Strong Plasmonic Coupling Research Articles

Thermally generated metals for plasmonic coloring and surface-enhanced Raman sensing

Spectral coloring glass and its application on the surface-enhanced Raman scattering are demonstrated experimentally via a simple and moderate heat-treating of the top ultrathin gold film to create discrete nanoparticles, which can produce localized surface plasmon resonances and strong plasmonic near-field coupling effects. Ultrathin metal films with a wide range of thicknesses are investigated by different heat-treatment processes. The annealed metal films have been demonstrated with a series of spectral coloring responses. Moreover, the microscopy images of the metal film structures confirm the formation of distinct geometry features in these operation procedures. Densely packed nanoparticles are observed for the ultrathin metal film with the single-digit level of thickness. With increasing the film thickness over 10 nm, metallic clusters and porous morphologies can be obtained. Importantly, the metallic resonators can provide enhanced Raman scattering with the detection limit down to 10 − 7 molL − 1 of Rhodamine 6G molecules due to the excitation of plasmon resonances and strong near-field coupling effects. These features hold great potential for large-scale and low-cost production of colored glass and Raman substrate.

PH‐Regulated Surface Plasmon Absorption from Ultrasmall Luminescent Gold Nanoparticles

AbstractLuminescent gold nanoparticles (AuNPs) with ultrasmall sizes (2–3 nm) and few free electrons have attracted fundamental science and application research interests due to their robust emission properties, but discoveries on their fantastic plasmonic properties are limited. Herein, controllable surface plasmon resonance (SPR) absorption (>520 nm) is reported from ultrasmall luminescent AuNPs (≈2.0 nm) coated with a small thiolate surface ligand, mercaptoimidazole (MIZ), through pH regulation. The 690 nm emitting MIZ‐AuNPs show SPR absorption and emission with a reversibly pH‐dependent response, i.e., a strong emission with no SPR band at high pH values (e.g., pH 5.0) and strong SPR absorption (570 nm) with weak emission at low pH values (e.g., pH 2.0). The MIZ surface coating, which has a low steric hindrance and high tendency to form intermolecular hydrogen bonds, is shown to play an important role in the creation of strong plasmon coupling and the emergence of plasmonic properties from ultrasmall MIZ‐AuNPs with 44% Au(I) species. The discovery of a plasmonic property in semiconducting luminescent MIZ‐AuNPs opens a new pathway for further understanding the optical properties of AuNPs and designing a new generation of optical AuNPs for various future applications.

Compact Plasmonic Blackbody for Cancer Theranosis in the Near-Infrared II Window.

We have developed a class of blackbody materials, i. e., hyperbranched Au plasmonic blackbodies (AuPBs), of compact sizes (<50 nm). The AuPBs were prepared in a seedless and surfactant-free approach based on the use of mussel-inspired dopamine. Strong intraparticle plasmonic coupling among branches in close proximity leads to intense and uniform broadband absorption across 400-1350 nm. The blackbody absorption imparts the compact AuPB with a superior photothermal efficiency of >80% and closely matched photothermal activity in the first near-infrared (NIR-I) and the second near-infrared (NIR-II) spectral windows, making it a rare broadband theranostic probe for integrated photoacoustic imaging and photothermal therapy (PTT). Our comparative study, using the same probe, has demonstrated that the improved PTT outcome of NIR-II over NIR-I primarily results from its higher maximum permission exposure (MPE) rather than the deeper tissue penetration favored by longer wavelengths. The compact plasmonic broadband nanoabsorbers with tailored surface properties hold potential for a wide spectrum of light-mediated applications.

Broadband Plasmonic Antenna Enhanced Upconversion and Its Application in Flexible Fingerprint Identification

AbstractPlasmonic antennas based on metallic nanostructures that can trap long‐wavelength light can be used to substantially enhance the efficiency of optoelectronic devices by utilizing light beyond the visible region. This study experimentally and theoretically demonstrates that a silver nanowire network (AgNW‐net) plasmonic antenna exhibits superwide surface plasmon extinction because of the strong plasmon coupling between AgNWs, providing the ability to trap light spanning the entire solar spectrum. As a proof‐of‐concept demonstration, the AgNW‐net is used to greatly improve the luminescence of lanthanide‐doped upconversion nanocrystals (UCNCs) under dual wavelength excitation and the periodic alternating multilayer structure of AgNWs/UCNCs is further successfully introduced to improve the absolute luminescence intensity of AgNWs/UCNCs composite films. Furthermore, evidence has been provided that this improvement is attributable to excitation field enhancement rather than Purcell effect or plasmon‐enhanced energy transfer. Finally, an upconversion flexible fingerprint identification technology is developed based on AgNW‐net/UCNCs/polyvinyl alcohol composite materials, which allows us extracting fingerprints on various uneven bending surfaces.

Polarization-resolved optical response of plasmonic particle-on-film nanocavities

Placing a metal nanoparticle atop a metal film forms a plasmonic particle-on-film nanocavity. Such a nanocavity supports strong plasmonic coupling that results in rich hybridized plasmon modes, rendering the cavity a versatile platform for exploiting a wide range of plasmon-enhanced spectroscopy applications. In this paper, we fully address the polarization-resolved, orientation-dependent far-field optical responses of plasmonic monomer- and dimer-on-film nanocavities by numerical simulations and experiments. With polarization-resolved dark-field spectroscopy, the distinct plasmon resonances of these nanocavities are clearly determined from their scattering spectra. Moreover, the radiation patterns of respective plasmon modes, which are often mixed together in common dark-field imaging, can be unambiguously resolved with our proposed quasi-multispectral imaging method. Explicitly, the radiation pattern of the monomer-on-film nanocavity gradually transitions from a solid spot in the green imaging channel to a doughnut ring in the red channel when tuning the excitation polarization from parallel to perpendicular to the sample surface. This observation holds true for the plasmonic dimer-on-film nanocavity with the dimer axis aligned in the incidence plane; when the dimer axis is normal to the incidence plane, the pattern transitions from a solid spot to a doughnut ring both in the red channel. These studies not only demonstrate a flexible polarization control over the optical responses of plasmonic particle-on-film nanostructures but also enrich the optical tool kit for far-field imaging and spectroscopy characterization of various plasmonic nanostructures.

Molecular cage-bridged plasmonic structures with well-defined nanogaps as well as the capability of reversible and selective guest trapping.

Creating well-defined plasmonic hotspots with enormous field enhancements as well as the capability of selectively trapping targeted molecules into hotspots is of critical importance and a prerequisite for numerous plasmon-assisted applications, but it represents a great challenge. In this work, a robust molecular cage decorated with thioether moieties at the periphery was designed and synthesized. By using the synthesized cage as a linker, a series of molecular cage-bridged plasmonic structures with well-defined nanogaps (hotspots) were fabricated in an efficient and controllable fashion. It was found both experimentally and theoretically that the nanogaps of about 1.2 nm created by the molecular cage in the resultant plasmonic structures led to a strong plasmon coupling, thus inducing great field enhancement inside the nanogaps. More importantly, the embedded molecular cages endowed the formed hotspots with the capability of selectively trapping targeted molecules, offering huge opportunities for many emergent applications. As a demonstration, the hotspots constructed were used as a unique nanoreactor, and under mild conditions two types of plasmon-driven chemical transformation were successfully performed. All the results clearly indicate that the integration of the host-guest chemistry of the molecular cage with the plasmon-coupling effect of metal particles afforded a new class of plasmonic structures, showing great potential for facilitating a broad variety of plasmon-based applications.

The construction of silver aggregate with inbuilt Raman molecule and gold nanowire forest in SERS-based immunoassay for cancer biomarker detection

Abstract Heterostructures of one-dimensional gold nanowires supported silver aggregates with a large amount of hotspots are promising for future SERS-based immunoassay. In this paper, silver aggregates with various coordination numbers were first obtained through adjusting the ligand incubation time and encapsulated by polystyrene-block-poly(acrylic acid). The SERS intensity of inbuilt Raman molecule (2-naphthalenethiol) in silver aggregates increased gradually with the increase of coordination number and the largest SERS enhancement ratio of the aggregates to single nanoparticles finally reached to 10. After decorating the silver aggregates onto the vertically aligned ultrathin gold nanowire forest, much more intensive SERS signals were observed compared with those on bare silica wafer. This promising result can be attributed to the strong surface plasmon coupling at the interface regions of the two materials that introduced multiple co-enhanced hotspots in the heterostructures. Then, the silver aggregates were modified with antibody and employed in immunoassay with immune gold nanowire forest as substrate. This SERS immunosensor exhibited a wide linear range (1 μg mL−1 to 1 fg mL−1) and an ultra-low detection limitation of 1 fg mL−1 for PSA.

Atomic-Layer-Deposition Assisted Formation of Wafer-Scale Double-Layer Metal Nanoparticles with Tunable Nanogap for Surface-Enhanced Raman Scattering

A simple high-throughput approach is presented in this work to fabricate the Au nanoparticles (NPs)/nanogap/Au NPs structure for surface enhanced Raman scattering (SERS). This plasmonic nanostructure can be prepared feasibly by the combination of rapid thermal annealing (RTA), atomic layer deposition (ALD) and chemical etching process. The nanogap size between Au NPs can be easily and precisely tuned to nanometer scale by adjusting the thickness of sacrificial ALD Al2O3 layer. Finite-difference time-domain (FDTD) simulation data indicate that most of enhanced field locates at Au NPs nanogap area. Moreover, Au NPs/nanogap/Au NPs structure with smaller gap exhibits the larger electromagnetic field. Experimental results agree well with FDTD simulation data, the plasmonic structure with smaller nanogap size has a stronger Raman intensity. There is highly strong plasmonic coupling in the Au nanogap, so that a great SERS effect is obtained when detecting methylene blue (MB) molecules with an enhancement factor (EF) over 107. Furthermore, this plasmonic nanostructure can be designed on large area with high density and high intensity hot spots. This strategy of producing nanoscale metal gap on large area has significant implications for ultrasensitive Raman detection and practical SERS application.

Photothermal therapy of single cancer cells mediated by naturally created gold nanorod clusters

Gold nanorods (GNRs) are generally considered to be nontoxic to normal and cancer cells. They are usually accumulated at lysosomes after entering into cells, forming GNR clusters in which strong plasmonic coupling between GNRs is expected. We investigated the photothermal therapy of single cancer cells by exploiting the significantly enhanced two-photon-induced absorption of GNR clusters naturally created in the lysosomes of cancer cells. It was revealed numerically that the plasmonic coupling between GNRs in GNR clusters can effectively enhance the photothermal conversion efficiency. As a result, the thermal damage of single cancer cells can be induced by using pulse energy as low as ~70 pJ. In experiments, the locations of GNR clusters can be accurately determined through the detection of the two-photon-induced luminescence, which is also significantly enhanced, by using a confocal laser scanning microscope. The photothermal therapy was conducted by focusing femtosecond laser light on the targeted GNR clusters, generating bubbles and deforming cell membranes. The photothermal therapy proposed in this work can lead to the rapid and acute injury of single cancer cells. The dependence of the apoptosis time on the pulse energy of femtosecond laser light was also examined. Our findings suggest a novel strategy for the photothermal therapy of single cancer cells with ultralow energy.

Manipulating Coherent Plasmon-Exciton Interaction in a Single Silver Nanorod on Monolayer WSe2.

Strong coupling between plasmons and excitons in nanocavities can result in the formation of hybrid plexcitonic states. Understanding the dispersion relation of plexcitons is important both for fundamental quantum science and for applications including optoelectronics and nonlinear optics devices. The conventional approach, based on statistics over different nanocavities, suffers from large inhomogeneities from the samples, owing to the nonuniformity of nanocavities and the lack of control over the locations and orientations of the excitons. Here we report the first measurement of the dispersion relationship of plexcitons in an individual nanocavity. Using a single silver nanorod as a Fabry-Pérot nanocavity, we realize strong coupling of plasmon in single nanocavity with excitons in a single atomic layer of tungsten diselenide. The plexciton dispersion is measured by in situ redshifting the plasmon energy via successive deposition of a dielectric layer. Room-temperature formation of plexcitons with Rabi splittings as large as 49.5 meV is observed. The realization of strong plasmon-exciton coupling by in situ tuning of the plasmon provides a novel route for the manipulation of excitons in semiconductors.

Hot spot-mediated non-dissipative and ultrafast plasmon passage.

Plasmonic nanoparticles hold great promise as photon handling elements and as channels for coherent transfer of energy and information in future all-optical computing devices.1–5 Coherent energy oscillations between two spatially separated plasmonic entities via a virtual middle state exemplify electron-based population transfer, but their realization requires precise nanoscale positioning of heterogeneous particles.6–10 Here, we show the assembly and optical analysis of a triple particle system consisting of two gold nanoparticles with an inter-spaced silver island. We observe strong plasmonic coupling between the spatially separated gold particles mediated by the connecting silver particle with almost no dissipation of energy. As the excitation energy of the silver island exceeds that of the gold particles, only quasi-occupation of the silver transfer channel is possible. We describe this effect both with exact classical electrodynamic modeling and qualitative quantum-mechanical calculations. We identify the formation of strong hot spots between all particles as the main mechanism for the loss-less coupling and thus coherent ultra-fast energy transfer between the remote partners. Our findings could prove useful for quantum gate operations, but also for classical charge and information transfer processes.

Gold Nanoparticle/Graphene Oxide Hybrid Sheets Attached on Mesenchymal Stem Cells for Effective Photothermal Cancer Therapy

Cell-mediated nanoparticle delivery has been proposed for an effective cancer therapy. However, there are limitations in loading nanoparticles within cells as the internalized nanoparticles cause cytotoxicity and leak out of the cells via exocytosis. Here, we introduce hybrid sheets composed of gold nanoparticles (AuNPs) and graphene oxide (GO), which stably adhere to the cell surface and exhibit a remarkable photothermal effect. To form AuNP/GO sheets in which GO is sandwiched between two AuNP monolayers, AuNPs are coated with α-synuclein protein and subsequently adsorbed onto GO sheets. Attaching AuNP/GO sheets to the tumor-tropic mesenchymal stem cell (MSC) surface enhances the loading efficiency of AuNPs in MSCs by avoiding the cytotoxicity and exocytosis issues. Furthermore, the tight packing of AuNPs on microscaled GO sheets enhances the photothermal effect via strong plasmon coupling between AuNPs. The injection of AuNP/GO sheet-attached MSCs into tumor-bearing mice significantly improves the photo...

Plasmon-Modulated Excitation-Dependent Fluorescence from Activated CTAB Molecules Strongly Coupled to Gold Nanoparticles

Excitation-dependent fluorophores (EDFs) have been attracted increasing attention owing to their high tunability of emissions and prospective applications ranging from multicolor patterning to bio-imaging. Here, we report tunable fluorescence with quenching dip induced by strong coupling of exciton and plasmon in the hybrid nanostructure of CTAB* EDFs and gold nanoparticles (AuNPs). The quenching dip in the fluorescence spectrum is tuned by adjusting excitation wavelength as well as plasmon resonance and concentration of AuNPs. The observed excitation-dependent emission spectra with quenching dip are theoretically reproduced and revealed to be induced by resonant energy transfer from multilevel EDFs with wider width channels to plasmonic AuNPs. These findings provide a new approach to prepare EDF molecules and a strategy to modulate fluorescence spectrum via exciton-to-plasmon energy transfer.

A new heterostructured SERS substrate: free-standing silicon nanowires decorated with graphene-encapsulated gold nanoparticles.

Heterostructures of one-dimensional nanowire supported graphene/plasmonic nanoparticles are promising for future SERS-based chemical sensors. In this paper, we report a novel heterostructured SERS substrate composed of free-standing Si nanowires and surface-decorating Au/graphene nanoparticles. We successfully developed a unique CVD approach for the cost-effective and large-scale growth of free-standing Si nanowires. Au nanoparticles were decorated on the Si nanowires using a galvanic deposition - an annealing approach. This was followed by the selective growth of a multilayer graphene shell on the Au nanoparticles via a xylene-based CVD approach. Discrete dipole approximation simulation was used to understand the plasmonic properties of these Si nanowire-based heterostructures. The results indicate that the incorporation of Au nanoparticles and graphene on Si nanowires has a significant influence on their light absorption and scattering properties. Meanwhile, a strong surface plasmon coupling was observed at the interface regions of different materials (e.g., Si/Au, Au/graphene), introducing multiple co-enhanced "hot spots" on the heterostructures. We found that our new heterostructures have a combined effect of an electromagnetic mechanism and a chemical mechanism for SERS and demonstrate an enhancement factor of 106-107.

Strong coupling of localized surface plasmons and ensembles of dye molecules.

We have studied strong exciton-plasmon coupling in the films of Ag nanoislands as well as in the layer-by-layer (LBL) deposited films of Au nanoparticles (NPs) coated with highly concentrated rhodamine 6G (R6G) dye. Their absorbance and the reflectance spectra featured the peaks or dips, which were not characteristic of dye or NPs/nanoislands taken separately. The positions of the spectral maxima (or minima) in the dye-doped films, plotted against those in pristine Ag nanoislands films, resulted in the dispersion curves comprised of three branches. They could be described by the analytical model based on the Hamiltonian accounting for the unperturbed energies of the surface plasmon (SP) resonance, the two bands composing the absorption spectrum of R6G dye, and the exciton-plasmon coupling energy Δ. Its value was larger in Ag nanoislands films deposited on hyperbolic metamaterials (0.221 eV) than on glass (0.165 eV). The minimal gap between the upper and the lower branches was equal to ≈3Δ. The dispersion curves in the Au NPs LBL films could be described with the Hamiltonian equation at relatively small dye concentrations. At larger concentrations of R6G molecules, the spectral peaks shifted and became more pronounced. The corresponding dispersion curve could not be described in terms of the existing model, indicating the need for further theoretical studies.

Preparation of plasmonic vesicles from amphiphilic gold nanocrystals grafted with polymer brushes.

Gold nanovesicles contain multiple nanocrystals within a polymeric coating. The strong plasmonic coupling between adjacent nanoparticles in their vesicular shell makes ultrasensitive biosensing and bioimaging possible. In our laboratory, multifunctional plasmonic vesicles are assembled from amphiphilic gold nanocrystals (such as gold nanoparticles and gold nanorods) coated with mixed hydrophilic and hydrophobic polymer brushes or amphiphilic diblock co-polymer brushes. To fulfill the different requirements of biomedical applications, different polymers that are either pH=responsive, photoactive or biodegradable can be used to form the hydrophobic brush, while the hydrophilicity is maintained by polyethylene glycol (PEG). This protocol covers the preparation, surface functionalization and self-assembly of amphiphilic gold nanocrystals grafted covalently with polymer brushes. The protocol can be completed within 2 d. The preparation of amphiphilic gold nanocrystals, coated with amphiphilic diblock polymer brushes using a 'grafting to' method or mixed hydrophilic and hydrophobic polymer brushes using tandem 'grafting to' and 'grafting from' methods, is described. We also provide detailed procedures for the preparation and characterization of pH-responsive plasmonic gold nanovesicles from amphiphilic gold nanocrystals using a film-rehydration method that can be completed within ∼3 d.

Photoionization of multishell fullerenes studied by ab initio and model approaches*

Photoionization of two buckyonions, C60@C240 and C20@C60, is investigated by means of time-dependent density-functional theory (TDDFT). The TDDFT-based photoabsorption spectrum of C60@C240, calculated in a broad photon energy range, resembles the sum of spectra of the two isolated fullerenes, thus illustrating the absence of strong plasmonic coupling between the fullerenes which was proposed earlier. The calculated spectrum of the smaller buckyonion, C20@C60, differs significantly from the sum of the cross sections of the individual fullerenes because of strong geometrical distortion of the system. The contribution of collective electron excitations arising in individual fullerenes is evaluated by means of plasmon resonance approximation (PRA). An extension of the PRA formalism is presented, which allows for the study of collective electron excitations in multishell fullerenes under photon impact. An advanced analysis of photoionization of buckyonions, performed using modern computational and analytical approaches, provides valuable information on the response of complex molecular systems to the external electromagnetic field.

Tunable potential well for plasmonic trapping of metallic particles by bowtie nano-apertures.

In this paper, the tunable optical trapping dependence on wavelength of incident beam is theoretically investigated based on numerical simulations. The Monte Carlo method is taken into account for exploring the trapping characteristics such as average deviation and number distribution histogram of nanoparticles. It is revealed that both the width and the depth of potential well for trapping particles can be flexibly adjusted by tuning the wavelength of the incident beam. In addition, incident wavelengths for the deepest potential well and for the strongest stiffness at bottom are separated. These phenomena are explained as the strong plasmon coupling between tweezers and metallic nanoparticles. In addition, required trapping fluence and particles’ distributions show distinctive properties through carefully modifying the incident wavelengths from 1280 nm to 1300 nm. Trapping with lowest laser fluence can be realized with 1280 nm laser and trapping with highest precision can be realized with 1300 nm laser. This work will provide theoretical support for advancing the manipulation of metallic particles and related applications such as single-molecule fluorescence and surface enhanced Raman spectroscopy.

Strong coupling of surface plasmon resonances to molecules on a gold grating

The intense electromagnetic fields generated by a surface plasmon resonance can strongly couple to molecules in the vicinity of the surface, causing significant line shifts. By measuring the angle dependent transmission spectrum through gold gratings with Rhodamine-6G molecules deposited on them, the coupling of the surface plasmon resonance to the molecular levels at different frequencies was determined. The strong coupling within the absorption and fluorescence bands of the molecules leads to anti-crossing of the states of the coupled system evidenced by the transmission minima. In particular, simultaneous existence of two distinct resonances at different wavevectors for a given wavelength over the absorption and fluorescence bands is observed. The multiplicity of the molecular levels and the coupling fields involved in the process is captured in a three-level Λ-system model coherently driven by the enhanced surface plasmon fields. The enhanced surface plasmon fields and the resonant absorption/fluorescent fields form the two arms of the Λ-system with approriate detuning.

Highly efficient plasmon excitation in graphene-Bi_2Te_3 heterostructure

Graphene plasmons have attracted a lot of attention due to large confinement and small mode volume. However, the graphene-based plasmonic devices are still limited in the practical applications due to relatively small light absorption of graphene and limited light–matter coupling efficiency in general excitation strategy. Here, this work reported a strong plasmonic coupling effect observed in a novel graphene-Bi2Te3 heterostructure on the top of silicon gratings. It is interesting to find that the extinction spectra of the graphene-Bi2Te3 heterostructure has shown three times greater magnitude than that of graphene. This observation is mainly attributed to two factors: first, the coupling efficiency between the graphene and Bi2Te3; second, the higher light absorption in the graphene-Bi2Te3 heterostructure. Moreover, the plasmonic resonance peak of the graphene-Bi2Te3 heterostructure can be easily tuned by changing the grating period just like what happens in the graphene film. In all, this work utilizes the simple silicon grating to couple the light into the graphene-Bi2Te3 heterostructure, and further explores the hybridized Dirac plasmons in the graphene-Bi2Te3 heterostructure. We believe it will stimulate the interest to study the variant plasmonic heterostructure and trigger new terahertz device applications.