Plasmonic Arrays Research Articles

Superhydrophobic Ag‐Decorated CuO Nanowire Arrays with Analyte‐Concentrating and Self‐Cleaning Binary Functions for Ultrasensitive and Recyclable Surface‐Enhanced Raman Scattering

AbstractSurface‐enhanced Raman scattering (SERS) is considered a promising analytical technique for the detection of analytes. Considering the practical SERS detection, it is necessary to develop low‐cost, highly sensitive, and recyclable SERS‐active substrates. Here, a simple and flexible approach is proposed to fabricate a superhydrophobic Ag‐decorated CuO (named as CuO@Ag) nanowire array substrate with analyte‐concentrating and self‐cleaning binary functions for ultrasensitive and recyclable SERS detection. During this process, a superhydrophobic CuO@Ag nanowire array is made via fabrication of a CuO nanowire array by oxidizing and calcinating an ordered porous anodic aluminum oxide template on Cu foil, and following with Ag sputtering deposition on CuO nanowire array. Remarkably, this SERS substrate exhibits ultrasensitive SERS detection ability attributed to superhydrophobic plasmonic metal nanostructured arrays with high analyte‐concentrating ability and excellent photocatalytic capability due to this metal‐semiconductor composite nanostructure. These advantageous properties allow for SERS detection of malachite green with a limit of detection of 6.73 × 10−13 m and self‐cleaning via photodegradation of adsorbed analytes with visible‐light illumination. Consequently, it achieves recyclable SERS detection. This research demonstrates a simple and flexible approach for fabricating recyclable SERS‐active substrate, which expands the practical SERS applications in chemical and biological analysis, food safety, and healthcare.

Optical Response of CVD-Grown ML-WS2 Flakes on an Ultra-Dense Au NP Plasmonic Array

The combination of metallic nanostructures with two-dimensional transition metal dichalcogenides is an efficient way to make the optical properties of the latter more appealing for opto-electronic applications. In this work, we investigate the optical properties of monolayer WS2 flakes grown by chemical vapour deposition and transferred onto a densely-packed array of plasmonic Au nanoparticles (NPs). The optical response was measured as a function of the thickness of a dielectric spacer intercalated between the two materials and of the system temperature, in the 75–350 K range. We show that a weak interaction is established between WS2 and Au NPs, leading to temperature- and spacer-thickness-dependent coupling between the localized surface plasmon resonance of Au NPs and the WS2 exciton. We suggest that the closely-packed morphology of the plasmonic array promotes a high confinement of the electromagnetic field in regions inaccessible by the WS2 deposited on top. This allows the achievement of direct contact between WS2 and Au while preserving a strong connotation of the properties of the two materials also in the hybrid system.

Plasmonic Superstructure Arrays Fabricated by Laser Near-Field Reduction for Wide-Range SERS Analysis of Fluorescent Materials.

Surface-enhanced Raman scattering (SERS) enables trace-detection for biosensing and environmental monitoring. Optimized enhancement of SERS can be achieved when the energy of the localized surface plasmon resonance (LSPR) is close to the energy of the Raman excitation wavelength. The LSPR can be tuned using a plasmonic superstructure array with controlled periods. In this paper, we develop a new technique based on laser near-field reduction to fabricate a superstructure array, which provides distinct features in the formation of periodic structures with hollow nanoclusters and flexible control of the LSPR in fewer steps than current techniques. Fabrication involves irradiation of a continuous wave laser or femtosecond laser onto a monolayer of self-assembled silica microspheres to grow silver nanoparticles along the silica microsphere surfaces by laser near-field reduction. The LSPR of superstructure array can be flexibly tuned to match the Raman excitation wavelengths from the visible to the infrared regions using different diameters of silica microspheres. The unique nanostructure formed can contribute to an increase in the sensitivity of SERS sensing. The fabricated superstructure array thus offers superior characteristics for the quantitative analysis of fluorescent perfluorooctanoic acid with a wide detection range from 11 ppb to 400 ppm.

Plasmon-enhanced near-infrared fluorescence detection of traumatic brain injury biomarker glial fibrillary acidic protein in blood plasma

An ultrasensitive plasmonic near-infrared fluorescent biosensor substrate has been developed for detection of glial fibrillary acidic protein (GFAP) biomarker in blood plasma, an important protein biomarker of traumatic brain injury (TBI). To minimize the interference from blood plasma sample matrix, a near-infrared fluorophore in the first biological transparency window is used in the biosensor. To amplify the fluorescence signals, a plasmonic gold nanopyramid array has been coupled to the fluorophore. Finite-difference time-domain simulation reveals that the excitation enhancement is primarily responsible for the fluorescence enhancement owing to the intense local electric field excited on the corners and edges. As a result, this biosensor exhibits a lower limit of detection of 0.6 pg/mL toward detection of GFAP in blood plasma.

Microporous Multiresonant Plasmonic Meshes by Hierarchical Micro-Nanoimprinting for Bio-Interfaced SERS Imaging and Nonlinear Nano-Optics.

Microporous mesh plasmonic devices have the potential to combine the biocompatibility of microporous polymeric meshes with the capabilities of plasmonic nanostructures to enhance nanoscale light-matter interactions for bio-interfaced optical sensing and actuation. However, scalable integration of dense and uniformly structured plasmonic hotspot arrays with microporous polymeric meshes remains challenging due to the processing incompatibility of conventional nanofabrication methods with flexible microporous substrates. Here, scalable nanofabrication of microporous multiresonant plasmonic meshes (MMPMs) is achieved via a hierarchical micro-/nanoimprint lithography approach using dissolvable polymeric templates. It is demonstrated that MMPMs can serve as broadband nonlinear nanoplasmonic devices to generate second-harmonic generation, third-harmonic generation, and upconversion photoluminescence signals with multiresonant plasmonic enhancement under fs pulse excitation. Moreover, MMPMs are employed and explored as bio-interfaced surface-enhanced Raman spectroscopy mesh sensors to enable in situ spatiotemporal molecular profiling of bacterial biofilm activity. Microporous mesh plasmonic devices open exciting avenues for bio-interfaced optical sensing and actuation applications, such as inflammation-free epidermal sensors in conformal contact with skin, combined tissue-engineering and biosensing scaffolds for in vitro 3D cell culture models, and minimally invasive implantable probes for long-term disease diagnostics and therapeutics.

Uncovering surface plasmon optical resonances in nanohole arrays through interferometric photoemission electron microscopy

The role of surface plasmon polaritons (SPPs) in nanohole array optical extinction spectra is explored using a time-resolved technique capable of isolating the air/metal interfacial SPP contribution to the typical Fano profile in optical transmission curves. A pair of interferometrically locked broad-band femtosecond pulses is used to launch SPPs from lithographically patterned plasmonic nanohole arrays. SPPs launched in the co- and counter-propagating directions are probed using a third probe pulse in a photoemission electron microscope. Using this approach, we record interferometric SPP–SPP linear autocorrelations that selectively report on the resonances of SPPs launched from arrays of varying pitches and hole diameters. Aside from advancing an approach to selective SPP spectroscopy, we illustrate that resonant coupling in the counter-propagating direction may be exploited to control the spatial, temporal, and spectral characteristics of SPPs. For the counter-propagating direction, we show that tuning the array pitch near the fundamental plasmon resonance generates color-tuned (∼770–820 nm), narrow bandwidth SPPs, and the bandwidth may be controlled by changing the ratio of pitch to hole diameter. The SPP resonances we recover through Fourier transforms of the interferometric autocorrelations shed light on the classical problem of Fano interference in nanohole array extinction spectra.

Enhanced Faraday effects of magneto-plasmonic crystals with plasmonic hexagonal hole arrays.

Magneto-optical (MO) properties of the bilayed Au/BIG and trilayered Au/BIG/Au magneto-plasmonic crystals (MPCs) were analyzed by the finite-difference time-domain method. In contrast to the low deflection angle and transmission of the smooth thin film, all the heterostructures with perforated holes in the top Au film displayed a similar trend with two strong resonant bands in Faraday rotation and transmittance in the near infrared wavelength range. The bands and electric distribution relative to the component and hole structure were revealed. The MPC with plasmonic hexagonal holes was found to own superior Faraday effects with distinctive anisotropy. The evolution of the resonant bands with the size and period of hexagonal holes, the thickness of different layers, and the incident light polarization was illustrated. The Faraday rotation of the optimized bilayed and trilayered hexagonal MPCs was improved 15.3 and 17.5 times, and the transmittance was enhanced 12.1 and 11.1 folds respectively at the resonant wavelength in comparison to the continuous Au/BIG film, indicating that the systems might find potential application in MO devices.

High-order accurate schemes for Maxwell's equations with nonlinear active media and material interfaces

We describe a fourth-order accurate finite-difference time-domain scheme for solving dispersive Maxwell's equations with nonlinear multi-level carrier kinetics models. The scheme is based on an efficient single-step three time-level modified equation approach for Maxwell's equations in second-order form for the electric field coupled to ODEs for the polarization vectors and population densities of the atomic levels. The resulting scheme has a large CFL-one time-step. Curved interfaces between different materials are accurately treated with curvilinear grids and compatibility conditions. A novel hierarchical modified equation approach leads to an explicit scheme that does not require any nonlinear iterations. The hierarchical approach at interfaces leads to local updates at the interface with no coupling in the tangential directions. Complex geometry is treated with overset grids. Numerical stability is maintained using high-order upwind dissipation designed for Maxwell's equations in second-order form. The scheme is carefully verified for a number of two and three-dimensional problems. The resulting numerical model with generalized dispersion and arbitrary nonlinear multi-level system can be used for many plasmonic applications such as for ab initio time domain modeling of nonlinear engineered materials for nanolasing applications, where nano-patterned plasmonic dispersive arrays are used to enhance otherwise weak nonlinearity in the active media.

A theoretical study of broadband extraordinary optical transmission in gold plasmonic square nanohole arrays and its application on refractive index sensor

A theoretical study of broadband extraordinary optical transmission in gold plasmonic square nanohole arrays and its application on refractive index sensor

Instant Intracellular Delivery of miRNA via Photothermal Effect Induced on Plasmonic Pyramid Arrays (Adv. Funct. Mater. 9/2022)

Intracellular miRNA Delivery In article number 2107999, Zhen Fan, Xiaobin Xu, and co-workers report using scanning laser stimulation to generate instantaneous high temperature on plasmonic pyramid arrays to disrupt the cell membranes to facilitate intracellular delivery of biocargos like miRNA. Intracellular delivery of miRNA-185 to Taxol-resistance esophageal cancer cells is achieved within minutes.

Piezo-phototronic effect boosted catalysis in plasmonic bimetallic ZnO heterostructure with guided fermi level alignment

High photo-induced carriers (PCs) recombination rate, low PC mobility, and limited solar energy utilization rate are the three main roadblocks that severely limit the photocatalytic activity of semiconductors. In this work, we designed a plasmonic bimetallic ZnO nanorod array (Au/ZnO/Pt) with Au nanoparticles (NPs) located on top of ZnO nanorods and Pt NPs evenly distributed on the ZnO nanorods for improving catalysis through the piezo-phototronic effect. With the rational design of guided Fermi level alignment, the photoinduced hot electrons of Au NPs with localized surface plasmon resonance effect can transfer to Pt NPs through ZnO to promote the separation and migration of PC. More importantly, under the stimulation of ultrasound, ZnO with piezo-phototronic effect generates an interfacial piezo-potential, thereby further promoting the separation and transport of carriers in compliance with the direction of piezo-potential to promote the surface redox reaction. Under the synergy of piezo-phototronic effect and localized surface plasmon resonance effect, the Au/ZnO/Pt realized 97.5% dye degradation in 60 min, which was 1.2, 1.36, and 1.79 folds of that with Au/ZnO/Au, Pt/ZnO/Pt, and ZnO, respectively. The unique plasmonic bimetallic heterostructure with piezo-phototronic effect and guided Fermi level alignment can guide the directional migration of carriers and provides useful instruction for the design of high-efficiency catalysts.

Coupled Molecular Emitters in Superstructures Interact with Plasmonic Nanoparticles

Using hyperspectral measurements, J‐aggregate nanorods of porphyrin molecules embedded in plasmonic Au nanoparticles arrays are studied. Measurements of J‐aggregate nanorods that cross onto a plasmonic array exhibit a shift in their absorption peak, and display weak coupling properties only for the embedded part. Furthermore, a significant thickness‐dependent redshift in the plasmonic resonance for the J‐aggregate clusters is observed. Such redshift is also dependent on the ratio of J‐aggregate in the plasmonic dipole interaction area, reaching values of up to 120 meV for ≈40% coverage. In addition, for large clusters of J‐aggregates, the plasmonic spectrum shows coupling behavior between the systems indicated by a small Rabi splitting. The findings are validated by a quasi‐static model based on the change of the dielectric environment around the embedded nanoparticles. Using the model, the fraction of embedding J‐aggregates in the plasmonic interaction area is correlated with the change in plasmonic resonance peak. These results offer insight into the coupled nature of molecular emitters in supramolecular structures and their interaction with plasmonic nanoparticles and can lead to new types of sensitive optical detectors based on these interactions.

Remote Chemical Sensing by SERS with Self-Assembly Plasmonic Nanoparticle Arrays on a Fiber

An optical fiber was modified at the tip with a self-assembled plasmonic metamaterial that acts as a miniature surface-enhanced Raman spectroscopy (SERS) substrate. This optical fiber-based device co-localizes the laser probe signal and the chemical analyte at a distance remote from the spectrometer, and returns the scattered light signal to the spectrometer for analysis. Remote SERS chemical detection is possible in liquids and in dried samples. Under laboratory conditions, the analyte SERS signal can be separated from the background signal of the fiber itself and the solvent. An enhancement factor greater than 35,000 is achieved with a monolayer of the SERS marker 4-aminothiophenol.

Light Scattering by a Subwavelength Plasmonic Array: Anisotropic Model.

We calculate the light transmission by a subwavelength plasmonic array using the boundary element method for parallel cylinders with different cross-sections: circular or elliptic with axis ratio 4:1. We demonstrate that plasmonic resonance is sharper for the case of horizontal ellipses. This structure is susceptible to refractive index variations in the media since the high derivatives of reflection and transmission coefficients are near the angle of total internal reflection. To obtain an approximate analytical expression, we used the model of a metallic layer. We explore the “sandwich” structure with an anisotropic film between two dielectrics and demonstrate its quantitative agreement with numerical results.

Verification and Analysis of Single-Molecule SERS Events via Polarization-Selective Raman Measurement.

We propose polarization-selective Raman measurement as a decent method for single-molecule surface-enhanced Raman scattering (SMSERS) verification. This approach features rapid acquisition of SMSERS events and appeals liberal requirements for analyte concentration. It is demonstrated as an efficient tool in sorting out dozens of SMSERS events from a large-scale plasmonic dimer array. In addition, it allows identification of a mixed SMSERS event containing two different individual molecules. In this article, the RPM method is employed to explore the underlying mechanisms of signal blinking, spectral wandering, and other unique characteristics in SMSERS. We observed synchronized blinking of different modes from one Rhodamine 6G (R6G) molecule, but a disagreement is found in a mixed SMSERS event containing one R6G molecule and one crystal violet molecule. Our approach offers a reliable means to interpret SMSERS events in statistical terms and facilitate the fundamental understanding of SMSERS.

Ultra‐compact and ultra‐broadband hybrid plasmonic‐photonic vertical coupler with high coupling efficiency, directivity, and polarisation extinction ratio

An ultra-compact, ultra-broadband vertical coupler for dense photonic integrated circuits is reported with a 1.07 × 0.62 μm2 wavelength-scale footprint. This hybrid plasmonic-photonic coupler uses a unique two-plane plasmonic nanoantenna array on a silicon-on-insulator waveguide. The in- and out-of-plane interference of the multipole moments and dual-feed nanoantennas results in efficient, unidirectional coupling. Finite-element simulations show that, for a 0.8 μm diameter Gaussian beam, the maximum coupling efficiency (CE) is −3.4 dB across the telecommunication C-, L- and U-bands with a 3-dB bandwidth of 230 nm. The CE is > 9 dB higher than recently reported ultra-compact plasmonic couplers. The maximum directivity and polarisation extinction ratio across the C- to U-bands are 9.2 and 24.1 dB, respectively. Finally, as an out-coupler, it has a vertical directivity of >8.5 dB, enabling its use for vertical optical interconnects between two vertically separated circuits.

Pre- and post-assembly modifications of colloidal plasmonic arrays: the effect of size distribution, composition and annealing

Internal organization and composition of plasmonic colloidal array unit cells are engineered exploring both pre- and post- assembly modifications.

Pinpointing photothermal contributions in photochemical reactions on plasmonic gold nanoparticles

Laser-induced photocatalytic reduction of PNTP to DMAB on plasmonic GNP arrays through hot electron transfer and direct photothermal conversion.

Optical response of hyperbolic metamaterials with adsorbed nanoparticle arrays.

Experimental studies of have been recently performed to determine the optical effect of adsorption of arrays of gold nanoparticles, NPs (16 nm or 40 nm in diameter) on reflective substrates (Ma et al., ACS Photonics, 2018, 5, 4604-4616; Ma et al., ACS Nano, 2020, 14, 328-336) and on transparent interfaces (Montelongo et al., Nat. Mater., 2017, 16, 1127-1135). As predicted by the theory (Sikdar et al., Phys. Chem. Chem. Phys., 2016, 18, 20486-20498), a reflection quenching effect was observed on the reflective substrates, in the frequency domain centred around the nanoparticle localised plasmon resonance. Those results showed a broad dip in reflectivity, which was deepening and red-shifting with increasing array densities. In contrast, the second system has shown, also in accordance with the theory (Sikdar and Kornyshev, Sci. Rep., 2016, 6, 1-16), a broad reflectivity peak in the same frequency domain, increasing in intensity and shifting to the red with densification of the array. In the present paper, we develop a theory of an optical response of NP arrays adsorbed on the surface of stacked nanosheet hyperbolic substrates. The response varies between quenched and enhanced reflectivity, depending on the volume fractions of the metallic and dielectric components in the hyperbolic metamaterial. We reproduce the results of the earlier works in the two opposite limiting cases - of a pure metal and a pure dielectric substrates, while predicting novel resonances for intermediate compositions. Whereas the metal/dielectric ratio in the hyperbolic substrate cannot be changed in time - for each experiment a new substrate should be fabricated - the density of the adsorbed nanoparticle arrays can be controlled in real time in electrochemical photonic cells (Montelongo et al., Nat. Mater., 2017, 16, 1127-1135; Ma et al., ACS Photonics, 2018, 5, 4604-4616; Ma et al., ACS Nano, 2020, 14, 328-336). Therefore, we systematically study the effect of the array density on the optical response of such systems, which could be later verified experimentally. We also investigate the manifestation of these findings in a hyperbolic-Fabry-Perot cell.

High-performance plasmonic lab-on-fiber sensing system constructed by universal polymer assisted transfer technique

Plasmonic lab-on-fiber (LOF) system has become an emerging sensing platform for the realization of miniaturized and portable plasmonic sensors. Herein, a facile and efficient polymer assisted transfer technique was reported for the preparation of plasmonic LOF systems. The proposed plasmonic LOF system was constructed through transferring plasmonic arrays to the end surface of optical fibers using polylactic acid as the sacrificial layer. The morphology of the transferred plasmonic arrays maintains excellent consistency with the original arrays. Importantly, the as-prepared plasmonic LOF system also possesses outstanding sensing performance in refractive index sensing and quantitative label-free biosensing applications. Additionally, the proposed polymer assisted transfer technique shows broad universality for various plasmonic arrays. Together with the above features, it is believed that the polymer assisted transfer technique will show great potential for the application of future plasmonic LOF systems.