Ce3+掺杂Li2O-MgO-Al2O3-SiO2玻璃的结构与荧光猝灭现象

doi:10.15541/jim20130662

无机材料学报 ›› 2014, Vol. 29 ›› Issue (9): 967-971.DOI: 10.15541/jim20130662

Ce³⁺掺杂Li₂O-MgO-Al₂O₃-SiO₂玻璃的结构与荧光猝灭现象

陈艳平, 罗德礼, 徐钦英, 杨锁龙, 唐涛, 王小英

(表面物理与化学重点实验室, 绵阳 621907)

收稿日期:2013-12-16 修回日期:2014-03-04 出版日期:2014-09-17 网络出版日期:2014-08-21
作者简介:陈艳平(1980–), 男, 博士研究生. E-mail:ypchen07@126.com
基金资助:
国家自然科学基金(11105127) National Natural Science Foundation of China (11105127)

Structure and Fluorescence Quenching of Li₂O-MgO-Al₂O₃-SiO₂ Glasses
Doped with Trivalent Cerium

CHEN Yan-Ping, LUO De-Li, XU Qin-Ying, YANG Suo-Long, TANG Tao, WANG Xiao-Ying

(Science and Technology on Surface Physics and Chemistry Laboratory, Mianyang 621907, China)

Received:2013-12-16 Revised:2014-03-04 Published:2014-09-17 Online:2014-08-21
About author:CHEN Yan-Ping. E-mail:ypchen07@126.com

摘要/Abstract

摘要：

采用熔融淬冷法制备了不同浓度Ce³⁺离子掺杂的20Li₂O-5MgO-20Al₂O₃-55SiO₂玻璃闪烁材料。采用X射线衍射(XRD)、高分辨透射电镜(HRTEM)技术、密度检测等方法研究了玻璃的微观结构随Ce³⁺离子掺杂浓度的变化规律, 采用荧光分光技术检测了玻璃的紫外光致激发光谱(PLE)、发射光谱(PE)。研究结果表明: 在不对称的晶体场作用下, Ce³⁺离子5d能级被劈裂为5个组分; 随着玻璃基质内Ce³⁺离子掺杂浓度增大, 玻璃的非晶化程度加深; 5d能级的劈裂宽度随之增大, 由此导致激发带向低能量端展宽、发射光谱明显红移; Ce³⁺离子的荧光发射强度随Ce³⁺离子掺杂浓度先升高、后降低, 浓度猝灭过程成为其荧光发射效率降低的主要原因。

关键词: Ce3+掺杂浓度, Li2O-MgO-Al2O3-SiO2玻璃, 5d能级劈裂, 浓度猝灭

Abstract:

20Li₂O-5MgO-20Al₂O₃-55SiO₂glass doped with different concentrations of Ce³⁺ions was synthesized by using melt-quenching method. The glass density as a function of Ce³⁺ ions doping concentration was tested by Archimedes’ method. The structural characteristics of Ce³⁺-doped 20Li₂O-5MgO-20Al₂O₃-55SiO₂were detected by using X-rays diffraction (XRD), high resolution transmission electron microscope (HRTEM) techniques. The photoluminescence excitation (PLE) and emission (PL) spectra were recorded in a spectrofluorimeter by photon counting techniques. Results showed that 5d energy level of Ce³⁺ ion was splitted to five components under the strong crystal filed surrounding Ce³⁺ ions. The higher the doping concentration of Ce³⁺ ions, the higher the degree of non-crystalline configuration of lithium magnesium aluminosilicate glass was. With the increase of the degree of non-crystalline configuration, the splitting width of 5d energy level increased, resulting in the redshift of excitation and emission spectra apparently. The PL emission intensity first increased, and then decreased with the increase of Ce³⁺ ions doping concentration. The concentration quenching processes were found to be the key reason for the reduction of the PL emission efficiency.

Key words: Ce3+-doped concentration, Li2O-MgO-Al2O3-SiO2 glasses, 5d energy level splitting, concentration quenching

中图分类号:

TQ171

陈艳平, 罗德礼, 徐钦英, 杨锁龙, 唐涛, 王小英. Ce³⁺掺杂Li₂O-MgO-Al₂O₃-SiO₂玻璃的结构与荧光猝灭现象[J]. 无机材料学报, 2014, 29(9): 967-971.

CHEN Yan-Ping, LUO De-Li, XU Qin-Ying, YANG Suo-Long, TANG Tao, WANG Xiao-Ying. Structure and Fluorescence Quenching of Li₂O-MgO-Al₂O₃-SiO₂ Glasses
Doped with Trivalent Cerium[J]. Journal of Inorganic Materials, 2014, 29(9): 967-971.

图/表 8

表1 LMAS:xCe玻璃的成分

Table 1 Batch compositions of LMAS:xCe glasses

Glass samples	Composition/mol%
Glass samples	Li₂O	SiO₂	Al₂O₃	MgO	Ce₂O₃
LMAS:xCe	20	55	20	5	x=0, 0.25, 0.50, 0.80, 0.89, 1.00, 5.12, 10.24

图1 LMAS:xCe玻璃的密度随Ce2O3添加量的变化

Fig. 1 LMAS:xCe glass densities vs Ce2O3 content Inset is the photo of samples doped with 1.06mol%, 0.89mol%, 0.80mol% Ce2O3 from left to right

图2 LMAS:xCe玻璃的XRD图谱

Fig. 2 XRD patterns of LMAS:xCe glasses

图3 在紫外光作用下LMAS:0.89Ce的激发和发射光谱, 激发与发射狭缝分别为8 nm和12 nm

Fig. 3 Photoluminescence excitation and emission spectra of LMAS:0.89Ce glass, with the excitation and emission slit width of 8 nm and 12 nm

图4 LMAS:xCe玻璃的发射光谱, 激发波长280 nm

Fig. 4 Photoluminescence spectra of LMAS:xCe glasses under the excitation of 280 nm UV light

图5 LMAS:5.12Ce玻璃的HRTEM照片

Fig. 5 HRTEM image of LMAS:5.12Ce galss

表2 LMAS:xCe玻璃发射光谱参数

Table 2 The emission spectra parameters of LMAS:xCe glasses

Samples	Peak wavelength /nm	FWHM /nm	Integral intensity/% *
LMAS:0.25Ce	375.0	67.0	57.77±0.34
LMAS:0.50Ce	383.0	66.5	87.59±0.50
LMAS:0.80Ce	384.5	67.0	91.84±0.55
LMAS:0.89Ce	386.5	70.0	100.00±0.50
LMAS:1.00Ce	386.5	68.5	82.54±0.51
LMAS:5.12Ce	404.0	85.0	66.04±0.46
LMAS:10.24Ce	426.0	97.0	39.31±0.48

图6 LMAS:xCe的紫外光致激发光谱

Fig. 6 Photoluminescence excitation spectra of LMAS:xCe glasses

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Ce³⁺掺杂Li₂O-MgO-Al₂O₃-SiO₂玻璃的结构与荧光猝灭现象

Structure and Fluorescence Quenching of Li₂O-MgO-Al₂O₃-SiO₂ Glasses
Doped with Trivalent Cerium

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