Quantum Theory of Surface Plasmon Polaritons: Planar and Spherical Geometries

A quantum theory of retarded surface plasmons on a metal–vacuum interface is formulated, by analogy with the well-known and widely exploited theory of exciton-polaritons. The Hamiltonian for mutually interacting instantaneous surface plasmons and transverse electromagnetic modes is diagonalized with recourse to a Hopfield–Bogoljubov transformation, in order to obtain a new family of modes, to be identified with retarded plasmons. The interaction with nearby dipolar emitters is treated with a full quantum formalism based on a general definition of modal effective volumes. The illustrative cases of a planar surface and of a spherical nanoparticle are considered in detail. In the ideal situation of absence of dissipation, as an effect of the conservation of in-plane wavevector, retarded plasmons on a planar surface represent true stationary states (which are usually called surface plasmon polaritons), whereas retarded plasmons in a spherical nanoparticle, characterized by frequencies that overlap with the transverse electromagnetic continuum, become resonances with a finite radiative broadening. The theory presented constitutes a suitable full quantum framework for the study of nonperturbative and nonlinear effects in plasmonic nanosystems.     

Non-local Quantum Plasmon Resonance in Ultra-small Silver Nanoparticles

Understanding the mechanisms of light–matter interactions in ultra-small plasmonic nanoparticles (USNP) represents a major challenge because of the importance of size dependence and quantum effects. The plasmon resonance in such small metallic nanoparticles (< 5 nm) exhibits substantial deviation from classical theory predictions, with evident frequency shifts to a higher energy. This is due to the quantum nature of the free charge carriers and the dynamic response of metallic nanoparticle to the self-consistent electromagnetic fields. Such phenomena have so far been poorly understood in experiments while classical theory has mostly focused on nanostructures and sidestepped the size dependence. Here we report a quantum mechanical model of the metal permittivity to describe the USNP behaviour and experimental evidence. The proposed non-local quantum model of the permittivity for the propagation of plasmon waves in quantum-confined silver nanoparticles has no size limitations in the UNSP range.

     

Tunable Goos-Hänchen Shift of Surface Plasmon Beam Due to Graphene in a Metal-Dielectric System

The tunneling of surface plasmon waves between two slabs of dielectric prisms superposed on the metal surface is studied. The prism with the incident surface plasmon wave is superposed by a stack of graphene sheets. The analytical theory is built to connect the Fermi energy of graphene with the Goos-Hänchen shift of the transmitted surface plasmon waves. The obtained results may be useful for developing integral switching devices on the basis of surface plasmon polaritons.

     

Multiple Surface Plasmon Resonances in Compound Structure with Metallic Nanoparticle and Nanohole Arrays

The optical properties of a compound structure with metallic nanoparticle and nanohole arrays are numerically investigated by the means of finite-difference time domain method. We report on the observation of multi-valleys in the reflection spectra due to the excitation of surface plasmon (SP) resonant modes of the compound structure. Simulation results show that multiple SP resonances consist of surface plasmon polaritons on the gold film, localized surface plasmons on the nanoparticles, and coupling mode between them. These findings are important for applications utilizing multiple surface plasmon resonances.     

Optical investigation of the electron transfer protein azurin-gold nanoparticle system

The hybrid system obtained by conjugating the protein azurin, which is a very stable and well-described protein showing a unique interplay among its electron transfer and optical properties, with 20-nm sized gold nanoparticles has been investigated. Binding of azurin molecules to gold nanoparticle surface results in the red shift of the nanoparticle resonance plasmon band and in the quenching of the azurin single tryptophan fluorescence signal. These findings together with the estimate of the hydrodynamic radius of the composite, obtained by means of Dynamic Light Scattering, are consistent with the formation of a monolayer of protein molecules, with preserved natural folding, on nanoparticle surface. The fluorescence quenching of azurin bound molecules is explained by an energy transfer from protein to metal surface and it is discussed in terms of the involvement of the Az electron transfer route in the interaction of the protein with the nanoparticle.     

Simultaneous Excitation of Surface Plasmon Polaritons on Both Interfaces in an Asymmetric Dielectric-Metal Corrugated Structure

The simultaneous excitation of plasmon polaritons on both surfaces of metal film was studied for asymmetric dielectric-metal-dielectric corrugated structures. Due to the small resonant absorption of the incident light on the transmission side of the structure, we investigated the enhancement of the surface plasmon polaritons on the mentioned side by controlling the structure parameters. When the illuminate light changes from normal incidence to non-normal incidence, the resonant absorption peak splits into a doublet. The simultaneous excitation of surface plasmon polaritons on both surfaces of the metal film can be achieved by controlling the incident angle. Since the wave vector matching condition is not satisfied, there is no coupling between the plasmon polaritons modes on the two surfaces of the corrugated metallic film. The excitation and control of the non-coupled surface plasmon polartions simultaneously propagating on the different interfaces of one metallic film have potential applications for designing novel compact and tunable nano-photonic devices at visible frequency.     

Enhancing the Surface-State Emission in Trap-Rich CdS Nanocrystals by Silver Nanoparticles

It is well known that surface plasmon resonance (SPR) can selectively enhance the photoluminescence (PL) from nearby chromophores with a single emission peak at an appropriate distance. Here, we combine white light-emitting CdS quantum dot nanocrystals containing band-edge and surface-state emissions simultaneously with Ag nanoparticles and study the interaction between them. It is found that the surface-state emission is always enhanced while the band-edge emission quenched regardless of the SPR wavelength of Ag nanoparticles. This phenomenon reveals that the SPR of Ag nanoparticles is not enhancing the emission from a wavelength-matched state. We propose that the surface plasmon of Ag nanoparticles is first excited by the energy of the band-edge emission and then the excited energetic electrons transfer to the surface-state of CdS. Through this energy transfer process, the surface-state emission is enhanced and band-edge emission quenched. This investigation can not only deliver understanding of the complicated interaction between metallic nanoparticles and nearby multi-emission-peak contained chromophores, but it also has potential applications in tuning the color temperature of white light-emitting materials.     

InGaN/GaN MQW Photoluminescence Enhancement by Localized Surface Plasmon Resonance on Isolated Ag Nanoparticles

Spectroscopic study of photoluminescence (PL) enhancement due to the coupling of the light emitters in InGaN/GaN multiple quantum wells (MQWs) with the localized surface plasmon (LSP) resonance on silver (Ag) nanoparticles (NPs) is performed using the confocal microscopy and scanning near-field optical microscopy (SNOM) techniques. The paper is focused on revealing the emission enhancement due to coupling with a single metal nanoparticle. The enhancement is confirmed by time-resolved study of differential transmission (DT). The enhancement suppression caused by potential fluctuations due to the variations of indium content and quantum well (QW) width is also studied. A strong photoexcitation intensity dependence of the emission enhancement due to spectral runaway of the MQW emission from the resonance as carrier density increases is observed both in spatially integrated spectra and in the vicinity of a single nanoparticle.     

Theoretical Investigation of Plasmonic Properties of Quantum-Sized Silver Nanoparticles

Plasmonic nanoparticles (NPs) like silver (Ag) strongly absorb the incident light and produce enhanced localized electric field at the localized surface plasmon resonance (LSPR) frequency. Enormous theoretical and experimental research has focused on the plasmonic properties of the metallic nanoparticles with sizes greater than 10 nm. However, such studies on smaller sized NPs in the size range of 3 to 10 nm (quantum-sized regime) are sparse. In this size regime, the conduction band of the metal particles discretizes, thus altering plasmon properties of the NPs from classical to the quantum regime. In this study, plasmonic properties of the spherical Ag NPs in size range of 3 to 20 nm were investigated using both quantum and classical modeling to understand the importance of invoking quantum regime to accurately describing their properties in this size regime. Theoretical calculations using standard Mie theory were carried out to monitor the LSPR peak shift and electric field enhancement as a function of the size of the bare plasmonic nanoparticle and the refractive index (RI) of the surrounding medium. Comparisons were made with and without invoking quantum regime. Also, the optical properties of metallic NPs conjugated with a chemical ligand using multi-layered Mie theory were studied, and interesting trends were observed.

     

Folate-conjugated iron oxide nanoparticles for solid tumor targeting as potential specific magnetic hyperthermia mediators: synthesis, physicochemical characterization, and in vitro experiments

New folate-conjugated superparamagnetic maghemite nanoparticles have been synthesized for the intracellular hyperthermia treatment of solid tumors. These ultradispersed nanosystems have been characterized for their physicochemical properties and tumor cell targeting ability, facilitated by surface modification with folic acid. Preliminary experiments of nanoparticles heating under the influence of an alternating magnetic field at 108 kHz have been also performed. The nanoparticle size, surface charge, and colloidal stability have been assessed in various conditions of ionic strength and pH. The ability of these folate "decorated" maghemite nanoparticles to recognize the folate receptor has been investigated both by surface plasmon resonance and in folate receptor expressing cell lines, using radiolabeled folic acid in competitive binding experiments. The specificity of nanoparticle cellular uptake has been further investigated by transmission electron microscopy after incubation of these nanoparticles in the presence of three cell lines with differing folate receptor expression levels. Qualitative and quantitative determinations of both folate nanoparticles and nontargeted control nanoparticles demonstrated a specific cell internalization of the folate superparamagnetic nanoparticles.     

Gamma–Radiation-Assisted Synthesis of Luminescent ZnO/Ag Heterostructure Core–Shell Nanocomposites

There is increasing interest in tuning the physical properties of semiconductor nanostructures using metal nanoparticles. In this work, ZnO nanosphere covered with Ag nanoparticles were synthesized using gamma–radiation-assisted method. The amount of deposited Ag nanoparticles is controlled by changing irradiation dose in the range of 30–100 kGy in order to tune the semiconductor–metal interaction. The successful deposition of Ag on the ZnO nanoparticles is examined by analyzing the morphology, microstructure, optical, and magnetic properties of ZnO/Ag nanoparticles through field emission scanning electron (FESEM), microscopy X-ray diffraction spectra, UV-visible absorption, photoluminescence measurement, and vibrating sample magnetometer. FESEM and elemental mapping results confirmed that Ag nanoparticles have been concentrated at the surface of spherical ZnO particles. Moreover, formation of pure metallic Ag nanoparticles has been confirmed by XRD analysis. UV-visible absorption spectra of obtained ZnO/Ag showed two combined peaks, a weak peak at the shoulder around 360 nm corresponds to ZnO and a sharp absorption at 420 nm refers to spherical Ag nanoparticles. Obtained results from photoluminescence revealed that the near-band-edge emission and defect-related visible emission bands of ZnO could be enhanced dramatically at the same time by deposition of Ag nanoparticles, which was ascribed to localized surface plasmon–exciton coupling and surface plasmon scattering. Controlling the semiconductor and metal coupling effect is interesting because of its application in highly efficient optoelectronic devices and biosensor.     

Highly Sensitive Plasmonic Sensor Based on Fano Resonance from Silver Nanoparticle Heterodimer Array on a Thin Silver Film

We investigate the optical spectrum of a multilayer metallic slab using multiple-scattering formalism. A thin silver film is attached to a periodic array of heterodimers consisting of two vertically spaced silver nanoparticles of different radii. Depending on the radius of nanoparticles, heterodimer array presents a simple nanoscale geometry which gives rise to remarkable plasmonic properties of multipolar resonances. Due to the coherent interference of the localized nanoparticle plasmons (discrete mode) and surface plasmon polaritons of metallic film (continuous mode), the reflection spectrum represents a sharp asymmetric Fano resonance dip, which is strongly sensitive to the refractive index of the surrounding embedded dielectric host. The physical features contribute to a highly efficient plasmonic sensor for refractive index sensing with sensitivity of ～1.5?×?10^?3 RIU/nm.     

Van der Waals Forces Between Plasmonic Nanoparticles

We propose a new approach to calculate van der Waals forces between nanoparticles where the van der Waals energy can be reduced to the energy of localized plasmons in nanoparticles. The general theory is applied to describe the interaction between two metallic nanoparticles and between a nanoparticle and a perfectly conducting plane. Our results could be used to prove experimentally the existence of new, recently predicted type of plasmon oscillation (Klimov and Guzatov, Phys Rev B 75:024303, 2007a; Klimov and Guzatov, Quantum Electron 37:209, 2007b) and to elaborate new control mechanisms for the adherence of nanoparticles between each other or onto surfaces.     

On Plasmon Polariton Propagation Along Metallic Nano-Chain

The collective wave type plasmon polariton self–modes in the metallic (Au, Ag) nano-chain were determined and analyzed with respect to the nano-sphere size and chain separation parameters. At some regions for parameters, the undamped modes were identified when the interaction had been assumed as the near-field-zone dipole coupling. These modes were found on the rim of stability of the linear theory, which indicates artifact of the model of near-field coupling. Inclusion of the medium- and far-field zone contributions to dipole interaction removes, however, instability and allows for fully analytical demonstration of quenching of irradiation losses of plasmon polaritons in the chain to the level of only ohmic attenuation. The plasmon polariton dispersion and the group velocity of plasmon polariton wave packets were examined with respect to nano-sphere and chain parameters and mode polarization. Previous numerical results related to long-range plasmon polariton propagation in the chain are transparently interpreted within the analytical approach.     

Tunable Plasmonic Dispersion and Strong Coupling in Graphene Ribbon and Double Layer Sheets Structure

Based on the interplay between propagating surface plasmon polaritons (PSPs) in graphene ribbon and double layer sheets structure, we theoretically demonstrate a tunable strong coupling mechanism significantly different from reported conventional noble metal nanostructures. The strong electromagnetic coupling between the low order antisymmetric and high order symmetric PSPs modes occurs due to the intersections of dispersion curves, which leads to a modification of plasmonic dispersion and multiple significant anti-crossing regions. Of particular, this strong coupling is controllable through external gate voltage of graphene sheets or ribbon. The results offer an effective regime to dynamically tune the interaction of graphene PSPs, which may find applications in the field of nanophotonic devices in the mid-infrared range.     

Surface Plasmon Enhancement of Optical Absorption in Thin-Film Silicon Solar Cells

Strong electromagnetic field enhancement that occurs under conditions of the surface plasmon excitation in metallic nanoparticles deposited on a semiconductor surface is a very efficient and promising tool for increasing the optical absorption within semiconductor solar cells and, hence, their photocurrent response. The enhancement of the optical absorption in thin-film silicon solar cells via the excitation of localized surface plasmons in spherical silver nanoparticles is investigated. Using the effective medium model, the effect of the nanoparticle size and the surface coverage on that enhancement is analyzed. The optimum configuration and the nanoparticle parameters leading to the maximum enhancement in the optical absorption and the photocurrent response in a single p-n junction silicon cell are obtained. The effect of coupling between the silicon layer and the surface plasmon fields on the efficiency of the above enhancement is quantified as well.     

Plasmon Hybridization in Silver Nanoislands as Semishells Arrays Coupled to a Thin Metallic Film

We obtained experimentally strong plasmon interactions between localized surface plasmon with delocalized surface plasmon polaritons in a new nanosystem of silver semishells island film arrays arranged as a closed-packing structure coupled to an adjacent thin silver film. We show that plasmon interactions for such a nanosystem exhibits two pronounced resonances and interpret the coupling in terms of Fano resonances. The higher energy resonance is identified as a symmetric hybridization mode between localized plasmon resonances in the island semishell array and surface plasmon polaritons in the metal film and while the lower energy resonance is identified as a corresponding anti-symmetric hybridization mode. Increasing the size of the particle arrays enhances and red shifts the resonances. We show that adding a dielectric spacer between the semishell island array and the metal film results in a red shifting of the resonances and introduce an additional high energy spectral peak. The effect of the spacer layer is interpreted as a reduced hybridization and the generation of additional localized surface plasmon resonances.     

Correlation Between Surface Charge Distribution and Circular Dichroism of Elementary Planar Nanoparticles

A correlation is observed between surface charge distributions and the circular dichroism (CD) signature of nanoparticles excited by circularly polarized waves. These surface charge distributions arise as a result of charge separation and depend on the polarization of the externally excited light. This correlation can be observed by deriving the surface charge distribution profile of excited localized surface plasmon polaritons (SPPs) in elementary metal nanoparticles under the influence of circularly polarized light. Nanoparticles with strong CD signatures are especially desired for sensing of chiral biomolecules as well as to aid in photochemical catalysis. We also found out that CD signatures can even be induced via angular rotation. This is true for elementary non-rotated nanoparticles which do not possess a CD signature. The use of elementary nanoparticles for sensing poses a huge advantage over complex nanostructures due to the ease of fabrication. The observed CD signature can also be validated in accordance with theory and simulation results.

     

Temperature Dependence of Photoluminescence from Silver Nanoparticles

Strong temperature dependence of surface plasmon enhanced photoluminescence from silver nanoparticles embedded in a silica host matrix has been observed. The quantum yield of photoluminescence increases as the temperature decreases. Such an effect has been rationalized as being the result of an increase in the plasmonic enhancement factor as a consequence of the decrease in the plasmon damping constant. The decrease in the damping constant is due to a reduction in the electron–phonon scattering rate with the decrease in temperature. The temperature dependence of the photoluminescence quantum yield is stronger for small nanoparticles which reflects the strengthening of electron–phonon coupling in silver nanoparticles with a decrease of their size.