Vibrationally Hot Reactants in a Plasmon-Assisted Chemical Reaction.

Recent studies on plasmon-assisted chemical reactions postulate that the hot electrons of plasmon-excited nanostructures may induce a non-thermal vibrational activation of metal-bound reactants. However, the postulate has not been fully validated at the level of molecular quantum states. We directly and quantitatively prove that such activation occurs on plasmon-excited nanostructures: The anti-Stokes Raman spectra of reactants undergoing a plasmon-assisted reaction reveal that a particular vibrational mode of the reactant is selectively excited, such that the reactants possess >10 times more energy in the mode than is expected from the fully thermalized molecules at the given local temperature. Furthermore, a significant portion (∼20%) of the excited reactant is in vibrational overtone states with energies exceeding 0.5 eV. Such mode-selective multi-quantum excitation could be fully modeled by the resonant electron-molecule scattering theory. Such observations suggest that the vibrationally hot reactants are created by non-thermal hot electrons, not by thermally heated electrons or phonons of metals. The result validates the mechanism of plasmon-assisted chemical reactions and further offers a new method to explore the vibrational reaction control on metal surfaces.

Spatially Controlled Fabrication of Surface-Enhanced Raman Scattering Hot Spots through Photoinduced Dewetting of Silver Thin Films.

A well-designed narrow gap between noble metal nanostructures plays a prominent role in surface-enhanced Raman scattering (SERS) to concentrate electromagnetic fields at the local point, called a "hot spot". However, SERS-active substrate fabrication remains a substantial hurdle due to the high process cost and the difficulty of engineering efficient plasmonic hot spots at the target area. In this study, we demonstrate a simple photolithographic method for generating ultrasensitive SERS hot spots at desired positions. The solid-state dewetting of a Ag thin film (thickness of ∼10 nm) using a continuous-wave laser (∼1 MW/cm2) generates a closely packed assembly of hemispherical Ag nanoislands. Some of these nanoislands provide substantial plasmonic-field enhancement that is sufficient for single-molecule detection and plasmon-catalyzed chemical reaction. Such hot spot structures can be patterned on the substrate with a spatial resolution of better than 1 µm. In integrated analytical devices, the patterned SERS hot spots can be used as position-specific chemical-sensing elements.

Direct Visualization of Gap-Plasmon Propagation on a Near-Touching Nanowire Dimer.

Dimers of metallic nanowires (NWs) with nanometric gaps could be an alternative to overcome the limitations of existing plasmonic waveguides. The gap-surface plasmon polaritons (gap-SPPs) of the dimers may propagate along the NW without crosstalk and greatly enhance the coupling efficiency with an emitter, enabling ultracompact optical circuits. Such a possibility has not been realized, and we experimentally show its possibility. The gap-SPPs of the AgNW-molecule-AgNW structure, with a gap of 3-5 nm defined by the molecules, are visualized using the surface-enhanced Raman scattering (SERS) of the molecules. The SERS images, representing the gap-field intensity distribution, reveal the decay and beating of the monopole-monopole and dipole-dipole gap modes. The propagation lengths of the two (l1 = 0.5-2 µm and l2 = 5-8 µm) closely follow the model prediction with a uniform gap, confirming that the scattering loss induced by the gap irregularities is surprisingly low.

Single-Molecule Surface-Enhanced Raman Scattering as a Probe of Single-Molecule Surface Reactions: Promises and Current Challenges.

The initial observations of surface-enhanced Raman scattering (SERS) from individual molecules (single-molecule SERS, SMSERS) have triggered ever more detailed mechanistic studies on the SERS process. The studies not only reveal the existence of extremely enhanced and confined fields at the gaps of Ag or Au nanoparticles but also reveal that the spatial, spectral, and temporal behaviors of the SMSERS signal critically depend on many factors, including plasmon resonances of nanostructures, diffusion (lateral and orientational) of molecules, molecular electronic resonances, and metal-molecule charge transfers. SMSERS spectra, with their molecular vibrational fingerprints, should in principle provide molecule-specific information on individual molecules in a way that any other existing single-molecule detection method (such as the ones based on fluorescence, mechanical forces, or electrical currents) cannot. Therefore, by following the spectro-temporal evolution of SMSERS signals of reacting molecules, one should be able to follow chemical reaction events of individual molecules without any additional labels. Despite such potential, however, real applications of SMSERS for single-molecule chemistry and analytical chemistry are scarce. In this Account, we discuss whether and how we can use SMSERS to monitor single-molecule chemical kinetics. The central problem lies in the experimental challenges of separately characterizing and controlling various sources of fluctuations and spatial variations in such a way that we can extract only the chemically relevant information from time-varying SMSERS signals. This Account is organized as follows. First, we outline the standard theory of SMSERS, providing an essential guide for identifying sources of spatial heterogeneity and temporal fluctuations in SMSERS signals. Second, we show how single-molecule reaction events of surface-immobilized reactants manifest themselves in experimental SMSERS trajectories. Comparison of the reactive SMSERS data (magnitudes and frequencies of discrete transitions) and the predictions of SMSERS models also allow us to assess how faithfully the SMSERS models represent reality. Third, we show how SMSERS spectral features can be used to discover new reaction intermediates and to interrogate metal-molecule electronic interactions. Finally, we propose possible improvements in experimental design (including nanogap structures and molecular systems) to make SMSERS applicable to a broader range of chemical reactions occurring under ambient conditions. The specific examples discussed in this Account are centered around the single-molecule photochemistry of 4-nitrobenzenethiol on metals, but the conclusions drawn from each example are generally applicable to any reaction system involving small organic molecules.

Frequency-Domain Proof of the Existence of Atomic-Scale SERS Hot-Spots.

The existence of sub-nanometer plasmonic hot-spots and their relevance in spectroscopy and microscopy applications remain elusive despite a few recent theoretical and experimental evidence supporting this possibility. In this Letter, we present new spectroscopic evidence suggesting that Angstrom-sized hot-spots exist on the surfaces of plasmon-excited nanostructures. Surface-enhanced Raman scattering (SERS) spectra of 4,4'-biphenyl dithiols placed in metallic junctions show simultaneously blinking Stokes and anti-Stokes spectra, some of which exhibit only one prominent vibrational peak. The activated vibrational modes were found to vary widely between junction sites. Such site-specific, single-peak spectra could be successfully modeled using single-molecule SERS induced by a hot-spot with a diameter no larger than 3.5 Å, located at the specific molecular sites. Furthermore, the model, which assumes the stochastic creation of hot-spots on locally flat metallic surfaces, consistently reproduces the intensity distributions and occurrence statistics of the blinking SERS peaks, further confirming that the sources of the hot-spots are located on the metallic surfaces. This result not only provides compelling evidence for the existence of Angstrom-sized hot-spots but also opens up the new possibilities for the vibrational and electronic control of single-molecule photochemistry and real-space visualization of molecular vibration modes.