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.     

Optimal Dimensions of Gold Nanorod for Plasmonic Nanosensors

Localized surface plasmon resonance (LSPR) for longitudinal mode of gold nanorod is simulated by using Gans theory. The parameters like surface scattering, radiation damping, and dynamic depolarization of radiation across the surface of nanorod affecting response of free electrons towards optical excitation are considered. Simulation results show that refractive index sensitivity linearly rises with size and aspect ratio, whereas this leads to the broadening of resonant line width also. Therefore, to optimize the size of nanorod, figure of merit (FOM) is calculated and observed that optimized width is 15 nm for an aspect ratio of 2, whereas it is 12 nm for aspect ratios 3 and 4. Further, optimization by using newly modified figure of merit (MFOM) shows that optimized width is 39 nm for aspect ratio of 2 and 24 nm for 3 and 4 aspect ratios. It is also found that at aspect ratio 2, both FOM and MFOM are higher than the aspect ratios 3 and 4. The quality factor calculation for LSPR response of nanorod explains its dependence with aspect ratio and optimized dimensions.     

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.     

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.     

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.     

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.     

A label-free immunosensor for determination of salbutamol based on localized surface plasmon resonance biosensing

We developed a localized surface plasmon resonance (LSPR)-based label-free optical biosensor for detection of salbutamol (Sal). Hollow gold nanoparticles (HGNs) which deposited on transparent indium tin oxide (ITO) film coated glass was used to sensing platform. Antibody against Sal was immobilized on HGN surface to recognize the target Sal molecules. Thus, the change of LSPR peak was proportional to the concentration of Sal in the solution. The experimental results demonstrated that the LSPR immunosensor possessed a good sensitivity and a high selectivity for Sal. The detection range for Sal was from 0.05 to 0.8 μg/mL with a correlation coefficient of 0.996. The biosensor was applied for the detection for Sal in spiked animal feed and pork liver samples, and the recoveries were in the range of 97–105 %. Therefore, it is expected that this approach may offer a new method in designing label-free LSPR immunosensor for detection of small molecules.     

Tuning the Fano Resonance Between Localized and Propagating Surface Plasmon Resonances for Refractive Index Sensing Applications

Localized and propagating surface plasmon resonances are known to show very pronounced interactions if they are simultaneously excited in the same nanostructure. Here, we study the Fano interference that occurs between localized surface plasmon resonance (LSPR) and propagating surface plasmon polariton (SPP) modes by means of phase-sensitive spectroscopic ellipsometry. The sample structures consist of periodic gratings of gold nanodisks on top of a continuous gold layer and a thin dielectric spacer, in which the structural dimensions were tuned in such a way that the dipolar LSPR mode and the propagating SPP modes are excited in the same spectral region. We observe pronounced anti-crossing and strongly asymmetric line shapes when both modes move to each other’s vicinity, accompanied of largely increased phase differences between the respective plasmon resonances. Moreover, we show that the anti-crossing can be exploited to increase the refractive index sensitivity of the localized modes dramatically, which result in largely increased values for the figure-of-merit which reaches values between 24 and 58 for the respective plasmon modes.     

One Dimensional Plasmonic Grating: High Sensitive Biosensor

We report a simple 1D grating device fabrication on ～50 nm gold (Au) film deposited on glass, which is employed as a high performance refractive index (RI) sensor by exploiting the surface plasmon polaritons (SPP) excited by the grating device along the Au/analyte interface. A finite element analysis (FEA) method is employed to maximize the sensitivity of the sensor for a fixed period and thickness of a gold film and its close correspondence with experiment has given the insight for high sensitivity and enhanced transmission. Significantly, in the context of economic design and performance, it is shown that an optimally designed and fabricated 1D grating can be as sensitive as 524 nm/RIU (linearity RI?=?1.33303 to 1.47399), which is remarkably higher than existing reports operating in a similar wavelength region.     

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.     

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.

     

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.     

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.     

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.

     

Optimal Design for U-bent Fiber-optic LSPR Sensor Probes

The refractive index (RI) sensitivity of a localized surface plasmon resonance (LSPR)-based fiber-optic probes is dependent on surface coverage of gold nanoparticles (GNP), fiber core diameter, and probe geometry. For U-bent LSPR fiber-optic probes, which demonstrated an order higher absorption sensitivity over straight probes, bend diameter and probe length may also have a significant influence on the sensitivity. This study on U-bent fiber-optic LSPR probes is aimed at optimizing these parameters to obtain highest possible RI sensitivity. RI sensitivity increases linearly as a function of surface coverage of GNP in the range of 2–22 %. U-bent fiber-optic probes made of 200-, 400-, and 600-μm fiber core diameter show optimum bend diameter value as ～1.4 mm. In addition, RI sensitivity is almost the same irrespective of fiber core diameter demonstrating flexibility in choice of the fiber and ease in optical coupling. The length of the probe preceding and succeeding the bend region has significantly less influence on RI sensitivity allowing miniaturization of these probes. In addition to these experimental studies, we present a theoretical analysis to understand the relative contribution of evanescent wave absorbance of GNP and refractive losses in the fiber due to GNP, towards the RI sensitivity.     

Effects of Refractive Index Variations on the Optical Transmittance Spectral Properties of the Nano-Hole Arrays

The 3D finite difference time domain technique was carried out to study the optical transmission properties of nano-hole arrays in the gold thin film supported by materials with different index of refraction in the visible and infrared regions. A series of perforated nano-hole structures on the gold film at different hole radius, hole depth of 100 nm, and structural periodicity of 400 nm were studied. It was found that transmission properties (i.e., intensity, FWHM, and resonance position) were strongly affected by hole radius and surrounding medium index of refraction. The maximum optical transmittance was observed as 31.9 % in a nano-hole array of hole radius of 125 nm and refractive index of 1.3. The maximum sensitivity of 300 nm/RIU was obtained at index of refraction of 1.7, whereas the minimum one was calculated as 110 nm/RIU in a nano-hole array of hole radius of 50 nm. It was also found that on increasing the hole radius from 50 to 125 nm, the spectral sensitivity was decreased, whereas the index sensitivity was increased on increasing the refractive index.     

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.

     

Highly Sensitive Surface Plasmon Resonance Based D-Shaped Photonic Crystal Fiber Refractive Index Sensor

In this article, a D-shaped photonic crystal fiber based surface plasmon resonance sensor is proposed for refractive index sensing. Surface plasmon resonance effect between surface plasmon polariton modes and fiber core modes of the designed D-shaped photonic crystal fiber is used to measure the refractive index of the analyte. By using finite element method, the sensing properties of the proposed sensor are investigated, and a very high average sensitivity of 7700 nm/RIU with the resolution of 1.30 × 10^?5 RIU is obtained for the analyte of different refractive indices varies from 1.43 to 1.46. In the proposed sensor, the analyte and coating of gold are placed on the plane surface of the photonic crystal fiber, hence there is no necessity of the filling of voids, thus it is gentle to apply and easy to use.     

Optimization of Surface Plasmon Resonance Biosensor with Ag/Au Multilayer Structure and Fiber-Optic Miniaturization

In this paper, we report a novel wavelength interrogation-based surface plasmon resonance (SPR) system, in which a film of three Ag layers and three Au layers are alternately deposited on a Kretschmann configuration as sensing element. This multilayer film shows higher sensitivity for refractive index (RI) measurement by comparing with single Au layer structure, which is consistent with its theoretical calculation. A sensitivity range of 2056–5893 nm/RIU can be achieved, which is comparable to RI sensitivities of other wavelength-modulated SPR sensors. Compared with Ag film, this Ag/Au multilayer arrangement offers anti-oxidant protection. This SPR biosensor based on a cost-effective Ag/Au multilayer structure is applicable to the real-time detection of specific interactions and dissociation of low protein concentrations. To extend the application of this highly-sensitive metal film device, we integrated this concept on an optical fiber. The range of RI sensitivities with Ag/Au multilayer was 1847–3309 nm/RIU. This miniaturized Ag/Au multilayer-based fiber optic sensor has a broad application in chemical and biological sensing.     

Theoretical Studies of Tunable Localized Surface Plasmon Resonance of Gold-Dielectric Multilayered Nanoshells

Tunable properties of localized surface plasmon resonances (LSPR) of gold-dielectric multilayered nanoshells are studied by quasi-static theory and plasmon hybridization theory. Multilayered nanoshells with the gold core and nanoshell separated by a spacer layer exhibit strong coupling between the core and nanoshell plasmon resonance modes. It is found that the absorption spectra characteristics of LSPR are sensitive to multiple parameters including the surrounding medium refractive index, the dielectric constant of spacer layer, the radius of inner core gold sphere, outer shell layer thickness, and their coupling strength. The results show that LSPR is mainly influenced by the ratio of spacer layer dielectric constant ε ₂ to surrounding medium dielectric constant ε ₄. Absorption spectrum of \(\left |\omega _{-}^{+}\right \rangle \) mode is red-shifted with increasing core radius when ε ₂ > ε ₄. It is surprising to find that LSPR is blue-shifted with increasing core radius when ε ₂ < ε ₄, and no shift when ε ₂ = ε ₄. These interesting contrary shifts of \(\left |\omega _{-}^{+}\right \rangle \) mode with different ratios ε ₂/ε ₄ are well analysed with plasmon hybridization theory and the distributions of induced charges interaction between the inner core and outer shell. In addition, for the sake of clarity, the distributions of electric filed intensity at their plasmon resonance wavelengths are also calculated. This work may provide an alternative approach to analyse property of the core-shell nanoshell particles based on plasmon hybridization theory and the induced charge interaction.