Plasmonic Interactions Research Articles

Engineering the plasmonic activities of copper nanostructures for SERS and photocatalysis

Nanoparticles of plasmonic metals such as gold (Au), silver (Ag) and copper (Cu) have numerous applications due to their localized surface plasmon resonance. Among these, nanoparticles of Cu remain underexplored when compared to Au and Ag, although the former is much cheaper. Here we report the surface enhanced Raman spectroscopy (SERS), interaction of molecule with a plasmonics and photocatalysis applications of Cu nanostructures. Hexagonal and cubic shaped Cu nanostructures were successfully synthesized by varying the reaction conditions in a polyol synthesis method. Rapid nucleation at an elevated temperature (140 °C) and subsequent slow growth at lower temperature (80 °C) in presence of PVP polymeric stabilizer resulted in the formation of uniform cube shaped Cu nanoparticles (Cucube). Whereas polyol synthesis at a low temperature (80 °C) resulted in hexagonal Cu nanoparticles (Cuhex). Cuhex exhibited higher SERS enhancement compared to Cucube. Specifically, Using 532, 633 and 785 nm lasers, Cuhex showed enhancement factor 9.0×105. The detection limit as low as 10-10 M for RhB using Cuhex. Moreover, based on emission and time-dependent measurements, strong molecular and plasmonic interactions reveal energy transfer from RhB molecules to the Cu nanostructures. Additionally, Cuhex showed very good catalytic and visible light plasmonic photocatalytic activities for the para-nitrophenol (p-NP) reduction reaction.

Using polarization sensitive SMLM to infer the interaction strength of dye-plasmonic nanosphere systems

Single-molecule microscopy is an effective tool for the characterization of fluorophore–plasmonic structure interaction. However, sophisticated evaluation is required as specific information is hidden in the emission. Here, we theoretically and experimentally investigated the emission polarization of rotationally mobile fluorophores near plasmonic Au–Ag alloy nanospheres. We developed an elaborate calculation based on the Mie theory, which considers the rotational mobility of dyes near spherical plasmonic nanoparticles of any size. Furthermore, we have created a simplified model that describes the emission’s degree of polarization within 10% accuracy in the case of small nanoparticles, when dipole approximation is valid. Our results indicate the close relation of the polarization degree of the emission, which can reach up to be ∼0.8 in the resonant case, to fluorescence scattering. DNA-PAINT single-molecule localization microscopy experiments conducted using AF488 and Atto647N dyes revealed that the measured polarization degree distribution followed the tendency predicted by calculations.

Plasmonic coupling dependent sensitivity in localized surface plasmon resonance based optical sensors

This paper investigates the impact of environmental changes on silver nanoparticles (AgNp) immobilized sensor probe within strong and weak plasmonic coupling regimes. To monitor these interaction regimes, evanescent wave absorption based on fiber optic and attenuated total reflection techniques have been employed. In the weak coupling regime, variations in refractive index (RI) primarily affect intensity rather than wavelength. Conversely, in the strong coupling regime, intensity decreases, while wavelength sensitivity increases with changes in RI. Our findings qualitatively agree with a theoretical framework based on the discrete dipole approximation (DDA) for two-particle interacting systems, providing valuable insights for optimizing plasmonic interactions to enhance sensitivity. This information will aid the scientific and industrial community in understanding the plasmonic interaction region for maximizing sensitivity of Localized surface plasmon resonance (LSPR) based photonic devices.

Multi-wavelength and broadband plasmonic switching with V-shaped plasmonic nanostructures on a VO2 coated plasmonic substrate

In this paper, periodic arrays of identical V-shaped gold nanostructures and variable V-shaped gold nanostructures are designed on top of a gold-coated silicon dioxide (SiO2) substrate with a thin spacer layer of vanadium dioxide (VO2) to realize multi-wavelength and broadband plasmonic switches, respectively. The periodic array of identical V-shaped nanostructures (IVNSs) with small inter-particle separation leads to coupled interactions of the elementary plasmons of a V-shaped nanostructure (VNS), resulting in a hybridized plasmon response with two longitudinal plasmonic modes in the reflectance spectra of the proposed switches when the incident light is polarized in the x-direction. The x-direction is oriented along the axis that joins the V-junctions of all VNSs in one unit cell of the periodic array. On exposure to temperature, electric field, or optical stimulus, the VO2 layer transforms from its monoclinic semiconducting state to its rutile metallic state, leading to an overall change in the reflectance spectra obtained from the proposed nanostructures and resulting in an efficient multi-wavelength switching action. Finite difference time domain modelling is employed to demonstrate that an extinction ratio (ER) >12 dB at two wavelengths can be achieved by employing the proposed switches based on periodic arrays of IVNSs. Further, plasmonic switches based on variable V-shaped nanostructures—i.e. multiple VNSs with variable arm lengths in one unit cell of a periodic array—are proposed for broadband switching. In the broadband operation mode, we report an ER >5 dB over an operational wavelength range >1400 nm in the near-IR spectral range spanning over all optical communication bands, i.e. the O, E, S, C, L and U bands. Further, it is also demonstrated that the wavelength of operation for these switches can be tuned by varying the geometrical parameters of the proposed switches. These switches have the potential to be employed in communication networks where ultrasmall and ultrafast switches with multi-wavelength operation or switching over a wide operational bandwidth are inevitably required.

Pongamia pinnata seed extract-mediated green synthesis of silver nanoparticle loaded nanogel for estimation of their antipsoriatic properties.

This research describes the eco-friendly green synthesis of silver nanoparticles employing Pongamia pinnata seed extracts loaded with nanogel formulations (AgNPs CUD NG) to improve the retention, accumulation, and the penetration of AgNPs into the epidermal layer of psoriasis. AgNPs were synthesized using the Box-Behnken design. Optimized AgNPs and AgNPs CUD NG were physico-chemically evaluated using UV-vis spectroscopy, SEM, FT-IR, PXRD, viscosity, spreadability, and retention studies. It was also functionally assessed using an imiquimod-induced rat model. The entrapment efficiency of AgNPs revealed ~ 79.35%. Physico-chemical parameters announced the formation of AgNPs via surface plasmon resonance and interaction between O-H, C = O, and amide I carbonyl group of protein extract and AgNO3. Optimized AgNPs showed spherical NPs ~ 116nm with better physical stability and suitability for transdermal applications. AgNPs CUD NG revealed non-Newtonian, higher spreadability, and better extrudability, indicating its suitability for a transdermal route. AgNPs CUD NG enhanced the retention of AgNPs on the psoriatic skin compared to normal skin. Optimized formulations exhibit no irritation by the end of 72h, indicating formulation safety. AgNPs CUD NG at a dose of 1 FTU showed significant recovery from psoriasis with a PASI score of ~ 0.8 compared to NG base and marketed formulations. Results indicated that seed extract-assisted AgNPs in association with CUD-based NG formulations could be a promising nanocarrier for psoriasis and other skin disorders.

Giant Plasmonic Enhancement of Chiroptical Properties by Anisotropic Gold Nanocrystals Grown In Situ in a Chiral Polymer

AbstractPolymer‐based chiral materials with exceptional optical activity can dramatically impact integrated chiral photonics due to the tunability of their optical responses coupled with ease of fabrication. Realizing these applications requires increasing the absorbance dissymmetry factor. Here, in situ, the synthesis of gold nanostars is introduced in a chiral polymer medium to produce chiral polymer‐anisotropic plasmonic nanocrystal nanocomposites. The optimized nanocomposite shows a tenfold enhancement of dissymmetry factor, gabs (up to 0.64) and a corresponding 46‐fold augmented circular dichroism (CD) value upon annealing, relative to the annealed pure chiral polymer film. Moreover, the enhancement relative to the non‐annealed polymer‐gold nanostar nanocomposite is strikingly higher: a 35‐fold increase in gabs and a 4272‐fold increase in CD. Based on computational analysis, it is concluded that the local plasmon field enhancement around the crevices and tips of nanostars is mainly responsible for the observed effect which is further supported by a signal enhancement in Surface Enhanced Raman Scattering (SERS). Thus, this study underscores the significant role of close‐range plasmon interactions in altering the chiroptical response of nanocomposite materials and a practical pathway toward the realization of next‐generation integrated photonics and optoelectronic circuitry with photon spin control.

Plasmonically engineered nitrogen-vacancy spin readout.

Ultra-precise readout of single nitrogen-vacancy (NV) spins holds promise for major advancements in quantum sensing, computing, and communication technologies. Here we present a rigorous open quantum theory capable of simultaneously capturing the optical, vibronic, and spin interactions of the negatively charged NV center, both in the presence and absence of plasmonic interaction. Our theory is verified against existing experiments in the literature. We predict orders of magnitude brightness and contrast enhancements in optically detected magnetic resonance (ODMR) and NV spin qubit readout arising from plasmonic interaction. Such optimal enhancements occur in carefully engineered parameter regions, necessitating rigorous modelling prior to experimentation. Our theory equips the community with a tool to identify such regions.

Plasmonic Interaction of Gold Nanoparticles with the Anti-hypoglycemic Medicament Metformin

Plasmonic Interaction of Gold Nanoparticles with the Anti-hypoglycemic Medicament Metformin

Precise regulation of surface plasmonic hotspots in an Au split nanoring coupled system

The signal enhancement in plasmon-enhanced spectroscopy is primarily contributed by hotspots generated through the surface plasmon resonance effect. Precise control of hotspot positions within nanostructures is of great significance in surface-enhanced Raman spectroscopy (SERS) and high spatial resolution imaging. However, predicting the positions of hotspots is challenging due to the small nanogaps and complex plasmonic interactions. In this study, we theoretically investigate the localized surface plasmonic properties of split ring nanostructure. The effects of variations in the inner radius, gap distance and thickness of the split ring on the hotspot distribution at the nanogaps are systematically analyzed using a three-dimensional finite element method. The results demonstrate that precise control over the positions and quantities of hotspots can be achieved by choosing the excitation wavelength and the gap size of the split rings. The calculated maximum Raman enhancement obtained at the hotspots can reach nine orders of magnitude. Our findings not only contribute to a deeper understanding of the SERS enhancement mechanism, but also provide theoretical insights for further development of surface-enhanced fluorescence, plasmonic sensors, and super-resolution imaging in the field of interface spectroscopy.

Ni-based plasmonic photocatalysts for solar to energy conversion: A review

Plasmonic-based semiconductors are compelling contenders of current research endeavors to drive chemical reactions via plasmonic and phononic light-matter interactions. Among various plasmonic metals, Ni as a non-precious metal has been extensively studied due to its ability to participate in interband excitation and comparable metal-hydrogen binding energy to that of noble metals including Pt and Ag. The phenomenally high charge-carrier density in photoexcited Ni-based plasmonic nanomaterials offers photochemical conversion of high-energy chemical bonds accompanied by thermal effect. Since the research on the plasmonic activity of the non-precious metal is still emerging, no comprehensive review has addressed the significance of Ni as a plasmonic photocatalyst to the best of our knowledge. This review article sums up the recent progress in the field of plasmonic photocatalysis focusing on Ni-based photocatalysts. The basic principles of the plasmonic effect have been presented, along with an explanation of why Ni may be a viable option. Ni has been investigated for use as a co-catalyst and plasmonic photocatalyst in composite photocatalysis to achieve an accelerated process. After the energy transfer mechanism has been assessed, the review covers the state-of-the-art of two significant effects—plasmon energy transfer and the localized heating effect that are responsible for increased efficiency in energy production. In conclusion, we have included a synopsis of the assessment and emphasized the problems that must be resolved before the technology can be made available for purchase. In a nutshell, the chemistry of plasmonic photocatalysis is promising; but acquiring a detailed mechanism of charge transfer and utilization of charge carriers is still a roadblock in apprehending the full potential of plasmonic photocatalysis. Therefore, this study aims to motivate the scientific community to envision impactful work in the creation of next-generation plasmonic photocatalysts.

Plasmonic hybridized modes empowered by strong plasmon interaction in the nanograting-dielectric-metal stacked structure

Abstract The coupling between surface plasmon polaritons (SPPs) and waveguide (WG) modes has been widely investigated by using prism-coupled structures and has demonstrated a large number of interesting physical phenomena. However, these conventional structures mainly rely on the angle-dependent total internal reflection excitation. This is not conducive to their further development due to the large volume and the requirement of oblique incidence. In this paper, we theoretically propose a three-layer nanograting-dielectric-metal (NDM) plasmonic structure. Within this structure, a thickness-dependent plasmonic WG (PWG) mode in the middle dielectric cavity strongly couples with SPPs on the top surface, resulting in two new hybridized PWG-SPPs modes. This hybridization coupling phenomenon is analyzed in detail by using plasmonic hybridization and two coupled oscillator models. Besides, a thorough investigation is conducted on the sensing performance of these two PWG-SPPs hybridized modes. The difference in sensing characteristics between these two hybridized modes can be well explained by their coupling strength variation. This NDM plasmonic nanostructure owns unparalleled advantages in the generation and modulation of a variety of new modes, effectively promoting the development of miniaturized optoelectronic devices.

Investigation of a highly-sensitive aluminum-based plasmonic device using antimonene for sensing applications

Aluminum (Al) has gained popularity for surface plasmon resonance-based applications due to its affordability and compatibility with CMOS technology at the nanoscale. Over angle-interrogation mode, plasmonic interactions occurring at the metal-dielectric junction, are the outcomes of the attenuated total internal reflection phenomenon. Modified Al-based Kretschmann configuration results in phase-matching conditions that are seen as resonant points in the reflection characteristics. In our work, we have engineered an Al-based plasmonic device utilizing Antimonene as a 2D nanomaterial for bio-sensing purposes in the Near-Infrared (NIR) spectral domain. The study investigates the performance of Surface Plasmon Resonance (SPR) based refractive index sensor using different 2D nanomaterials with an optimized Al thickness of 30 nm. A comparative analysis of Al-based Kretschmann configurations in the presence of Graphene, Black Phosphorus, MXene, and Antimonene is presented using engineered intermediate layers. It is observed that the Al-antimonene-based plasmonic device exhibits improved sensing parameters in the NIR optical window.

Plasmon induced hot carrier distribution in Ag20 -CO composite.

The interaction between plasmons and the molecules leads to the transfer of plasmon-induced hot carriers, presenting innovative opportunities for controlling chemical reactions on sub-femtosecond timescales. Through real-time time-dependent density functional theory simulations, we have investigated the enhancement of the electric field due to plasmon excitation and the subsequent generation and transfer of plasmon-induced hot carriers in a linear atomic chain of Ag20 and an Ag20 -CO composite system. By applying a Gaussian laser pulse tuned to align with the plasmon frequency, we observe a plasmon-induced transfer of hot electrons from the occupied states of Ag to the unoccupied molecular orbitals of CO. Remarkably, there is a pronounced accumulation of hot electrons and hot holes on the C and O atoms. This phenomenon arises from the electron migration from the inter-nuclear regions of the C-O bond towards the individual C and O atoms. The insights garnered from our study hold the potential to drive advancements in the development of more efficient systems for catalytic processes empowered by plasmonic interactions.

Theoretical research on a broadband terahertz absorber for thermally controlled radiation emission based on the epsilon-near-zero mode.

In this paper, a tunable and ultra-broadband terahertz (THz) absorber is proposed. The absorber, which is built upon the conventional metal-dielectric-metal tri-layer configuration, incorporates a KCl thin film within the dielectric gap situated between the top resonator and the middle dielectric layer. The simulation indicates that the absorber effectively captures more than 90% of terahertz waves between 3.6 and 7.3 THz, achieving absorption of over 99% within the 5.8-6.9 THz range. This unique broadband absorber is enabled by the interaction of plasmon and epsilon-near-zero (ENZ) modes. Additionally, due to the utilization of VO2 in the top resonator, the designed absorber holds potential to function as a thermally controlled radiation emitter, exhibiting a high emissivity of 90.5% at high temperatures while maintaining a low emissivity of 8.2% at low temperatures. The absorber is uncomplicated and adjustable, offering great potential for use in thermal management, terahertz camouflage, and engineering insulation.

3D nanoplasmonic structure for ultrahigh enhanced SERS with less variability, polarization independence, and multimodal sensing applied to picric acid detection.

Surface-enhanced Raman scattering (SERS) is recognized as a powerful analytical method. However, its efficacy is hindered by considerable signal variability stemming from factors like surface irregularities, temporal instability of the substrate, interference with substrate signal, polarization sensitivity and uneven molecular distribution. To address these challenges, a new strategy is employed to enhance the reproducibility of SERS signals. Initially, a periodic 3D metallic structure is utilized to achieve polarization-independent ultrahigh enhancement. Additionally, signal averaging over multiple points and normalization are implemented. The integration of these techniques enables multimodal sensing (SERS, SEF, SPR) using a plasmonic chip, demonstrating ultrahigh enhancement through the interaction of extended and localized plasmons alongside nanoantenna-type resonances. The chip comprises a periodic silver 2D grating adorned with Au nanocubes, behaving as a 3D metasurface to amplify plasmonic local fields, thus facilitating SERS. Its uniformity and polarization independence together with signal averaging and normalization mitigate signal variability. Fabricated via electron beam lithography, the chip's performance is evaluated for surface-enhanced fluorescence (SEF) and SERS using Rhodamine 6G as the target molecule. Results exhibit two orders of magnitude enhancement factor for SEF and 2.5 × 107 for SERS. For chemical sensing, the chip is tested for picric acid detection across a concentration range from nanomolar to millimolar, demonstrating a detection limit of approximately 3 nM.

Periodical Ultra-Modulation of Broadened Laser Spectra in Dielectrics at Variable Ultrashort Laser Pulsewidths: Ultrafast Plasma, Plasmonic and Nanoscale Structural Effects

Self-phase modulation (SPM) broadening of prompt laser spectra was studied in a transmission mode in natural and synthetic diamonds at variable laser wavelengths (515 and 1030 nm), pulse energies and widths (0.3–12 ps, positively chirped pulses), providing their filamentary propagation. Besides the monotonous SPM broadening of the laser spectra versus pulse energy, which was more pronounced for the (sub)picosecond pulsewidths and more nitrogen-doped natural diamond with its intra-gap impurity states, periodical low-frequency modulation was observed in the spectra at the shorter laser pulsewidths, indicating dynamic Bragg filtering of the supercontinuum due to ultrafast plasma and nanoplasmonic effects. Damping of broadening and ultra-modulation for the longer picosecond pulsewidths was related to the thermalized electron-hole plasma regime established for the laser pulsewidths longer, than 2 ps. Unexpectedly, at higher pulse energies and corresponding longer, well-developed microfilaments, the number of low-intensity, low-frequency sideband spectral modulation features counterintuitively increases, thus indicating dynamic variation of the periods in the longitudinal plasma Bragg gratings along the filaments due to prompt secondary laser–plasmon interactions. The underlying sub- and/or near-wavelength longitudinal nanoscale Bragg gratings produced by femtosecond laser pulses in this regime could be visualized in less hard lithium niobate by atomic force microscopy cross-sectional analysis in the correlation with the corresponding sideband spectral components, supporting the anticipated Bragg filtering mechanism and envisioning the corresponding grating periods.

Phase time delay caused by quantum effects in nearby plasmonic nanostructures of a one-dimensional photonic crystal

A one-dimensional photonic crystal (1DPC) incorporated with a defect layer containing a four-level double V-type quantum system adjacent to a plasmonic nanostructure is employed to investigate the Hartman effect. The study involves the interaction of two orthogonal circularly polarized laser beams with the defect layer, possessing identical frequencies but vary in phase and electric field amplitude. The defect layer exhibits quantum system adjacent to plasmonic nanostructure and field interaction phenomena like optical transparency, nonzero dispersion with zero absorption, gain without inversion, and others related effects. By manipulating the phase of the driving fields and probe detuning, the 1DPC can function as either a positive index material (PIM) or a negative index material (NIM), correlating to the normal and anomalous dispersion of the defect layer, respectively. The positive and negative Hartman effects for PIM and NIM, respectively, can be observed by adjusting the relative phase with respect to the driving fields. Our suggested approach might be used in optical memory, all-optical switching, all-optical routing, and interferometry.

Optical Nanoimaging of Surface Plasmon Polaritons Supported by Ultrathin Metal Films.

The physics of electrons, photons, and their plasmonic interactions change dramatically when one or more dimensions are reduced to atomic-level thicknesses. For example, graphene exhibits unique electrical, plasmonic, and optical properties. Likewise, atomic-thick metal films are expected to exhibit extraordinary quantum optical properties. Several methods of growing ultrathin metal films were demonstrated, but the quality of the obtained films was much worse compared to bulk films. In this work, we propose a new method of making ultrathin gold films that are close in their properties to bulk gold films. Excellent plasmonic properties are revealed by directly observing quasi-short- and quasi-long-range plasmons in such a film via scanning near-field optical microscopy. The results pave the way for the use of ultrathin gold films in flexible and transparent nanophotonics and optoelectronic applications.

Defocused imaging-based quantification of plasmon-induced distortion of single emitter emission

Optical properties of single emitters can be significantly improved through the interaction with plasmonic structures, leading to enhanced sensing and imaging capabilities. In turn, single emitters can act as sensitive probes of the local electromagnetic field surrounding plasmonic structures, furnishing fundamental insights into their physics and guiding the design of novel plasmonic devices. However, the interaction of emitters in the proximity to a plasmonic nanostructure causes distortion, which hinders precise estimation of position and polarization state and is one of the reasons why detection and quantification of molecular processes yet remain fundamentally challenging in this era of super-resolution. Here, we investigate axially defocused images of a single fluorescent emitter near metallic nanostructure, which encode emitter positions and can be acquired in the far-field with high sensitivity, while analyzing the images with pattern matching algorithm to explore emitter-localized surface plasmon interaction and retrieve information regarding emitter positions. Significant distortion in defocused images of fluorescent beads and quantum dots near nanostructure was observed and analyzed by pattern matching and finite-difference time-domain methods, which revealed that the distortion arises from the emitter interaction with nanostructure. Pattern matching algorithm was also adopted to estimate the lateral positions of a dipole that models an emitter utilizing the distorted defocused images and achieved improvement by more than 3 times over conventional diffraction-limited localization methods. The improvement by defocused imaging is expected to provide a way of enhancing reliability when using plasmonic nanostructure and diversifying strategies for various imaging and sensing modalities.

Plasmonic effects in the neutralization of slow ions at a metallic surface

AbstractSecondary electron emission is an important process that plays a significant role in several plasma‐related applications. As measuring the secondary electron yield experimentally is very challenging, quantitative modelling of this process to obtain reliable yield data is critical as input for higher‐scale simulations. Here, we build upon our previous work combining density functional theory calculations with a model originally developed by Hagstrum to extend its application to metallic surfaces. As plasmonic effects play a much more important role in the secondary electron emission mechanism for metals, we introduce an approach based on Poisson point processes to include both surface and bulk plasmon excitations to the process. The resulting model is able to reproduce the yield spectra of several available experimental results quite well but requires the introduction of global fitting parameters, which describe the strength of the plasmon interactions. Finally, we use an in‐house developed workflow to calculate the electron yield for a list of elemental surfaces spanning the periodic table to produce an extensive data set for the community and compare our results with more simplified approaches from the literature.