单壁碳纳米管表面增强拉曼散射的新方法

依据碳纳米管独特的力学性能,在银表面直接研磨单壁碳纳米管(SWCNTs),在形成纳米级粗糙银表面的同时,SWCNTs管也吸附在银表面上,在银表面粗糙程度和SWCNTs厚度适中的区域得到了高质量的表面增强拉曼散射(SERS)谱。理论分析和实验结果表明,该方法是正确可行的。     

多元等离子体共振纳米结构的飞秒激光加工与拉曼检测应用

以多元金属纳米薄膜(金、银)为基底,利用飞秒激光加工技术制备得到多元等离子体纳米结构,并研究了其局域表面等离子体共振效应(Local Surface Plasmon Resonance,LSPR)和表面增强拉曼散射(Surface Enhanced Raman Scattering,SERS)性能。利用时域有限差分(Finite Difference Time Domain,FDTD)软件模拟了不同情况下(单层金膜、金银双层金属薄膜的平面以及阵列结构)的电场分布情况。根据仿真结果,相较于平面金属膜来说,飞秒激光制备的微纳结构阵列附近区域产生电磁场增强,集中在结构边缘处,且其强度变化与预期结果基本保持一致。此外,使用浓度为10-4 M和10-6 M的罗丹明(R6G)溶液进行SERS性能测试。测试的结果表明,单层平面金膜基本没有SERS峰值信号出现,而单层金膜上制备的等离子体纳米结构附近出现峰值信号,双层金属薄膜上制备的等离子体纳米结构展现出更高的SERS峰值信号。多元金属等离子体纳米结构展示出更强的局域表面等离子体共振效应,从而在表面增强拉曼散射、光催化、生物传感等领域具有广泛的应用。     

纳米金修饰碳纳米管阵列结构的表面增强拉曼散射

研究了纳米金粒子修饰碳纳米管阵列结构的表面增强拉曼散射性能.通过FDTD理论模拟仿真了不同粒径纳米金颗粒的场强分布;并采用化学还原的方法制备出直径分别为20、40和60 nm三种不同粒径的金颗粒,然后将纳米金粒子修饰到有序定向的碳纳米管阵列表面,并将该结构作为表面增强拉曼基底.FDTD软件仿真结果表明,60 nm粒径的纳米金颗粒周围场强分布最强,是入射场场强的15倍.同时将罗丹明6G溶液用于测试几组不同尺寸的金颗粒对拉曼散射光强的影响,发现60 nm金颗粒对R6G拉曼信号增强最大.FDTD理论模拟仿真和罗丹明6G溶液实验测试结果表明:金颗粒尺寸在20～60 nm内,颗粒尺寸越大,拉曼散射光的光强越大.     

Ag纳米粒子修饰多模光纤的拉曼增强特性实验

为了分析研究光纤表面增强拉曼散射(SERS)探针 的拉曼增强特性,采用简单廉价的化学方法制备Ag纳米颗粒修饰 光纤SERS探针,采用罗丹明6G(R6G,Rhodamine 6G)作为探针分子进行了不同浓度R6G溶 液(10－7~10－9M)的拉曼测试实 验和浓度为10－6M的R6G溶液的Time-course SERS Mapping实验,研究了该光纤 SER S探针的拉曼增强特性,制备的光纤SERS 探针样品检测R6G的极限浓度低至10－9M;在Time-course SE RS Mapping实验中,分 析验证了探针分子溶液蒸发过程对光纤 SERS探针的拉曼增强特性的影响。研究表明,由于制备的光纤SERS探针对荧光噪声没有抑 制作用,导致所测得探针分子 的拉曼光谱受探针分子溶液状态、测试方式的极大影响。当溶液充足时(浸泡状态),所测 光谱信号荧光噪声与有效拉曼光 谱信号都比较大;在溶液干燥过程中,所测光谱信号荧光噪声与有效拉曼光谱信号都减少, 但荧光噪声减小幅度远大于拉曼光谱信号。     

C层包覆Ag纳米颗粒基底的表面增强拉曼散射研究

Ag纳米结构是最常用的表面增强拉曼散射(SERS) 活性基底,缺点是Ag的化学稳定性和 生物相容性比较差。为此,利用化学方法合成了一种新型的SERS活性基底—纳米碳层包覆的 Ag(Ag@C)纳米颗粒。利用透射电子显微镜(TEM)和紫外- 可见吸收光谱对制备的核壳结构纳米颗粒进行了表征,并研究了颗粒的SERS活性。结果表明 ,罗丹明6G(R6G)、结晶紫(CV)和孔雀石绿(MG)分子在Ag@C悬浮液中的SERS光谱强度 与在Ag胶中的SERS光谱强度相比显著增强。根据光谱 的变化规律推断,额外的增强来自于化学增强。由于C层的存在,相比于Ag纳米颗粒, Ag@C颗粒的化学稳定性和生物相容性都有所改进。     

在银胶体系中罗丹明B单分子水平上拉曼光谱研究

采用表面增强托曼散射（SERS）技术,比较了单分子水平上银胶纳米体系中罗丹明B（RhB）浓度为10^-11mol／L以下的拉曼光谱和通常单分子水平上罗丹明6G（Rh6G）浓度在10^-11mol／L的拉曼光谱,无论自由沉积在玻璃表面还是在液体环境下的结果显示,单分子水平上Rh B的拉曼光谱灵敏度是Rh 6G的2倍多。因此,利用RhB作为探测试剂将能够提供更加丰富的信息,这对单分子的光谱研究以及高灵敏度探测试剂的应用研究具有重要的意义。     

金属纳米二聚体结构的局域表面等离子体激元共振特性研究

将金属纳米粒子二聚体结构作为光学谐振腔,采用 时域有限差分(FDTD)法仿真模拟了一种新型局域表面等离子体激光器(SPASER)。 使用洛伦兹复介电常数模型研究二聚体的增益介质特性,探讨了二聚体结构中 两个纳米局域表面等离子体激元共振(LSPR)以及相互作用机制,进一步研究了 LSPR相互作用对SPASER的局域场增强的影响。 模拟结果表明,相比较单纳米颗粒SPASER,LSPR的相互作用使得二聚体SPASER的局域电场显著 增强,增强因子最 大可以相差27倍。本文研究为纳米光学器件尤其是激光器件的设计提 供了依据。LSPR效应的 研究可以用于探索一些光与物质相互作用的极限效 应,从而为有源光子线路、生物传感以及量子信息处理等研究开辟道路。     

基于COMSOL的柔性表面增强拉曼散射基底研究

为提高表面增强拉曼散射(Surface-enhanced Raman scattering, SERS)基底的性能,采用COMSOL Multiphysics仿真软件通过有限元法对两个相邻的纳米颗粒的模型进行仿真。仿真结果表明,当纳米颗粒半径一定时,增强因子随间距的增大而快速减小;当间距一定时,增强因子随半径的增大而增大,半径达到300 nm后,增强因子趋于稳定,且呈一定的下降趋势。同时,设计并构建了倒圆锥模型的SERS基底,仿真得到其增强因子为2.66×10⁵,相比于倒金字塔模型(增强因子为1.57×10⁵)具有更优异的性能。基于所得到的仿真结果对倒圆锥模型进行优化,银纳米颗粒间距从10 nm依次减小为5 nm,增强因子得到显著提高,极大地提高了表面增强拉曼散射基底的性能。     

交叉蝴蝶结纳米结构的Fano共振效应用于表面增强相干反斯托克斯拉曼散射的理论研究

Fano共振效应拥有独特的局域场增强效果,在表面增强相干反斯托克斯拉曼散射中,不同波长局域场增强空间位置相同的结构结合Fano共振效应,可以实现混合频率共振模式,使得表面增强相干反斯托克斯拉曼散射总的增强因子得到大幅度提高。采用FDTD软件系统研究了对称的交叉蝴蝶结Au纳米结构的Fano共振效应,该效应使得交叉蝴蝶结结构中心位置附近的电场强度得到大幅度的增强,把该结构应用到表面增强相干反斯托克斯拉曼散射中,可以使表面增强相干反斯托克斯拉曼散射信号的增强因子高达1013,达到单分子检测的水平。     

基于球状光纤的表面增强拉曼散射探针

通过烧制光纤小球制备球状光纤探针,并通过自组装法使银纳米颗粒较为均匀地分布在光纤探针表面,经测量计算得到球状光纤探针上银纳米颗粒的增强因子为7.2×104。利用浓度为10-5 mol·L-1的罗丹明6G（R6G）溶液检测得到光纤小球直径在200 μm左右时SERS增强效果最佳,且在相同实验条件下,制备的球状光纤探针与锥柱组合型光纤探针的SERS增强效果基本一致。球状光纤探针制作工艺简单安全、灵敏度高且结构稳定,在分子检测方面具有很大的应用前景。     

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。     

Supported Faceted Gold Nanoparticles with Tunable Surface Plasmon Resonance for NIR‐SERS

A novel dry plasma methodology for fabricating directly stabilized substrate‐supported gold nanoparticle (NP) ensembles for near infrared surface enhanced Raman scattering (NIR SERS) is presented. This maskless stepwise growth exploits Au‐sulfide seeds by plasma sulfidization of gold nuclei to produce highly faceted Au NPs with a multiple plasmon resonance that can be tuned from the visible to the near infrared, down to 1400 nm. The role of Au sulfidization in modifying the dynamics of Au NPs and of the corresponding plasmon resonance is discussed. The tunability of the plasmon resonance in a broad range is shown and the effectiveness as substrates for NIR SERS is demonstrated. The SERS response is investigated by using different laser sources operating both in the visible and in the NIR. SERS mapping of the SERS enhancement factor is carried out in order to evaluate their effectiveness, stability, and reproducibility as NIR SERS substrates, also in comparison with gold NPs fabricated by conventional sputtering and with the state‐of‐the‐art in the current literature.     

Hierarchically Ordered Arrays of Noncircular Silicon Nanowires Featured by Holographic Lithography Toward a High‐Fidelity Sensing Platform

A novel, highly uniform and tunable hybrid plasmonic array is created via ion‐milling, catalytic wet‐etching and electron‐beam evaporation, using a holographically featured structure as a milling mask. A simple and low‐cost prism holographic lithography (HL) technique is applied to create an unprecedentedly coordinated array of elliptic gold (Au) holes, which act as the silicon (Si) etching catalyst in the reaction solution used to fabricate an elliptic silicon nanowire (SiNW) array; here, the SiNWs are arrayed hierarchically in such a way that three SiNWs are triangularly coordinated, and the triangles are arranged hexagonally. After removing the polymeric mask and metal thin film, the highly anisotropic thick Au film is deposited on the SiNW arrays. This hybrid substrate shows tunable optical properties in the near‐infrared (NIR) region from 875 nm to 1030 nm and surface‐enhanced Raman scattering (SERS) activities; these characteristics depend on the catalytic wet etching time, which changes the size of the vertical gap between the Au thick films deposited separately on the SiNWs. In addition, lateral interparticle coupling induces highly intensified SERS signals with good homogeneity. Finally, the Au‐capped elliptical SiNW arrays can be hierarchically patterned by combining prism HL and conventional photolithography, and the highly enhanced fluorescence intensity associated with both the structural effects and the plasmon resonances is investigated.     

Exploring How to Increase the Brightness of Surface‐Enhanced Raman Spectroscopy Nanolabels: The Effect of the Raman‐Active Molecules and of the Label Size

Due to the surface‐enhanced Raman scattering (SERS) effect, SERS labels based on noble‐metal nanoparticles loaded with Raman‐active molecules are good candidates for ultrasensitive multiplexed assays and in vitro/in vivo imaging. However, understanding how to maximize the brightness of such labels is of paramount importance for their widespread application. The effective differential Raman scattering cross‐section (dσ_R/dΩ) of SERS labels made of pegylated gold nanoparticles loaded with various Raman active molecules (Raman reporters) is studied. It is found that proper choice of the Raman reporter and of nanoparticle size can enhance the dσ_R/dΩ by several orders of magnitude. The experimental results are understood by considering the molecular cross‐section for resonant Raman scattering and the local electromagnetic enhancement factor (G_SERS) in the nearby of gold nanoparticles. These results are useful to guide the design of SERS labels with improved performances and to provide a reference for the comparison of the absolute value of the dσ_R/dΩ of SERS labels based on metal nanoparticles.     

Multilayer Graphene with a Rippled Structure as a Spacer for Improving Plasmonic Coupling

The plasmonic coupling, the enhanced electromagnetic field occurring through a uniform and small separation between metallic particles, is required for better application to localized surface plasmon resonance. Graphene has been studied as a good spacer candidate because of its precise controllability at subnanoscale. Here, the enhancement of plasmonic coupling among metallic nanoparticles (NPs) uniformly spread out on both sides of a graphene spacer is experimentally and simulatively investigated. Additionally, the post‐evaporated flat structure is rippled along one direction to reduce the separation between nanoparticles. As the amount of rippling increases, the enhancement factor (EF) of the plasmonic coupling increases almost linearly or quadratically depending on the size of nanoparticles. Such a highly rippled nanostructure is believed to not only increase the plasmonic coupling in either side of the spacer but lead to a higher density of “hot spots” through the spacer gap also. The observed EFs of a structure with the MLG spacer are consistent with the simulation results obtained from the classical electrodynamics. On the other hand, the SLG case appears to be inconsistent with such a classical approach, indicating that the plasmon tunneling through the thin barrier is prevalent in the case of the SLG spacer.     

High enhancement factor of Au nano triangular prism structure for surface enhanced coherent anti-Stokes Raman scattering

Coherent anti-Stokes Raman scattering spectroscopy(CARS) is a well-known detecting tool in biosensing and nonlinear spectroscopy. It can provide a non-invasive alternative without the need for exogenous labels, while the enhancement factor for surface plasmon resonances(SPR) are extensively used to increase the local field close to the oscillators and which can obtain high enhancement. In this work, we investigate the enhancement factor of our structure for surface-enhanced coherent anti-Stokes Raman scattering. The absorption spectrum of the structure has been studied, a wide range of absorption has been realized. The enhancement can be as high as 10¹⁶ over standard CARS. Our design is very useful for improving the enhancement factor of surface-enhanced coherent anti-Stokes Raman scattering.     

纳米银颗粒表面增强荧光效应与其覆盖率的关联

实验上获得了纳米银颗粒对光敏剂二氢卟吩f-甲醚(CPD4)的荧光增强效应,基于纳米银颗粒覆盖率对表面增强荧光效应的影响,初步探讨了荧光增强的物理增强机制。不同覆盖率纳米银基底表面吸附的CPD4的增强荧光结果显示,在低颗粒覆盖率时(<30%),激发效率和激发态分子衰减速率不依赖于覆盖率变化;当颗粒覆盖率大于30%接近40%时,激发效率和激发态分子衰减速率都得到提高。实验和理论结果均表明,相比于单个银纳米颗粒,颗粒覆盖率增加提高了颗粒间电磁耦合效应,能够产生更强的表面增强荧光效应。     

Surface Plasmon Resonance Sensors Based on Polymer Optical Fiber

Surface Plasmon Resonance （SPR） is a powerful technique for directly sensing in biological studies, chemical detection and environmental pollution monitoring. In this paper, we present polymer optical fiber application in SPR sensors, including wavelength interrogation surface enhanced Raman scattering SPR sensor and surface enhanced Raman scattering （SERS） probe.
Long-period fiber gratings are fabricated on single mode polymer optical fiber （POF） with 120 μm period and 50% duty cycle. The polarization characteristic of this kind of birefringent grating is studied. Theoretical analysis shows it will be advantageous in SPR sensing applications.     

金属尖端角度对表面增强拉曼散射的影响

金属尖端对于表面拉曼散射有增强的效果,但尖端的尖锐程度对于表面增强拉曼散射(Surface-Enhanced Raman Scattering, SERS)的影响很少有定量的报道。为了研究角度大小与SERS的关系,需要制备具有不同角度的结构。利用数字微镜设备（Digital Micro mirror Device, DMD）进行光学投影光刻制备了四组样品,分别具有30°60°90°120°角金属微结构,测量了这些结构对应的SERS谱,研究金属尖端角度大小对于SERS的影响。研究发现,锐角具有更好的表面增强拉曼散射效果,而且增强效果对角度依赖强烈,角度越小增强效果越明显;钝角情况下,SERS对于角度大小依赖的敏感度下降。