Vapor Phase Deposition, Structure, and Plasmonic Properties of Polymer-Based Composites Containing Ag–Cu Bimetallic Nanoparticles

Nanocomposite (NC) thin films with noble metal nanoparticles embedded in a dielectric material show very attractive plasmonic properties due to dielectric and quantum confinement effects. For single component nanoparticles (NPs), the plasmon resonance frequency can only be tuned in a narrow range. Much interest aroused in bimetallic nanoparticles (BNPs), however many wet chemical approaches do not allow large variation of the NP alloy composition and filling factor. Here, we report a vapor phase co-deposition method to produce polymer–metal NCs with embedded Ag_1 − x Cu _x alloy particles. The method allows production of NPs with controlled alloy composition (x), metal filling (f) and nanostructure in a protecting Teflon AF matrix. The nanostructure size and shape were characterized by transmission electron microscope. Energy dispersive X-ray spectroscopy was used to determine x and f. The optical properties and the position of surface plasmon resonances were studied by UV–Vis spectroscopy. The plasmon resonances can be tuned over a large range of the visible spectrum associated with the change in x, f, and nanostructure. For low filling factors and small particle sizes, only one resonance peak was observed. This is attributed to enhanced miscibility at the nanoscale. Double plasmon resonances were seen for larger particle sizes in accord with phase separation expected from the bulk phase diagram and were explained in terms of the formation of core-shell structures with Cu core and Ag shell. Changes upon annealing at 200 °C are also reported.     

Resonant Broadband Field Enhancement in Cylindrical Plasmonic Structure Surrounded by Perovskite Environment

We demonstrate the optical response of metal nanoparticles and their interaction with organic-inorganic perovskite (methyl ammonia lead halide (CH₃NH₃PbI₃)) environment using discrete dipole approximation (DDA) simulation technique. Important optical properties like absorption, scattering, and electric field calculations for metal nanoparticle using different geometry have been analyzed. The metal nanoparticles embedded in the perovskite media strongly support surface plasmon resonances (SPRs). The plasmonic interaction of metal nanoparticles with perovskite matrix is a strong function of MNP’s shape, size, and surrounding environment that can manipulate the optical properties considerably. The cylindrical shape of MNPs embedded in perovskite environment supports the SPR which is highly tunable to subwavelength range of 400–800 nm. Wide range of particle sizes has been selected for Ag, Au, and Al spherical and cylindrical nanostructures surrounded by perovskite matrix for simulation. The chosen hybrid material and anisotropy of structure together make a complex function for resonance shape and width. Among all MNPs, 70-nm spherical silver nanoparticle (NP) and cylindrical Ag NP having diameter of 50 nm and length of 70 nm (aspect ratio 1.4) generate strong electric field intensity that facilitates increased photon absorption. The plasmonic perovskite interaction plays an important role to improve the absorption of photon inside the thin film perovskite environment that may be applicable to photovoltaics and photonics.

     

Surface Plasmon as a Probe of Local Field Enhancement

New method of experimental determination of local field enhancement at metal nanoparticles is suggested. It uses surface plasmon as a probe. Alternating-sign shift of surface plasmon resonance in copper nanoparticles incorporated in silica matrix has been observed under irradiation by intense femtosecond laser pulse. The red shift of plasmon observed during the action of pump pulse is interpreted as a result of change of dielectric constant of silica matrix due to optical Kerr effect in electric field of pump pulse enhanced in a vicinity of metal nanoparticles. The field enhancement factor is estimated from the value of the observed red shift of plasmon resonance.     

Tunable Localized Surface Plasmon Resonances in a New Graphene-Like Si2BN’s Nanostructures

The optical response of a new graphene-like material Si₂BN’s nanostructures and some kinds of hybrid structures formed by Si₂BN and metal nanoparticles was studied by using time-dependent density functional theory (TDDFT). We found that the periodic structures of Si₂BN have wider absorption ranges than graphene. When the impulse excitation polarizes in different directions (armchair-edge direction and zigzag-edge direction), the absorption spectra of Si₂BN nanostructures would be different (optical anisotropy). And in the hybrid structures, the increase of metal nanoparticles’ number brings the absorption intensity strengthening and red shift, which means a stronger ability of localized surface plasmon tuning. Also, the different metal nanoparticles were used to form the hybrid structures; they show an obviously different property as well. In addition, in the kinds of situations mentioned above, the plasmons were produced in visible region. This investigation provides an improved understanding of the plasmon enhancement effect in graphene-like photoelectric devices.

     

Third-Order Nonlinear Optical Response of Layered Composites Materials Containing Gold Nanoparticles

Nonlinear third-order susceptibility \(\chi _{\text {eff}}^{(3)}\) of composites materials having alternated layers of dielectric and plasmonic nanostructures of gold nanoparticles was theoretically studied using the effective medium theory and the degenerate electron gas model. Real and imaginary parts of χeff(3) for the proposed composite material were calculated for the spectral region around the plasmon resonance of gold nanoparticles. The results reveal an enhanced nonlinear optical response compared with the obtained one for individual layers, as well as a reversal signal of \(\chi _{\text {eff}}^{(3)}\) for different volume fraction conditions.     

Plasmon Peak Sensitivity Investigation of Individual Cu and Cu@Cu<Subscript>2</Subscript>O Core–Shell Nanoparticle Sensors

It is crucial to reveal the plasmon peak sensitivity responses of individual Cu nanoparticles, which provide another kind of plasmon sensors besides Au/Ag ones. In this paper, such responses to both the bulk and local refractive index (RI) of individual Cu nanosphere sensors are theoretically investigated by Mie theory. Both of them are revealed to be quadratic. The underlying mechanisms are elucidated well in terms of Rayleigh approximation. The corresponding sensitivity factors are demonstrated to increase with the RI of the nanospheres’ bulk and local surrounding mediums linearly. The plasmon peak sensitivities and sensitivity factors of experimentally encountered Cu@Cu₂O core–shell nanoparticles are calculated as well, which reveals that appropriate dielectric encapsulations to Cu nanospheres are favored for their potential plasmonic sensing and detection applications.     

Nanoscale Dielectric Function of Fe,Pt, Ti,Ta, Al,and V: Application to Characterization of Al Nanoparticles Synthesized by Fs Laser Ablation

Development and applications of new nanomaterials and nanocomposites that include metal nanoparticles have received much attention in the last years. However, there are relatively few studies concerning basic physical characteristics of the dielectric function at the nanoscale, which is needed for predicting their optical and plasmonic response. The size-dependent complex dielectric function of metal Fe, Pt, Ti, Ta, Al, and V nanoparticles (NPs) is calculated for the first time for an extended wavelength range from UV to FIR, based on experimental bulk complex refractive index measurements in the mentioned range at room temperature. Calculation is based on a “top-down” approach, based on a stepwise modification of the Drude model. Bulk plasma frequency (ω _p) and damping constant (γ _free) in this model are determined using a method that improves the relative uncertainties in their values and provide an insight about the wavelength range over which the metal may be considered Drude like. Validation of ω _p and γ _free values is demonstrated by the improved accuracy with which the experimental bulk dielectric function is reproduced. For nanometric and subnanometric scales, dielectric function is made size dependent considering size-corrective terms for free and bound electron contributions to the bulk dielectric function. These results are applied to analyze the synthesis of Al NP suspensions using a 120-fs pulse laser to ablate an Al solid target in n-heptane and water. The presence of Al, Al-Al₂O₃, and air-Al core-shell structures is also reported for the first time in these type of colloids. Analysis of the structure, configuration, sizing, and relative abundance was carried out using optical extinction spectroscopy (OES). Sizing results are compared with those provided by atomic force microscopy (AFM) studies.     

Field distribution and quality factor of surface plasmon resonances of metal meshes for mid-infrared sensing

We studied surface plasmon sensors based on micrometric metal meshes by optical transmission spectroscopy as a function of the angle of incidence. The mesh period was set to 2 μm for operation at mid-infrared wavelengths. Metal meshes on dielectric substrates were compared to suspended meshes obtained with a lift-off-free fabrication process, which reduces plasmon damping and increases the quality factor up to 25. We have numerically calculated the electric field distribution of “dark” quadrupole-like modes and found that the suspended mesh provides an enhanced interaction volume extending up to hundreds of nanometers in free space. Our sensors have been experimentally tested and they exhibited a sensitivity up to 1.4?·?10^?3?nm^?1, at least 1 order of magnitude better than standard mid-infrared absorption spectroscopy.     

Metal-Dielectric-Graphene Hybrid Heterostructures with Enhanced Surface Plasmon Resonance Sensitivity Based on Amplitude and Phase Measurements

Metal-dielectric-graphene hybrid heterostructures based on oxides Al₂O₃, HfO₂, and ZrO₂ as well as on complementary metal–oxide–semiconductor compatible dielectric Si₃N₄ covering plasmonic metals Cu and Ag have been fabricated and studied. We show that the characteristics of these heterostructures are important for surface plasmon resonance biosensing (such as minimum reflectivity, sharp phase changes, resonance full width at half minimum and resonance sensitivity to refractive index unit (RIU) changes) can be significantly improved by adding dielectric/graphene layers. We demonstrate maximum plasmon resonance spectral sensitivity of more than 30,000 nm/RIU for Cu/Al₂O₃ (ZrO₂, Si₃N₄), Ag/Si₃N₄ bilayers and Cu/dielectric/graphene three-layers for near-infrared wavelengths. The sensitivities of the fabricated heterostructures were?~?5–8 times higher than those of bare Cu or Ag thin films. We also found that the width of the plasmon resonance reflectivity curves can be reduced by adding dielectric/graphene layers. An unexpected blueshift of the plasmon resonance spectral position was observed after covering noble metals with high-index dielectric/graphene heterostructures. We suggest that the observed blueshift and a large enhancement of surface plasmon resonance sensitivity in metal-dielectric-graphene hybrid heterostructures are produced by stationary surface dipoles which generate a strong electric field concentrated at the very thin top dielectric/graphene layer.

     

Study of Broadband Tunable Properties of Surface Plasmon Resonances of Noble Metal Nanoparticles Using Mie Scattering Theory: Plasmonic Perovskite Interaction

We suggest semi-analytical approach to study the optical properties of noble metal nanoparticles and their interaction to the perovskite material (methyl ammonia lead halide: CH₃NH₃PbI₃). Metal nanoparticles embedded in perovskite matrix exhibits broadband surface plasmon resonances, and the tunability of these plasmonic resonances is highly sensitive to particle size. The calculation of optical cross section have been done using Mie scattering theory which is applicable to arbitrary size and spherical-shape metal nanoparticles. We have taken five different radii ranging from 15 to 100 nm to understand the plasmonic resonances and its spectral width in the wavelength range 300 to 800 nm. Out of these noble metal nanoparticles, silver have highest scattering efficiency nearly of the order of 18 for the case of 15 nm radii at resonance wavelength 613 nm. Our finding reveals a new concept to understand the applications of plasmonic resonances in order to enhance the photon absorption inside the thin film of perovskite.     

Review of Some Interesting Surface Plasmon Resonance-enhanced Properties of Noble Metal Nanoparticles and Their Applications to Biosystems

Noble metal, especially gold (Au) and silver (Ag) nanoparticles exhibit unique and tunable optical properties on account of their surface plasmon resonance (SPR). In this review, we discuss the SPR-enhanced optical properties of noble metal nanoparticles, with an emphasis on the recent advances in the utility of these plasmonic properties in molecular-specific imaging and sensing, photo-diagnostics, and selective photothermal therapy. The strongly enhanced SPR scattering from Au nanoparticles makes them useful as bright optical tags for molecular-specific biological imaging and detection using simple dark-field optical microscopy. On the other hand, the SPR absorption of the nanoparticles has allowed their use in the selective laser photothermal therapy of cancer. We also discuss the sensitivity of the nanoparticle SPR frequency to the local medium dielectric constant, which has been successfully exploited for the optical sensing of chemical and biological analytes. Plasmon coupling between metal nanoparticle pairs is also discussed, which forms the basis for nanoparticle assembly-based biodiagnostics and the plasmon ruler for dynamic measurement of nanoscale distances in biological systems.     

Optical Properties of Silver-Coated Silicon Nanowires: Morphological and Plasmonic Excitations

The optical extinction spectra of micro- and nanoparticles made up of high-contrast dielectrics exhibit a set of very intense peaks due to the excitations of morphology-dependent resonances (MDRs). These kind of resonances are well known at the microscopic scale as whispering gallery modes. In this work, we study numerically the optical spectra corresponding to a core–shell structure composed by an infinite silicon nanowire coated with a silver shell. This structure shows a combination of both excitations: MDRs and the well-known surface plasmon resonances in dielectric metallic core–shell nanoparticles (Ekeroth Abraham and Lester, Plasmon 2012). We compute in an exact form the complete electromagnetic response for both bare and coated silicon nanowires in the range of 24–200 nm of cross-sectional sizes. We take into account an experimental bulk dielectric function of crystalline silicon and silver by using a correction by size of the metal dielectric function. In this paper, we consider small silver shells in the range of 1–10 nm of thickness as coatings. We analyze the optical response in both the far and near fields, involving wavelengths in the extended range of 300–2,400 nm. We show that the MDRs excited at the core are selectively perturbated by the metallic shell through the bonding and antibonding surface plasmons (SPs). This perturbation depends on both the size of the core and the thickness of the shell, and, as a consequence, we get an efficient tuneable and detectable simple system. Our calculations apply perfectly to long nanotubes compared to the wavelength for the two fundamental polarizations (s, p).     

Surface Plasmon Polariton Propagation at the Interface of a Metal and an Ambichiral Nanostructured Medium

The propagation of a surface plasmon polariton wave at the interface of a metal and an ambichiral nanostructured medium was theoretically investigated in the Kretschmann configuration using transfer matrix method. The dependence of optical absorption linear polarization on structural parameters was reported. The results were compared with those obtained from the interface of a metal and a chiral dielectric medium as a reference structure. We found that multiple plasmon modes are excited at the interface of metal and ambichiral dielectric medium. Our calculations revealed that there exist five plasmon modes for chiral, trigonal, and tetragonal structures; three plasmon modes for pentagonal structure; two plasmon modes for hexagonal structure; and one plasmon mode for dodecagonal structure that propagate with different phase speeds. The obtained results showed that only one plasmon mode occurs at all pitches, while other modes exist at some of the pitches of anisotropic chiral and ambichiral dielectric mediums. The time-averaged Poynting vector versus the thickness of metal film confirmed that the energy of photons of incident light is transferred to surface plasmon polariton quasiparticles and the surface plasmon polariton wave is localized at the interface of metal and ambichiral dielectric medium.     

Effective Dielectric Constant of Plasmonic Nanofluid Containing Core-Shell Nanoparticles

This paper focuses on the effective dielectric constant of water-based plasmonic nanofluid containing SiO₂/Ag core/shell nanoparticles (NPs). Two effective models, based on S-parameter retrieval method and Maxwell-Garnett effective medium theory, are employed. The effective dielectric constants predicted by the two effective models are compared and the applicability is evaluated by comparing the reflectance and absorptance. Three influence factors, including volume fraction, core-shell ratio, and size of NPs, are considered. Results show both of the two effective models can predict reliable effective dielectric constants when the volume fraction, size, and core-shell ratio of nanoparticles are 5%, 25 nm, and 4:1 respectively. Only small deviations appear in the resonant region under this condition. With the increase of volume fraction, shell proportion, or size, deviations in the resonant region become larger for both of the two effective models. Therefore, the predicted effective dielectric constants are not suitable for the prediction of optical properties, because the resonant region is the key region of the solar conversion for plasmonic nanofluids. Hence, the parameters of NPs need to be changed to make the effective models applicable. Moreover, the effective model based on S-parameter retrieval can predict more reliable dielectric constant than the effective model based on Maxwell-Garnett theory.

     

Plasmonic, Low-Frequency Raman, and Nonlinear Optical-Limiting Studies in Copper–Silica Nanocomposites

Nanocomposite thin films consisting of Cu nanoparticles embedded in silica matrix were synthesized by atom beam co-sputtering technique. Plasmonic, optical, and structural properties of the nanocomposite films were investigated by using ultraviolet (UV)–visible absorption spectroscopy, nonlinear optical transmission, X-ray diffraction (XRD), and low-frequency Raman scattering. UV–visible absorption studies revealed the surface plasmon resonance absorption at 564 nm which showed a red shift with increase in Cu fraction. XRD results together with surface plasmon resonance absorption confirmed the presence of Cu nanoparticles of different size. Low-frequency Raman studies of nanocomposite films revealed breathing modes in Cu nanoparticles. Nanocomposites with lower metal fractions were found to behave like optical limiters. The possibility of controllably tuning the optical nonlinearity of these nanocomposites could enable them to be the potential candidates for applications in nanophotonics.     

Study of Design Tunable Optical Sensor and Monochromatic Filter of the One-Dimensional Periodic Structure of TiO2/MgF2 with Defect Layer of Liquid Crystal (LC) Sandwiched with Two Silver Layers

In this paper, we have inspected the optical characteristics of one-dimensional periodic structure (1DPS) of TiO₂ and MgF₂ dielectric materials with defect layer of liquid crystal (LC) sandwiched with two silver layers, i.e., (TiO₂|MgF₂)³|Ag|LC|Ag|(TiO₂/MgF₂)³ using transfer matrix method (TMM). The optical tunable properties of considered periodic structures investigated at different incident angles and temperatures for TE and TM modes. Our study shows that absorption peak of 1DPS varies with incident angle and temperature. The defect layer (Ag-LC-Ag), sandwiched LC within two metallic (Ag) layers, exhibits the surface plasmon waves at the metal LC interfaces. The effect of surface plasmon waves can be better understand through the optical sensing property of such defect periodic structure. The detailed study concludes that such a type of one-dimensional periodic structure (1DPS) may be useful to design a tunable sensor and monochromatic filter.

     

Search of Extremely Sensitive Near-Infrared Plasmonic Interfaces: A Theoretical Study

The sensitivity of the wavelength position of localized surface plasmon resonance (LSPR) in metal nanostructures to local changes in the refractive index has been widely used for label-free detection strategies. Tuning the optical properties of the nanostructures from the visible to the infrared region is expected to have a drastic effect on the refractive index sensitivity. Here, we theoretically investigate the optical response of a newly designed plasmonic interface to changes in the bulk refractive index by the finite difference time domain method. It consists of a structured interface, where the planar interface is superposed with dielectric pillars 30 nm in height and 125 nm in length with a separation distance of 15 nm. The pillars are covered with U-shaped gold nanostructures of 50 nm in height, 125 nm in length, and 5 nm of gold base thickness. The whole structure is finally covered with a 5-nm thick dielectric layer of n ₂?=?2.63. This plasmonic structure shows bulk refractive index sensitivities up to 1750 nm/RIU (RIU : refractive index unit) in the near infrared (λ?=?2621 nm). The enhanced sensitivity is a consequence of the extremely enhanced electrical field between the gold nanopillars of the plasmonic interface.     

Photothermal Enhancement in Core-Shell Structured Plasmonic Nanoparticles

Plasmonic nanoparticles (NPs) with photothermal effects can be exploited as efficient heat sources in various applications. Here, the photothermal properties in core-shell structured plasmonic NPs, including metal/silica NP, silica/metal NP, and metal/silica/metal NP, are investigated. Compared with bare metal NPs, the core-shell plasmonic NPs not only exhibit extremely agile tunability in the surface plasmon resonances but also show considerably enhanced photothermal effects in terms of the maximum temperature rise. For metal/silica NPs and metal/silica/metal NPs, the SiO₂ shells function as effective thermal-protective layers for enhanced photothermal effect. For silica/metal NPs, the SiO₂ core and the metal shell show uniform temperature rise. These findings are essential for applying the core-shell structured plasmonic NPs on photothermal imaging, nanofluidics, etc.     

Double-Layered Metal Nano-Strip Antennas for Sensing Applications

A coupled plasmonic system based on double-layered metal nano-strips for sensing applications is investigated by means of mode analysis and two-dimensional finite-difference time-domain simulations. The nano-strips act as optical antennas through constructive interference of short-range surface plasmon polaritons, thus increasing their scattering cross-section and optical field enhancement. Near-field modulation by optical trapped metal nanoparticles (NPs) is also demonstrated. Our results reveal that the device exhibits a refractive index sensitivity of ～200 nm/RIU, and a maximum surface-enhanced Raman scattering (SERS) factor of 10⁹–10¹⁰ from metal NPs trapped in the near-field region. The proposed device shows reasonable figure-of-merit and is ready for integration with common optofluidic biosensors.     

Numerical Simulation of Broadband Scattering by Coated and Noncoated Metal Nanostructures Using Discrete Dipole Approximation Method

We suggest numerical method to study the optical response of metal nanostructures. The analysis of optical properties such as scattering and absorption by coated and noncoated nanogeometry has been done using discrete dipole approximation (DDA) method. The core-shell nanogeometry supports surface plasmon resonances, which are highly tunable from 400 to 1100 nm. The tunability of surface plasmon resonance (SPR) highly depends on the structural anisotropy and chosen core-shell material. Further, we have observed that aspect ratio is one of the key parameter to decide the nature and position of the plasmonic peaks and magnitude of optical cross section. We have also shown that coated nanospheroid is a more appropriate geometry as compared to coated nanosphere and noncoated nanospheroid in terms of wide tunability of surface plasmon resonance. The wide tunability in SPR is observed for the effective radii 90 nm core-shell (Au@SiO₂) nanospheroid with aspect ratio 0.1.