金属基底上光学偶极纳米天线的自发辐射宽带增强:表面等离激元直观模型

本文提出一种具有宽波段自发辐射增强性能的金属基底上光学偶极纳米天线,实现的总辐射速率与远场辐射速率增强因子分别达到5454和1041,在近红外波段,自发辐射增强(Purcell因子超过1000)波长范围达到260 nm,并且能够实现远场定向辐射.为了阐明天线性能背后的物理机制,本文考虑天线臂上表面等离激元激发和多重散射的直观物理过程,基于Maxwell方程组第一性原理,建立了一个半解析模型,能够全面复现天线的辐射特性,包括总辐射速率、远场辐射速率、远场辐射方向图等.该模型提供了一个直观的物理图像,即在模型导出的两个相位匹配条件下,表面等离激元在天线臂上形成了一对Fabry-Perot共振获得增强,然后传播到纳米间隙内点辐射源位置和散射到自由空间,由此分别提高了总辐射速率和远场辐射速率.并且,这一对Fabry-Perot共振产生了一对相互靠近的谐振峰,由此形成了宽波段自发辐射增强.本文提出的偶极纳米天线可以应用于荧光增强、拉曼散射增强及高速、高亮度纳米光源等领域,所提出的模型可用于光学天线的物理理解和直观设计.

Surface Plasmon Assisted Directional Rayleigh Scattering

The origin of the Rayleigh scattering ring effect has been experimentally examined on a quantum dot/metal film system, in which CdTe quantum dots embedded in PVP are spincoated on a thin Au film. On the basis of the angle-dependent, optical measurements under different excitation schemes （i.e., wavelength and polarization）, we demonstrate that surface plasmon assisted directional radiation is responsible for such an effect. Moreover, an interesting phase-shift behavior is addressed.

Self-assembly of α-6T Molecule on Ag（100） and Related STM Induced Luminescence

We have investigated the self-assembly and light emission properties of organic α- sexithiophene （α-6T） molecules on Ag（100） under different coverage by scanning tunneling microscopy （STM）. At very low coverage, the α-6T molecules form a unique enantiomer by grouping four molecules into a windmill supermolecular structure. As the coverage is increased,α-6T molecules tend to pack side by side into a denser stripe structure. Further increase of the coverage will lead to the layer-by-layer growth of molecules on Ag（100） with the lower-layer stripe pattern serving as a template. Molecular fluorescence for α-6T molecules on Ag（100） at a coverage of five monolayers has been detected by light excitations, which indicates a well decoupled electronic states for the top-layer α-6T molecules. However, the STM induced luminescent spectra for the same sample reveal only plasmonic-like emission. The absence of intramolecular fluorescence in this case suggests that the electronic decoupling is not a sufficient condition for generating photon emission from molecules. For intramolecular fluorescence to occur, the orientation of the dynamic dipole moment of molecules and the energy-level alignment at the molecule-metal interface are also important so that molecules can be effectively excited through efficient dipolar coupling with local plasmons and by injecting holes into the molecules.

Effects of Au nanoparticle size and metal-support interaction on plasmon-induced photocatalytic water oxidation

Plasmonic photocatalysis with tunable light absorption has aroused significant attention in so-lar-to-chemical energy conversion.However,the energy conversion efficiency of plasmonic photo-catalysts is impeded by ineffective charge separation and the lack of highly active sites for redox reactions.In this work,the Au nanoparticle size and Au-TiO2 interaction of the Au/TiO2 plasmonic photocatalyst were adjusted simultaneously using a post-calcination treatment.The visi-ble-ight-induced water oxidation activity exhibited a volcano-like relationship with the calcination temperature;the treated photocatalyst at 600°C manifested the highest activity.Characterization with UV-visible spectra,XRD,SEM,and XPS revealed that the effect of the Au nanoparticle size and Au-TiO2 interaction were both responsible for the increase in plasmon-induced water oxidation activity.

Fluorescence Emission Mediated by Metal-Dielectric-Metal Fishnet Metasurface: Spatially Selective Excitation and Double Enhancement

Enhancement of uorescent radiation is of great importance for applications including biological imaging,high-sensitivity detectors,and integrated light sources.Strong electromagnetic elds can be created around metallic nanoparticles or in gap of nanostructures,where the local state density of radiating mode is then dramatically enhanced.While enhanced uorescent emission has been demonstrated in many metallic nanoparticles and nanoparticle pairs,simultaneous mediation of absorption and emission processes of uorescent emitters remains challenging in metallic nanostructures.Here,we investigate uorescent emission mediated by metal-dielectric-metal fishnet metasurface,in which localized surface plasmon(LSP)and magnetic plasmon polaritons(MPPs)modes are coupled with absorption and emission processes,respectively.For absorption process,coupling of the LSP mode enables spatially-selective excitation of the uorescent emitters by rotating the polarization of the pump laser beam.In addition,the polarization-dependent MPP mode enables manipulation of both polarization and wavelength of the uorescent emission by introducing a rectangular fishnet structure.All the experimental observations are further corroborated by nite-difference time-domain simulations.The structure reported here has great potential for application to color light-emitting devices and nanoscale integrated light sources.

Film Thickness and Surface Plasmon Tune the Contribution of SFG Signals from Buried Interface and Air Surface

Sum frequency generation vibrational spectroscopy(SFG-VS)is a powerful technique for determining molecular structures at both buried interface and air surface.Distinguishing the contribution of SFG signals from buried interface and air surface is crucial to the applications in devices such as microelectronics and bio-tips.Here we demonstrate that the SFG spectra from buried interface and air surface can be differentiated by controlling the film thickness and employment of surface-plasmon enhancement.Using substrate-supported PMMA(poly(methyl methacrylate))films as a model,we have visualized the variations in the contribution of SFG signals from buried interface and air surface.By monitoring carbonyl and C-H stretching groups,we found that SFG signals are dominated by the moieties(-CH2,-CH3,-OCH3 and C=O)segregated at the PMMA/air surface for the thin films while they are mainly contributed by the groups(-OCH3 and C=O)at the substrate/PMMA buried interface for the thick films.At the buried interface,the tilt angle of C=O decreases from65°to 43°as the film preparation concentration increases;in contrast,the angles at the air surface fall in the range from 38°to 21°.Surface plasmon generated by gold nanorods can largely enhance SFG signals,particularly the signals from the buried interface.

Tunable and stable localized surface plasmon resonance in SrMoO_(4) for enhanced visible light driven nitrogen reduction

Photocatalytic nitrogen reduction for the green synthesis of ammonia at ambient conditions has been slowed by the narrow light harvesting range,low activity and high charge recombination of photocatalysts.Plasmonic semiconducting nanomaterials are becoming the promising candidates for nitrogen photofixation because of the broad absorption spectrum,rich defects and hot carriers.In the present study,plasmonic SrMoO_(4) is developed by regulating the concentration of oxygen vacancies that are accompanied in the reduction process from Mo^(6+) to Mo^(5+).The stable and tunable localized surface plasmon resonance(LSPR)absorption in visible and near infrared light range makes the wide bandgap SrMoO_(4) utilize the solar energy more efficiently.Energetic electrons from both the intrinsic band excitation and the LSPR excitation enable the reduction of dinitrogen molecules thermodynamically in ultrapure water to ammonia.This work provides a unique clue to design efficient photocatalysts for nitrogen fixation.

Simulation Study of Electron Beam Induced Surface Plasmon Excitation at Nanoparticles

Phenomenon of localized surface plasmon excitation at nanostructured materials has attracted much attention in recent decades for their wide applications in single molecule detection,surface-enhanced Raman spectroscopy and nano-plasmonics.In addition to the excitation by external light field,an electron beam can also induce the local surface plasmon excitation.Nowadays,electron energy loss spectroscopy(EELS)technique has been increasingly employed in experiment to investigate the surface excitation characteristics of metallic nanoparticles.However,a present theoretical analysis tool for electromagnetic analysis based on the discrete dipole approximation(DDA)method can only treat the case of excitation by light field.In this work we extend the DDA method for the calculation of EELS spectrum for arbitary nanostructured materials.We have simulated EELS spectra for different incident locations of an electron beam on a single silver nanoparticle,the simulated results agree with an experimental measurement very well.The present method then provides a computation tool for study of the local surface plasmon excitation of metallic nanoparticles induced by an electron beam.

Electron Energy Spectroscopic Mapping of Surface Plasmon by Parallel Scanning Method

In this work,electron energy spectroscopic mapping of surface plasmon of Ag nanostructures on highly oriented pyrolytic graphite is reported.Benefitting from the angular dispersive feature of the present scanning probe electron energy spectrometer,a multi-channel detection mode is developed.By scanning along one direction,the two-dimensional intensity distribution of Ag surface plasmon excitation due to the collision of electron emitted from the tip can be obtained in parallel.The spectroscopic spatial resolution is determined to be around 80 nm.

Optical Nonlinearity of Surface Plasmon Resonance Emission from Au Colloidal Nanoparticles

Suspended gold nanoparticles have been synthesized via electrochemical method.Fluorescence excitation and emission spectra were obtained using a spectrofluorophotometer.With varying the excitation wavelength,an emission peak fixed at 485 nm has always been observed.We believe that this peak is attributed to the surface plasmon resonance.When the detection wavelength was fixed at 485 nm (0.619×10 15 Hz),a double frequency exciting peak at 242 nm(2×0.619×10 15 Hz), a 3/2 fraction frequency exciting peak at 330 nm (about 3/2×0.619×10 15 Hz)and a 3/4 fraction frequency exciting peak at 640 nm(3/4×0.619×10 15 Hz)display.The nonlinear exciting peak at 640 nm corresponds to the two-photon absorption.Therefore,as the excitation wavelength is at 320 and 640 nm respectively,single-photon and two-photon absorption induced surface plasmon resonance emission peaks were observed. These nonlinear surface plasmon resonance emission characters of Au colloidal nanoparticles make it possible to enhance the sensitivity of conventional surface plasmon resonance device.

The Surface Plasmons＇ Frequencies of Two Adjacent Metallic Nanospheres by Bloch-Jensen Hydrodynamical Model

The wave guides and optical fibers have long been known to transmit light and electromagnetic fields in large dimensions. Recently, surface plasmons, which are collective plasma oscillations of valence electrons at metal surfaces, have been introduced as an entity that is able to guide light on the surfaces of the metal and to concentrate light in subwavelength volumes. It has been found that periodic array of metallic nanospheres, could be able to enhance the light transmission, and guiding light at nanoscale. The coupling between two nanoparticles in these devices is very important. The Bloch-Jensen hydrodynamical method has been used for computing surface plasmons＇ frequencies of a single metallic nanosphere. It contains the entire pole spectrum automatically, so it is more exactly than the other computational methods. In this research, we have computed the surface plasmons＇ frequencies of two adjacent nanospheres by Bloch-Jensen hydrodynamical model for the first time. The results show that there are two modes for this system, which depend explicitly on interparticle spacing. In addition, we have shown that the excitation modes yield to a single mode of a nanoparticle as the interparticle spacing increases.

Gold nanorods core/AgPt alloy nanodots shell： A novel potent antibacterial nanostructure

In the light of the current problems of silver nanoparticles （Ag NPs） in terms of antibacterial performance, we have designed a novel trimetallic corelshell nanostructure with AgPt alloy nanodots epitaxially grown on gold nanorods （Au@PtAg NRs） as a potential antibacterial agent. Both Escherichia coli （E. coli） and Staphylococcus aureus （S. aureus） were studied. The antibacterial activity exhibits an obvious composition-dependence. On increasing the Ag fraction in the alloy shell up to 80%, the antibacterial activity gradually increases, demonstrating a flexible way to tune this activity. At 80% Ag, tile antibacterial activity is better than that of a pure Ag shell. The improved antibacterial ability mainly results from the high exposure of silver on the shell surface due to the dot morphology. We thus demonstrate that forming alloys is an effective way to improve antibacterial activity while retaining high chemical stability for Ag-based nanomaterials. Furthermore, due to the tunable localized surface plasmonic response in the near-infrared （NIR） spectral region, additional control over antibacterial activity using light--such as photothermal killing and photo- triggered silver ion release--is expected. As a demonstration, highly enhanced antibacterial activity is shown by utilizing the NIR photothermal effect of the nanostructures. Our results indicate that such tailored nanostructures will find a role in the future fight against bacteria, including the challenge of the increasing severity of multidrug resistance.

A novel strategy for improving upconversion luminescence of NaYF4：Yb, Er nanocrystals by coupling with hybrids of silver plasmon nanostructures and poly（methyl methacrylate） photonic crystals

The coupling of upconversion nanophosphors （UCNPs） with the surface plasmonic resonance （SPR） of noble metals is a promising way to improve luminescent efficiency of UCNPs; however, it is still a challenge to achieve stable, reproducible and effective upconversion luminescence （UCL） enhancement through such coupling. In this work, we present a novel strategy to improve UCL of NaYF4：ybB,Er3. UCNPs, by combining the near-field coupling of SPR of silver and the far-field coupling of poly（methyl methacrylate） （PMMA） opal photonic crystals （OPCs） with the UCNPs. In order to control the effective interaction distance between the UCNPs and the SPR, a porous silver film consisting of randomly distributed silver nanoparticles （NPs） （〉 100 nm） was prepared which demonstrated strong SPR over a broad wavelength range, and its coupling to the UCNPs was found to be much stronger than that of a dense film. In the far-field coupling of OPCs, the photonic stop band （PSB） of the PMMA OPCs was tuned to 980 nm, matching exactly the excitation light. By modulating the particle size of the UCNPs, and the direction and excitation power of the incident light, a maximum enhancement of 60-fold was observed, which is an important advance for metaMnduced UCL enhancement systems.

New progress of plasmonics in complex metal nanostructures

Noble metal nanostructures possess novel optical properties because of their collective electronic oscillations, known as sur- face plasmons （SPs）. The resonance of SPs strongly depends on the material, surrounding environment, as well as the geome- try of the nanostructures. Complex metal nanostructures have attracted research interest because of the degree of freedom in tailoring the plasmonic properties for more advanced applications that are unattainable by simple ones. In this review, we dis- cuss the plasmonic properties of several typical types of complex metal nanostructures, that is, electromagnefically coupled nanoparticles （NPs）, NPs/metal films, NPs/nanowires （NWs）, NWs/NWs, and metal nanostructures supported or coated by di- electrics. The electromagnetic field enhancement and surface-enhanced Raman scattering applications are mainly discussed in the NPs systems where localized SPs have a key role. Propagating surface plasmon polaritons and relevant applications in plasmonic routers and logic gates using NWs network are also reviewed. The effect of dielectric substrates and surroundings of metal nanostructures to the plasmonic properties is also discussed.

Surface plasmonic effect and scattering effect of Au nanorods on the performance of polymer bulk heterojunction solar cells

The surface plasmonic effect and scattering effect of gold nanorods(AuNRs) on the performance of bulk heterojunction photovoltaic devices based on the blend of polythiophene and fullerene are investigated.AuNRs enhance the excitation since the plasmonic effect increases the electric field,mainly in the area near the interface between the active layer and AuNRs.The results show that the incident photo-to-electron conversion efficiency(IPCE) obviously increases for the device with a layer of gold nanorods,resulting from the plasmonic effect of AuNRs in the range of 500-670 nm and the scattering effect in the range of 370-410 nm.The power conversion efficiency(PCE) is increased by 7.6% due to the near field effect of the localized surface plasmons(LSP) of AuNRs and the scattering effect.The short circuit current density is also increased by 9.1% owing to the introduction of AuNRs.However,AuNRs can cause a little deterioration in open circuit voltage.

Advanced experimental methods toward understanding biophysicochemical interactions of interfacial biomolecules by using sum frequency generation vibrational spectroscopy

Sum frequency generation vibrational spectroscopy(SFG-VS)has been demonstrated to be a powerful technique to study the interfacial structures and interactions of biomolecules at the molecular level.Yet most previous studies mainly collected the SFG spectra in the frequency range of 1500–4000 cm-1,which is not always sufficient to describe the detailed interactions at surface and interface.Thorough knowledge of the complex biophysicochemical interactions between biomolecules and surface requires new ideas and advanced experimental methods for collecting SFG vibrational spectra.We introduced some advanced methods recently exploited by our group and others,including(1)detection of vibration modes in the fingerprint region;(2)combination of chiral and achiral polarization measurements;(3)SFG coupled with surface plasmon polaritons(SPPs);(4)imaging and microscopy approaches;and(5)ultrafast time-resolved SFG measurements.The technique that we integrated with these advanced methods may help to give a detailed and high-spatial-resolution 3D picture of interfacial biomolecules.

Modeling of Gold Circular Sub-Wavelength Apertures on a Fiber Endface for Refractive Index Sensing

A finite-difference time-domain approach was used to investigate the excitation of surface plasmons of the circular sub-wavelength apertures on an optical fiber endface. This phenomenon provided the basis of a sensitive liquid refractive index sensor. The proposed sensor is compact and has the potential to be used in biomedical applications, having a sensitivity of （373 ± 16）nm per refractive index unit （RIU） as found through the variation of a reflection minimum with the wavelength.

Multiplexed cytokine detection on plasmonic gold substrates with enhanced near-infrared fluorescence

Protein microarrays based on fluorescence detection have been widely utilized for high-throughput functional proteomic analysis. However, a drawback of such assays has been low sensitivity and narrow dynamic range, limiting their capabilities, especially for detecting low abundance biological molecules such as cytokines in human samples. Here, we present fluorescence-enhancing microarrays on plasmonic gold films for multiplexed cytokine detection with up to three orders of magnitude higher sensitivity than on conventional nitrocellulose and glass substrates. Cytokine detection on the gold plasmonic substrate is about one to two orders of magnitude more sensitive than enzyme-linked immunosorbent assay （ELISA） and can be multiplexed. A panel of six cytokines （Vascular endothelial growth factor （VEGF）, Interleukin 1β （IL-1β）, Interleukin 4 （IL-4）, Interleukin 6 （IL-6）, Interferon γ （IFN-γ）, and Tumor necrosis factor （TNF）） were detected in the culture media of cancer cells. This work establishes a new method of high throughput multiplexed cytokine detection with higher sensitivity and dynamic range than ELISA.

Wide range temperature detection with hybrid nanoparticles traced by surface-enhanced Raman scattering

We report on the fabrication of a class of surface-enhanced Raman scattering(SERS)active thermometers,which consists of60 nm gold nanoparticles,encoded with Raman-active dyes,and a layer of thermoresponsive poly(N-isopropylacrylamide)(PNIPAM)brush with different chain lengths.These SERS-active nanoparticles can be optimized to maintain spectrally silent when staying as single particles in dispersion.Increasing temperature in a wide range from 25 to 55°C can reversibly induce the interparticle self-aggregation and turn on the SERS fingerprint signals with up to 58-fold of enhancement by taking advantage of the interparticle plasmonic coupling generated in the process of thermo-induced nanoparticles self-aggregation.Moreover,the most significative point is that these SERS probes could maintain their response to temperature and present all fingerprint signals in the presence of a colored complex.However,the UV-Vis spectra can distinguish the differences faintly and the solution color shows little change in such complex mixture.This proof-of-concept and Raman technique applied here allow for dynamic SERS platform for onsite temperature detection in a wide temperature range and offer unique advantages over other detection schemes.

Coherence preservation during light-surface plasmon polaritons-light transformation

We constructed a four-layer system composed of a prism,a silver film,an air layer and a lithium niobate crystal.Initially we used two coherent light beams to excite surface plasmons.The surface plasmons were then decoupled into light in the photorefractive crystal where a holographic grating was recorded.The two beams remained coherent through light to surface plasmons to light transformation.Studying the characteristics of the holographic grating we found out that the thickness of the grating was to the order of hundreds of microns.The thick holographic grating suggests that the holographic recording in the photorefractive materials was induced by the leaky waves rather than by surface plasmon polaritons directly.