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1. 中国科学技术大学, 国家同步辐射实验室, 安徽合肥230029
2. 中国科学技术大学物理系,安徽 合肥,230026
收稿日期:2000-07-24,
修回日期:2001-03-05,
纸质出版日期:2001-08-30
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周东方, 施朝淑, 张庆礼, 陈永虎. 稀土Gd<SUP>3+</SUP>掺杂对PbWO<SUB>4</SUB>发光的增强[J]. 发光学报, 2001,22(3): 248-252
ZHOU Dong-fang, SHI Chao-shu, ZHANG Qing-li, CHEN Yong-hu. Rare Earth Gd<sup>3+</sup> Doping Improving Luminescence of Pb WO<sub>4</sub> Microcrystal[J]. Chinese Journal of Luminescence, 2001,22(3): 248-252
周东方, 施朝淑, 张庆礼, 陈永虎. 稀土Gd<SUP>3+</SUP>掺杂对PbWO<SUB>4</SUB>发光的增强[J]. 发光学报, 2001,22(3): 248-252 DOI:
ZHOU Dong-fang, SHI Chao-shu, ZHANG Qing-li, CHEN Yong-hu. Rare Earth Gd<sup>3+</sup> Doping Improving Luminescence of Pb WO<sub>4</sub> Microcrystal[J]. Chinese Journal of Luminescence, 2001,22(3): 248-252 DOI:
本文研究了稀土Gd
3+
掺杂于PbWO4的发射光谱、激发光谱及其浓度依赖。Gd
3+
在PWO4中的发光完全被猝灭
而PWO4的发射光谱形状不变。掺入约50ppm后PWO4的绿光带有所增强
掺入约100ppm后PWO4的蓝光带有所增强。Gd
3+
的激发态进入PWO4的导带并把能量反向传递给PWO4基质是其可能的发光增强机制。低掺杂的PWO4:Gd是一种性能优良的闪烁体材料。
The luminescence properties of PbWO 4 doped with Gd
3+
have been studied. The PbWO 4:Gd
3+
microcrystal powder was obtained by solid phase reaction method. The microcrystal with strong green emission band was prepared in air with rich oxygen at 875℃ for 10 hours
and the microcrystal with strong blue emission band was prepared in vacuum with active carbon at 800℃ for 8 hours. By measuring the emission of PbWO 4:Gd
3+
for 311nm excited by 274nm
and measuring the excitation spectrum of PbWO 4:Gd
3+
from 200~300nm of 311nm emission
it can be concluded that the luminescence of Gd
3+
in PWO was quenched. So both the excited states 6I 7/2 and 6P 7/2 of Gd
3+
are located in the conduction band of PWO. The luminescence from 4f 4f transition of Gd
3+
is slow
its quenching should not increase the slow components of luminescence of PWO in general
so the luminescence of PWO:Gd is still that of PbWO 4 host dominated by fast components. As a structure sensitive material
PWO is sensitive to oxygen during preparing and annealing. The strong green component of luminescence from PWO:Gd powder compounded in air with rich oxygen is as about 100 times as that of crystal compounded in a atmosphere lack of oxygen
similar to that of crystal sample annealed in air. Its emission and excitation spectra are showed in Fig.1
and the concentration dependence of the peak emission intensity of PWO:Gd is showed in Fig.2. For PWO:Gd prepared in air
the intensity of the green emission of PWO is increased by doping with 50~100ppm Gd. But beyond 100 ppm
Gd doping will quench the luminescence of PWO. For PWO:Gd powder prepared in vacuum with active carbon
its emission is mainly in blue band and the blue emission intensity is increased remarkably as 3~4 times as that from PWO crystal grown by Bridgman method. As shown in Fig.3
the main wide excitation band peaked at 378nm is very different from that prepared and annealed by other method or in other atmosphere. It is a new phenomenon. The new excitation band at 378nm can not excite the green emission. It excites directly the blue centers. The luminescence of PWO doped with low concentration of Gd is stronger than that of pure PWO
and its concentration dependence of the blue band intensity is shown in Fig.4. For PWO:Gd emitting in blue band
prepared in vacuum with active carbon
doping with about 100ppm Gd would improve the luminescence of PWO best
and doping with over 300ppm Gd would make the quenching of PWO luminescence. Low concentration doping of Gd could improve the luminescence intensity of the green and the blue band of PWO. This is not caused by the compensation process of the structural defects of PWO. Because green band and blue band are produced by two different kinds of luminescence centers
these two kinds of luminescence centers could not be compensated by one kind of defects. Mechanism of the Gd
3+
enhancing PWO is probably due to the inverse energy transfer in crystal
Gd
3+
→
PWO host
as the excited states of Gd
3+
are included in the conduction band of PWO host. The PWO doped with Gd is a good scintillating material.
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