Zn2+掺杂诱导Eu3+激活BiOCl层状半导体的反常发光性能研究

doi:10.15541/jim20160597

摘要/Abstract

摘要：

采用固相法在500℃下成功制备Zn²⁺掺杂BiOCl:Eu³⁺层状半导体, 并研究了Zn²⁺ (0~20mol%)掺杂对Eu³⁺激活BiOCl层状半导体发光性能的影响。利用X射线衍射(XRD)、X射线光电子能谱(XPS)、扫描电镜(SEM)、傅里叶变换红外光谱(FT-IR)、激发-发射光谱、荧光寿命衰减曲线对样品的结构和性能进行表征。研究发现, 随Zn²⁺掺杂浓度增大, BiOCl晶体结构不变, Eu³⁺荧光寿命延长, 但发光强度却出现先减后增的反常现象。综合分析表明这可能与BiOCl特殊的层状结构有关。通过XRD和XPS的表征可以推断: 当Zn²⁺掺杂浓度≤10mol%, Zn²⁺在BiOCl中掺杂方式以晶胞层间隙掺杂为主; 当Zn²⁺掺杂浓度>10mol%后, 掺杂方式逐渐向取代掺杂转变。两种掺杂机制对Eu³⁺荧光寿命的改变以及形成缺陷对基质能量传递效率的影响可能是形成上述反常现象的主要原因。研究结果有助于认识稀土掺杂层状半导体的发光性能及影响规律, 并对Eu³⁺掺杂BiOCl这类新型发光材料的开发设计具有指导意义。

关键词: BiOCl, Eu³⁺离子, Zn²⁺掺杂, 层状半导体

Abstract:

Eu³⁺-activated BiOCl layered phosphors induced by doping Zn²⁺ were prepared by traditional solid reaction method, and the effect of Zn²⁺ ion dopants (0-20mol%) on the photoluminescence properties were characterized by X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), Fourier transform infrared absorption (FT-IR), excitation and emission spectra, and luminescence decay curves measurement. It is found that increase of concentration of Zn²⁺ ion dopants almost has no influence on the structure of BiOCl crystals but decreases the emission intensity of Eu³⁺ ion at first and then increases it, accompanying with continually enhancing luminescence lifetime of Eu³⁺ ions. The comparative experiments suggest that this results are involved in special layered structure of BiOCl semiconductor. Zn²⁺ ions would be incorporated into interlayer space of the BiOCl layered crystals when the concentration of Zn²⁺ ions ≤10%. Then, Zn²⁺ ions tend to incorporate into crystal lattices by substituting Bi³⁺ ions. Different doping mechanism of Zn²⁺ may change Eu³⁺ lifetime and modify energy transfer efficiency from the host, leading to above emission behavior of Eu³⁺ ion dopants. The result is helpful to improve performance of novel red Eu³⁺ doped BiOCl phosphor and to understand emission property of rare earth ion in layered phosphors.

Key words: BiOCl, Eu³⁺ ion, Zn²⁺ doped, layered semiconductor

中图分类号:

TQ174

陈凡丽, 李永进, 张相周, 徐祖元, 胡锐, 邱建备, 杨正文, 宋志国. Zn²⁺掺杂诱导Eu³⁺激活BiOCl层状半导体的反常发光性能研究[J]. 无机材料学报, 2017, 32(8): 877-883.

CHEN Fan-Li, LI Yong-Jin, ZHANG Xiang-Zhou, XU Zhu-Yuan, HU Rui, QIU Jian-Bei, YANG Zheng-Wen, SONG Zhi-Guo. Anomalous Emission Performance of Eu³⁺-activated BiOCl Layered Phosphors Induced by Doping Zn²⁺[J]. Journal of Inorganic Materials, 2017, 32(8): 877-883.

图/表 8

图1 (a) BiOCl: 1%Eu3+荧光粉激发光谱(λem= 698 nm), (b) 335 nm激发下的Bi(1-x-0.01)Eu0.01ZnxOCl(x = 0, 5%, 10%, 15%, 20%)的发射光谱和(c) 594 nm、620 nm和698 nm处发光强度随Zn2+离子浓度变化关系图

Fig. 1 (a) Excitation spectrum of BiOCl: Eu3+ phosphor recorded at λem= 698 nm, (b) emission spectra of Bi(1-x-0.01) Eu0.01ZnxOCl (x = 0, 5%, 10%, 15%, 20%) phosphor exciting at 335 nm, and (c) change of the emission intensity of 594, 620 and 698 nm with Zn2+ concentration

表1 I620 nm/I594 nm和I698 nm/I620 nm随Zn2+离子浓度变化

Table 1 Change of the ratios of I620 nm/I594 nm and I698 nm/I620 nm with Zn2+ concentration

Zn²⁺ /mol%	I_{620 nm}/I_{594 nm}	I_{698 nm}/I_{620 nm}
0	2.73	2.04
5	2.89	2.02
10	2.90	1.81
15	2.97	1.79
20	3.17	1.77

图2 (a) Bi(1-x-0.01)Eu0.01ZnxOCl (x = 0, 5%, 10%, 15%, 20%, 摩尔百分比)的XRD图谱和(b) Zn2+掺杂浓度对BiOCl主衍射峰位置的影响(2θ=32.2º~34º)

Fig. 2 (a) XRD patterns of Bi(1-x-0.01)Eu0.01ZnxOCl (x = 0, 5%, 10%, 15%, 20%) phosphors and (b) effect of Zn2+ concentration on the main diffraction peaks near 2θ = 32.2º~34º

表2 Bi(1-x-0.01)Eu0.01ZnxOCl晶格常数随Zn2+浓度的变化

Table 2 Lattice constants of Bi(1-x-0.01)Eu0.01ZnxOCl phosphor with different Zn2+ concentrations

Zn²⁺/mol%		Lattice constant /nm
Zn²⁺/mol%		a=b	c
0	0.3887±0.0001		0.7358±0.0001
5	0.3889±0.0002		0.7361±0.0002
10	0.3898±0.0003		0.7383±0.0001
15	0.3883±0.0002		0.7348±0.0007
20	0.3874±0.0003		0.7326±0.0013

图3 Bi(1-x-0.01)Eu0.01ZnxOCl (x = 0, 10%, 20%, 摩尔百分比)的XPS图谱

Fig. 3 XPS spectra of Bi(1-x-0.01)Eu0.01ZnxOCl (x = 0, 10%, 20%) phosphors

图4 Bi(1-x-0.01)Eu0.01ZnxOCl (x = 0, 5%, 10%, 15%, 20%, 摩尔百分比)的SEM照片

Fig. 4 SEM images of Bi(1-x-0.01)Eu0.01ZnxOCl (x = 0, 5%, 10%, 15%, 20%) phosphors

图5 Bi(1-x-0.01)Eu0.01ZnxOCl(x = 0, 5%, 10%, 15%, 20%, 摩尔百分比)荧光粉的FT-IR图谱

Fig. 5 FT-IR spectra of Bi(1-x-0.01)Eu0.01ZnxOCl (x = 0, 5%, 10%, 15%, 20%) phosphor

图6 335 nm激发下Bi(1-x-0.01)Eu0.01ZnxOCl(x = 0, 5%, 10%, 15%, 20%, 摩尔百分比)度荧光粉(a)620 nm (5D1→7F2)和(b) 698 nm(5D0→7F4)发射的荧光衰减曲线图

Fig. 6 Luminescence decay curves of (a) 5D0→7F2 and (b) 5D0→7F4 transitions of Eu3+ ions in BiOCl crystals with different Zn2+ dopant concentrations

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Zn²⁺掺杂诱导Eu³⁺激活BiOCl层状半导体的反常发光性能研究

Anomalous Emission Performance of Eu³⁺-activated BiOCl Layered Phosphors Induced by Doping Zn²⁺

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