Ce 3+/Yb 3+共掺LiLuF4单晶的紫外和近红外发光研究

doi:10.15541/jim20190215

无机材料学报 ›› 2020, Vol. 35 ›› Issue (5): 556-560.DOI: 10.15541/jim20190215 CSTR: 32189.14.10.15541/jim20190215

所属专题：功能陶瓷论文精选(一)：发光材料

Ce ³⁺/Yb ³⁺共掺LiLuF₄单晶的紫外和近红外发光研究

周雄¹,方立志¹,黄双武¹,夏海平¹(),胡建旭¹,章践立¹,陈宝玖²

1.宁波大学光电子功能材料重点实验室, 宁波 315211
2.大连海事大学物理系, 大连 116026

收稿日期:2019-05-10 修回日期:2019-06-01 出版日期:2020-05-20 网络出版日期:2019-09-04
作者简介:周雄(1974-), 男, 博士研究生. E-mail: zhouxiong@nbu.edu.cn<br/>ZHOU Xiong(1974-), male, PhD candidate. E-mail: zhouxiong@nbu.edu.cn
基金资助:
国家自然科学基金(51772159);浙江省自然科学基金(LZ17E020001);宁波大学王宽诚幸福基金

Ultraviolet and Near-infrared Luminescence of Ce ³⁺/Yb ³⁺ Co-doping LiLuF₄ Single Crystal

ZHOU Xiong¹,FANG Lizhi¹,HUANG Shuangwu¹,XIA Haiping¹(),HU Jianxu¹,ZHANG Jianli¹,CHEN Baojiu²

1.Key Laboratory of Photo-electronic Materials, Ningbo University, Ningbo 315211, China
2.Department of Physics, Dalian Maritime University, Dalian 116026, China

Received:2019-05-10 Revised:2019-06-01 Published:2020-05-20 Online:2019-09-04
Supported by:
National Natural Science Foundation of China(51772159);Natural Science Foundation of Zhejiang Province(LZ17E020001);K.C. Wong Magna Fund in Ningbo University

摘要/Abstract

摘要：

采用改进的坩埚下降法成功生长了Ce ³⁺/Yb ³⁺离子双掺杂LiLuF₄单晶, Ce ³⁺的初始离子掺杂浓度为0.1mol%, Yb ³⁺离子浓度从0变化到2.0mol%。在波长291 nm激发时观察到Yb ³⁺在1020 nm( ²F_5/2→ ²F_7/2)附近的强近红外发射以及Ce ³⁺在300~350 nm(5d→4f)的紫外发射。通过吸收光谱、荧光光谱研究了Yb ³⁺离子掺杂浓度对Ce ³⁺/Yb ³⁺共掺杂LiLuF₄单晶光谱性质的影响及Ce ³⁺到Yb ³⁺离子的能量转移机理。通过变温光谱的研究发现, 当环境温度从298 K增加到443 K时, 其荧光发射强度不断降低。Ce ³⁺/Yb ³⁺共掺杂LiLuF₄单晶发光波长主要位于紫外和近红外, 这种独特的发光属性可望用于防伪技术和公共安全事务中。

关键词: Ce ³⁺/Yb ³⁺, 紫外和近红外发射, LiLuF₄单晶, 能量转移

Abstract:

LiLuF₄ single crystals doped with Ce ³⁺ ion of 0.1mol% and Yb ³⁺ ion of concentration varying from 0 to 2.0mol% were successfully synthesized by an improved Bridgman method. Intense near-infrared emission at around 1020 nm, attributed to the ²F_5/2→ ²F_7/2 transition of Yb ³⁺, and ultraviolet emission of Ce ³⁺ at 300-350 nm (5d→4f) was observed using excitation at 291 nm. Influence of Yb ³⁺ ions concentration on the spectroscopic properties of Ce ³⁺/Yb ³⁺ co-doped LiLuF₄ single crystal and the mechanism of energy transfer from Ce ³⁺ to Yb ³⁺ ions were explored through optical absorption and emission spectra. The temperature dependent emission indicated that the emission intensity constantly decreases with the increase of temperature from 298 to 443 K due to the enhancement of non-radiative quenching at high temperature. Ce ³⁺/Yb ³⁺ co-doped LiLuF₄ single crystals mainly emit in the ultraviolet and near-infrared ranges. This unique property may be suitable for applications in anti-counterfeiting techniques and public security affairs.

Key words: Ce ³⁺ and Yb ³⁺, ultraviolet and infrared emissions, LiLuF₄ single crystal, energy transfer

中图分类号:

TQ174

周雄, 方立志, 黄双武, 夏海平, 胡建旭, 章践立, 陈宝玖. Ce ³⁺/Yb ³⁺共掺LiLuF₄单晶的紫外和近红外发光研究[J]. 无机材料学报, 2020, 35(5): 556-560.

ZHOU Xiong, FANG Lizhi, HUANG Shuangwu, XIA Haiping, HU Jianxu, ZHANG Jianli, CHEN Baojiu. Ultraviolet and Near-infrared Luminescence of Ce ³⁺/Yb ³⁺ Co-doping LiLuF₄ Single Crystal[J]. Journal of Inorganic Materials, 2020, 35(5): 556-560.

图/表 8

表1 Ce3+和Yb3+在原料中的摩尔分数以及单晶中的离子数浓度

Table 1 Molar fractions of Ce3+ and Yb3+ in raw materials and the number of Ce3+ ions (N) and Yb3+ ions in single crystals

Sample	C0	CY1	CY2	CY3	CY4
Ce³⁺ in raw material/mol%	0.1	0.1	0.1	0.1	0.1
Ce³⁺molar concentration in crystal/mol%	0.023	0.022	0.024	0.022	0.024
Ce³⁺measured in crystal/(×10²⁰, ions·cm^-1)	0.023	0.022	0.024	0.022	0.024
Yb³⁺ in raw material/mol%	0	0.5	1.0	1.5	2.0
Yb³⁺molar concentration in crystal/mol%	0	0.499	0.987	1.486	1.982
Yb³⁺measured in crystal/(×10²⁰, ions·cm^-1)	0	0.502	0.993	1.495	1.994

图1 毛坯晶体照片(a)和C0、CY3及标准LiLuF4晶体样品的XRD图谱(b)

Fig. 1 (a) Photo of the grown single crystal; (b) XRD patterns of C0, CY3 and standard card of LiLuF4 (1) XRD pattern of 0.1mol% Ce3+ doped LiLuF4 single crystal; (2) XRD pattern of 0.1mol% Ce3+/1.5mol% Yb3+ co-doped LiLuF4 single crystal; (3) Standard card of (JCPD No.27-1251) of LiLuF4

图2 (a)LiLuF4的晶体结构、(b)Li和(c)Lu位点的配位

Fig. 2 (a) Crystal structure of LiLuF4, and (b) coordination for lithium and (c) lutetium sites

图3 LiLuF4单晶的吸收光谱

Fig. 3 Absorption spectra of the LiLuF4 single crystals (a) 0.1mol%Ce3+/1.5mol%Yb3+ co-doped; (b) 0.1mol%Ce3+ singly doped LiLuF4

图4 (a)291 nm激发的Ce3+/Yb3+共掺杂LiLuF4单晶的荧光光谱, (b)Ce3+和Yb3+离子的发射强度随Yb3+浓度的变化

Fig. 4 (a) Emission spectra of Ce3+/Yb3+ co-doped LiLuF4 single crystals excited at 291 nm, and (b) emission intensity of Ce3+ and Yb3+ ions as a function of Yb3+ concentration

图5 Ce3+/Yb3+共掺杂LiLuF4单晶的能级图

Fig. 5 Partial energy level diagram in Ce3+/Yb3+ co-doped LiLuF4 single crystal

图6 (a)Ce3+单掺样品中在326 nm处的荧光衰减曲线, (b)根据Inokuti-Hirayama模型拟合所得曲线

Fig. 6 (a) Fluorescence decay curves of active Ce3+ ions near 326 nm in Ce3+ singly doped LiLuF4 single crystal; (b) Fitting curves with Inokuti-Hirayama model

图7 (a)291 nm激发下0.1mol% Ce3+/1.5mol% Yb3+样品的变温光谱, (b)Ce3+/Yb3+的发射强度随温度变化情况

Fig. 7 (a) Temperature dependent emission spectra of 0.1mol% Ce3+/1.5mol% Yb3+ sample under 291 nm excitation, and (b) emission intensity of Ce3+ and Yb3+ as a function of temperature

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Ce ³⁺/Yb ³⁺共掺LiLuF₄单晶的紫外和近红外发光研究

Ultraviolet and Near-infrared Luminescence of Ce ³⁺/Yb ³⁺ Co-doping LiLuF₄ Single Crystal

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