表面增强荧光效应研究进展

在外光场激励下,金属纳米结构衬底表面所形成的集体电子振荡模式可有效调制其局域电磁场分布,对居于衬底附近的荧光分子的荧光辐射产生调控。其影响因素主要取决于衬底金属表面所形成的电磁振荡模式和电磁场分布性质。归纳了光谱学中表面增强荧光效应研究的关键问题,指出了周期性有序衬底金属增强荧光及其金属纳米颗粒增强荧光研究的主要研究进展。基于局域电磁场增强机理模型,讨论了不同形貌衬底金属对荧光分子的荧光调控机理和影响因素。对表面增强荧光效应的研究前景进行了展望。     

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。     

具有分形结构Ag纳米衬底的荧光增强效应

利用电化学沉积方法,制备出具有分形结构的Ag纳米荧光增强衬底。实验中,采用532nm连续光激发居于Ag纳米结构衬底表面附近的罗丹明6G(Rh6G)荧光分子,结果表明,具有分形结构的Ag纳米金属衬底对沉积在其表面的Rh6G分子表现出明显的荧光增强效应。根据局域场增强理论对所得实验结果进行分析,经过电化学方法制备出的分形Ag纳米结构,在外电磁场激发下能够形成较强的局域电磁场分布,从而有效地激发Rh6G荧光分子,增强其荧光辐射强度。     

纳米结构分子吸附引起的表面增强拉曼散射研究

利用模板印刷技术,制备了具有不同局域表面等离子体共振(LSPR)峰的Au纳米空心半球壳结构,并以4-巯基苯胺(4-ATP)为探针分子研究了纳米结构表面吸附分子对表面增强拉曼散射(SERS)强度的影响。结果表明,当纳米结构的LSPR峰位处于激发光波长的短波长或"马鞍型"位置时,SERS强度随吸附分子数的增加而增大;当处于长波长位置时,SERS强度呈现先增大后减小的趋势。利用分子吸附理论和纳米结构表面局域场强度变化,对此现象进行了解释。     

基于局域表面等离激元Ag/金刚石纳米结构增强NV色心的荧光

在纳米光子学中,提高量子点的荧光强度是一个需要迫切解决的难题,现如今金属纳米材料是一种很有前途的荧光增强材料。通过Ag纳米结构的局域表面等离激元效应提高金刚石氮空位(NV)色心的荧光强度,制备了不同的Ag纳米结构(Ag纳米柱阵列和Ag纳米层),探究其对NV色心的荧光增强效果。结果表明,Ag纳米柱阵列结构的加入可将金刚石NV色心的荧光强度增强2.30倍,Ag纳米层结构的加入可将其增强1.54倍。并且,采用时域有限差分(FDTD)法分析激发和发射两个过程发现,金刚石NV色心的荧光强度随着Ag纳米结构的加入显著提高,由此验证了实验中Ag纳米结构对金刚石NV色心荧光增强的效果。此研究结果为后续进行量子点光致发光器件的设计提供了一定的参考。     

自组装法制备Au纳米结构衬底及其表面增强荧光效应研究

采用自组装方法,在(APS)分子修饰后的玻璃衬底 表面,制备得 到Au纳米结构衬底。采取激光光谱学方法,研究所制备衬底对沉积其表面的Rhodamine 6G(R h6G) 分子的荧光辐射增强效应。实验发现,利用自组装方法制备的Au纳米结构衬底具有较强的荧 光增 强特性。理论分析表明,制备的Au纳米结构在外光场激发下,所形成的强局部电磁场分布 能够有效提升探针分子的电子跃迁速率,从而实现增强荧光效应。     

银纳米颗粒的局域表面等离子体共振传感

采用微波法合成银纳米颗粒,通过化学自组装技术将银纳米颗粒吸附在玻璃基片上,制备了银纳米颗粒的局域表面等离子体传感器。在纯水中,紫外可见光消光谱表明局域表面等离子体共振位于428nm处。随外界折射率增加,共振峰发生红移,其折射率灵敏度达到173±6nm/RIU。在350oC温度下退火处理后,改变银颗粒在基片上的形貌,峰位发生约65nm的红移,灵敏度下降约20%。理论分析表明,银纳米颗粒形状和基底的相互作用影响折射率传感的波长响应和灵敏度特性。     

纳米银立方体与银膜耦合结构的电场特性

纳米金属颗粒及其与金属膜的耦合结构具有比单元结构更优越的物理性质。为了给实验研究纳米银立方体和银膜耦合结构在传感中的应用提供理论依据,运用FDTD方法数值分析了纳米银立方体与银膜耦合体系在波长为514.5 nm的激光激发下的电场性质。结果表明,耦合结构的电场分布与纳米银立方体的大小、及其与银膜间的介质层厚度有关;纳米银立方体与银膜耦合结构局域电场比纳米银立方体的局域电场强;当其间没有介质层时,局域电场主要分布在纳米银立方体的上表面顶点;当有介质层时,局域电场会有部分转向高折射率介质层中。因此,可根据需要,通过调控纳米银立方体的大小及其与银膜间的介质厚度来获得理想的局域电场。     

Plasmonically enhanced lasing by different size silver nanoparticles-silver film hybrid structure

We reported on the enhanced lasing in organic dyes based on plasmonic hybrid structure of Ag nanoparticles (NPs)-Ag film, the diameters of Ag NPs ranged from 20 nm to 100 nm. The lowest lasing threshold was achieved by the optimal size Ag NPs-Ag film hybrid structure, which was reduced by 5.2 times than that of the neat gain medium. Comparing to the separate Ag NPs or Ag film, the hybrid structure presented the more intense local electric field due to the plasmonics coupling between the localized surface plasmons of Ag NPs and the surface plasmon polariton of Ag film, and the stronger scattering due to the reinjection of the leaking photons by external feedback of Ag film. The effects of different sizes Ag NPs-Ag film hybrid structures on lasing were investigated. It found that when the Ag NPs in hybrid structure is small (diameter≤40 nm), the enhanced localized electric field plays a major role on enhanced lasing; with the increase of Ag NPs size, the enhanced electric field and scattering have comparable contribution on enhancing lasing; for the larger size Ag NPs-Ag film (diameter≥80 nm), the scattering effect is the dominant mechanism for random lasing. Then the lowest threshold was dominated by the balance of enhanced localized electric field and scattering effect. Our results could provide us a unique idea to effectively enhance the lasing of organic dyes, and realize the lower pumped threshold and stronger lasing.     

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.     

Nonlinear optical dynamics of glass-embedded silver nanoparticles

The nonequilibrium carrier dynamics in Ag nanoparticles was explored by femtosecond optical pump-probe spectroscopy. Metal-dielectric nanocomposite materials containing Ag nanoparticles of different sizes were prepared by thermal treatment of aluminophosphate glasses. The ultrafast relaxation dynamics of the electron scattering on the 10⁻¹³–10⁻¹² sec scale shows size-and pump power-dependent properties. The two-photon absorption process in nanoparticles of different sizes is discussed. The laser-induced coherent vibrations of nanoparticles were observed in transient transmission experiments.     

荧光光谱法研究分子间相互作用的应用进展

本文综述了基于荧光淬灭的荧光光谱法应用于生物大分子与小分子之间相互作用的研究.重点介绍了荧光光谱研究药物与DNA相互作用,药物与蛋白相互作用,药物与其它分子之间的相互作用.     

Periodic Arrays of Diamond‐Shaped Silver Nanoparticles: From Scalable Fabrication by Template‐Assisted Solid‐State Dewetting to Tunable Optical Properties

Periodic arrays of anisotropic silver nanoparticles having peculiar optical properties are fabricated at a macroscopic scale. The proposed scalable method is based on temperature‐assisted solid‐state dewetting of a continuous thin layer deposited on a silica substrate patterned by the nanoimprint technique. The resulting nanoparticles are shaped like diamonds and are half‐embedded into the patterned silica. A period‐dependent optimum in film thickness for the quality of spatial organization is found and discussed in terms of thermodynamics and, for the first time, in terms of the role of grains in the dewetting process. The optical properties of the arrays are driven by not only simply the particle shape but also the lattice period and the degree of order. A surface lattice resonance that disperses with the underlying period is evidenced experimentally and confirmed by optical simulations. The opportunity to fabricate and tune such an assembly of plasmonic particles on transparent substrate opens interesting perspectives for not only fundamental photonics but also potential optical applications.     

金纳米颗粒增强富硅氮化硅发光特性的研究

采用时域有限差分(FDTD)方法,对Au纳米颗粒的尺寸和形貌对于其光学特性的影响进行了系统的理论研究。通过采用等离子体增强化学气相沉积(PECVD)、晶化处理、电子束蒸发和高温退火等工艺,制备基于局域表面等离子共振(LSPR)效应的富硅氮化硅发光芯片。利用拉曼光谱仪、扫描电子显微镜(SEM)、奥林巴斯显微镜等对不同结构Au纳米颗粒富硅氮化硅发光器件的特性进行了表征。研究表明,通过对Au纳米颗粒的大小、形状和分布合理优化,富硅氮化硅芯片的发光强度在570nm波长附近提升了7倍,增强峰的位置红移了10nm。     

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.     

受纳米结构损伤限制的光纤拉曼探头SERS探测灵敏度

利用光线追迹法,研究了典型光纤拉曼探头在纳米结构损伤限制下收集到的SERS功率与样品位置之间关系,结果表明,对于不同焦距构成的同轴等光程光纤拉曼探头,在给定的纳米结构损伤阈值激发光功率密度下,样品偏离焦平面反而会使探头收集到的SERS功率增加,相比于样品远离探头方向偏离焦平面,靠近探头方向偏离焦平面时收集到的SERS功率更高。此外,收集光纤芯径越大,探头所收集的SERS功率越大。