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退火对SrWO4:Ln(3+)(Dy(3+)、Eu(3+)和Sm(3+))纳米粒子的结构、光学和发光性能的影响

Effect of annealing on the structural, optical and emissive properties of SrWO4:Ln(3+) (Dy(3+), Eu(3+) and Sm(3+)) nanoparticles.

作者信息

Singh B P, Singh R A

机构信息

Department of Physics, Dr. Harisingh Gour University, Sagar 470003, India.

Department of Physics, Indian Institute of Technology (BHU), Varanasi 221005, India.

出版信息

Spectrochim Acta A Mol Biomol Spectrosc. 2016 Jan 5;152:199-207. doi: 10.1016/j.saa.2015.07.074. Epub 2015 Jul 20.

Abstract

Lanthanide ions, Ln(3+) (Dy(3+), Eu(3+) and Sm(3+)) doped SrWO4 nanoparticles were synthesized using ethylene glycol (EG) as a capping agent as well as reaction medium. The X-ray diffraction (XRD) study reveals that all the Ln(3+) (Dy(3+), Eu(3+) and Sm(3+)) doped samples are well crystalline in nature with a tetragonal scheelite structure of SrWO4 phase. TG study reveals that the nanophosphors are thermally stable. Fourier transform infrared spectroscopy (FTIR) and Raman spectroscopy techniques were used to obtain the information about internal and external vibrational modes present in the SrWO4 structure. Optical properties were investigated using UV-vis and photoluminescence (PL) spectroscopy. The average crystallite size was calculated using Debye-Scherrer's for as-prepared and 800°C annealed samples and is found to be in the range of ∼35-70nm. The luminescence intensity of Eu(3+) doped SrWO4 nanoparticles under 364nm excitation wavelength reveals that (5)D0→(7)F2 transition at ∼613nm (red) is more prominent than that of (5)D0→(7)F1 transition at ∼590nm (orange). Also upon excitation by UV radiation, the SrWO4:Dy(3+) phosphor shows the yellow and blue transition lines appearing at ∼572 and 484nm which are the characteristic electronic transitions of (4)F9/2-(6)H13/2 and (4)F9/2-(6)H15/2 emission line of Dy(3+), respectively. Also Sm(3+) doped SrWO4 nanophosphor shows its characteristic emission lines in the range of 550-720nm, corresponding to (4)G5/2→(6)HJ (J=5/2, 7/2, 9/2 and 11/2) transitions of Sm(3+) ions. The predominant orange red color can be attributed to (4)G5/2→(6)H9/2 located at ∼642nm. This is related to the polarizing effect due to the energy transfer from WO4(2-) to the Eu(3+), Dy(3+) and Sm(3+) sites, respectively. Effect of annealing on the photoluminescence properties of samples has been studied and it was found that luminescence intensity increases up to ∼3 times on heating the samples at 800°C. This may be due to reduction in non-radiative decay channels pathways and reduced surface defects associated with the samples. These studies show that these Ln(3+) (Dy(3+), Eu(3+) and Sm(3+)) doped SrWO4 nanophosphors may be used as potential candidates for the advancement in LEDs.

摘要

以乙二醇(EG)作为封端剂和反应介质,合成了镧系离子Ln(3+)(Dy(3+)、Eu(3+)和Sm(3+))掺杂的SrWO4纳米颗粒。X射线衍射(XRD)研究表明,所有Ln(3+)(Dy(3+)、Eu(3+)和Sm(3+))掺杂样品在本质上都是结晶良好的,具有SrWO4相的四方白钨矿结构。热重(TG)研究表明,纳米磷光体具有热稳定性。利用傅里叶变换红外光谱(FTIR)和拉曼光谱技术获取了SrWO4结构中存在的内部和外部振动模式的信息。使用紫外可见光谱和光致发光(PL)光谱研究了光学性质。使用德拜-谢乐公式计算了制备态和800°C退火样品的平均微晶尺寸,发现其在约35-70nm范围内。Eu(3+)掺杂的SrWO4纳米颗粒在364nm激发波长下的发光强度表明,在约613nm(红色)处的(5)D0→(7)F2跃迁比在约590nm(橙色)处的(5)D0→(7)F1跃迁更显著。此外,在紫外辐射激发下,SrWO4:Dy(3+)磷光体在约572和484nm处显示出黄色和蓝色跃迁线,它们分别是Dy(3+)的(4)F9/2-(6)H13/2和(4)F9/2-(6)H15/2发射线的特征电子跃迁。同样,Sm(3+)掺杂的SrWO4纳米磷光体在550-720nm范围内显示出其特征发射线,对应于Sm(3+)离子的(4)G5/2→(6)HJ(J = 5/2、7/2、9/2和11/2)跃迁。主要的橙红色可归因于位于约642nm处的(4)G5/2→(6)H9/2。这分别与从WO4(2-)到Eu(3+)、Dy(3+)和Sm(3+)位点的能量转移所导致的极化效应有关。研究了退火对样品光致发光性质的影响,发现将样品在800°C加热时发光强度增加了约3倍。这可能是由于非辐射衰减通道途径的减少以及与样品相关的表面缺陷的减少。这些研究表明,这些Ln(3+)(Dy(3+)、Eu(3+)和Sm(3+))掺杂的SrWO4纳米磷光体可能作为发光二极管发展的潜在候选材料。

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