Quantum plexcitonics: strongly interacting plasmons and excitons

We present a fully quantum mechanical approach to describe the coupling between plasmons and excitonic systems such as molecules or quantum dots. The formalism relies on Zubarev's Green functions, which allow us to go beyond the perturbative regime within the internal evolution of a plasmonic nanostructure and to fully account for quantum aspects of the optical response and Fano resonances in plasmon-excition (plexcitonic) systems. We illustrate this method with two examples consisting of an exciton-supporting quantum emitter placed either in the vicinity of a single metal nanoparticle or in the gap of a nanoparticle dimer. The optical absorption of the combined emitter-dimer structure is shown to undergo dramatic changes when the emitter excitation level is tuned across the gap-plasmon resonance. Our work opens a new avenue to deal with strongly interacting plasmon-excition hybrid systems.     

Photonic Crystal Hydrogel Enhanced Plasmonic Staining for Multiplexed Protein Analysis

Plasmonic nanoparticles are commonly used as optical transducers in sensing applications. The optical signals resulting from the interaction of analytes and plamsonic nanoparticles are influenced by surrounding physical structures where the nanoparticles are located. This paper proposes inverse opal photonic crystal hydrogel as 3D structure to improve Raman signals from plasmonic staining. By hybridization of the plasmonic nanoparticles and photonic crystal, surface‐enhanced Raman spectroscopy (SERS) analysis of multiplexed protein is realized. It benefits the Raman analysis by providing high‐density “hot spots” in 3D and extra enhancement of local electromagnetic field at the band edge of PhC with periodic refractive index distribution. The strong interaction of light and the hybrid 3D nanostructure offers new insights into plasmonic nanoparticle applications and biosensor design.     

Induced chirality through electromagnetic coupling between chiral molecular layers and plasmonic nanostructures

We report a new approach for creating chiral plasmonic nanomaterials. A previously unconsidered, far-field mechanism is utilized which enables chirality to be conveyed from a surrounding chiral molecular material to a plasmonic resonance of an achiral metallic nanostructure. Our observations break a currently held preconception that optical properties of plasmonic particles can most effectively be manipulated by molecular materials through near-field effects. We show that far-field electromagnetic coupling between a localized plasmon of a nonchiral nanostructure and a surrounding chiral molecular layer can induce plasmonic chirality much more effectively (by a factor of 10(3)) than previously reported near-field phenomena. We gain insight into the mechanism by comparing our experimental results to a simple electromagnetic model which incorporates a plasmonic object coupled with a chiral molecular medium. Our work offers a new direction for the creation of hybrid molecular plasmonic nanomaterials that display significant chiroptical properties in the visible spectral region.     

Plasmonic properties of the multispot copper-capped nanoparticle array chip and its application to optical biosensors for pathogen detection of multiplex DNAs

A localized surface plasmon resonance (LSPR)-based optical biosensor in connection with a multispot copper-capped nanoparticle array (MC-NPA) chip was proposed and developed. The copper (Cu) films, used as a shell, formed a "cap-like" layer on the top of the silica nanoparticles, used as a core, in an orderly fashion, to form the surface called a "Cu-capped nanoparticle array chip". The plasmonic properties of this nanostructure type were initially investigated while controlling the shell thickness of the deposited Cu. Also, we quantified the sensitivity of MC-NPA chip to changes in bulk refractive index (RI). As a result of its LSPR properties, the MC-NPA chip displayed a sensitivity of 67.8 nm per RI unit, and the wavelength shift of the LSPR spectrum peak was sensitive to the RI of the surrounding bulk medium, such as the biomolecular layers. Using MC-NPA chips, multiplex sensing of target DNAs from reference bacteria and clinical samples was possible in a quantitative manner with a detection limit of 10 fM (50 zmol). The optical biosensor developed in this study represents a unique approach to performing LSPR that utilizes a simple and cost-effective optical setup with disposable chips.     

Nanoparticle layer deposition for plasmonic tuning of microstructured optical fibers

Plasmonic nanoparticles with spectral properties in the UV-to-near-IR range have a large potential for the development of innovative optical devices. Similarly, microstructured optical fibers (MOFs) represent a promising platform technology for fully integrated, next-generation plasmonic devices; therefore, the combination of MOFs and plasmonic nanoparticles would open the way for novel applications, especially in sensing applications. In this Full Paper, a cost-effective, innovative nanoparticle layer deposition (NLD) technique is demonstrated for the preparation of well-defined plasmonic layers of selected particles inside the channels of MOFs. This dynamic chemical deposition method utilizes a combination of microfluidics and self-assembled monolayer (SAM) techniques, leading to a longitudinal homogeneous particle density as long as several meters. By using particles with predefined plasmonic properties, such as the resonance wavelength, fibers with particle-adequate spectral characteristics can be prepared. The application of such fibers for refractive-index sensing yields a sensitivity of about 78 nm per refractive index unit (RIU). These novel, plasmonically tuned optical fibers with freely selected, application-tailored optical properties present extensive possibilities for applications in localized surface plasmon resonance (LSPR) sensing.     

Three-dimensional chiral plasmonic oligomers

The living world is chiral. Chirality or the handedness of a structure or molecule is at the heart of life itself. Recently, it has been shown that plasmonic structures exhibit unprecedented and gigantic chiral optical responses. Here we show that truly three-dimensional arrangements of plasmonic "meta-atoms" only exhibit a chiral optical response if similar plasmonic "atoms" are arranged in a handed fashion as we require resonant plasmonic coupling. Moreover, we demonstrate that such particle groupings, similarly to molecular systems, possess the capability to encode their three-dimensional arrangement in unique and well-modulated spectra making them ideal candidates for a three-dimensional chiral plasmon ruler. Our results are crucial for the future design and improvement of plasmonic chiral optical systems, for example, for ultrasensitive enantiomer sensing on the single molecule level.     

Tunable plasmon-induced transparency based on graphene nanoring coupling with graphene nanostrips

We numerically and theoretically demonstrate a plasmon-induced transparency (PIT) at the mid-infrared region with finite-difference time-domain method. The system consists of an optically bright dipole mode and a dark quadrupole mode, which are supported by the graphene nanoring and graphene nanostrips, respectively. The coupling between the two modes introduces transparency window and large group delays. The pronounced PIT resonance can be easily modified by adjusting the geometric parameters and the Fermi level of graphene nanostructure. Our results suggest that the demonstrated PIT effect may be applicated in the slow-light device, active plasmonic switching, and optical sensing.     

Hydrogen storage in Pd nanodisks characterized with a novel nanoplasmonic sensing scheme

A novel nanoplasmonic sensing scheme is introduced based on remote real-time detection of induced electronic and shape/structural changes in a metal nanoparticle during the metal-hydride formation process. The localized surface plasmon resonance (LSPR) of the nanoparticle is utilized as signal transducer for optical readout. As a model system, hydrogen storage through metal-hydride formation is studied in Pd nanodisks. The experimentally obtained plasmonic response to hydrogen uptake yields pressure-LSPR-response isotherms. These isotherms are found to obey Sievert's law in the low-pressure range and exhibit a characteristic "plateau" at 18 Torr upon hydrogen charging and 7.5 Torr upon hydrogen discharging. An additional experiment also clearly shows the typical temperature dependence of the plateau pressure. Conversion of the LSPR signal to absolute hydrogen concentration, based on a proposed linear dependence of the LSPR response to hydrogen uptake, results in p-C isotherms in excellent agreement with those in the literature. This puts forward that the LSPR response is an extremely sensitive, remote, and real-time probe for "bulk" changes in a metal nanoparticle and can readily be used to study processes such as metal-hydride formation for hydrogen storage applications, alloying on the nanoscale, thermal reshaping, and so forth.     

Palladium bridged gold nanocylinder dimer: plasmonic properties and hydrogen sensitivity

Plasmonic nanodimers facilitate electromagnetic hotspots at their gap junction. By loading these gap junctions with nanomaterials, the plasmonic properties of nanodimer can be varied. In this study, we bridged the gap junction of gold (Au) nanocylinder dimer with palladium (Pd), and numerically evaluated the plasmonic properties of the designed nanostructure. We simulated the far-field extinction spectra of Pd bridged Au nanocylinder dimer, and identified the dipole and quadrupole plasmon modes at 839 and 578 nm, respectively. By varying the geometrical parameters of the Pd bridge, we revealed the ability to tune the dipolar plasmon resonance of the bridged dimer. Further, we exploited the hydrogen sensitivity of Pd bridge to harness the bridged-Au dimer as nanoplasmonic hydrogen sensor. Such nano-optical detection platforms have minimal spatial footprint and can be further harnessed for chip-based plasmonic sensing.     

Sensing with multipolar second harmonic generation from spherical metallic nanoparticles

We show that sensing in the nonlinear optical regime using multipolar surface plasmon resonances is more sensitive in comparison to sensing in the linear optical regime. Mie theory, and its extension to the second harmonic generation from a metallic nanosphere, is used to describe multipolar second harmonic generation from silver metallic nanoparticles. The standard figure of merit of a potential plasmonic sensor based on this principle is then calculated. We finally demonstrate that such a sensor is more sensitive to optical refraction index changes occurring in the vicinity of the metallic nanoparticle than its linear counterpart.     

Temperature Determination of Resonantly Excited Plasmonic Branched Gold Nanoparticles by X‐ray Absorption Spectroscopy

The fields of bioscience and nanomedicine demand precise thermometry for nanoparticle heat characterization down to the nanoscale regime. Since current methods often use indirect and less accurate techniques to determine the nanoparticle temperature, there is a pressing need for a direct and reliable element‐specific method. In‐situ extended X‐ray absorption fine structure (EXAFS) spectroscopy is used to determine the thermo‐optical properties of plasmonic branched gold nanoparticles upon resonant laser illumination. With EXAFS, the direct determination of the nanoparticle temperature increase upon laser illumination is possible via the thermal influence on the gold lattice parameters. More specifically, using the change of the Debye–Waller term representing the lattice disorder, the temperature increase is selectively measured within the plasmonic branched nanoparticles upon resonant laser illumination. In addition, the signal intensity shows that the nanoparticle concentration in the beam more than doubles during laser illumination, thereby demonstrating that photothermal heating is a dynamic process. A comparable temperature increase is measured in the nanoparticle suspension using a thermocouple. This good correspondence between the temperature at the level of the nanoparticle and at the level of the suspension points to an efficient heat transfer between the nanoparticle and the surrounding medium, thus confirming the potential of branched gold nanoparticles for hyperthermia applications. This work demonstrates that X‐ray absorption spectroscopy‐based nanothermometry could be a valuable tool in the fast‐growing number of applications of plasmonic nanoparticles, particularly in life sciences and medicine.     

Actively controllable EIT-like resonance between localized and propagating surface plasmons for optical switching

We theoretically investigate the plasmonic interaction between radiative localized surface plasmon resonances and subradiative propagating surface plasmon modes in a nanostructure consisting of a periodic array of gold nanobars and an optically thick gold film, separated by a silica dielectric spacer layer. A controllable transparency window within the broad dipole resonance profile is observed clearly in the reflectance spectra via tailoring the length of the bar, the periodicity of the nanoparticle array, or the incident angle of applied field, respectively, a classic analog of electromagnetically induced transparency (EIT). We believe that the last excitation configuration is particularly beneficial for the realization of active manipulation of plasmonic optical switching without using coupling/control fields required in the conventional EIT scheme.     

Palladium-based plasmonic perfect absorber in the visible wavelength range and its application to hydrogen sensing

We report on the experimental realization of a palladium-based plasmonic perfect absorber at visible wavelengths and its application to hydrogen sensing. Our design exhibits a reflectance <0.5% and zero transmittance at 650 nm and the operation wavelength of the absorber can be tuned by varying its structural parameters. Exposure to hydrogen gas causes a rapid and reversible increase in reflectance on a time scale of seconds. This pronounced response introduces a novel optical hydrogen detection scheme with very high values of the relative intensity response.     

Chiral Plasmonic Hydrogen Sensors

In this article, a chiral plasmonic hydrogen‐sensing platform using palladium‐based nanohelices is demonstrated. Such 3D chiral nanostructures fabricated by nanoglancing angle deposition exhibit strong circular dichroism both experimentally and theoretically. The chiroptical properties of the palladium nanohelices are altered upon hydrogen uptake and sensitively depend on the hydrogen concentration. Such properties are well suited for remote and spark‐free hydrogen sensing in the flammable range. Hysteresis is reduced, when an increasing amount of gold is utilized in the palladium‐gold hybrid helices. As a result, the linearity of the circular dichroism in response to hydrogen is significantly improved. The chiral plasmonic sensor scheme is of potential interest for hydrogen‐sensing applications, where good linearity and high sensitivity are required.     

Plasmonic‐Nanopore Biosensors for Superior Single‐Molecule Detection

Plasmonic and nanopore sensors have separately received much attention for achieving single‐molecule precision. A plasmonic “hotspot” confines and enhances optical excitation at the nanometer length scale sufficient to optically detect surface–analyte interactions. A nanopore biosensor actively funnels and threads analytes through a molecular‐scale aperture, wherein they are interrogated by electrical or optical means. Recently, solid‐state plasmonic and nanopore structures have been integrated within monolithic devices that address fundamental challenges in each of the individual sensing methods and offer complimentary improvements in overall single‐molecule sensitivity, detection rates, dwell time and scalability. Here, the physical phenomena and sensing principles of plasmonic and nanopore sensing are summarized to highlight the novel complementarity in dovetailing these techniques for vastly improved single‐molecule sensing. A literature review of recent plasmonic nanopore devices is then presented to delineate methods for solid‐state fabrication of a range of hybrid device formats, evaluate the progress and challenges in the detection of unlabeled and labeled analyte, and assess the impact and utility of localized plasmonic heating. Finally, future directions and applications inspired by the present state of the art are discussed.     

Toward plasmonic polymers

We establish the concept of a plasmonic polymer, whose collective optical properties depend on the repeat unit. Experimental and theoretical analyses of the super- and sub- radiant plasmon response of plasmonic polymers comprising repeat units of single nanoparticles or dimers of gold nanoparticles show that (1) the redshift of the lowest energy coupled mode becomes minimal as the chain approaches the infinite chain limit at a length of ～10 particles, (2) the presence and energy of the modes are sensitive to the geometries of the constituents, that is, repeat unit, but (3) spatial disorder and nanoparticle heterogeneity have only small effects on the super-radiant mode.     

Localized surface plasmon resonance spectroscopy of single silver triangular nanoprisms

The plasmonic properties of single silver triangular nanoprisms are investigated using dark-field optical microscopy and spectroscopy. Two distinct localized surface plasmon resonances (LSPR) are observed. These are assigned as in-plane dipolar and quadrupolar plasmon excitations using electrodynamic modeling based on the discrete dipole approximation (DDA). The dipole resonance is found to be very intense, and its peak wavelength is extremely sensitive to the height, edge length, and tip sharpness of the triangular nanoprism. In contrast, the intensity of the quadrupole resonance is much weaker relative to the dipole resonance in the single particle spectra than in the ensemble averaged spectrum. Several parameters relevant to the chemical sensing properties of these nanoprisms have been measured. The dependence of the dipole plasmon resonance on the refractive index of the external medium is found to be as high as 205 nm RIU(-1) and the plasmon line width as narrow as approximately 0.17 eV. These data lead to a sensing figure of merit (FOM), the slope of refractive index sensitivity in eV RIU(-1)/line width (eV), as high as 3.3. In addition, the LSPR shift response to alkanethiol chain length was found to be linear with a slope of 4.4 nm per CH2 unit. This is the highest short-range refractive index sensitivity yet measured for a nanoparticle.     

Synthesis, electron tomography and single-particle optical response of twisted gold nano-bipyramids

A great number of works focus their interest on the study of gold nanoparticle plasmonic properties. Among those, sharp nanostructures appear to exhibit the more interesting features for further developments. In this paper, a complete study on bipyramidal-like gold nanostructures is presented. The nano-objects are prepared in high yield using an original method. This chemical process enables a precise control of the shape and the size of the particles. The specific photophysical properties of gold bipyramids in suspension are ripened by recording the plasmonic response of single and isolated objects. Resulting extinction spectra are precisely correlated to their geometrical structure by mean of electron tomography at the single-particle level. The interplay between the geometrical structure and the optical properties of twisted gold bipyramids is further discussed on the basis of numerical calculations. The influence of several parameters is explored such as the structural aspect ratio or the tip truncation. In the case of an incident excitation polarized along the particle long axis, this study shows how the plasmon resonance position can be sensitive to these parameters and how it can then be efficiently tuned on a large wavelength range.     

Plasmonic Heterodimers with Binding Site‐Dependent Hot Spot for Surface‐Enhanced Raman Scattering

A novel plasmonic heterodimer nanostructure with a controllable self‐assembled hot spot is fabricated by the conjugation of individual Au@Ag core–shell nanocubes (Au@Ag NCs) and varisized gold nanospheres (GNSs) via the biotin–streptavidin interaction from the ensemble to the single‐assembly level. Due to their featured configurations, three types of heterogeneous nanostructures referred to as Vertice, Vicinity, and Middle are proposed and a single hot spot forms between the nanocube and nanosphere, which exhibits distinct diversity in surface plasmon resonance effect. Herein, the calculated surface‐enhanced Raman scattering enhancement factors of the three types of heterodimers show a narrow distribution and can be tuned in orders of magnitude by controlling the size of GNSs onto individual Au@Ag NCs. Particularly, the Vertice heterodimer with unique configuration can provide extraordinary enhancement of the electric field for the single hot spot region due to the collaborative interaction of lightning rod effect and interparticle plasmon coupling effect. This established relationship between the architecture and the corresponding optical properties of the heterodimers provides the basis for creating controllable platforms which can be exploited in the applications of plasmonic devices, electronics, and biodetection.