Ultralow Auger-Assisted Interlayer Exciton Annihilation in WS2/WSe2 Moiré Heterobilayers.

Transition metal dichalcogenide (TMD) heterobilayers have emerged as a promising platform for exploring solid-state quantum simulators and many-body quantum phenomena. Their type II band alignment, combined with the moiré superlattice, inevitably leads to nontrivial exciton interactions and dynamics. Here, we unveil the distinct Auger annihilation processes for delocalized interlayer excitons in WS2/WSe2 moiré heterobilayers. By fitting the characteristic efficiency droop and bimolecular recombination rate, we quantitatively determine an ultralow Auger coefficient of 1.3 × 10-5 cm2 s-1, which is >100-fold smaller than that of excitons in TMD monolayers. In addition, we reveal selective exciton upconversion into the WSe2 layer, which highlights the significance of intralayer electron Coulomb interactions in dictating the microscopic scattering pathways. The distinct Auger processes arising from spatial electron-hole separation have important implications for TMD heterobilayers while endowing interlayer excitons and their strongly correlated states with unique layer degrees of freedom.

Enhanced Spontaneous Emission of Monolayer MoS2 on Epitaxially Grown Titanium Nitride Epsilon-Near-Zero Thin Films.

Room-temperature photoluminescence enhancement of molybdenum disulfide (MoS2) monolayers on epitaxial titanium nitride (TiN) thin films grown by molecular-beam-epitaxy as well as magnetron-sputtered TiN films is observed by a confocal laser scanning microscope with excitation wavelengths covering the transition of TiN's macroscopic optical properties from dielectric to plasmonic. The photoluminescence enhancement increases as TiN becomes more metallic, and strong enhancement is obtained at the excitation wavelengths equal to or longer than the epsilon-near-zero (ENZ) wavelength of TiN films. A good agreement is observed between measured and calculated enhancements. The enhancement is attributed to the increased excitation field in MoS2 at TiN's ENZ wavelength and interference effects for thick spacers that separate the MoS2 flakes from TiN films in the metallic regime. This study enriches the fundamental understanding of emission properties on ENZ substrates that could be important for the development of advanced nanoscale lasers/light sources, optical/biosensors, and nano-optoelectronic devices.

Engineering Giant Rabi Splitting via Strong Coupling between Localized and Propagating Plasmon Modes on Metal Surface Lattices: Observation of √N Scaling Rule.

We present a strong coupling system realized by coupling the localized surface plasmon mode in individual silver nanogrooves and propagating surface plasmon modes launched by periodic nanogroove arrays with varied periodicities on a continuous silver medium. When the propagating modes are in resonance with the localized mode, we observe a √N scaling of Rabi splitting energy, where N is the number of propagating modes coupled to the localized mode. Here, we confirm a giant Rabi splitting on the order of 450-660 meV (N = 2) in the visible spectral range, and the corresponding coupling strength is 160-235 meV. In some of the strong coupling cases studied by us, the coupling strength is about 10% of the mode energy, reaching the ultrastrong coupling regime.

Tuning of Two-Dimensional Plasmon-Exciton Coupling in Full Parameter Space: A Polaritonic Non-Hermitian System.

Non-Hermitian photonic systems with gains and/or losses have recently emerged as a powerful approach for topology-protected optical transport and novel device applications. To date, most of these systems employ coupled optical systems of diffraction-limited dielectric waveguides or microcavities, which exchange energy spatially or temporally. Here, we introduce a diffraction-unlimited approach using a plasmon-exciton coupling (polariton) system with tunable plasmonic resonance (energy and line width) and coupling strength. By designing a chirped silver nanogroove cavity array and coupling a single tungsten disulfide monolayer with a large contrast in resonance line width, we show the tuning capability through energy level anticrossing and plasmon-exciton hybridization (line width crossover), as well as spontaneous symmetry breaking across the exceptional point at zero detuning. This two-dimensional hybrid material system can be applied as a scalable and integratable platform for non-Hermitian photonics, featuring seamless integration of two-dimensional materials, broadband tuning, and operation at room temperature.

Demonstration of a Superior Deep-UV Surface-Enhanced Resonance Raman Scattering (SERRS) Substrate and Single-Base Mutation Detection in Oligonucleotides.

In life science, rapid mutation detection in oligonucleotides is in a great demand for genomic and medical screening. To satisfy this demand, surface-enhanced resonance Raman spectroscopy (SERRS) in the deep-UV (DUV) regime offers a promising solution due to its merits of label-free nature, strong electromagnetic confinement, and charge transfer effect. Here, we demonstrate an epitaxial aluminum (Al) DUV-SERRS substrate that resonates effectively with the incident Raman laser and the ss-DNA at 266 nm, yielding significant SERRS signals of the detected analytes. For the first time, to the best of our knowledge, we obtaine SERRS spectra for all bases of oligonucleotides, not only revealing maximum characteristic Raman peaks but also recording the highest enhancement factor of up to 106 for a 1 nm thick adenine monomer. Moreover, our epitaxial Al DUV-SERRS substrate is able to enhance the Raman signal of all four bases of 12-mer ss-DNA and to further linearly quantify the single-base mutation in the 12-mer ss-DNA.

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.

Plasmonic Nanolasers Enhanced by Hybrid Graphene-Insulator-Metal Structures.

Graphene is a two-dimensional (2D) structure that creates a linear relationship between energy and momentum that not only forms massless Dirac fermions with extremely high group velocity but also exhibits a broadband transmission from 300 to 2500 nm that can be applied to many optoelectronic applications, such as solar cells, light-emitting devices, touchscreens, ultrafast photodetectors, and lasers. Although the plasmonic resonance of graphene occurs in the terahertz band, graphene can be combined with a noble metal to provide a versatile platform for supporting surface plasmon waves. In this study, we propose a hybrid graphene-insulator-metal (GIM) structure that can modulate the surface plasmon polariton (SPP) dispersion characteristics and thus influence the performance of plasmonic nanolasers. Compared with values obtained when graphene is not used on an Al template, the propagation length of SPP waves can be increased 2-fold, and the threshold of nanolasers is reduced by 50% when graphene is incorporated on the template. The GIM structure can be further applied in the future to realize electrical control or electrical injection of plasmonic devices through graphene.

Ultracompact Pseudowedge Plasmonic Lasers and Laser Arrays.

Concentrating light at the deep subwavelength scale by utilizing plasmonic effects has been reported in various optoelectronic devices with intriguing phenomena and functionality. Plasmonic waveguides with a planar structure exhibit a two-dimensional degree of freedom for the surface plasmon; the degree of freedom can be further reduced by utilizing metallic nanostructures or nanoparticles for surface plasmon resonance. Reduction leads to different lightwave confinement capabilities, which can be utilized to construct plasmonic nanolaser cavities. However, most theoretical and experimental research efforts have focused on planar surface plasmon polariton (SPP) nanolasers. In this study, we combined nanometallic structures intersecting with ZnO nanowires and realized the first laser emission based on pseudowedge SPP waveguides. Relative to current plasmonic nanolasers, the pseudowedge plasmonic lasers reported in our study exhibit extremely small mode volumes, high group indices, high spontaneous emission factors, and high Purell factors beneficial for the strong interaction between light and matter. Furthermore, we demonstrated that compact plasmonic laser arrays can be constructed, which could benefit integrated plasmonic circuits.

Optical Observation of Plasmonic Nonlocal Effects in a 2D Superlattice of Ultrasmall Gold Nanoparticles.

The advances in recent nanofabrication techniques have facilitated explorations of metal structures into nanometer scales, where the traditional local-response Drude model with hard-wall boundary conditions fails to accurately describe their optical responses. The emerging nonlocal effects in single ultrasmall silver nanoparticles have been experimentally observed in single-particle spectroscopy enabled by the unprecedented high spatial resolution of electron energy loss spectroscopy (EELS). However, the unambiguous optical observation of such new effects in gold nanoparticles has yet not been reported, due to the extremely weak scattering and the obscuring fingerprint of strong interband transitions. Here we present a nanosystem, a superlattice monolayer formed by sub-10 nm gold nanoparticles. Plasmon resonances are spectrally well-separated from interband transitions, while exhibiting clearly distinguishable blueshifts compared to predictions by the classical local-response model. Our far-field spectroscopy was performed by a standard optical transmission and reflection setup, and the results agreed excellently with the hydrodynamic nonlocal model, opening a simple and widely accessible way for addressing quantum effects in nanoplasmonic systems.

Substantially Enhancing Quantum Coherence of Electrons in Graphene via Electron-Plasmon Coupling.

The interplays between different quasiparticles in solids lay the foundation for a wide spectrum of intriguing quantum effects, yet how the collective plasmon excitations affect the quantum transport of electrons remains largely unexplored. Here we provide the first demonstration that when the electron-plasmon coupling is introduced, the quantum coherence of electrons in graphene is substantially enhanced with the quantum coherence length almost tripled. We further develop a microscopic model to interpret the striking observations, emphasizing the vital role of the graphene plasmons in suppressing electron-electron dephasing. The novel and transformative concept of plasmon-enhanced quantum coherence sheds new insight into interquasiparticle interactions, and further extends a new dimension to exploit nontrivial quantum phenomena and devices in solid systems.

n-Alkanethiols Directly Grown on a Bare Si(111) Surface: From Disordered to Ordered Transition.

We observed the growth phase transition of n-alkanethiols (AT), CH3(CH2)n-1SH, n = 4-16, directly implanted on a bare Si(111) surface, forming an AT monolayer. These monolayers were characterized with static water-contact angle, high-resolution X-ray photoelectron spectroscopy, near-edge X-ray fine-structure spectroscopy, and grazing-angle reflection absorption Fourier-transform infrared spectroscopy. The integrated spectral results indicated that the implanted n-AT molecules formed a self-oriented and densely packed monolayer through formation of an S-Si bond. With the number of carbons in the alkyl chain at six or more, namely beginning at hexanethiol, the molecular monolayer began to develop an orientation-ordered structure, which is clearly shorter than that for AT monolayers on Au and Ag. This result implies that, with a stronger molecule-substrate interaction, an ordered molecular monolayer can form with a short chain.

Nanomanipulation and controlled self-assembly of metal nanoparticles and nanocrystals for plasmonics.

Localized surface plasmon resonances (LSPRs) associated with metallic nanostructures offer unique possibilities for light concentration beyond the diffraction limit, which can lead to strong field confinement and enhancement in deep subwavelength regions. In recent years, many transformative plasmonic applications have emerged, taking advantage of the spectral and spatial tunability of LSPRs enabled by near-field coupling between constituent metallic nanostructures in a variety of plasmonic metastructures (dimers, metamolecules, metasurfaces, metamaterials, etc.). For example, the "hot spot" formed at the interstitial site (gap) between two coupled metallic nanostructures in a plasmonic dimer can be spectrally tuned via the gap size. Capitalizing on these capabilities, there have been significant advances in plasmon enhanced or enabled applications in light-based science and technology, including ultrahigh-sensitivity spectroscopies, light energy harvesting, photocatalysis, biomedical imaging and theranostics, optical sensing, nonlinear optics, ultrahigh-density data storage, as well as plasmonic metamaterials and metasurfaces exhibiting unusual linear and nonlinear optical properties. In this review, we present two complementary approaches for fabricating plasmonic metastructures. We discuss how meta-atoms can be assembled into unique plasmonic metastructures using a variety of nanomanipulation methods based on single- or multiple-probes in an atomic force microscope (AFM) or a scanning electron microscope (SEM), optical tweezers, and focused electron-beam nanomanipulation. We also provide a few examples of nanoparticle metamolecules with designed properties realized in such well-controlled plasmonic metastructures. For the spatial controllability on the mesoscopic and macroscopic scales, we show that controlled self-assembly is the method of choice to realize scalable two-dimensional, and three-dimensional plasmonic metastructures. In the section of applications, we discuss some key examples of plasmonic applications based on individual hot spots or ensembles of hot spots with high uniformity and improved controllability.

Semiconductor plasmonic nanolasers: current status and perspectives.

Scaling down semiconductor lasers in all three dimensions holds the key to the development of compact, low-threshold, and ultrafast coherent light sources, as well as integrated optoelectronic and plasmonic circuits. However, the minimum size of conventional semiconductor lasers utilizing dielectric cavity resonators (photonic cavities) is limited by the diffraction limit. To date, surface plasmon amplification by stimulated emission of radiation (spaser)-based plasmonic nanolaser is the only photon and plasmon-emitting device capable of this remarkable feat. Specifically, it has been experimentally demonstrated that the use of plasmonic cavities based on metal-insulator-semiconductor (MIS) nanostructures can indeed break the diffraction limit in all three dimensions. In this review, we present an updated overview of the current status for plasmonic nanolasers using the MIS configuration and other related metal-cladded semiconductor microlasers. In particular, by using composition-varied indium gallium nitride/gallium nitride core-shell nanorods, it is possible to realize all-color, single-mode nanolasers in the full visible wavelength range with ultralow continuous-wave (CW) lasing thresholds. The lasing action in these subdiffraction plasmonic cavities is achieved via a unique auto-tuning mechanism based on the property of weak size dependence inherent in plasmonic nanolasers. As for the choice of metals in the plasmonic structures, epitaxial silver films and giant colloidal silver crystals have been shown to be the superior constituent materials for plasmonic cavities due to their low plasmonic losses in the visible and near-infrared (NIR) spectral regions. In this review, we also provide some perspectives on the challenges and opportunities in this exciting new research frontier.

Large-Scale Hot Spot Engineering for Quantitative SERS at the Single-Molecule Scale.

Quantitative surface enhanced Raman spectroscopy (SERS) requires precise control of Raman enhancement factor and detection uniformity across the SERS substrate. Here, we show that alkanethiolate ligand-regulated silver (Ag) nanoparticle films can be used to achieve quantitative SERS measurements down to the single-molecule level. The two-dimensional hexagonal close-packed superlattices of Ag nanoparticles formed in these films allow for SERS detection over a large area with excellent uniformity and high Raman enhancement factor. In particular, the SERS signal from the thiolate ligands on Ag nanoparticle surfaces can be utilized as a stable internal calibration standard for reproducible quantitative measurements. We demonstrate the capability of quantitative SERS by measuring the areal densities of crystal violet molecules embedded in an ultrathin spin-on-glass detection "hot zone", which is a planar and uniformly enhanced region several nanometers above the Ag nanoparticles. The Raman measurement results exhibit a linear response over a wide dynamic range of analyte concentration.

Complete replacement of metal in metal oxide nanowires via atomic diffusion: In/ZnO case study.

Atomic diffusion is a fundamental process that dictates material science and engineering. Direct visualization of atomic diffusion process in ultrahigh vacuum in situ TEM could comprehend the fundamental information about metal-semiconductor interface dynamics, phase transitions, and different nanostructure growth phenomenon. Here, we demonstrate the in situ TEM observations of the complete replacement of ZnO nanowire by indium with different growth directions. In situ TEM analyses reveal that the diffusion processes strongly depend and are dominated by the interface dynamics between indium and ZnO. The diffusion exhibited a distinct ledge migration by surface diffusion at [001]-ZnO while continuous migration with slight/no ledges by inner diffusion at [100]-ZnO. The process is explained based on thermodynamic evaluation and growth kinetics. The results present the potential possibilities to completely replace metal-oxide semiconductors with metal nanowires without oxidation and form crystalline metal nanowires with precise epitaxial metal-semiconductor atomic interface. Formation of such single crystalline metal nanowire without oxidation by diffusion to the metal oxide is unique and is crucial in nanodevice performances, which is rather challenging from a manufacturing perspective of 1D nanodevices.

All-color plasmonic nanolasers with ultralow thresholds: autotuning mechanism for single-mode lasing.

We report on the first demonstration of broadband tunable, single-mode plasmonic nanolasers (spasers) emitting in the full visible spectrum. These nanolasers are based on a single metal-oxide-semiconductor nanostructure platform comprising of InGaN/GaN semiconductor nanorods supported on an Al2O3-capped epitaxial Ag film. In particular, all-color lasing in subdiffraction plasmonic resonators is achieved via a novel mechanism based on a property of weak size dependence inherent in spasers. Moreover, we have successfully reduced the continuous-wave (CW) lasing thresholds to ultrasmall values for all three primary colors and have clearly demonstrated the possibility of "thresholdless" lasing for the blue plasmonic nanolaser.

Chain-network anatase/TiO2 (B) thin film with improved photocatalytic efficiency.

A 3-dimensional chain-network anatase/TiO2 (B) was obtained via the basic hydrothermal treatment of a sandwich Ti/TiO2/Ti film on a glass substrate that was prepared from 16 nm anatase TiO2 nanoparticles. The Ti film was converted to the TiO2 (B) phase in a Teflon vessel containing a 10 M NaOH aqueous solution that was encapsulated in a stainless-steel autoclave and heated at 130 °C for 2 h. The TiO2 (B) then served as a binder layer that enabled the formation of pearl-necklace chains made of anatase TiO2 nanoparticles, and these chain-like structures thoroughly interpenetrated into the textured layer. Decomposition tests using methylene blue indicated that the chain-network anatase/TiO2 (B) mixed-phase film had a photocatalytic half-life that was 0.84 and 0.69 times shorter than those of as-prepared anatase TiO2 and P25, respectively. In addition, the intensity of the room temperature photoluminescence spectra of anatase TiO2 was 2.55-fold higher than that of the chain-network anatase/TiO2 (B). We thus conclude that the remarkable photocatalytic activity of the chain-network anatase/TiO2 (B) is attributed to the chain-network structural characteristics and a synergistic effect of the matching band gap potentials, which increases the transfer of photogenerated electrons and reduces electron-hole recombination.

Au nanocrystal array/silicon nanoantennas as wavelength-selective photoswitches.

Au nanocrystal array/silicon nanoantennas exhibiting wavelength-selective photocurrent enhancement were successfully fabricated by a facile and inexpensive method combining colloidal lithography (CL) and a metal-assisted chemical etching (MaCE) process. The localized surface plasmon resonance (LSPR) response and wavelength-selective photocurrent enhancement characteristics were achieved by tuning the depth of immersion of Au nanocrystal arrays in silicon through a MaCE process. The wavelength selectivity of photocurrent enhancement contributed by LSPR induced local field amplification was confirmed by simulated near-field distribution. In addition, it can be integrated to well-developed Si-based manufacturing process. These characteristics make Au nanocrystal array/Si nanoantennas promising as low power-consumption photoswitches and nano-optoelectronic and photonic communication devices.

Superior Visible Photoelectric Response with Au/Cu2NiSnS4 Core-Shell Nanocrystals.

The incorporation of plasmonic metal nanostructures into semiconducting chalcogenides in the form of core-shell structures provides a promising approach to enhancing the performance of photodetectors. In this study, we combined Au nanoparticles with newly developed copper-based chalcogenides Cu2NiSnS4 (Au/CNTS) to achieve an ultrahigh optoelectronic response in the visible regime. The high-quality Au/CNTS core-shell nanocrystals (NCs) were synthesized by developing a unique colloidal hot-injection method, which allowed for excellent control over sizes, shapes, and elemental compositions. The as-synthesized Au/CNTS hybrid core-shell NCs exhibited enhanced optical absorption, carrier extraction efficiency, and improved photosensing performance owing to the plasmonic-induced resonance energy transfer effect of the Au core. This effect led to a significant increase in the carrier density of the Au/CNTS NCs, resulting in a measured responsivity of 1.2 × 103 AW-1, a specific detectivity of 6.2 × 1011 Jones, and an external quantum efficiency of 3.8 × 105 % at an incident power density of 318.5 µW cm-2. These results enlighten a new era in the development of plasmonic core-shell nanostructure-based visible photodetectors.

Contrast between surface plasmon polariton-mediated extraordinary optical transmission behavior in epitaxial and polycrystalline Ag films in the mid- and far-infrared regimes.

In this Letter we report a comparative study, in the infrared regime, of surface plasmon polariton (SPP) propagation in epitaxially grown Ag films and in polycrystalline Ag films, all grown on Si substrates. Plasmonic resonance features are analyzed using extraordinary optical transmission (EOT) measurements, and SPP band structures for the two dielectric/metal interfaces are investigated for both types of film. At the Si/Ag interface, EOT spectra show almost identical features for epitaxial and polycrystalline Ag films and are characterized by sharp Fano resonances. On the contrary, at the air/Ag interface, dramatic differences are observed: while the epitaxial film continues to exhibit sharp Fano resonances, the polycrystalline film shows only broad spectral features and much lower transmission intensities. In corroboration with theoretical simulations, we find that surface roughness plays a critical role in SPP propagation for this wavelength range.