Nanorod Dimers Research Articles

Circular Differential Scattering of Single Chiral Self-Assembled Gold Nanorod Dimers

Circular dichroism spectroscopy is essential for structural characterization of proteins and chiral nanomaterials. Chiral structures from plasmonic materials have extraordinary strong circular dichroism effects compared to their molecular counterparts. While being extensively investigated, the comprehensive account of circular dichroism effects consistent with other plasmonic phenomena is still missing. Here we investigated the circular differential scattering of a simple chiral plasmonic system, a twisted side-by-side Au nanorod dimer, using single-particle circular dichroism spectroscopy complimented with electromagnetic simulations. This approach enabled us to quantify the effects of structural symmetry breaking, namely, size-mismatch between the constituent Au nanorods and large twist angles on the resulting circular differential scattering spectrum. Our results demonstrate that, if only scattering is considered as measured by dark-field spectroscopy, a homodimer of Au nanorods with similar sizes prod...

Geometry-dependent anti-Stokes SERS radiation patterns from gold nanorod dimers

The geometry of individual plasmonic nanostructures and their collective arrangement plays a critical role in electromagnetic enhancement of surface-enhanced Raman scattering (SERS). Concomitantly, the same attributes also have a direct implication on plasmon resonance line-shapes that further affect the far-field radiation pattern of SERS in Rayleigh, Stokes and anti-Stokes spectral regimes. Here we numerically show how Fano-type plasmon resonance lineshapes in certain geometrical configurations of gold nanorod dimers can selectively influence the far-field radiation pattern in the anti-Stokes spectral region of SERS. We explored a variety of dimer angles (0° to 180°) between the gold nanorods, and compared their far-field radiation patterns in the anti-Stokes, Rayleigh and Stokes regions of their plasmon resonance. We found that angles 30° to 60° exhibited greater in-plane forward-to-backward intensity ratios in the anti-Stokes region, compared to other configurations. The results discussed herein highlight a three-way connection between the geometrical arrangement of plasmonic nanostructures, Fano-type lineshapes and far-field radiation patterns in SERS, especially in the anti-Stokes region. Our work will have implications not only in designing optical antennas for linear and nonlinear Raman scattering, but also in creating directional light sources based on nonlinear optical processes such as two-photon fluorescence and photon frequency upconversion.

Tuning near-field enhancements on an off-resonance nanorod dimer via temporally shaped femtosecond laser

We theoretically investigated ultrafast thermal dynamics tuning of near-field enhancements on an off-resonance gold nanorod dimer via temporally shaped femtosecond (fs) laser double pulses. The nonequilibrium thermal excitation is self-consistently coupled into a near-field scattering model for exploring the ultrafast near-field enhancement effects. It is revealed that the near electric-field localized within the gold nanorod dimer can be largely promoted via optimizing the temporal separation and the pulse energy ratio of temporally shaped femtosecond laser double pulses. The results are explained as thermal dynamics manipulation of plasmon resonances in the nanorod dimer via tailoring temporally shaped femtosecond laser. This study provides basic understanding for tuning near-field properties on poorly fabricated metallic nano-structures via temporally shaped femtosecond laser, which can find potential applications in the fields such as fs super-resolution near-field imaging, near-field optical tweezers, and fs photothermal therapy.

Hybridization in Three Dimensions: A Novel Route toward Plasmonic Metamolecules.

Plasmonic metamolecules have received much interest in the last years because they can produce a wide spectrum of different hybrid optical resonances. Most of the configurations presented so far, however, considered planar resonators lying on a dielectric substrate. This typically yields high damping and radiative losses, which severely limit the performance of the system. Here we show that these limits can be overcome by considering a 3D arrangement made from slanted nanorod dimers extruding from a silver baseplate. This configuration mimics an out-of-plane split ring resonator capable of a strong near-field interaction at the terminations and a strong diffractive coupling with nearby nanostructures. Compared to the corresponding planar counterparts, higher values of electric and magnetic fields are found (about a factor 10 and a factor 3, respectively). High-quality-factor resonances (Q ≈ 390) are produced in the mid-IR as a result of the efficient excitation of collective modes in dimer arrays.

Chirality-based Au@Ag Nanorod Dimers Sensor for Ultrasensitive PSA Detection.

A novel biosensor for ultrasensitive detection of prostate-specific antigen (PSA) was established based on gold nanorod (Au NR) dimers assembly. The circular dichroism signal was significantly amplified by a silver shell depositing on the surface of the Au NR dimers. A low limit of detection of 0.076 aM and high specificity were observed within the range of 0.1 to 50 aM target PSA. The developed biosensor has the potential to serve as a general platform for the detection of cancer biomarkers.

Single-Particle Spectroscopic Study on Fluorescence Enhancement by Plasmon Coupled Gold Nanorod Dimers Assembled on DNA Origami.

Metal-enhanced fluorescence has attracted much attention due to its scientific importance and lots of potential applications. Plasmon coupled metal nanoparticles have been demonstrated to further improve the enhancement effects. Conventional studies of metal-enhanced fluorescence on the bulk systems are complicated by the ensemble average effects over many critical factors with large variations. Here, fluorescence enhancement of ATTO-655 by a plasmon coupled gold nanorod dimer fixed on a DNA origami nanobreadboard was studied on the single-particle level. A series of gold nanorod dimers with linear orientation and different gap distances ranging from 6.1 to 26.0 nm were investigated to explore the plasmon coupling effect on fluorescence enhancement. The results show that the dimer with the smallest gap (6.1 nm) gives the highest enhancement (470-fold), and the enhancement gradually decreases as the gap distance increases and eventually approaches that from a monomer (120-fold). This trend is consistent with the numerical calculation results. This study indicates that plasmon coupling in gold nanorod dimers offers further increased excitation efficiency to achieve large fluorescence enhancement.

Double Fano resonances in plasmon coupling nanorods

Fano resonances are investigated in nanorods with symmetric lengths and side-by-side assembly. Single Fano resonance can be obtained by a nanorod dimer, and double Fano resonances are shown in nanorod trimers with side-by-side assembly. With transverse plasmon excitation, Fano resonances are caused by the destructive interference between a bright superradiant mode and dark subradiant modes. The bright mode originates from the electric plasmon resonance, and the dark modes originate from the magnetic resonances induced by near-field inter-rod coupling. Double Fano resonances result from double dark modes at different wavelengths, which are induced and tuned by the asymmetric gaps between the adjacent nanorods. Fano resonances show a high figure of merit and large light extinction in the periodic array of assembled nanorods, which can potentially be used in multiwavelength sensing in the visible and near-infrared regions.

Analysis of Asymmetric Dipoles Interacting in Heterogeneous Metal Nanorod Dimers

The localized electric field enhancement of Au-Ag nanorods dimer is theoretically investigated based on finite element method (FEM). An analytical mutual-interference model between asymmetric dipole-dimer has been built to describe the dipoles coupling with different resonance modes in heterogeneous dimer. Three prominent enhancement peaks could be observed from ultraviolet to visible spectrum, in which the ultraviolet resonance especially corresponds to a higher mode in both Ag and Au nanorods. The results reveal the strong coupling mechanism among different dipoles existing in the asymmetric dipole system, which could support the design of plasmonic nanodevices in larger resonance wavelength range.

Plasmon ruler with gold nanorod dimers: utilizing the second-order resonance.

The idea of utilizing the second-order plasmon resonance of gold nanorod π-dimers for plasmon rulers is introduced. We report on a qualitatively different dependence of the plasmon resonance shift on the interparticle distance for the first- and second-order longitudinal modes of the nanorods, extending the working range of plasmon rulers up to the distance values of approximately 400 nm.

Extinction properties of gold nanorod complexes

Plasmonics with subwavelength characteristics can break the diffraction limit of light and be used to produce the sub-wavelength optoelectronic device, thus it has aroused great interest for decades. Local surface plasmon resonance of metal nanoparticles has become one of the research hotspots due to the fact it can produce extinction and near-field enhancement effect. How to achieve controllable plasmon line shape and generate strong electromagnetic field enhancement is of great significance for improving the sensing performance, nonlinear effect and surface enhanced Raman factor of metallic nanostructures. The optical properties of plasmonic oligomer clusters composed of normal and L-shaped nanrod dimers are investigated by using the finite-difference time-domain method in this paper. There are two energy modes for an L-shaped nanorod due to its shaped anisotropy, where plasmons oscillate along the arms of the L-shaped nanorod or oscillate over the whole length of the L-shaped nanorod. Therefore, two bonding resonances appear in the spectrum of an L-shaped nanorod dimer, while only one bonding resonance exists for normal nanorod dimer. When a normal nanorod dimer and an L-shaped nanorod dimer are aligned together to form a quadrumer, the three bonding resonances can be excited simultaneously and radiative damping can be suppressed effectively around the dip spectral positions. It is shown that the optical responses of quadrumer can be strongly tuned by manipulating the geometry parameters. For example, the coupling between the two dimers can be modified by adjusting the separation, and the three resonances shift toward higher energies with the increasing of the separation. In addition, the optical responses of individual nanorod depend on the corresponding arm length. As a result, the three resonances of the quadrumer can also be well tuned by adjusting the arm length. Comparing the variation of resonance peak positions between L-shaped nanorod dimer and normal nanorod dimer, we can more intuitively understand spectral lineshape variation of quadrumer. These results can be used for guiding the design of nano-photonic devices for plasmonic oligomer clusters and also for developing the application of surface-enhanced Raman scattering and biological sensing.

Tunable optical activity of plasmonic dimers assembled by DNA origami.

We investigate the optical response of gold nanorod (AuNR) dimers assembled in parallel on a DNA origami template. Plasmonic circular dichroism (CD) was found to be highly dependent on the orientation of the dimers relative to the DNA axis and the inter-rod distances. Dipole-dipole distances play a critical role in the induced plasmonic chirality. The orientation dependence of induced CD was further verified by AuNR/Au nanosphere (AuNS) heterodimers. The experimental results of the plasmonic CD agreed well with theoretical calculations.

Systematic Study of Antibonding Modes in Gold Nanorod Dimers and Trimers

Using on-wire lithography to synthesize well-defined nanorod dimers and trimers, we report a systematic study of the plasmon coupling properties of such materials. By comparing the dimer/trimer structures to discrete nanorods of the same overall length, we demonstrate many similarities between antibonding coupled modes in the dimers/trimers and higher-order resonances in the discrete nanorods. These conclusions are validated with a combination of discrete dipole approximation and finite-difference time-domain calculations and lead to the observation of antibonding modes in symmetric structures by measuring their solution-dispersed extinction spectra. Finally, we probe the effects of asymmetry and gap size on the occurrence of these modes and demonstrate that the delocalized nature of the antibonding modes lead to longer-range coupling compared to the stronger bonding modes.

Feedback-driven self-assembly of symmetry-breaking optical metamaterials in solution.

Thermodynamically driven self-assembly offers a direct route to organize individual nanoscopic components into three-dimensional structures over a large scale. The most thermodynamically favourable configurations, however, may not be ideal for some applications. In plasmonics, for instance, nanophotonic constructs with non-trivial broken symmetries can display optical properties of interest, such as Fano resonance, but are usually not thermodynamically favoured. Here, we present a self-assembly route with a feedback mechanism for the bottom-up synthesis of a new class of symmetry-breaking optical metamaterials. We self-assemble plasmonic nanorod dimers with a longitudinal offset that determines the degree of symmetry breaking and its electromagnetic response. The clear difference in plasmonic resonance profiles of nanorod dimers in different configurations enables high spectra selectivity. On the basis of this plasmonic signature, our self-assembly route with feedback mechanism promotes the assembly of desired metamaterial structures through selective excitation and photothermal disassembly of unwanted assemblies in solution. In this fashion, our method can selectively reconfigure and homogenize the properties of the dimer, leading to highly monodispersed aqueous metamaterials with tailored symmetries and electromagnetic responses.

Circular dichroism from single plasmonic nanostructures with extrinsic chirality.

Circular dichroism (CD) studies on single nanostructures can yield novel insights into chiroptical physics that are not available from traditional ensemble-based measurements, yet they are challenging because of their weak signals. By introducing an oblique excitation beam, we demonstrate the observation and spectroscopic analysis of a prominent plasmonic chiroptical response from a single v-shaped gold nanorod dimer nanostructure. We show that circular differential scattering from the obliquely excited gold nanorod dimer yields a characteristic bisignate peak-dip spectral shape at hybridized energies of the dimer. This chiroptical response can be ascribed to extrinsic chirality which depends on the geometry configurations of the chiral arrangement. Due to strong near-field coupling, the dipole orientations of the hybridized resonance modes can be in favor of the incident circularly polarized light where a maximum g-factor of ∼0.4 is observed. Promising applications of this chiroptical arrangement as a key component can be in electronics, photonics, or metamaterials.

Design of an efficient single photon source from a metallic nanorod dimer: a quasi-normal mode finite-difference time-domain approach.

We describe how the finite-difference time-domain (FDTD) technique can be used to compute the quasi-normal mode (QNM) for metallic nano-resonators, which is important for describing and understanding light-matter interactions in nanoplasmonics. We use the QNM to model the enhanced spontaneous emission rate for dipole emitters near a gold nanorod dimer structure using a newly developed QNM expansion technique. Enhanced single photon emission factors of around 1500 and output β-factors of around 60% are found near the localized plasmon resonance.

Highly tunable gold nanorod dimer resonances mediated through conductive junctions

We study the optical properties of gold nanorod (Au NR) dimers connected end-to-end by a thin metallic junction. The plasmonic oscillations along the long axis of the dimer gives rise to two dominant modes: a bonding dimer plasmon emerging from the dipolar mode of each individual nanorod and a charge transfer plasmon involving the entire dimer structure. We find the charge transfer plasmon absorbance peak shift from the dimer structure is proportional to the NR aspect ratio (AR) behaving as it was a single NR with an AR nearly an order of magnitude larger. The charge transfer plasmon absorbance peak sensitively depends on the material and geometry of the connecting junction, theoretically tuning the absorbance peak from 1 μm to 10 μm. A straightforward “Drude-like” model to describe the charge transfer plasmon response is presented. The development of charge transfer plasmon nanostructures may open up new classes of plasmonic nanostructures leading to disruptive metamaterial technologies.

Synthesis and Characterization of a Plasmonic–Semiconductor Composite Containing Rationally Designed, Optically Tunable Gold Nanorod Dimers and Anatase TiO2

Herein we utilize on-wire lithography (OWL) to synthesize a composite plasmonic–semiconductor material composed of Au nanorod dimers embedded within anatase TiO2 sheets. We demonstrate that, despite the harsh conditions necessary to synthesize crystalline TiO2, the gapped nanostructures remain intact. Additionally, we show that the optical properties of these structures can be tailored via the geometric control afforded by the OWL process to produce structures with various gap sizes exhibiting different electric field intensities near the surface of the metal particles and that those fields penetrate into the semiconductor material. Finally, we show that this composite amplifies the electric field of incident light on it by a factor of 103, which is more that 750 times greater than the isotropic materials typically used for these systems.

Tunable Fano resonances in heterogenous Al–Ag nanorod dimers

We theoretically investigate the plasmonic coupling in heterogenous Al–Ag nanorod dimers. A pronounced Fano dip is found in the extinction spectrum produced by the destructive interference between the bright dipole mode from a short Al nanorod and the dark quadrupole mode from a long Ag nanorod nearby. This Fano resonance can be widely tuned in both wavelength and amplitude by varying the rod dimensions and end geometry, the separation distance and the local dielectric environment. The Al–Ag heterogeneous nanorod dimer shows a high sensitivity to the surrounding environment with a local surface plasmon resonance figure of merit of 7.0, which enables its promising applications in plasmonic sensing and detection.

Rational design for the controlled aggregation of gold nanorods via phospholipid encapsulation for enhanced Raman scattering.

This study describes a procedure that found a balance between the ability of polymer-stabilized nanorods (NRs) to self-assemble and the creation of narrow gaps to make reproducibly bright surface-enhanced Raman scattering (SERS) nanorod dimers. NRs were end-functionalized with polymers, which enabled end-to-end self-assembly of NR chains and control over inter-rod separation through polymer molecular weight (MW). We found a way to quench the self-assembly, by phospholipid encapsulation, reducing the polydispersity of the aggregates while rendering them water-soluble. This reduction in polydispersity and preferential isolation of short-chain nanorod species is important for maximizing SERS enhancement from nanorod chains. We prepared NR aggregates that exhibit ∼5-50 times greater SERS intensity than isolated rods (and ∼750× greater than bare dye) depending on inter-rod separation, when using Oxazine 725 reporter molecules. Colloidal stability of NR aggregates and temporal stability of the SERS signal in water were observed for 110 days. With enhanced SERS intensity, water solubility, and stability, these NR aggregates are promising optical probes for future biological applications.

Fano Resonances Induced by Strong Interactions Between Dipole and Multipole Plasmons in T-Shaped Nanorod Dimer

A simple T-shaped plasmonic nanostructure composed of two perpendicular coupled nanorods is proposed to produce strong Fano resonances. By the near-field coupling between the “bright” dipole and “dark” quadrupole plasmons of the nanorods, a deep Fano dip is formed in the extinction spectrum, which can be well fitted by the Fano interference model. The effects of the geometry parameters including nanorod length, coupling gap size, and coupling location to the Fano resonances are analyzed in detail, and a very high refractive index sensitivity is achieved by the Fano resonance. Also by adjusting the incident polarization direction, double Fano resonances can be formed by the interferences of the dipole, quadrupole, and hexapole plasmons. The proposed nanorod dimer structure is agile, and a trimer which supports double Fano resonances can be easily formed by introducing a third perpendicular coupled nanorod. The proposed T-shaped nanorod dimer structure may have applications in the fields of biological sensing and plasmon-induced transparency.