基于模板法的银纳米结构的可控制备及其SERS性能调控研究

发布时间：2018-05-06 00:45

本文选题：超薄氧化铝模板 + 银点阵　；参考：《上海大学》2015年硕士论文

【摘要】：超薄氧化铝模板(ultra-thin alumina mask,UTAM)作为多孔氧化铝模板的一种特殊结构,具有大面积、结构参数(大小、间距、形貌)可控、超高密度、高产出、低设备投入等优点。这些优点使得UTAM表面纳米制备方法被认为是很有前景的表面纳米阵列结构制备技术。基于氧化铝模板开发的铝凹坑阵列模板法同样具有上述优点,其也具有易操作、不需转移、不需去除模板等独有的优点。表面增强拉曼散射(Surface-enhanced Raman Scattering,SERS)目前被广泛认为是检测和表征低浓度生物和化学试剂分子最强大的光谱工具。已被广泛用于生物、化学传感技术中痕量分析物的检测,表面增强拉曼光谱技术克服了普通拉曼光谱技术低灵敏度的缺点。在生物、化学、医学应用以及环境监测的领域有着广泛的应用。目前,具有大量可控的“热点”、信号均一、可重复性好、大面积、低成本、性能可靠的SERS活性基底的制备仍是SERS研究中的巨大挑战。本论文首次利用调控超薄氧化铝模板的高径比来制备不同结构形貌的金属银纳米点阵作为SERS基底,得到了罗丹明6G(Rhodamine 6G,R6G)分子水溶液在金属银纳米点阵基底上的SERS光谱,并探索了其SERS性能。UTAM具有高度有序的紧密六角排列、超高密度的纳米孔阵列的结构,在制备UTAM的过程中,经过一次氧化之后去除氧化层得到的具有规则有序的六边形纳米阵列结构的铝基底是制备UTAM的必要条件。本论文首次利用了经过一次氧化之后去除氧化层的铝基底为模板,制备了结构新颖的大面积有序的嵌入式金属银纳米阵列,用R6G分子水溶液作为探针分子,对其SERS性能进行研究,并且考察了其制备条件对结构的影响。具体内容归纳如下:1.在温度2℃条件下浓度0.3 M草酸电解质溶液中采用两步阳极氧化法制备了结构高度有序的UTAM,通过改变氧化电压,扩孔时间,二次氧化时间制备了一系列结构参数可调可控的UTAM。利用扫描电子显微镜(SEM)对这些不同结构参数的UTAM进行形貌表征。2.我们利用通过改变二次氧化时间制备的UTAM作为蒸发掩模板,采用真空镀膜技术制备了大面积高度有序的银纳米点阵。首次利用调控超薄氧化铝模板的高径比来制备不同结构形貌的金属银纳米点阵作为SERS基底,得到了R6G分子水溶液在金属银纳米点阵基底上的SERS光谱,并探索了其SERS性能。3.利用UTAM一次氧化后去除氧化层留下的具有有序凹坑阵列的铝基底为模板,采用真空气相沉积技术,成功制备了新型的有序嵌入式银纳米点阵结构。选用R6G作为探针分子,探索嵌入式银纳米点阵基底的SERS性能。结果表明,这种新型的嵌入型纳米结构具有很高的SERS活性,R6G分子浓度为10-10 M时增强因子高达3.74×1010,检出浓度低至10-11 M。因此这种基底可用于化学物质和生物分子的痕量检测和分析。与此同时我们还研究了制备条件(氧化电压、蒸发厚度、蒸发速率)对这种嵌入式纳米点阵的结构及其SERS性能的影响,最终得到制备这种结构的最佳优化条件。
[Abstract]:Ultra-thin alumina mask (UTAM), as a special structure of porous alumina template, has the advantages of large area, controllable structure parameters (size, spacing, morphology), high density, high yield, low input and so on. These advantages make the nano preparation method of UTAM surface is considered as a promising surface nanoarray junction. The aluminum concave pit array template based on alumina template also has the advantages mentioned above. It also has the advantages of easy operation, no transfer, and no need to remove the template. Surface enhanced Raman scattering (Surface-enhanced Raman Scattering, SERS) is currently widely considered to be the detection and characterization of low concentration biological and chemical tests. The most powerful spectroscopic tools have been widely used in the detection of trace analytes in biological and chemical sensing techniques. Surface enhanced Raman spectroscopy has overcome the disadvantages of low sensitivity in common Raman spectroscopy. It has been widely used in the fields of biology, chemistry, medical applications and environmental monitoring. The preparation of SERS active substrates with high signal uniformity, good repeatability, large area, low cost and reliable performance is still a great challenge in the study of SERS. In this paper, the high diameter ratio of ultrathin alumina templates was used for the first time to prepare metallic silver nanoparticles with different structure morphology as the SERS substrate, and Luo Danming 6G (Rhodamine 6G, R6G) was obtained. The SERS spectra of the molecular water solution on the metal silver nanoparticle substrate, and explore the structure of the highly ordered compact six angle array, the ultrahigh density nanoscale array of the SERS property.UTAM, and the regular ordered hexagonal nanoarray structure obtained after the oxidation layer was removed after one oxidation. The aluminum substrate is a necessary condition for the preparation of UTAM. In this paper, a novel and highly ordered embedded metallic silver nanoarray has been prepared by using the aluminum substrate of the oxidation layer after one oxidation. The R6G molecular water solution is used as a probe molecule, and its SERS properties are studied and the preparation conditions are investigated. The specific content of the structure is summarized as follows: 1. a highly ordered UTAM was prepared by two step anodizing in the concentration of 0.3 M oxalic acid electrolyte at 2 centigrade temperature. A series of adjustable UTAM. using scanning electron microscope (SEM) was prepared by changing the oxidation voltage, reaming time, and two times of oxidation time. UTAM morphology characterization of these different structural parameters.2. we use UTAM as an evaporative mask by changing the two times of oxidation time to prepare a large area and highly ordered silver nano lattice by vacuum coating technology. For the first time, the high diameter ratio of ultra-thin alumina template is used to prepare metal silver nanoscale with different structure morphology. As the SERS substrate, the SERS spectra of the R6G molecule water solution on the metal silver nano lattice base are obtained. The aluminum substrate with the ordered concave array with the ordered concave array left by the UTAM first oxidation after the UTAM one oxidation is explored, and the new type of ordered embedded silver nanostructure is successfully prepared by vacuum vapor deposition. R6G is used as a probe to explore the SERS properties of embedded silver nanolattice substrates. The results show that this new type of embedded nanostructure has high SERS activity. When the concentration of R6G is 10-10 M, the enhancement factor is up to 3.74 x 1010 and the detection concentration is low to 10-11 M., so this substrate can be used in chemical and raw materials. At the same time, we also studied the influence of the preparation conditions (oxidation voltage, evaporation thickness, evaporation rate) on the structure of the embedded nanolattice and its SERS properties, and finally obtained the optimal optimization conditions for the preparation of this structure.

【学位授予单位】：上海大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：O614.122;TB383.1

【共引文献】