Ce3+浓度对YVO4: Ce3+晶体发光性能的影响

doi:10.15541/jim20160173

无机材料学报 ›› 2016, Vol. 31 ›› Issue (10): 1073-1080.DOI: 10.15541/jim20160173

Ce³⁺浓度对YVO₄: Ce³⁺晶体发光性能的影响

杨广武^1,2, 杨瑞霞^1,3, 张守超², 朱飞²

(1. 河北工业大学电子信息工程学院, 天津300401; 2. 天津城建大学理学院, 天津300384; 3. 天津市电子材料与器件重点实验室, 天津300401)

收稿日期:2016-03-23 修回日期:2016-05-18 出版日期:2016-10-20 网络出版日期:2016-09-23
作者简介:杨广武(1970–), 男, 博士研究生. E-mail: yanggw204@163.com
基金资助:
国家自然科学基金(11504261);河北省自然科学基金(F2014202184);天津市自然科学基金(15JCZDJC37800)

Ce Doping Concentration on Luminescence Property of YVO₄:Ce³⁺ Crystals

YANG Guang-Wu^1,2, YANG Rui-Xia^1,3, ZHANG Shou-Chao², ZHU Fei²

(1. School of Electronic and Information Engineering, Hebei University of Technology, Tianjin 300401, China; 2. School of Science, Tianjin Chengjian University, Tianjin 300384, China; 3. Tianjin Key Laboratory of Electronic Materials and Devices, Tianjin 300401, China)

Received:2016-03-23 Revised:2016-05-18 Published:2016-10-20 Online:2016-09-23
About author:YANG Guang-Wu. E-mail: yanggw204@163.com
Supported by:
National Natural Science Foundation of China(11504261);Natural Science Foundation of Hebei Province(F2014202184);Natural Science Foundation of Tianjin (15JCZDJC37800)

摘要/Abstract

摘要：

利用提拉法生长了掺杂浓度为1.0at%~10.0at%的YVO₄:Ce³⁺单晶, XRD分析显示Ce³⁺ 的掺入没有改变晶体结构。晶体的激发和发射谱测试表明, 在325 nm激发下YVO₄:Ce³⁺发射出峰值在445 nm的蓝光和620 nm附近的红光。蓝光发光强度随Ce³⁺浓度增加而增强, 当浓度为8.0at%时达到最强, 10.0at%时出现浓度淬灭, 发光减弱; 红光则随着Ce³⁺浓度的增加而持续增强。通过实验分析推测蓝光来源于Ce³⁺电子从激发态²D_3/2到基态²F_5/2的跃迁, 而红光则是由于V⁴⁺的电子能级跃迁而形成的。XPS测试显示部分Ce³⁺失去电子被氧化成为Ce⁴⁺, 失去的电子大部分被V⁵⁺捕获形成V⁴⁺。V⁴⁺的d轨道分裂为三个轨道单态²A₁、²B₁、²B₂和一个轨道简并态²E等4个能级, 基态为²B₂。V⁴⁺中电子通过能量传递、辐射跃迁和无辐射跃迁等过程, 可以实现波长在620 nm附近的红光发射以及在620 nm激发下的451 nm蓝光上转换发光。实验证实了上转换发光为双光子过程。研究结果对紫外激发下YVO₄:Ce³⁺红、蓝光发光行为提供了理论支撑。

null

关键词: 铈离子, 上转换发光, V⁴⁺, 能量传递, 红光发射

Abstract:

Pure YVO₄ crystal and YVO₄ crystal doped with different Ce concentrations were grown by Czochralski method. XRD pattern shows Ce³⁺ ion enters the YVO₄ lattice by occupying the Y³⁺ site and the crystal structure was not significantly changed. The detection of UV excitation spectrum and emission spectrum of YVO₄: Ce³⁺ at room temperature showed that excited at 325 nm the YVO₄: Ce³⁺ emits two spectra. The main emission spectrum at 445 nm is a broadband peak, caused by transition of ²D_3/2→²F_5/2 of Ce³⁺. The other one is a weak peak emission centered around 620 nm, which presents the emission of V⁴⁺. With increase of Ce mole fraction from 1at% to 8at%, the blue emission intensity gradually increases to a maximum value. As Ce fraction increases to 10.0at%, the emission intensity decreases gradually, indicating an obvious concentration quenching. The red emission intensity gradually increases to a maximum value when Ce fraction increases to 10.0at%. Detection by X-ray photoelectron spectroscopy (XPS) shows that Ce⁴⁺ and V⁴⁺ ions coexist in YVO₄:Ce³⁺, which may result from some of the Ce³⁺ losing electrons to be oxidized into Ce⁴⁺, and most of them being captured by the V⁵⁺ ions and, therefore, resulting in V⁵⁺→V⁴⁺ transformation. Based on V⁴⁺ d orbital splitting into ²A₁, ²B₁, ²B₂, and ²E, the 620 nm red emission under 325 nm and 450 nm excitation probably originated from electronic transitions between the V⁴⁺splitted d orbits. In conclusion, present analytical data of the luminescence spectra of YVO₄: Ce³⁺ provide a theoretical support for YVO₄:Ce³⁺ emitting red light and blue light simultaneously under UV excitation.

Key words: Ce³⁺, up-conversion, V⁴⁺, energy transfer, red-emitting

中图分类号:

TQ174

杨广武, 杨瑞霞, 张守超, 朱飞. Ce³⁺浓度对YVO₄: Ce³⁺晶体发光性能的影响[J]. 无机材料学报, 2016, 31(10): 1073-1080.

YANG Guang-Wu, YANG Rui-Xia, ZHANG Shou-Chao, ZHU Fei. Ce Doping Concentration on Luminescence Property of YVO₄:Ce³⁺ Crystals[J]. Journal of Inorganic Materials, 2016, 31(10): 1073-1080.

图/表 14

图1 YVO4和YVO4: Ce3+晶体的XRD图谱

Fig. 1 XRD patterns of YVO4 and YVO4: Ce3+ crystals

表1 YVO4:Ce3+晶胞参数

Table 1 Cell parameters of YVO4:Ce3+ compound

Samples	Cell parameter/nm		Cell Volume/nm³ V=a²c
Samples	a=b	c	Cell Volume/nm³ V=a²c
YVO₄	0.712140	0.629113	0.319050
1.0at%	0.712641	0.630389	0.320148
2.0at%	0.712730	0.630577	0.320323
3.0at%	0.712782	0.630741	0.320453
5.0at%	0.712823	0.63081	0.320525
8.0at%	0.713023	0.630851	0.320725
10.0at%	0.713103	0.631013	0.320880

图2 5.0at% YVO4:Ce3+晶体的SEM形貌分析及能谱分析

Fig. 2 SEM image and EDS result of 5.0at% YVO4:Ce3+ crystal

图3 YVO4和YVO4: Ce3+晶体吸收光谱及吸收峰Gauss拟合

Fig. 3 Absorption spectra and Gauss fitting of YVO4 and YVO4: Ce3+ crystals (line 1 to 7 represents absorption spectrum of YVO4 and 1.0at%, 2.0at%, 3.0at%, 5.0at%, 8.0at% and 10.0at% YVO4:Ce3+ crystals, respectively)

图4 YVO4和YVO4:Ce3+晶体激发谱(λem=450 nm)

Fig. 4 Excitation spectra of YVO4 and YVO4: Ce3+ crystal under λem=450 nm

图5 YVO4:Ce3+晶体发射光谱(λex=325 nm)

Fig. 5 Emission spectra of YVO4 and YVO4: Ce3+ crystals (λex = 325 nm)

图6 YVO4:Ce3+晶体中Ce3d和V2p XPS谱

Fig. 6 Ce3d and V2p XPS spectra in YVO4: Ce3+ crystal

表2 XPS分析YVO4:Ce3+晶体中Ce3+/Ce4+相对含量

Table 2 Ce3+/Ce4+ relative content in YVO4:Ce3+ crystals

Ce Concentration	Ce³⁺ Binding energy/eV	Ce⁴⁺ Binding energy/eV	Ce³⁺ Relative content/%	Ce⁴⁺ Relative content/%	Ce³⁺ Rela content/%	Ce⁴⁺ Rela content/%
1.0at%	891.1,906.8	916.3	64.8	35.2	0.613%	0.333%
2.0at%	884.2,904.3	898.1,916.2	75.0	25.0	1.426%	0.476%
3.0at%	886.3,904.8	898.1,898.3,915.6	65.4	34.6	1.896%	1.003%
5.0at%	885.4,904.6	882.5,899.3,916.7	69.0	31.0	3.284%	1.45%
8.0at%	885.3,903.8	882.7,898.5,914.6	68.2	31.8	5.356%	2.498%
10.0at%	884.5,903.1	882.6,899.2,915.7	71.4	28.6	6.877%	2.755%

表3 XPS分析YVO4:Ce3+晶体中V4+/V5+相对含量

Table 3 V4+/V5+ relative content in YVO4:Ce3+ crystals

Ce concentration	V⁴⁺ binding energy/eV	V⁵⁺ binding energy/eV	V⁴⁺ relative content/%	V⁵⁺ relative content/%
1.0at%	515.5	517	0.24	99.76
2.0at%	515.5	517	0.32	99.68
3.0at%	515.5	517	0.58	99.42
5.0at%	515.5	517	0.8	99.2
8.0at%	515.5	517	1.37	98.63
10.0at%	515.5	517	1.62	98.38

图7 离子的浓度与发光强度之间关系

Fig. 7 Relationship between the concentration of different ions and luminous intensity

图8 5.0at% YVO4:Ce3+晶体中O1s和Ce3d的XPS曲线

Fig. 8 XPS spectra of O1s (up) and Ce3d (down) in 5.0at% YVO4: Ce3+ crystal

图9 YVO4:Ce3+ 晶体蓝、红发光电子路径及上转换发光示意图

Fig. 9 Schematic diagram of the electronic transition and up-conversion luminescence of YVO4:Ce3+ crystal

图10 YVO4:Ce3+晶体在620 nm激发下的上转换发光和450 nm激发下的红光发射

Fig. 10 Up-conversion luminescence (λex = 620 nm ) and red emission (λex = 450 nm ) of YVO4:Ce3+ crystal

图11 YVO4:Ce3+晶体荧光积分强度和泵浦功率之间的关系

Fig. 11 Power dependence curves of YVO4:Ce3+ crystal emission under 620 nm laser excitation

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Ce³⁺浓度对YVO₄: Ce³⁺晶体发光性能的影响

Ce Doping Concentration on Luminescence Property of YVO₄:Ce³⁺ Crystals

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