Understanding Spatial Distributions of Dye Molecules Coupled to the Surface Lattice Resonance Mode through Electrochemical Reaction Control.

The strong coupling, which is the light-matter interaction, leads to changes in the energy landscape of the chemical dynamics, resulting in the modulation of the reaction pathways. In this study, we achieved strong coupling between dye molecules dispersed in the polymer films and the surface lattice resonance mode, which is excited on plasmonic lattice arrays. In addition, we successfully tuned the coupling strength by introducing the electrochemical potential control method. Reversible decreases and increases in the coupling strength were observed as a result of the reversible electrochemical redox reactions of dye molecules. It is important that the spatial distribution of the molecules coupled to the lattice resonance mode was clarified by using various polymer film thicknesses. Our present electrochemical method for controlling strong coupling states represents a promising method for tuning the light-absorption properties of systems.

Unique Electronic Excitations at Highly Localized Plasmonic Field.

ConspectusUnder visible light illuminations, noble metal nanostructures can condense photon energy into the nanoscale region. By precisely tuning the metal nanostructures, the ultimate confinement of photoenergy at the molecular scale can be obtained. At such a confined photon energy field, various unique photoresponses of molecules, such as efficient visible light energy conversion processes or efficient multielectron transfer reactions, can be observed. Light-matter interactions also increase with the condensation of photons with nanoscale regions, leading to efficient light energy utilizations. Moreover, the strong field confinement can often modulate electronic excitations beyond normal selection rules. Such unique electronic excitations could realize innovative photoenergy conversion systems. On the other hand, such interactions lead to changes in the optical absorption property of the system via the formation of hybridized electronic energy states. This hybridized state is expected to have the potential to modulate the chemical reaction pathways. Taking these facts into consideration, a probe for the molecular absorption process with high sensitivity allows us to find novel ways for further precise tuning of light-matter interactions. In this Account, we review phenomena of unique electronic excitations from the perspective of our previous investigations using surface-enhanced Raman scattering (SERS) spectroscopy at electrified interfaces. Because the enhancement mechanism of Raman scattering at interfaces is deeply correlated with the photon absorption process accompanied by the electronic excitations between molecules and electrode surfaces, the detailed SERS investigations of the well-defined system can provide information on the electronic excitation processes. Through SERS observations of single-molecule junctions at electrodes or well-defined low-dimensional carbon materials, we have observed the characteristic Raman bands containing additional polarization tensors, indicating the occurrence of electronic polarization induced by electronic excitations based on a distinct selection rule. The origins for the observed facts were attributed to the highly condensed electric field producing the huge intensity gradient at the nano scale. The electrochemical potential control of the system would be valuable for the control of the excitation process. Additionally, from Raman spectra of dye molecules coupled to the plasmonic field, the changes in the Raman scattering intensity depending on the strength of interactions suggested the modulation of the absorption characteristics of the system. In addition, we have proved that the electrochemical potential control method can be a powerful tool for the active tuning of the light-matter interaction, leading to the change in the light absorption property. The molecular behaviors of dyes in the strong-coupling regime were reversibly tuned to show intense SERS. The current descriptions provide novel insights for these unique electronic excitations, realized by the plasmon excitation, that lead to advanced photoenergy conversions beyond the limits of present systems.

Room-Temperature Molecular Manipulation via Plasmonic Trapping at Electrified Interfaces.

For the motion control of individual molecules at room temperature, optical tweezers could be one of the best approaches to realize desirable selectivity with high resolution in time and space. Because of physical limitations due to the thermal fluctuation, optical manipulation of small molecules at room temperature is still a challenging subject. The difficulty of the manipulation also emerged from the variation of molecular polarizability depending on the choice of molecules as well as the molecular orientation to the optical field. In this article, we have demonstrated plasmonic optical trapping of small size molecules with less than 1 nm at the gap of a single metal nanodimer immersed in an electrolyte solution. In situ electrochemical surface-enhanced Raman scattering measurements prove that a plasmonic structure under electrochemical potential control realizes not only the selective molecular condensation but also the formation of unique mixed molecular phases which is distinct from those under a thermodynamic equilibrium. Through detailed analyses of optical trapping behavior, we established the methodology of plasmonic optical trapping to create the novel adsorption isotherm under applying an optical force at electrified interfaces.

Tuning Electrogenerated Chemiluminescence Intensity Enhancement Using Hexagonal Lattice Arrays of Gold Nanodisks.

Electrogenerated chemiluminescence (ECL) microscopy shows promise as a technique for mapping chemical reactions on single nanoparticles. The technique's spatial resolution is limited by the quantum yield of the emission and the diffusive nature of the ECL process. To improve signal intensity, ECL dyes have been coupled with plasmonic nanoparticles, which act as nanoantennas. Here, we characterize the optical properties of hexagonal arrays of gold nanodisks and how they impact the enhancement of ECL from the coreaction of tris(2,2'-bipyridyl)dichlororuthenium(II) hexahydrate and tripropylamine. We find that varying the lattice spacing results in a 23-fold enhancement of ECL intensity because of increased dye-array near-field coupling as modeled using finite element method simulations.

Spatial distribution of active sites for plasmon-induced chemical reactions triggered by well-defined plasmon modes.

Plasmon-induced chemical reactions triggered by near-infrared light illumination might enable efficient photo energy conversion. Here, electrochemical oxidative polymerization of a conductive polymer was conducted on plasmonic photoconversion electrodes. The absolute electrochemical potential of the generated holes was estimated from the redox potentials of the monomers. In addition, well-defined plasmonic structures were examined to better understand the relationship between the excited plasmon mode and spatial distribution of reaction active sites. Rod structures with various lengths had distinct spatial distributions of reaction active sites that depended on the higher plasmon modes, as visualized by Raman measurements.

Ultra-fine electrochemical tuning of hybridized plasmon modes for ultimate light confinement.

Highly reproducible control of metal plasmonic nanostructures has been achieved via precise tuning of the electrochemical Au dissolution reaction that occurs at the surfaces of well-defined bridged nanodisk dimer structures on an atomic scale. It was found that the scattering intensity is strongly suppressed during the transition from the conductive mode to the gap mode of the localized surface plasmon resonance during the period when the gap is formed and increased between Au nanodisks. The characteristic shift of the plasmon mode during this suppression of the scattering intensity verifies the excitation of the bonding quadrupolar mode, which appears only at sub-nanometer gap distances (d < 1 nm). Electrochemical potential control demonstrates that the scattering suppression states with estimated gap distances of less than 1 nm can be maintained for more than 100 s under ambient conditions. The method and phenomena presented here will be useful in the preparation of plasmonic structures for ultimate light confinement applications.

Potential energy shift of the Fermi level at plasmonic structures for light-energy conversion determined by graphene-based Raman measurements.

Single layer graphene was used to determine the electrochemical potential of plasmonic nano-structures for photoelectrochemical energy conversions. From electrochemical Raman measurements of the graphene layer under near-infrared light, illumination has revealed the relationship between the photoenergy conversion ability and the Fermi level of the plasmonic structure. The determination is based on in situ monitoring of G and 2D Raman bands of the graphene layer on plasmonic structures. The correlation plots of G and 2D bands show the dependence on the photoconversion ability. The present electrochemical Raman measurements provide detailed understanding of the plasmon-induced charge transfer process for further developments on the ability.

Nonzero Wavevector Excitation of Graphene by Localized Surface Plasmons.

Electrochemical surface-enhanced Raman scattering measurements of single layer graphene provide unique information on resonant excitation induced by localized surface plasmons under controlled electron or hole doping. The highly confined electromagnetic field from the LSPs of the Au nanodimer structures prepared on defect-free graphene can generate holes and electrons of the electrochemical potentials beyond the limit of far-field light illumination. The electrochemical in situ SERS spectra prove nonzero wavevector excitation through the observation of normally forbidden Raman bands in graphene. The present findings point to a novel approach to breaking the limit of optoelectronic interactions and photochemical reactions of graphene and other semiconductors.

Photoelectrochemical Formation of Polysulfide at PbS QD-Sensitized Plasmonic Electrodes.

Effective electron-hole separation is a key to enhance photoenergy conversion of semiconductor quantum dot (QD)-sensitized plasmonic solar cells. However, in contrast to intense studies on electron transfer, hole transfer from QDs and consequent chemical reactions with donors in electrolytes remain unclear. Herein, in situ electrochemical surface-enhanced Raman scattering (SERS) measurement on a PbS QD-sensitized TiO2/Au/TiO2 photoelectrode indicated formation of cyclo-octasulfur (α-S8) via tuning the electrochemical potential. A photocurrent density of 100 nA/cm2 was recorded simultaneously even with an extremely low QD loading. Two-dimensional correlation analysis of the SERS revealed subsequent formation of S8- and S42- at -1.1 to -0.1 V (vs Ag/AgCl), S8 from -0.3 V, and S52- and S62- at ≥0.2 V via complex disproportionation reactions. The sensitive detection is attributed to the enhanced electromagnetic field of localized surface plasmon resonance, which provides a better understanding of charge separation processes in QD-sensitized solar cells.

Plasmonically enhanced electromotive force of narrow bandgap PbS QD-based photovoltaics.

Electromotive force of photovoltaics is a key to define the output power density of photovoltaics. Multiple exciton generation (MEG) exhibited by semiconductor quantum dots (QDs) has great potential to enhance photovoltaic performance owing to the ability to generate more than one electron-hole pairs when absorbing a single photon. However, even in MEG-based photovoltaics, limitation of modifying the electromotive force exists due to the intrinsic electrochemical potential of the conduction band-edges of QDs. Here we report a pronouncedly improved photovoltaic performance by constructing a PbS QD-sensitized electrode that comprises plasmon-active Au nanoparticles embedded in a titanium dioxide thin film. Significant enhancement on electromotive force is characterized by the onset potential of photocurrent generation using MEG-effective PbS QDs with a narrow bandgap energy (Eg = 0.9 eV). By coupling with localized surface plasmon resonance (LSPR), such QDs exhibit improved photoresponses and the highest output power density over the other QDs with larger bandgap energies (Eg = 1.1 and 1.7 eV) under visible light irradiation. The wavelength-dependent onset potential and the output power density suggest effective electron injection owing to the enhanced density of electrons excited by energy overlapping between MEG and LSPR.

Electrochemical surface-enhanced Raman scattering measurement on ligand capped PbS quantum dots at gap of Au nanodimer.

The vibrational characteristics of ligand-capped lead sulfide (PbS) quantum dots (QDs) were clarified via electrochemical surface-enhanced Raman spectroscopy (EC-SERS) using a hybridized system of gold (Au) nanodimers and PbS QDs under electrochemical potential control. Enhanced electromagnetic field caused by the coupling of QDs with plasmonic Au nanodimers allowed the characteristic behavior of the ligand oleic acid (OA) on the PbS QD surface to be detected under electrochemical potential control. Binding modes between the QDs and OA molecules were characterized using synchronous two-dimensional correlation spectra at distinct electrochemical potentials, confirming that the bidentate bridging mode was probably the most stable mode even under relatively negative potential polarization. Changes in binding modes and molecular orientations resulted in fluctuations in EC-SERS spectra. The present observations strongly recommend the validity of the QD-plasmonic nanostructure coupled system for sensitive molecular detection via EC-SERS.

Sensitive Raman Probe of Electronic Interactions between Monolayer Graphene and Substrate under Electrochemical Potential Control.

In situ electrochemical Raman spectroscopic measurements of defect-free monolayer graphene on various substrates were performed under electrochemical potential control. The G and 2D Raman band wavenumbers (ωG, ω2D) of graphene were found to depend upon the electrochemical potential, i.e., the charge density of graphene. The values of ωG and ω2D also varied depending on the choice of substrates. On metal substrates where graphene was synthesized by chemical vapor deposition, a strong blue shift of ω2D was induced, which could not account for the strain and charge doping. We attributed the blue shift of ω2D to a change in the electronic properties of graphene induced by distinct electronic interactions with the metal substrates. To explain the unique characteristics in the Raman spectrum of graphene on various substrates, a novel mechanism is proposed considering reduction of the Fermi velocity in graphene owing to dielectric screening from the metal substrates.

Nanoscale control of plasmon-active metal nanodimer structures via electrochemical metal dissolution reaction.

Herein, we report the control of the optical properties of metal nanodimer structures using electrochemical metal dissolution reactions. The reaction rate could be precisely tuned by changing the electrochemical potential and, as a consequence, fine tuning of the size and gap distance of metal nanodimers was achieved as the functions of applied potential and polarization time. The observed linear correlation between the scattering intensity and charge resulting from nanostructure dissolutions suggested that the surface dissolution rate was 0.30 nm min-1, corresponding to the surface dissolution of a single atomic layer per min. The present method can control the change in the volume of the structures, leading to the change in the gap distance of nanodimers at an atomic-scale level.

Electrochemical control of strong coupling states between localized surface plasmons and molecule excitons for Raman enhancement.

The intensity of Raman scattering from dye molecules strongly coupled with localized surface plasmons of metal nanostructures was controlled by the electrochemical potential. Through in situ electrochemical extinction and surface-enhanced Raman scattering measurements, it is found that the redox state of the molecules affects the coupling strength, leading to the change in the intensity of the Raman scattering. Analysis of the Raman spectrum provides information on the molecules in strong coupling states showing effective enhancement of Raman scattering.

Three-dimensional micro/nano-scale structure fabricated by combination of non-volatile polymerizable RTIL and FIB irradiation.

Room-temperature ionic liquid (RTIL) has been widely investigated as a nonvolatile solvent as well as a unique liquid material because of its interesting features, e.g., negligible vapor pressure and high thermal stability. Here we report that a non-volatile polymerizable RTIL is a useful starting material for the fabrication of micro/nano-scale polymer structures with a focused-ion-beam (FIB) system operated under high-vacuum condition. Gallium-ion beam irradiation to the polymerizable 1-allyl-3-ethylimidazolium bis((trifluoromethane)sulfonyl)amide RTIL layer spread on a Si wafer induced a polymerization reaction without difficulty. What is interesting to note is that we have succeeded in provoking the polymerization reaction anywhere on the Si wafer substrate by using FIB irradiation with a raster scanning mode. By this finding, two- and three-dimensional micro/nano-scale polymer structure fabrications were possible at the resolution of 500,000 dpi. Even intricate three-dimensional micro/nano-figures with overhang and hollow moieties could be constructed at the resolution of approximately 100 nm.