Elucidating refractive index sensitivity on subradiant, superradiant, and fano resonance modes in single palladium-coated gold nanorods.

Herein, we investigated the distinctive scattering properties exhibited by single gold nanorods coated with palladium (AuNRs@Pd), with variations in the Pd shell thicknesses and morphologies. AuNRs@Pd were synthesized through bottom-up epitaxial Pd growth using two different concentrations of Pd precursor. These single AuNRs@Pd displayed the characteristic of subradiant and superradiant localized surface plasmon resonance peaks, characterized by a noticeable gap marked by a Fano dip. We revealed the effect of local refractive index (RI) on the subradiant and superradiant peak energies, as well as the Fano dip in the scattering spectra of AuNRs@Pd with different Pd shell thicknesses. We demonstrated the applicability of the inflection points (IFs) method on detecting peaks and dip changes across different RIs. Thin AuNRs@Pd1mM displayed more pronounced sensitivity to peak shifts in response to variations in local RIs compared to thick AuNRs@Pd2mM. In contrast, thick AuNRs@Pd2mM exhibited greater sensitivity to changes in curvature near the subradiant and superradiant peak energies rather than peak shift sensitivity across different local RIs. Moreover, the Fano dip shift was more noticeable in thick AuNRs@Pd2mM compared to thin AuNRs@Pd1mM across different local RIs. Therefore, we provided new insight into the RI sensitivity on subradiant, superradiant, and Fano resonance modes in single AuNRs@Pd.

Enhancing the Extinction Efficiency and Plasmonic Response of Bimetallic Nanoparticles of Au-Ag in Robust Thin Film Sensing Platforms.

The extinction efficiency of noble metal nanoparticles (NPs), namely gold (Au) and silver (Ag), are dependent on their size and surrounding dielectric. Exploiting the Localized Surface Plasmon Resonance (LSPR) phenomenon, the composition and structure of the NPs might be tailored to achieve a configuration that optimizes their response (sensitivity) to environmental changes. This can be done by preparing a bimetallic system, benefiting from the chemical stability of Au NPs and the higher scattering efficiency of Ag NPs. To enhance the LSPR sensing robustness, incorporating solid supports in the form of nanocomposite thin films is a suitable alternative. In this context, the NPs composed of gold (Au), silver (Ag), and their mixture in bimetallic Au-Ag NPs, were grown in a titanium dioxide (TiO2) matrix using reactive DC magnetron sputtering. Thermal treatment at different temperatures (up to 700 °C) tuned the LSPR response of the films and, consequently, their sensitivity. Notably, the bimetallic film with Au/Ag atomic ratio 1 exhibited the highest refractive index sensitivity (RIS), with a value of 181 nm/RIU, almost one order of magnitude higher than monometallic Au-TiO2. The nanostructural analysis revealed a wide NP size distribution of bimetallic NPs with an average size of 31 nm, covering about 20% of the overall surface area. These findings underscore the significant potential of bimetallic film systems, namely AuAg-TiO2, in LSPR sensing enhancement.

Tuning the Refractive Index Sensitivity of LSPR Transducers Based on Nanocomposite Thin Films Composed of Noble Metal Nanoparticles Dispersed in TiO2.

This work reports on the development of nanoplasmonic thin films consisting of Au, Ag, or Au-Ag nanoparticles dispersed in a TiO2 matrix and the optimization of the deposition parameters to tune their optical response. The thin films were produced by reactive DC magnetron sputtering of a Ti target with Au and/or Ag pellets placed on the erosion zone. The thicknesses (50 and 100 nm) of the films, the current density (75 and 100 A/m2) applied to the target (titanium), and the number of pellets placed on its surface were the deposition conditions that were used to tailor the optical (LSPR) response. The total noble metal content varied between 13 and 28 at.% for Au/TiO2 films, between 22 and 30 at.% for Ag/TiO2 films, and 8 to 29 at% for the Au-Ag/TiO2 systems with 1:1, 1:1.5, and 1:2 Au:Ag atomic ratios. After thermal annealing at 400 and 600 °C, LSPR bands were found for all films concerning the Au-TiO2 and Au-Ag/TiO2, while for Ag/TiO2, only for thin films with 28 and 30 at.% of Ag concentration. Refractive index sensitivity (RIS) was evaluated for Au and Au-Ag/TiO2 thin films. It was found that for bimetallic nanoparticles, the sensitivity can increase up to five times when compared to a monometallic nanoplasmonic system. Using Au-Ag/TiO2 thin films can decrease the cost of fabrication of LSPR transducers while improving their sensitivity.

High Sensitivity Optical Fiber Mach-Zehnder Refractive Index Sensor Based on Waist-Enlarged Bitaper.

A Mach-Zehnder fiber optic sensor with high refractive index response sensitivity was developed. By fabricating a waist-enlarged bitaper structure on the interference arm of a single mode-multimode-single mode (SMS) Mach-Zehnder interferometer (MZI), the spectral contrast and response sensitivity were improved. Subsequently, the response sensitivity was further improved by etching the interference arm. When a beam of light was introduced into the sensor, due to the structural mismatch between the multimode fiber and the normal transmission light, the difference between the low-order mode and the high-order mode was generated in the fiber core and the fiber cladding. In the process of transmission in the sensing arm, due to the different refractive indices of the core and cladding, the optical path difference of the high-order mode and the low-order mode was different, which eventually generated interference fringes. The experimentally measured response sensitivity of SMS MZI in the range of 1.351 RIU to 1.402 RIU is 57.623 nm/RIU; the response sensitivity of a single mode-multimode-bitaper-multimode-single mode (SMBMS) MZI is 61.607 nm/RIU; and the response sensitivity of the etched SMBMS (ESMBMS) MZI is 287.65 nm/RIU. The response sensitivity of the new ESMBMS MZI is three times higher than that of the original SMS MZI. The sensor has the characteristics of compact structure, high sensitivity, easy manufacture, and a wide range of refractive index measurements, and can be used in food processing, pharmaceutical manufacturing and other fields.

Pedestal High-Contrast Gratings for Biosensing.

High-contrast gratings (HCG) are an excellent candidate for label-free detection of various kinds of biomarkers because they exhibit sharp and sensitive optical resonances. In this work, we experimentally show the performance of pedestal HCG (PHCG), which is significantly enhanced in comparison with that of conventional HCG. PCHGs were found to provide a 11.2% improvement in bulk refractive index sensitivity, from 482 nm/RIU for the conventional design to 536 nm/RIU. The observed resonance was narrower, resulting in a higher Q-factor and figure of merit. By depositing Al2O3, HfO2, and TiO2 of different thicknesses as model analyte layers, surface sensitivity values were estimated to be 10.5% better for PHCG. To evaluate the operation of the sensor in solution, avidin was employed as a model analyte. For avidin detection, the surface of the HCG was first silanized and subsequently functionalized with biotin, which is well known for its ability to bind selectively to avidin. A consistent red shift was observed with the addition of each of the functional layers, and the analysis of the spectral shift for various concentrations of avidin made it possible to calculate the limit of detection (LoD) and limit of quantification (LoQ) for the structures. PHCG showed a LoD of 2.1 ng/mL and LoQ of 85 ng/mL, significantly better than the values 3.2 ng/mL and 213 ng/mL respectively, obtained with the conventional HCG. These results demonstrate that the proposed PHCG have great potential for biosensing applications, particularly for detecting and quantifying low analyte concentrations.

Rapid and sensitive detection of PD-L1 exosomes using Cu-TCPP 2D MOF as a SPR sensitizer.

Two-dimensional metal organic framework (2D MOF Cu-TCPP) with significantly enhanced photoelectric properties was synthesized by a simple hydrothermal method. The π-stacked electroactive porphyrin molecules of TCPP-based 2D MOF carry out charge transport in the MOF structure. The d-d band transition of Cu2+ and its 2D ultra-thin characteristics can produce excellent near-infrared light absorption to couple with SPR. Three key parameters including the refractive index sensitivity, detection accuracy and quality factor were improved significantly for 2D MOF modified gold chips. Especially, the refractive index sensitivity was increased from 98 to 137.67°/RIU after modified with 2D MOF. Thus, for the first time, we applied it as a signal enhancer to improve direct SPR assay for the Programmed death ligand-1 (PD-L1) exosomes. Owning to its large specific surface area, excellent photoelectric properties, highly ordered structure, good dispersion and biocompatibility, the LOD of the SPR sensor was 16.7 particles/mL. The reliability and practicability were further validated by analysis of PD-L1 exosomes in human serum samples. The recovery rate was 93.43 %-102.35%, with RSD of 5.79 %-14.6%. Given their excellent signal amplification ability, 2D MOF Cu-TCPP could serve as an ideal SPR sensitizer for rapid and sensitive detection of trace disease markers.

Magnetic field-aligned Fe3O4-coated silver magnetoplasmonic nanochain with enhanced sensitivity for detection of Siglec-15.

Noble metal nanoparticles could provide a significant gain in sensitivity of surface plasmon resonance (SPR) sensor by electromagnetic field coupling between the localized plasmon resonance of nanoparticles and gold film. A facile and cost-effective SPR sensor based on magnetic field-aligned Fe3O4-coated silver magnetoplasmonic nanoparticles (Ag@MNPs) nanochain (M-Ag@MNPs) was proposed to improve the sensitivity of the sensor, which gave access to detect clinical targets at low concentration. Optimization experiments proved that 80 ng mL-1 M-Ag@MNPs-based SPR sensor showed high refractive index sensitivity and increased detection accuracy and quality factor when comparing with those of bare gold. Sialic acid binding Ig like lectins-15 (Siglec-15) was used as proof of concept to verify the sensitivity enhancement performance of M-Ag@MNPs in the actual detection process. SPR angle shifts of M-Ag@MNPs/gold sensor were significantly higher than those of traditional gold sensor under the same concentration of Siglec-15, which was consistent with previous performance analysis. Also, the detection limit of M-Ag@MNPs/gold sensor was calculated to be 1.36 pg mL-1. All these results had proved that aligning M-Ag@MNPs onto the gold chip could improve the performance of the SPR sensor and achieve sensitive detection of small amounts of clinical biomarkers.

Binary Chiral Nanoparticles Exhibit Amplified Optical Activity and Enhanced Refractive Index Sensitivity.

Metallic chiral nanoparticles (CNPs) with a nominal helical pitch (P) of sub-10 nm contain inherent chirality and are promisingly applied to diverse prominent enantiomer-related applications. However, the sub-wavelength P physically results in weak optical activity (OA) to prohibit the development of these applications. Herein, a facile method to amplify the CNPs' OA by alloying the host CNPs with metals through a three-step layer-by-layer glancing angle deposition (GLAD) method is devised. Promoted by the GLAD-induced heating effect, the solute metallic atoms diffuse into the host CNPs to create binary alloy CNPs. Chiral alloying not only induces the plasmonic OA of the diffused solute and the created alloys but also amplifies that of the host CNPs, generally occurring for alloying Ag CNPs with diverse metals (including Cu, Au, Al, and Fe) and alloying Cu CNPs with Ag. Furthermore, the chiral alloying leads to an enhancement of refractive index sensitivity of the CNPs. The alloy CNPs with amplified plasmonic OA pave the way for potentially developing important chirality-related applications in the fields of heterogeneous asymmetric catalysis, enantiodifferentiation, enantioseparation, biosensing, and bioimaging.

Au-WO3 Nanocomposite Coatings for Localized Surface Plasmon Resonance Sensing.

Localized surface plasmon resonance (LSPR) gas sensors are gaining increasing importance due to their unique tuneable functional properties. Au-WO3-x nanocomposite coatings, in particular, can be outstandingly sensitive to many different gases. However, a proper understanding of their optical properties and the way in which those properties are correlated to their structure/microstructure, is still needed. In this work, Au-WO3 nanocomposite coatings, with Au contents between 0-11 atomic percent, were grown using reactive magnetron co-sputtering technique and were characterized concerning their optical response. The precipitation of Au nanoparticles in the oxide matrix was promoted through thermal annealing treatments until 500 °C. Along with the Au nanoparticles' morphological changes, the annealing treatments stimulated the crystallization of WO3, together with the appearance of oxygen-deficient WO3-x phases. Through theoretical simulations, we have related the LSPR effect with the different structural and morphological variations (namely, size and distribution of the nanoparticles and their local environment), which were a function of the Au content and annealing temperature. Our results suggest that local voids were present in the vicinity of the Au nanoparticles, for all temperature range, and that they should be present in a wide variety of Au-WO3 nanocomposites. A theoretical study concerning the refractive index sensitivity was carried out in order to predict the optimal coating design parameters for gas sensing experiments.

Dewetting Metal Nanofilms-Effect of Substrate on Refractive Index Sensitivity of Nanoplasmonic Gold.

The localized surface plasmon resonance (LSPR) sensitivity of metal nanostructures is strongly dependent on the interaction between the supporting substrate and the metal nanostructure, which may cause a change in the local refractive index of the metal nanostructure. Among various techniques used for the development of LSPR chip preparation, solid-state dewetting of nanofilms offers fast and cost effective methods to fabricate large areas of nanostructures on a given substrate. Most of the previous studies have focused on the effect of the size, shape, and inter-particle distance of the metal nanostructures on the LSPR sensitivity. In this work, we reveal that the silicon-based supporting substrate influences the LSPR associated refractive index sensitivity of gold (Au) nanostructures designed for sensing applications. Specifically, we develop Au nanostructures on four different silicon-based ceramic substrates (Si, SiO2, Si3N4, SiC) by thermal dewetting process and demonstrate that the dielectric properties of these ceramic substrates play a key role in the LSPR-based refractive index (RI) sensitivity of the Au nanostructures. Among these Si-supported Au plasmonic refractive index (RI) sensors, the Au nanostructures on the SiC substrates display the highest average RI sensitivity of 247.80 nm/RIU, for hemispherical Au nanostructures of similar shapes and sizes. Apart from the significance of this work towards RI sensing applications, our results can be advantageous for a wide range of applications where sensitive plasmonic substrates need to be incorporated in silicon based optoelectronic devices.

Highly sensitive label-free in vitro detection of aflatoxin B1 in an aptamer assay using optical planar waveguide operating as a polarization interferometer.

This work reports on further development of an optical biosensor for the in vitro detection of mycotoxins (in particular, aflatoxin B1) using a highly sensitive planar waveguide transducer in combination with a highly specific aptamer bioreceptor. This sensor is built on a SiO2-Si3N4-SiO2 optical planar waveguide (OPW) operating as a polarization interferometer (PI), which detects a phase shift between p- and s-components of polarized light propagating through the waveguide caused by the molecular adsorption. The refractive index sensitivity (RIS) of the recently upgraded PI experimental setup has been improved and reached values of around 9600 rad per refractive index unity (RIU), the highest RIS values reported, which enables the detection of low molecular weight analytes such as mycotoxins in very low concentrations. The biosensing tests yielded remarkable results for the detection of aflatoxin B1 in a wide range of concentrations from 1 pg/mL to 1 µg/mL in direct assay with specific DNA-based aptamers. Graphical abstract Optical planar waveguide polarization interferometry biosensor for detection of aflatoxin B1 using specific aptamer.

Mycotoxin Biosensor Based on Optical Planar Waveguide.

The research aim of this work is to develop a simple and highly sensitive optical biosensor for detection of mycotoxins. This sensor is built on a planar waveguide operating on the polarization interferometry principle, i.e., detecting a phase shift between p- and s-components of polarized light developed during the binding of analyte molecules. The operation of the proposed sensor is similar to that of a Mach⁻Zehnder interferometer, while its design is much simpler and it does not require splitting the waveguide into two arms. The refractive index sensitivity of the polarization interferometer sensor was in the range of 5200 radians per refractive index unit (RIU). Several tests were conducted to detect ochratoxin A (OTA) at different concentrations in direct immunoassay with specific antibodies immobilized in the sensing window. The lowest concentration of OTA of 0.01 ng/mL caused a phase shift of nearly one period. The results obtained prove high sensitivity of the sensors, which are capable of detecting even lower concentrations of mycotoxins at the ppt (part-per-trillion) level.

Fiber-Optic Thermal Sensor for TiN Film Crack Monitoring.

The study focuses on the thermal and temperature sensitivity behavior of an optical fiber sensor device. In this article, a titanium nitride (TiN)-coated fiber Bragg grating (FBG) sensor fabricated using an ion beam sputtering system was investigated. The reflection spectra of the FBG sensor were tested using R-soft optical software to simulate the refractive index sensitivity. In these experiments, the temperature sensitivity of the TiN FBG was measured at temperatures ranging from 100 to 500 °C using an optical spectrum analyzer (OSA). The results showed that the temperature sensitivity of the proposed TiN FBG sensor reached 12.8 pm/°C for the temperature range of 100 to 300 °C and 20.8 pm/°C for the temperature range of 300 to 500 °C. Additionally, we found that the produced oxidation at temperatures of 400-500 °C caused a crack, with the crack becoming more and more obvious at higher and higher temperatures.

Assessing the Location of Surface Plasmons Over Nanotriangle and Nanohole Arrays of Different Size and Periodicity.

The increasing popularity of surface plasmon resonance (SPR) and surface enhanced Raman scattering (SERS) sensor design based on nanotriangle or nanohole arrays, and the possibility to manufacture substrates at the transition between these plasmonic substrates, makes them ideal candidates for the establishment of structure-property relationships. This work features near diffraction-limited Raman images and FDTD simulations of nanotriangle and nanohole arrays substrates, which clearly demonstrate that the localization of the hot spot on these SERS substrates is significantly influenced by the ratio of diameter/periodicity (D/P). The experimental and simulation data reveal that the hot spots are located around nanotriangles (D/P = 1), characteristic of localized SPR. Decreasing the D/P ratio to 0.75-0.7 led to the creation of nanohole arrays, which promoted the excitation of a propagating surface plasmon (SP) delocalized over the metal network. The optimal SERS intensity was consistently achieved at this transition from nanotriangles to nanoholes, for every periodicity (650 nm to 1.5 µm) and excitation wavelength (633 and 785 nm) investigated, despite the presence or absence of a plasmonic band near the laser excitation. Further decreasing the D/P ratio led to excitation of a localized SP located around the rim of nanohole arrays for D/P of 0.5-0.6, in agreement with previous reports. In addition, this manuscript provides the first evidence that the hot spots are positioned inside the hole for D/P of 0.4, with the center being the region of highest electric field and Raman intensity. The compelling experimental evidence and FDTD simulations offer an overall understanding of the plasmonic properties of nanohole arrays as SERS and SPR sensors, which is of significant value in advancing the diversity of applications from such surfaces.

Improved Sensitivity of Localized Surface Plasmon Resonance Transducers Using Reflection Measurements.

The refractive index sensitivity (RIS) of a localized surface plasmon resonance (LSPR) transducer is one of the key parameters determining its effectiveness in sensing applications. LSPR spectra of nanoparticulate gold films, including Au island films prepared by evaporation on glass and annealing as well as immobilized Au nanoparticle (NP) films, were measured in the transmission and reflection modes. It is shown that the RIS, measured as the wavelength shift in solvents with varying refractive index (RI), is significantly higher in reflection measurements.