Coherent acoustic vibrations of Au nanoblocks and their modulation by Al2O3 layer deposition.

Coherent acoustic phonons induced in metallic nanostructures have attracted tremendous attention owing to their unique optomechanical characteristics. The frequency of the acoustic phonon vibration is highly sensitive to the material adsorption on metallic nanostructures and, therefore, the acoustic phonon offers a promising platform for ultrasensitive mass sensors. However, the physical origin of acoustic frequency modulation by material adsorption has been partially unexplored so far. In this study, we prepared Al2O3-deposited Au nanoblocks and measured their acoustic phonon frequencies using time-resolved pump-probe measurements. By precisely controlling the thickness of the Al2O3 layer, we systematically investigated the relation between the acoustic phonon frequency and the deposited Al2O3 amounts. The time-resolved measurements revealed that the acoustic breathing modes were predominantly excited in the Au nanoblocks, and their frequencies increased with the increment of the Al2O3 thickness. From the relationship between the acoustic phonon frequency and the Al2O3 thickness, we revealed that the acoustic phonon frequency modulation is attributed to the density change of the whole sample. Our results would provide fruitful information for developing quantitative mass sensing devices based on metallic nanostructures.

Photoinduced Copper-Catalyzed Asymmetric Acylation of Allylic Phosphates with Acylsilanes.

We report a visible-light-induced copper-catalyzed highly enantioselective umpolung allylic acylation reaction with acylsilanes as acyl anion equivalents. Triplet-quenching experiments and DFT calculations supported our reaction design, which is based on copper-to-acyl metal-to-ligand charge transfer (MLCT) photoexcitation that generates a charge-separated triplet state as a highly reactive intermediate. According to the calculations, the allylic phosphate substrate in the excited state undergoes novel molecular activation into an allylic radical weakly bound to the copper complex. The allyl radical fragment undergoes copper-mediated regio- and stereocontrolled coupling with the acyl group under the influence of the chiral N-heterocyclic carbene ligand.

Science of 2.5 dimensional materials: paradigm shift of materials science toward future social innovation.

The past decades of materials science discoveries are the basis of our present society - from the foundation of semiconductor devices to the recent development of internet of things (IoT) technologies. These materials science developments have depended mainly on control of rigid chemical bonds, such as covalent and ionic bonds, in organic molecules and polymers, inorganic crystals and thin films. The recent discovery of graphene and other two-dimensional (2D) materials offers a novel approach to synthesizing materials by controlling their weak out-of-plane van der Waals (vdW) interactions. Artificial stacks of different types of 2D materials are a novel concept in materials synthesis, with the stacks not limited by rigid chemical bonds nor by lattice constants. This offers plenty of opportunities to explore new physics, chemistry, and engineering. An often-overlooked characteristic of vdW stacks is the well-defined 2D nanospace between the layers, which provides unique physical phenomena and a rich field for synthesis of novel materials. Applying the science of intercalation compounds to 2D materials provides new insights and expectations about the use of the vdW nanospace. We call this nascent field of science '2.5 dimensional (2.5D) materials,' to acknowledge the important extra degree of freedom beyond 2D materials. 2.5D materials not only offer a new field of scientific research, but also contribute to the development of practical applications, and will lead to future social innovation. In this paper, we introduce the new scientific concept of this science of '2.5D materials' and review recent research developments based on this new scientific concept.

Dumbbell-Shaped 2,2'-Bipyridines: Controlled Metal Monochelation and Application to Ni-Catalyzed Cross-Couplings.

2,2'-Bipyridine ligands (dsbpys) with dumbbell-like shapes and differently substituted triarylmethyl groups at the C5 and C5' positions showed high ligand performance in the Ni-catalyzed cross-electrophile coupling and the Ni/photoredox-synergistically catalyzed decarboxylative coupling reactions. The superior ligand effects of dsbpys compared to the conventional bpy ligands were attributed to the monochelating nature of dsbpys.

Correlation between Near-Field Enhancement and Dephasing Time in Plasmonic Dimers.

Near-field enhancement and dephasing time play critical roles in several applications of localized surface plasmon resonance. Here, using an example gold dimer system, we reveal the correlation between the near-field enhancement and dephasing time via time-resolved photoemission electron microscopy. Compared with isolated particles, dimers with small gap sizes show stronger near-field enhancement and shorter dephasing times. These results are well reproduced by numerical simulations and further explained by a coupled dipole approximation model. The roles of near- and far-field coupling and plasmon localization in balancing near-field enhancement and dephasing time are also unveiled.

Solid-State Plasmonic Solar Cells.

Metallic nanoparticles such as silver and gold show localized surface plasmon resonances (LSPRs), which are associated with near-field enhancement effects in the vicinity of nanoparticles. Therefore, strong light-matter interaction is induced by the near-field enhancement effects of LSPRs. Because the resonant wavelength of LSPRs can be easily controlled by the size and shape of the metallic nanoparticles in the visible and near-infrared wavelength range, LSPRs have received considerable attention as optical antennae for light energy conversion systems such as solar cells. LSPRs decay very quickly as a result of light scattering and excitation of electron-hole pairs in the metal itself. However, in addition to the near-field enhancement effect, this light scattering and electron-hole pair excitation, which are known to cause loss of LSPRs, can be utilized as a solar cell enhancement mechanism. Here, we focus on plasmonic solid-state solar cells. The mechanisms of the light scattering by LSPRs, near-field enhancement, and plasmon-induced charge separation based on electron-hole pair excitations can be clarified. We review the related studies from the viewpoint of these mechanisms rather than material science.

Further enhancement of the near-field on Au nanogap dimers using quasi-dark plasmon modes.

Metallic nanogap dimers are extremely useful for enhancing surface-enhanced Raman scattering and various nonlinear optical effects employing near-field enhancement effects induced by the localized surface plasmon resonance. However, the metallic nanogap dimers exhibit an intense light scattering due to the strong dipole-dipole interaction between two metallic nanostructures and, therefore, are not necessarily a structural design that exhibits the highest near-field enhancement due to the radiation loss. Here, we propose further enhancement of the near-field on metallic nanogap dimers using quasi-dark plasmon modes. By coupling with gold (Au) nanorods having the same plasmon resonant wavelength, but completely different sizes, a quasi-dark plasmon mode, which reduces the radiation loss slightly, is induced, resulting in the elongation of the plasmon dephasing time. As a result, the signal of surface-enhanced Raman scattering of crystal violet molecules adsorbed on the Au nanogap dimer is enhanced up to about three times as compared to that measured using the Au nanogap dimer without the Au nanorods. Scattering spectrum measurements as well as electromagnetic simulations were performed to clarify the mechanism for further enhancement of the near-field. The proposed coupled plasmonic system is expected to be advantageous, especially in enhancing nonlinear optical effects using plasmonic enhancement effects.

Arbitrary control of the diffusion potential between a plasmonic metal and a semiconductor by an angstrom-thick interface dipole layer.

Localized surface plasmon resonances (LSPRs) are gaining considerable attention due to the unique far-field and near-field optical properties and applications. Additionally, the Fermi energy, which is the chemical potential, of plasmonic nanoparticles is one of the key properties to control hot-electron and -hole transfer at the interface between plasmonic nanoparticles and a semiconductor. In this article, we tried to control the diffusion potential of the plasmonic system by manipulating the interface dipole. We fabricated solid-state photoelectric conversion devices in which gold nanoparticles (Au-NPs) are located between strontium titanate (SrTiO3) as an electron transfer material and nickel oxide (NiO) as a hole transport material. Lanthanum aluminate as an interface dipole layer was deposited on the atomic layer scale at the three-phase interface of Au-NPs, SrTiO3, and NiO, and the effect was investigated by photoelectric measurements. Importantly, the diffusion potential between the plasmonic metal and a semiconductor can be arbitrarily controlled by the averaged thickness and direction of the interface dipole layer. The insertion of an only one unit cell (uc) interface dipole layer, whose thickness was less than 0.5 nm, dramatically controlled the diffusion potential formed between the plasmonic nanoparticles and surrounding media. This is a new methodology to control the plasmonic potential without applying external stimuli, such as an applied potential or photoirradiation, and without changing the base materials. In particular, it is very beneficial for plasmonic devices in that the interface dipole has the ability not only to decrease but also to increase the open-circuit voltage on the order of several hundreds of millivolts.

Near-field spectroscopic properties of complementary gold nanostructures: applicability of Babinet's principle in the optical region.

We examine the far-field and near-field properties of complementary screens made of nanostructured gold thin films, a rectangular nanowire and a nanovoid, using an aperture-type scanning near-field optical microscope and electromagnetic field calculations, and discuss the applicability of Babinet's principle in the optical region. The far-field transmission spectra of the complementary screens are considerably different from each other. On the other hand, genuine near-field extinction spectra exhibit nearly complementary characteristics. The spatial features of the observed near-field images for the complementary screens show little correlation. We have found from the Fourier analysis of the simulated images that high spatial-frequency components of the electromagnetic fields show mutual spatial correlation. These results suggest that Babinet's principle is applicable to the high spatial-frequency components of electromagnetic fields for the complementary screens.

Near-field spectral properties of coupled plasmonic nanoparticle arrays.

We investigated the grating effect in complex gold dolmen structures, in which multiple plasmon modes are present due to plasmon hybridization, experimentally from both the far field and the near field. In particular, the near-field properties were investigated using photoemission electron microscopy, and it was demonstrated that two hybridized plasmon modes on the dolmen structures could be influenced by the grating effect. For comparison, we also investigated the grating effect in arrays of simple nanoblocks and heptamer structures, which were supposed to support a strong bright plasmon mode and a strong dark plasmon mode, respectively, in the near field. We found that the spectral responses of the two hybridized modes on the dolmen structures as the pitch size changed evolved in a manner similar to that of the bright dipole mode on the nanoblocks, whereas the dark mode on the heptamer structures is less sensitive to the pitch size.

Surface plasmon optical antennae in the infrared region with high resonant efficiency and frequency selectivity.

Infrared light has received attention for sensor applications, including fingerprint spectroscopy, in the bioengineering and security fields. Surface plasmon physics enables the operation of a light harvesting optical antenna. Gold nanochains exhibit localized surface plasmon resonance (LSPR) in the infrared region with high frequency selectivity. However, a feasible design for optical antennae with a higher resonant efficiency and frequency selectivity as a function of structural design and periodicity is still unknown. In the present study, we investigated the relationship between the resonant efficiency and frequency selectivity as a function of the structural design of gold nanochains and explored structural periodicity for obtaining highly frequency-selective optical antennae. An optical antenna design with higher resonant efficiency is proposed on the basis of its efficient interaction with non-polarized light.

Plasmon-Induced Water Splitting Using Metallic-Nanoparticle-Loaded Photocatalysts and Photoelectrodes.

Visible- and near-infrared-light-driven water splitting, which splits water molecules to generate hydrogen and oxygen gases, is a significant subject in artificial photosynthesis with the goal of achieving a low-carbon society. In recent years, considerable attention has been paid to studies on the development of a plasmon-induced water-splitting system responding to visible light. In this review, we categorized water-splitting systems as gold-nanoparticle-loaded semiconductor photocatalytic particles system and metallic-nanoparticles-loaded semiconductor photoelectrode systems, and introduce the latest studies according to these categories. Especially, we describe the studies that optimize a material or a structural design of metallic-nanoparticle-loaded semiconductor photoelectrodes and consider a whole water-splitting system, including a cathode design. Furthermore, we discuss important points when studying plasmon-induced water splitting, and we describe a methodology that enhances plasmon-induced water-splitting efficiency.

Selective Dinitrogen Conversion to Ammonia Using Water and Visible Light through Plasmon-induced Charge Separation.

The generation of ammonia from atmospheric nitrogen and water using sunlight is a preferable approach to obtaining ammonia as an energy carrier and potentially represents a new paradigm for achieving a low-carbon and sustainable-energy society. Herein, we report the selective conversion of dinitrogen into ammonia through plasmon-induced charge separation by using a strontium titanate (SrTiO3) photoelectrode loaded with gold nanoparticles (Au-NPs) and a zirconium/zirconium oxide (Zr/ZrOx ) thin film. We observed the simultaneous stoichiometric production of ammonia and oxygen from nitrogen and water under visible-light irradiation.

Surface-enhanced terahertz spectroscopy using gold rod structures resonant with terahertz waves.

Terahertz (THz) spectroscopy is a promising method to measure the spectrum of low-frequency modes of molecules or ensembles, such as crystals and polymers, including proteins. However, the main drawback of THz spectroscopy is its extremely low sensitivity. In the present study, we report on signal enhancement in THz spectroscopy achieved by depositing amino acid molecules or their derivatives on a gold rod structured silicon substrate whose localized surface plasmon resonance is exhibited in the THz frequency region. The distinct peaks derived from the enhancement of the inherent spectrum based on a molecular crystal were clearly observed when a longitudinal plasmon resonance mode of the gold rod structure was excited and the plasmon resonance band overlapped the molecular/intermolecular vibrational mode. We discuss the mechanism by which surface-enhanced THz spectroscopy was induced from the viewpoint of the enhancement of light-matter coupling due to plasmon excitation and the modulation of the plasmon band by dipole coupling between the plasmon dipole and molecular/intermolecular vibrational modes.

Plasmon-induced ammonia synthesis through nitrogen photofixation with visible light irradiation.

We have successfully developed a plasmon-induced technique for ammonia synthesis that responds to visible light through a strontium titanate (SrTiO3) photoelectrode loaded with gold (Au) nanoparticles. The photoelectrochemical reaction cell was divided into two chambers to separate the oxidized (anodic side) and reduced (cathodic side) products. To promote NH3 formation, a chemical bias was applied by regulating the pH value of these compartments, and ethanol was added to the anodic chamber as a sacrificial donor. The quantity of NH3 formed at the ruthenium surface, which was used as a co-catalyst for SrTiO3, increases linearly as a function of time under irradiation with visible light at wavelengths longer than 550 nm. The NH3 formation action spectrum approximately corresponds to the plasmon resonance spectrum. We deduced that plasmon-induced charge separation at the Au/SrTiO3 interface promotes oxidation at the anodic chamber and subsequent nitrogen reduction on the cathodic side.

Plasmon-assisted water splitting using two sides of the same SrTiO3 single-crystal substrate: conversion of visible light to chemical energy.

A plasmon-induced water splitting system that operates under irradiation by visible light was successfully developed; the system is based on the use of both sides of the same strontium titanate (SrTiO3) single-crystal substrate. The water splitting system contains two solution chambers to separate hydrogen (H2) and oxygen (O2). To promote water splitting, a chemical bias was applied by regulating the pH values of the chambers. The quantity of H2 evolved from the surface of platinum, which was used as a reduction co-catalyst, was twice the quantity of O2 evolved from an Au-nanostructured surface. Thus, the stoichiometric evolution of H2 and O2 was clearly demonstrated. The hydrogen-evolution action spectrum closely corresponds to the plasmon resonance spectrum, indicating that the plasmon-induced charge separation at the Au/SrTiO3 interface promotes water oxidation and the subsequent reduction of a proton on the backside of the SrTiO3 substrate. The chemical bias is significantly reduced by plasmonic effects, which indicates the possibility of constructing an artificial photosynthesis system with low energy consumption.

Single molecule dynamics at a mechanically controllable break junction in solution at room temperature.

The in situ observation of geometrical and electronic structural dynamics of a single molecule junction is critically important in order to further progress in molecular electronics. Observations of single molecular junctions are difficult, however, because of sensitivity limits. Here, we report surface-enhanced Raman scattering (SERS) of a single 4,4'-bipyridine molecule under conditions of in situ current flow in a nanogap, by using nano-fabricated, mechanically controllable break junction (MCBJ) electrodes. When adsorbed at room temperature on metal nanoelectrodes in solution to form a single molecule junction, statistical analysis showed that nontotally symmetric b(1) and b(2) modes of 4,4'-bipyridine were strongly enhanced relative to observations of the same modes in solid or aqueous solutions. Significant changes in SERS intensity, energy (wavenumber), and selectivity of Raman vibrational bands that are coincident with current fluctuations provide information on distinct states of electronic and geometrical structure of the single molecule junction, even under large thermal fluctuations occurring at room temperature. We observed the dynamics of 4,4'-bipyridine motion between vertical and tilting configurations in the Au nanogap via b(1) and b(2) mode switching. A slight increase in the tilting angle of the molecule was also observed by noting the increase in the energies of Raman modes and the decrease in conductance of the molecular junction.

Spectral properties and electromagnetic field enhancement effects on nano-engineered metallic nanoparticles.

Plasmonic chemistry, a new research field dedicated to understanding plasmon-enhanced photochemical reactions, has become a principal area of chemical research, especially in the field of physical chemistry. In this perspective review article, we describe our recent research regarding the development of a fabrication methodology for metallic nanostructures that exhibit localized surface plasmon resonance, the spectral properties of the fabricated metallic nanostructures and their electromagnetic field enhancement effects using two-photon-induced photoluminescence from gold nanoparticles.

Expression of concern: Versatile plasmonic-effects at the interface of inverted perovskite solar cells.

Expression of concern for 'Versatile plasmonic-effects at the interface of inverted perovskite solar cells' by Ahmed Esmail Shalan, et al., Nanoscale, 2017, 9, 1229-1236, https://doi.org/10.1039/C6NR06741G.

Plasmonic antenna effects on photochemical reactions.

Efficient solar energy conversion has been vigorously pursued since the 1970s, but its large-scale implementation hinges on the availability of high-efficiency modules. For maximum efficiency, it is important to absorb most of the incoming radiation, which necessitates both efficient photoexcitation and minimal electron-hole recombination. To date, researchers have primarily focused on the latter difficulty: finding a strategy to effectively separate photoinduced electrons and holes. Very few reports have been devoted to broadband sunlight absorption and photoexcitation. However, the currently available photovoltaic cells, such as amorphous silicon, and even single-crystal silicon and sensitized solar cells, cannot respond to the wide range of the solar spectrum. The photoelectric conversion characteristics of solar cells generally decrease in the infrared wavelength range. Thus, the fraction of the solar spectrum absorbed is relatively poor. In addition, the large mismatch between the diffraction limit of light and the absorption cross-section makes the probability of interactions between photons and cell materials quite low, which greatly limits photoexcitation efficiency. Therefore, there is a pressing need for research aimed at finding conditions that lead to highly efficient photoexcitation over a wide spectrum of sunlight, particularly in the visible to near-infrared wavelengths. As characterized in the emerging field of plasmonics, metallic nanostructures are endowed with optical antenna effects. These plasmonic antenna effects provide a promising platform for artificially sidestepping the diffraction limit of light and strongly enhancing absorption cross-sections. Moreover, they can efficiently excite photochemical reactions between photons and molecules close to an optical antenna through the local field enhancement. This technology has the potential to induce highly efficient photoexcitation between photons and molecules over a wide spectrum of sunlight, from visible to near-infrared wavelengths. In this Account, we describe our recent work in using metallic nanostructures to assist photochemical reactions for augmenting photoexcitation efficiency. These studies investigate the optical antenna effects of coupled plasmonic gold nanoblocks, which were fabricated with electron-beam lithography and a lift-off technique to afford high resolution and nanometric accuracy. The two-photon photoluminescence of gold and the resulting nonlinear photopolymerization on gold nanoblocks substantiate the existence of enhanced optical field domains. Local two-photon photochemical reactions due to weak incoherent light sources were identified. The optical antenna effects support the unprecedented realization of (i) direct photocarrier injection from the gold nanorods into TiO(2) and (ii) efficient and stable photocurrent generation in the absence of electron donors from visible (450 nm) to near-infrared (1300 nm) wavelengths.