CN112098390A - Surface enhanced Raman scattering substrate and preparation method thereof - Google Patents
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Abstract
Description
技术领域technical field
本发明涉及表面增强拉曼检测技术领域，尤其涉及一种银纳米粒子/ZnO纳米塔表面增强拉曼散射(Surface-enhanced Raman Scattering，简称SERS)基底的制备方法。The invention relates to the technical field of surface-enhanced Raman detection, in particular to a preparation method of a surface-enhanced Raman Scattering (SERS) substrate of silver nanoparticles/ZnO nano-towers.
背景技术Background technique
1928年，C.V.Raman发现了拉曼散射现象。60年代激光器大幅提高了激发效率，成为拉曼光谱的理想光源，拉曼散射的研究进入全新时期。后期单色仪、检测器、光学显微镜、微弱信号检测技术与计算机技术的发展，使拉曼光谱技术在化学、物理和生物等许多领域取得很大的进展。目前，拉曼光谱技术己被广泛应用于材料、化工、石油、高分子、生物、环保、地质等领域。In 1928, C.V.Raman discovered the phenomenon of Raman scattering. In the 1960s, lasers greatly improved the excitation efficiency and became an ideal light source for Raman spectroscopy, and the research on Raman scattering entered a new era. The later development of monochromator, detector, optical microscope, weak signal detection technology and computer technology has made great progress in Raman spectroscopy in many fields such as chemistry, physics and biology. At present, Raman spectroscopy has been widely used in the fields of materials, chemicals, petroleum, polymers, biology, environmental protection, and geology.
拉曼散射效应非常弱，其散射光强度约为入射光强度的10-6～10-9，极大地限制了拉曼光谱的应用和发展。1974年Fleischmann等人发现吸附在粗糙金银表面的tt旋分子的拉曼信号强度得到很大程度的提高，同时信号强度随着电极所加电位的变化而变化。1977年，Jeanmaire与Van Duyne，Albrecht与Creighton等人经过***的实验研究和理论计算，将这种与银、金、铜等粗糙表面相关的增强效应称为表面增强拉曼散射(Surface enhancedRaman Scattering，SERS)效应，对应的光谱称为表面增强拉曼光谱。随后，人们在其它粗糙表面也观察到SERS现象。The Raman scattering effect is very weak, and the scattered light intensity is about 10 -6 to 10 -9 of the incident light intensity, which greatly limits the application and development of Raman spectroscopy. In 1974, Fleischmann et al. found that the Raman signal intensity of tt spin molecules adsorbed on rough gold and silver surfaces was greatly improved, and the signal intensity changed with the change of the potential applied to the electrode. In 1977, Jeanmaire and Van Duyne, Albrecht and Creighton, etc., after systematic experimental research and theoretical calculations, called this enhanced effect related to rough surfaces such as silver, gold, and copper as surface enhanced Raman scattering (Surface enhanced Raman Scattering, SERS) effect, the corresponding spectrum is called surface-enhanced Raman spectroscopy. Subsequently, the SERS phenomenon was also observed on other rough surfaces.
过去的几十年以来，SERS光谱作为一种快速、无损、环保的检测手段，在化学、食品、药学和生物分子等高灵敏度检测领域受到了广泛的关注。SERS基底上最大的拉曼信号和较大比例的平均增强通常都来自极高增强的高度局部化位置(hot-spots，即热点)。因此制备负载高密度热点的SERS基底对进一步降低基底的检测限来扩展SERS技术的应用领域而言非常重要，特别是对于最近研究非常热的单分子拉曼检测技术。热点的主要来源包括：金属粒子的纳米间隙和金属的纳米尖端，因此可以从这两方面入手提高基底的热点密度。此外，Eric C.Le Ru等人报道要从热点上获的高的信号增强，待测分子必须接近或位于热点区域(通常要求为小于10nm)，这一点受到极少的关注且挑战性非常大。Over the past few decades, SERS spectroscopy, as a rapid, non-destructive, and environmentally friendly detection method, has received extensive attention in the fields of high-sensitivity detection in chemistry, food, pharmacy, and biomolecules. The largest Raman signal and a large proportion of the average enhancement on the SERS substrate usually come from highly localized locations (hot-spots) of extremely high enhancement. Therefore, the preparation of SERS substrates loaded with high-density hot spots is very important to further reduce the detection limit of the substrates and expand the application field of SERS technology, especially for the recently studied very hot single-molecule Raman detection technology. The main sources of hot spots include: the nano-gap of metal particles and the nano-tip of metal, so the hot spot density of the substrate can be improved from these two aspects. In addition, Eric C. Le Ru et al. reported that to obtain high signal enhancement from the hot spot, the molecule to be tested must be close to or located in the hot spot region (usually required to be less than 10 nm), which has received very little attention and is very challenging. .
传统的SERS基底由纯贵金属组成，但是这种基底成本昂贵，且对技术需求高，不适用于实际应用。最近，贵金属/半导体异质SERS基底受到了关注，因为它不仅具有纯贵金属基底的电磁增强，而且通过贵金属、半导体、待测分子三者之间的电子转移还可以拥有较强的化学增强，此外半导体的各种结构可以负载众多贵金属粒子从而实现高密度的三维热点。其中银/ZnO异质基底由于ZnO多变的结构和银与ZnO的功函数差导致的电子转移共振而受到了广泛的研究。但是，目前的银/ZnO异质基底制备方法主要有离子溅射、化学镀、光化学还原、电沉积等，存在几个缺点：Conventional SERS substrates consist of pure precious metals, but such substrates are expensive and technically demanding, making them unsuitable for practical applications. Recently, noble metal/semiconductor hetero SERS substrates have attracted attention because they not only possess the electromagnetic enhancement of pure noble metal substrates, but also possess strong chemical enhancement through electron transfer between noble metals, semiconductors, and molecules to be tested. Various structures of semiconductors can support numerous noble metal particles to achieve high-density three-dimensional hot spots. Among them, Ag/ZnO heterosubstrates have been widely studied due to the variable structure of ZnO and the electron transfer resonance caused by the difference in work function between Ag and ZnO. However, the current preparation methods of silver/ZnO heterogeneous substrates mainly include ion sputtering, electroless plating, photochemical reduction, electrodeposition, etc., which have several disadvantages:
首先，其制备设备昂贵，难以通过简单而廉价的方式大规模制备出低检测限具有实际应用价值的SERS基底，First, its preparation equipment is expensive, and it is difficult to prepare a large-scale SERS substrate with low detection limit and practical application value in a simple and cheap way.
其次，现有的方法制备的银/ZnO异质基底对于拉曼光谱的增强作用并不理想，还有很大可以改进的空间。Secondly, the silver/ZnO hetero-substrate prepared by the existing method is not ideal for the enhancement of Raman spectrum, and there is still much room for improvement.
发明内容SUMMARY OF THE INVENTION
为了进一步提高银/ZnO异质基底对于拉曼光谱的增强效果，也为了研发更加简便的方法制备银/ZnO异质表面增强拉曼散射基底的方法，本发明的发明人进行了深入细致的研究，结果发现并提供了简便且廉价的制备表面增强拉曼散射基底的方法，及制备了具有高灵敏度的表面增强拉曼散射基底。In order to further improve the enhancement effect of the Ag/ZnO hetero-substrate on Raman spectroscopy, and to develop a more convenient method for preparing the Ag/ZnO hetero-surface-enhanced Raman scattering substrate, the inventors of the present invention have conducted in-depth and meticulous research. , the results found and provided a simple and inexpensive method for preparing a surface-enhanced Raman scattering substrate, and a surface-enhanced Raman scattering substrate with high sensitivity was prepared.
具体而言，本发明提供一种表面增强拉曼散射基底，其包含四面体和立方体银纳米粒子以及ZnO纳米塔阵列，四面体和立方体的银纳米粒子平均直径约为50～110nm，ZnO纳米塔形似六棱柱，在尖端处棱柱直径逐渐减小，形成阶梯状形貌，ZnO纳米塔的平均长度为2～4μm，半身高处平均直径为500～800nm。Specifically, the present invention provides a surface-enhanced Raman scattering substrate comprising tetrahedral and cubic silver nanoparticles and ZnO nanotower arrays, the average diameter of the tetrahedral and cubic silver nanoparticles is about 50-110 nm, and the ZnO nanotowers have an average diameter of about 50-110 nm. Shaped like a hexagonal prism, the diameter of the prism gradually decreases at the tip, forming a stepped shape. The average length of the ZnO nanotower is 2-4 μm, and the average diameter at the half height is 500-800 nm.
本发明的表面增强拉曼散射基底的制备方法，其包含：The preparation method of the surface-enhanced Raman scattering substrate of the present invention comprises:
纳米银溶胶制备工序，将无机银盐和聚乙烯吡咯烷酮溶于有机溶剂中，混合均匀，在160～180℃加热反应20～24小时，冷却至室温，将产物纯化后分散在乙醇中得到纳米银溶胶；In the preparation process of nano silver sol, inorganic silver salt and polyvinyl pyrrolidone are dissolved in an organic solvent, mixed evenly, heated at 160-180 ° C for 20-24 hours, cooled to room temperature, purified and dispersed in ethanol to obtain nano-silver sol;
纳米塔准备工序，将羟基化处理过的硅片，悬挂于由氯化锌和氨水构成的ZnO纳米塔生长溶液中，密封加热至85～95℃，进行50～90分钟的反应，生长ZnO纳米塔阵列，反应结束后，取出硅片，清洗干燥，得到ZnO纳米塔阵列；Nano tower preparation process, the hydroxylated silicon wafer is suspended in the ZnO nano tower growth solution composed of zinc chloride and ammonia water, sealed and heated to 85 ~ 95 ℃, and the reaction is carried out for 50 ~ 90 minutes to grow ZnO nanometer towers. tower array, after the reaction is over, take out the silicon wafer, wash and dry to obtain a ZnO nano-tower array;
组装工序，将纳米银溶胶滴铸于ZnO纳米塔阵列，从而组装得到银/ZnO纳米塔表面增强拉曼散射基底。In the assembly process, the nano-silver sol is drop-cast on the ZnO nano-tower array, thereby assembling the silver/ZnO nano-tower surface-enhanced Raman scattering substrate.
上述方法中首先通过溶剂热法合成由四面体和立方体银纳米粒子组成的纳米银溶胶，然后在硅基底上通过化学浴沉积法制备ZnO纳米塔阵列，最后通过滴铸法将银溶胶与ZnO纳米塔阵列结合，由此本发明的表面增强拉曼散射基底的合成方法不涉及高温高压，也不需要昂贵的大型仪器，本发明可以以非常简便的方法制备检测限超低的表面增强拉曼散射基底。In the above method, a nano-silver sol composed of tetrahedral and cubic silver nanoparticles was first synthesized by a solvothermal method, and then a ZnO nanotower array was prepared on a silicon substrate by a chemical bath deposition method. Combined with tower arrays, the method for synthesizing the surface-enhanced Raman scattering substrate of the present invention does not involve high temperature and high pressure, nor does it require expensive large-scale instruments. The present invention can prepare ultra-low detection limit surface-enhanced Raman scattering in a very simple method. base.
附图说明Description of drawings
图1是本发明中制备的银溶胶的TEM图；Fig. 1 is the TEM image of the silver sol prepared in the present invention;
图2是本发明中制备的ZnO纳米塔的SEM图；Fig. 2 is the SEM image of the ZnO nano tower prepared in the present invention;
图3是本发明中制备的银纳米粒子/ZnO纳米塔基底的SEM图；Fig. 3 is the SEM image of the silver nanoparticle/ZnO nano tower base prepared in the present invention;
图4是本发明中制备的银纳米粒子/ZnO纳米塔基底的XRD图；Fig. 4 is the XRD figure of the silver nanoparticle/ZnO nano tower base prepared in the present invention;
图5是本发明中制备的银纳米粒子/ZnO纳米塔基底检测10-7～10-18mol/L罗丹明的拉曼图谱，图5b为检测10-16、10-18mol/L R6G的放大拉曼图谱；Fig. 5 is the Raman spectrum of detecting 10 -7 ～10 -18 mol/L rhodamine by the silver nanoparticle/ZnO nano tower substrate prepared in the present invention, and Fig. 5b is the Raman spectrum of detecting 10 -16 , 10 -18 mol/L R6G Zoom in on the Raman spectrum;
图6是本发明中用于对比的制备银纳米粒子/ZnO纳米棒的SEM图。(a)俯视图，(b)截面图；FIG. 6 is a SEM image of the prepared silver nanoparticles/ZnO nanorods used for comparison in the present invention. (a) top view, (b) sectional view;
图7是分别在ZnO纳米塔基底和ZnO纳米棒基底上滴加浓度为10-7M R6G溶液的SERS光谱图；Fig. 7 is the SERS spectrum of 10-7 M R6G solution dripping on ZnO nano-tower base and ZnO nano-rod base respectively;
图8是不同反应时间制备的不同粒径和形貌的银溶胶的TEM图。(a)为11小时，(b)为12小时，(c)为14小时，(d)16小时，(e)22小时，(f)44小时；Figure 8 is the TEM images of silver sols with different particle sizes and morphologies prepared at different reaction times. (a) 11 hours, (b) 12 hours, (c) 14 hours, (d) 16 hours, (e) 22 hours, (f) 44 hours;
图9是R6G滴铸于球状银纳米粒子/ZnO纳米塔基底上收集的拉曼信号图。Figure 9 is a graph of Raman signals collected by drop casting of R6G on spherical silver nanoparticles/ZnO nanotower substrates.
具体实施方式Detailed ways
以下，参照附图对本发明的实施方式进行说明。Hereinafter, embodiments of the present invention will be described with reference to the drawings.
本发明提供一种表面增强拉曼散射基底，包含四面体和立方体银纳米粒子以及ZnO纳米塔阵列，四面体和立方体的银纳米粒子平均直径约为50～110nm，ZnO纳米塔形似六棱柱，在尖端处棱柱直径逐渐减小，形成阶梯状形貌，ZnO纳米塔的平均长度为2～4μm，半身高处平均直径为500～800nm。The invention provides a surface-enhanced Raman scattering substrate, comprising tetrahedral and cubic silver nanoparticles and ZnO nano-tower arrays. The average diameter of the tetrahedral and cubic silver nanoparticles is about 50-110 nm, and the ZnO nano-tower is shaped like a hexagonal prism. The diameter of the prism at the tip gradually decreases, forming a stepped shape. The average length of the ZnO nanotower is 2-4 μm, and the average diameter at the half height is 500-800 nm.
本发明的表面增强拉曼散射基底由四面体和立方体银纳米粒子散落在ZnO纳米塔阵列上构成，其中的银纳米粒子的四面体和立方体的形貌是很重要的，本发明的发明人也测试了球状形貌的银纳米粒子与ZnO纳米塔的组合，发现其表面增强效果下降很多，其原因是：四面体和立方体银纳米粒子的顶角可以将光聚焦到顶角附近的纳米级体积中，并显著增加这些区域的近场强度，从而产生位于金属纳米尖端处的热点。优选地，四面体和立方体银纳米粒子平均直径约为60～80nm。另外，本发明的ZnO纳米塔的形似六棱柱，在尖端处棱柱直径逐渐减小，而形成阶梯状的形貌也是非常重要的。发明人也测试了柱状的ZnO纳米棒与纳米银颗粒的组合，发现表面增强效果相较于本发明的形貌的ZnO纳米塔减弱很多。本发明的ZnO纳米塔的形似六棱柱，在尖端处棱柱直径逐渐减小，而形成阶梯状的形貌能够带来更好的拉曼光谱表面增强的效果的原因是：这种阶梯的形貌不但可以使银纳米粒子坐落于阶梯上，还能减小待测溶液的动能，将待测溶液留于阶梯上的银纳米粒子附近，从而达到使待测分子更接近热点区域的目的。优选地，ZnO纳米塔的平均长度为2.5～3.5μm，半身高处平均直径为650nm～750nm。The surface-enhanced Raman scattering substrate of the present invention is composed of tetrahedral and cubic silver nanoparticles scattered on the ZnO nano-tower array, and the tetrahedral and cubic morphology of the silver nanoparticles is very important. The inventor of the present invention also The combination of silver nanoparticles with spherical morphology and ZnO nanotowers was tested and it was found that the surface enhancement effect was greatly reduced. The reason is: the vertex angle of tetrahedral and cubic Ag nanoparticles can focus light into the nanoscale volume near the vertex angle. , and significantly increase the near-field strength in these regions, resulting in hot spots located at the metal nanotips. Preferably, the average diameter of the tetrahedral and cubic silver nanoparticles is about 60-80 nm. In addition, the shape of the ZnO nanotower of the present invention is similar to a hexagonal prism, and the diameter of the prism gradually decreases at the tip, and it is also very important to form a stepped topography. The inventors also tested the combination of columnar ZnO nanorods and nano-silver particles, and found that the surface enhancement effect is much weaker than that of the ZnO nanotower with the morphology of the present invention. The ZnO nano tower of the present invention is shaped like a hexagonal prism, and the diameter of the prism gradually decreases at the tip, and the reason why the stepped topography can bring about a better Raman spectrum surface enhancement effect is: the stepped topography Not only can the silver nanoparticles be located on the steps, but also the kinetic energy of the solution to be tested can be reduced, and the solution to be tested can be left near the silver nanoparticles on the steps, so as to achieve the purpose of making the molecules to be tested closer to the hot spot. Preferably, the average length of the ZnO nanotower is 2.5˜3.5 μm, and the average diameter at the half height is 650 nm˜750 nm.
银纳米粒子有多种形貌。ZnO纳米材料根据不同制备方法也有不同形貌，例如常见的纳米棒结构和本发明的纳米塔结构。本发明得到的低检测限银/ZnO异质表面增强拉曼散射基底通过上述特定形貌的银纳米粒子和特定形貌的ZnO纳米塔组合，发挥纳米间隙和尖端两种热点效果，且能够滞留待测分子于热点区域，因此在测试中极大的提高了拉曼光谱增强效应。以罗丹明6G(以下也计作R6G)作为检测对象分子时，可获得最低可检测到浓度为1×10-18mol/L的结果，这优于目前所报道的大部分银/ZnO异质SERS基底。Silver nanoparticles have various morphologies. ZnO nanomaterials also have different morphologies according to different preparation methods, such as the common nanorod structure and the nanotower structure of the present invention. The silver/ZnO heterogeneous surface-enhanced Raman scattering substrate with low detection limit obtained by the present invention exerts two hot spot effects of nano-gap and tip through the combination of the above-mentioned silver nanoparticles with specific shapes and ZnO nano-towers with specific shapes, and can retain The molecules to be tested are located in the hot spot area, so the Raman spectrum enhancement effect is greatly improved in the test. When rhodamine 6G (also referred to as R6G hereinafter) was used as the detection target molecule, the lowest detectable concentration of 1×10 -18 mol/L was obtained, which was better than most of the silver/ZnO heterogeneities reported so far. SERS substrate.
本发明的表面增强拉曼散射基底的制备方法，其包含：The preparation method of the surface-enhanced Raman scattering substrate of the present invention comprises:
纳米银溶胶制备工序，将无机银盐和聚乙烯吡咯烷酮溶于有机溶剂中，混合均匀，在160～180℃加热反应20～24小时，冷却至室温，将产物纯化后分散在乙醇中得到纳米银溶胶；In the preparation process of nano silver sol, inorganic silver salt and polyvinyl pyrrolidone are dissolved in an organic solvent, mixed evenly, heated at 160-180 ° C for 20-24 hours, cooled to room temperature, purified and dispersed in ethanol to obtain nano-silver sol;
纳米塔准备工序，将羟基化处理过的硅片，悬挂于由氯化锌和氨水构成的ZnO纳米塔生长溶液中，密封加热至85～95℃，进行50～90分钟的反应，生长ZnO纳米塔阵列，反应结束后，取出硅片，清洗干燥，得到ZnO纳米塔阵列；Nano tower preparation process, the hydroxylated silicon wafer is suspended in the ZnO nano tower growth solution composed of zinc chloride and ammonia water, sealed and heated to 85 ~ 95 ℃, and the reaction is carried out for 50 ~ 90 minutes to grow ZnO nanometer towers. tower array, after the reaction is over, take out the silicon wafer, wash and dry to obtain a ZnO nano-tower array;
组装工序，将纳米银溶胶滴铸于ZnO纳米塔阵列，从而组装得到银/ZnO纳米塔表面增强拉曼散射基底。In the assembly process, the nano-silver sol is drop-cast on the ZnO nano-tower array, thereby assembling the silver/ZnO nano-tower surface-enhanced Raman scattering substrate.
纳米银溶胶制备工序中，使用溶剂热法合成纳米银溶胶，无机银盐典型的是使用硝酸银，相对于1质量份的硝酸银，一般聚乙烯吡咯烷酮的投料量是8质量份～20质量份，优选9～10质量份。有机溶剂，考虑到溶解性，优选使用N，N-二甲基甲酰胺，但不限于此，溶剂的投料量适量即可没有限制，一般是相对于硝酸银为100质量份～1000质量份。典型的制备四面体和立方体银纳米粒子组成的银溶胶的实验室工序，例如：In the preparation process of the nano-silver sol, the solvothermal method is used to synthesize the nano-silver sol, and the inorganic silver salt is typically silver nitrate. Relative to 1 mass part of silver nitrate, the general feeding amount of polyvinylpyrrolidone is 8 to 20 mass parts. , preferably 9 to 10 parts by mass. As the organic solvent, N,N-dimethylformamide is preferably used in consideration of solubility, but it is not limited to this, and the amount of the solvent to be charged is not limited. Generally, it is 100 to 1000 parts by mass relative to silver nitrate. Typical laboratory procedures for the preparation of silver sols composed of tetrahedral and cubic silver nanoparticles, such as:
将0.01～0.04g硝酸银和0.155～0.4g聚乙烯吡咯烷(PVP，K85-95，Mw＝1300000)溶于20～60ml N，N-二甲基甲酰胺(DMF，购买自ALADDIN)溶液中，使用磁力搅拌30～50min至淡黄色。将淡黄色溶液转移至反应釜中，加热至160～180℃反应20～24h。反应结束后，立即取出高压釜，在流动的水中冷却至室温。反复用乙醇离心纯化产物，并最终分散在10～30mL乙醇中得到浓度为2×10-4g/ml～2.5×10-3g/ml的纳米银溶胶。Dissolve 0.01～0.04g silver nitrate and 0.155～0.4g polyvinylpyrrolidine (PVP, K85-95, Mw=1300000) in 20～60ml N,N-dimethylformamide (DMF, purchased from ALADDIN) solution , use magnetic stirring for 30-50min to light yellow. The pale yellow solution was transferred to the reaction kettle, heated to 160-180°C and reacted for 20-24 h. After the reaction was completed, the autoclave was taken out immediately and cooled to room temperature in flowing water. The product was purified by repeated centrifugation with ethanol, and finally dispersed in 10-30 mL of ethanol to obtain a nano-silver sol with a concentration of 2 × 10 -4 g/ml - 2.5 × 10 -3 g/ml.
本发明人发现，为了得到粒径50～110nm的四面体和立方体银纳米粒子，控制160～180℃加热反应20～24小时的条件是重要的，发明人监测了在上述示例的反应中银纳米粒子形貌粒径的变化，其随着时间推移，银纳米粒子粒径和形状改变有着一定规律，具体见图8，20～24小时的反应时间可以获得合适粒径的四面体和立方体银纳米粒子。The inventors found that in order to obtain tetrahedral and cubic silver nanoparticles with a particle size of 50 to 110 nm, it is important to control the conditions of the heating reaction at 160 to 180° C. for 20 to 24 hours. The inventors monitored the reaction of the silver nanoparticles in the above examples. The change of morphology and particle size, with the passage of time, the particle size and shape of silver nanoparticles have a certain regularity, as shown in Figure 8. The reaction time of 20 to 24 hours can obtain tetrahedral and cubic silver nanoparticles of suitable particle size. .
本发明人最新发现，纳米塔准备工序中，将硅片进行羟基化然后在生长ZnO是获得纳米塔的关键，表面富有羟基的硅片有利于纳米塔的成核。硅片的羟基化操作与现有技术并无区别，典型的硅片羟基化实验室流程可以举例如下：The inventors recently discovered that in the preparation process of the nanotower, hydroxylation of silicon wafers and then growth of ZnO is the key to obtain nanotowers, and silicon wafers rich in hydroxyl groups on the surface are conducive to the nucleation of nanotowers. The hydroxylation operation of silicon wafers is no different from the existing technology. A typical laboratory process for hydroxylation of silicon wafers can be exemplified as follows:
将硅片(2cm×2cm)分别使用丙酮、乙醇、蒸馏水超声清洗10～15min，将清洗后的硅片在浓硫酸中90～95℃下加热1～1.5h，之后将硅片放于蒸馏水：氨水：过氧化氢体积比为5：1：1的混合溶液中超声25～40min，最后在蒸馏水中超声10min并吹干待用。The silicon wafers (2cm×2cm) were ultrasonically cleaned with acetone, ethanol and distilled water for 10-15min respectively. The cleaned silicon wafers were heated in concentrated sulfuric acid at 90-95°C for 1-1.5h, and then the silicon wafers were placed in distilled water: Ammonia:Hydrogen peroxide volume ratio of 5:1:1 in the mixed solution of ultrasonic 25 ~ 40min, and finally in distilled water for 10min and dried for use.
纳米塔准备工序中，构成的ZnO纳米塔生长溶液可以通过混合氯化锌和氨水获得，ZnO纳米塔生长溶液中氯化锌和氨水的配比可以影响ZnO纳米塔的形貌，本发明中，相对于1g氯化锌，投料1.48～5.56ml的氨水，可以获得本发明所需形貌的ZnO纳米塔。In the nano tower preparation process, the formed ZnO nano tower growth solution can be obtained by mixing zinc chloride and ammonia water, and the ratio of zinc chloride and ammonia water in the ZnO nano tower growth solution can affect the morphology of the ZnO nano tower. In the present invention, With respect to 1 g of zinc chloride, 1.48-5.56 ml of ammonia water is fed, and a ZnO nano-tower with the desired shape of the present invention can be obtained.
典型的ZnO纳米塔生长溶液的实验室制备例子如下：将0.32～0.65g氯化锌溶于38ml蒸馏水中，搅拌5min，再加入1.2～3ml氨水，搅拌8～15min。A typical laboratory preparation example of ZnO nanotower growth solution is as follows: dissolve 0.32-0.65 g of zinc chloride in 38 ml of distilled water, stir for 5 min, add 1.2-3 ml of ammonia water, and stir for 8-15 min.
本发明使用硅基底上通过化学浴沉积法制备ZnO纳米塔阵列，反应的温度控制在85～95℃，进行50～90min的时间是重要的。典型的ZnO纳米塔生长过程的实验室制备例子如下：The present invention uses the chemical bath deposition method to prepare the ZnO nano-tower array on the silicon substrate, the temperature of the reaction is controlled at 85-95 DEG C, and the time for 50-90 min is important. Examples of laboratory preparations for a typical ZnO nanotower growth process are as follows:
使用聚酰亚胺胶带将羟化过的硅片悬挂于生长溶液中，并用保鲜膜将烧杯密封。再将烧杯放于烘箱中，85～95℃加热50～90min。反应完成后，取出硅片，使用蒸馏水超声清洗1min，吹干，即得到ZnO纳米塔阵列。The hydroxylated silicon wafer was suspended in the growth solution using polyimide tape and the beaker was sealed with plastic wrap. The beaker was then placed in an oven, and heated at 85 to 95°C for 50 to 90 minutes. After the reaction was completed, the silicon wafer was taken out, ultrasonically cleaned with distilled water for 1 min, and dried to obtain a ZnO nano-tower array.
上述的组装工序，用简单的滴铸法将纳米银溶胶制备工序中制备的浓度2×10-4g/ml～2.5×10-3g/ml的银胶液滴铸在ZnO纳米塔阵列上，作为滴加的比率，每1cm2滴加的银溶胶的量为0.2～0.6ml，可以获得成本和最佳增强效果的平衡。In the above assembly process, a simple drop casting method was used to drop the silver colloid with a concentration of 2 × 10 -4 g/ml to 2.5 × 10 -3 g/ml prepared in the preparation process of the nano silver sol onto the ZnO nano-tower array. , as the dripping ratio, the amount of silver sol dripped per 1 cm 2 is 0.2-0.6 ml, which can achieve a balance between cost and the best enhancement effect.
典型的银纳米粒子/ZnO纳米塔SERS基底的组装实验室制备例子如下：An example of the assembly laboratory preparation of a typical AgNP/ZnO nanotower SERS substrate is as follows:
将ZnO纳米塔阵列切为0.5cm×0.5cm大小，然后用注射器将0.05ml银胶体滴在ZnO纳米塔阵列上，并在38～55℃下干燥，最后将该步骤重复2～3遍。The ZnO nanotower array was cut into a size of 0.5cm×0.5cm, and then 0.05ml of silver colloid was dropped on the ZnO nanotower array with a syringe, and dried at 38-55°C. Finally, this step was repeated 2-3 times.
下面结合附图并通过实施例对本发明作进一步的详细说明，以下实施例是对本发明的解释而本发明并不局限于以下实施例。The present invention will be further described in detail below in conjunction with the accompanying drawings and through the examples. The following examples are to explain the present invention and the present invention is not limited to the following examples.
实施例1Example 1
工序A：由四面体和立方体银纳米粒子组成的银溶胶的制备。将0.0238g硝酸银和0.155g PVP溶于29ml DMF溶液中，使用磁力搅拌30min至淡黄色。将淡黄色溶液转移至反应釜中，加热至170℃反应22h。反应结束后，立即取出高压釜，在流动的水中冷却至室温。反复用乙醇离心纯化产物，并最终分散在20ml乙醇中。制备出的银溶胶的透射电镜(TEM)图，如图1(a)所示，银纳米粒子形状主要是立方体和四面体，且其中立方体占比更大，平均直径约为64nm。立方体和四面体银纳米粒子均有顶角，在偶极等离子体共振条件下，可以在这些高曲率顶角区域附近产生更高的电场(即，热点)，因此比球形和准球形银纳米粒子具有更强的SERS性能。Procedure A: Preparation of a silver sol consisting of tetrahedral and cubic silver nanoparticles. Dissolve 0.0238 g of silver nitrate and 0.155 g of PVP in 29 ml of DMF solution, and use magnetic stirring for 30 min until pale yellow. The pale yellow solution was transferred to the reaction kettle, heated to 170°C and reacted for 22h. After the reaction was completed, the autoclave was taken out immediately and cooled to room temperature in flowing water. The product was purified by repeated centrifugation with ethanol and finally dispersed in 20 ml of ethanol. The transmission electron microscope (TEM) image of the prepared silver sol is shown in Fig. 1(a), the shape of silver nanoparticles is mainly cube and tetrahedron, and the cube accounts for a larger proportion, and the average diameter is about 64nm. Both cubic and tetrahedral silver nanoparticles have vertex angles, and under dipole plasmon resonance conditions, higher electric fields (i.e., hot spots) can be generated near these high-curvature vertex angle regions, and thus are more likely than spherical and quasi-spherical silver nanoparticles. Has stronger SERS performance.
工序B：羟化硅片的制备。将硅片(2cm×2cm)分别使用丙酮、乙醇、蒸馏水超声清洗15min，将清洗后的硅片在浓硫酸中90℃下加热1h，之后将硅片放于蒸馏水：氨水：过氧化氢体积比为5：1：1的混合溶液中超声30min，最后在蒸馏水中超声10min并吹干待用。Step B: Preparation of Hydroxylated Silicon Wafers. The silicon wafers (2cm×2cm) were ultrasonically cleaned with acetone, ethanol and distilled water for 15min respectively. The cleaned silicon wafers were heated in concentrated sulfuric acid at 90°C for 1h, and then placed in distilled water:ammonia:hydrogen peroxide volume ratio It was sonicated for 30 min in a 5:1:1 mixed solution, and finally sonicated in distilled water for 10 min and dried for use.
工序C：ZnO纳米塔阵列的制备。在50ml烧杯中，将0.54g氯化锌溶于38ml蒸馏水中，搅拌5min，再加入2ml氨水，搅拌10min制备成ZnO纳米塔生长溶液。之后使用2mm宽聚酰亚胺胶带将羟化过的硅片悬挂于生长溶液中，并用保鲜膜将烧杯密封。再将烧杯放于烘箱中，95℃加热75min。反应完成后，取出硅片，使用蒸馏水超声清洗1min，吹干，即得到ZnO纳米塔阵列。其场发射扫描电镜图(SEM)，如图2(b)所示，纳米塔半身高处平均直径约为700nm，长度约为3.2μm。塔身为六棱柱，塔尖棱柱直径逐渐减小，从而构成塔状阶梯。Procedure C: Preparation of ZnO nanotower arrays. In a 50ml beaker, dissolve 0.54g of zinc chloride in 38ml of distilled water, stir for 5min, add 2ml of ammonia water, and stir for 10min to prepare a ZnO nano-tower growth solution. The hydroxylated silicon wafer was then suspended in the growth solution using 2 mm wide polyimide tape and the beaker was sealed with plastic wrap. The beaker was then placed in an oven and heated at 95°C for 75min. After the reaction was completed, the silicon wafer was taken out, ultrasonically cleaned with distilled water for 1 min, and dried to obtain a ZnO nano-tower array. Its field emission scanning electron microscope (SEM) image, as shown in Figure 2(b), shows that the average diameter at the half height of the nanotower is about 700 nm and the length is about 3.2 μm. The tower body is a hexagonal prism, and the diameter of the spire prism gradually decreases to form a tower-like staircase.
工序D：银纳米粒子/ZnO纳米塔SERS基底的组装。首先将ZnO纳米塔阵列切为0.5cm×0.5cm大小，然后用注射器将0.05ml银胶体滴在ZnO纳米塔阵列上，并在55℃下干燥，最后将该步骤重复3遍，其SEM图见图3。如图3(a)所示，银纳米粒子在ZnO纳米塔阵列上均匀分布，纳米塔的侧面和顶端均存在大量银纳米粒子，且银纳米粒子之间的距离非常小，这将产生在相邻的纳米粒子之间产生强的局域表面等离子激元耦合，即银纳米粒子间隙热点。如图3(b)所示，可见大量银纳米粒子滞留在纳米塔尖端的阶梯上，因此纳米塔尖端将存在大量热点。Procedure D: Assembly of Silver Nanoparticles/ZnO Nanotower SERS Substrate. First, the ZnO nanotower array was cut into a size of 0.5cm×0.5cm, and then 0.05ml of silver colloid was dropped on the ZnO nanotower array with a syringe, and dried at 55°C. Finally, this step was repeated 3 times, and its SEM image is shown in
所得到的银纳米粒子/ZnO纳米塔基底的X-射线衍射谱图，如图4所示，所有的衍射峰(不包括硅峰)与六方相ZnO和立方相银的标准衍射峰(JCPDS***36-1451；JCPDS***04-0783)一致，表明了ZnO纳米塔和银纳米粒子的高纯度和结晶性。在34.4°处强烈而尖锐的衍射峰表明ZnO纳米塔阵列优先沿[0001]方向生长，并且装饰有银纳米粒子的纳米台阶属于(002)晶面。The X-ray diffraction pattern of the obtained silver nanoparticles/ZnO nanotower substrate, as shown in Figure 4, all the diffraction peaks (excluding the silicon peak) and the standard diffraction peaks of hexagonal ZnO and cubic silver (JCPDS card number) 36-1451; JCPDS Card No. 04-0783), indicating the high purity and crystallinity of the ZnO nanotower and silver nanoparticles. The strong and sharp diffraction peak at 34.4° indicates that the ZnO nanotower arrays grow preferentially along the [0001] direction, and the nanosteps decorated with silver nanoparticles belong to the (002) crystal plane.
使用R6G作为检测对象分子评估这种银纳米粒子/ZnO纳米塔基底的SERS性能。测试在Xplora Plus拉曼光谱仪上完成，激光波长为532nm，激光功率为0.32mW。如图5(a)所示，对于10-7～10-18mol/L不同浓度的R6G溶液，在611，771，1125，1189，1308，1360，1508，1573和1649cm-1处的R6G特征峰均能明显被观察出，且随浓度减小特征峰峰强逐渐减小。如图5(b)所示，即使R6G溶液浓度低至10-16、10-18mol/L依然能观察到明显的R6G特征峰。The SERS performance of this silver nanoparticle/ZnO nanotower substrate was evaluated using R6G as the detection target molecule. The tests were done on an Xplora Plus Raman spectrometer with a laser wavelength of 532 nm and a laser power of 0.32 mW. As shown in Fig. 5(a), for R6G solutions with different concentrations of 10 -7 to 10 -18 mol/L, the R6G characteristics at 611, 771, 1125, 1189, 1308, 1360, 1508, 1573 and 1649 cm -1 All peaks can be clearly observed, and the peak intensity of characteristic peaks gradually decreases with the decrease of concentration. As shown in Figure 5(b), even if the concentration of R6G solution is as low as 10 -16 , 10 -18 mol/L, obvious R6G characteristic peaks can still be observed.
对比例1Comparative Example 1
银纳米粒子/ZnO纳米棒阵列(AZR)基底与银纳米粒子/ZnO纳米塔阵列(AZT)基底SERS性能对比Comparison of SERS performance between silver nanoparticles/ZnO nanorod arrays (AZR) substrates and silver nanoparticles/ZnO nanotower arrays (AZT) substrates
为了评估AZT基底的拉曼活性，制备了银纳米粒子/ZnO纳米棒阵列(AZR)基底，用以与AZT阵列基底进行比较。To evaluate the Raman activity of AZT substrates, silver nanoparticle/ZnO nanorod array (AZR) substrates were prepared for comparison with AZT array substrates.
除了改变实施例1中的工序B和C替换为下述工序C’，其他与实施例等同操作。这是因为，溅射了ZnO种子层的硅片可以辅助纳米棒成核，进行ZnO的生长时会获得纳米棒，具体而言步骤如下。Except that the steps B and C in Example 1 are changed and replaced by the following step C', other operations are equivalent to those of the embodiment. This is because the silicon wafer sputtered with the ZnO seed layer can assist the nucleation of nanorods, and nanorods will be obtained during the growth of ZnO, and the specific steps are as follows.
工序C’：Process C':
使用磁控溅射在2cm×2cm Si基底上溅射一层50nm厚的ZnO种子层，然后使用工序C相同的方法悬挂于0.1M ZnCl2、2ml氨水配制的生长溶液，并在95℃加热75min。反应完成后，取出硅片，使用蒸馏水超声清洗1min，吹干，即得到ZnO纳米棒阵列。A 50nm thick ZnO seed layer was sputtered on a 2cm×2cm Si substrate by magnetron sputtering, then suspended in the growth solution prepared by 0.1M ZnCl 2 and 2ml ammonia water using the same method as in step C, and heated at 95°C for 75min . After the reaction was completed, the silicon wafer was taken out, ultrasonically cleaned with distilled water for 1 min, and dried to obtain a ZnO nanorod array.
然后通过滴铸法将由立方体和四面体银纳米粒子组成的银溶胶组装到ZnO纳米棒阵列上。图6所示为AZR阵列基底的SEM图，ZnO纳米棒的直径约为35nm，长度约为2μm，从图中可以看出，银纳米粒子均匀地分布在ZnO纳米棒阵列上，如图6(a)所示，且被捕获在纳米棒间的间隔大约100nm深度处，如图6(b)所示，因此，ZnO纳米棒上的银纳米粒子相当于2D分布。The silver sol consisting of cubic and tetrahedral silver nanoparticles was then assembled onto ZnO nanorod arrays by drop casting. Figure 6 shows the SEM image of the AZR array substrate. The diameter of the ZnO nanorods is about 35 nm and the length is about 2 μm. It can be seen from the figure that the silver nanoparticles are uniformly distributed on the ZnO nanorod array, as shown in Figure 6 ( a) and trapped at a depth of about 100 nm in the spacing between nanorods, as shown in Fig. 6(b), thus, the silver nanoparticles on the ZnO nanorods correspond to a 2D distribution.
如图7为在AZT基底和AZR基底上滴加浓度为10-7M R6G溶液的SERS光谱图。从图中可以清楚地识别R6G的拉曼特征峰，其中611cm-1、771cm-1、1125cm-1处的特征峰分别与R6G分子的C–C–C面内弯曲振动、C–C–C面外弯曲振动、C–H平面弯曲振动有关，1189cm-1、1360cm-1、1508cm-1和1649cm-1处的特征峰归因于C–C面内拉伸振动对称模式。由于立方体和四面体银纳米粒子顶角产生的强局域表面等离子体共振(LSPR)以及银纳米粒子与ZnO之间的电子转移共振，AZR阵列基底的SERS活性较高。然而，AZT基底的所有特征峰的强度是AZR阵列的1.5倍。这是因为，与直径约35nm纳米棒相比，ZnO纳米塔具有更大的直径(约700nm)及丰富的纳米阶梯，如图3所示，可以将大量粒径约60nm的银纳米粒子锚定在塔表面，从而实现高密度3D热点分布，特别是纳米阶梯上可以滞留银纳米粒子的同时又保证了它们有合适的距离，使得纳米阶梯上有丰富的拉曼热点，如图3(d)所示。另外，当待测溶液滴铸于纳米塔上时，粗糙的纳米阶梯可将溶液滞留在纳米阶梯上，溶液蒸发后，R6G分子保留在热点区域周围。此外，和没有尖端的ZnO纳米棒相比，纳米塔的倾斜顶点有利于将这些位置的银纳米粒子更多地暴露于入射激光下，从而产生强的热点。Figure 7 shows the SERS spectra of the R6G solution with a concentration of 10 -7 M dropped on the AZT substrate and the AZR substrate. The Raman characteristic peaks of R6G can be clearly identified from the figure, among which the characteristic peaks at 611cm -1 , 771cm -1 , and 1125cm -1 are related to the C–C–C in-plane bending vibration, C–C–C in-plane bending vibration of R6G molecule, respectively. The out-of-plane bending vibration and C–H plane bending vibration are related, and the characteristic peaks at 1189 cm -1 , 1360 cm -1 , 1508 cm -1 and 1649 cm -1 are attributed to the C–C in-plane tensile vibrational symmetry mode. The SERS activity of the AZR array substrate is high due to the strong localized surface plasmon resonance (LSPR) generated by the vertex corners of the cubic and tetrahedral silver nanoparticles and the electron transfer resonance between the silver nanoparticles and ZnO. However, the intensity of all characteristic peaks of the AZT substrate is 1.5 times higher than that of the AZR array. This is because, compared with nanorods with a diameter of about 35 nm, ZnO nanotowers have a larger diameter (about 700 nm) and abundant nanosteps, as shown in Figure 3, which can anchor a large number of silver nanoparticles with a particle size of about 60 nm. On the surface of the tower, high-density 3D hot spot distribution can be achieved, especially the nano-step can retain silver nanoparticles while ensuring that they have a suitable distance, so that there are abundant Raman hot spots on the nano-step, as shown in Figure 3(d) shown. In addition, when the solution to be tested is drop-cast on the nanotower, the rough nanosteps can hold the solution on the nanosteps, and after the solution evaporates, the R6G molecules remain around the hot spot area. Furthermore, the sloping apex of the nanotower facilitates greater exposure of silver nanoparticles at these positions to incident laser light, resulting in strong hot spots, compared to ZnO nanorods without tips.
对比例2Comparative Example 2
银纳米粒子形貌对银纳米粒子/ZnO纳米塔阵列SERS性能的影响Effect of Silver Nanoparticle Morphology on SERS Performance of Silver Nanoparticle/ZnO Nanotower Arrays
为了研究银纳米粒子形貌对银纳米粒子/ZnO纳米塔阵列SERS性能的影响，制备了球状银纳米粒子组装的AZT基底，将之与立方体、四面体银纳米粒子组装的AZT基底进行比较。In order to study the effect of silver nanoparticle morphology on the SERS performance of silver nanoparticle/ZnO nanotower arrays, spherical silver nanoparticle-assembled AZT substrates were prepared and compared with cubic and tetrahedral silver nanoparticle-assembled AZT substrates.
除了改变实施例1中的工序A为下述工序A’，其他与实施例等同操作Except for changing the process A in Example 1 to the following process A', other operations are equivalent to those in the embodiment.
A’：在工序A基础上改变反应时间为16h，得到纳米银溶胶。A': On the basis of step A, the reaction time was changed to 16h to obtain nano silver sol.
工序A’得到图8(d)所示球形纳米银溶胶，将其滴加到ZnO纳米塔阵列上制成基底，分别将1×10-6M至1×10-13M不同浓度的R6G滴于球状银纳米粒子/ZnO纳米塔基底上，并收集拉曼信号。结果如图9所示，随R6G浓度从1×10-6M降至1×10-13M，拉曼特征峰强度逐渐减小，1×10-13M依稀能分辨出R6G拉曼特征峰，说明球状银纳米粒子/ZnO纳米塔基底对R6G的检测限为1×10-13M。球状银纳米粒子/ZnO纳米塔1×10-7M浓度R6G的拉曼峰强是AZT基底峰强的3/4，检测限也比AZT基底低五个数量级，这说明立方体、四面体状银纳米粒子可以增加AZT基底的拉曼活性。Step A' obtained the spherical nano-silver sol as shown in Figure 8(d), which was added dropwise to the ZnO nano-tower array to form a substrate, and R6G with different concentrations of 1×10 -6 M to 1×10 -13 M were dropped respectively. on spherical silver nanoparticles/ZnO nanotower substrates, and collect Raman signals. The results are shown in Fig. 9. As the concentration of R6G decreases from 1×10 -6 M to 1×10 -13 M, the intensity of the Raman characteristic peak gradually decreases, and 1×10 -13 M can vaguely distinguish the Raman characteristic peak of R6G , indicating that the detection limit of spherical silver nanoparticles/ZnO nanotower substrate for R6G is 1×10 -13 M. The Raman peak intensity of R6G at 1×10 -7 M concentration of spherical silver nanoparticles/ZnO nanotower is 3/4 of the peak intensity of AZT substrate, and the detection limit is also five orders of magnitude lower than that of AZT substrate, which indicates that the cubic and tetrahedral silver Nanoparticles can increase the Raman activity of AZT substrates.
可以理解的是，上述各实施例中相同或相似部分可以相互参考，在一些实施例中未详细说明的内容可以参见其他实施例中相同或相似的内容。本发明提供的多个方案包含本身的基本方案，相互独立，并不互相制约，但是其也可以在不冲突的情况下相互结合，达到多个效果共同实现。It can be understood that, the same or similar parts in the above embodiments may refer to each other, and the content not described in detail in some embodiments may refer to the same or similar content in other embodiments. The multiple solutions provided by the present invention include their own basic solutions, which are independent of each other and do not restrict each other, but they can also be combined with each other without conflict to achieve multiple effects.
以上所述，仅为本发明的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，可轻易想到变化或替换，都应涵盖在本发明的保护范围之内。因此，本发明的保护范围应以所述权利要求的保护范围为准。The above are only specific embodiments of the present invention, but the protection scope of the present invention is not limited to this. Any person skilled in the art can easily think of changes or substitutions within the technical scope disclosed by the present invention. should be included within the protection scope of the present invention. Therefore, the protection scope of the present invention should be based on the protection scope of the claims.
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