Magnetic–Plasmonic FePt@Ag Core–Shell Nanoparticles and Their Magnetic and SERS Properties

Magnetic–plasmonic FePt@Ag core–shell nanoparticles (NPs) with different Ag shell thicknesses were successfully synthesized using a seed-mediated method. They presented not only localized surface plasmon resonance in the visible region, but also superparamagnetic behavior at room temperature. When normalized by the weight of FePt, the saturation magnetization of the FePt@Ag NPs was found to be higher than that of FePt NPs, suggesting that the Ag shell effectively passivated the FePt NP surfaces, avoiding the direct interaction between the FePt core and surface capping ligands that typically forms a magnetically dead layer in FePt NPs. Despite the high colloidal stability and the small size of the FePt@Ag NPs, the NPs were easily separated using a permanent magnet. The surface enhanced Raman scattering (SERS) activity of the FePt@Ag NPs was then examined using thiophenol as a Raman reporter molecule and was found to be equivalent to that of Ag NPs. Moreover, the SERS activity of the FePt@Ag NPs was enhanced when a magnetic field was applied during the preparation of the SERS substrate (FePt@Ag NP film). These FePt@Ag NPs hold promise as dual-functional sensing probes for environmental and diagnostic applications.     

Tunable Plasmon Resonance and Enhanced Photocatalytic Activity of Au–CdS Core–Shell Nanodogbones

Plasmonics - Au–CdS core–shell nanodogbones with controllable shell thickness were facilely synthesized by one-pot method. Their tunable optical properties have been investigated with...     

The Effect of Negative Curvature on the Plasmonic Coupling of Concentric Core–Shell Metallic Nanostructures

Negative curvature-dependent localized surface plasmon resonance (LSPR) properties of concentric core–shell metallic nanostructure have been studied using quasistatic approach and plasmon hybridization theory. Whether in single-layered gold nanoshell or double gold nanoshells, the oscillating surface charges always concentrate close to the poles of the metal surface with negative curvature, which results in the anisotropic local electric field distribution and affects both the inter-surface plasmonic coupling and inter-shell plasmonic coupling. Therefore, the change of the radius of the gold surface with negative curvature could modulate the plasmon hybridization and lead to the LSPR shifting. The physical mechanism of the negative curvature-dependent LSPR presents a potential for design and fabrication of nanoscale optical device based on core–shell type metallic nanostructures.     

Speckled SiO2@Au Core–Shell Particles as Surface Enhanced Raman Scattering Probes

Silica particles of ~800 nm size were functionalized using 3-amino propyl triethoxysilane molecules on which gold particles (~20 nm size) were deposited. The resulting particles appeared to form speckled SiO₂@Au core–shell particles. The surface roughness, along with hot spots, due to nanogaps between the gold nanoparticles was responsible for the enhancement of the Raman signal of crystal violet molecules by ~3.2?×?10⁷ and by ~1.42?×?10⁸ of single-wall carbon nanotubes. It has also been observed that the electromagnetic excitation near surface plasmon resonance (SPR) of core–shell particles is more effective than off resonance SPR excitation.     

Oligonucleotide-Mediated Au–Ag Core–Shell Nanoparticles

The bimetallic core–shell nanoparticles show unique plasmonic properties and their preparations and characterizations are currently under investigation. A new type of Au core–Ag shell (Au@Ag) nanoparticles is prepared by sandwiching the chemically attached Raman reporter molecules (RRMs) and a 12-base-long oligonucleotide between the 13 nm average size core-gold nanoparticles (AuNPs) and 9 nm and 21 nm average size of Ag shell. The synthesized Au@Ag nanoparticles are tested for their surface-enhanced Raman scattering (SERS) performance. It is found that the chemical attachment of the oligonucleotides along with the RRM improved the enhancement in Raman scattering more than one order of the magnitude with the Au@Ag nanoparticles with an average 9-nm shell thickness while the Au@Ag nanoparticles with 21 nm average shell thickness have poor SERS activity. A minimum enhancement factor of 1.0 × 10⁷ is estimated for the SERS active oligonucleotide-mediated Au@Ag nanoparticles. The approach may provide new routes for preparation of highly sensitive new generation of bimetallic core–shell nanoparticles.     

Solar Selective Absorbers for High-efficiency Photothermal Conversion via Core–Shell Nanocone Structured Surface

Nanostructured surface, a promising photon management strategy, enables to enhance photon-to-heat conversion efficiency by manipulating spectral radiative properties ranging from solar spectrum (0.3–2.5 μm) to mid-infrared spectrum (2.5–20 μm). Here, a core–shell nanocone structured surface made of silica core and tungsten shell as a solar selective absorber is introduced. The photothermal conversion efficiency (PTCE) is calculated in consideration of solar spectrum absorption and mid-infrared emission. It is obvious that high solar spectrum absorption and low mid-infrared emission are beneficial for high PTCE. The influence of structural parameters on the PTCE is studied, and then the absorption enhancement mechanism is elucidated in detail. Meanwhile, the influences of incident angle, polarized state, and lattice arrangement are also presented. The calculated results exhibit that our optimized solar absorber possesses the total solar absorption of 97.3% and total thermal emission of 7.6%, resulting in a maximum PTCE of 91.4% under one sun illumination conditions at normal incidence. Moreover, our solar selective absorber is independent to the incident angle and polarization state. The excellent photothermal conversion performance with wide-angle and polarization-insensitive properties for the solar selective absorber can serve as a good candidate for various solar thermal applications including seawater desalination, steam generation, thermophotovoltaic, and photocatalysis.

     

Plasmon Spectroscopy for Subnanometric Copper Particles: Dielectric Function and Core–Shell Sizing

In the last years, there has been a growing interest in the study of transition metal nanoparticles (Nps) due to their potential applications in several fields of science and technology. In particular, their optical properties are governed by the characteristics of the dielectric function of the metal, its size and environment. This work analyses the separated contribution of free and bound electrons on the optical properties of copper Nps. Usually, the contribution of free electrons to the dielectric function is corrected for particle size through the modification of the damping constant, which is changed as usual introducing a term inversely proportional to the particle’s radius to account for the extra collisions with the boundary when the size approaches the electronic mean free path limit (about 10 nm). For bound electron contribution, the interband transitions from the d-band to the conduction band are considered together with the fact that the electronic density of states in the conduction band must be made size-dependent to account for the larger spacing between electronic energy levels as the particle decreases in size below 2 nm. Taking into account these specific modifications of free and bound electron contributions to the dielectric function, it was possible to fit the bulk complex dielectric function, and consequently, determine optical parameters and band energy values such as the coefficient for bound electron contribution Q _bulk?=?2?×?10²⁴, gap energy E _g?=?1.95 eV, Fermi energy E _F?=?2.15 eV, and damping constant for bound electrons γ _b?=?1.15?×?10¹⁴ Hz. With both size-dependent contributions to the dielectric function, extinction spectra of copper Nps in the subnanometer radius range can be calculated using Mie’s theory and its behaviour with size can be analysed. These studies are applied to fit experimental extinction spectra of very small spherical core–shell Cu–Cu₂O Nps generated by ultrafast laser ablation of a solid target in water. Theoretical calculations for subnanometric core radius are in excellent agreement with experimental results obtained from core–shell colloidal Nps. From the fitting, it is possible determining core radius and shell thickness of the Nps, showing that optical extinction spectroscopy is a good complementary technique to standard high-resolution electron microscopy for sizing spherical nanometric-subnanometric Nps.     

Preparation and Optical Characterization of Core–Shell Bimetal Nanoparticles

Chemical approaches allow for the synthesis of highly defined metal heteronanostructures, such as core–shell nanospheres. Because the material in the metal nanoparticles determines the plasmon resonance-induced absorption band, control of particle composition results in control of the position of the absorption band. Metal deposition on gold or silver nanoparticles yielded core–shell particles with modified optical properties. UV–vis spectroscopy on solution-grown, as well as surface-grown, particles was conducted and provided ensemble measurements in solution. Increasing the layers of a second metal leads to a shift in the absorption band. A shell diameter comparable to the original particle diameter leads to a predominant influence by the shell material. Extent of shell growth could be controlled by reaction time or the concentration of metal salt or reducing agent. Besides optical characterization, the utilization of atomic force microscopy, scanning electron microscopy, and transmission electron microscopy yielded important information about the ultrastructure of nanoparticle complexes. Surface-grown core–shell particles were superior in terms of achievable shell thickness, because of difficulties encountered with solution-grown particles due to salt-induced aggregation.     

Structural SPR Tunability of Metal@Graphene Core–Shell Nano-Needle and Nano-Disk

Plasmonics - In present paper, a design of the graphene-coated metal (Ag/Au/Cu) nano-disk (2D) and nano-needle (1D) has been studied within the quasi-static approximation. The core@shell...     

Optical Properties of Core–Shell Gold–Silver and Silver–Gold Nanoparticles for Near UV and Visible Radiation Wavelengths

Modeling of optical properties of spherical core–shell gold–silver and silver–gold nanoparticles (NPs) was carried out based on extended Mie theory for radiation wavelengths in the range 300?≤?λ?≤?650 nm. Efficiency factors of absorption, scattering, and extinction of radiation by core–shell NPs in the range of the radii 5–100 nm and in the range of shell thicknesses 0–40 nm were calculated. Results show the nonlinear dependences of optical properties of core–shell gold–silver and silver–gold nanoparticles on radiation wavelengths, core radii, and shell thicknesses. These results can be applied for photonic technologies of 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.     

Hybrid Polymer Electrolyte Encased Cathode Particles Interface-Based Core–Shell Structure for High-Performance Room Temperature All-Solid-State Batteries

A smooth interfacial contact between electrode and electrolyte, alleviation of dendrite formation, low internal resistance, and preparation of thin electrolyte (<20 µm) are the key challenging tasks in the practical application of Li₇La₃Zr₂O₁₂ (LLZO)-based solid-state batteries (SSBs). This paper develops a unique strategy to reduce interfacial resistance by designing an interface-based core–shell structure via direct integration of Al-LLZO ceramic nanofibers incorporated poly(vinylidene fluoride)/LiTFSI on the surface of a porous cathode electrode (HPEIC). This yields an ultrathin solid polymer electrolyte with a thickness of 7 µm. The integrated HPEIC/Li SSB with LiFePO₄/C exhibits an initial specific capacity of 166 mAh g⁻¹ at 0.1 C and 159 mAh g⁻¹ with capacity retention of 100% after 120 cycles at 0.5 C (25 °C). The HPEIC/Li SSB with LiNi_0.8Mn_0.1Co_0.1O₂ cathode delivers a good discharge capacity of 134 mAh g⁻¹ after 120 cycles at 0.5 C. The rational design of interface-based core–shell structure outperforms the conventional assembly of solid-state cells using free-standing solid electrolytes in specific capacity, internal resistance, and rate performance. The proposed strategy is simple, cost-effective, robust, and scalable manufacturing, which is essential for the practical applicability of SSBs.     

The Periodically Graded Metal–Insulator–Metal Gap Structure for Plasmonic Waveguides

In this paper, we explore the potential of the plasmonic metal–insulator–metal (MIM) periodically graded structure. Based on the coupled modes approach, an analytical model has been observed for the surface plasmon polariton (SPP) propagation. The band modes of SPP can be also supported by the MIM structure and we have analyzed the strong dependence of band width on structure parameters. The obtained analytical expressions allow one to easily choose the structure parameters for the desired band width.     

Location-Dependent Local Field Enhancement Along the Surface of the Metal–Dielectric Core–Shell Nanostructure

A theoretical study based on quasi-static approximation is performed to investigate the location-dependent local field enhancement around the dielectric shell-coated gold nanosphere. Our calculation results show that the local field distribution near a gold nanoparticle can be altered greatly by coating with a dielectric shell. Because of the polarizability of the dielectric shell, increasing azimuth angle along the inner surface leads to the increase of the local field, which is opposite to that of the outer surface. Furthermore, the location-dependent local field enhancement and resonance frequency at both the inner and outer surfaces can also be modulated by varying the shell thickness and shell dielectric constant. These calculation results about the location-dependent local field enhancement show the potential of dielectric-coated metallic nanostructure for single-molecule detection based on surface-enhanced Raman scattering and surface enhanced fluorescence.     

SiO2–Silver Metasurface Architectures for Ultrasensitive and Tunable Plasmonic Biosensing

Plasmonics - Here, we indicate that metasurface-based biosensors consisting of silver-metasurface with SiO2 and working in the near-infrared (NIR) spectral range can obtain simultaneous...     

A Study of Metal@Graphene Core–Shell Spherical Nano-Geometry to Enhance the SPR Tunability: Influence of Graphene Monolayer Shell Thickness

Graphene, new generation advance material of two dimensional hexagonal lattice having extraordinary optical signatures, is used as coating material to enhance the surface plasmon resonance (SPR) effect of core@shell metal nanospheres. In a core@shell nanosphere, we have chosen metal as a core and graphene monolayer (GML) as a shell. We have analysed optical signature of coated and non-coated nanospheres in terms of extinction efficiency (Q _ext) and tunabilty of surface plasmon resonances using electrostatic model, where particle size is much smaller than the wavelength of incident light. We analysed this model over different metals (silver, gold and aluminium) core, coated with different thickness of GML (d?=?0.1 to 0.5 nm). These core@shell nanospheres are embedded in refractive index media of air (n _em?=?1), SiO₂ (n _em?=?1.47) and TiO₂ (n _em?=?2.79). The Q _ext has been calculated by varying both the core radii as well as the GML shell thickness. Graphene-coated metal nanosphere exhibits SPRs that have wide range tunability from 300 to 1500 nm. In the presenting work, we also analysed that extinction efficiency for metal@GML is higher in TiO₂ than others. The optimum value of GML shell thickness is 0.4 nm for TiO₂, the magnitude of extinction efficiency is maximum for the optimum thickness. The tunability of these plasmonic resonances is highly dependent on the core@shell material, thickness of Graphene shell and surrounding environment while non-coated metal nano-spheres do not show appropriate SPR tunability.     

Synthesis of Peptide Mediated Au Core–Ag Shell Nanoparticles as Surface-Enhanced Raman Scattering Labels

As the fundamental understanding of metal–light interactions gains solid grounds, further research has been devoted to construct novel structures that take full advantage of such unique interactions, which is called plasmonics. In this report, the preparation of Au–Ag core–shell structures obtained by coating the Au surface with peptide and Raman reporter molecule and depositing an Ag layer on it is reported. The prepared Au–Ag NPs are tested for their surface-enhanced Raman scattering (SERS) performance. The negatively charged peptides with three different lengths, which are 3 (P1), 15 (P2), and 21 (P3) amino acid long, were chemically attached to 13 nm AuNPs along with Raman reporter molecule, carboxytetramethylrhodamine, and these modified AuNPs were coated with three different shell thickness of Ag metal. The prepared Au–Ag NPs were tested for their SERS performance and found that the Au–Ag NPs prepared with P2 and thickest shell performs best as SERS label.     

Simulation of the Nonlinear Optical Properties of Colloids Containing Metallic Core–Dielectric Shell Nanoparticles

Nonlinear (NL) optical properties of composite materials containing metallic core–dielectric shell nanoparticles in aqueous solution were investigated numerically using the Maxwell–Garnett model and the degenerate electron gas model. Influence of geometry and excitation laser intensity was considered to describe the local field factor and the third-order NL susceptibility.     

Optimization of the Field Enhancement and Spectral Bandwidth of Single and Coupled Bimetal Core–Shell Nanoparticles for Few-Cycle Laser Applications

We have theoretically studied and optimized the field enhancement and temporal response of single and coupled bimetal Ag/Au core–shell nanoparticles (NPs) with a diameter of 160 nm and compared the results to pure Ag and Au NPs. Very high-field enhancements with an amplitude reaching 100 (with respect to the laser field centered at 800 nm) are found at the center of a 2-nm gap between Ag/Au core–shell dimers. We have explored the excitation of the bimetal core–shell particles by Fourier transform-limited few-cycle optical pulses and identified conditions for an ultrafast plasmonic decay on the order of the excitation pulse duration. The high-field enhancement and ultrafast decay makes bimetal core–shell particles interesting candidates for applications such as the generation of ultrashort extreme ultraviolet radiation pulses via nanoplasmonic field enhancement. Moreover, in first experimental studies, we synthesized small bimetal Ag/Au core–shell NPs and compared their optical response with pure Au and Ag NPs and numerical results.     

Two-dimensional PtSe2 Theoretically Enhanced Goos-Hänchen Shift Sensitive Plasmonic Biosensors

Platinum diselenide (PtSe₂), an emerging two-dimensional transition metal dichalcogenide, exhibits thickness-dependent refractive index, and hence, intriguing optical properties. Here, we employ it as a plasmonic sensing substrate to achieve significant enhancement in Goos-Hänchen shift sensitivity. Through systematic optimization of all parameters, four optimum sensing configurations have been achieved at different wavelengths ranging from visible to near-infrared region, where the Goos-Hänchen shift sensitivity receives four times enhancement in comparison with the conventional bare gold sensing substrate. There is a linear range of Goos-Hänchen shift with the tiny change of refractive index for each optimal configuration. The detection limit of the refractive index change can be as low as 5 × 10⁻⁷ RIU which is estimated to be lower by 2 orders of magnitude, and the corresponding sensitivity of biomolecules has a 1000-fold increment compared with that of bare gold-based sensors.