Zn3Ga2Ge2O10： Cr3+， Pr3+纳米磷光体的发光特性、第一性原理计算和剂量率响应研究

doi:10.11949/0438-1157.20250310

化工学报 ›› 2025, Vol. 76 ›› Issue (12): 6739-6747.DOI: 10.11949/0438-1157.20250310

• 材料化学工程与纳米技术 • 上一篇下一篇

Zn₃Ga₂Ge₂O₁₀： Cr³⁺， Pr³⁺纳米磷光体的发光特性、第一性原理计算和剂量率响应研究

陈俊廷¹(), 陈泽鑫², 赖铭浩³, 张佳琳², 郭竞渊¹(), 熊正烨¹

^1.广东海洋大学电子与信息工程学院，广东湛江 524088
^2.广东海洋大学化学与环境学院，广东湛江 524088
^3.深圳大学机电与控制工程学院，广东深圳 518054

收稿日期:2025-03-27 修回日期:2025-05-21 出版日期:2025-12-31 发布日期:2026-01-23
通讯作者: 郭竞渊
作者简介:陈俊廷（2003—），男，本科生，2549878577@qq.com
基金资助:
广东海洋大学博士启动基金项目(060302112102)

Luminescence characterization, first-principle calculations and dose-rate response studies of Zn₃Ga₂Ge₂O₁₀: Cr³⁺, Pr³⁺ nanophosphors

Junting CHEN¹(), Zexin CHEN², Minghao LAI³, Jialin ZHANG², Jingyuan GUO¹(), Zhengye XIONG¹

^1.College of Electronic and Information Engineering, Guangdong Ocean University, Zhanjiang 524088, Guangdong, China
^2.School of Chemistry and Environment, Guangdong Ocean University, Zhanjiang 524088, Guangdong, China
^3.College of Electromechanical and Control Engineering, Shenzhen University, Shenzhen 518054, Guangdong, China

Received:2025-03-27 Revised:2025-05-21 Online:2025-12-31 Published:2026-01-23
Contact: Jingyuan GUO

摘要/Abstract

摘要：

Zn₃Ga₂Ge₂O₁₀（ZGGO）是一种具有优异性能的近红外长余辉基质材料，广泛应用于夜视、防伪、光学记录和生物成像等新技术上。采用柠檬酸溶胶-凝胶方法制备了ZGGO：Cr³⁺，Pr³⁺纳米磷光体材料。测试结果表明，晶体结构不随着杂质的掺入而改变，样品纯度较高，颗粒尺度在500 nm左右，且样品可被X射线和410 nm的蓝光有效激发，特征发射峰位于700 nm和715 nm，对应于Cr离子的²E和⁴T₂(⁴F) 能级到⁴A₂能级的跃迁。在X射线的辐照下，样品热释光灵敏度较高，其主要发光峰温度为389 K，ZGGO：Cr³⁺，Pr³⁺的热释光强度明显高于ZGGO：Cr³⁺。由DFT结果可知ZGGO：Cr³⁺，Pr³⁺比ZGGO： Cr³⁺的能带间隙更窄、能带明显变密集，说明双掺杂样品更有利于电子的转移。剂量率响应结果表明其辐射发光随X射线剂量率的增加而增加，并呈良好的线性关系。因此，ZGGO：Cr³⁺，Pr³⁺长余辉纳米荧光粉具有实时剂量率测量的潜力，对剂量学研究和应用有重要的参考意义。

关键词: 镓锗酸锌, Cr³⁺, 长余辉, 凝胶, 磷光体

Abstract:

Zn₃Ga₂Ge₂O₁₀ (ZGGO) is considered a near-infrared (NIR) long-afterglow matrix material with excellent performance and is widely used in new technologies such as night vision, anti-counterfeiting, optical recording, and bioimaging. ZGGO: Cr³⁺, Pr³⁺ nanometer phosphor materials were prepared by citric acid sol-gel method. XRD results show that the crystal structure does not change with the inclusion of impurities, and the sample purity is high. The SEM results show that the particle size of the sample is about 500 nm. PL results show that the sample can be efficiently excited by X-ray and 410 nm blue light, and the characteristic emission wavelength is located at 700 nm and 715 nm, corresponding to transitions from the ²E and ⁴T₂(4F) energy levels to the ⁴A₂. TL3D results show that the sample has high thermoluminescence sensitivity under X-ray irradiation, and its main luminescent peak temperature is 389 K. TL results show that the thermoluminescence intensity of ZGGO: Cr³⁺, Pr³⁺ was significantly higher than that of ZGGO: Cr³⁺. DFT results show that ZGGO: Cr³⁺, Pr³⁺ has narrower band gaps and significantly denser bands than ZGGO: Cr³⁺, indicating that double-doped samples are more conducive to electron transfer. The XEL results show that the radiation luminescence increases with the increase of X-ray dose rate, and the relationship is linear. Therefore, ZGGO: Cr³⁺, Pr³⁺ long-afterglow nano-phosphors have the potential of real-time dose rate measurement, and have important reference significance in dosimetry research and application.

Key words: zinc gallium germanate, Cr³⁺, long-afterglow, gels, phosphor

中图分类号:

O 483

陈俊廷, 陈泽鑫, 赖铭浩, 张佳琳, 郭竞渊, 熊正烨. Zn₃Ga₂Ge₂O₁₀： Cr³⁺， Pr³⁺纳米磷光体的发光特性、第一性原理计算和剂量率响应研究[J]. 化工学报, 2025, 76(12): 6739-6747.

Junting CHEN, Zexin CHEN, Minghao LAI, Jialin ZHANG, Jingyuan GUO, Zhengye XIONG. Luminescence characterization, first-principle calculations and dose-rate response studies of Zn₃Ga₂Ge₂O₁₀: Cr³⁺, Pr³⁺ nanophosphors[J]. CIESC Journal, 2025, 76(12): 6739-6747.

图/表 11

图1 Zn3Ga2Ge2O10 : Cr3+，Pr3+样品XRD谱图与标准XRD卡的对比

Fig.1 Comparison of the XRD pattern of Zn3Ga2Ge2O10 : Cr3+,Pr3+ sample d and the standard XRD cards

图2 Zn3Ga2Ge2O10 : Cr3+,Pr3+样品的SEM图

Fig.2 SEM images of the Zn3Ga2Ge2O10 : Cr3+,Pr3+

图3 ZGGO基质和引入Cr3+和Pr3+后样品的晶体结构示意图

Fig.3 Schematic crystal structure of ZGGO and the sample after introduction of Cr3+ and Pr3+

图4 Zn3Ga2Ge2O10:Cr3+,Pr3+的TL发光曲线

Fig.4 TL glow curve of Zn3Ga2Ge2O10:Cr3+,Pr3+

表1 Zn3Ga2Ge2O10：Cr3+，Pr3+的TL发光曲线主要发光峰的动力学参数

Table 1 Kinetics parameters of glow peaks in TL glowcurve of Zn3Ga2Ge2O10：Cr3+，Pr3+

No.	Temperature of TL peak/℃	E(activation energy of the captured electrons)/eV	s(frequency factor)/s^-1	n₀(electron concentration)	b(kinetic order)
Peak1	73.80	0.60	5.6×10⁷	1.29×10⁷	2
Peak2	103.80	1.01	4.9×10¹²	5.04×10⁶	2
Peak3	131.01	1.14	2.9×10¹³	5.67×10⁶	2
Peak4	159.40	1.32	3.8×10¹⁴	3.14×10⁶	1.97
Peak5	193.90	0.75	1.0×10⁷	5.49×10⁶	2

图5 Zn3Ga2Ge2O10:Cr3+与Zn3Ga2Ge2O10:Cr3+,Pr3+的TL强度对比

Fig.5 TL intensity comparison of Zn3Ga2Ge2O10:Cr3+ and Zn3Ga2Ge2O10:Cr3+,Pr3+

图6 ZGGO:Cr3+,Pr3+在室温下的PL光谱

Fig.6 PL spectrum of ZGGO:Cr3+,Pr3+ phosphor

图7 ZGGO:Cr3+,Pr3+、ZGGO:Cr3+在波长410 nm激发下的发射谱对比

Fig.7 Comparison of emission spectra of ZGGO:Cr3+,Pr3+ and ZGGO:Cr3+ under excitation at wavelength 410 nm

图8 ZGGO:Cr3+,Pr3+在X射线辐照后的TL3D光谱(100~650 K)

Fig.8 TL3D spectra of ZGGO:Cr3+,Pr3+ after X-ray irradiation (100—650 K)

图10 ZGGO基质(a)，ZGGO:Cr3+(b)和ZGGO:Cr3+,Pr3+(c)的分波态密度以及总态密度

Fig.10 Split-wave state densities and total state density of ZGGO matrix (a), ZGGO:Cr3+ (b) and ZGGO:Cr3+,Pr3+ (c)

图11 (a) ZGGO:Cr3+,Pr3+在不同剂量率X射线下的XEL光谱；(b) XEL强度与剂量率之间的现线性关系

Fig.11 (a)XEL spectra of ZGGO:Cr3+,Pr3+ at different dose rate X-rays；(b) A linear relationship between XEL intensity and dose rate

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Zn₃Ga₂Ge₂O₁₀： Cr³⁺， Pr³⁺纳米磷光体的发光特性、第一性原理计算和剂量率响应研究

Luminescence characterization, first-principle calculations and dose-rate response studies of Zn₃Ga₂Ge₂O₁₀: Cr³⁺, Pr³⁺ nanophosphors

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