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.     

Dielectric Nanocup Coating Effect on the Resonant Optical Properties of Individual Au Nanosphere

By finite element method (FEM), dielectric nanocup coating effect on the resonant optical properties of individual Au nanosphere was investigated. It is demonstrated not deleterious to the sensing signals of the nanosphere. The proposed nanocomposite provides an interesting localized surface plasmon resonance (LSPR) sensor with quadratic response, which refractive index (RI) sensitivity is revealed to increase with the RI both of its surrounding and local environment. The differences between the LSPR peak positions of the nanocomposite measured from far-field and near-field spectra are discussed, too. It is believed to shed light on the future applications in surface enhanced Raman spectroscopy, biochemical sensing, and detections.     

Gold Nanoring Arrays for Near Infrared Plasmonic Biosensing

Gold nanoring array surfaces that exhibit strong localized surface plasmon resonances (LSPR) at near infrared (NIR) wavelengths from 1.1 to 1.6 μm were used as highly sensitive real-time refractive index biosensors. Arrays of gold nanorings with tunable diameter, width, and spacing were created by the nanoscale electrodeposition of gold nanorings onto lithographically patterned nanohole array conductive surfaces over large areas (square centimeters). The bulk refractive index sensitivity of the gold nanoring arrays was determined to be up to 3,780 cm⁻¹/refractive index unit by monitoring shifts in the LSPR peak by FT-NIR transmittance spectroscopy measurements. As a first application, the surface polymerization reaction of dopamine to form polydopamine thin films on the nanoring sensor surface from aqueous solution was monitored with the real-time LSPR peak shift measurements. To demonstrate the utility of the gold nanoring arrays for LSPR biosensing, the hybridization adsorption of DNA-functionalized gold nanoparticles onto complementary DNA-functionalized gold nanoring arrays was monitored. The adsorption of DNA-modified gold nanoparticles onto nanoring arrays modified with mixed DNA monolayers that contained only 0.5 % complementary DNA was also detected; this relative surface coverage corresponds to the detection of DNA by hybridization adsorption from a 50 pM solution.

     

Refractive Index Sensitivity Analysis of Ag, Au, and Cu Nanoparticles

The localized surface plasmon resonance (LSPR) spectrum of noble metal nanoparticles is studied by quasi-static approximation. Taking the sensitivity of LSPR shape to the size and shape of nanoparticle along with surrounding refractive index, parameters like refractive index sensitivity and sensing figure of merit have been determined. In the present analysis from the sensing relevant parameters, it is concluded that Ag represents a better sensing behavior than Au and Cu over the entire visible to infrared regime of EM spectrum.     

Surface Plasmon-Enhanced Spontaneous Emission from InGaN/GaN Multiple Quantum Wells by Indium Nanoparticles Fabricated Using Nanosphere Lithography

Economic nanofabrication of Ag, Al, Au nanotriangle arrays and In nanoparticle arrays are demonstrated using nanosphere lithography. The sizes of the nanoparticles are precisely tuned when nanospheres with different diameters are used. Localized surface plasmon resonances (LSPR) of the nanoparticle arrays are observed to be strongly dependent on their sizes and the LSPR of In nanoparticle arrays with various sizes cover the whole visible spectrum. By placing In nanoparticle arrays near the InGaN/GaN multiple quantum wells (MQWs), enhanced spontaneous emission is observed when the LSPR of the In nanoparticles matches the emission wavelength of InGaN/GaN MQWs.     

LSPR Sensor Combining Sharp Resonance and Differential Optical Measurements

A new optical sensor based on the localized surface plasmon resonance (LSPR) in 2D arrays of silver nanoparticles (AgNPs) combined with a differential optical measurement method is developed. LSPR substrates comprised of self-assembled, 2D arrays of AgNPs exhibit coherent plasmon coupling manifested as a sharp peak in the blue spectral region. A bottom-up approach was used to fabricate reproducible and cost-effective substrates with a figure of merit (FOM) of ~24. The LSPR shift was determined by measuring the difference between light extinction at two wavelengths selected on each side of the sharp peak. The sharpness of the coherent plasmon resonance together with the differential measurement method enabled a record sensing resolution in bulk for a LSPR sensor of ~4.8E-6 RIU.     

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.     

Tailoring LSPR-Based Absorption and Scattering Efficiencies of Semiconductor-Coated Au nanoshells

Absorption and scattering efficiencies of semiconductor-coated Au nanoshell have been studied by the extended Mie theory for their possible solar cell, optical imaging, and photothermal applications, etc. The effect of Au shell layer thickness, core size, and surrounding medium on the absorption and scattering efficiencies at the localized surface plasmon resonance (LSPR) wavelengths has been reported. It has been found that both the absorption and scattering efficiencies get blue-shifted with an increase in Au shell layer thickness from 2 to 10 nm and with an increase in surrounding refractive index whereas the corresponding LSPR peaks shift towards red. It has also been found that the spectra are red-shifted with an increase in the core radius from 20 to 40 nm while keeping the shell thickness same. The effect of shell thickness on the absorption peak position and absorption linewidth has also been studied. Hence, the optical response of both CdSe- and CdTe-coated Au nanoshells can be tuned and controlled from the visible to the near-infrared (NIR) region of the electromagnetic (EM) spectrum. Finally, the CdSe-coated Au nanoshell exhibits high scattering and absorption efficiencies in comparison to the CdTe-coated nanoshell.     

Individual Split Au Square Nanorings for Surface-Enhanced Raman and Hyper-Raman Scattering

In this paper, individual split Au square nanorings were numerically proposed as novel substrates for surface-enhanced Raman and hyper-Raman scattering (SERS and SEHRS) simultaneously. The peak wavelengths of their localized surface plasmon resonance (LSPR) fall in the near-infrared and visible light regions, respectively, which are able to be finely tuned to match well with the wavelengths of the incident laser and hyper-Raman scattered light beams. Their SEHRS and SERS performances along with electromagnetic (EM) field distributions are numerically investigated by finite element method. With the enhancement of near electric-fields generated by LSPRs, the maximum SEHRS and SERS enhancement factors are demonstrated to reach 1.22?×?10¹² and 10⁸, respectively. Meanwhile, the corresponding SERS-based refractive index (RI) sensitivity factor reaches as high as 258 nm/RIU and 893 nm/RIU, at visible and near-infrared wavelengths, respectively. The proposed structure holds great promise both for developing SEHRS- and SERS-based RI sensing substrates, which shows strong potential applications in nanosensing and enhanced Raman scattering.

     

Nanostructure shape effects on response of plasmonic aptamer sensors

A localized surface plasmon resonance (LSPR) sensor surface was fabricated by the deposition of gold nanorods on a glass substrate and subsequent immobilization of the DNA aptamer, which specifically bind to thrombin. This LSPR aptamer sensor showed a response of 6‐nm λ_max shift for protein binding with the detection limit of at least 10 pM, indicating one of the highest sensitivities achieved for thrombin detection by optical extinction LSPR. We also tested the LSPR sensor fabricated using gold bipyramid, which showed higher refractive index sensitivity than the gold nanorods, but the overall response of gold bipyramid sensor appears to be 25% less than that of the gold nanorod substrate, despite the approximately twofold higher refractive index sensitivity. XPS analysis showed that this is due to the low surface density of aptamers on the gold bipyramid compared with gold nanorods. The low surface density of the aptamers on the gold bipyramid surface may be due to the effect of shape of the nanostructure on the kinetics of aptamer monolayer formation. The small size of aptamers relative to other bioreceptors is the key to achieving high sensitivity by biosensors on the basis of LSPR, demonstrated here for protein binding. The generality of aptamer sensors for protein detection using gold nanorod and gold nanobipyramid substrates is anticipated to have a large impact in the important development of sensors toward biomarkers, environmental toxins, and warfare agents. Copyright © 2013 John Wiley & Sons, Ltd.     

Self-Referencing Plasmonic Array Sensors

A self-referencing plasmonic platform is proposed and analyzed. By introducing a thin gold layer below a periodic two-dimensional nano-grating, the structure supports multiple modes including localized surface plasmon resonance (LSPR), surface plasmon resonance (SPR), and Fabry-Perot resonances. These modes get coupled to each other creating multiple Fano resonances. A coupled mode between the LSPR and SPR responses is spatially separated from the sensor surface and is not sensitive to refractive index changes in the surrounding materials or surface attachments. This mode can be used for self-referencing the measurements. In contrast, the LSPR dominant mode shifts in wavelength when the refractive index of the surrounding medium is changed. The proposed structure is easy to fabricate using conventional lithography and electron beam deposition methods. A bulk sensitivity of 429 nm/RIU is achieved. The sensor also has the ability to detect nanometer thick surface attachments on the top of the grating.

     

Localized Surface Plasmon Resonance and Refractive Index Sensitivity of Metal–Dielectric–Metal Multilayered Nanostructures

The localized surface plasmon resonances of multilayered nanostructures are studied using finite difference time domain simulations and plasmon hybridization method. Concentric metal–dielectric–metal (MDM) structure with metal core and nanoshell separated by a thin dielectric layer exhibits a strong coupling between the core and nanoshell plasmon resonance modes. The coupled resonance mode wavelengths show dependence on the dielectric layer thickness and composition of core and outer layer metal. The aluminum-based MDM structures show lower plasmon wavelength compared with Ag- and Au-based MDM nanostructures. The calculated refractive index sensitivity (RIS) factor is in the order Ag–Air–Ag>Au–Air–Au>Al–Air–Al for monometallic multilayered nanostructures. Bimetallic multilayered nanostructures support strong and tunable plasmon resonance wavelengths as well as high RIS factor of 510 nm/refractive index unit (RIU) and 470 nm/RIU for Al–Air–Au and Ag-Air-Au, respectively. The MDM structures not only exhibit higher index sensitivity but also cover a wide ultraviolet–near-infrared wavelengths, making these structures very promising for index sensing, biomolecule sensing, and surface-enhanced Raman spectroscopy.     

Scattering Efficiency and LSPR Tunability of Bimetallic Ag,Au, and Cu Nanoparticles

Scattering efficiencies of Ag–Cu, Ag–Au, and Au–Cu alloy nanoparticles are studied based on Mie theory for their possible applications in solar cells. The effect of size (radius), surrounding medium, and alloy composition on the scattering efficiency at the localized surface plasmon resonance (LSPR) wavelengths has been reported. In the alloy nanoparticles of Ag_1?x Cu _x , Au_1?x Cu _x and Ag_1?x Au _x ; the scattering efficiency gets red-shifted with increase in x. Moreover, the scattering efficiency enhancement can be tuned and controlled with both the alloy composition and the surrounding medium refractive index. A linear relationship which is in good agreement to the experimental observations between the scattering efficiency and metal composition in the alloys are found. The effect of nanoparticle size and LSPR wavelength (scattering peak position) on the full width half maxima and scattering efficiency has also been studied. Comparison of Au–Ag, Au–Cu, and Ag–Cu alloy nanoparticles with 50-nm radii shows the optical response of Ag–Cu alloy nanoparticle with wide bandwidth in the visible region of the electromagnetic spectrum making them suitable for plasmonic solar cells. Further, the comparison of Ag–Cu alloy and core@shell nanoparticles of similar size and surrounding medium shows that Cu@Ag nanoparticle exhibits high scattering efficiency with nearly the same bandwidth.     

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.

     

Improvement of Figure of Merit for Gold Nanobar Array Plasmonic Sensors

We report a strategy to improve two types of the figure of merit (FOM and FOM*) of the refractive index sensitivity of a gold nanobar array localized surface plasmon resonance (LSPR) biosensor by simply placing it close to a thin gold film with a dielectric spacer. The thickness of the dielectric spacer determines the plasmon coupling strength between the gold nanobars and the gold film and consequently the FOM and FOM* of the biosensor. From our calculations, when the spacer thickness is 20 nm, the FOM and FOM* reach maximal (4.68 and 310, respectively) and the sensitivity remains at a high value of 600 nm per refractive index unit. This biosensor scheme is practically realizable, and this strategy is also potentially applicable to the LSPR biosensors with other geometries.     

Application of chromogenic reagents in surface plasmon resonance (SPR)

In this paper, a new simple approach for sensitivity optimization in surface plasmon resonance (SPR) chemosensors based on colorimetric ligands is presented. A new design of SPR sensor with tunable analytical wavelength (lambda(SPR)) was constructed for this purpose, to perform studies on the ligand absorbance spectra related sensitivity enhancement. Unlike commercial SPR sensors which operate at one lambda(SPR), the new device can be used for sensitivity analysis at selected lambda(SPR) in the range 550-750 nm, offering the possibility to identify the highest sensitivity lambda(SPR) in regard to the spectral changes of the selected ligand. Measurements can be easily done in ligand bulk solutions without immobilization steps. Sensitivity enhancement analysis and optimization of lambda(SPR) on chromogenic reagents with hypsochromic shift in their absorption spectra are demonstrated in this contribution. Optimal selection of analytical wavelength, set at the absorbance peak of chromogenic reagent Eriochrome Black T (EBT) was observed to result in up to two times increased SPR sensitivity to Cd(2+) compared to wavelengths selected in other parts of the ligand absorbance spectra, with a limit of detection (LOD) 0.2 ppm. The sensitivity enhancement at optimal lambda(SPR) was observed to be related to increased refractive index (n), drop in extinction coefficient (alpha) and simultaneous hypsochromic shift of the EBT absorbance spectra causing the lambda(SPR) to match the absorbance peak shoulder.     

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.     

Numerical Simulation of Extinction Spectra of Plasmonically Coupled Nanospheres Using Discrete Dipole Approximation: Influence of Compositional Asymmetry

We demonstrate plasmon coupling phenomenon between equivalent (homodimer) and non-equivalent (heterodimer) spherical shape noble metal nanoparticle (Ag, Au and Al). A systematic comparison of surface plasmon resonance (SPR) and extinction properties of various configurations (monomer, homodimer and heterodimer) has been investigated to observe the effect of compositional asymmetry. Numerical simulation has been done by using discrete dipole approximation method to study the optical properties of plasmonically coupled metal nanoparticles (MNPs). Plasmon coupling between similar nanoparticles allows only higher wavelength bonding plasmon mode while both the plasmon modes lower wavelength antibonding mode as well as higher wavelength bonding mode in the case of heterodimer. Au monomer of radius 50 nm shows resonance peak at 518 nm while plasmon coupling between Au-Au homodimer results in a spectral red shift around 609 nm. Au-Ag plasmonic heterodimer (radius 50 nm) reveals two resonant modes corresponding to higher energy antibonding mode (422 nm) as well as lower energy bonding mode (533 nm). Further, we have shown that interparticle edge-to-edge separation is the most significant parameter affecting the surface plasmon resonances of MNPs. As the inter particle separation decreases, resonance wavelength shows red spectral shift which is maximum for the touching condition. It is shown that plasmon coupling is a reliable strategy to tune the SPR.

     

Plasmonic Perfect Absorbers for Biosensing Applications

We present a theoretical modal investigation of plasmonic perfect absorbers (PPAs) based on the localized surface plasmon resonance (LSPR) for biosensing applications. We design the PPA geometry with a layer of periodic metallic nanoparticles on one side of a dielectric substrate and a single metallic layer on the opposite side. The electromagnetic (EM) fields confine partly in the surrounding medium above the substrate and within the substrate itself. We examine the modes of the PPA geometry for a wavelength range of 600–1500 nm. The fundamental mode of the system provides perfect absorption for a wide angle of incidence 0–70°. The second-order mode shows a strong angular dependence with a sharp resonance and exhibits perfect optical absorption when the critical coupling condition for LSPR is achieved. The coupling condition depends on the size, periodicity, dielectric spacer, and the surrounding material of the system. The strong dependence on the surrounding material makes it a promising candidate for biosensing applications. We introduce a novel approach to investigate the angular dependence of the refractive index change for the PPA system. This novel technique contributes the significant attributes of the LSPR sensors, can be used for any required resonance wavelength depending on geometric design, and it also provides sensitivity analogous to the standard surface plasmon resonance (SPR) biosensors.     

Dependence of Apertureless Scanning Near-Field Spectroscopy on Nanoscale Refractive Index Changes

We numerically investigate the spectral dependence of the electric field enhancement on a gold tip above PbTiO₃ on platinum systems by means of a finite element approach. The localized surface plasmon resonance (LSPR) is verified to change with the incident angle, the tip radius, and the tip-sample distance as well as with the refractive index of the sample underneath the tip. The refractive index sensitivity reveals detectable variations of the LSPR peak’s wavelength and maximum field enhancement, respectively, large enough to discriminate, e.g., between ferroelectric and paraelectric PbTiO₃ in tip-enhanced Raman spectroscopy (TERS) configuration.