Periodic Nanoparticle Arrays Research Articles

An atomistic-electrodynamics theory for the optical response of periodic lattices of metallic nanoparticles in the quantum size regime

We present a new theoretical method for calculating the optical properties of periodic arrays of metallic nanoparticles whose dimensions are in the quantum-size limit and cannot, therefore, be described by macroscopic electrodynamic theory based on Maxwell’s equations. In the first stage, the method calculates the scattering matrix for a single metal nanoparticle described as a polyhedral cluster of atoms, via a discrete-dipole approximation/point-matching technique. The resulting scattering matrix is incorporated into a layer-multiple-scattering technique which allows the modeling of two- and three-dimensional nanostructures containing very small metal nanoparticles. The method is demonstrated for square arrays of silver nanoparticles with radii below 2 nm and the corresponding results are compared against classical local and nonlocal electrodynamic approaches.

General point dipole theory for periodic metasurfaces: magnetoelectric scattering lattices coupled to planar photonic structures.

We study semi-analytically the light emission and absorption properties of arbitrary stratified photonic structures with embedded two-dimensional magnetoelectric point scattering lattices, as used in recent plasmon-enhanced LEDs and solar cells. By employing dyadic Green's function for the layered structure in combination with the Ewald lattice summation to deal with the particle lattice, we develop an efficient method to study the coupling between planar 2D scattering lattices of plasmonic, or metamaterial point particles, coupled to layered structures. Using the 'array scanning method' we deal with localized sources. Firstly, we apply our method to light emission enhancement of dipole emitters in slab waveguides, mediated by plasmonic lattices. We benchmark the array scanning method against a reciprocity-based approach to find that the calculated radiative rate enhancement in k-space below the light cone shows excellent agreement. Secondly, we apply our method to study absorption-enhancement in thin-film solar cells mediated by periodic Ag nanoparticle arrays. Lastly, we study the emission distribution in k-space of a coupled waveguide-lattice system. In particular, we explore the dark mode excitation on the plasmonic lattice using the so-called array scanning method. Our method could be useful for simulating a broad range of complex nanophotonic structures, i.e., metasurfaces, plasmon-enhanced light emitting systems and photovoltaics.

Efficient anomalous reflection through near-field interactions in metasurfaces

Gradient metasurfaces have been extensively used in the past few years for advanced wave manipulation over a thin surface. These metasurfaces have been mostly designed based on the generalized laws of reflection and refraction. However, it was recently revealed that metasurfaces based on this approach tend to suffer from inefficiencies and complex design requirements. We have recently proposed a different approach to the problem of efficient beam steering using a surface, based on bianisotropic particles in a periodic array. Here, we show highly efficient reflective metasurfaces formed by pairs of isotropic dielectric rods, which can offer asymmetrical scattering of normally incident beams with unitary efficiency. Our theory shows that moderately broadband anomalous reflection can be achieved with suitably designed periodic arrays of isotropic nanoparticles. We also demonstrate practical designs using ${\mathrm{TiO}}_{2}$ cylindrical nanorods to deflect normally incident light toward a desired direction. The proposed structures may pave the way to a broader range of light management opportunities, with applications in energy harvesting, signaling, and communications.

Graphene Terahertz Plasmons: A Combined Transmission Spectroscopy and Raman Microscopy Study

Graphene provides a promising materials platform for fundamental studies and device applications in plasmonics. Here we investigate the excitation of THz plasmon polaritons in large-area graphene samples on standard oxidized silicon substrates, via diffractive coupling from an overlying periodic array of metallic nanoparticles. Pronounced plasmonic absorption features are measured, whose frequencies can be tuned across a large portion of the THz spectrum by varying the array period. At the same time, the ability to tune these resonances actively via electrostatic doping is found to be strongly limited by the presence of large carrier density variations across the sample area induced by the underlying SiO2, which are measured directly by Raman microscopy. These results highlight the importance of minimizing charge “puddles” in graphene plasmonic devices, e.g., through the use of more inert substrates, in order to take full advantage of their expected dynamic tunability for applications in THz optoelectronics.

Optical properties of anisotropic 3D nanoparticles arrays(a)(a)Contribution to the Focus Issue Self-assemblies of Inorganic and Organic Nanomaterials edited by Marie-Paule Pileni.

The optical properties of 3D periodic arrays of spheroidal Au nanoparticles are calculated using a Bruggeman effective medium approximation. The optical response of the supra-crystal depends on the volume fraction of the nanoparticles and their aspect or size ratio (major/minor axis). All the nanoparticles have the same orientation, and this defines an anisotropic dielectric function of the crystal. As a function of the filling fraction, while keeping the size ratio fixed, the maximum in the extinction spectra along the major and minor axes does not show a significant change. However, for a fixed filling fraction, varying the aspect ratio of the particles induces a shift of several hundred of nanometers in the maximum of the extinction spectra along the major axis and almost no changes along the minor axis. Depending on the aspect ratio and the filling fraction, we show that the supra-crystal has three regimes with different values of an effective plasma frequency.

Plasmonic lattice resonance-enhanced light emission from plastic scintillators by periodical Ag nanoparticle arrays

We have demonstrated that periodical arrays of silver nanoparticles can enhance the light emission from a plastic scintillator layer on the surface of a silicon substrate. The enhancement is attributed to surface lattice resonances with a photonic-plasmonic nature. Although the enhancement exhibits directional characteristics for individual wavelengths, the wavelength-integrated enhancement shows a monotonous increase with increasing emission angle. As a result, an overall 1.81-fold wavelength- and angle-integrated enhancement has been obtained. This observation is promising for fundamental and applied research into enhanced luminescent material layers on opaque substrates.

Effect of the Fabrication Parameters of the Nanosphere Lithography Method on the Properties of the Deposited Au-Ag Nanoparticle Arrays.

The nanosphere lithography (NSL) method can be developed to deposit the Au-Ag triangle hexagonal nanoparticle arrays for the generation of localized surface plasmon resonance. Previously, we have found that the parameters used to form the NSL masks and the physical methods required to deposit the Au-Ag thin films had large effects on the geometry properties of the nanoparticle arrays. Considering this, the different parameters used to grow the Au-Ag triangle hexagonal nanoparticle arrays were investigated. A single-layer NSL mask was formed by using self-assembly nano-scale polystyrene (PS) nanospheres with an average radius of 265 nm. At first, the concentration of the nano-scale PS nanospheres in the solution was set at 6 wt %. Two coating methods, drop-coating and spin-coating, were used to coat the nano-scale PS nanospheres as a single-layer NSL mask. From the observations of scanning electronic microscopy (SEM), we found that the matrixes of the PS nanosphere masks fabricated by using the drop-coating method were more uniform and exhibited a smaller gap than those fabricated by the spin-coating method. Next, the drop-coating method was used to form the single-layer NSL mask and the concentration of nano-scale PS nanospheres in a solution that was changed from 4 to 10 wt %, for further study. The SEM images showed that when the concentrations of PS nanospheres in the solution were 6 and 8 wt %, the matrixes of the PS nanosphere masks were more uniform than those of 4 and 10 wt %. The effects of the one-side lifting angle of substrates and the vaporization temperature for the solvent of one-layer self-assembly PS nanosphere thin films, were also investigated. Finally, the concentration of the nano-scale PS nanospheres in the solution was set at 8 wt % to form the PS nanosphere masks by the drop-coating method. Three different physical deposition methods, including thermal evaporation, radio-frequency magnetron sputtering, and e-gun deposition, were used to deposit the Au-Ag triangle hexagonal periodic nanoparticle arrays. The SEM images showed that as the single-layer PS nanosphere mask was well controlled, the thermal evaporation could deposit the Au-Ag triangle hexagonal nanoparticle arrays with a higher quality than the other two methods.

Top-down design of magnonic crystals from bottom-up magnetic nanoparticles through protein arrays

We show that chemical fixation enables top-down micro-machining of large periodic 3D arrays of protein-encapsulated magnetic nanoparticles (NPs) without loss of order. We machined 3D micro-cubes containing a superlattice of NPs by means of focused ion beam etching, integrated an individual micro-cube to a thin-film coplanar waveguide and measured the resonant microwave response. Our work represents a major step towards well-defined magnonic metamaterials created from the self-assembly of magnetic nanoparticles.

Plasmonic–Photonic Hybrid Modes Excited on a Titanium Nitride Nanoparticle Array in the Visible Region

Conventionally used plasmonic materials generally have low thermal stability, low chemical durability (except gold), and are incompatible with complementary metal–oxide semiconductor processes. However, titanium nitride (TiN), an emerging plasmonic material, possesses gold-like optical properties, but displays relatively large ohmic losses. We fabricated a periodic array of TiN nanoparticles to effectively reduce these losses by coupling the localized surface plasmon resonance with light diffraction. The height of the nanoparticle and the periodicity of the array were designed to match the excitation conditions of both the localized surface plasmon resonance and light diffraction. As a result, the array supported a plasmonic–photonic hybrid mode in the visible region. For the loss mitigation effect to be assessed, photoluminescence (PL) from the light emitting layer on the array was measured. The PL intensity was larger than that from the same layer on a TiN thin film, demonstrating reduced loss. The angu...

Design and simulate the properties of triangular periodic nanoparticle arrays with the structure of bi-layer hexagonal lattice

In this study, the discrete dipole approximation (DDA) method was used to simulate the hybrid bi-layer hexagonal lattice of triangular periodic nanoparticle arrays (PNAs). The PNAs nanophotonic devices could be fabricated with pure silver, but their performances would be easily degenerated because of the oxidation (forming Ag2O) and sulfuration (forming Ag2S). Theoretical results show that the oxidation and sulfuration of Ag thin film lead to a significant red shift in the wavelength to reveal the maximum extinction efficiency (λmax) and to a significant decrease in the maximum peak value of localized surface plasmon resonances (LSPRs). The structures with the bi-layer materials of Ag2O–Ag and Ag2S–Ag were used to prove the degeneration of the properties in the extinction spectra of the LSPRs by using DDA method for simulation. We would find that the maximum peak value of the wavelength of the extinction efficiency spectra critically decreased and λmax had a red shift as the thicknesses of Ag2O and Ag2S increased. The structures with the bi-layer materials of Au–Ag and TiO2–Ag were also used to investigate their extinction spectra of the LSPRs. The simulation results of DDA method found that the maximum peak value of the wavelength of the extinction efficiency spectra slightly decreased as the thicknesses Au and TiO2 increased. Based on the Ag triangular nanostructure, the use of Au and TiO2 to form hybrid Au–Ag and TiO2–Ag triangular nanostructure cannot only be used to put forth of preventing oxidation and sulfuration but have a better performance than the Ag2O–Ag and Ag2S–Ag hybrid triangular nanostructures. Meanwhile, the thicknesses of TiO2 or Au layers could be used to decide the refractive index sensitivity (RIS) and figure of merit (FOM) of the hybrid Au–Ag and TiO2–Ag PNAs.

Plasmon-drag-assisted terahertz generation in a graphene layer incorporating an asymmetric plasmon nanostructure

This Rapid Communication presents a structure and full theoretical analysis to exploit the photon drag effect for THz signal generation in a graphene layer integrated with a plasmonic structure. The plasmonic structure is composed of a periodic array of asymmetric nanoparticles patterned over a graphene layer. The nanoparticles are designed to accomplish two goals: field localization due to the plasmonic resonance and manipulating the phase of the near field to effectively drag the quasiparticles in graphene. Combining the asymmetry with the plasmon resonances of nanoparticles, we show that an enhancement as large as three orders of magnitude is attainable in the power of the generated THz wave. This level of unprecedented enhancement mostly stems from the phase manipulation of the near field caused by asymmetric nanoparticles. Using the achieved enhancement, it is demonstrated that an ultra-wideband THz signal carrying the power of $1\phantom{\rule{0.28em}{0ex}}\ensuremath{\mu}\mathrm{W}$ can be generated using a commercially available femtosecond pulsed laser.

Fabrication of metallic nanodisc hexagonal arrays using nanosphere lithography and two-step lift-off

Nanosphere lithography (NSL) has been widely used as an inexpensive method to create periodic arrays of metallic nanoparticles or nanodiscs on substrates. However, most nanodisc arrays derived from a NSL template are restricted to hexagonally-ordered triangular arrays because the metal layer is deposited onto the interstices between the nanospheres. Metallic nanodisc arrays with the same arrangement as the original nanosphere array have been rarely reported. Here, we demonstrate a facile, low-cost method to fabricate large-area hexagonal arrays of metallic nanodiscs using an NSL template combined with a two-step lift-off process. We employ a bi-layer of two dissimilar metals to create a re-entrant sidewall profile to undercut the sacrificial layer and facilitate the final lift-off of the metallic nanodiscs. The quality of the nanodisc pattern and the array periodicity is determined using statistical image analysis and compared to the original nanosphere array in terms of size distribution, surface smoothness, and array pitch. This nanodisc array is used as an etch mask to create a vertically-aligned Si nanowire array. This combined approach is a scalable and inexpensive fabrication method for creating relatively large-area, ordered arrays of various nanostructures.

Generation of Localized Surface Plasmon Resonance Using Hybrid Au-Ag Nanoparticle Arrays as a Sensor of Polychlorinated Biphenyls Detection.

In this study, the hybrid Au–Ag hexagonal lattice of triangular and square lattice of quadrate periodic nanoparticle arrays (PNAs) were designed to investigate their extinction spectra of the localized surface plasmon resonances (LSPRs). First, their simulating extinction spectra were calculated by discrete dipole approximation (DDA) numerical method by changing the media refractive index. Simulation results showed that as the media refractive index was changed from 1.0 to 1.2, the maximum peak intensity of LSPRs spectra had no apparent change and the wavelength to reveal the maximum peak intensity of LSPRs spectra was shifted lower value. Polystyrene (PS) nanospheres with two differently arranged structures were used as the templates to deposit the hybrid Au–Ag hexagonal lattice of triangular and square lattice of quadrate periodic PNAs by evaporation method. The hybrid Au–Ag hexagonal lattice of triangular and square lattice of quadrate PNAs were grown on single crystal silicon (c-Si) substrates, and their measured extinction spectra were compared with the calculated results. Finally, the fabricated hexagonal lattices of triangular PNAs were investigated as a sensor of polychlorinated biphenyl solution (PCB-77) by observing the wavelength to reveal the maximum extinction efficiency (λmax). We show that the adhesion of β-cyclodextrins (SH-β-CD) on the hybrid Au–Ag hexagonal lattice of triangular PNAs could be used to increase the variation of λmax. We also demonstrate that the adhesion of SH-β-CD increases the sensitivity and detection effect of PCB-77 in hexagonal lattice of triangular PNAs.

Excitonic surface lattice resonances

Electromagnetic resonances are important in controlling light at the nanoscale. The most studied such resonance is the surface plasmon resonance that is associated with metallic nanostructures. Here we explore an alternative resonance, the surface exciton-polariton resonance, one based on excitonic molecular materials. Our study is based on analytical and numerical modelling. We show that periodic arrays of suitable molecular nanoparticles may support surface lattice resonances that arise as a result of coherent interactions between the particles. Our results demonstrate that excitonic molecular materials are an interesting alternative to metals for nanophotonics; they offer the prospect of both fabrication based on supramolecular chemistry and optical functionality arising from the way the properties of such materials may be controlled with light.

Plasmon-Enhanced Performance of an Array of Core-Shell Silver Nanoparticles Photodeposited onto a Titanium Dioxide Layer

A plasmonic photocatalytic reactor which composed of a periodic array of core-shell silver nanoparticles (CSSNPs) photodeposited onto a Titanium Dioxide (TiO2) thin film in a multilayer rotating-disk system was numerically investigated by using three-dimensional finite element method. Results show that the proposed structure can exhibit much higher photocalytic activity in a broad range of incident angle of light that are not observed for the same counterpart without the CSSNPs on the SiO2 surface. The enhanced electric field distribution and intensity could be expanded as the inner diameter of CSSNPs and incident angle of light increased.

Multiple beam interference lithography: A tool for rapid fabrication of plasmonic arrays of arbitrary shaped nanomotifs.

A novel method enabling rapid fabrication of 2D periodic arrays of plasmonic nanoparticles across large areas is presented. This method is based on the interference of multiple coherent beams originating from diffraction of large-diameter collimated beam on a transmission phase mask. Mutual orientation of the interfering beams is determined by parameters of the used phase mask. Herein, parameters of the phase mask (periods and modulation depth) are selected to yield an interference pattern with high contrast and narrow well-separated maxima. Finally, multiple beam interference lithography (MBIL)-based fabrication of periodic plasmonic arrays with selected nanomotifs including discs, disc dimers, rods and bowtie antennas is demonstrated.

Theory of patch-antenna metamaterial perfect absorbers

A metasurface that absorbs waves from all directions of incidence can be achieved if the surface impedance is made to vary as a function of incidence angle in a specific manner. Here we show that a periodic array of planar nanoparticles coupled to a metal film can act as an absorbing metasurface with an angle-dependent impedance. Through a semi-analytical calculation based on coupled-mode theory, we find the perfect absorbing condition is equivalent to balancing the Ohmic and radiative losses of the nanoparticles at normal incidence. Absorption over a wide range of incidence angles can then be obtained by tailoring the scattered far-field pattern of the individual planar nanoparticles such that their radiative losses remain constant. The theory provides a means of understanding the behavior of perfect absorbing structures that have been observed experimentally or numerically, reconciling previously published theories and enabling the optimization of absorbing surfaces.

Directional sideward emission from luminescent plasmonic nanostructures.

Periodic arrays of metallic nanoparticles can be used to enhance the emission of light in certain directions. We fabricated hexagonal arrays of aluminium nanoparticles combined with thin layers of luminescent material and optimized period (275 nm) and thickness (1500 nm) to obtain sideward directional emission into glass for a wavelength band around 620 nm. The key physics is that the luminescent layer acts as a waveguide, from which light is emitted at preferential angles using diffractive effects. This phenomenon has applications in the field of solid-state lighting, where there is a desire for small, bright and directional sources.

Thermal dewetting with a chemically heterogeneous nano-template for self-assembled L1(0) FePt nanoparticle arrays.

A design for the fabrication of metallic nanoparticles is presented by thermal dewetting with a chemically heterogeneous nano-template. For the template, we fabricate a nanostructured polystyrene-b-polydimethylsiloxane (PS-b-PDMS) film on a Si|SiO2 substrate, followed by a thermal annealing and reactive ion etching (RIE) process. This gives a template composed of an ordered hexagonal array of SiOC hemispheres emerging in the polystyrene matrix. After the deposition of a FePt film on this template, we utilize the rapid thermal annealing (RTA) process, which provides in-plane stress, to achieve thermal dewetting and structural ordering of FePt simultaneously. Since the template is composed of different composition surfaces with periodically varied morphologies, it offers more tuning knobs to manipulate the nanostructures. We show that both the decrease in the area of the PS matrix and the increase in the strain energy relaxation transfer the dewetted pattern from the randomly distributed nanoparticles into a hexagonal periodic array of L10 FePt nanoparticles. Transmission electron microscopy with the in situ heating stage reveals the evolution of the dewetting process, and confirms that the positions of nanoparticles are aligned with those of the SiOC hemispheres. The nanoparticles formed by this template-dewetting show an average diameter and center-to-center distance of 19.30 ± 2.09 nm and 39.85 ± 4.80 nm, respectively. The hexagonal array of FePt nanoparticles reveals a large coercivity of 1.5 T, much larger than the nanoparticles fabricated by top-down approaches. This approach offers an efficient pathway toward self-assembled nanostructures in a wide range of material systems.

Colloidal nanocrystal superlattices as phononic crystals: plane wave expansion modeling of phonon band structure

Colloidal nanocrystal superlattices are a natural platform for high frequency three-dimensional phononic crystals (~102 GHz) because they consist of a periodic array of hard nanoparticles in a soft organic matrix.