Halide Perovskite Single Crystals and Nanocrystal Films as Electron Donor-Acceptor Heterojunctions.

Halide perovskites are materials for future optical displays and solar cells. Electron donor-acceptor perovskite heterostructures with distinguishing halide compositions are promising for transporting and harvesting photogenerated charge carriers. Combined e-beam lithography and anion exchange are promising to develop such heterostructures but challenging to prepare multiple heterojunctions at desired locations in single crystals. We demonstrate swift laser trapping-assisted band gap engineering at the desired locations in MAPbBr3 microrods, microplates, or nanocrystal thin films. The built-in donor-acceptor double and multi-heterojunction structures let us transport and trap photogenerated charge carriers from wide-band gap bromide to narrow-band gap iodide domains. We discuss the charge carrier transport and trapping mechanisms from the viewpoints of engineered bands and band continuity. This work offers a convenient method for designing single-, double- and multi-heterojunction donor-acceptor halide perovskites for photovoltaic, photonic, and electronic applications.

Boosting Hydrogen Evolution at Visible Light Wavelengths by Using a Photocathode with Modal Strong Coupling between Plasmons and a Fabry-Pérot Nanocavity.

Hot-hole injection from plasmonic metal nanoparticles to the valence band of p-type semiconductors and reduction by hot electrons should be improved for efficient and tuneable reduction to obtain beneficial chemical compounds. We employed the concept of modal strong coupling between plasmons and a Fabry-Pérot (FP) nanocavity to enhance the hot-hole injection efficiency. We fabricated a photocathode composed of gold nanoparticles (Au-NPs), p-type nickel oxide (NiO), and a platinum film (Pt film) (ANP). The ANP structure absorbs visible light over a broad wavelength range from 500 nm to 850 nm via hybrid modes based on the modal strong coupling between the plasmons of Au-NPs and the FP nanocavity of NiO on a Pt film. All wavelength regions of the hybrid modes of the modal strong coupling system promoted hot-hole injection from the Au-NPs to NiO and proton/water reduction by hot electrons. The incident photon-to-current efficiency based on H2 evolution through water/proton reduction by hot electrons reached 0.2 % at 650 nm and 0.04 % at 800 nm.

Revealing the Chiroptical Response of Plasmonic Nanostructures at the Nanofemto Scale.

The spatiotemporal origin of plasmonic chiroptical responses in nanostructures remains unexplored and unclear. Here, two orthogonally oriented Au nanorods as a prototype were investigated, with a giant chiroptical response caused by antisymmetric and symmetric mode excitations for obliquely incident left-handed circular polarization (LCP) and right-handed circular polarization (RCP) light. Time-resolved photoemission electron microscopy (PEEM) was employed to measure the near-field spatial distributions, spectra, and spatiotemporal dynamics of plasmonic modes associated with the chiroptical responses at the nanofemto scale, verifying the characteristic near-field distributions at the resonant wavelengths of the two modes and a very large spectral dichroism for LCP and RCP. More importantly, eigenmode excitations and their contributions to the ultrafast plasmonic chiroptical response in the space-time domain were directly revealed, promoting a full understanding of the ultrafast chiral origin in complex nanostructures. These findings open a way to design chiroptical nanophotonic devices for spatiotemporal control of chiral light-matter interactions.

Near-Perfect Absorption of Light by Coherent Plasmon-Exciton States.

We experimentally demonstrate and theoretically study the formation of coherent plasmon-exciton states which exhibit absorption of >90% of the incident light (at resonance) and cancellation of absorption. These coherent states result from the interaction between a material supporting an electronic excitation and a plasmonic structure capable of (near) perfect absorption of light. We illustrate the potential implications of these coherent states by measuring the charge separation attainable after photoexcitation. Our study opens the prospect for realizing devices that exploit coherent effects in applications.

Near-Field Imaging and Time-Domain Dynamics of Photonic Topological Edge States in Plasmonic Nanochains.

Time-domain dynamic evolution properties of topological states play an important role in both fundamental physics study and practical applications of topological photonics. However, owing to the absence of available ultrafast time-domain dynamic characterization methods, studies have mostly focused on the frequency-domain-based properties, and there are few reports demonstrating the time-domain-based properties. Here, we measured the dynamic near-field responses of plasmonic topological structures of gold nanochains with the configuration of the Su-Schrieffer-Heeger model by using ultrahigh spatial-temporal resolution photoemission electron microscopy. The dephasing time of plasmonic topological edge states increases with increasing the bulk lattice number that has a threshold requirement and finally reaches saturation. We directly revealed through simulation that there is a transient bulk state in the evolution of topological edge states, that is, the energy undergoes relaxation from oscillation between the bulk lattice and the edge. This work shows a new perspective of time-domain dynamic topological photonics.

Varifocal Metalens for Optical Sectioning Fluorescence Microscopy.

Fluorescence microscopy with optical sectioning capabilities is extensively utilized in biological research to obtain three-dimensional structural images of volumetric samples. Tunable lenses have been applied in microscopy for axial scanning to acquire multiplane images. However, images acquired by conventional tunable lenses suffer from spherical aberration and distortions. Here, we design, fabricate, and implement a dielectric Moiré metalens for fluorescence imaging. The Moiré metalens consists of two complementary phase metasurfaces, with variable focal length, ranging from ∼10 to ∼125 mm at 532 nm by tuning mutual angles. In addition, a telecentric configuration using the Moiré metalens is designed for high-contrast multiplane fluorescence imaging. The performance of our system is evaluated by optically sectioned images obtained from HiLo illumination of fluorescently labeled beads, as well as ex vivo mice intestine tissue samples. The compact design of the varifocal metalens may find important applications in fluorescence microscopy and endoscopy for clinical purposes.

Ultrafast Electron Cooling and Decay in Monolayer WS2 Revealed by Time- and Energy-Resolved Photoemission Electron Microscopy.

A comprehensive understanding of the ultrafast electron dynamics in two-dimensional transition metal dichalcogenides (TMDs) is necessary for their applications in optoelectronic devices. In this work, we contribute a study of ultrafast electron cooling and decay dynamics in the supported and suspended monolayer WS2 by time- and energy-resolved photoemission electron microscopy (PEEM). Electron cooling in the Q valley of the conduction band is clearly resolved in energy and time, on a time scale of 0.3 ps. Electron decay is mainly via a defect trapping process on a time scale of several picoseconds. We observed that the trap states can be produced and increased by laser illumination under an ultrahigh vacuum, and the higher local optical-field intensity led to the faster increase of trap states. The enhanced defect trapping could significantly modify the carrier dynamics and should be paid attention to in photoemission experiments for two-dimensional materials.

Chiral Second-Harmonic Generation from Monolayer WS2/Aluminum Plasmonic Vortex Metalens.

Two-dimensional spiral plasmonic structures have emerged as a versatile approach to generate near-field vortex fields with tunable topological charges. We demonstrate here a far-field approach to observe the chiral second-harmonic generation (SHG) at designated visible wavelengths from a single plasmonic vortex metalens. This metalens comprises an Archimedean spiral slit fabricated on atomically flat aluminum epitaxial film, which allows for precise tuning of plasmonic resonances and subsequent transfer of two-dimensional materials on top of the spiral slit. The nonlinear optical measurements show a giant SHG circular dichroism. Furthermore, we have achieved an enhanced chiral SHG conversion efficiency (about an order of magnitude greater than the bare aluminum lens) from monolayer tungsten disulfide (WS2)/aluminum metalens, which is designed at the C-exciton resonance of WS2. Since the C-exciton is not a valley exciton, the enhanced chiral SHG in this hybrid system originates from the plasmonic vortex field-enhanced SHG under the optical spin-orbit interaction.

Water Oxidation under Modal Ultrastrong Coupling Conditions Using Gold/Silver Alloy Nanoparticles and Fabry-Pérot Nanocavities.

We developed a photoanode consisting of Au-Ag alloy nanoparticles (NPs), a TiO2 thin film and a Au film (AATA) under modal strong coupling conditions with a large splitting energy of 520 meV, which can be categorized into the ultrastrong coupling regime. We fabricated a photoanode under ultrastrong coupling conditions to verify the relationship between the coupling strength and photoelectric conversion efficiency and successfully performed efficient photochemical reactions. The AATA photoanode showed a 4.0 % maximum incident photon-to-current efficiency (IPCE), obtained at 580 nm, and the internal quantum efficiency (IQE) was 4.1 %. These results were attributed to the high hot-electron injection efficiency due to the larger near-field enhancement and relatively negative potential distribution of the hot electrons. Furthermore, hybrid mode-induced water oxidation using AATA structures was performed, with a Faraday efficiency of more than 70 % for O2 evolution.

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.

Ultrafast photoemission electron microscopy: Capability and potential in probing plasmonic nanostructures from multiple domains.

The near-field properties and dynamics of plasmonic nanostructures play a crucial role in several fundamental concepts in physics and chemistry, and they are widely relevant in plasmonic applications. Ultrafast photoemission electron microscopy (PEEM) is a novel approach that has been widely applied to probe plasmonic nanostructures from multiple domains. Furthermore, PEEM is the only technique that provides nanometer spatial resolution, sub-femtosecond temporal resolution, and tens to hundreds of millielectron volt energy resolution. This allows for extremely sensitive observations of plasmonic field oscillations, field dephasing, and hot electrons. This Perspective provides a brief overview of the basic principles and main applications of ultrafast PEEM. The research progress of ultrafast PEEM in plasmonics is highlighted from three points of view: near-field imaging, near-field spectroscopy, and ultrafast dynamics. Future applications of PEEM in plasmonics for the probing of plasmonic hot electron dynamics in the energy and time domains are proposed and discussed.

Special topic on emerging directions in plasmonics.

Plasmonics enables a wealth of applications, including photocatalysis, photoelectrochemistry, photothermal heating, optoelectronic devices, and biological and chemical sensing, while encompassing a broad range of materials, including coinage metals, doped semiconductors, metamaterials, 2D materials, bioconjugates, and chiral assemblies. Applications in plasmonics benefit from the large local electromagnetic field enhancements generated by plasmon excitation, as well as the products of plasmon decay, including photons, hot charge carriers, and heat. This special topic highlights recent work in both theory and experiment that advance our fundamental understanding of plasmon excitation and decay mechanisms, showcase new applications enabled by plasmon excitation, and highlight emerging classes of materials that support plasmon excitation.

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.