Plasmonic Nanoparticle Arrays Research Articles

Second harmonic generation under doubly resonant lattice plasmon excitation.

Second harmonic generation is enhanced at the surface lattice resonance in plasmonic nanoparticle arrays. We carried out a parametric investigation on two-dimensional lattices composed of gold nanobars where the centrosymmetry is broken at oblique incidence. We study the influence of the periodicity, the incidence angle and the direction of the linear input polarization on the second harmonic generation. Excitation of the surface lattice resonance either at the fundamental or second harmonic wavelength, achieved by varying the incidence angle, enhance the conversion efficiency. As a special case, we demonstrate that both the wavelengths can be simultaneously in resonance for a specific period of the lattice. In this double resonant case, maximum second harmonic power is achieved.

(Invited, Digital Presentation) Rational Design of Nanoplasmonic Array Geometries for Biosensing

Background: Molecular diagnostics provide early and accurate diagnosis, which is essential for the prevention and treatment of infectious as well as chronic diseases. These tests are designed to detect disease-specific bioanalytes such as nucleic acid (DNA or RNA) or protein (antigens, antibodies) biomarkers. In the context of infectious disease diagnosis, nucleic acid-based detection methods are known to provide more specific and sensitive results. Here, the presence of a unique sequence belonging to the pathogenic genomic material is targeted to identify species, organism, genera and/or antimicrobial resistant gene markers. The majority of the common nucleic acid based diagnostic techniques require amplification (polymerase chain reaction, isothermal amplification etc.) of the pathogenic genetic material prior to detection impacting diagnostic speed, complexity, and cost thereby limiting ease of use. Thus, the development of simplified nucleic acid-based diagnostics that can be even used in resource-poor settings may hugely benefit patients across the globe.Nanopath is a molecular diagnostics company utilizing a solid-state nanosensor to enable sequence-specific detection of target nucleic acids without the need of amplification. These nanostructures enable ultra-sensitive biomarker detection using geometric, feature-dependent properties highly dependent on the local dielectric environment, allowing them to be sensitive to low concentration binding events. This paper describes an application of this approach to provide highly relevant clinical information within a single doctor’s office visit. Introduction: The Nanopath team is in collaboration with NASA (National Aeronautics and Space Administration) and NIST (National Institute of Standards and Technology) to push the bounds of the fundamental physics associated with their biosensing platform. The ability of metals to support electromagnetic surface waves gives rise to surface plasmons when optically illuminated. This property, and its strong sensitivity to changes in the local refractive index, allows for the use of metal nanoparticles as ultra-sensitive transducers. In prior work by members of this team, ensembles of randomly oriented nanoparticles (i.e., colloidal nanorods dispersed on chip) were employed for sequence-specific nucleic acid sensing (1-3). While these particle sensors have the advantage of rapid fabrication, they suffer from low sensitivity and quality factor due to the random particle dispersity. In contrast, in this study we employ ordered array nanoparticle ensembles which can be used to improve sensor sensitivity and figure-of-merit. Study Methods Overview: In this talk, we detail the results of sensing experiments and computational simulations to outline a rational design of the structure of these plasmonic nanoparticle arrays for biomolecular sensing. Through simulation and experiment, we iteratively tailor nanostructure dimension to provide high quality signal and large resonance shifts upon modeled nucleic acid binding.In particular, full-wave electromagnetic simulations were conducted using Lumerical photonic simulation software in which periodic boundary conditions were applied in the x- and y- dimensions for each of the nanoplasmonic sensor geometries. To simulate the resonance response to changes in the bulk solution in contact with the sensor surface, the refractive index of the surrounding media was changed appropriately. Nucleic acid hybridization events were modeled using either using spherical structures approximating the relevant radius of genomic material as estimated by polymer models, or as conformal layers with the known refractive indices for nucleic acids. On the basis of initial simulations, nanosensors were fabricated using traditional electron-beam lithography protocols at NIST. To evaluate consensus between simulations and experiments, bulk sensing experiments were carried out in which the resonance peaks were obtained by submerging the sensors in refractive index standards. Key nanosensor characteristics including resonance peak locations, resonance peak shifts as a function of refractive index, and figure of merit (FOM) of extinction curves were examined between the experimental and simulation results prior to proceeding with simulations on additional geometries and more complex solution conditions, and further device fabrication. This iterative process is repeated toward a rational design of nanoplasmonic array geometries for biosensing optimizing response for targeted disease detection.In summary, this study puts forth a methodology for rational design and characterization of regularly spaced nanoparticle arrays for optics-based biosensing. The results of this study will allow for more informed design of nanostructure geometries towards sequence-specific nucleic acid detection. These improved designs have the potential to improve clinical sensitivity and limit-of-detection across disease indication.

Plasmon resonance of gold and silver nanoparticle arrays in the Kretschmann (attenuated total reflectance) vs. direct incidence configuration

While the behaviour of plasmonic solid thin films in the Kretschmann (also known as Attenuated Total Reflection, ATR) configuration is well-understood, the use of discrete nanoparticle arrays in this optical configuration is not thoroughly explored. It is important to do so, since close packed plasmonic nanoparticle arrays exhibit exceptionally strong light-matter interactions by plasmonic coupling. The present work elucidates the optical properties of plasmonic Au and Ag nanoparticle arrays in both the direct normal incidence and Kretschmann configuration by numerical models, that are validated experimentally. First, hexagonal close packed Au and Ag nanoparticle films/arrays are obtained by air–liquid interfacial assembly. The numerical models for the rigorous solution of the Maxwell’s equations are validated using experimental optical spectra of these films before systematically investigating various parameters. The individual far-field/near-field optical properties, as well as the plasmon relaxation mechanism of the nanoparticles, vary strongly as the packing density of the array increases. In the Kretschmann configuration, the evanescent fields arising from p- and s-polarized (or TM and TE polarized) incidence have different directional components. The local evanescent field intensity and direction depends on the polarization, angle of incidence and the wavelength of incidence. These factors in the Kretschmann configuration give rise to interesting far-field as well as near-field optical properties. Overall, it is shown that plasmonic nanoparticle arrays in the Kretschmann configuration facilitate strong broadband absorptance without transmission losses, and strong near-field enhancement. The results reported herein elucidate the optical properties of self-assembled nanoparticle films, pinpointing the ideal conditions under which the normal and the Kretschmann configuration can be exploited in multiple light-driven applications.

Time-Resolved Thickness and Shape-Change Quantification using a Dual-Band Nanoplasmonic Ruler with Sub-Nanometer Resolution.

Time-resolved measurements of changes in the size and shape of nanobiological objects and layers are crucial to understand their properties and optimize their performance. Optical sensing is particularly attractive with high throughput and sensitivity, and label-free operation. However, most state-of-the-art solutions require intricate modeling or multiparameter measurements to disentangle conformational or thickness changes of biomolecular layers from complex interfacial refractive index variations. Here, we present a dual-band nanoplasmonic ruler comprising mixed arrays of plasmonic nanoparticles with spectrally separated resonance peaks. As electrodynamic simulations and model experiments show, the ruler enables real-time simultaneous measurements of thickness and refractive index variations in uniform and heterogeneous layers with sub-nanometer resolution. Additionally, nanostructure shape changes can be tracked, as demonstrated by quantifying the degree of lipid vesicle deformation at the critical coverage prior to rupture and supported lipid bilayer formation. In a broader context, the presented nanofabrication approach constitutes a generic route for multimodal nanoplasmonic optical sensing.

Nano meets macro: Furnishing the surface of polymer molds with gold‐nanoparticle arrays

AbstractThe formation of well‐defined, functional surfaces that incorporate the unique properties of inorganic nanoparticles (NPs) requires robust and scalable fabrication strategies. Herein, we report a methodology for the decoration of polymer molds with plasmonic (gold) nanoparticle arrays. Wrinkled soft templates were used to assemble gold NPs (74 nm) into line arrays. These pre‐formed nanoparticle arrays were transferred in a subsequent step onto polycarbonate molds via an injection molding process. Scanning electron microscopy analysis revealed the structural fidelity of the pattern structure upon transfer. The preservation of the optical functionality of the gold nanoparticle line arrays was proven by surface‐enhanced Raman scattering (SERS) experiments. The reported strategy of nanoparticle pattern transfer to polymer bodies by this robust process is expected to prove useful for the fabrication of polymer surfaces with tailored optical functionality.

Uncovering strong π-metal interactions on Ag and Au nanosurfaces under ambient conditions via in-situ surface-enhanced Raman spectroscopy

Uncovering strong π-metal interactions on Ag and Au nanosurfaces under ambient conditions via in-situ surface-enhanced Raman spectroscopy

Multiscale Optical Modeling of Perovskite-Si Tandem Solar Cells

With the success of silicon (Si) solar cell technology, research and development on higher efficiency multijunction solar cells is gaining much attention. Tandem cells with a perovskite top cell and a Si bottom cell show particular potential. However, the optical modeling of such devices is complicated by the broad range of length scales involved; the optically thin layers and nanoscale features of a perovskite solar cell require some version of wave optics or even full field electromagnetic (EM) calculations, while the micrometer scale structuring and large dimensions of Si cells are much more manageable using geometrical (ray) optics. In the present work, a method for combining EM and ray optical calculations is developed and described in detail, with examples provided in the software Comsol Multiphysics. For regions with thin films or nanoscale features, EM wave calculations are performed using the finite element method. These calculations provide the phase and amplitude of the waves diffracted into different orders, of which only the regular reflection and transmission are typically of relevance for nanoscale periodicity. In the ray optics simulation, the corresponding regions are implemented as diffracting interfaces, with deterministic transformations of the Stokes vector components according to the EM wave calculations. Meanwhile, the absorbed intensity of intersecting rays is recorded. The method is applied to separate perovskite and Si solar cells and to a few tandem solar cells of relevance for two- versus four-terminal configurations. Corrections for strongly absorbing media in the ray tracing algorithm, which use generalized versions of the Fresnel coefficients, Snell’s law and the Beer-Lambert law, are also evaluated. In a typical Si solar cell with a front surface structure of inverted pyramids, such corrections are found to reduce the absorption by up to 0.5 percentage units compared to a conventional ray tracing calculation. The difference is concluded to originate mainly from reduced absorption rates of inhomogeneous waves, rather than from enhanced escape probabilities for (quasi-) trapped rays at the Si front surface. The method is further applied to evaluate the effects of a plasmonic nanoparticle array, embedded in a perovskite solar cell stack that is located directly on the microstructured Si surface.

Nanoparticle-on-Mirror Metamaterials for Full-Spectrum Selective Solar Energy Harvesting.

Most broadband metamaterial absorbers are realized by patterning periodic arrays of plasmonic nanoparticles (>100 nm) on dielectric/metallic substrates to enable both electric and magnetic resonances. These metamaterials, however, require costly nanolithographic top-down techniques for fabrication. Here, we demonstrate new-concept nanoparticle-on-mirror (NoM) metamaterial absorbers by densely packing plasmonic nanoparticles of much smaller size (∼30 nm) on metal films directly. Such a simple but rational design enables the use of all-solution-based bottom-up processes. Because of the decoupling of electric and magnetic polarizations in these ultrasmall nanoparticles, excellent impedance match and near-perfect light absorption can be achieved in a broad band over the solar spectrum with weak thermal emission. Proof-of-concept large-area NoM metamaterial absorbers that offer a solar absorptance of 94% but a low IR emittance of 2% are experimentally demonstrated. The outstanding performance, bottom-up process, and great compatibility render the design promising for efficient and large-scale solar energy harvesting.

Controlling Exciton Propagation in Organic Crystals through Strong Coupling to Plasmonic Nanoparticle Arrays.

Exciton transport in most organic materials is based on an incoherent hopping process between neighboring molecules. This process is very slow, setting a limit to the performance of organic optoelectronic devices. In this Article, we overcome the incoherent exciton transport by strongly coupling localized singlet excitations in a tetracene crystal to confined light modes in an array of plasmonic nanoparticles. We image the transport of the resulting exciton–polaritons in Fourier space at various distances from the excitation to directly probe their propagation length as a function of the exciton to photon fraction. Exciton–polaritons with an exciton fraction of 50% show a propagation length of 4.4 μm, which is an increase by 2 orders of magnitude compared to the singlet exciton diffusion length. This remarkable increase has been qualitatively confirmed with both finite-difference time-domain simulations and atomistic multiscale molecular dynamics simulations. Furthermore, we observe that the propagation length is modified when the dipole moment of the exciton transition is either parallel or perpendicular to the cavity field, which opens a new avenue for controlling the anisotropy of the exciton flow in organic crystals. The enhanced exciton–polariton transport reported here may contribute to the development of organic devices with lower recombination losses and improved performance.

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.

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.

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.

Fabry-Perot interference pattern scattered by a sub-monolayer array of nanoparticles

Understanding scattering of visible and infrared photons from nanomaterials and nanostructured materials is increasingly important for imaging, thermal management, and detection, and has implications for other parts of the electromagnetic spectrum (e.g., x-ray scattering and radar). New, interesting reports of photon scattering as a diagnostic probe, from inelastic x-ray scattering and interference to ‘nano-FTIR’ microscopy using infrared photons, have been published and are under active investigation in laboratories around the world. Here, we report, for the first time to our best knowledge, the experimental discovery of a Fabry–Perot interference pattern that is scattered by the sub-monolayer array of plasmonic Ag nanoparticles, and confirm it analytically and with rigorous numerical FDTD simulations.

Laser nanoprinting of floating three-dimensional plasmonic color in pH-responsive hydrogel

Recent demonstrations of metasurfaces present their great potential to implement flat and multifunctional optical elements, which are accomplished with the designs of planar optics and micro-/nano- fabrications. Integrating metasurfaces in three dimensions has manifested drastically increasing advantages in manipulating light fields by extending design freedom. However, fabricating three-dimensional metasurfaces remain a tough challenge due to the lack of stereo printing protocols. Herein, we demonstrate laser nanoprinting of floated silver nanoparticle array in transparent hydrogel films for 3D metasurface to achieve color patterning. It is found that spatially resolved nanoparticles can be produced through laser induced photoreduction of silver ions and robustly anchored to the gel backbones by a focused femtosecond laser beam within a pH-responsive smart hydrogel matrix. With the aid of expansion properties of the pH-responsive hydrogel, repetitive coloration of the patterned plasmonic nanoparticle array over a wide spectrum range is achieved via reversible regulation of nanoparticle spacing from 550 to 350 nm and vice versa. This approach allows broadband 3D color-regulation in nanoscale for applications in active spectral filtering, information encryption, security tagging and biological colorimetric sensing, etc.

In Situ Chemical Patterning Technique

AbstractPlasmonic nanochemistry is employed to develop a chemical patterning technique for multiscale distributed plasmonic nanoparticle (NP) arrays by a spatial confined in situ growth process. Ag NPs grow exclusively following the maximum plasmonic field areas of Au nanohole arrays under light illumination, and Ag NP‐assembly arrays (NAAs) with controllable morphology from nanoring to nanodisk are realized precisely. Combining with conventional photolithography, letters, and patterns ranging from macroscopic to sub‐microscale are accurately obtained. The region‐specific generated Ag NAAs acted as an excellent surface‐enhanced Raman scattering substrate to realize quantitative detection and Raman imaging, which are further applied to multilevel encryption applications. Moreover, the lithography strategy shows good universality where it can be utilized to fabricate Au NAAs and polypyrrole nanodisks, and applied on flexible polydimethylsiloxane and curved glass substrates. Overall, this lithography strategy has good general applicability to obtain a multiscale engineered large‐area array of colloidal metallic NPs and organic polymers without the presence of either heat or specific adhesive layers, thus offers an approach to plasmonic engineering for a myriad of applications ranging from plasmonic anti‐counterfeit labels to electrical devices.

Plasmonic Au Nanoparticle Arrays for Monitoring Photopolymerization at the Nanoscale

The localized surface plasmon resonance (LSPR) of Au nanoparticles (NPs) was used to monitor photopolymerization at the nanoscale by in situ monitoring the optical response of AuNPs during the light-induced polymerization process. To show the interest of this approach, two configurations were used, which correspond to a resonant and a nonresonant excitation regime between the photopolymer and the AuNPs used as nanoprobes. We show that not only this method enables the progress monitoring of the photopolymerization reaction at the nanometric scale but also can highlight the near-field coupling effect responsible for the acceleration of the photoinduced reaction. This methodology appears very interesting to study the photoinduced nanofabrication processes of metal/polymer hybrid nanoparticles and more globally to study the photopolymerization reactions at the nanometric scale.

Square-root topological state of coupled plasmonic nanoparticles in a decorated Su-Schrieffer-Heeger lattice.

The square-root operation can generate systems with new (to the best of our knowledge) topological phases whose topological properties are inherited from the parent Hamiltonian. In this Letter, we introduce the concept of square-root topology in the two-dimensional (2D) Su-Schrieffer-Heeger (SSH) model and construct a square-root topological square nanoparticle lattice (SRTL) by inserting additional sites into the original 2D SSH model. We find that the topological states in the SRTL are intriguingly different from those in the corresponding SSH model (with on-site potential) due to the change in symmetrical characteristics. Plasmonic nanoparticle arrays are used to demonstrate this by including both nearest-neighbor and next-nearest-neighbor interactions within the dipole approximation. These unique topological states, such as the single corner mode and multiple topological edge modes, enrich the topological features produced by square-root operation and expand the scope to apply such topological features into photonic systems.

Infrared Open Cavities for Strong Vibrational Coupling.

Arrays of subwavelength plasmonic nanoparticles exhibiting narrowband lattice resonances are referred to as open cavities because of their ability to strongly couple with electronic excitations in molecular chromophores. However, realization of these ideas in the mid-infrared spectral region has been limited. We demonstrated a dramatic reduction in the bandwidth of lattice resonances in large-area arrays of half-wavelength mid-infrared antennas, reaching resonance quality factors above 200. By tuning the wavelength of the antenna-lattice resonances (ALR) to match the transition frequency of the molecular vibrational modes, we achieved a strong coupling between the ALR and the carbonyl stretching excitation in a thin film of (poly)methyl methacrylate (PMMA) polymer deposited on the array. Splitting of the polaritonic transitions, reduction of their bandwidth below that of the bare molecular transition, and characteristic dispersion confirmed the strong coupling regime. Our results pave the way for exciting research on the many-body correlated dynamics of vibrational polaritons.

Substrate-mediated lattice Kerker effect in Al metasurfaces

Surface lattice resonances (SLRs) emerging in regular arrays of plasmonic nanoparticles (NPs) are known to be exceptionally sensitive to the homogeneity of the environment. It is considered necessary to have a homogeneous environment for engineering narrowband SLRs, while in a half-space environment, SLRs rapidly vanish as the contrast between the refractive indices of the substrate and superstrate increases. From this conventional wisdom, it is apparent that the delicate lattice Kerker effect emerging from SLRs and resonances on constituent NPs should be difficult to achieve in a non-homogeneous environment. Using a rigorous theoretical treatment with multipolar decomposition, we surprisingly find and explain a narrowband substrate-mediated lattice Kerker effect in two-dimensional arrays of Al nanocylinders in a half-space geometry. We propose to use this effect for sensing applications and demonstrate its broad tunability across the UV/Vis wavelength range.

Computational Sub-10 nm Plasmonic Nanogap Patterns by Block Copolymer Self-Assembly

Plasmonic nanoparticle (NP) arrays with narrow gaps have been suggested as an effective light collection solution for plasmonic structures. For an effective low-cost bottom-up strategy, block copolymer (BCP) self-assembly with evaporative metal-deposition is mentioned as one of the best effective ways to produce Au NP arrays with narrow gaps. In this paper, BCP self-assembly for nanopost-template arrays and metal-deposition over the nanotemplate surface for positional arrangement of Au NPs are described using a self-consistent field theory (SCFT) and a level-set method, respectively. According to the of BCP self-assembly simulation results, both the diameter of the cylinder post and gap size become larger due to the increase of polymerization degree (N). However, these parameters become smaller in terms of the increase of the Flory-Huggins interaction parameter χ. For plasmonic phenomena about a top-down incident wavelength of 600-nm, according to a rigorous coupled-wave analysis (RCWA), although the electric field around a single spherical post becomes larger at smaller diameter, there is no top-down plasmonic phenomenon at a gap size of 10-nm between nanoposts.