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中国铝业河南分公司研究所,河南 郑州,450041
收稿日期:2006-04-06,
修回日期:2006-05-15,
纸质出版日期:2006-11-20
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李春潮, 张学英, 吴钢, 管督. n(Zn):n(Ga)比值对合成ZnGa<sub>2</sub>O<sub>4</sub>结构及光致发光性能的影响[J]. 发光学报, 2006,27(6): 963-966
LI Chun-chao, ZHANG Xue-ying, WU Gang, GUAN Du. Influence of the Ratio of n(Zn):n(Ga) on the Structure and the Photoluminescence Properties of ZnGa<sub>2</sub>O<sub>4</sub>[J]. Chinese Journal of Luminescence, 2006,27(6): 963-966
李春潮, 张学英, 吴钢, 管督. n(Zn):n(Ga)比值对合成ZnGa<sub>2</sub>O<sub>4</sub>结构及光致发光性能的影响[J]. 发光学报, 2006,27(6): 963-966 DOI:
LI Chun-chao, ZHANG Xue-ying, WU Gang, GUAN Du. Influence of the Ratio of n(Zn):n(Ga) on the Structure and the Photoluminescence Properties of ZnGa<sub>2</sub>O<sub>4</sub>[J]. Chinese Journal of Luminescence, 2006,27(6): 963-966 DOI:
以ZnO和HGaO
2
为原料
用不同配比合成出系列ZnGa
2
O
4
并对其晶体结构和发光性能进行了研究。用荧光分光光度计检测了ZnGa
2
O
4
的激发和发射光谱
用X射线衍射仪检测了ZnGa
2
O
4
的衍射图谱
用热重差热仪绘制了TGA-DAT曲线。对检测结果分析认为:1.ZnGa
2
O
4
属于尖晶石结构
稍过量的Zn或Ga能进入ZnGa
2
O
4
结构中
并对ZnGa
2
O
4
的晶格常数产生一定影响。2.ZnGa
2
O
4
存在两个自激发光中心
当Ga稍过量时
自激发光中心是四面体镓氧键[T
d
(GaO)]
最大激发波长约248nm
最大发射波长约367nm;当Zn稍过量时
自激发光中心是八面体镓氧键[O
h
(GaO)]
最大激发波长约270nm
最大发射波长约441nm。当n(Zn):n(Ga)在理论值附近
激发和发射光强度最大
而且光谱峰位发生了红移。3.ZnGa
2
O
4
的热稳定性能非常好。上述结论对研究ZnGa
2
O
4
基质或掺杂的发光材料具有一定意义。
Recently
zinc gallate (ZnGa
2
O
4
) phosphors have gained much attentions for use in vacuum fluorescent displays (VFD)
thin film electroluminescent devices (TFED)
field emission displays (FED) and low-voltage cathodeluminescence (LVC)
because they exhibit higher chemical stability than sulfide phosphors. ZnGa
2
O
4
is also expected as a new photoluminescence material. The influence of the ratio of n(Zn):n(Ga) on the structure and the photoluminescence properties of ZnGa
2
O
4
was investigated mainly. Using our rich compounds of gallium
ZnGa
2
O
4
with the nominal formula with ZnO/HGaO
2
(n(Zn):n(Ga)) ratio ranging from 0.350 to 0.650 was prepared by high temperature solid-state reaction methods. ZnO-HGaO
2
system compounds near the ZnGa
2
O
4
stoichiometric composition have been tested with diverse characterization techniques. Fluorescence spectrophotometer was used to measure the photoluminescence excitation and emission spectra of ZnGa
2
O
4
. X-ray diffraction measurements were performed to investigate the phase states in the ZnGa
2
O
4
phosphors dependent on the mixture molar ratio of ZnO and HGaO
2
. Thermal analyzer was used for recording TGA-DTA curves of ZnGa
2
O
4
. The results show that ZnGa
2
O
4
has a spinel structure
consists of a cubic cell with Fd3m symmetry
which contains a close-packed array of 32 oxygen atoms with cations in tetrahedral and octahedral interstices. The excess Ga or Zn is soluble in ZnGa
2
O
4
and don't affect the spinel lattice of ZnGa
2
O
4
. The lattice constants increased along with increasing of n(Zn):n(Ga) ratio. When Zn excess
the formula of ZnGa
2
O
4
changed into Zn(Ga
1-x
Zn
x
)
2
O
4
this formula leaded to the increase O
2-
vacancy. When Ga excess
the formula of ZnGa
2
O
4
changed into (Zn
1-x
Ga
x
)Ga
2
O
4
this formula leaded to the increase Zn
2+
vacancy. ZnGa
2
O
4
is a new n-semiconductor material
its lattice interval exist the vacancies and ions
belong to structure defect or crystal defect. The luminescence mechanism is similar the luminescence of semiconducter
with an optical band gap of 4.4 eV. ZnGa
2
O
4
is a kind of self-activated luminescence material with two self-activated optical center
e.g. [T
d
(GaO)] and [O
h
(GaO)]
its excitation and emission spectras are wider. In n(Zn):n(Ga)0.500
the absorption band at 248 nm and the fluorescence band at 367 nm originated from self-activation optical centers of the tetrahedral [T
d
(GaO)] in the spinel lattice. In n(Zn):n(Ga)0.550
the absorption and the fluorescence band at 270 nm and 441 nm originated from self-activation optical centers of the octahedral [O
h
(GaO)] in the spinel lattice. The peak of excitation and emission shifted to longer wavelength when n(Zn):n(Ga) ratio between 0.500 and 0.550. TGA-DTAanalyses showed ZnGa
2
O
4
had excellent chemical stability properties. These results can help improve understanding ZnGa
2
O
4
or doped ZnGa
2
O
4
phosphors for the application research with high brightness.
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