Dy, Cr共掺杂ZnGa2O4长余辉纳米粒子的制备及发光性能研究

doi:10.15541/jim20160079

摘要/Abstract

摘要：

以乙二醇辅助水热法制备了Dy³⁺, Cr³⁺共掺杂ZnGa₂O₄的小尺寸、近红外长余辉纳米粒子(PLNPs)。通过优化反应条件、锌的比例和共掺杂稀土离子Dy³⁺等措施, 不仅提高了PLNPs的余辉发光性能, 而且有效控制了PLNPs的粒径。结果表明, 当起始溶液pH为7、Ga:Zn的比例为2:1.2、Dy³⁺的掺杂量为1%时, 所合成的PLNPs的尺寸在6 nm左右, 而且具有良好的余辉发光性能, 其近红外余辉时间大于72 h, 在高信噪比生物医学成像中具有潜在应用价值。

关键词: 镓酸锌, 长余辉纳米颗粒, 余辉发光时间, 水热法, 近红外

Abstract:

Dy³⁺, Cr³⁺co-doped ZnGa₂O₄ persistent luminescence nanoparticles (PLNPs) with long near-infrared afterglow were synthesized by an ethylene glycol assisted hydrothermal method. Persistent luminescence properties of the PLNPs are improved and size of the PLNPs is controlled efficiently via optimization of reaction condition, modification of zinc ratio and co-doping of Dy³⁺ ion. The results show that the PLNPs have long afterglow time more than 72 h and small grain size of approximately 6 nm, when the pH of the reaction solution, Ga:Zn ratio and doping amount of Dy³⁺ are 7, 2:1.2 and 1%, respectively. The as-prepared PLNPs exhibit great potential as a molecular probe for biomedical imaging with high signal to noise ratio.

Key words: zinc gallate, persistent luminescence nanoparticles, afterglow time, hydrothermal method, near infrared

中图分类号:

TQ174

阿不都卡德尔·阿不都克尤木, 艾力江·吐尔地, 热娜古丽·阿不都热合曼, 马木提江·吐尔逊, 努尔比亚·努尔买提. Dy, Cr共掺杂ZnGa₂O₄长余辉纳米粒子的制备及发光性能研究[J]. 无机材料学报, 2016, 31(12): 1363-1369.

ABDUKAYUM Abdukader, TUERDI Ailijiang, ABDURAHMAN Renagul, TURSUN Mamutjan, NURMAT Nurbiya. Synthesis and Luminescence Properties of Dy,Cr Co-doped ZnGa₂O₄Persistent Luminescence Nanoparticles[J]. Journal of Inorganic Materials, 2016, 31(12): 1363-1369.

图/表 8

图1 起始溶液pH对ZnGa2O4:Cr3+的(a)激发和(b)发射光谱的影响

Fig. 1 (a) Excitation and (b) emission spectra of the ZnGa2O4:Cr3+ prepared in solution with different Ph^n(Ga):n(Zn)=2:1, c(Dy)=0

图2 不同Ga:Zn比例的ZnGa2O4:Cr3+的发射光谱图

Fig. 2 Emission spectra of the ZnGa2O4:Cr3+ with different Ga:Zn ratios^pH=7, cDy=0

图3 Dy3+, Cr3+ 共掺杂ZnGa2O4的发射光谱

Fig. 3 Emission spectra of the Dy3+, Cr3+ co-doped ZnGa2O4^n(Ga):n(Zn)=2:1.2, pH=7

图4 (a~c)在不同pH起始溶液中制备的和(d~g)不同含量Dy3+共掺杂的ZnGa2O4:Cr3+纳米颗粒TEM照片; (h)1% Dy3+共掺杂的ZnGa2O4: Cr3+纳米颗粒粒径分布图

Fig. 4 TEM images of ZnGa2O4: Cr3+ (a-c) prepared in solution with different pH and (d-e) co-doped with different amounts of Dy3+, (h) nanoparticles size distribution of 1% Dy3+ co-doped ZnGa2O4: Cr3+ ^(a) pH = 11, (b) pH = 9 and (c) pH = 11 with n(Ga):n(Zn)=2:1, cDy=0; (d) 0.8 % Dy3+ , (e) 1.0% Dy3+ , (f) 1.2% Dy3+ and (g) 1.5% Dy3+ with n(Ga):n(Zn)=2:1.2, pH=7

图5 (a~c) 在不同pH起始溶液中制备和 (d~g)不同含量Dy3+共掺杂的ZnGa2O4:Cr3+纳米颗粒XRD图谱

Fig. 5 XRD patterns of ZnGa2O4: Cr3+ (a-c) prepared in solution with different pH (d-g) and co-doped with different amounts of Dy3+^(a) pH = 11, (b) pH = 9 and (c) pH = 11 with n(Ga):n(Zn)=2:1, cDy=0; (d) 0.8 % Dy3+ , (e) 1.0% Dy3+ , (f) 1.2% Dy3+ and (g) 1.5% Dy3+ with n(Ga):n(Zn)=2:1.2, pH=7

图6 (a) 在不同pH起始溶液中制备和 (b)不同含量Dy3+共掺杂的ZnGa2O4:Cr3+纳米颗粒的余辉衰减曲线

Fig. 6 Afterglow decay curve of ZnGa2O4: Cr3+ (a) prepared in solution with different pH and (b) co-doped with different amounts of Dy3+^(a) n(Ga):n(Zn)=2:1, cDy=0; (b) n(Ga):n(Zn)=2:1.2, pH=7

表1 NIR余辉发光衰减曲线拟合参数

Table 1 The parameters of NIR afterglow decay curve fitting

τ₁/s	A₁	τ₂/s	A₂	τ₃/s	A₃
6.56±0.02	41280.54	70.82±0.95	910.07	292.61±6.73	208.62

图7 (a) ZnGa2O4:Cr3+, Dy3+的余辉光谱、(b) NIR余辉衰减曲线、(c) NIR余辉图和(d)NIR余辉发光机理示意图

Fig. 7 (a) Persistent luminescence spectra of the ZnGa2O4:Cr3+, Dy3+ at 1, 2, 3, 5, 10, 20, 30, 40, 50, and 60 min after stopping excitation; (b) NIR afterglow decay curve of the ZnGa2O4:Cr3+, Dy3+; (c) NIR afterglow images of the ZnGa2O4:Cr3+, Dy3+ at different times; (d) NIR persistent luminescence mechanism in the ZnGa2O4:Cr3+, Dy3+^n(Ga):n(Zn)=2:1, pH=7, cDy =1%

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Dy, Cr共掺杂ZnGa₂O₄长余辉纳米粒子的制备及发光性能研究

Synthesis and Luminescence Properties of Dy,Cr Co-doped ZnGa₂O₄Persistent Luminescence Nanoparticles

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