Far-field Optical Properties Research Articles

Distribution of Single-Particle Resonances Determines the Plasmonic Response of Disordered Nanoparticle Ensembles.

Understanding how colloidal soft materials interact with light is crucial to the rational design of optical metamaterials. Electromagnetic simulations are computationally expensive and have primarily been limited to model systems described by a small number of particles-dimers, small clusters, and small periodic unit cells of superlattices. In this work we study the optical properties of bulk, disordered materials comprising a large number of plasmonic colloidal nanoparticles using Brownian dynamics simulations and the mutual polarization method. We investigate the far-field and near-field optical properties of both colloidal fluids and gels, which require thousands of nanoparticles to describe statistically. We show that these disordered materials exhibit a distribution of particle-level plasmonic resonance frequencies that determines their ensemble optical response. Nanoparticles with similar resonant frequencies form anisotropic and oriented clusters embedded within the otherwise isotropic and disordered microstructures. These collectively resonating morphologies can be tuned with the frequency and polarization of incident light. Knowledge of particle resonant distributions may help to interpret and compare the optical responses of different colloidal structures, correlate and predict optical properties, and rationally design soft materials for applications harnessing light.

Tuning the Geometry and Optical Chirality of Pentatwinned Au Nanoparticles with 5-Fold Rotational Symmetry.

Chirality transfer from chiral molecules to chiral nanomaterials represents an important topic for exploring the origin of chirality in many natural and artificial systems. Moreover, developing a promising class of chiral nanomaterials holds great significance for various applications, including sensing, photonics, catalysis, and biomedicine. Here we demonstrate the geometric control and tunable optical chirality of chiral pentatwinned Au nanoparticles with 5-fold rotational symmetry using the seed-mediated chiral growth method. A distinctive growth pathway and optical chirality are observed using pentatwinned decahedra as seeds, in comparison with the single-crystal Au seeds. By employing different peptides as chiral inducers, pentatwinned Au nanoparticles with two distinct geometric chirality (pentagonal nanostars and pentagonal prisms) are obtained. The intriguing formation and evolution of geometric chirality with the twinned structure are analyzed from a crystallographic perspective upon maneuvering the interplay of chiral molecules, surfactants, and reducing agents. Moreover, the interesting effects of the molecular structure of peptides on tuning the geometric chirality of pentatwinned Au nanoparticles are also explored. Finally, we theoretically and experimentally investigate the far-field and near-field optical properties of chiral pentatwinned Au nanoparticles through numerical simulations and single-particle chiroptical measurements. The ability to tune the geometric chirality in a controlled manner represents an important step toward the development of chiral nanomaterials with increasing architectural complexity for chiroptical applications.

Polarization states and far-field optical properties in dielectric photonic crystal slabs.

We study the role of topological singularities like Bound States in a Continuum (BICs) or Circularly Polarized States (CPSs) in determining ellipticity of the far-field polarization in dielectric metasurfaces. Using finite-difference time-domain as well as rigorous coupled-wave analysis simulations, we determine the behavior of the Stokes parameter S3 in the whole k space above the light cone, with special regard to the region close to the singularities. Moreover, we clarify the relation between the topological singularities and the circular dichroism in reflectivity.

Near- and Far-Field Optical Properties of Dipole-Multipole Plasmonic Coupled Building Blocks

The plasmonic hybridization in the complex nanostructure innovates multiple fields, such as chemistry, physics, materials science, and biology. In this article, we systematically studied the near- and far-field optical properties of building blocks of coupled dipoles or coupled dipoles and multipoles or a multipole in a coupled plasmonic system through numerical simulations. To be specific, the far-field spectrum, near-field phase changes, and angular radiation patterns of plasmonic hybridized structures were calculated. Also, the “gap separation effect” on the strength of plasmonic hybridization was discussed via spectral and near-field evaluation. Additionally, we investigated the coupling between building blocks and different shapes of dipoles through the near- and far-field study. To some extent, our studies have theoretically proven that, compared to the plasmonic coupling among dipoles, the coupling between multipoles and dipoles show mostly comparative and even stronger hybridization in terms of both near- and far-field, which led to the expanded broad range of resonance and stronger localized E-field. We believe that our work may contribute to the fundamental understanding of the plasmonic hybridization system and pave the path for new applications and opportunities in vast regimes of plasmonic-photonic and nanoplasmonic.

Engineered near- and far-field optical response of dielectric nanostructures using focused cylindrical vector beams

Near- and far-field optical properties of silicon nanostructures under linear polarization (Gaussian beam) and azimuthally or radially focused cylindrical vector beams are investigated by finite-difference time-domain method (FDTD) in Meep open-source software. A python toolkit allowing FDTD simulations in Meep for using those excitation sources is provided. In addition to the preferential excitation of specific electric or magnetic resonance modes as a function of the excitation beam polarization, it is shown in the case of spheroids that shape anisotropy affects the resonance wavelength and the dipole orientation of the magnetic or electric dipole mode. Depending on the spheroid symmetry axis with respect to the electric field orientation, the electric dipole resonance can be split into two peaks, giving quasi-unidirectional scattering, separated by an anapole mode. The optical properties in both far-field (scattering pattern) and near-field (electric and magnetic field hot spots) can be tuned by changing the excitation polarization at a fixed wavelength and selecting properly the spheroid shape and dimensions. These numerical simulations are extended to top-down fabrication-friendly nanostructures such as nanocylinders with circular or elliptic sections.

Multiple scattering of light in nanoparticle assemblies: User guide for the terms program

We introduce terms, an open-source Fortran program to simulate near-field and far-field optical properties of clusters of particles. The program solves rigorously the Maxwell equations via the superposition T-matrix method, where incident and scattered fields are decomposed into series of vector spherical waves.terms implements several algorithms to solve the coupled system of multiple scattering equations that describes the electromagnetic interaction between neighbouring scatterers. From this formal solution, the program can compute a number of physically-relevant optical properties, such as far-field cross-sections for extinction, absorption, scattering and their corresponding circular dichroism, as well as local field intensities and degree of optical chirality. By describing the incident and scattered fields in a basis of spherical waves the T-matrix framework lends itself to analytical formulas for orientation-averaged quantities, corresponding to systems of particles in random orientation; terms offers such computations for both far-field and near-field quantities of interest. This user guide introduces the program, summarises the relevant theory, and is supplemented by a comprehensive suite of stand-alone examples in the website accompanying the code.

Near-field and Far-field Optical Properties of Silver Nanospheres: Theoretical and Experimental Investigations of the Size, Shape, Dielectric Environment, and Composition Effects

Near-field and Far-field Optical Properties of Silver Nanospheres: Theoretical and Experimental Investigations of the Size, Shape, Dielectric Environment, and Composition Effects

Shaping the Color and Angular Appearance of Plasmonic Metasurfaces with Tailored Disorder.

The optical properties of plasmonic nanoparticle ensembles are determined not only by the particle shape and size but also by the nanoantenna arrangement. To investigate the influence of the spatial ordering on the far-field optical properties of nanoparticle ensembles, we introduce a disorder model that encompasses both "frozen-phonon" and correlated disorder. We present experimental as well as computational approaches to gain a better understanding of the impact of disorder. A designated Fourier microscopy setup allows us to record the real- and Fourier-space images of plasmonic metasurfaces as either RGB images or fully wavelength-resolved data sets. Furthermore, by treating the nanoparticles as dipoles, we calculate the electric field based on dipole-dipole interaction, extract the far-field response, and convert it to RGB images. Our results reveal how the different disorder parameters shape the optical far field and thus define the optical appearance of a disordered metasurface and show that the relatively simple dipole approximation is able to reproduce the far-field behavior accurately. These insights can be used for engineering metasurfaces with tailored disorder to produce a desired bidirectional reflectance distribution function.

Surface roughness and substrate induced symmetry-breaking: influence on the plasmonic properties of aluminum nanostructure arrays.

The surface topography is known to play an important role on the near- and far-field optical properties of metallic nanoparticles. In particular, aluminum (Al) nanoparticles are commonly fabricated through evaporation techniques, therefore exhibiting elevated surface roughness additionally to their native oxide layer. In this study, the mode-dependent influence of surface roughness on the plasmonic properties sustained by Al nanodisks (NDs) is first numerically investigated using a realistic model taking into account the thin native oxide layer. Due to the symmetry-breaking induced by the supporting dielectric substrate to Al ND, it appears that the roughness affects differently the substrate-induced out-of-plane quadrupolar mode (below 300 nm) and the in-plane dipolar mode sustained by the Al ND. By increasing the top surface roughness of the Al ND, the substrate-induced quadrupolar mode is significantly damped especially in the ultraviolet regime, while the dipolar resonance is broadened and redshifted. The explanation of these effects relies in the decoherence and dissipation of the collective electronic oscillations as a result of the top surface roughness to the different near-field distribution of the out-of-plane quadrupolar mode and in-plane dipolar mode. Moreover, the influences of the diameter of Al ND, dielectric substrate with different refractive index, and the oxidation of Al ND on these two modes are also investigated. Particularly, the quadrupolar mode disappears with surface roughness and oxidation, explaining why this mode is very weak and sometimes barely visible on evaporated Al nanostructures reported in the literature. Finally, these results are experimentally confirmed by characterizing the optical properties of periodic Al ND arrays.

Plasmonic Particle-on-Film Nanocavity in Tightly Focused Vector Beam: a Full-Wave Theoretical Analysis from Near-Field Enhancement to Far-Field Radiation

Based on the local electric field enhancement of gap-mode surface plasmon resonance, the plasmonic particle-on-film nanocavity (PPoFN) can realize Raman signal enhancement of multiple orders of magnitude, even single molecule detection. The tightly focused radially polarized (Bessel-Gaussian) beam (TFRPB), containing a cylindrical symmetry longitudinal component, is a superior excitation source for PPoFN to generate a more intriguing electromagnetic hot spot in the gap. For the optical response of PPoFN in TFRPB, some theoretical and experimental studies at a certain wavelength have been reported, but a full-wave analysis about the near- and far-field optical properties is still lacking because it is still difficult to generate a full-wave radially polarized beam and achieve a dispersion-free confocal light field in the experiment. In this paper, we analyze the full-wave near- and far-field optical properties of PPoFN in TFRPB by using numerical simulation with the finite element method (FEM). For comparison, a full-wave analysis of PPoFN in tightly focused linearly polarized (Gaussian) beam (TFLPB) is also implemented. Based on the comprehensive results of local field enhancement, nanofocusing property, and far-field radiation, it is found that the PPoFN in TFRPB with the strongest toroidal dipole (TD) mode at a certain wavelength can achieve good performance in Raman signal excitation and detection. Importantly, this result will provide a theoretical reference for the application of PPoFN in tightly focused vector beam.

Field enhancement of optical bowtie nano‐antenna using exponential tapered profile

In this work, both the near-field and far-field optical properties of curved sides bowtie nano-antenna are investigated in the near-infrared range. The curvature of the proposed structure is based on the Vivaldi antenna tapering shape. The effect of tapering rate on the near-field enhancement is studied, and the results show that the proposed antenna structure produces better field enhancement compared with conventional bowtie antenna with linear sides and hence it is promising for energy harvesting and microscopy applications. Also, the far-field properties are studied to decide the validity of the structure in optical communication applications.

Arbitrary control of the diffusion potential between a plasmonic metal and a semiconductor by an angstrom-thick interface dipole layer.

Localized surface plasmon resonances (LSPRs) are gaining considerable attention due to the unique far-field and near-field optical properties and applications. Additionally, the Fermi energy, which is the chemical potential, of plasmonic nanoparticles is one of the key properties to control hot-electron and -hole transfer at the interface between plasmonic nanoparticles and a semiconductor. In this article, we tried to control the diffusion potential of the plasmonic system by manipulating the interface dipole. We fabricated solid-state photoelectric conversion devices in which gold nanoparticles (Au-NPs) are located between strontium titanate (SrTiO3) as an electron transfer material and nickel oxide (NiO) as a hole transport material. Lanthanum aluminate as an interface dipole layer was deposited on the atomic layer scale at the three-phase interface of Au-NPs, SrTiO3, and NiO, and the effect was investigated by photoelectric measurements. Importantly, the diffusion potential between the plasmonic metal and a semiconductor can be arbitrarily controlled by the averaged thickness and direction of the interface dipole layer. The insertion of an only one unit cell (uc) interface dipole layer, whose thickness was less than 0.5 nm, dramatically controlled the diffusion potential formed between the plasmonic nanoparticles and surrounding media. This is a new methodology to control the plasmonic potential without applying external stimuli, such as an applied potential or photoirradiation, and without changing the base materials. In particular, it is very beneficial for plasmonic devices in that the interface dipole has the ability not only to decrease but also to increase the open-circuit voltage on the order of several hundreds of millivolts.

TiO2 Nanocolumn Arrays for More Efficient and Stable Perovskite Solar Cells.

Organic-inorganic hybrid perovskite solar cells have attracted much attention due to their high power conversion efficiency (>25%) and low-cost fabrication. Yet, improvements are still needed for more stable and higher-performing solar cells. In this work, a series of TiO2 nanocolumn photonic structures have been intentionally fabricated on half of the compact TiO2-coated fluorine-doped tin oxide substrate by glancing angle deposition with magnetron sputtering, a method particularly suitable for industrial applications due to its high reliability and reduced cost when coating large areas. These vertically aligned nanocolumn arrays were then applied as the electron transport layer into triple-cation lead halide perovskite solar cells based on Cs0.05(FA0.83MA0.17)0.95Pb(I0.83Br0.17)3. By comparison to solar cells built onto the same substrate without nanocolumns, the use of TiO2 nanocolumns can significantly enhance the power conversion efficiency of the perovskite solar cells by 7% and prolong their shelf life. Here, detailed characterizations on the morphology and the spectroscopic aspects of the nanocolumns, their near-field and far-field optical properties, solar cells characteristics, as well as the charge transport properties provide mechanistic insights on how one-dimensional TiO2 nanocolumns affect the performance of perovskite halide solar cells in terms of charge transport, light harvesting, and stability, knowledge necessary for the future design of higher-performing and more stable perovskite solar cells.

Evolution of near- and far-field optical properties of Au bipyramids upon epitaxial deposition of Ag.

Bimetallic plasmonic nanostructures provide composition and spatial distribution of the individual components in the nanostructure in addition to overall size and morphology as degrees of freedom for tuning near- and far-field optical responses. AgAuAg nanorods (NRs) generated through epitaxial deposition of Ag on the tips of Au bipyramids (BPs) are an important bimetallic model system whose longitudinal dipolar plasmon mode first shows a spectral blue-shift upon initial deposition of Ag on the Au BP tips followed by a red-shift after additional deposition of Ag. Here, we quantify the relative contributions from morphological and compositional effects to the far-field spectral shift of the longitudinal and vertical dipolar plasmon modes during the initial deposition of Ag and compare the near-field in Ag and AgAuAg NRs with lengths between L = 130 nm-280 nm under whitelight illumination through electromagnetic simulations. Subsequently, we experimentally characterize the near-field around AgAuAg NRs with lengths between L = 88.1-749.0 nm at a constant excitation wavelength of 1064 nm on a silicon (Si) support through scattering type near-field scanning microscopy (sNSOM). We detect Fabry-Perot resonance-like higher order multipolar plasmon resonances whose order and near-field pattern depends on the length and composition of the NRs as well as the refractive index of the ambient medium. We find that under oblique illumination higher order multipolar modes with an even symmetry dominate on the high refractive index Si substrate due to strong electromagnetic interactions between the NR and the substrate.

Numerical Analysis of Nonlocal Optical Response of Metallic Nanoshells

Nonlocal and quantum effects play an important role in accurately modeling the optical response of nanometer-sized metallic nanoparticles. These effects cannot be described by conventional classical theories, as they neglect essential microscopic details. Quantum hydrodynamic theory (QHT) has emerged as an excellent tool to correctly predict the nonlocal and quantum effects by taking into account the spatial dependence of the charge density. In this article, we used a QHT to investigate the impact of nonlocality and electron spill-out on the plasmonic behavior of spherical Na and Au nanoshells. We adopted a self-consistent way to compute the equilibrium charge density. The results predicted by QHT were compared with those obtained with the local response approximation (LRA) and the Thomas–Fermi hydrodynamic theory (TFHT). We found that nonlocal effects have a strong impact on both the near- and far-field optical properties of nanoshells, in particular, for the antibonding resonant mode. We also investigated the optical response of these systems for different thicknesses of the shell, both for Na and Au metals.

Near-field and far-field optical properties of magnetic plasmonic core-shell nanoparticles with non-spherical shapes: A discrete dipole approximation study

The combined optical and magnetic properties of magnetic-plasmonic core-shell nanoparticles (NPs) makes them ideal candidates for many applications in biomedical fields. Plasmonic properties of the shell gives rise to Surface Enhanced Raman Scattering (SERS) that can be utilized for sensitive detections, while magnetic properties are useful for magnetic separation and magnetic guided delivery. The plasmonic properties of the shell depends on both the size and shape of the core and shell, and this property, in principle, can be calculated using the Discrete Dipole Approximation (DDA) method. However, since the DDA is an approximation method, its accuracy to calculate the plasmonic properties of the shell, especially the near-field enhancement relevant to SERS, has not been examined carefully. We present a systematic test on the accuracy of the DDA to calculate the plasmonic properties in terms of both the extinction spectra and the near-field enhancement of the magnetic-plasmonic core-shell NPs. Accuracy of the DDA method was first investigated in comparison to Mie theory results for spherical core-shell NPs, since Mie theory gives the exact solution to spherical shaped particles. DDA calculations were further extended to core-shell nanoparticles with octahedral cores. We elucidate convergence of the DDA results by considering the effects of dipole distance and shell thickness in regard to the NP spectral properties. This work validates application of the DDA methods for calculating electrodynamic properties of core-shell NPs and highlights plasmonic properties of core-shell with non-spherical cores.

Electron Transport Across Plasmonic Molecular Nanogaps Interrogated with Surface-Enhanced Raman Scattering.

Charge transport plays an important role in defining both far-field and near-field optical response of a plasmonic nanostructure with an ultrasmall built-in nanogap. As the gap size of a gold core-shell nanomatryoshka approaches the sub-nanometer length scale, charge transport may occur and strongly alter the near-field enhancement within the molecule-filled nanogap. In this work, we utilize ultrasensitive surface-enhanced Raman spectroscopy (SERS) to investigate the plasmonic near-field variation induced by the molecular junction conductance-assisted electron transport in gold nanomatryoshkas, termed gap-enhanced Raman tags (GERTs). The GERTs, with interior gaps from 0.7 to 2 nm, are prepared with a wet chemistry method. Our experimental and theoretical studies suggest that the electron transport through the molecular junction influences both far-field and near-field optical properties of the GERTs. In the far-field extinction response, the low-energy gap mode predicted by a classical electromagnetic model (CEM) is strongly quenched and hence unobservable in the experiment, which can be well explained by a quantum-corrected model (QCM). In the near-field SERS response, the optimal gap size for maximum Raman enhancement at the excitation wavelength of 785 nm (633 nm) is about 1.35 nm (1.8 nm). Similarly, these near-field results do not tally with the CEM calculations but agree well with the QCM results where the molecular junction conductance in the nanogap is fully considered. Our study may improve understanding of charge-transport phenomena in ultrasmall plasmonic molecular nanogaps and promote the further development of molecular electronics-based plasmonic nanodevices.

Optical properties of plasmonic core-shell nanomatryoshkas: a quantum hydrodynamic analysis.

Plasmonic response of the metallic structure characterized by sub-nanometer dielectric gaps can be strongly affected by nonlocal or quantum effects. In this paper, we investigate these effects in spherical Na and Au nanomatryoshka structures with sub-nanometer core-shell separation. We use the state-of-the-art quantum hydrodynamic theory (QHT) to study both near-field and far-field optical properties of these systems: results are compared with the classical local response approximation (LRA), Thomas-Fermi hydrodynamic theory (TF-HT), and the reference time-dependent density functional theory (TD-DFT). We find that the results obtained using the QHT method are in a very good agreement with TD-DFT calculations, whereas other LRA and TF-HT significantly overestimate the field-enhancements. Thus, the QHT approach efficiently and accurately describes microscopic details of multiscale plasmonic systems whose sizes are computationally out-of-reach for a TD-DFT approach; here, we report results for Na and Au nanomatryoshka with a diameter of 60 nm.

Multipolar Nanocube Plasmon Mode-Mixing in Finite Substrates.

Facile control of the radiative and nonradiative properties of plasmonic nanostructures is of practical importance to a wide range of applications in the biological, chemical, optical, information, and energy sciences. For example, the ability to easily tune not only the plasmon spectrum but also the degree of coupling to light and/or heat, quality factor, and optical mode volume would aid the performance and function of nanophotonic devices and molecular sensors that rely upon plasmonic elements to confine and manipulate light at nanoscopic dimensions. While many routes exist to tune these properties, identifying new approaches-especially when they are simple to apply experimentally-is an important task. Here, we demonstrate the significant and underappreciated effects that substrate thickness and dielectric composition can have upon plasmon hybridization as well as downstream properties that depend upon this hybridization. We find that even substrates as thin as ∼10 nm can nontrivially mix free-space plasmon modes, imparting bright character to those that are dark (and vice versa) and, thereby, modifying the plasmonic density of states as well as the system's near- and far-field optical properties. A combination of electron energy-loss spectroscopy (EELS) experiment, numerical simulation, and analytical modeling is used to elucidate this behavior in the finite substrate-induced mixing of dipole, quadrupole, and octupole corner-localized plasmon resonances of individual silver nanocubes.

Polyelectrolyte induced controlled assemblies for the backbone of robust and brilliant Raman tags.

Near-field and far-field optical properties of plasmonic materials can be tailored by coupling the existing structures. However, fabricating 3D coupled structures in the solution by molecular linkers may suffer from low yield, low stability (particle aggregates), long reaction time, complex surface modification or multiple purification steps. In this report, stable 3D plasmonic core-satellite assemblies (CSA) with a ~1 nm interior gap accompanied by high field enhancement (|E/Einc|>200) are formed in a few seconds through a single polyelectrolyte linker layer. In addition, by covalently binding different reporter molecules and core particles, three distinct RamSSan tags based on this CSA backbone are demonstrated and compared with conventional fluorophores in terms of stability. This general assembly method can be applied to any type of colloidal particles carrying stable surface charge, even non-plasmonic nanoparticles. It will facilitate the development of various robust Raman tags for multiplexed biomedical imaging/sensing by efficiently combining constituent particles of differing size/shape/composition. The CSA backbone with an embedded high field not only makes the brightness of Raman tags more comparable to the fluorophores and can also be utilized in the platform of molecule-light quantum strong coupling.