Plasmonic Nanodimers Research Articles

Second-harmonic radiation by on-chip integrable mirror-symmetric nanodimers with sub-nanometric plasmonic gap

Abstract Second-harmonic generation (SHG) facilitated by plasmonic nanostructures has drawn considerable attention, owing to its efficient frequency up-conversion at the nanoscale and potential applications in on-chip integration and nanophotonic devices. Herein, we present a nanodimer array fabricated by nanoimprinting, composed of nanofinger-pair symmetrically leaning at an off-angle with a well-defined sub-nanometric gap. Commonly, geometric symmetry would suppress the far-field SHG due to the near-field cancelling of symmetric surface SH polarization. However, we find that the light-induced surface SH polarization distribution along the wave-vector of incidence could be influenced by the off-angle, which is consistent to the requirement of SH polarization symmetry-breaking in symmetric metallic nanocavity. A dramatic enhancement of far-field SHG is achieved by tuning the off-angle of nanofinger-pair, even approaching up to over 4 orders of magnitude for an optimal value. The demonstration of SHG enhancement on our well-defined plasmonic nanodimer provides a new way of on-chip integration to activate high-efficient SH radiation, which might be potential for applications in novel nonlinear optical nanodevices with remarkable efficiency and sensitivity.

Deterministic positioning and alignment of a single-molecule exciton in plasmonic nanodimer for strong coupling.

Experimental realization of strong coupling between a single exciton and plasmons remains challenging as it requires deterministic positioning of the single exciton and alignment of its dipole moment with the plasmonic fields. This study aims to combine the host-guest chemistry approach with the cucurbit[7]uril-mediated active self-assembly to precisely integrate a single methylene blue molecule in an Au nanodimer at the deterministic position (gap center of the nanodimer) with the maximum electric field (EFmax) and perfectly align its transition dipole moment with the EFmax, yielding a large spectral Rabi splitting of 116 meV for a single-molecule exciton-matching the analytical model and numerical simulations. Statistical analysis of vibrational spectroscopy and dark-field scattering spectra confirm the realization of the single exciton strong coupling at room temperature. Our work may suggest an approach for achieving the strong coupling between a deterministic single exciton and plasmons, contributing to the development of room-temperature single-qubit quantum devices.

Hot carrier creation in a nanoparticle dimer-molecule composite.

Light-matter interactions have garnered considerable interest owing to their burgeoning applications in quantum optics and plasmonics. Utilizing first principles calculations, this work explores the hot carrier (HC) generation and distribution within a composite system made up of a plasmonic nanoparticle dimer and linear polycyclic aromatic hydrocarbon (PAH) molecules. We examine the spatial and energetic distributions of HCs by initiating photoexcitation and allowing localized surface plasmon dephasing. By positioning PAH molecules within the plasmonic nanodimer's gap region, our investigation uncovers HC tuning. Notably, depending on the size of the PAH molecules, there are significant alterations in the HC distribution. Hot electrons (HEs) are distributed across both the nanodimer and the PAH molecule, while hot holes (HHs) become entirely localized on the PAH as the PAH grows larger. These findings improve our understanding of plasmon-molecule coupled states and provide guidance on how to customize HC distributions through the creation of hybrid plasmonic materials.

Multifunctional charge transfer plasmon resonance sensors

Abstract Charge transfer plasmon (CTP) modes arise when metallic nanoparticle dimers are connected by a conductive junction. This offers a unique opportunity to explore electron transport at optical frequencies as well as to attain narrow plasmon resonances that can be broadly modulated from visible to IR regimes, implying their potentials for applications in single-molecule electronics and sensing. This article showcases recent developments in theory and applications of charge transfer plasmon resonances (CTPRs) in various configurations of conductively linked plasmonic nanodimers. In particular, we give a due attention to exploiting ultratunable spectral features of charge transfer plasmon resonances for developing multifunctional plasmonic sensors for bulk, surface, gas and molecular sensing applications. We also discuss the implications of the charge and energy transfer between two plasmonic nanoparticles linked by sub-nanometer thick self-assembled monolayers for single-molecule conductance sensing and molecular electronics. In addition to the well-established plasmonic sensing schemes based on propagating and localized surface plasmon resonances, charge transfer plasmon resonance sensors may open up a new route in efforts to develop multifunctional sensing technologies.

Far-Field Polarization Optics Control the Nanometer-Scale Pattern of High-Fluorescence Dissymmetry Emission from Achiral Molecules near Plasmonic Nanodimers

Chiroptical spectroscopies like circular dichroism report on the handedness of molecules but are often limited to the high-concentration regime because of the mismatch between the wavelength of propagating visible light and the size of molecules. Recent work has demonstrated that the electromagnetic fields generated near chiral plasmonic nanostructures can have high optical chirality that bridges these length scales and can induce high-fluorescence dissymmetry signals from achiral dyes by redirecting their emission. As a step toward single-molecule chiral sources, the induced fluorescence dissymmetry and apparent emission pattern near chiral plasmonic nanoparticles must be quantified. Here, we measure the induced fluorescence dissymmetry from the achiral dye Cy5.5 near a chiral gold nanodimer structure, and we map out the apparent emission pattern of the dyes using super-resolution single-molecule microscopy. Our high-sensitivity approach quantifies the fluorescence dissymmetry from sampling only ∼100 zeptomoles of Cy5.5 and measures from Cy5.5 near gold nanodimers median fluorescence dissymmetry factors that are 2 orders of magnitude greater than those of synthesized chiral fluorescent molecules. We observe a spatial correlation between the simulated optical chirality about a plasmonic gold nanodimer and experimentally obtained super-resolution apparent emission patterns, and we use the incident polarization to control our detection bias for the brightest molecules to sample nanometer-scale regions of high electric flux.

Plasmon–Exciton Strong Coupling Effects of the Chiral Hybrid Nanostructures Based on the Plexcitonic Born–Kuhn Model

A deep understanding of the optical properties of the chiral plexcitonic systems not only adds a new dimension to the exploration of the strong plasmon–exciton interaction but also provides a new method to design chiroptical devices. We develop a plexcitonic Born–Kuhn model to explore the strong coupling dynamics of the chiral hybrid nanostructures made of corner-stacked nanorod dimers and molecules from the chiroptical perspective. As a consequence of strong interaction between plasmons and excitons, double normal mode splittings/Rabi splittings and an anti-crossing phenomenon appear in circular dichroism (CD) spectroscopy. The character of dual plexciton (symmetric and anti-symmetric plexciton) and associated chiroptical properties have been demonstrated. The interplay between mirror symmetry breaking and plasmon–plasmon/plasmon–exciton interaction leads to an optimal configuration with the maximal chiroptical response. Moreover, chirality (of incident light) selective excitation of plexcitonic modes has been achieved by structural design. Finally, we verify our theory experimentally by synthesizing chiral plasmonic nanodimers and coating these structures with J-aggregate dye molecules.

Boosting Light–Matter Interaction in a Longitudinal Bonding Dipole Plasmon Hybrid Anapole System

Achieving strong electromagnetic enhancement is critical for realizing strong light–matter coupling at the nanoscale. In this study, we constructed a hybrid anapole system composed of a nanohole silicon disk and a longitudinal bonding dipole plasmon mode-supported plasmonic dimer. Compared with the bare dimer plasmon, the hybrid system shows strong plasmonic resonance tuning ability, and its resonance peak can be tuned to the near-infrared region only by adjusting the radius of the silicon disk. Meanwhile, the E-field enhancement in the gap region can exceed four orders of magnitude without sacrificing the quality factor of the system. Furthermore, it is demonstrated that the emitter’s radiative decay rate enhancement in the hybrid system is much higher than that of a similar LBDP mode-supported plasmonic dimer nanodisk and the reported plasmonic nanocavity. In summary, our hybrid anapole systems combine the advantages of metal plasmonic nanodimers and conventional anapole mode-supported systems and avoid their disadvantages. This study provides a useful reference for the further exploration of single-photon emission sources, light harvesting, and other quantum nanophotonic applications.

Neural-Network-Enabled Design of a Chiral Plasmonic Nanodimer for Target-Specific Chirality Sensing.

Quantitative analysis of chiral molecules in various solvents is essential. However, there are still many challenges to enhancing the sensitivity in precisely determining both concentration and chirality. Here, we built an algorithmic methodology to predict and optimally design the chiroptical response of chiral plasmonic sensors for a specific target chiral analyte with the aid of deep learning. Based upon the analytic and intuitive understanding of the Born-Kuhn type plasmonic nanodimer, we designed and trained the neural networks that can successfully predict the chiroptical properties and further inversely design the plasmonic structure to achieve the intended circular dichroism. The developed algorithm could identify the optimum structure exhibiting the maximum sensitivity for the given specific analytes. Surprisingly, we discovered that sensitivity strongly depends on the various conditions of analytes and can be finely tuned with the structural parameters of plasmonic nanodimers. We envision that this study can provide a general platform to develop ultrasensitive chiral plasmonic sensors whose structure and sensitivity have been evolved algorithmically for adoption in specific applications.

Sub-1.5 nm-gapped heterodimeric plasmonic nanomolecules.

Plasmonic molecules are discrete assemblies of similar/dissimilar nanomaterials (atomic equivalents) with efficient inter-unit coupling toward electromagnetic hybridization. Albeit fundamentally and technologically very important, these structures are rare due to the lack of a general way to manipulate the structure, composition, and coupling of the nanoassemblies. While DNA nanotechnology offers a precious chance to build such structures, the weak coupling of DNA-bonded materials and the very limited material building blocks are two obstacles. This work aims to remove the bottlenecking barriers on the road to dimeric (and possibly more complicated) plasmonic molecules. After solving key synthetic issues, DNA-guided, solvo-driven Ag ion soldering is utilized to build a whole set (10 combinations of 4 metals) of homo/heterodimeric plasmonic nanomolecules with prescribed compositions. Importantly, strong in-solution electric-dipole coupling mediated by a sub-1.5 nm interparticle dielectric gap is achieved for materials with strong (Au, Ag) or damped (Pt, Pd) plasmonic responses. The involvement of Pt/Pd materials is of great value for plasmon-mediated catalysis. The broken dimeric symmetry is desirable for Fano-like resonance and photonic nanodiode devices, as well as lightening-up of plasmon dark states. The generality and reliability of the method would allow excitonic, nonlinear-optical, and magnetic units to be involved toward correspondingly enhanced functions.

Plasmonic Nanoarchitectures for Single‐Molecule Explorations: An Overview

Plasmonic nanostructures have immense potentials for extreme concentration of light into deep‐subwavelength spaces with giant local field intensity, which can be exploited for novel applications including nanoscale optical trapping, biosensing, and enhanced spectroscopy. Herein, a succinct overview of the potentials of engineered plasmonic nanoarchitectures of various geometries including nanoparticles, nanodimers, nanoapertures, nanoporous surfaces, and picometer‐scale gap systems for single‐molecule analysis is provided. In particular, the potentials of single plasmonic nanoparticles for single‐molecule sensing, coupled plasmonic nanodimers for few‐molecule strong coupling, metallic nanocavities for optical manipulation of single molecules, nanoporous metasurfaces for enhanced single‐molecule spectroscopy, and plasmonic picocavities for single‐molecule optomechanics are extensively discussed. Finally, as an outlook, exploiting such novel nanoarchitectures for developing innovative biosensing platforms that will be able to trap and detect objects at the single‐molecule level is forwarded.

Plasmon-enhanced fluorescence correlation spectroscopy for super-localized detection of nanoscale subcellular dynamics

In this report, we investigate plasmon-enhanced imaging fluorescence correlation spectroscopy (p-FCS). p-FCS takes advantage of extreme light confinement by localization at nanogap-based plasmonic nanodimer arrays (PNAs) for enhanced signal-to-noise ratio (SNR) and improved precision by registration with surface plasmon microscopy images. Theoretical results corroborate the enhancement by PNAs in the far-field. Near-field scanning optical microscopy was used to confirm near-field localization experimentally. Experimental confirmation was also conducted with fluorescent nanobeads. The concept was further applied to studying the diffusion dynamics of lysosomes in HEK293T cells stimulated by phorbol 12-myristate 13-acetate treatment. It was found that lysosomes demonstrate stronger super-diffusive behavior with relatively weaker sub-diffusion after stimulation. SNR measured of p-FCS was improved by 9.77 times over conventional FCS. This report is expected to serve as the foundation for an enhanced analytical tool to explore subcellular dynamics.

Topology Optimization‐Based Inverse Design of Plasmonic Nanodimer with Maximum Near‐Field Enhancement

AbstractThe near‐field enhancement factor is one of the most significant parameters to evaluate the performance of plasmonic nanostructures. Numerous efforts have been made to maximize the enhancement factor through optimizing the size, shape, and spatial arrangement of metallic nanostructures with simple geometries, such as disk, triangle, and rod. This work implements topology optimization to inversely design a metallic nanoparticle dimer with the goal of optimizing the near‐field enhancement factor in its sub‐10 nm gap. By optimizing the material layout within a given design space, the topology optimization algorithm results in a plasmonic nanodimer of two heart‐shaped particles having both convex and concave features. Full‐wave electromagnetic analysis reveals that the largest near‐field enhancement in the heart‐shaped nanoparticle dimer is originated from the greatest concentration of surface charges at the nano‐heart apex. Inversely designed heart‐, bowtie‐, and disk‐shaped nanodimers are fabricated by using focused helium ion beam milling with a “sketch and peel” strategy, and their near‐field enhancement performances are characterized with nonlinear optical spectroscopies at the single‐particle level. Indeed, the heart‐shaped nanodimer exhibits much stronger signal intensities than the other two structures. The present work corroborates the validity and effectiveness of topology optimization‐based inverse design in achieving desired plasmonic functionalities.

Simulation of light scattering and electron energy loss (EELS) by small spatially dispersive plasmonic nanodimers

Despite the tremendous progress in the field of nanoplasmonics, complex plasmonic nanostructures such as dimers still present a significant challenge for proper numerical characterization. In particular, for the particles which size is smaller than electron mean free path in metals it is necessary to account for effects of spatial nonlocality in simulations. To address these problems a new mathematical model based on the Discrete Sources Method was developed and corresponding computer model was implemented. It enables one to successfully resolve the problem of accounting for spatial dispersion effects, which is especially important in the systems with very small gap and particle size, and it retains all key features of the Discrete Sources numerical approach including flexibility and a posteriori error estimation. We compute such scattering characteristics as electron energy loss probability and total scattered field intensity of nanodimers as one typically has to rely on methods of both optical and electron spectroscopy to experimentally investigate these structures. The developed model also allows to simultaneously consider several external excitations of the plasmonic system, including both electron and plane wave, in order to obtain more information about the system and to significantly speed up computational performance.

Silencing the second harmonic generation from plasmonic nanodimers: A comprehensive discussion.

The silencing of the second harmonic generation process from plasmonic nanostructures corresponds to the limited far-field second harmonic radiation despite the huge fundamental electric field enhancement in the interstice between two plasmonic nanoparticles forming a nanodimer. In this article, we report a comprehensive investigation of this effect using a surface integral equation method. Various geometries are considered, including nanoantennas with cylindrical and rectangular arms as well as nanodimers with surface defects. The existence of the silencing of the second harmonic generation from plasmonic nanogaps is first confirmed, and the problem of the origin of the second harmonic light from these plasmonic nanostructures is addressed in detail. Our results show that the distribution of the second harmonic sources, especially on the arm sides, plays a non-negligible role in the overall second harmonic emission. This contribution is induced by retardation effects at the pump wavelength and results in a dipolar second harmonic emission.

Boosting the Photoluminescence of Monolayer MoS2 on High‐Density Nanodimer Arrays with Sub‐10 nm Gap

AbstractPatterned plasmonic nanodimers are fabricated exploiting an ultrathin porous anodic aluminum oxide membrane as a mask during angle‐resolved shadow deposition. The fabricated nanodimer arrays exhibit consistent sub‐10 nm gaps and a high particle density up to 1.0 × 1010 cm−2 over a large area. The ultrasmall dimer gaps provide highly confined electromagnetic fields, which strongly enhance the photoluminescence (PL) emission and Raman scattering from the surrounding monolayer molybdenum disulphide (MoS2). The ensemble PL intensity from MoS2/dimers is enhanced by up to a factor of ≈160 by resonant excitation of the dimer modes. Anisotropic polarization‐dependent characteristics of PL and Raman from the MoS2/dimers confirm that the dominant enhancement originates from the dimer configuration. These experiments demonstrate a facile approach for the fabrication of low‐cost high‐performance 2D material‐based optoelectronic devices.

Influences of dipole–quadrupole strong interactions on optical properties of plasmonic nanodimers

An extended analytical method based on the dipole-quadrupole electromagnetic interaction is proposed to investigate the optical properties of strongly interacting plasmonic nanoparticles for which the known coupled dipoles approximation (CDA) is inaccurate. The introduced simple and novel method used here, namely coupled dipole-quadrupole approximation (CDQA), is used to elaborate on the optical interactions of individual modes including dipole-dipole, dipole-quadrupole and quadrupole-quadrupole. A simple and versatile formula is presented for the modified dipole-polarizability by considering an adjacent quadrupole effect, leading to accurate prediction of remarkable features in the optical properties of nanoparticle clusters in simple or complex forms. Interestingly, in a nanodimer configuration, it is shown that the quadrupole strongly affects the dipolar resonance energy, though the dipole impact on quadrupole properties are negligible. The findings are verified by the approximated methods, numerical computations and generalized Mie theory.

Plasmonic enhancement of SERS measured on molecules in carbon nanotubes.

We isolated the plasmonic contribution to surface-enhanced Raman scattering (SERS) and found it to be much stronger than expected. Organic dyes encapsulated in single-walled carbon nanotubes are ideal probes for quantifying plasmonic enhancement in a Raman experiment. The molecules are chemically protected through the nanotube wall and spatially isolated from the metal, which prevents enhancement by chemical means and through surface roughness. The tubes carry molecules into SERS hotspots, thereby defining molecular position and making it accessible for structural characterization with atomic-force and electron microscopy. We measured a SERS enhancement factor of 106 on α-sexithiophene (6T) molecules in the gap of a plasmonic nanodimer. This is two orders of magnitude stronger than predicted by the electromagnetic enhancement theory (104). We discuss various phenomena that may explain the discrepancy (including hybridization, static and dynamic charge transfer, surface roughness, uncertainties in molecular position and orientation), but found all of them lacking in enhancement for our probe system. We suggest that plasmonic enhancement in SERS is, in fact, much stronger than currently anticipated. We discuss novel approaches for treating SERS quantum mechanically that appear promising for predicting correct enhancement factors. Our findings have important consequences on the understanding of SERS as well as for designing and optimizing plasmonic substrates.

Microfluidic device for continuous single cells analysis via Raman spectroscopy enhanced by integrated plasmonic nanodimers.

In this work a Raman flow cytometer is presented. It consists of a microfluidic device that takes advantages of the basic principles of Raman spectroscopy and flow cytometry. The microfluidic device integrates calibrated microfluidic channels- where the cells can flow one-by-one -, allowing single cell Raman analysis. The microfluidic channel integrates plasmonic nanodimers in a fluidic trapping region. In this way it is possible to perform Enhanced Raman Spectroscopy on single cell. These allow a label-free analysis, providing information about the biochemical content of membrane and cytoplasm of the each cell. Experiments are performed on red blood cells (RBCs), peripheral blood lymphocytes (PBLs) and myelogenous leukemia tumor cells (K562).

Nano-Analysis of DNA Conformation Changes Induced by Transcription Factor Complex Binding Using Plasmonic Nanodimers

The plasmon resonant wavelength for a pair of gold nanoparticles, or gold nanodimer, increases inversely with the gap distance between the two nanoparticles. Taking advantage of this property, we performed nanoscale measurements of DNA conformation changes induced by transcription factor binding. Gold nanoparticles were bridged by double-stranded DC5 DNA that included binding sequences for the transcription factors SOX2 and PAX6, which interact on the DC5 enhancer sequence and activate transcription. The gold nanodimers bound by SOX2 shifted the plasmon resonant wavelength from 586.8 to 604.1 nm, indicating that SOX2 binding induces DNA bending. When the SOX2 formed a ternary complex with PAX6 on DC5, the plasmon resonant wavelength showed a further shift to 611.6 nm, indicating additional bending in the DC5 sequence. Furthermore, we investigated DNA conformation changes induced by SOX2 and PAX6 on the DC5-con sequence, which is a consensus sequence of DC5 for the PAX6 binding region that strengthens the PAX6 binding but at the same time disrupts SOX2-PAX6-dependent transcriptional activation. When the PAX6 binding sequence in DC5 was altered to DC5-con, the plasmon resonant wavelength shifted much less to 606.5 nm, which is more comparable to the 603.9 nm by SOX2 alone. These results demonstrate that SOX2-PAX6 cobinding induces a large conformation change in DC5 DNA.

Effects of classical nonlocality on the optical response of three-dimensional plasmonic nanodimers

We examine the optical scattering from a variety of axially symmetric plasmonic nanoparticle dimers separated by nanoscale gaps, quantifying the role of classical nonlocality on their optical properties. Due to the rotational symmetry of the analyzed structures, a high degree of accuracy is achieved using a computational approach termed 2.5D modeling, in which a small number of simulations on a two-dimensional domain can replace a memory- and time-intensive simulation on a three-dimensional domain. We find that scattered light from dimers consisting of nanoparticles with flat surfaces, such as nanodisks, exhibits pronounced spectral shifts due to the nonlocality of the electron fluid; these significant shifts persist even at relatively large (>1 nm) gap dimensions, where quantum tunneling effects are believed to be negligible. The 2.5D modeling technique accurately incorporates all responses due to any nonaxially symmetric eigenmodes of the system, such as dipolar and quadrupolar modes, thereby providing a complete characterization of the system for any excitation.