Spatially Uniform and Quantitative Surface-Enhanced Raman Scattering under Modal Ultrastrong Coupling Beyond Nanostructure Homogeneity Limits.

We developed a substrate that enables highly sensitive and spatially uniform surface-enhanced Raman scattering (SERS). This substrate comprises densely packed gold nanoparticles (d-AuNPs)/titanium dioxide/Au film (d-ATA). The d-ATA substrate demonstrates modal ultrastrong coupling between localized surface plasmon resonances (LSPRs) of AuNPs and Fabry-Pérot nanocavities. d-ATA exhibits a significant enhancement of the near-field intensity, resulting in a 78-fold increase in the SERS signal for crystal violet (CV) compared to that of d-AuNP/TiO2 substrates. Importantly, high sensitivity and a spatially uniform signal intensity can be obtained without precise control of the shape and arrangement of the nanoscale AuNPs, enabling quantitative SERS measurements. Additionally, SERS measurements of rhodamine 6G (R6G) on this substrate under ultralow adsorption conditions (0.6 R6G molecules/AuNP) show a spatial variation in the signal intensity within 3%. These findings suggest that the SERS signal under modal ultrastrong coupling originates from multiple plasmonic particles with quantum coherence.

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.

Photoinduced interfacial electron transfer from perovskite quantum dots to molecular acceptors for solar cells.

Bandgap-engineered inorganic and hybrid halide perovskite (HP) films, nanocrystals, and quantum dots (PQDs) are promising for solar cells. Fluctuations of photoinduced electron transfer (PET) rates affect the interfacial charge separation efficiencies of such solar cells. Electron donor- or acceptor-doped perovskite samples help analyze PET and harvest photogenerated charge carriers efficiently. Therefore, PET in perovskite-based donor-acceptor (D-A) systems has received considerable attention. We analyzed the fluctuations of interfacial PET from MAPbBr3 or CsPbBr3 PQDs to classical electron acceptors such as 7,7,8,8-tetracyanoquinodimethane (TCNQ) and 1,2,4,5-tetracyanobenzene (TCNB) at single-particle and ensemble levels. The significantly negative Gibbs free energy changes of PET estimated from the donor-acceptor redox potentials, the donor-acceptor sizes, and the solvent dielectric properties help us clarify the PET in the above D-A systems. The dynamic nature of PET is apparent from the decrease in photoluminescence (PL) lifetimes and PL photocounts of PQDs with an increase in the acceptor concentrations. Also, the acceptor radical anion spectrum helps us characterize the charge-separated states. Furthermore, the PL blinking time and PET rate fluctuations (108 to 107 s-1) provide us with single-molecule level information about interfacial PET in perovskites.

Quantum-Coherence-Enhanced Hot-Electron Injection under Modal Strong Coupling.

Modal strong coupling between localized surface plasmon resonance and a Fabry-Pérot nanocavity has been studied to improve the quantum efficiency of artificial photosynthesis. In this research, we employed Au nanodisk/titanium dioxide/Au film modal strong coupling structures to investigate the mechanism of quantum efficiency enhancement. We found that the quantum coherence within the structures enhances the apparent quantum efficiency of the hot-electron injection from the Au nanodisks to the titanium dioxide layer. Under near-field mapping using photoemission electron microscopy, the existence of quantum coherence was directly observed. Furthermore, the coherence area was quantitatively evaluated by analyzing the relationship between the splitting energy and the particle number density of the Au nanodisks. This quantum-coherence-enhanced hot-electron injection is supported by our theoretical model. Based on these results, applying quantum coherence to photochemical reaction systems is expected to effectively enhance reaction efficiencies.

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.

Metasurface-Based Abrupt Autofocusing Beam for Biomedical Applications.

Manipulation and precise delivery of optical energies in the regions of interest within specimens require different strategies. Hence, proper control of input beam parameters is a prerequisite. One of the prominent methods is metasurface optics, capable of crafting properties of light at nanoscales. Here, the generation of an abrupt autofocusing (AAF) beam by a nanophotonic metasurface for biomedical applications is demonstrated. Fluorescence guided laser microprofiling of mouse cardiac samples is experimentally investigated, using the AAF beam to deliver optical energy selectively to specific locations. In addition, photocoagulation of ex vivo swine skin tissue is performed and observed through optical coherence tomography. The results show great potentials for integrating metasurface optics to realize miniature laser surgery instruments for wide applications in biomedicine.

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.

Improved water splitting efficiency of Au-NP-loaded Ga2O3 thin films in the visible region under strong coupling conditions.

We fabricate a novel photoanode consisting of TiO2/Au nanoparticles (Au-NPs)/Ga2O3/TiN/Au-film (TAGA), efficiently increasing light absorption and electron transfer from Au-NPs to Ga2O3 under modal strong coupling. A TiN thin layer deposited on an Au film enables stable high-temperature deposition of Ga2O3 onto the reflective Au film mirror. Modal strong coupling is observed when the resonance wavelength of the Ga2O3/TiN/Au-film Fabry-Pérot cavity overlaps with the plasmon resonance wavelength of Au-NPs partially inlaid in a thin TiO2 layer. Under strong coupling conditions, the light absorption and photoelectrochemical conversion efficiency in the visible region increased more than in the samples without coupling. In this structure, the TiO2 layer partially inlaying Au-NPs plays a vital role in effectively enhancing the coupling strength. We accomplish water splitting at zero bias potential by taking advantage of the intrinsically negative conduction band potential of Ga2O3.

A Fabry-Pérot cavity coupled surface plasmon photodiode for electrical biomolecular sensing.

Surface plasmon resonance is a well-established technology for real-time highly sensitive label-free detection and measurement of binding kinetics between biological samples. A common drawback, however, of surface plasmon resonance detection is the necessity for far field angular resolved measurement of specular reflection, which increases the size as well as requiring precise calibration of the optical apparatus. Here we present an alternative optoelectronic approach in which the plasmonic sensor is integrated within a photovoltaic cell. Incident light generates an electronic signal that is sensitive to the refractive index of a solution via interaction with the plasmon. The photogenerated current is enhanced due to the coupling of the plasmon mode with Fabry-Pérot modes in the absorbing layer of the photovoltaic cell. The near field electrical detection of surface plasmon resonance we demonstrate will enable a next generation of cheap, compact and high throughput biosensors.

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.

Extrinsic Chirality by Interference between Two Plasmonic Modes on an Achiral Rectangular Nanostructure.

The optical near field (NF) induced by circularly polarized light (CPL) is a hot scientific topic. We observed a chiral NF intensity distribution on a series of achiral gold nanorectangular structures (Au-NRs) under CPL irradiation by using multiphoton photoemission electron microscopy (MP-PEEM). Additionally, the differential NF spectra under left and right CPL irradiation, which represent the asymmetry of the NF intensity distribution, were investigated. We propose an interpretation that the chiral NF intensity distribution on an achiral metallic nanostructure is extrinsically generated by the interference between two plasmonic modes by combining state-of-the-art MP-PEEM techniques and the classical oscillator model. Our interpretation well explains both the experimental and simulation results. Furthermore, the intensity of the NF and its phase angle of each mode under linearly polarized light irradiation were revealed to be critical factors for the generation of extrinsic chirality in the NF intensity distribution.

Cubic-Phase Metasurface for Three-Dimensional Optical Manipulation.

The optical tweezer is one of the important techniques for contactless manipulation in biological research to control the motion of tiny objects. For three-dimensional (3D) optical manipulation, shaped light beams have been widely used. Typically, spatial light modulators are used for shaping light fields. However, they suffer from bulky size, narrow operational bandwidth, and limitations of incident polarization states. Here, a cubic-phase dielectric metasurface, composed of GaN circular nanopillars, is designed and fabricated to generate a polarization-independent vertically accelerated two-dimensional (2D) Airy beam in the visible region. The distinctive propagation characteristics of a vertically accelerated 2D Airy beam, including non-diffraction, self-acceleration, and self-healing, are experimentally demonstrated. An optical manipulation system equipped with a cubic-phase metasurface is designed to perform 3D manipulation of microscale particles. Due to the high-intensity gradients and the reciprocal propagation trajectory of Airy beams, particles can be laterally shifted and guided along the axial direction. In addition, the performance of optical trapping is quantitatively evaluated by experimentally measured trapping stiffness. Our metasurface has great potential to shape light for compact systems in the field of physics and biological applications.

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.

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.

Feasibility of using bimetallic Au-Ag nanoparticles for organic light-emitting devices.

Matching the resonant wavelength of plasmonic nanoparticles (NPs) and the emission band of organic materials is critical for achieving optimal plasmon-enhanced luminescence in organic light-emitting devices (OLEDs). However, the spectral matching is often unsatisfactory because the interior architecture of OLEDs limits the dimensions of the NPs to support the desired wavelength adjustment. In this article, we proposed a design strategy via AuxAg1-x alloy NPs to enable resonance tuning while preserving the size of the NP to suit the OLED design requirements. The bimetallic NPs, especially for x < 0.6, not only add one more degree of freedom to vary the plasmon wavelength but also provide the benefits of higher scattering and more intense and outspread electric fields over a broader spectrum compared to Au monometallic NPs. These features allow smaller NPs, which are more compatible with OLED interiors, to scatter electric fields more efficiently and increase the density of molecules interacting with the NP plasmons. In the presence of a nearby dipole emitter, the bimetallic NPs can simultaneously increase radiative enhancement and suppress non-radiative losses, which are advantageous for increasing the quantum yield and luminescence efficiency of the emitter. These improvements are associated with lower intraband and interband activities resulting from the higher molar fraction of Ag in the alloy NPs. We provided composition mappings to achieve enhanced luminescence for specified wavelengths at fixed NP sizes. Finally, we theoretically demonstrated that the bimetallic NPs could improve the light-extraction efficiency of OLEDs better than Au monometallic NPs. This work provides essential guidance to enable versatile plasmon-enhanced applications with predefined nanostructural geometries and wavelengths to match the device requirements.

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.

Enhanced x-ray emission coinciding with giant radio pulses from the Crab Pulsar.

Giant radio pulses (GRPs) are sporadic bursts emitted by some pulsars that last a few microseconds and are hundreds to thousands of times brighter than regular pulses from these sources. The only GRP-associated emission outside of radio wavelengths is from the Crab Pulsar, where optical emission is enhanced by a few percentage points during GRPs. We observed the Crab Pulsar simultaneously at x-ray and radio wavelengths, finding enhancement of the x-ray emission by 3.8 ± 0.7% (a 5.4σ detection) coinciding with GRPs. This implies that the total emitted energy from GRPs is tens to hundreds of times higher than previously known. We discuss the implications for the pulsar emission mechanism and extragalactic fast radio bursts.

Near-field engineering for boosting the photoelectrochemical activity to a modal strong coupling structure.

Near-field engineering is considered a significant strategy in constructing plasmonic nanostructures for efficient plasmonic chemistry. We demonstrate interfacial near-field engineering on a Au-NP/TiO2/Au-film (ATA) photoanode to improve the water oxidation efficiency. To tailor the near-field distribution, postdeposited Au on an ATA electrode (Au@ATA) is implemented using a facile constant potential electrolysis technique. As a result, the average photocurrent conversion efficiency of Au@ATA is approximately 1.3-fold higher than that of ATA.

Plasmon-induced electron injection into the large negative potential conduction band of Ga2O3 for coupling with water oxidation.

In this study, an interfacial modification layer was applied to improve the plasmon-induced light energy conversion of a gallium(iii) oxide (Ga2O3) photoelectrode, which possesses a much more negative conduction band potential compared with the reduction potential of photons to hydrogen. The plasmon-induced photocurrent generation under visible light irradiation was observed with Au nanoparticle-loaded Ga2O3 (Au-NPs/Ga2O3). An interfacial modification was carried out by depositing a titanium dioxide (TiO2) thin-film layer on Au-NPs/Ga2O3via atomic layer deposition. Since the surface states of TiO2 possess excellent hole-trapping ability, this interfacial modification remarkably improved the generation of plasmon-induced photocurrent in the visible region. The photoelectric conversion efficiency of interfacially modified Au-NPs/Ga2O3 showed a TiO2 thin-film thickness dependence because the migration of hot carriers was suppressed with increasing TiO2 thickness. The Au-NPs/Ga2O3 photoelectrode modified with 2 nm-thick TiO2 showed the best photoelectric conversion performance, and the thermodynamic energy conversion efficiency under irradiation with 600 nm light was approximately two times larger than that of the Au-NPs/TiO2-thin film due to the extremely negative onset potential of Au-NPs/Ga2O3 with TiO2. Therefore, the plasmonic Ga2O3 photoanode with the interfacial TiO2 modification could provide both a high reduction ability for H2 evolution and an oxidation ability for water oxidation, because of the negative conduction band of Ga2O3 and the hole-trapping property from TiO2, respectively.