yong-hui. Preparation and Luminescent Properties of ZnGa<sub>2</sub>O<sub>4</sub>Doped with Mn<sup>2+</sup>/Eu<sup>3+</sup> by the Citric-gel Method[J]. Chinese Journal of Luminescence, 2002,23(3): 287-290
于敏, 林君, 周永慧. 柠檬酸-凝胶法合成ZnGa<sub>2</sub>O<sub>4</sub>:Mn<sup>2+</sup>/Eu<sup>3+</sup>及其发光性能的研究[J]. 发光学报, 2002,23(3): 287-290 DOI:
YU Min, LIN Jun, ZHOU Yong-hui. Preparation and Luminescent Properties of ZnGa<sub>2</sub>O<sub>4</sub>Doped with Mn<sup>2+</sup>/Eu<sup>3+</sup> by the Citric-gel Method[J]. Chinese Journal of Luminescence, 2002,23(3): 287-290 DOI:
采用柠檬酸凝胶法合成了纯的ZnGa
2
O
4
粉末以及ZnGa
2
O
4
:Mn
2+
/Eu
3+
粉末
利用X射线衍射(XRD)、热重及差热分析(TGDTA)、发光光谱等测试手段对ZnGa
2
O
4
和ZnGa
2
O
4
:Mn
2+
/Eu
3+
的结晶过程、发光性质进行了研究。XRD结果表明
柠檬酸凝胶法合成的样品在500℃时已开始结晶
在700℃时可得到纯相的ZnGa
2
O
4
多晶粉末
这比传统固相法的烧结温度低500℃。发光光谱测试表明ZnGa
2
O
4
:Mn
2+
在450nm和506nm处出现两个发射带
前者属于ZnGa
2
O
4
基质的发射
后者属于Mn
2+
的
4
T
1
→
6
A
1
的跃迁发射。ZnGa
2
O
4
:Eu
3+
则呈现Eu
3+
的特征红光发射
最强峰位于613nm
属于Eu
3+
的
5
D
0
→
7
F
2
超灵敏跃迁。通过光谱分析进一步证实了ZnGa
2
O
4
:Mn
2+
/Eu
3+
的发光机理是基质敏化
吸收能量并向激活离子传递能量。
The development of flat panel display devices such as field emission displays (FEDs) and vacuum fluorescent displays (VFDs) requires highly efficient cathodoluminescent materials.While many efficient sulfide based phosphors have been explored as possible low-voltage phosphors
the volatility of sulfur has prohibited their use in FEDs or VFDs.Sulfide-base phosphors often degrade under high energy electron bombardment due to dissociation of the cation sulfur bonds.Oxide phosphors offer potential advantage because of their superior stability under electron bombardment and excellent luminescent properties.ZnGa
2
O
4
is an attractive oxide phosphor for low-voltage cathodoluminscence applications in VFDs and FEDs.ZnGa
2
O
4
is a binary compound oxide consisting of ZnO and Ga
2
O
3
with the formula AB
2
O
4
and has a cubic structure that can be viewed as a combination of rock salt and zinc blend structures
a normal spinel structure [space group is Fd3m(O
h
7
)].The optical bandgap of ZnGa
2
O
4
is about 4.4eV.Like other wide bandgap semiconductors ZnGa
2
O
4
exhibits a blue emission under excitation by both ultraviolet light and low voltage electrons.Activation with Mn
2+
or Eu
3+
ions
the emission shifts to green or red.The citrate gel method allows preparation of highly dispersed mixed oxide at low temperature.This method involves the formation of a mixed ions citrate that due to the three ligand nature of the citric acid
resulting a transparent three dimensional network upon drying (gel).The pyrolysis of the gel yields a homogeneous mixed oxides.The method was widely used to prepare multicomponent oxides
such as superconductors.In this paper
we report the synthesis of ZnGa
2
O
4
and ZnGa
2
O
4
:Mn
2+
/Eu
3+
by a citrate gel method.XRD
TG-DTA
and luminescence excitation and emission spectra were used to characterize the resulting products.The results of XRD reveal that the powders begin to crystallize at 500℃ and pure ZnGa
2
O
4
phase is obtained at 700℃
which agrees well with the results of TG-DTA and FT-IR.This temperature is much lower than that (1200℃) by solid state reaction method.In the crystalline ZnGa
2
O
4
the Eu
3+
shows its characteristic red (613nm
5
D
0
→
7
F
2
) emission with a quenching concentration of 5mol%(of Ga
3+
)
and the Mn
2+
shows green emission (506nm
4
T
1
→
6
A
1
) with a quenching concentration of 0.1mol%(of Zn
2+
).The luminescence mechanism of ZnGa
2
O
4
:Mn
2+
/Eu
3+
is presented.Activator sensitization and host-to-activator energy transfer are suggested.
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