两种基底对中药溶液喇曼光谱增强作用的比较

为了对比分析TiO₂-AgNPs薄膜与银胶纳米颗粒溶液两种表面增强喇曼光谱散射（SERS）基底对中药溶液样品的SERS增强效果，选取中药附子溶液作为实验样品，分别采用两种SERS基底通过喇曼散射实验取得其表面增量喇曼光谱，并进行了解析对比。结果表明，TiO₂-AgNPs薄膜与银胶纳米颗粒溶液两种SERS基底都对中药附子溶液的喇曼散射光谱起到了明显的增强作用；TiO₂-AgNPs薄膜的增强效果相对于银胶纳米颗粒溶液更为敏感，如在喇曼位移1398cm-1的相对峰强比，TiO₂-AgNPs薄膜基底为27.85%，银胶纳米颗粒溶液基底为11.97%，但其具有易氧化、可用时间短、制备难度大、可重复性不高等缺点，因此更适于样品成分的精确鉴定，银胶纳米颗粒溶液具有制备更简单、使用时间长、稳定性和重复性好等优点，适于大量样品成分确定对比的检测；两种基底对中药溶液样品的SERS增强各有优势。此结果对国内外利用SERS技术分析中药有效成分的基底选择有一定参考作用。     

贵金属纳米颗粒/石墨烯复合基底SERS研究进展

由于贵金属纳米颗粒/石墨烯复合基底可为喇曼光谱分析技术提供灵敏度高、稳定性好、生物相容性好的基底而备受关注。首先从电磁原理和化学原理两个角度出发,系统地探讨了贵金属纳米颗粒/石墨烯复合基底表面增强喇曼散射(SERS)的机理,进而概述了石墨烯及贵金属纳米颗粒的制备方法及其性能特征,并详细介绍了化学气相沉积法制备石墨烯和物理法制备贵金属纳米颗粒的过程。在此基础上,对不同贵金属纳米颗粒/石墨烯复合基底SERS的国内外研究进展进行了综合的阐述和分析,主要介绍了贵金属Ag,Au和Pt的纳米颗粒复合体系,最后对贵金属纳米颗粒/石墨烯复合基底SERS技术在各个领域的应用及其发展前景进行了展望。     

不同尺寸金纳米颗粒的制备及其SERS性能

为了研究不同尺寸的金纳米颗粒作为表面增强喇曼散射(SERS)活性基底对表面增强喇曼光谱的影响,采用氯金酸作为金源,柠檬酸三钠作为还原剂及保护剂,通过控制柠檬酸三钠的加入量合成了不同尺寸的金纳米颗粒。通过扫描电子显微镜(SEM)和紫外可见分光光度计(UV-vis)等技术对金纳米颗粒进行了性质表征。利用喇曼光谱仪,以罗丹明B作为被检测探针,研究了三种不同尺寸的金纳米颗粒(20、50和100 nm)喇曼增强效果。通过喇曼光谱图发现20和50 nm的金纳米颗粒具有较好的SERS效果。随后以20 nm的金纳米颗粒为SERS活性基底,对表面增强喇曼光谱检测罗丹明B的检测限进行了研究,可以使罗丹明检测限灵敏度达到10-9 mol/L。     

基于金银合金纳米线SERS活性基底的制备

首先采用液相软模板方法合成银纳米线,然后采用静电吸附法将带负电荷的银纳米线和带正电荷的金纳米颗粒组装形成金银合金纳米线。通过扫描电子显微镜(SEM)、透射电子显微镜(TEM)和X射线能谱分析仪(EDS)对材料的形貌和成分进行表征,结果表明金纳米颗粒被均匀吸附在银纳米线的表面。之后将金银合金纳米线偶联到氨基化处理后的硅片抛光面上,组装得到均匀、致密排列的金银合金纳米线表面增强喇曼散射(SERS)基底,该基底具有良好的重现性、均一性和SERS活性。使用尼罗蓝A (NBA)作为喇曼信号分子,SERS基底的最低检测浓度为7.93×10~(-10)mol/L,其分析增强因子(AEF)为6.31×10~7,SERS增强效应很高。此外金银合金纳米线具有高稳定性和良好的生物相容性,因此该基底在SERS生物传感方面具有广阔的应用前景。     

石墨烯/双金属纳米颗粒基底的制备及实验研究

提出了一种用化学气相沉积法(CVD)直接在贵金属表面生长石墨烯,得到石墨烯覆盖金属纳米颗粒的表面增强拉曼基底的方法,并对得到的基底进行了形貌表征、拉曼光谱表征和探针分子表征,从而分析讨论了基底结构的稳定性和增强因子。实验结果表明:制备得到的基底均匀,稳定性好,并且增强因子能够达到107。主要是石墨烯在拉曼基底中起到了保护贵金属而不被氧化的作用,并且能够有效抑制荧光,其化学增强对增强因子也有贡献。     

银光栅/银纳米颗粒复合结构的光场增强研究

通过时域有限差分法模拟了银光栅/银纳米颗粒复合结构的消光光谱和分布于光栅槽底的银纳米颗粒周围的电场分布。光栅的周期显著影响光栅和纳米颗粒之间的耦合作用,复合结构的共振峰随周期的增加而红移;在不同激发波长下,纳米颗粒周围的电场随周期的变化呈现出不同的规律。为了考察这种复合结构在表面增强拉曼散射光谱(SERS)研究中作为基底时的增强效果,比较了复合结构在785,633,532nm激光激发下的光场增强随周期的变化规律,得到综合增强性能最优的光栅周期为520nm。为了进一步提高复合结构的光场增强效果,对光栅栅脊宽度进行了优化。在优化好光栅周期和栅脊宽度的基础上,从SERS基底化学稳定性的需求出发,仿真了在光栅表面添加4nm金膜层后的银-金光栅/银纳米颗粒复合结构的电场增强效果。     

表面增强喇曼光谱研究脐橙中亚胺硫磷农药残留

为了证实以团絮状银胶为基底的表面增强喇曼光谱（SERS）技术结合化学计量学方法能有效实现脐橙中农药残留检测,采用德国布鲁克公司的共焦显微喇曼光谱仪,对脐橙中的亚胺硫磷农药残留的快速无损检测进行了研究。通过留一交互验证法得出农药检出限为4.113mg/L,并对SERS光谱进行7种方法的预处理。结果表明,先基线校正后卷积平滑预处理的建模预测效果最好;结合偏最小二乘法建模,预测集的相关系数和预测均方根误差分别为0.904和4.890mg/L,校正集的相关系数和预测均方根误差分别为0.919和3.990mg/L。结果证明了SERS定量分析的科学性和可行性,这对国内水果的生产和出口水果的农药残留检测有一定的参考作用。     

蓝紫光的腔增强空气喇曼光谱

喇曼光谱是一种无损、快速检测物质成分的方法。为了提高监测灵敏度, 对408nm波段半导体激光器的腔增强自发喇曼散射进行了研究。利用输出功率500mW、线宽0.9nm的408nm半导体激光器作激发光, 把激光耦合入共焦球面镜腔, 两面共焦球面镜的反射率分别为96.5%和99.5%, 部分激光返回半导体激光器形成光反馈, 半导体激光器与共焦腔形成共振。对装置的光反馈过程进行了探讨, 并对外腔的模式匹配和频率匹配分别进行了分析。结果表明, 共焦腔内功率达到15W, 功率增强了30倍; 用90°探测构型收集喇曼信号, 完成了空气喇曼信号检测; 1s积分时间, 获得N₂信号900个计数。此共振增强腔大大增强了喇曼散射信号, 有潜力应用于多种气体的在线检测或高灵敏度检测。     

表面增强喇曼散射两种增强机制的实验研究

本文通过在各种条件下银电极表面增强喇曼散射(SERS)的实验研究表明了“物理”和“化学”这两种增强机制的性质和所起的作用。     

表面增强喇曼光谱的Au@SiO2核壳纳米粒子制备北大核心

研究了核壳纳米颗粒的表面增强喇曼光谱（SERS）,并制备了不同SiO2厚度的Au@SiO2核壳纳米粒子进行喇曼光谱分析测试。首先,采用化学还原法制备出酒红色的金溶胶溶液。接着,添加不同量的正硅酸四乙酯（TEOS）制备了以Au为核、不同厚度SiO2为壳包裹的Au@SiO2核壳纳米粒子。然后,采用紫外-可见光（UV-Vis）和扫描电子显微镜（SEM）对Au@SiO2核壳纳米粒子的结构进行表征。最后,不同SiO2厚度的Au@SiO2核壳纳米粒子和未进行表面修饰的金溶胶溶液中滴入等量质量浓度为0.1 mg/L的罗丹明B,离心干燥后用喇曼光谱仪测试表面增强喇曼光谱效应。结果表明：罗丹明B的检出限可达到2.1×10^-7 mol/L,在扫描范围为300-1 800 cm^-1,激发波长为532 nm的条件下,SERS活性随TEOS用量的增加先增大后减小。TEOS的用量为120μL时,罗丹明B的表面喇曼增强效应最佳。     

修饰银纳米粒子的石墨烯泡沫镍衬底制备及其SERS活性研究

为了解决表面增强拉曼散射(SERS)衬底的吸附性差、稳定性低以及灵敏度不高的问题,设计了一种沉积银纳米粒子的石墨烯泡沫镍SERS衬底,并进行了实验研究.利用化学气相沉积法在泡沫镍衬底上生长石墨烯,并通过溶液沉积的方法将合成的银纳米粒子沉积在石墨烯泡沫镍衬底表面,烘干后制备成石墨烯泡沫镍修饰银纳米粒子的新型SERS衬底.采用罗丹明6G(R6G)对SERS衬底进行拉曼实验研究,结果表明石墨烯能够较好地淬灭SERS衬底的背景荧光;泡沫镍的独特三维结构能够增大衬底对检测分子的吸附;同时,银纳米粒子也可大幅增强衬底的SERS活性.而修饰了银纳米粒子的石墨烯泡沫镍新型衬底同时具有以上优异特性,是一种具有很大应用潜力的新型SERS衬底.     

Graphene as an Electron Shuttle for Silver Deoxidation: Removing a Key Barrier to Plasmonics and Metamaterials for SERS in the Visible

The role of graphene in enabling deoxidation of silver nanostructures, thereby contributing to enhance plasmonic properties and to improve the temporal stability of graphene/silver hybrids for both general plasmonic and meta‐materials applications, as well as for surface enhanced Raman scattering (SERS) substrates, is demonstrated. The chemical mechanism occurring at the graphene–silver oxide interface is based on the reduction of silver oxide triggered by graphene that acts as a shuttle of electrons and as a kind of catalyst in the deoxidation. A mechanism is formulated, combining elements of electron transfer, role of defects in graphene, and electrochemical potentials of graphene, silver, and oxygen. Therefore, the formulated model represents a step forward from the simple view of graphene as barrier to oxygen diffusion proposed so far in literature. Single layer graphene grown by chemical vapor deposition is transferred onto silver thin films, a periodic silver fishnet structure fabricated by nanoimprint lithography, and onto silver nanoparticle ensembles supporting a localized surface plasmon resonance in the visible range. Through the study of these nanostructured graphene/Ag hybrids, the effectiveness of graphene in preventing and reducing oxidation of silver plasmonic structures, keeping silver in a metallic state over months at air exposure, is demonstrated. The enhanced and stable plasmonic properties of the silver‐fishnet/graphene hybrids are evaluated through their SERS response for detecting benzyl mercaptane.     

Tunable Enhancement of Raman Scattering in Graphene‐Nanoparticle Hybrids

The realization of graphene‐gold‐nanoparticle (G‐AuNP) hybrids is presented here through a versatile electrochemical approach, which allows the continuous tuning of the size and density of the particles obtainable on the graphene surface. Raman scattering from graphene, which is significantly enhanced in such hybrids, is systematically investigated as a function of the size and density of particles at the same location. In agreement with theory, it is shown that the Raman enhancement is tunable by varying predominantly the density of the nanoparticles. Furthermore, it is observed that the increase in Raman cross‐section and the strength of Raman enhancement varies as a function of the frequency of the vibrational mode, which may be correlated with the plasmonic fingerprint of the deposited AuNPs. In addition to this electromagnetic enhancement, support is found for a chemical contribution through the occurrence of charge transfer from the AuNPs onto graphene. Finally, G‐AuNP hybrids can be efficiently utilized as SERS substrates for the detection of specifically bound non‐resonant molecules, whose vibrational modes can be unambiguously identified. With the possibility to tune the degree of Raman enhancement, this is a platform to design and engineer SERS substrates to optimize the detection of trace levels of analyte molecules.     

Improving Graphene Diffusion Barriers via Stacking Multiple Layers and Grain Size Engineering

It is shown that the performance of graphene diffusion barriers can be enhanced by stacking multiple layers of graphene and increasing grain size. The focus is on large‐area barriers of graphene grown by chemical vapor deposition (CVD) in the context of passivating an underlying Cu substrate from oxidation in air at 200 °C and use imaging Raman spectroscopy as a tool to temporally and spatially map the barrier performance and to guide barrier design. At 200 °C in air, Cu oxidation proceeds in multiple regimes: first slowly via transport through atomic‐scale grain boundary defects inherent to CVD‐graphene and then more rapidly as the graphene itself degrades and new defects are formed. In the initial regime, the graphene passivates better than previously reported. Whereas oxidation through single sheets primarily occurs through grain boundaries, oxidation through multiple sheets is spatially confined to their intersection. Performance further increases with grain‐size. The degradation of the graphene itself at 200 °C ultimately limits high temperature but suggests superior low temperature barrier performance. This study is expected to improve the understanding of mass transport through CVD‐graphene materials and lead to improved large area graphene materials for barrier applications.     

Enhanced storage/operation stability of small molecule organic photovoltaics using graphene oxide interfacial layer

Graphene and graphene oxide (GO) have been applied in flexible organic electronic devices with enhanced efficiency of polymeric photovoltaic (OPV) devices. In this work, we demonstrate that storage/operation stability of OPV can be substantially enhanced by spin-coating a GO buffer layer on ITO without any further treatment. With a 2 nm GO buffer layer, the power conversion efficiency (PCE) of a standard copper phthalocyanine (CuPc)/fullerene (C₆₀) based OPV device shows about 30% enhancement from 1.5% to 1.9%. More importantly, while the PCE of the standard device drop to 1/1000 of its original value after 60-days of operation-storage cycles; those of GO-buffered device maintained 84% of initial PCE even after 132-days. Atomic force microscopy studies show that CuPc forms larger crystallites on the GO-buffered ITO substrate leading to better optical absorption and thus photon utilization. Stability enhancement is attributed to the diffusion barrier of the GO layer which slow down diffusion of oxygen species from ITO to the active layers.     

自组装法制备团簇Ag纳米结构衬底及其SERS

采用自组装方法,在3-Aminopropyltrimethoxy silane(APS)分子修饰后的玻璃衬底表面,获得了二维Ag纳 米结构衬底。在波长为532nm激光激发下,研究了沉积在衬底表面的 Rhodamine 6G(Rh6G)分子的拉曼光谱特性。结 果表明,制备的二维Ag纳米结构衬底具有强的拉曼增强特性,增强因子可以达到 10⁷ 倍。这说明,在外光场作用下,制备的Ag纳米结构衬底表面能够形成的强局部电磁场分布, 可以有效提升探针分子的光谱辐射效率,从而获得高增强拉曼散射。     

米状银纳米颗粒对局域电场增强的理论模拟

为了提高表面增强拉曼散射技术中基底的增强效果,采用时域有限差分算法从理论上对不同入射光偏振方向下米状银纳米颗粒的电场增强进行了模拟分析,分别研究了单个银纳米颗粒和不同组合的二聚体以及三聚体的形状、间距对局域电场强度的影响,并且详细讨论了导致电场增强的原因。结果表明,当米状银纳米颗粒长度约为300 nm时,应控制其短轴约为36 nm,间距约为2 nm,且入射光偏振方向平行于长轴,此时在颗粒的尖端处均会产生最大电场增强,其中二聚体尖端对尖端情形下增强效果尤为明显。该结论为拉曼基底实验中纳米颗粒的制备提供了一定的理论基础。     

Nondestructive Characterization of Graphene Defects

An effective method is reported for oxidizing graphene/copper film in which air oxidation of the underlying copper film occurs through the grain boundary lines of graphene without oxidizing graphene. This oxidation is realized by partially immersing the graphene/copper film in sodium chloride solution. Electrons generated during etching of the graphene/copper film in electrolyte diffuse into the film in contact with air, which eventually enhances air oxidation of copper through the graphene layer. While the graphene layer acts as a protective layer against oxidation of the copper film, oxidation of the underlying Cu film near graphene grain boundary lines is observed by optical microscopy. This observation could be attributed to the selective diffusion of oxygen radicals through isolated defects and graphene grain boundaries. The process involves no appreciable oxidation of the graphene layer including the graphene grain boundary, as confirmed by use of detailed Raman and X‐ray photoelectron spectroscopy.     

Enhanced Electrical Properties of Anisotropic Conductive Adhesive With $pi$ -Conjugated Self-Assembled Molecular Wire Junctions

We have investigated the electrical properties of anisotropic conductive adhesive (ACA) joint using submicrometer-sized (~500 nm in diameter) silver (Ag) particle as conductive filler with the effect of pi-conjugated self-assembled molecular wires. The ACAs with submicrometer-sized Ag particles have higher current carrying capability (~3400 mA) than those with micro-sized Au-coated polymer particles (~2000 mA) and Ag nanoparticles (~2500 mA). More importantly, by construction of pi-conjugated self-assembled molecular wire junctions between conductive particles and integrated circuit (IC)/substrate, the electrical conductivity has increased by one order of magnitude and the current carrying capability of ACAs has improved by 600 mA. The crucial factors that govern the improved electrical properties are discussed based on the study of alignments and thermal stability of molecules on the submicrometer-sized Ag particle surface with surface-enhanced Raman spectroscopy (SERS), providing a fundamental understanding of conduction mechanism in ACA joints and guidelines for the formulation of high-performance ACAs in electronic packaging industry.