Efficient Plasmonic Au/CdSe Nanodumbbell for Photoelectrochemical Hydrogen Generation beyond Visible Region

In this communication, light harvesting and photoelectrochemical (PEC) hydrogen generation beyond the visible region are realized by an anisotropic plasmonic metal/semiconductor hybrid photocatalyst with precise control of their topology and heterointerface. Controlling the intended configuration of the photocatalytic semiconductor to anisotropic Au nanorods' plasmonic hot spots, through a water phase cation exchange strategy, the site‐selective overgrowth of a CdSe shell evolving from a core/shell to a nanodumbbell is realized successfully. Using this strategy, tip‐preferred efficient photoinduced electron/hole separation and plasmon enhancement can be realized. Thus, the PEC hydrogen generation activity of the Au/CdSe nanodumbbell is 45.29 µmol cm^?2 h^?1 (nearly 4 times than the core/shell structure) beyond vis (λ > 700 nm) illumination and exhibits a high faradic efficiency of 96% and excellent stability with a constant photocurrent for 5 days. Using surface photovoltage microscopy, it is further demonstrated that the efficient plasmonic hot charge spatial separation, which hot electrons can inject into CdSe semiconductors, leads to excellent performance in the Au/CdSe nanodumbbell.     

Grating-based surface plasmon resonance detection of core-shell nanoparticle mediated DNA hybridization

In this report, we have investigated enhanced surface plasmon resonance (SPR) detection of DNA hybridization using gold core - silica shell nanoparticles in localized plasmonic fields. The plasmonic fields were localized by periodic linear gratings. Experimental results measured for hybridization of 24-mer single-stranded DNA oligomers suggest that core-shell nanoparticles (CSNPs) on gratings of 400 nm period provide enhanced optical signatures by 36 times over conventional thin film-based SPR detection. CSNP-mediated DNA hybridization produced 3 times larger angular shift compared to gold nanoparticles of the same core size. We have also analyzed the effect of structural variation. The enhancement using CSNPs was associated with increased surface area and index contrast that is combined by improved plasmon coupling with localized fields on gratings. The combined approach for conjugated measurement of a biomolecular interaction on grating structures is expected to lower the limit of detection to the order of a few tens of fg/mm(2).     

Plasmonic Biosensor Based on Triangular Au/Ag and Au/Ag/Au Core/Shell Nanoprisms onto Indium Tin Oxide Glass

Gold–silver core–shell triangular nanoprisms (Au/AgTNPs) were grown onto transparent indium tin oxide (ITO) thin film-coated glass substrate through a seed-mediated growth method without using peculiar binder molecules. The resulting Au/AgTNPs were characterized by scanning electron microscopy, atomic force microscopy, X-ray diffraction, UV–vis spectroscopy, and cyclic voltammograms. The peak of dipolar plasmonic resonance was located at near infrared region of ～700 nm, which showed the refractive index (RI) sensitivity of 248 nm/RIU. Moreover, thin gold shells were electrodeposited onto the surface of Au/AgTNPs in order to stabilize nanoparticles. Compared with the Au/AgTNPs, this peak of localized surface plasmon resonance (LSPR) was a little red-shift and decreased slightly in intensity. The refractive index sensitivity was estimated to be 287 nm/RIU, which showed high sensitivity as a LSPR sensing platform. Those triangular nanoprisms deposited on the ITO substrate could be further functionalized to fabricate LSPR biosensors. Results of this research show a possibility of improving LSPR sensor by using core–shell nanostructures.     

Broadband Enhancement of PbS Quantum Dot Solar Cells by the Synergistic Effect of Plasmonic Gold Nanobipyramids and Nanospheres

For the first time, the plasmonic gold bipyramids (Au BPs) are introduced to the PbS colloidal quantum dot (CQD) solar cells for improved infrared light harvesting. The localized surface plasmon resonance peaks of Au BPs matches perfectly with the absorption peaks of conventional PbS CQDs. Owing to the geometrical novelty of Au BPs, they exhibit significantly stronger far‐field scattering effect and near‐field enhancement than conventional plasmonic Au nanospheres (NSs). Consequently, device open‐circuit voltage (V_oc) and short‐circuit current (J_sc) are simultaneously enhanced, while plasmonic photovoltaic devices based on Au NSs only achieve improved J_sc. The different effects and working mechanisms of these two Au nanoparticles are systematically investigated. Moreover, to realize effective broadband light harvesting, Au BPs and Au NSs are used together to simultaneously enhance the device optical and electrical properties. As a result, a significantly increased power conversion efficiency (PCE) of 9.58% is obtained compared to the PCE of 8.09% for the control devices due to the synergistic effect of the two plasmonic Au nanoparticles. Thus, this work reveals the intriguing plasmonic effect of Au BPs in CQD solar cells and may provide insight into the future plasmonic enhancement for solution‐processed new‐generation solar cells.     

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.     

Fluorescent (Au@SiO2)SiC Nanohybrids: Influence of Gold Nanoparticle Diameter and SiC Nanoparticle Surface Density

Gold@silica core–shell nanoparticles were prepared with various gold core diameters (ranging from 20 to 150 nm) and silica thicknesses (ranging from 10 to 30 nm). When the gold diameter is increased, the size dispersion became larger, leading to a broader plasmon band. Then, silicon carbide (SiC) nanoparticles were covalently immobilized onto silica to obtain hybrid (Au@SiO₂) SiC nanoparticles. The absorption properties of these hybrid nanoparticles showed that an excess of SiC nanoparticles in the dispersion can be identified by a strong absorption in the UV region. Compared to SiC reference samples, a blue shift of the fluorescence emission, from 582 to 523 nm, was observed, which was previously attributed to the strong surface modification of SiC when immobilized onto silica. Finally, the influence of several elaboration parameters (gold diameter, silica thickness, SiC concentration) on fluorescence enhancement was investigated. It showed that the highest enhancements were obtained with 10 nm silica thickness, low concentration of SiC nanoparticles, and surprisingly, with a 20-nm gold core diameter. This last result could be attributed to the broad plasmon band of big gold colloids. In this case, SiC emission strongly overlapped gold absorption, leading to possible quenching of SiC fluorescence by energy transfer.     

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.     

Plasmonic Perovskite Solar Cells Utilizing Au@SiO<Subscript>2</Subscript> Core-Shell Nanoparticles

The role of Au@SiO₂ core-shell nanoparticles on optical properties of perovskite solar cells has been explored using both the theoretical computations and the experiments. A quasi-static model is used to study the surface plasmon resonances (SPRs) of Au@SiO₂ core-shell nanospheres. Au@SiO₂ core-shell nanoparticles, with varying shell thickness and core radius, were assumed to be embedded in methylammonium lead triiodide (CH₃NH₃PbI₃) perovskite active layer. Enhanced absorption in the active layer is obtained due to the near-field plasmonic effect of the embedded core-shell nanoparticles. Theoretical modelling shows that a shell thickness of 1 nm and core diameter of 20 nm provide absorption enhancement in the orange-red region of the electromagnetic spectrum. Experiments performed using ～20-nm-sized Au@SiO₂ core-shell nanoparticles (with a shell thickness of ～1 nm) clearly demonstrate the enhanced absorption and the resulting enhancement in photocurrent due to the plasmonic effects. An efficiency enhancement of over 18 % is obtained for the best plasmonic perovskite solar cell containing Au@SiO₂ nanoparticles in Au@SiO₂-TiO₂ weight ratio of ～1 %. Incident photon-to-current conversion efficiency (IPCE) data also showed enhancement in photocurrent for the plasmonic device. The quasi-static modelling approach provides a good correlation between theory and experiment.     

Elucidating the Sole Contribution from Electromagnetic Near‐Fields in Plasmon‐Enhanced Cu2O Photocathodes

Despite many promising reports of plasmon‐enhanced photocatalysis, the inability to identify the individual contributions from multiple enhancement mechanisms has delayed the development of general design rules for engineering efficient plasmonic photocatalysts. Herein, a plasmonic photocathode comprised of Au@SiO₂ (core@shell) nanoparticles embedded within a Cu₂O nanowire network is constructed to exclusively examine the contribution from one such mechanism: electromagnetic near‐field enhancement. The influence of the local electromagnetic field intensity is correlated with the overall light‐harvesting efficiency of the device through variation of the SiO₂ shell thickness (5–22 nm) to systematically tailor the distance between the plasmonic Au nanoparticles and the Cu₂O nanowires. A threefold increase in device photocurrent is achieved upon integrating the Au@SiO₂ nanoparticles into the Cu₂O nanowire network, further enabling a 40% reduction in semiconductor film thickness while maintaining photocathode performance. Photoelectrochemical results are further correlated with photoluminescence studies and optical simulations to confirm that the near‐field enhancement is the sole mechanism responsible for increased light absorption in the plasmonic photocathode.     

Tunable Properties of Surface Plasmon Resonances: The Influence of Core–Shell Thickness and Dielectric Environment

In the present study, we have investigated the extinction spectra of coated sphere (using dipole model) with different core–shell radius, in which the core is TiO₂ and the shell is made up of silver or gold nanoparticles. Nanoparticles exhibit surface plasmon resonance peak; these plasmonic peaks are highly tunable in wavelength range of 300 to 1,100 nm; in fact, the blue and red shifting of resonance peak highly depends on the core–shell thickness. The broadness of resonance peaks are analysed in terms of full width at half maxima (FWHM), and the width of these resonance peaks is also the function of core–shell radius.     

The Effect of Ag Nanoparticles on Surface-Enhanced Luminescence from Au Nanovoid Arrays

Studies comparing the effect of adding two different nanoparticle compositions on the plasmonic properties of Au nanovoid arrays were undertaken. Surface-enhanced resonance luminescence and surface-enhanced resonance Raman studies comparing dispersed Ag nanoparticles and Ag nanoparticle aggregates on gold nanovoid arrays were undertaken. These studies showed that using Ag nanoparticle aggregates increased both luminescence and Raman efficiency relative to when dispersed nanoparticles were used; in addition, these studies also showed that adding dispersed Ag nanoparticles supported a more reproducible enhancement in luminescence and Raman across the substrate compared to using Ag nanoparticle aggregates. Finite element analysis simulations indicated that surface plasmon polariton distribution in the sample was affected by the presence of the Ag nanoparticles on the Au nanovoid array.     

Optimization of Nanoparticle Size for Plasmonic Enhancement of Fluorescence

This paper reports on the enhancement of fluorescence that can result from the proximity of fluorophores to metallic nanoparticles (NPs). This plasmonic enhancement, which is a result of the localized surface plasmon resonance at the metal surface, can be exploited to improve the signal obtained from optical biochips and thereby lower the limits of detection. There are two distinct enhancement effects: an increase in the excitation of the fluorophore and an increase in its quantum efficiency. This study focuses on the first of these effects where the maximum enhancement occurs when the NP plasmon resonance wavelength coincides with the fluorophore absorption band. In this case, the excitation enhancement is proportional to the square of the amplitude of the electric field. The scale of the enhancement depends on many parameters, such as NP size and shape, metal type, and NP–fluorophore separation. A model system consisting of spherical gold/silver alloy NPs, surrounded by a silica spacer shell, to which is attached a fluorescent ruthenium dye, was chosen and the dependence of the fluorescence enhancement on NP diameter was investigated. Theoretical calculations, based on Mie theory, were carried out to predict the maximum possible enhancement factor for spherical NPs with a fixed composition and a range of diameters. Spherical NPs of the same composition were fabricated by chemical preparation techniques. The NPs were coated with a thin silica shell to overcome quenching effects and the dye was attached to the shell.     

Near-Infrared Absorption Enhancement Mechanism Investigations of Deep-Trench Silicon Microstructures Covered with Gold Films

We design a deep-trench microstructure covered with thin gold films to enhance near-infrared absorption of silicon material. This deep-trench microstructure exhibits a much higher absorption compared with plane nanoantenna arrays. We investigate its absorption enhancement in detail and find that the trench-shaped plasmonic waveguide greatly contributes an absorption enhancement by concentrating light effectively. Further, we clarify the influence of both trench depth and gold films covering on different positions of deep trench on the absorption. Finally, we use surface plasmon polaritons offered by plasmonic waveguide to explain well the significant enhancement of near-infrared absorption.     

Plasmonic Properties of Gold Nanostructures on Gold Film

This paper reports on a systematic study of the plasmonic properties of periodic arrays of gold cylindrical nanoparticles in contact with a gold thin film. Depending on the gold film thickness, it observes several plasmon bands. Using a simple analytical model, it is able to assign all these modes and determine that they are due to the coupling of the grating diffraction orders with the propagating surface plasmons travelling along the film. With finite difference time domain (FDTD) simulations, it demonstrates that large field enhancement occurs at the surface of the nanocylinders due to the resonant excitation of these modes. By tilting the sample, it also observes the evolution of the spectral position of these modes and their tuning through nearly the whole visible range is possible. Such plasmonic substrates combining both advantages of the propagative and localised surface plasmons could have large applications in enhanced spectroscopies.

     

Numerical Study of Plasmonic Effects of Ag Nanoparticles Embedded in the Active Layer on Performance Polymer Organic Solar Cells

In this paper, the light absorption in the active layer of polymer solar cells (OPV) by using plasmonic nanocrystals with a hexagonal lattice structure is investigated. To study the relationship between the performance of the OPV solar cell and its active layer, a three-dimensional model of its morphology is utilized. Therefore, the three-dimensional (3D) finite-difference time-domain method and Lumerical software were used to measure the field distribution and light absorption in the active layer in terms of wavelength. OPV solar cells with bilayer and bulk heterojunction structured cells were designed using hexagonal lattice crystals with plasmonic nanoparticles, as well as core–shell geometry to govern a design to optimize light trapping in the active layer. The parameters of shape, material, periodicity, size, and the thickness of the active layer as a function of wavelength in OPV solar cells have been investigated. A very thin active layer and an ultra-thin shell were used to achieve the highest increase in optical absorption. The strong alternating electromagnetic field around the core–shell plasmonic nanoparticles resulting from the localized surface plasmon resonance (LSPR) suggested by the Ag plasmonic nanocrystals increased the intrinsic optical absorption in the active layer poly(3-hexylthiophene):phenyl-C61-butyric acid methyl ester (P3HT:PCBM). Based on the photovoltaic results, the short circuit current ranged from 19.7 to 26.7 mA/cm².

     

Intracellular Localized Surface Plasmonic Sensing for Subcellular Diagnosis

This paper proposes a method for diagnosing intracellular conditions and organelles of cells with localized surface plasmonic resonance (LSPR) by directly internalizing the gold nanoparticles (AuNPs) into the cells and measuring their plasmonic properties through hyperspectral imaging. This technique will be useful for direct diagnosis of cellular organelles, which have potential for cellular biology, proteomics, pharmaceuticals, drug discovery etc. Furthermore, localization and characterization of citrate-capped gold nanoparticles in HeLa cells were studied, by hyperspectral microscopy and other imaging techniques. Here, we present the method of internalizing the gold nanoparticles into the cells and subcellular organelles to facilitate subcellular plasmonic measurements. An advanced label-free visualization technique, namely hyperspectral microscopy providing images and spectral data simultaneously, was used to confirm the internalization of gold nanoparticles and to reveal their optical properties for possible intracellular plasmonic detection. Hyperspectral technology has proved to be effective in the analysis of the spectral profile of gold nanoparticles, internalized under different conditions. Using this relatively novel technique, it is possible to study the plasmonic properties of particles, localized in different parts of the cell. The position of the plasmon bands reflects the interactions of gold nanoparticles with different subcellular systems, including particle-nucleus interactions. Our results revealed the effect of the different intracellular interactions on the aggregation pattern of gold nanoparticles, inside the cells. This novel technique opens the door to intracellular plasmonics, an entirely new field, with important potential applications in life sciences. Similarly, the characterization of AuNP inside the cell was validated using traditional methods such as light microscopy and scanning electron microscopy. Under the conditions studied in this work, gold nanoparticles were found to be non-toxic to HeLa (cervical cancer) cells.     

Correlating Metal-Enhanced Fluorescence and Structural Properties in Ag@SiO2 Core-Shell Nanoparticles

Metal@silica concentric nanoparticles capable of metal-enhanced fluorescence (MEF) represent a powerful means to improve the brightness and stability of encapsulated organic fluorophores and are finding numerous applications in biology, analytical chemistry, and medical diagnostics. The rational design of MEF-enabled labels and sensors often involves comparing fluorescence enhancement factors (EF) between nanostructures having different structural properties (e.g., metal core diameter, silica shell thickness, extent of spectral overlap between plasmon band and fluorophore). Accurate determination of EFs requires the measurement of fluorescence emission intensity in the presence and absence of the plasmonic core while minimizing the impact of physical and chemical artifacts (e.g., signal variations due to scattering, adsorption, sedimentation). In this work, Ag@SiO₂@SiO₂ + x (where x is fluorescein, eosin, or rhodamine B) nanostructures were synthesized with excellent control of core size, silica spacer shell thickness and fluorophore concentration. Using UV-VIS spectrometry, spectrofluorimetry, time-resolved fluorometry, and transmission electron microscopy, we investigated the influence of these key structural factors on fluorescence emission intensity, and the results were used to develop a generalized methodology for the determination of fluorescence enhancement factors in Ag@SiO₂ core-shell nanoparticles. This methodology should be of general importance to designing MEF-enabled nanostructures, sensors, and related analytical techniques.

     

Optical and Thermal Enhancement of Plasmonic Nanofluid Based on Core/Shell Nanoparticles

The plasmonic effect is introduced in solar thermal areas to enhance light harvest and absorption. The optical properties of plasmonic nanofluid are simulated by finite difference time domain (FDTD) method. Due to the excitation of localized surface plasmon resonance (LSPR) effect, an intensive absorption peak is observed at 0.5 μm. The absorption characteristics are sensitive to particle size and concentration. As the particle size increases, the absorption peak is broadened and shifted to longer wavelength. The absorption of SiO₂/Ag plasmonic nanofluid is improved gradually as the volume concentration increases, especially in the UV region. The absorption edge is shifted from 0.6 to 1.0 μm as the volume concentration increases from 0.001 to 0.01. The thermal simulation of suspended SiO₂/Ag nanoparticle shows a uniform temperature rise of 17.91 K under solar irradiation (AM 1.5), while under the same condition, the temperature rises in Ag nanoparticle and Al nanoparticle are 11.12 and 5.39 K, respectively. The core/shell plasmonic nanofluid exhibits a higher photothermal performance, which has a potential application in photothermal areas. A higher temperature rise can be obtained by improving the incident light intensity or optical absorption properties of nanoparticles.     

Enhancement of Extraordinary Optical Transmission in a Double Heterostructure Plasmonic Bandgap Cavity

In this paper, a novel plasmonic bandgap cavity inducing the enhancement of extraordinary optical transmission is presented. Numerical simulations have been performed to model a free-standing structure made of a one-dimensional periodic arrangement of gold strips. Two different values of the lattice constant have been properly chosen to realize a double heterostructure-like cavity to accomplish extraordinary optical transmission assisted by the formation of a plasmonic bandgap in the adjacent regions. Numerical results prove the capability of this optical device to efficiently transmit input light beams with far-field transmission values close to 100% due to the excitation of surface plasmon polariton resonant modes.     

Plasmonic Spectral Detection of Carcinoembryonic Antigen by Preventing the Direct Binding of Rhodamine 6G with Au Nanoparticles

Carcinoembryonic antigen (CEA) was used as a separator to prevent the Rhodamine 6G (R6G)-induced aggregation of colloidal gold nanoparticles. The destroyed aggregation has been monitored by measuring the absorption and resonance light scattering peaks corresponding to the longitudinal surface plasmon resonance (SPR) of the chain-like aggregated gold nanoparticles (AuNPs). It was found that the pre-adding of CEA with different concentrations to the gold colloids before mixing them with R6G could lead to the longitudinal SPR peak decrease and blue shift. By analysing the intensity changing and wavelength shifting of the absorption spectra, CEA could be detected in a linear range from 0.2 to 4 ng/mL, and the limit of detection reaches to 0.1 ng/mL. The sensitivity of the CEA concentration dependent shifting and quenching of the plasmonic absorption and scattering corresponding to the AuNPs aggregation presents a well potential application of biologic spectral sensing.