Yurui Fang

Remote-Excitation Surface-Enhanced Raman Scattering Using Propagating Ag Nanowire Plasmons

Using propagating plasmons on silver nanowires as an excitation source we perform surface-enhanced Raman scattering (SERS) at a nanoparticle/wire junction located remotely from the laser illumination spot with sensitivities in a few molecules range. Simultaneous multisite remote-excitation SERS sensing can also be achieved.

Correlation between Incident and Emission Polarization in Nanowire Surface Plasmon Waveguides

Nanowire plasmons can be launched by illumination at one terminus of the nanowire and emission can be detected at the other end of the wire. Using polarization dependent dark-field scattering spectroscopy, we measure how the polarization of the emitted light depends on the polarization of the incident light. We observe that the shape of the nanowire termination plays an important role in determining this polarization change. Depending on termination shape, a nanowire can serve as either a polarization-maintaining waveguide, or as a polarization-rotating, nanoscale half-wave plate. The understanding of how plasmonic waveguiding influence the polarization of the guided light is important for optimizing the structure of integrated plasmonic devices.

Directional Light Emission from Propagating Surface Plasmons of Silver Nanowires

Thin metallic nanowires are highly promising candidates for plasmonic waveguides in photonic and electronic devices. We have observed that light from the end of a silver nanowire, following excitation of plasmons at the other end of the wire, is emitted in a cone of angles peaking at nominally 45-60 degrees from the nanowire axis, with virtually no light emitted along the direction of the nanowire. This surprising characteristic can be explained in a simple picture invoking Fabry-Perot resonances of the forward- and back-propagating plasmons on the nanowire. This strongly angular-dependent emission is a critical property that must be considered when designing coupled nanowire-based photonic devices and systems.

Propagating Surface Plasmon Polaritons: Towards Applications for Remote‐Excitation Surface Catalytic Reactions

Plasmonics is a well‐established field, exploiting the interaction of light and metals at the nanoscale; with the help of surface plasmon polaritons, remote‐excitation can also be observed by using silver or gold plasmonic waveguides. Recently, plasmonic catalysis was established as a new exciting platform for heterogeneous catalytic reactions. Recent reports present remote‐excitation surface catalytic reactions as a route to enhance the rate of chemical reactions, and offer a pathway to control surface catalytic reactions. In this review, we focus on recent advanced reports on silver plasmonic waveguide for remote‐excitation surface catalytic reactions. First, the synthesis methods and characterization techniques of sivelr nanowire plasmonic waveguides are summarized, and the properties and physical mechanisms of plasmonic waveguides are presented in detail. Then, the applications of plasmonic waveguides including remote excitation fluorescence and SERS are introduced, and we focus on the field of remote‐excitation surface catalytic reactions. Finally, forecasts are made for possible future applications for the remote‐excitation surface catalysis by plasmonic waveguides in living cells.

Activated vibrational modes and Fermi resonance in tip-enhanced Raman spectroscopy.

Using p-aminothiophenol (PATP) molecules on a gold substrate and high-vacuum tip-enhanced Raman spectroscopy (HV-TERS), we show that the vibrational spectra of these molecules are distinctly different from those in typical surface-enhanced Raman spectroscopy. Detailed first-principles calculations help to assign the Raman peaks in the TERS measurements as Raman-active and IR-active vibrational modes of dimercaptoazobenzene (DMAB), providing strong spectroscopic evidence for the dimerization of PATP molecules to DMAB under the TERS setup. The activation of the IR-active modes is due to enhanced electromagnetic field gradient effects within the gap region of the highly asymmetric tip-surface geometry. Fermi resonances are also observed in HV-TERS. These findings help to broaden the versatility of TERS as a promising technique for ultrasensitive molecular spectroscopy.

High vacuum tip-enhanced Raman spectroscope based on a scanning tunneling microscope

In this paper, we present the construction of a high-vacuum tip-enhanced Raman spectroscopy (HV-TERS) system that allows in situ sample preparation and measurement. A detailed description of the prototype instrument is presented with experimental validation of its use and novel ex situ experimental results using the HV-TERS system. The HV-TERS system includes three chambers held under a 10(-7) Pa vacuum. The three chambers are an analysis chamber, a sample preparation chamber, and a fast loading chamber. The analysis chamber is the core chamber and contains a scanning tunneling microscope (STM) and a Raman detector coupled with a 50 × 0.5 numerical aperture objective. The sample preparation chamber is used to produce single-crystalline metal and sub-monolayer molecular films by molecular beam epitaxy. The fast loading chamber allows ex situ preparation of samples for HV-TERS analysis. Atomic resolution can be achieved by the STM on highly ordered pyrolytic graphite. We demonstrate the measurement of localized temperature using the Stokes and anti-Stokes TERS signals from a monolayer of 1,2-benzenedithiol on a gold film using a gold tip. Additionally, plasmonic catalysis can be monitored label-free at the nanoscale using our device. Moreover, the HV-TERS experiments show simultaneously activated infrared and Raman vibrational modes, Fermi resonance, and some other non-linear effects that are not observed in atmospheric TERS experiments. The high spatial and spectral resolution and pure environment of high vacuum are beneficial for basic surface studies.

Plasmon Enhanced Internal Photoemission in Antenna-Spacer-Mirror Based Au/TiO2 Nanostructures

Emission of photoexcited hot electrons from plasmonic metal nanostructures to semiconductors is key to a number of proposed nanophotonics technologies for solar harvesting, water splitting, photocatalysis, and a variety of optical sensing and photodetector applications. Favorable materials and catalytic properties make systems based on gold and TiO2 particularly interesting, but the internal photoemission efficiency for visible light is low because of the wide bandgap of the semiconductor. We investigated the incident photon-to-electron conversion efficiency of thin TiO2 films decorated with Au nanodisk antennas in an electrochemical circuit and found that incorporation of a Au mirror beneath the semiconductor amplified the photoresponse for light with wavelength λ = 500-950 nm by a factor 2-10 compared to identical structures lacking the mirror component. Classical electrodynamics simulations showed that the enhancement effect is caused by a favorable interplay between localized surface plasmon excitations and cavity modes that together amplify the light absorption in the Au/TiO2 interface. The experimentally determined internal quantum efficiency for hot electron transfer decreases monotonically with wavelength, similar to the probability for interband excitations with energy higher than the Schottky barrier obtained from a density functional theory band structure simulation of a thin Au/TiO2 slab.

Plasmon-driven sequential chemical reactions in an aqueous environment

Plasmon-driven sequential chemical reactions were successfully realized in an aqueous environment. In an electrochemical environment, sequential chemical reactions were driven by an applied potential and laser irradiation. Furthermore, the rate of the chemical reaction was controlled via pH, which provides indirect evidence that the hot electrons generated from plasmon decay play an important role in plasmon-driven chemical reactions. In acidic conditions, the hot electrons were captured by the abundant H+ in the aqueous environment, which prevented the chemical reaction. The developed plasmon-driven chemical reactions in an aqueous environment will significantly expand the applications of plasmon chemistry and may provide a promising avenue for green chemistry using plasmon catalysis in aqueous environments under irradiation by sunlight.

Chemical and electromagnetic mechanisms of tip-enhanced Raman scattering

In this paper, we attempt to reveal the nature of the chemical and electromagnetic mechanisms of tip-enhanced Raman scattering (TERS). Direct visual evidence regarding the chemical mechanism via charge transfer was obtained with charge difference density. It is found that there are several kinds of charge transfer: (1) tip to molecule, (2) surface to molecule, (3) tip and surface to molecule simultaneously, and (4) tunneling charge transfer between the tip and the surface. Direct evidence regarding the electromagnetic mechanism via intracluster (tip or surface) charge redistribution was also revealed via charge difference density. The distance (between tip and surface) dependence of the near electric field distribution and the TERS enhancement at different incident lights is also discussed using the three-dimensional finite-difference time-domain (FDTD) method. The electromagnetic enhancement of double-tip TERS is approximately 10 times larger than that of conventional TERS. Theoretical results reveal that plasmon coupling effects between the metal tip and surface play an important role in TERS.

Electromagnetic field redistribution in hybridized plasmonic particle-film system

Combining simulation and experiment, we demonstrate that a metal nanoparticle dimer on a gold film substrate can confine more energy in the particle/film gap because of the hybridization of the dimer resonant lever and the continuous state of the film. The hybridization may even make the electric field enhancement in the dimer/film gap stronger than in the gap between particles. The resonant peak can be tuned by varying the size of the particles and the film thickness. This electromagnetic field redistribution has tremendous applications in sensor, photocatalysis and solar cell, etc., especially considering ultrasensitive detection of tracing molecule on substrates.