Plasmonic Field Research Articles

Surface plasmon field enhanced upconversion luminescence for the screening and detection of phenolic environmental estrogens

The endocrine system's interference caused by environmental estrogens (EEs) residue in food is a topic of public concern. Here, we construct an aptasensor for the sensitive detection of EEs based on luminescence resonance energy transfer (LRET). With MoS2 nanosheets acting as the energy acceptor and upconversion luminescence nanoparticles@gold nanoparticles (UCNPs@Au) as the luminescence donor, autofluorescence from food is prevented from interfering. The in-situ deposition of AuNPs not only induces local field enhancement to significantly increase the luminescence intensity of UCNPs, but also conduces to the modification of aptamer through Au-S bond. This aptasensor can respond to multiple estrogens thanks to the choice of a universal aptamer that recognizes phenolic hydroxyl group, and it offers the probability to screen unidentified phenolic estrogens. This method has a high sensitivity and a low limit of detection (LOD), and the satisfactory recovery rates acquired from water and milk samples confirmed its considerable application value.

Characterizing excited states of single donor-acceptor molecule by high-resolution Raman images

The excited states of charge transfer (CT), local donor (LD) and local acceptor (LA) for donor-acceptor molecules play an important role in many applications. However, these excited quantum states are still impossible to be characterized by conventional experimental techniques. Optical spectroscopy with the supplement of density functional theory calculations is widely adopted to investigate excited states, but is often inefficient for the donor-acceptor molecule owing to substantial errors of functionals in describing CT states. Our calculations show that the resonance tip-enhanced Raman scattering images that utilizes the confined plasmonic field for CT, LD and LA states possess their exclusive imaging characterizations, giving unambiguous identification of different excited-state properties. In addition, the resonance Raman images provide a benchmark to reasonably estimate the accuracy of different functionals in describing excited states of the charge-transfer system. These findings extend the emerging Raman images to the characterization and improvement of functional donor-acceptor molecular materials.

Observation of Ultrabroadband Striped Space-Time Surface Plasmon Polaritons

Because surface plasmon polaritons (SPPs) are surface waves characterized by one free transverse dimension, the only monochromatic diffraction-free spatial profiles for SPPs are cosine and Airy waves. Pulsed SPP wave packets have been recently formulated that are propagation-invariant and localized in the in-plane dimensions by virtue of a tight spectral association between their spatial and temporal frequencies, which have thus been dubbed “space-time” (ST) SPPs. Because of the spatiotemporal spectral structure unique to ST-SPPs, the optimal launching strategy of such novel plasmonic field configurations remains an open question. We present here a critical step toward realizing ST-SPPs by reporting observations of ultrabroadband striped ST-SPPs. These are SPPs in which each wavelength travels at a prescribed angle with respect to the propagation axis to produce a periodic (striped) transverse spatial profile that is diffraction-free. We start with a free-space ST wave packet that is coupled to a ST-SPP at a gold-dielectric interface, and unambiguously identify the ST-SPP via an axial beating detected in two-photon fluorescence produced by the superposition of incident ST wave packet and the excited surface-bound ST-SPP. These results highlight a viable approach for efficient and reliable coupling to ST-SPPs and, thus, represent the first crucial step toward realization of the full potential of ST-SPPs for plasmonic sensing and imaging.

Exploiting the Momentum Distribution in Atomically Confined Plasmonic Fields by Inelastic Scatterings

The utilization of atomically confined plasmonic fields has revolutionized the imaging technique. According to the fundamental position-momentum uncertainty principle, such a narrow spatial distribution certainly leads to a broad momentum distribution in the fields, which has however been overlooked. Here we propose a novel exploitation for the momentum distribution by adaptively satisfying the conservation law of momentum in inelastic Raman scatterings in periodic systems, providing a unique optical means of directly measuring the whole phonon dispersions. The proposed technique is particularly useful for measuring phonon dispersions of low-dimensional hydrogen-rich materials, which are completely inaccessible via other techniques. The numerical results for a single all-trans polyacetylene chain demonstrate that all phonon dispersion branches can be conclusively measured from their Raman images for the first time. Our findings highlight a unique advantage of the emerging momentum-based nanophotonics and open the door for exploiting highly confined plasmonic fields in another dimension.

Band alignment and charge transport study of Au nanoparticles decorated over MoS2/MoSe2 hybrid heterostructure for plasmon enhanced photodetection

This paper demonstrates the fabrication of MoS2/MoSe2 hybrid heterostructure and decorating it with Au nanoparticles for enhanced photodetection. The measured responsivity values of the fabricated devices at 505 nm with and without Au nanoparticles were found to be 2.54 A/W and 0.262 A/W suggesting a clear indication of the enhanced photodetection with Au NPs. Detailed band alignment studies of the hybrid heterostructure are performed using Ultra-Violet Photoelectron Spectroscopy (UPS) which also explains the real-time charge transport phenomenon of the fabricated device. Further, simulations and numerical analysis for Au decorated MoS2/MoSe2 are performed to understand the electrical field distribution across Au NPs and the enhancement of absorption due to Mie Scattering. Successful demonstration of plasmon-enhanced photodetection of MoS2/MoSe2 will be essential in the field of 2D plasmonics with potential applications in optical detection in the harsh environment, photovoltaic solar energy conversion, chemical sensing applications, etc.

Charge-driven arrested phase-separation of polyelectrolyte-gold nanoparticle assemblies leading to plasmonic oligomers

Aggregates of charged metal particles obtained by electrostatic coupling with a compound of opposite charge in the vicinity of the net zero charge ratio are of interest in the field of plasmonics because the inter-particle distance is minimal, which favours plasmonic coupling. However, these structures present a low colloidal stability limiting the development of applications. In this article we show that globally neutral aggregates formed by electrostatic complexation of citrate-stabilized gold particles and a quaternized chitosan (i.e., polycation) around the net zero charge ratio could be stabilized at a nanometric size by the subsequent addition of polyelectrolyte chains. Furthermore, the sign of the charge carried by the stabilizing chains determines the sign of the global charge carried by the stabilized complexes. The stabilization is demonstrated in saline environment on a broad pH range as well as in a cell culture media over periods of several days. Contrarily to stabilization by charged particles, our stabilized complexes are found to retain their initial characteristics (i.e. shape, size, internal structure and optical properties) after stabilization. Hence, the plasmonic coupling allows to maximize the optical absorption around the 800nm wavelength at which the lasers used for thermoplasmonic and surface enhanced Raman scattering analysis operate.

A plasmonic fluorescent ratiometric temperature sensor for self-limiting hyperthermic applications utilizing FRET enhancement in the plasmonic field.

Nanoparticle mediated photo-induced hyperthermia holds much promise as a therapeutic solution for the management of diseases like cancer. The conventional methods of temperature measurements do not measure the actual temperature generated in the vicinity of the nanoparticles during illumination. In contrast, nano temperature sensors built on hyperthermic nanoparticles can relay local temperatures around the nanoparticles during thermal induction. In this study, we present a core shell construct consisting of a plasmonic core and a silica shell encapsulating a FRET pair of organic dyes for such application. The plasmonic core imparts photo-induced hyperthermic properties to the nanoconstruct, while the fluorescent shell enables ratiometric sensing of temperature. We see that even at a low dye encapsulation concentration, the shell displays a linear ratiometric fluorescence response to temperature and high energy transfer between the dye pair. Interestingly, Monte Carlo simulations, without considering the plasmonic core, show that the energy transfer in the system should be much smaller than that observed, confirming plasmon enhancement in the FRET energy transfer. We also show the ratiometric temperature measurement using these particles during photoinduced hyperthermia. This study suggests the use of plasmonic nanoparticles in the next generation "self-limiting" photothermal therapy.

Approaching PetaVolts per Meter Plasmonics Using Structured Semiconductors

A newly uncovered class of plasmons in the strongly excited limit opens access to unprecedented Petavolts per meter electromagnetic fields with wide-ranging, transformative impact. Unlike conventional plasmons, such plasmons are constituted by non-perturbative, large-amplitude oscillations of the ultradense, delocalized free electron Fermi gas inherent in conductive media. Here structured semiconductors doped to have an appropriate conduction electron density are introduced to tune the properties of the Fermi gas for matched excitation of large-amplitude plasmons using readily available electron beams which enables immediate experimental validation. Specifically, an electrostatic, surface “crunch-in” plasmon is collisionlessly excited by the beam launched inside a tube. Strong excitation due to matching results in relativistic oscillations of the electron gas and unravels unique phenomena. Relativistically induced ballistic electron transport comes about due to relativistic multifold increase in the mean free path and also leads to unconventional heat deposition beyond Ohm’s law. This explains the absence of observed damage or solid-plasma formation in past experiments on conductive samples interacting with electron bunches shorter than 10−13 seconds. Furthermore, relativistic momentum leads to copious tunneling of electron gas across the surface, which then crunches inside the tube. Relativistic effects along with large, localized electron density variations underlying these modes necessitate kinetic approach to theoretical and computational modeling. Kinetic model presented here demonstrates experimental viability of observing tens of gigavolts per meter plasmonic fields excited by matching readily available electron beams to plasmons in semiconductors with 1018cm−3 free electron density, and paves the way for Petavolts per meter plasmonics.

Metal-Dielectric Nanopillar Antenna-Resonators for Efficient Collected Photon Rate from Silicon Carbide Color Centers.

A yet unresolved challenge in developing quantum technologies based on color centres in high refractive index semiconductors is the efficient fluorescence enhancement of point defects in bulk materials. Optical resonators and antennas have been designed to provide directional emission, spontaneous emission rate enhancement and collection efficiency enhancement at the same time. While collection efficiency enhancement can be achieved by individual nanopillars or nanowires, fluorescent emission enhancement is achieved using nanoresonators or nanoantennas. In this work, we optimise the design of a metal-dielectric nanopillar-based antenna/resonator fabricated in a silicon carbide (SiC) substrate with integrated quantum emitters. Here we consider various color centres known in SiC such as silicon mono-vacancy and the carbon antisite vacancy pair, that show single photon emission and quantum sensing functionalities with optical electron spin read-out, respectively. We model the dipole emission fluorescence rate of these color centres into the metal-dielectric nanopillar hybrid antenna resonator using multi-polar electromagnetic scattering resonances and near-field plasmonic field enhancement and confinement. We calculate the fluorescence collected photon rate enhancement for these solid state vacancy-centers in SiC in these metal-dielectric nanopillar resonators, showing a trade-off effect between the collection efficiency and radiative Purcell factor enhancement. We obtained a collected photon rate enhancement from a silicon monovacancy vacancy center embedded in an optimised hybrid antenna-resonator two orders of magnitude larger compared to the case of the color centres in bulk material.

Tailoring spatiotemporal dynamics of plasmonic vortices

Plasmonic vortices confining orbital angular momentums to surface have aroused wide research interest in the last decade. Recent advances of near-field microscopes have enabled the study on the spatiotemporal dynamics of plasmonic vortices, providing a better understanding of optical orbital angular momentums in the evanescent wave regime. However, these works only focused on the objective characterization of plasmonic vortex and have not achieved subjectively tailoring of its spatiotemporal dynamics for specific applications. Herein, it is demonstrated that the plasmonic vortices with the same topological charge can be endowed with distinct spatiotemporal dynamics by simply changing the coupler design. Based on a near-field scanning terahertz microscopy, the surface plasmon fields are directly obtained with ultrahigh spatiotemporal resolution, experimentally exhibiting the generation and evolution divergences during the whole lifetime of plasmonic vortices. The proposed strategy is straightforward and universal, which can be readily applied into visible or infrared frequencies, facilitating the development of plasmonic vortex related researches and applications.

Coupling of plasmonic hot spots with shurikens for superchiral SERS-based enantiomer recognition.

Detection of enantiomers is a challenging problem in drug development as well as environmental and food quality monitoring where traditional optical detection methods suffer from low signals and sensitivity. Application of surface enhanced Raman scattering (SERS) for enantiomeric discrimination is a powerful approach for the analysis of optically active small organic or large biomolecules. In this work, we proposed the coupling of disposable chiral plasmonic shurikens supporting the chiral near-field distribution with SERS active silver nanoclusters for enantio-selective sensing. As a result of the plasmonic coupling, significant difference in SERS response of optically active analytes is observed. The observations are studied by numerical simulations and it is hypothesized that the silver particles are being excited by superchiral fields generated at the surface inducing additional polarizations in the probe molecules. The plasmon coupling phenomena was found to be extremely sensitive to slight variations in shuriken geometry, silver nanostructured layer parameters, and SERS excitation wavelength(s). Designed structures were able to discriminate cysteine enantiomers at concentrations in the nanomolar range and probe biomolecular chirality, using a common Raman spectrometer within several minutes. The combination of disposable plasmonic substrates with specific near-field polarization can make the SERS enantiomer discrimination a commonly available technique using standard Raman spectrometers.

Surface Lattice Resonances in 3D Chiral Metacrystals for Plasmonic Sensing.

Chiral lattice modes are hybrid states arising from the chiral plasmonic particles assembled in ordered arrays with opportune periodicity. These resonances exhibit dependence on excitation handedness, and their observation in plasmonic lattices is strictly related to the chiroptical features of the fundamental plasmonic unit. Here, the emergence of chiral surface lattice resonances (c-SLRs) is shown in properly engineered arrays of nanohelices (NHs), fully three dimensional (3D)chiral nano-objects fabricated by focused ion beam processing. By tuning the relative weight of plasmonic and photonic components in the hybrid mode, the physical mechanism of strong diffractive coupling leading to the emergence of the lattice modes is analyzed, opening the way to the engineering of chiral plasmonic systems for sensing applications. In particular, a coupling regime is identified where the combination of a large intrinsic circular dichroism (CD) of the plasmonic resonance with a well-defined balance between the photonic quality factor (Q factor) and the plasmonic field enhancement (M) maximizes the capability of the system to discriminate refractive index (RI) changes in the surrounding medium. The results lay the foundation for exploiting CD in plasmonic lattices to high performance refractometric sensing.

Polarization optical switching between supercell states of plasmonic metasurfaces

We study, experimentally and numerically, in-plane light scattering (side scattering) and near- and far-field collective excitations in plasmonic metasurfaces consisting of periodic arrays of Au $\mathsf{V}$-shaped nanoantennas. Each unit cell in these arrays includes a pair of such nanoantennas facing each other ($<>$). We show that, depending on the polarization of the incident light, such metasurfaces can support two types of supercells ($<+>$ and $>+<$). $<+>$ is a braket supercell wherein two nanoantennas of the same unit cells are coupled to each other via their plasmonic fields. When the polarization of the incident light is rotated by ${90}^{\ensuremath{\circ}}$, a plasmonic conjugate supercell is formed ($>+<$). In this case the plasmon fields couple two $\mathsf{V}$-shaped nanoantennas of the neighboring cells, supporting a geometrical and near-field coupling process different from $<+>$. We show that braket and conjugate supercells support sharp infrared resonances at two different wavelengths, offering a high extinction polarization optical switching process associated with the transition between $<+>$ and $>+<$. Our results show that while $<+>$ supercells tend to be optically noninteracting with each other, $>+<$ supercells can get coupled to the lattice modes, spatially extending coherent properties across the arrays. We investigate the in-plane scattering of these arrays, demonstrating how variations of the charge configuration and phase by the incident light polarization can be used to coherently control the in-plane scattering of $\mathsf{V}$-shaped nanoantennas arrays.

Fano resonances and slow light in a nanocavity assisted by metallic nanoparticles‐quantum dot system

AbstractDouble Fano resonances in a nanocavity assisted by metallic nanoparticles (MNPs)‐quantum dot (QD) system are demonstrated theoretically. The nanocavity is assumed to couple with the QD and QD is assumed to locate in the plasmon field produced by two excited MNPs nearby. The nanocavity is driven by a control field and a probing field. Double Fano resonances can be manipulated by the system parameters such as frequency detuning and coupling strength among the nanocavity, the mechanical oscillator, MNPs and QD. Especially, we find the second Fano resonance appears due to the interaction between the nanocavity with the QD‐MNPs. We also discuss the transmission and group delay in the double Fano resonance transparency windows which show tunable fast and slow light for different probe frequency. Our results may provide possible applications in designing optical buffer, switching, and so forth.

Nanoplasmon‐Nanoplasma Transition in Cu Nanoparticle: Distinction of Electron Emission

AbstractThe electron response of nanoplasmon and nanoplasma in the laser field is greatly important for improving the functionality and efficiency of many potential applications. However, how and under what conditions the nanoplasmon‐nanoplasma transition works remains poorly understood due to radiation damage and charge buildup. Utilizing the combined aerodynamic lens and velocity map imaging spectrometer, this transition mediated by different mechanisms are demonstrated, as verified by the distinct photoelectron momentum distributions from Cu nanoparticles. Initially the polarization‐dependent distributions emphasize the domination of surface emission driven by the plasmonic field. Subsequently the transition starts and the competition of volume‐multiphoton and thermionic emission plays the intermediate state dominating the transition process. Finally, a complete plasma is generated with the leading role of thermionic emission, which is confirmed by first observing the correlated electronic decay in metal nanoparticles. These findings bridge the gap between electron emission in nanoplasmonic and nanoplasma states and identify the mechanism‐specific contributions, which will offer general principles for designing nanostructure and laser fields to control electron excitation and emission in practice.

The Effect of Relative In-Plane Twisting in Graphene Bilayer on Sensing Using Surface Plasmon Resonance

Surface plasmon resonance (SPR) is generally observed by the excitation of surface plasmon polaritons on the metal (Au/Ag) surface. In order to utilize the SPR phenomenon for sensing application, the metal surface is functionalized with suitable ligands. Although such functionalization can enhance the specific adsorption capability of the sensor however due to the large thickness of the ligands, the plasmonic field of the metal surface becomes less sensitive towards the adsorption of analytes. In the next generation SPR-based sensor, graphene can be utilized not only as plasmonic material but also as a suitable ligand for attracting analytes through π-π interaction. In this article, we present our theoretical simulation studies on the observation of the SPR phenomenon using graphene monolayer (MLG), bilayer graphene (BLG), and in-plane twisted layers of BLG (T-BLG) as plasmonic materials deposited over zinc-selenide substrate. The Kretschmann configuration under wavelength interrogation setup was simulated, and SPR wavelength for graphene systems/water interface was estimated. The bio-sensing simulation was performed, and the sensing parameters viz. sensitivity, figure-of-merit (FOM), and plasmonic field for different graphene systems were obtained. Interestingly, the excellent sensing parameters were found in T-BLG system with relative in-plane twist angle near to magic angle viz. 1°. The enhancement is due to strong coupling between the layers twisted at the magic angle. This study demonstrates that the MLG, BLG and T-BLG can be employed as a standalone layer system for not only the generation of plasmonic fields but also enhanced sensing due to its intrinsic interactions with bio-analytes.

Optical Trapping of a Single Molecule of Length Sub-1 nm in Solution

Optical Trapping of a Single Molecule of Length Sub-1 nm in Solution

Fabrication of a large scale metasurface with high resolution and enhanced absorption

Plasmonic metasurface nanostructures have the potential to enable nonlinear optical functionality in metasurfaces by reducing power operating thresholds and enabling ultra-thin subwavelength devices. However, low absorption caused by resistive losses of unwanted metallic appearance and irregular corners in the fabrication process significantly reduces this promise, leading the metasurface community toward the new approaches to fabricate large area metasurfaces with Electron Beam lithography (EBL). In this article, with controlled proximity effect and high dose exposure rate in EBL setup, large area (2 cm2) metasurfaces are fabricated with high resolution of structure. The effect of absorption resonance in Infrared (LWIR) is experimentally studied through Fourier Transform Infrared Spectroscopy (FTIR). The results signify that the metasurface with high resolution and fine metallic corners outperforms the fabricated prototype with metal residue and non-uniform corners. When compared to conventional EBL, our nanofabrication approach speeds the patterning time by three times. The experimental measurements reveal enhanced absorption performance at 8 µm wavelength. Whereas, the developed metasurface is numerically studied to explain the absorption performance with plasmonic field distributions. This approach could be used in optoelectronic devices involving plasmonic applications, such as biosensing and infrared imaging.

Tunable plasmonics on epsilon-near-zero materials: the case for a quantum carrier model.

The carrier density profile in metal-oxide-semiconductor (MOS) capacitors is computed under gating using two classical models - conventional drift-diffusion (CDD) and density-gradient (DG) - and a self-consistent Schrödinger-Poisson (SP) quantum model. Once calibrated the DG model approximates well the SP model while being computationally more efficient. The carrier profiles are used in optical mode computations to determine the gated optical response of surface plasmons supported by waveguides incorporating MOS structures. Indium tin oxide (ITO) is used as the semiconductor in the MOS structures, as the real part of its optical permittivity can be driven through zero to become negative under accumulation, enabling epsilon-near-zero (ENZ) effects. Under accumulation the predictions made by the CDD and SP models differ considerably, in that the former predicts one ENZ point but the latter predicts two. Consequently, the CDD model significantly underestimates perturbations in n e f f of surface plasmons (by ∼4×) and yields incorrect details in surface plasmon fields near ENZ points. The discrepancy is large enough to invalidate the CDD model in MOS structures on ENZ materials under accumulation, strongly motivating a quantum carrier model in this regime.

Plasmonic Modes and Fluorescence Enhancement Coupling Mechanism: A Case with a Nanostructured Grating.

The recent development and technological improvement in dealing with plasmonic metasurfaces has triggered a series of interesting applications related to sensing challenges. Fluorescence has been one of the most studied tools within such a context. With this in mind, we used some well characterized structures supporting plasmonic resonances to study their influence on the emission efficiency of a fluorophore. An extended optical analysis and a complementary investigation through finite-difference time-domain (FDTD) simulations have been combined to understand the coupling mechanism between the excitation of plasmonic modes and the fluorescence absorption and emission processes. The results provide evidence of the spectral shape dependence of fluorescence on the plasmonic field distribution together with a further relationship connected with the enhancement of its signal. It has made evident that the spectral region characterized by the largest relative enhancement closely corresponds to the strongest signatures of the plasmonic modes, as described by both the optical measurements and the FDTD findings.