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。     

Catalytic Performance of Nanoscale‐Corrugated Gold and Silver Films for Surface‐Enhanced Chemiluminescence

Biochips of corrugated gold and silver displaying surface plasmon resonance at different energies are fabricated to determine the nature of the mechanism responsible for the surface‐enhanced chemiluminescence (SECL) of luminol. This Full Paper proves that, whereas silver possesses the strongest resonance and the greatest plasmon overlap with luminol emission, silver is also the metal that induces the lowest CL enhancement (two orders of magnitude less than gold). Therefore, the enhancement mechanism is not related to plasmon‐assisted processes but rather originates from catalytic properties induced by corrugation of the metal film.     

表面等离子体近场光刻制作二维纳米阵列

重点介绍了采用表面等离子体增强效应的近场光刻制作亚微米结构的二维点阵图形的技术。在研究亚波长纳米孔阵列超透射现象基本原理的基础上,应用有限差分时域(FDTD)算法数值模拟了周期性孔阵列的电场强度分布,讨论了纳米孔阵列所激发的表面等离子体激元提高近场光刻分辨率的微观机制。以金膜上的亚波长纳米孔阵列作为掩模版进行了接触式曝光实验,实际制作出了光刻胶的亚波长二维点阵图形,点阵图形的直径约为300nm,周期约为700nm。这种新型的微纳加工技术具有应用简单、成本低等特点,在大规模二维纳米点阵的制作方面有一定的应用潜力。     

All thermal-evaporated surface plasmon enhanced organic solar cells by Au nanoparticles

Au nanoparticles (NPs) are fabricated on indium-tin-oxide substrates by a thermal evaporation method and incorporated to an efficient small molecule organic solar cell (OSC). This renders an all thermal evaporated surface plasmon enhanced OSC. The optimized device shows a power conversion efficiency of 3.40%, which is 14% higher than that of the reference device without Au NPs. The improvement is mainly contributed to the increased short-circuit current which resulted from the enhanced light harvesting due to localized surface plasmon resonance of Au NPs and the increased conductivity of the device.     

Surface plasmon enhanced blue organic light emitting diode with nearly 100% fluorescence efficiency

Surface plasmon (SP) enhanced blue organic light emitting diodes (OLEDs) have been realized by using silver nanoclusters (SNCs) deposited using thermal evaporation technique. SNCs were found to have the surface plasmon resonance at wavelength 445 nm and were used with blue emitting layer BCzVBi. The optimized OLED (in terms of the size of SNCs and the distance between SNCs and emitting layer) were found to have the efficiency two times higher than reference OLED without SNCs. Internal quantum efficiency was calculated to be 24% for SP enhanced OLED owing to 96% fluorescence efficiency. Energy transfer between exciton and SPs with the separation distance have been studied experimentally and using 2D-FDTD simulation and surface–dipole energy transfer has been observed.     

Self‐Assembly of Nanoparticle‐Spiked Pillar Arrays for Plasmonic Biosensing

Plasmonic biosensors have demonstrated superior performance in detecting various biomolecules with high sensitivity through simple assays. Scaled‐up, reproducible chip production with a high density of hotspots in a large area has been technically challenging, limiting the commercialization and clinical translation of these biosensors. A new fabrication method for 3D plasmonic nanostructures with a high density, large volume of hotspots and therefore inherently improved detection capabilities is developed. Specifically, Au nanoparticle‐spiked Au nanopillar arrays are prepared by utilizing enhanced surface diffusion of adsorbed Au atoms on a slippery Au nanopillar arrays through a simple vacuum process. This process enables the direct formation of a high density of spherical Au nanoparticles on the 1 nm‐thick dielectric coated Au nanopillar arrays without high‐temperature annealing, which results in multiple plasmonic coupling, and thereby large effective volume of hotspots in 3D spaces. The plasmonic nanostructures show signal enhancements over 8.3 × 10⁸‐fold for surface‐enhanced Raman spectroscopy and over 2.7 × 10²‐fold for plasmon‐enhanced fluorescence. The 3D plasmonic chip is used to detect avian influenza‐associated antibodies at 100 times higher sensitivity compared with unstructured Au substrates for plasmon‐enhanced fluorescence detection. Such a simple and scalable fabrication of highly sensitive 3D plasmonic nanostructures provides new opportunities to broaden plasmon‐enhanced sensing applications.     

Sinusoidal plasmonic crystals for bio-detection sensors

Corrugated gratings coated with thin films of noble metals have been recognized to be useful substrates for bio-detection by means of the excitation of surface plasmon polaritons (SPP). These substrates show superior performances in terms both of detection limit and of simplicity of detection configuration compared to the classical Kretschmann SPP. A 1D sinusoidal corrugation of the metal-air interface has been fabricated by means of laser interference lithography and metal evaporation. In this paper we report progress in the optimization of the sinusoidal grating surface profile. The quality of the fabricated samples has been proved by the good agreement between experimental and simulated results.     

Real‐Time Probing Nanopore‐in‐Nanogap Plasmonic Coupling Effect on Silver Supercrystals with Surface‐Enhanced Raman Spectroscopy

Nanopore structures have displayed attractive prospects in diverse important applications such as nanopore‐based biosensors and enhanced spectroscopy. However, on the one hand, the fabrication techniques to obtain sub‐10 nm sized nanopores so far is very limited. On the other hand, the electromagnetic enhancement of nanopores is still relatively low. In this work, using a facile chemical etching strategy on 2D plasmonic Ag nanoparticle supercrystals, fine nanopore arrays with sub‐10 nm pore size have been successfully fabricated and a “nanopore‐in‐nanogap” hybrid plasmon mode has been investigated. An in situ etching and surface‐enhanced Raman spectroscopy (SERS) detection indicate that novel hybrid plasmon structure may create an enhanced electromagnetic coupling and increase SERS signal at ≈10× magnification. The breaking of plasmon bonding dipolar mode and generation of antibonding‐like plasmon mode contribute to this enhanced electromagnetic coupling. The facile etching strategy, as a common approach, may open the doors for the fabrication of nanopores in various compositions for numerous applications.     

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。     

Research on the impact of spin coating silver nano clusters on the performance of OLED devices

To achieve uniform distribution of silver nano clusters (SNCs) on substrate and reveal its effect on the performance of organic light-emitting diode (OLED), the SNCs incorporated OLED was fabricated and SNCs were coated by multi-step spin coating. Compared with the device without SNCs film, the brightness and current efficiency of the OLED devices with SNCs film were highly raised. The enhancement is attributed to SNCs induced local surface plasmon (LSP) oscillation, which can increase the radiative rate of excitons on Alq₃ molecules.     

具有金属纳米颗粒结构的微小孔面发射激光器

在普通850nm垂直腔面发射激光器基础上制备出带有金属纳米颗粒结构的微小孔径垂直腔面发射激光器。当小孔和金属颗粒的直径分别为400nm和100nm时,其最大输出光功率达到0.5mW。介绍了该器件的制备工艺,从实验和理论两方面验证了金属纳米颗粒结构激发局域表面等离子体,从而使输出光功率得到提高。     

金属颗粒对微小孔激光器增强透射的研究

制备了带有金属纳米颗粒结构的微小孔径垂直腔面发射激光器(NA-VCSEL)。当小孔和金属颗粒的直径分别为400 nm和100 nm时,其最大输出光功率达到了0.5 mW,比400 nm单个小孔的最大输出光功率提高了0.2 mW。实验和理论验证了金属纳米颗粒结构对NA-VCSEL输出光功率的增强作用。     

Surface-enhanced fluorescence from copper nanoparticles on silicon nanowires

A method to enhance surface plasmon coupled fluorescence from copper nanoparticles on silicon nanowires is presented. Owing to resonant plasmons oscillation on the surface of Cu/Si nanostructure, the fluorescence peaks of several lanthanide ions (praseodymium ions, Pr3+,neodymium ions Nd3+, holmium ions Ho3+, and erbium ions Er3+) were markedly enhanced with the enhancement of maximal 2 orders of magnitude, which was larger than that caused by unsupported Cu nanoparticles. These results might be explained by the local field overlap originated from the closed and fixed copper nanoparticles on silicon nanowires.     

Enhancement of top emission for organic light-emitting diode via scattering surface plasmons by nano-aggregated outcoupling layer

A stable self nano-aggregated bathocuproine film was fabricated and introduced atop of a conventional organic light emitting diode for enhancing top emission. It leads to a 2.7–2.1-fold enhancement on top emission at applied voltage from 4 to 9 V which is much larger than the 1.5–1.3-fold enhancement for a device overlaid with an amorphous bathocuproine film. The more effective outcoupling of this method probably arises from surface plasmon modes being scattered by only the nanostructured surface, and thus without phase cancellation, at the bathocuproine/air boundary. Moreover, this method nearly preserves the original electroluminescent spectra and has no damage on electrical properties.     

High efficiency polymer solar cells with wet deposited plasmonic gold nanodots

We report the enhanced performance of poly(3-hexylthiophene)/[6,6]-phenyl-C₆₁ butyric acid methyl ester (P3HT/PCBM) bulk heterojunction solar cells with wet deposited interfacial gold nanostructures on their indium tin oxide (ITO) surfaces. To produce localized surface plasmons at the ITO surfaces, gold nanostructures were fabricated through the layer-by-layer deposition of gold nanorods onto the ITO substrates and transformed into nanodots through a thermally induced shape transition. The incorporation of plasmonic gold nanodots on the ITO surface was found to result in an increase in the power conversion efficiency from 3.04% to 3.65%, which is due to the presence of the resulting plasmon field.     

透射式金属光栅耦合SPR传感器

用磁控溅射技术在双面抛光的蓝宝石衬底上沉积了20 nm Ti和100 nm Au的金属薄膜,通过标准光刻工艺制备出1.6和2.0μm两种周期结构的一维光栅表面等离子体共振(SPR)传感器。用时域有限差分算法(FDTD)模拟仿真并结合实验测试的透射光谱,研究分析了不同周期结构的金属薄膜光栅型SPR传感器的特性。基于金属光栅耦合,利用表面等离子体激元(SPP)的局域特性和光栅的选频特性,实现了SPR传感器的信号增强和滤波功能。研究结果表明,利用金属薄膜光栅表面介质的变化引起的光栅透射光谱中激发表面等离子体共振峰的位置变化,可以获得被测物体的物理、生物和化学等相关特征信息。     

Enhanced ultraviolet emission of ZnO microrods array based on Au surface plasmon

In this work, the Au/ZnO hybrid microstructure was fabricated by assembling Au nanoparticles (NPs) onto the surface of ZnO microrods, and an obviously improved ultraviolet (UV) emission of ZnO is observed in the hybrid microstructure. About 27-fold enhancement ratio of the UV emission to the green band emission of ZnO is achieved. The underlying enhanced mechanism of the UV emission intensities can be ascribed to the charge transfer and the efficient coupling between ZnO excitons and Au surface plasmon (SP).     

Tailored Plasmonic Gratings for Enhanced Fluorescence Detection and Microscopic Imaging

The ability to precisely control the pattern of metallic structures at the micro‐ and nanoscale for surface plasmon coupling has been demonstrated to be essential for signal enhancement in fields such as fluorescence and surface‐enhanced Raman scattering. In the present study, a series of silver coated gratings with tailored duty ratio and depth and a periodical pitch of 400 nm are designed and implemented. The influence of the grating profile on plasmonic properties and the corresponding enhancement factor are investigated by angular scanning measurement of reflectivity and fluorescence intensity and by finite difference time domain simulation. The application of the substrate in the enhanced fluorescence imaging detection of labeled protein is also investigated. This substrate has a wide range of potential applications in areas including biodiagnostics, imaging, sensing, and photovoltaic cells.     

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.     

Enhanced Fluorescence Microscopic Imaging by Plasmonic Nanostructures: From a 1D Grating to a 2D Nanohole Array

A two‐dimensional (2D) plasmonic coupling nanostructure for enhanced fluorescence observation using a microscope is presented. The substrate contained periodically assembled nanohole arrays with a pitch of 400 nm and a depth of 25 nm. In comparison with one‐dimensional (1D) gratings, this new substrate presented an excellent surface plasmon coupling ability to illuminate light from all directions. Under an optical microscope, an enhancement in the fluorescence intensity of up to 100 times compared with a plain glass slide was observed. The ability to markedly increase the fluorescence intensity means this technique has great potential for application in biodiagnostics, imaging, sensing, and photovoltaic cells.