硅铬共掺杂尖晶石长余辉材料Zn1+xGa2-2xSixO4:Cr3+中近红外余辉的增强及陷阱分布分析

doi:10.15541/jim20180586

摘要/Abstract

摘要：

本论文基于硅铬共掺杂, 合成得到了一种尖晶石长余辉材料Zn₁₊_xGa_2-2_xSi_xO₄:Cr ³⁺。实验采用高温固相法, 按照设计的化学计量比精确称量ZnO、Ga₂O₃、SiO₂和Cr₂O₃等原料, 制备了一系列硅铬共掺杂的镓酸锌尖晶石长余辉材料, 其化学式为Zn₁₊_xGa_2-2_xSi_xO₄:Cr ³⁺(x=0, 0.1, 0.15, 0.2, 0.5, 1)。实验结果表明: 采用硅铬共掺杂方式后, 引入合适浓度的硅离子可有效改善余辉性能。当x=0.2时, 样品余辉强度最佳, 相比ZnGa₂O₄:Cr ³⁺增强了3倍, 并且余辉持续时间长达24 h。进一步的陷阱分布分析表明, 在ZnGa₂O₄基质基础上引入硅掺杂, 可有效调控不同陷阱深度的分布。即在丰富的反位缺陷基础上, 硅的共掺杂可增加不等价替换缺陷和填隙缺陷等, 并可调控禁带宽度及缺陷形成, 从而实现改善余辉性能的目的。

关键词: Zn₁₊_xGa_2-2_xSi_xO₄:Cr³⁺, 长余辉, 不等价掺杂, 陷阱分布

Abstract:

Co-doping of silicon in zinc gallate spinel persistent luminescent phosphor was adopted to enhance the afterglow properties. Firstly, a series of silicon-chromium co-doping zinc gallate spinel samples were prepared by high temperature solid state reaction method. Phosphor with chemical formula of Zn₁₊_xGa_2-2_xSi_xO₄:Cr ³⁺ (x = 0, 0.1, 0.15, 0.2, 0.5, 1) was obtained with the raw materials of ZnO, Ga₂O₃, SiO₂, and Cr₂O₃. The experimental results show that the introduction of suitable concentration of silicon improves the afterglow performance effectively. The strongest afterglow intensity was obtained for sample with x = 0.2, which is 3 times higher than ZnGa₂O₄:Cr ³⁺, and the afterglow duration is up to 24 h. Through further trap distribution analysis, it is shown that the introduction of silicon in the ZnGa₂O₄ host can regulate the distribution of trap depths. Particularly, besides the antisite defects, the co-doping of silicon can induce the formation of aliovalent substitution defects and interstitial defects, as well as tune the band gap value, thereby achieving the purpose of improving the afterglow performance.

Key words: Zn₁₊_xGa_2-2_xSi_xO₄:Cr³⁺, persistent luminescence, non-equivalent doping, trap distribution

中图分类号:

TQ174

王锴, 严丽萍, 邵康, 张聪, 潘再法. 硅铬共掺杂尖晶石长余辉材料Zn₁₊_xGa_2-2_xSi_xO₄:Cr³⁺中近红外余辉的增强及陷阱分布分析[J]. 无机材料学报, 2019, 34(9): 983-990.

WANG Kai, YAN Li-Ping, SHAO Kang, ZHANG Cong, PAN Zai-Fa. Near-infrared Afterglow Enhancement and Trap Distribution Analysis of Silicon-chromium Co-doped Persistent Luminescence Materials Zn₁₊_xGa_2-2_xSi_xO₄:Cr³⁺[J]. Journal of Inorganic Materials, 2019, 34(9): 983-990.

图/表 11

表1 硅铬共掺杂长余辉材料的化学组成

Table 1 Chemical composition of silicon-chromium co-doped persistent luminescent material

Sample	x	Chemical components
ZGO1	0	ZnGa₂O₄: Cr³⁺
ZGSiO2	0.1	Zn_1.1Ga_1.8Si_0.1O₄: Cr³⁺
ZGSiO3	0.15	Zn_1.15Ga_1.7Si_0.15O₄:Cr³⁺
ZGSiO4	0.2	Zn_1.2Ga_1.6Si_0.2O₄: Cr³⁺
ZGSiO5	0.5	Zn_1.5GaSi_0.5O₄: Cr³⁺
ZSiO6	1	Zn₂SiO₄: Cr³⁺

图1 ZGSiO系列样品的XRD图谱以及ZnGa2O4和Zn2SiO4标准衍射峰

Fig. 1 XRD patterns of ZGSiO series samples and standard diffraction peak of ZnGa2O4 and Zn2SiO4

图2 ZGSiO4的HRTEM照片(a)和电子衍射照片(b)

Fig. 2 HRTEM image (a) and electron diffraction pattern (b) of ZGSiO4

图3 ZGSiO系列样品漫反射吸收光谱图(a)和${{(h\nu \times F({{R}_{\infty }}))}^{2}}-h\nu$曲线(b)(以切线与x轴截距估算带隙能量)

Fig. 3 Diffuse reflection absorption spectra (a) and ${{(h\nu \times F({{R}_{\infty }}))}^{2}}-h\nu $ diagram (b) of ZGSiO series samples (band gap energy is estimated by intercept of the tangential)

图4 ZGSiO系列样品的激发光谱图(a)和发射光谱图(b)

Fig. 4 Excitation (a) and emission (b) spectra of ZGSiO series samples

图5 ZGSiO系列样品的余辉发射光谱(a)和余辉衰减曲线(b)

Fig. 5 Afterglow emission spectra (a) and decay curves (b) of ZGSiO series samples

图6 ZGSiO4在272 (a)和620 nm(b)波长的光照下循环5次的余辉衰减曲线

Fig. 6 Five cycles afterglow decay curves of ZGSiO4 illuminated at 272 (a) and 620 nm (b)

图7 ZGO1~ZGSiO5的热释曲线(a)和峰强度对比(b)

Fig. 7 TL curves (a) and peak intensities (b) of ZGO1-ZGSiO5

表2 ZGSiO系列样品TL峰的陷阱深度

Table 2 Trap depths of TL peaks of ZGSiO series samples

Trap Type	Type Ⅰ			Type Ⅱ
Trap Type	Temperature/K	Depth/eV		Temperature/K	Depth/eV
ZGO1	357	0.71	420		0.84
ZGSiO2	353	0.71	414		0.83
ZGSiO3	356	0.71	415		0.83
ZGSiO4	355	0.71	417		0.83
ZGSiO5	354	0.71	411		0.82

图8 不同清空温度处理后ZGSiO4样品的热释发光曲线(a)(加热速率, 20 K/min)和热释曲线的初始上升法分析(b)

Fig. 8 TL curves (a) (heating rate, 20 K/min) and initial rise analysis of TL curves (b) of ZGSiO4 sample after treatment at different emptying temperatures

图9 ZGSiO4样品在氙灯激发10 min后不同延迟时间下的热释衰减曲线(a)和陷阱密度-时间分布(b)

Fig. 9 TL curves (a) and trap density-time distribution (b) of ZGSiO4 sample at different delay time after 10 min excitation of xenon lamp

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硅铬共掺杂尖晶石长余辉材料Zn₁₊_xGa_2-2_xSi_xO₄:Cr³⁺中近红外余辉的增强及陷阱分布分析

Near-infrared Afterglow Enhancement and Trap Distribution Analysis of Silicon-chromium Co-doped Persistent Luminescence Materials Zn₁₊_xGa_2-2_xSi_xO₄:Cr³⁺

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