表面均匀的、稳定的金膜的制备及其在表面增强拉曼光谱上的应用
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摘要
多年的研究表明,现已研制的SERS活性基底的种类主要有金属电极、金属溶胶、金属二维薄膜、化学刻蚀和化学沉积、双金属纳米粒子、富含结点的网络状结构、平板印刷及有序组装、针尖增强拉曼等作为探针分子用于表面增强拉曼光谱技术的检测。在这些基底中,两维的金属薄膜由于其具有稳定性、良好的重现性和高增强因子,因而被广泛的使用。在目前,有很多的方法来制备二维金属薄膜,例如:自组装法、电沉积法、模板法、光刻法、纳米印刷技术等。但后三种方法麻烦并且乏味,因此,自组装技术和电沉积技术由于其简便、并能够形成一个相对较为有序的形式,而成为一种制备二维金属膜的普遍方法。最近的研究表明,通过桥连剂链接ITO导电玻璃和金属纳米粒子可获得有序的二维金属膜,然而,要实现制备一种重现性好的SERS型活性基底仍然是一个艰巨的项目。
使用植酸钠盐作为架桥剂,由于其结构中共有12个酸根和六个磷酸酯根,可与金属离子相互作用。基于以上的性质,通过调节植酸pH值,以不同pH条件下的植酸为桥连剂就可以准备了一种具良好重现性和SERS活性的金膜。在前两个工作中我们制备具有SERS活性的金膜所用到的衬底有ITO玻璃。目前,常用到的用来制备二维纳米薄膜的衬底材料有硅片、金属薄片以及氧化铟锡玻璃(ITO)。由于这些材料具有易碎,僵硬的特点,因此,限制了制备的二维纳米薄膜的应用。本论文最后一个工作尝试采用定性滤纸作为衬底材料制备二维纳米金膜。由于定性滤纸具有微米级的粗糙度和相互交错的纤维结构,用自组装方法在其表面吸附金纳米粒子,形成一层纳米级金薄膜,用于表面增强拉曼散射上研究。
Surface enhanced Raman scattering (SERS) spectroscopy as one of the most sensitive technologies for detection of adsorbed molecules on nanostructured metal surfaces at monolayer or sub-monolayer level has been broadly applied in chemistry, biology, and anti-corrosion of metal. Hence, preparation of the SERS-active substrate with reproducible and high Raman scattering enhancement in two-dimension becomes a key and attractive project for meeting the need of Raman chemical mapping or imaging. A lot of methods to prepare metal film or array have been investigated, such as self-assembly, template method, photolithography, nanoimprint lithography and so on.
Inositol hexakisphosphoric molecules (shortly named as IP6) are easy to form IP6 micelles by their self-organization due to 6 phosphates of IP6 separately in the both sides of cyclohexane and IP6 micelles possess capability of capturing metal nanoparticles. Due to the existing fashion of inositol hexakisphosphoric molecule depending on the pH media, in present work, we adjust pH values of IP6 solutions for forming various structures of IP6-micelles films at the indium tin oxide (ITO) glass surfaces and then the resulting IP6-micelles film can capture gold nanoparticles (AuNPs) for two-dimensional SERS substrates. A group of materials contain foil, silicon wafer and ITO glass can be used as framework of two-dimensional metal film. At present, these substrate materials have put up satisfactory performance in the fields of SERS research.
使用植酸钠盐作为架桥剂,由于其结构中共有12个酸根和六个磷酸酯根,可与金属离子相互作用。基于以上的性质,通过调节植酸pH值,以不同pH条件下的植酸为桥连剂就可以准备了一种具良好重现性和SERS活性的金膜。在前两个工作中我们制备具有SERS活性的金膜所用到的衬底有ITO玻璃。目前,常用到的用来制备二维纳米薄膜的衬底材料有硅片、金属薄片以及氧化铟锡玻璃(ITO)。由于这些材料具有易碎,僵硬的特点,因此,限制了制备的二维纳米薄膜的应用。本论文最后一个工作尝试采用定性滤纸作为衬底材料制备二维纳米金膜。由于定性滤纸具有微米级的粗糙度和相互交错的纤维结构,用自组装方法在其表面吸附金纳米粒子,形成一层纳米级金薄膜,用于表面增强拉曼散射上研究。
Surface enhanced Raman scattering (SERS) spectroscopy as one of the most sensitive technologies for detection of adsorbed molecules on nanostructured metal surfaces at monolayer or sub-monolayer level has been broadly applied in chemistry, biology, and anti-corrosion of metal. Hence, preparation of the SERS-active substrate with reproducible and high Raman scattering enhancement in two-dimension becomes a key and attractive project for meeting the need of Raman chemical mapping or imaging. A lot of methods to prepare metal film or array have been investigated, such as self-assembly, template method, photolithography, nanoimprint lithography and so on.
Inositol hexakisphosphoric molecules (shortly named as IP6) are easy to form IP6 micelles by their self-organization due to 6 phosphates of IP6 separately in the both sides of cyclohexane and IP6 micelles possess capability of capturing metal nanoparticles. Due to the existing fashion of inositol hexakisphosphoric molecule depending on the pH media, in present work, we adjust pH values of IP6 solutions for forming various structures of IP6-micelles films at the indium tin oxide (ITO) glass surfaces and then the resulting IP6-micelles film can capture gold nanoparticles (AuNPs) for two-dimensional SERS substrates. A group of materials contain foil, silicon wafer and ITO glass can be used as framework of two-dimensional metal film. At present, these substrate materials have put up satisfactory performance in the fields of SERS research.
引文
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