Rational Selection of Nanorod Plasmons: Material, Size, and Shape Dependence Mechanism for Optical Sensors

The localized surface plasmon resonance dependence on surrounding medium refractive index of Ag, Al, Au, and Cu nanoparticles is examined by electrodynamic approach. The refractive index sensitivity and sensing figure of merit (FOM) dependence of selected metal nanoparticles with similar geometry shows that although, sensing relevant parameters are shape (i.e., aspect ratio), and material dependent below the width 20 nm, but above this size these parameters are material independent under similar geometrical conditions. We have concluded that at optimum size, however, Al shows much higher refractive index sensitivity (RIS) in comparison to Au, Cu, and Ag, but FOM is higher for Ag in comparison to other metals. The observed sensing behavior is expected due to parameters like surface scattering, dynamic depolarization, radiation damping, and interband transitions, which may influence the nanorod plasmons.     

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.     

The Effect of Aspect Ratio of Gold Nanorods on Cell Imaging with Two-Photon Excitation

To make the gold nanorod (AuNR) a better photoluminescence (PL) probe for cell imaging under two-photon excitation (TPE), the effect of the aspect ratio of AuNRs was studied. The AuNRs with the aspect ratios of 2.7, 3.2, 4.1, and 4.5 and correlated longitudinal surface plasmon resonance (LSPR) bands of 710, 760, 820, and 870 nm were compared. The approach of two-photon excited PL was used to measure the two-photon absorption cross section (TPACS) of these AuNRs in aqueous solutions. Under TPE of an 800-nm femtosecond laser, the TPACS of AuNRs with an aspect ratio of 3.2 was found to be the highest (about 3?×?10⁹ GM), and that of AuNRs (aspect ratio of 2.7) was only 1.5?×?10⁹ GM. The probe function of these two AuNRs was further compared in cell imaging studies using the human liver cancer cell (QGY) as the cell model. Both TPE PL image and confocal reflectance image of AuNR-loaded cells were acquired comparatively in measurements. The brightness and contrast of confocal reflectance images for these two AuNRs in cells are similar. In contrast, the PL images of cellular AuNRs (2.7) under TPE of 800 nm are weak but that of cellular AuNRs (3.2) is much better. These results show that when the LSPR band of AuNRs is coincided with the excitation wavelength, the TPACS of these AuNRs will be enhanced ensuring a good quality of cell imaging under TPE. The LSPR band is correlated to the aspect ratio of AuNRs. Therefore, in cell imaging studies with TPE, the aspect ratio effect of AuNRs should be taken into consideration.     

Design of Infrared Plasma Absorber with High Refractive Index Sensitivity

Three layers of periodic artificial metamaterial sensing structure (including the upper metal particles, intermediate dielectric layer, and the lower reflective layer) with ultra-narrow band absorption were designed. The resonance characteristics and sensing properties were analyzed by the finite difference time domain (FDTD) method. The effect of localized surface plasmon resonance (LSPR) was obviously observed at the resonance wavelength of 911 nm, and it achieves nearly perfect absorption of exceeding 98% with a full width at half maximum (FWHM) of 3.5 nm. In addition, a wavelength sensitivity of 542 nm/RIU with a figure of merit (FOM) of 155 was obtained in the refractive index (RI) range from 1.00 to 1.35, which has a wide range of applications. The results show that the proposed structure has high absorption and RI sensitivity, which is suitable for bioengineering and medical detection.

     

Investigation on the Sensitivity and FOM of Ag Nanoparticles and Nanoarrays

The localized surface plasmon resonance (LSPR) spectroscopy of Ag nanoparticles (NPs) is sensitive to the changes of the surrounding medium, which enables the NPs to serve as plasmonic nanosensors. In this paper, the refractive index (RI) sensitivity and figure of merit (FOM) of individual NPs and nanoarrays are investigated by employing the finite difference time domain (FDTD) method. The influence of shape and size are analyzed for individual NPs, and the influence of particle spacing is analyzed for nanoarrays. It is found that the NP with shorter size in incident direction or longer size in polarization direction exhibits better sensing performance. And when the a_eff is between 20 and 60 nm, the larger NP exhibits higher sensitivity but lower FOM. The results of nanoarrays show that when particle spacing is large, the sensitivity of nanoarrays is large, and the sensitivity of nanoarrays decreases first and then increases as particle spacing decreases. In addition, the FOM of nanoarrays exhibits the similar trend.

     

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.     

Quantification of a Cardiac Biomarker in Human Serum Using Extraordinary Optical Transmission (EOT)

Nanoimprinting lithography (NIL) is a manufacturing process that can produce macroscale surface areas with nanoscale features. In this paper, this technique is used to solve three fundamental issues for the application of localized surface plasmonic resonance (LSPR) in practical clinical measurements: assay sensitivity, chip-to-chip variance, and the ability to perform assays in human serum. Using NIL, arrays of 140 nm square features were fabricated on a sensing area of 1.5 mm x 1.5 mm with low cost. The high reproducibility of NIL allowed for the use of a one-chip, one-measurement approach with 12 individually manufactured surfaces with minimal chip-to-chip variations. To better approximate a real world setting, all chips were modified with a biocompatible, multi-component monolayer and inter-chip variability was assessed by measuring a bioanalyte standard (2.5−75 ng/ml) in the presence of a complex biofluid, human serum. In this setting, nanoimprinted LSPR chips were able to provide sufficient characteristics for a ‘low-tech’ approach to laboratory-based bioanalyte measurement, including: 1) sufficient size to interface with a common laboratory light source and detector without the need for a microscope, 2) high sensitivity in serum with a cardiac troponin limit of detection of 0.55 ng/ml, and 3) very low variability in chip manufacturing to produce a figure of merit (FOM) of 10.5. These findings drive LSPR closer to technical comparability with ELISA-based assays while preserving the unique particularities of a LSPR based sensor, suitability for multiplexing and miniaturization, and point-of-care detections.     

Enhancing LSPR Sensitivity of Au Gratings through Graphene Coupling to Au Film

A particular interesting plasmonic system is that of metallic nanostructures interacting with metal films. As the localized surface plasmon resonance (LSPR) behavior of gold nanostructures (Au NPs) on the top of a gold thin film is exquisitely sensitive to the spacer distance of the film-Au NPs, we investigate in the present work the influence of a few-layered graphene spacer on the LSPR behavior of the NPs. The idea is to evidence the role of few-layered graphene as one of the thinnest possible spacer. We first show that the coupling to the Au film induces a strong lowering at around 507 nm and sharpening of the main LSPR of the Au NPs. Moreover, a blue shift in the main LSP resonance of about 13 nm is observed in the presence of a few-layered graphene spacer when compared to the case where gold nanostructures are directly linked to a gold thin film. Numerical simulations suggest that this LSP mode is dipolar and that the hot spots of the electric field are pushed to the top corners of the NPs, which makes it very sensitive to surrounding medium optical index changes and thus appealing for sensing applications. A figure of merit of such a system (gold/graphene/Au NPs) is 2.8, as compared to 2.1 for gold/Au NPs. This represents a 33 % gain in sensitivity and opens-up new sensing strategies.     

Zirconium Nitride for Plasmonic Cloaking of Visible Nanowire Photodetectors

Light scattered by a photodetector disturbs the probing field, resulting in noise. Cloaking is an effective method to reduce this noise. Here we investigate theoretically an emerging plasmonic material, zirconium nitride (ZrN), as a plasmonic cloak for silicon (Si) nanowire-based photodetectors and compare it with a traditional plasmonic material, gold (Au). Using Mie formalism, we have obtained the scattering cancelation across the visible spectrum. We found that ZrN cloaks produce a significant decrease in the scattering from bare Si nanowires, which is 40% greater than that obtained with Au cloaks in the wavelength region of 400–500 nm. The scattering cancelations become comparable at 550 nm, with Au providing a better scattering cancelation compared to ZrN over the wavelength region of 600–700 nm. To include the absorption and provide a measure of overall performance on noise reduction, a figure of merit (FOM), defined as the ratio of the absorption efficiency and the scattering efficiency of the cloaked nanowire to that of the bare Si nanowire, was calculated. We show that the optimized ZrN cloak provides up to 3 times enhancement of the FOM over a bare Si NW and a 60% improvement over an optimized Au-cloaked NW, in the wavelength region of 400–500 nm. An optimized Au-cloaked NW shows up to 17.69 times improvement in the wavelength region of 600–700 nm over a bare Si NW and up to a 2.7 times improvement over an optimized ZrN-cloaked NW. We also predicted the optimal dimensions for the cloaked NWs with respect to the largest FOM at various wavelengths between 400 and 650 nm.

     

Ultrasmall Plasmonic Cavity for Chemical Sensing

We propose an ultrasmall plasmonic cavity based on the channel waveguides for chemical sensing. The plasmonic mode gap due to cutoff angular frequency enables strong optical confinement in a subwavelength volume and suppression of radiation loss. Due to strong field overlap of the surface plasmon polariton mode with environmental material, large sensitivity (1,100 nm/refractive index unit) and a high figure of merit (330) are achieved in the plasmonic cavity with a small physical size of 600?×?800?×?2,500 nm having a telecommunication resonant wavelength. This plasmonic cavity can introduce a broad range of applications including biochemical sensing and strong light–matter interactions.     

A High-Performance Refractive Index Sensor Based on Fano Resonance in Si Split-Ring Metasurface

We present a high-performance refractive index sensor based on Fano resonance with a figure of merit (FOM) about 56.5 in all-dielectric metasurface which consists of a periodically arranged silicon rings with two equal splits dividing them into pairs of arcs of different lengths. A Fano resonance with quality factor ~133 and spectral contrast ratio ~100% arises from destructive interference of two antiphase electric dipoles in the two arcs of the split-ring. We can turn on and/or off the Fano resonance with a modulation depth nearly 100% at the operating wavelength of 1067 nm by rotating the polarization of incident light. We believe that our results will open up avenues for the development of applications using Fano resonance with dynamically controllability such as biochemical sensors, optical switching, and modulator.     

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.     

Large Scale Fabrication of Gold Nano-Structured Substrates Via High Temperature Annealing and Their Direct Use for the LSPR Detection of Atrazine

The present work is reporting on the fabrication of localized surface plasmonic resonant (LSPR) gold nano-structures on glass substrate by using different high annealing temperatures (500 °C, 550 °C, 600 °C) of initially created semi-continue gold films (2 nm and 5 nm) by the electron beam evaporation technique. Interestingly, well-defined gold nano-structures were also obtained from continuous 8 nm evaporated gold film - known as the value above gold percolated thickness - once exposed to high temperatures. The surface morphology and plasmonic spectroscopy of “annealed” nano-structures were controlled by key experimental parameters such as evaporated film thickness and annealing temperature. By using scanning electron microscopy (SEM) characterization of annealed surface it was noticed that the size and inter-particle distance between nano-structures were highly dependent on the evaporated thin film thickness, while the nanoparticle shape evolution was mainly affected by the employed annealing temperature. Due to the well-controlled morphology of gold nano-particles, prominent and stable LSPR spectra were observed with good plasmon resonance tunability from 546 nm to 780 nm that recommend the developed protocol as a robust alternative to fabricate large scale LSPR surface. An example of a LSPR-immunosensor is reported. Thus, the monoclonal anti-atrazine antibodies immobilizion on the “annealed” gold nano-structures, as well as the specific antigen (atrazine) recognition were monitored as variations of the resonance wavelength shifts and optical density changes in the extinction measurements.     

Tailoring Plasmon Lifetime in Suspended Nanoantenna Arrays for High-Performance Plasmon Sensing

We demonstrate significantly longer plasmon lifetime and stronger electric field enhancement by lifting the nanoantenna arrays above the substrate by dielectric nanopillars. The role of the pillar is to offer a more homogeneous dielectric background allowing stronger diffraction coupling among plasmonic nanoantennas leading to a Fanolike asymmetric lineshape. It is found that the electric fields around the nanoantennas can be greatly enhanced when the Fanolike resonance is excited, and a 4.2 times enhancement is achieved compared with the pure resonance in individual nanoantennas. Furthermore, only a collective surface mode with its electric fields of the same direction as the induced electric moment in the nanoantennas could mediate the excitation of such a Fanolike resonance. More importantly, the sensitivity and the figure of merit (FOM) of this plasmonic structure can reach as high as 900 nm/RIU and 53, respectively. Our study offers a new, simple, and efficient way to design the plasmonic systems with desired electric field enhancement and spectral lineshape for different applications.     

Substrate-Independent Lattice Plasmon Modes for High-Performance On-Chip Plasmonic Sensors

We systematically study the lattice plasmon resonance structures, which are known as core/shell SiO₂/Au nanocylinder arrays (NCAs), for high-performance, on-chip plasmonic sensors using the substrate-independent lattice plasmon modes (LPMs). Our finite-difference time-domain simulations reveal that new modes of localized surface plasmon resonances (LSPRs) show up when the height-diameter aspect ratio of the NCAs is increased. The height-induced LSPRs couple with the superstrate diffraction orders to generate the substrate-independent LPMs. Moreover, we show that the high wavelength sensitivity and the narrow linewidth of the substrate-independent LPMs lead to the plasmonic sensors with high figure of merit (FOM) and high signal-to-noise ratio (SNR). In addition, the plasmonic sensors are robust in asymmetric environments for a wide range of working wavelengths. Our further study of both far- and near-field electromagnetic distribution in the NCAs confirms the height-enabled tunability of the plasmonic “hot spots” at the sub-nanoparticle resolution and the large field enhancement in the substrate-independent LPMs, which are responsible for the high FOM and SNR of the plasmonic sensors.     

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.     

Surface-Enhanced Raman Scattering in Tunable Bimetallic Core-Shell

In this paper, optical properties of multilayer spherical core-shell nanoparticles based on quasi-static approach and plasmon hybridization theory are investigated. Calculations show that light absorption spectrum of bimetallic multilayer core-shell has three intense plasmon resonance peaks, which are more suitable for multiplex biosensing based on surface-enhanced Raman scattering (SERS) and localized surface plasmon resonance (LSPR). The plasmon resonance peaks in bimetal nanshells are optimized by tuning the geometrical parameters. In addition, the optimal geometry is discussed to obtain the Raman enhancement factor in bimetallic multilayer nanoshell. SERS enhancement factor is calculated with consideration of dampings due to both the electron scattering and the radiation at the boundary and modified Drude model in dielectric function of bimetallic nanoshell. It is shown that bimetallic nanoshell with the small size exhibits strong SERS enhancement factor (~6.63 × 10⁵) with additional collision dampings and ~2.9 × 10⁹ with modified Drude model which are suitable for biosensing applications. In addition, any variation in blood concentration and oxygen level can be detected by this bimetallic core-shell nanoparticle with sensitivity of Δλ/Δn = 264.91 nm/RIU.     

Localized Surface Plasmon Resonance (LSPR) Biosensor for the Protein Detection

In this paper, we investigate the ability of the gold nanorods (GNRs) to detect some proteins and demonstrate their potential to be used as plasmonic nanobiosensors. The GNRs were synthesized by a two-step seed-mediated growth procedure at room temperature. Firstly, a seed solution of gold nanoparticles was synthesized in the presence of cetyltrimethylammonium bromide surfactant and, subsequently, incorporated with appropriate amount of silver nitrate and tetrachloroauric acid solutions to grow GNRs with average length of 50 nm and diameter of 14 nm. We study the interaction of GNRs with proteins whose molecular weight varies from 6.5 up to 75 kDa. We investigate the resulting solutions by means of UV–vis absorption spectroscopy to determine the effect of the proteins characteristics on the shift of the localized surface plasmon resonance (LSPR). We show that for the case when proteins are in large excess compared to the GNRs concentration, whatever the protein is, the LSPR shift is constant and does not depend on the protein molecular weight. Moreover, we have been able to demonstrate that the sensitivity of such LSPR sensor is around 10^–9 M/nm on a concentration range from 10^–10 to 10^–8 M. Some comparison with finite-difference time-domain simulations have also shown that the number of proteins adsorbed at the GNRs surface is around 40.     

Coupled-Resonator-Induced Fano Resonances for Plasmonic Sensing with Ultra-High Figure of Merits

Fano resonances are numerically predicted in an ultracompact plasmonic structure, comprising a metal-isolator-metal (MIM) waveguide side-coupled with two identical stub resonators. This phenomenon can be well explained by the analytic model and the relative phase analysis based on the scattering matrix theory. In sensing applications, the sensitivity of the proposed structure is about 1.1?×?10³ nm/RIU and its figure of merit is as high as 2?×?10⁵ at λ?=?980 nm, which is due to the sharp asymmetric Fano line-shape with an ultra-low transmittance at this wavelength. This plasmonic structure with such high figure of merits and footprints of only about 0.2 μm² may find important applications in the on-chip nano-sensors.     

Plasmonically Tunable Blue-Shifted Emission from Coumarin 153 in Ag Nanostructure Random Media: A Demonstration of Fast Dynamic Surface-Enhanced Fluorescence

Enhancement of intensity and wavelength tunability of emission are desirable features for light-emitting device applications. We report on the large and tunable blue shift (60 nm) in emission from an environment-sensitive fluorophore (Coumarin153) embedded in Ag plasmonic random media. Coumarin 153 having emission at 555 nm, show a systematic blue shift (to 542, 503 and 495 nm) upon infiltration into random media fabricated by Ag nanowires of different aspect ratio (hence, surface plasmon resonances at 426, 445 and 464 nm). The blue shift is due to the fast dynamic surface-enhanced fluorescence mechanism and can be tuned by controlling the surface plasmon resonance and hotspot density in random media. Enhanced emission at desired wavelength is achieved by using nanostructures having higher extinction coefficient but same-surface plasmon resonance. Ag nanostructures of different aspect ratio used for fabricating the random media are synthesized by chemical route.