Plasmon-exciton Coupling Research Articles

Fluorescence from a single-molecule probe directly attached to a plasmonic STM tip

The scanning tunneling microscope (STM) provides access to atomic-scale properties of a conductive sample. While single-molecule tip functionalization has become a standard procedure, fluorescent molecular probes remained absent from the available tool set. Here, the plasmonic tip of an STM is functionalized with a single fluorescent molecule and is scanned on a plasmonic substrate. The tunneling current flowing through the tip-molecule-substrate junction generates a narrow-line emission of light corresponding to the fluorescence of the negatively charged molecule suspended at the apex of the tip, i.e., the emission of the excited molecular anion. The fluorescence of this molecular probe is recorded for tip-substrate nanocavities featuring different plasmonic resonances, for different tip-substrate distances and applied bias voltages, and on different substrates. We demonstrate that the width of the emission peak can be used as a probe of the exciton-plasmon coupling strength and that the energy of the emitted photons is governed by the molecule interactions with its environment. Additionally, we theoretically elucidate why the direct contact of the suspended molecule with the metallic tip does not totally quench the radiative emission of the molecule.

Plasmon-Exciton Strong Coupling in Colloidal Au Nanocubes with Layered Molecular J-Aggregates.

Strong coupling between light and matter forms hybrid states, such as exciton-polaritons, which are crucial for advancements in quantum science and technology. Plasmonic metal nanoparticles, with their ultrasmall mode volumes, are effective for generating these states, but the coupling strength is often limited by surface saturation of excitonic materials. Additionally, cubic nanoparticles, which can generate strong local fields, have not been systematically explored. This study investigates strong coupling in Au nanocubes (AuNCs) coupled with J-aggregates, observing spectral splitting in both extinction and scattering spectra. Our findings suggest that smaller AuNCs, with higher-quality resonances and reduced mode volumes, achieve stronger coupling. Furthermore, a layer-by-layer (LBL) coating of J-aggregates on AuNCs results in a ∼21% increase in coupling strength. Simulations reveal the mechanism behind the enhanced coupling and confirm that the layering method effectively increases coupling, surpassing the limitations of the finite surface area of nanoparticles.

Probing plexciton emission from 2D materials on gold nanotrenches

Probing strongly coupled quasiparticle excitations at their intrinsic length scales offers unique insights into their properties and facilitates the design of devices with novel functionalities. In this work, we investigate the formation and emission characteristics of plexcitons, arising from the interaction between surface plasmons in narrow gold nanotrenches and excitons in monolayer WSe2. We study this strong plasmon–exciton coupling in both the far-field and the near-field. Specifically, we observe a Rabi splitting in the far-field reflection spectra of about 80 meV under ambient conditions, consistent with our theoretical modeling. Using a custom-designed near-field probe, we find that plexciton emission originates predominantly from the lower-frequency branch, which we can directly probe and map its local field distribution. We precisely determine the plexcitonʼs spatial extension, similar to the trench width, with nanometric precision by collecting spectra at controlled probe locations. Our work opens exciting prospects for nanoscale mapping and engineering of plexcitons in complex nanostructures with potential applications in nanophotonic devices, optoelectronics, and quantum electrodynamics in nanoscale cavities.

Photocatalytic Seawater Splitting by Earth-Abundant Catalysts: Metal-Semiconductor Metamaterials Made of Plasmonic Magnesium Diboride and Transitional Metal Dichalcogenides.

Metal-semiconductor metamaterials hold great promise for photocatalytic water splitting due to their excellent light harvesting in a broad spectral range as well as efficient charge carrier generation and transfer. In the majority of such metamaterials, semiconductors are used to initiate the water splitting reaction, while their metal counterparts are employed to improve light harvesting through plasmonic effects. Here, we describe for the first time an exceptional reversed case of metal-semiconductor photocatalysts in which metals are used to initiate the water splitting reaction and semiconductors are employed to improve light harvesting through the blackbody effect and serve as co-catalysts. The studied photoanodes are made of non-noble plasmonic MgB2 combined with transition metal dichalcogenides (TMDCs). The plasmonic resonances of the MgB2 component contribute to field confinement, plasmon-exciton coupling, and hot-electron transfer providing an enhancement of photoactivity in the entire solar spectrum capable of water splitting. The TMDC component provides impedance matching and enhances light absorption by the metal catalyst. We demonstrate seawater splitting with MgB2-TMDCs photoanodes attaining current densities of ~3 mA cm-2 at solar radiation. The overall efficiency of hydrogen production in seawater splitting by sunlight with the help of the studied photoanodes is 3 % at a bias voltage of Vbias=0.3 V.

Boosting Light-Matter Interactions in Plasmonic Nanogaps.

Plasmonic nanogaps in strongly coupled metal nanostructures can confine light to nanoscale regions, leading to huge electric field enhancement. This unique capability makes plasmonic nanogaps powerful platforms for boosting light-matter interactions, thereby enabling the rapid development of novel phenomena and applications. This review traces the progress of nanogap systems characterized by well-defined morphologies, controllable optical responses, and a focus on achieving extreme performance. The properties of plasmonic gap modes in far-field resonance and near-field enhancement are explored and a detailed comparative analysis of nanogap fabrication techniques down to sub-nanometer scales is provided, including bottom-up, top-down, and their combined approaches. Additionally, recent advancements and applications across various frontier research areas are highlighted, including surface-enhanced spectroscopy, plasmon-exciton strong coupling, nonlinear optics, optoelectronic devices, and other applications beyond photonics. Finally, the challenges and promising emerging directions in the field are discussed, such as light-driven atomic effects, molecular optomechanics, and alternative new materials.

Drastic Enhancement of Hydrogen Production from Water in Gold–Silver Sulfide Hybrid Quantum Dot-Sensitized Photoelectrochemical Cell through Plasmon–Plasmon–Exciton Coupling

Drastic Enhancement of Hydrogen Production from Water in Gold–Silver Sulfide Hybrid Quantum Dot-Sensitized Photoelectrochemical Cell through Plasmon–Plasmon–Exciton Coupling

Influence of atomistic features in plasmon-exciton coupling and charge transfer driven by a single molecule in a metallic nanocavity.

When an organic molecule is placed inside a plasmonic cavity formed by two metallic nanoparticles (MNP) under illumination, the electronic excitations of the molecule couple to the plasmonic electromagnetic modes of the cavity, inducing new hybrid light-matter states called polaritons. Atomistic abinitio methods accurately describe the coupling between MNPs and molecules at the nanometer scale and allow us to analyze how atomistic features influence the interaction. In this work, we study the optical response of a porphine molecule coupled to a silver nanoparticle dimer from first principles, within the linear-response time-dependent density functional theory framework, using the recently developed Python Numeric Atomic Orbitals implementation to compute the optical excitations. The optical spectra show the splitting of the resonances of the plasmonic dimer and the molecule into two distinct polaritons, a characteristic feature of the strong light-matter coupling regime. Our results stress the importance of atomistic features, such as the gap configuration in determining the plasmon-exciton coupling strength and in the emergence of molecule-mediated charge-transfer plasmon (CTP) resonances at lower frequencies. Moreover, we show that the strength of the CTP resonance can be tuned by shifting the alignment of the molecular energy levels with respect to the Fermi level of the MNPs.

Plasmon-Exciton Interaction at the Nanoscale: Silver Is More "Precious" than Gold!

Predictive understanding of factors affecting plasmon-exciton coupling is crucial for the successful realization of the exciting potentials of plexcitonic nanostructures. Here, we systematically investigate the role of plasmonic metals in controlling the plasmon-exciton coupling strength. We use gold and silver nanoprisms, having identical LSPR maxima, as the plasmonic components and form two plexciton hybrids with the J-aggregates of a cyanine dye. Single-particle spectroscopy is employed to study and compare the abilities of gold and silver in influencing plasmon-exciton interaction at the nanoscale. Despite much faster plasmon dephasing than its gold counterpart, the silver nanoprism exhibits greater Rabi splitting. We reveal that the smaller plasmon mode-volume despite having larger physical volume, superior local electric-field enhancement, and smaller Ohmic losses compared to gold, enables the silver nanoprism to defy the pronounced plasmon decoherence effects and to show stronger plasmon-exciton coupling. These findings suggest that silver nanostructures should be the unequivocal choice over gold when "strong coupling" is desired for any application.

Polarization dependent exciton-plasmon coupling in PEA2PbI4/Al and its application to perovskite solar cell.

This paper reports the strong coupling between Al nanostructure and two-dimensional (2D) layered perovskite PEA2PbI4 (PEPI) films. The high exciton binding energy of 118 meV and long carrier lifetime of 216 ps are characterized from the 2D PEA2PbI4 film, which indicates that the excitons in perovskite are robust and can couple to metal plasmons. The ordinary and extraordinary optical dispersions are revealed from the anisotropic 2D perovskite. The transmission spectra of PEA2PbI4/Al nanoparticle arrays are simulated under different polarization excitations, and the typical anti-crossing behaviors originating from exciton-plasmon strong coupling are demonstrated. We found that compared with transverse magnetic (TM) polarization, transverse electric (TE) polarization excitation is more conducive to the realization of exciton-plasmon coupling with a larger Rabi splitting. Furthermore, the PEA2PbI4/Al nanoparticle arrays are proposed, which present polarization-dependent local electrical field enhancement due to the exciton-local surface plasmon polariton coupling. Additionally, it is noticed that the proposed plasmonic structure increases the photo-generation rate inside the active material with improved current density. Therefore, the 2D proposed plasmonic design increases the power conversion efficiency (PCE) with an enhancement of 3.3% and 1.3% relative to the planar structures for TE and TM polarizations, respectively. This study provides a deeper understanding of polarized exciton-plasmon coupling properties, promoting the development of the field of plasmon and providing guidance for the design and preparation of efficient optoelectronic devices.

Enhanced trapping properties of coupled plasmonic tweezers via plasmon-exciton interaction.

Excited plasmonic nanoantennas enable the manipulation of photons coupled with quantum emitters or the trapping of particles as plasmonic tweezers, leveraging the strong evanescent gradient fields at the nanoscale. However, the ohmic loss of metals presents a significant challenge for the stable and high-precision manipulation of nanoparticles without causing damage. In this study, we investigated the enhanced trapping properties induced by plasmon-exciton interaction for coupled plasmonic tweezers. Through the coupling between plasmons and excitons, dynamic particle trapping is achievable under low excitation power conditions of 0.45 mW, with the trapping stiffness increasing by nearly 20 times. Furthermore, the trapping stiffness can be fine-tuned by modulating the quantity of excitons to regulate the coupling strength. Coupled plasmonic tweezers offer an effective strategy to mitigate the influence of ohmic loss on trapping performance, by manipulating particles with minimal laser power. These findings provide insights into enhancing trapping performance through plasmon-exciton coupling, with potential applications in biomedicine and quantum information science.

Aqueous Topological Synthesis of Au@semiconductor Core-Shell Nanocrystals with Morphology and Composition Engineering.

Core-shell nanocrystals (C-S NCs) are an essential class of materials whose structural engineering has attracted wide attention due to their tunable optical and electrical properties, especially noble metal@semiconductor (NMS) C-S NCs with flexible plasmon-exciton coupling. Due to their diverse critical applications, especially aqueous biological applications, herein we propose an aqueous topological strategy enabled by cation exchange reactions (CER) to synthesize various plasmonic Au@semiconductor C-S NCs, in which environmentally friendly triphenylphosphine (TPP) is used as an initiator instead of inflammable tributyl phosphine (TBP). The introduction of the milder, solid TPP facilitated a new aqueous CER strategy for synthesizing Au@semiconductor NCs with tailored chalcogenide compositions and morphologies. For example, the as-synthesized Au@ZnS C-S NRs had better absorption and biocompatibility and exhibited excellent photodynamic therapy efficacy.

Unraveling Exciton-Plasmon Coupling and the PIRET Mechanism in Decorated Silicon Nanowires.

Exciton-plasmon coupling is a fascinating physical phenomenon that has been investigated in various metal semiconductor systems. Intentionally chosen silicon nanowires (SiNWs) systems act as a host material for providing exciton as well as silicon oxide as a thin dielectric. A clear blue-shift in photoluminescence (PL) peak and a significant increase in visible range absorption were observed for metal nanoparticle (MNP) decorated SiNWs (D-SiNWs) which signifies the presence of exciton-plasmon coupling. A further investigation reveals that the possibility of the occurrence of the plasmon-induced resonance energy transfer (PIRET) mechanism is higher. The PL intensity enhancement in Au-decorated SiNWs is higher (∼38 times) in comparison to that in Pt due to the presence of a strong and localized electric field of plasmons near the interface of metal and semiconductors. Moreover, splitting in PL for gold-decorated SiNWs might be due to the presence of dipole-quadrupole coupling along with dipole-dipole coupling, which further increases the strength of the PIRET mechanism.

Giant Photoluminescence Enhancement of Monolayer WSe2 Using a Plasmonic Nanocavity with On-Demand Resonance.

Monolayer transition metal dichalcogenides (TMDs) are considered promising building blocks for next-generation photonic and optoelectronic devices, owing to their fascinating optical properties. However, their inherent weak light absorption and low quantum yield severely hinder their practical applications. Here, we report up to 18000-fold photoluminescence (PL) enhancement in a monolayer WSe2-coupled plasmonic nanocavity. A spectroscopy-assisted nanomanipulation technique enables the assembly of a nanocavity with customizable resonances to simultaneously enhance the excitation and emission processes. In particular, precise control over the magnetic cavity mode facilitates spectral and spatial overlap with the exciton, resulting in plasmon-exciton intermediate coupling that approaches the maximum emission rate in the hybrid system. Meanwhile, the cavity mode exhibits high radiation directivity, which overwhelmingly directs surface-normal PL emission and leads to a 17-fold increase in the collection efficiency. Our approach opens up a new avenue to enhance the PL intensity of monolayer TMDs, facilitating their implementation in highly efficient optoelectronic devices.

Ultrafast photoluminescence and multiscale light amplification in nanoplasmonic cavity glass.

Interactions between plasmons and exciton nanoemitters in plexcitonic systems lead to fast and intense luminescence, desirable in optoelectonic devices, ultrafast optical switches and quantum information science. While luminescence enhancement through exciton-plasmon coupling has thus far been mostly demonstrated in micro- and nanoscale structures, analogous demonstrations in bulk materials have been largely neglected. Here we present a bulk nanocomposite glass doped with cadmium telluride quantum dots (CdTe QDs) and silver nanoparticles, nAg, which act as exciton and plasmon sources, respectively. This glass exhibits ultranarrow, FWHM = 13 nm, and ultrafast, 90 ps, amplified photoluminescence (PL), λem≅503 nm, at room temperature under continuous-wave excitation, λexc = 405 nm. Numerical simulations confirm that the observed improvement in emission is a result of a multiscale light enhancement owing to the ensemble of QD-populated plasmonic nanocavities in the material. Power-dependent measurements indicate that >100 mW coherent light amplification occurs. These types of bulk plasmon-exciton composites could be designed comprising a plethora of components/functionalities, including emitters (QDs, rare earth and transition metal ions) and nanoplasmonic elements (Ag/Au/TCO, spherical/anisotropic/miscellaneous), to achieve targeted applications.

Ultrastrong exciton-plasmon couplings in WS2 multilayers synthesized with a random multi-singular metasurface at room temperature.

Van der Waals semiconductors exemplified by two-dimensional transition-metal dichalcogenides have promised next-generation atomically thin optoelectronics. Boosting their interaction with light is vital for practical applications, especially in the quantum regime where ultrastrong coupling is highly demanded but not yet realized. Here we report ultrastrong exciton-plasmon coupling at room temperature in tungsten disulfide (WS2) layers loaded with a random multi-singular plasmonic metasurface deposited on a flexible polymer substrate. Different from seeking perfect metals or high-quality resonators, we create a unique type of metasurface with a dense array of singularities that can support nanometre-sized plasmonic hotspots to which several WS2 excitons coherently interact. The associated normalized coupling strength is 0.12 for monolayer WS2 and can be up to 0.164 for quadrilayers, showcasing the ultrastrong exciton-plasmon coupling that is important for practical optoelectronic devices based on low-dimensional semiconductors.

Hollow gold nanoparticles coated with ZnS with distance-dependent plasma coupling and surface enhanced Raman spectroscopy for applications

Metal@semiconductor core-shell heterostructure with strong exciton-plasmon coupling can integrate multiple functions of each component and exhibit extraordinary benefits in the optical, catalytic, electrical, and magnetic properties due to its excellent synergistic properties at the heterointerfaces. In our work, hollow gold nanoparticles (HGNs)- 4-mercaptobenzoic acid (MBA) @ZnS core-shell heterostructure with the adjustable shell thickness (tshell) of ZnS varied from 1 to 19 nm were successfully prepared for the first time by low temperature and simple two-step method. Here, we report our findings that the surface enhanced Raman scattering (SERS) spectral intensity of HGNs-MBA@ZnS under the 633 nm excitation correlates with the tshell of ZnS, and the experimental results are consistent with theoretical studies. Furthermore, we also investigated the excitation wavelength-dependent SERS enhancement mechanism of HGNs-MBA@ZnS (tshell = 2 nm) and the result showed that the near-field enhancement and plasmon-induced interfacial charge transfer transition (PICTT) synergistically increase the SERS intensity under the excitation line at 633 nm. Our work not only provides guidance for the design and synthesis of other important metal@semiconductor core-shell heterostructure, but presents significant insights into their SERS enhancement mechanism.

Optical Susceptibility of Hybrid Semiconductor Quantum Dot-Metallic Nano Ellipsoid System Under the Effect of the Exciton-Plasmon Coupling Field Interaction

AbstractWe examine the optical susceptibility of the semiconductor quantum dot-metallic nano ellipsoid system under the effect of the exciton-plasmon coupling field. Also, we determine the optical susceptibility for the semiconductor quantum dot and the three metallic nano ellipsoids under the responses to the total effect of the three applied electromagnetic fields. The phenomena of Fano-resonance with amplification and Autler-Town doublet peaks are obtained and discussed. The phenomena of Fano-resonances and Autler-Town doublet peaks can be controlled by varying the depolarization factor of nano ellipsoid, semi-axes, and other parameters in a hybrid system.

Obtaining Ligand-Free Aqueous Au-Nanoparticles Using Reversible CsPbBr3 ↔ Au@CsPbBr3 Nanocrystal Transformation.

Water-hexane interfacial preparation of photostable Au@CsPbBr3 (Au@CPB) hybrid nanocrystals (NCs) from pure CsPbBr3 (CPB) NCs is reported, with the coexistence of exciton and localized surface plasmon resonance with equal dominance. This enables strong exciton-plasmon coupling in these plasmonic perovskite NCs where not only the photoluminescence is quenched intrinsically due to ultrafast charge separation, but also the light absorption property increases significantly, covering the entire visible region. Using a controlled interfacial strategy, a reversible chemical transformation between CPB and Au@CPB NCs is shown, with the simultaneous eruption of larger-size ligand-free aqueous Au nanoparticles (NPs). An adsorption-desorption mechanism is proposed for the reversible transformation, while the overgrowth reaction of the Au NPs passes through the Au aggregation intermediate. This study further shows that the plasmonic Au@CPB hybrid NCs as well as ligand-free Au NPs exhibit clear surface enhanced Raman scattering (SERS) effect of a commercially available probe molecule. Overall, the beautiful interfacial chemistry delivers two independent plasmonic materials, i.e., Au@CPB NCs and ligand-free aqueous Au NPs, which may find important implications in photocatalytic and biomedical applications.

Anomalous Dispersion in Reflection and Emission of Dye Molecules Strongly Coupled to Surface Plasmon Polaritons.

We have studied dispersion of surface plasmon polaritons (SPPs) in the Kretschmann geometry (prism/Ag/dye-doped polymer) in weak, intermediate, and ultra-strong exciton-plasmon coupling regimes. The dispersion curves obtained in the reflection experiment were in good agreement with the simple model predictions at small concentrations of dye (Rhodamine 590, Rh590) in the polymer (Poly(methyl methacrylate), PMMA). At the same time, highly unusual multi-segment "staircase-like" dispersion curves were observed at extra-large dye concentrations, also in agreement with the simple theoretical model predicting large, small, and negative group velocities featured by different polariton branches. In a separate experiment, we measured angular dependent emission of Rh590 dye and obtained the dispersion curves consisting of two branches, one nearly resembling the SPP dispersion found in reflection and the second one almost horizontal. The results of our study pave the road to unparalleled fundamental science and future applications of weak and strong light-matter interactions.

Electroluminescence as a Probe of Strong Exciton-Plasmon Coupling in Few-Layer WSe2.

The manipulation of coupled quantum excitations is of fundamental importance in realizing novel photonic and optoelectronic devices. We use electroluminescence to probe plasmon-exciton coupling in hybrid structures consisting of a nanoscale plasmonic tunnel junction and few-layer two-dimensional transition-metal dichalcogenide transferred onto the junction. The resulting hybrid states act as a novel dielectric environment that affects the radiative recombination of hot carriers in the plasmonic nanostructure. We determine the plexcitonic spectrum from the electroluminescence and find Rabi splittings exceeding 50 meV in the strong coupling regime. Our experimental findings are supported by electromagnetic simulations that enable us to explore systematically and in detail the emergence of plexciton polaritons as well as the polarization characteristics of their far-field emission. Electroluminescence modulated by plexciton coupling provides potential applications for engineering compact photonic devices with tunable optical and electrical properties.