纳米金刚石基稀土杂化发光材料的制备及发光性能的研究

发布时间：2018-02-28 04:45

本文关键词： 纳米金刚石(NDs) 稀土杂化材料光电特性　出处：《郑州大学》2017年硕士论文　论文类型：学位论文

【摘要】：近年来,纳米金刚石(NDs)由于其化学物理稳定性、丰富的表面基团和低毒性等优异性质,使其在光学和生物医学领域中引起了全世界的注意。然而,对于初级尺寸为3~5 nm的NDs的发光通常非常差,这已经变成阻碍其在生物成像和发光装置中应用的巨大障碍。因此,对如何弥补NDs的发光弱的研究就显得尤为重要。基于以上考虑,本论文主要通过一系列简单的液相化学合成和修饰方法来制备了一系列的纳米金刚石基稀土杂化发光材料,并对其形貌结构、发光性能和潜在应用进行了研究。主要取得了一下成果:1.纳米金刚石-均苯四甲酸-稀土杂化发光材料通过用稀土(RE)配合物共价官能化NDs表面来制备明亮的杂化发光材料。其中,均苯四甲酸(PMA)作为有机敏化剂,通过化学反应共价连接到氨基封端的NDs表面上以螯合镧系元素离子(Eu3+和Tb3+)的发光。通过调节Eu3+与Tb3+的摩尔比率(x:y=1:0、1:1、1:5和0:1),ND-PMA-EuxTby的杂化材料的发射颜色可以从红色分别调节到橙色、黄色和绿色。未共掺的ND-PMA-Eu和ND-PMATb杂化发光材料的荧光衰减曲线与相应的稀土配合物相比较可以得到我们所制备的杂化材料具有更长的寿命,分别是0.82和0.92 ms。此外,杂化复合材料在254 nm紫外灯下照射60 h,在该过程中其发光强度与稀土配合物相比衰减较慢,具有很好的光稳定性。值得注意的是为了验证所制备的杂化发光材料的应用前景,我们使用合成后的ND-PMA-Eu和ND-PMA-Tb作为磷光体,涂覆在紫外(UV)芯片(280 nm)上,通过封装工艺技术制备出了红色和绿色两种发光二极管(LED)器件。此外,我们对合成的杂化材料的温度传感特性进行了研究,发现共掺杂的复合材料ND-PMA-Eu1Tb5从10 K到300 K的温度范围内能够显示出明显的温度依赖性发光行为。在温度变化的过程中发生了从Tb离子到Eu离子的能量转移。因此,基于纳米金刚石的发光杂化材料可能在光学件、生物成像和温度传感等领域中发现潜在的应用。2.纳米金刚石-α-噻吩甲酰三氟丙酮-稀土杂化发光材料首先我们对α-噻吩甲酰三氟丙酮(TTA)进行了硅烷化,得到功能化的TTASi有机配体。通过使用TTA-Si作为有机敏化剂,共价连接到硅烷化的NDs表面上来螯合镧系元素离子Eu3+发光。结果显示,通过360 nm的激发波长激发下,可以得到稀土Eu离子的特征发射,该波长对目前成熟的器件封装工艺具有很大的优势。
[Abstract]:In recent years, nanocrystalline diamond (NDS) has attracted worldwide attention in the field of optics and biomedicine due to its excellent properties of chemical and physical stability, abundant surface groups and low toxicity. The luminescence of NDs with a primary size of 3 ~ 5 nm is usually very poor, which has become a huge obstacle to its application in biometric imaging and luminescence devices. It is very important to study how to make up for the weak luminescence of NDs. Based on the above considerations, a series of nanocrystalline diamond-based rare earth hybrid luminescent materials were prepared by a series of simple liquid-phase chemical synthesis and modification methods. And its morphology and structure, The luminescence properties and potential applications were studied. The main achievements were obtained: 1. Nanocrystalline diamond-phenyltetracarboxylic acid rare earth hybrid luminescent materials were prepared by covalent functionalized NDs surface of rare earth complexes to prepare bright hybrids. Luminous materials. Of which, Phenyltetracarboxylic acid (PMA) as an organic sensitizer, The luminescence of lanthanide ions EU _ 3 and Tb3) is chemically covalently attached to the surface of NDs with amino capping. The emission color of hybrid materials of ND-PMA-EU _ x Tby can be adjusted from red to orange by adjusting the molar ratio of Eu3 to Tb3 (x: 1: 0: 1: 1: 5 and 0: 1 / 1). Yellow and green. The fluorescence decay curves of undoped ND-PMA-Eu and ND-PMATb hybrid luminescent materials are 0.82 and 0.92 msrespectively, which are longer than those of the corresponding rare earth complexes. The luminescence intensity of hybrid composites irradiated under 254 nm ultraviolet lamp for 60 h is slower than that of rare earth complexes and has good light stability. It is worth noting that the application prospect of the hybrid luminescent materials is verified. Using synthesized ND-PMA-Eu and ND-PMA-Tb as phosphors and coated on UV UV chip 280nm), red and green LEDs were fabricated by packaging technology. In addition, We have studied the temperature sensing characteristics of the hybrid materials. It is found that the co-doped composite ND-PMA-Eu1Tb5 can exhibit obvious temperature-dependent luminescence behavior in the temperature range from 10K to 300K. The energy transfer from TB ion to EU ion takes place in the process of temperature change. Luminescent hybrid materials based on nanocrystalline diamond may be present in optical components, Nanocrystalline diamond-伪 -thiophene trifluoroacetone-rare earth hybrid luminescent materials were first silanized by 伪 -thiophenyl trifluoroacetone (TTAA). A functionalized TTASi organic ligand was obtained. By using TTA-Si as an organic sensitizer, the lanthanide ion Eu3 was chelated on the surface of silanized NDs by covalent ligand. The results showed that the ligand was excited by the excitation wavelength of 360nm. The characteristic emission of rare earth EU ion can be obtained, and this wavelength has a great advantage over the current mature device packaging technology.
【学位授予单位】：郑州大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O482.31

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