Nanorod Chains Research Articles

Using click reaction to covalently link heterogeneous gold nanorods into head‐to‐head one‐dimensional chains with an alternating sequence as plasmonic Fano resonators

AbstractWe present the deterministic linkage of short and long gold nanorods into one‐dimensional (1D) alternating nanorod chains in a head‐to‐head manner using click reactions. By precisely controlling the surface chemistry, we achieve orientation‐specific and robust covalent linkage between nanorods with high‐product yield. The optical response of the alternating nanorod chains exhibits Fano‐like resonances. This method enables the high‐throughput production of covalently linked plasmonic particle networks consisting of heterogeneous nanoparticles with specifically chosen spectral responses.

High performance blended nanofluid based on gold nanorods chain for harvesting solar radiation

Colloids composed of metallic nanoparticles are promising working fluids for solar radiation harvesting using Direct Absorption Solar Collectors (DASC), due to a high thermal conductivity characteristic and a broad optical absorption that can be tuned to match the solar spectrum. Recently, different studies report gold nanorod (Au-NR) chains for biosensing and photothermal applications, which have broadband and high absorption cross-section and potential possibilities to orientate the nanoparticle using electromagnetic fields. Moreover, colloids with nanoparticles blended configuration show efficient solar radiation absorption characteristics. Here, working fluids for DASC based on gold nanorod chains in an unblended and blended configuration are evaluated using numerical simulations. The results indicate that the solar absorption increases proportional to the size of the Au-NR assembly, and the best configuration is obtained for a tetramer structure. By using different blended arrangements such as single Au monomers, dimers, trimmers, and tetramers nanorods, it is possible to obtain solar weighted absorption coefficients close to an ideal solar thermal collector, even obtained at low volume fraction ( 1 × 1 0 − 5 ). Moreover, the results show an enhancement of the temperature of 58.45 °C for tetramer compared with a monomer structure, both under one sun excitation. Therefore, the Au-NR assembly shows a high potentiality to be explored as a high-performance working fluid for solar thermal collectors. • Colloids composed of metallic nanoparticles containing gold decorated assembly have been used for solar energy harvesting. • The opto-thermal conversion potency improved by blended Au configurations. • The blended nanofluid can exhibit both effective absorption and thermal conductance. • The temperature of thermal collector improved up to 58 o C for tetramer structure compared with a monomer at a low concentration.

Tapered arrangement of metallic nanorod chains for magnified plasmonic nanoimaging

Plasmonic nanolens, a 3-dimensional tapered arrangement of metallic nanorod chains, holds a great promise as a new plasmonics-based optical nano-imaging technique. While multiple nanorod chains can transfer the near-field signal originating from a sample to an image at a distance larger than a micro-meter, where each nanorod chain contributes in forming one pixel in the image, the tapered arrangement of the nanorod chains with a certain taper angle allows image magnification. We experimentally demonstrate the feature of image formation and magnification in a nanolens by fabricating a tapered arrangement of two silver nanorod chains, which were separated by a distance smaller than the diffraction limit at one end and larger than the diffraction limit at the other end. We placed two nano-sized optical sources of quantum dots near the first ends of the chains, which served as two subwavelength objects. In the optical measurement, we demonstrated that the unresolved subwavelength optical sources could be imaged at the other ends of the chains and were well resolved in accordance with the magnification feature of a nanolens. This verification is an experimental proof of the image magnification, and an important step toward the realization of plasmonic nanolens.

Plasmonic transfer of near-field light from subwavelength objects through a gold-nanorod chain

Plasmonics-based nanoimaging techniques have recently attracted significant attention owing to their ability to confine light to the nanoscale for super-resolution imaging. A recent report has theoretically predicted that a plasmonic nanolens, a well-designed array of metallic nanorod chains, can produce a magnified color image of subwavelength objects through a plasmonic transfer of near-field light as a new class of nanoimaging technique. In this study, we fabricate a gold-nanorod chain through a self-assembly method to experimentally validate this concept, and observe the plasmonic transfer of near-field light from subwavelength objects, which demonstrates the significant potential of plasmonic nanolens for super-resolution imaging.

Subwavelength dielectric nanorod chains for energy transfer in the visible range.

We report a new type of energy transfer device, formed by a dielectric nanorod array embedded in a silver slab. Such dielectric chain structures allow surface plasmon wave guiding with large propagation length and highly suppressed crosstalk between adjacent transmission channels. The simulation results show that our proposed design can be used to enhance the energy transfer along the waveguide-like dielectric nanorod chains via coupled plasmons, where the energy spreading is effectively suppressed, and superior imaging properties in terms of resolution and energy transfer distance can be achieved.

Oriented Gold Nanorods and Gold Nanorod Chains within Smectic Liquid Crystal Topological Defects.

We show that the use of oriented linear arrays of smectic A defects, the so-called smectic oily streaks, enables the orientation of gold nanorods (GNRs) for a large range of GNR diameters, ranging from 7 to 48 nm, and for various ligands. For the small GNRs it enables oriented end-to-end small chains of GNRs when the density is increased from around 2 GNRs/μm2 to around 6 GNRs/μm2. We have characterized the orientation of single GNRs by spectrophotometry and two-photon luminescence (TPL). A strongly anisotropic absorption of the composites and an on-off switching of GNR luminescence, both controlled by incident light polarization, are observed, revealing an orientation of the GNRs mostly parallel to the oily streaks. A more favorable trapping of GNRs by smectic dislocations with respect to ribbon-like defects is thus demonstrated. The dislocations appear to be localized at a specific localization, namely, the summit of rotating grain boundaries. Combining plasmonic absorption measurements, TPL measurements, and simulation of the plasmonic absorption, we show that the end-to-end GNR chains are both dimers and trimers, all parallel to each other, with a small gap between the coupled GNRs, on the order of 1.5 nm, thus associated with a large red-shift of 110 nm of the longitudinal plasmonic mode. A motion of the GNRs along the dislocations appears as a necessary ingredient for the formation of end-to-end GNR chains, the gap value being driven by the balance between the attracting van der Waals interactions and the steric repulsion between the GNRs and leading to interdigitation of the neighboring ligands. We thus obtain electromagnetic coupling of nanorods controlled by light polarization.

An ultra-sensitive electrochemical sensor for hydrazine based on AuPd nanorod alloy nanochains

In this work, bimetallic alloyed AuPd nanorod chains (NRCs) were synthesized by a rapid and simple one-step wet-chemical method, using 4-aminopyridine (4-AP) as the structure director and stabilizing agent, while no any seed, polymer or surfactant was involved during the synthetic process. The architecture was characterized by transmission electron microscopy (TEM) and high-resolution TEM, high-angle annular dark-field scanning TEM (HAADF-STEM), energy-dispersive X-ray spectrometer (EDS) patterns and EDS line scanning profiles, X-ray diffraction, and X-ray photoelectron spectroscopy. An amperometric sensor for hydrazine detection was constructed, and exhibited wide linear range of 0.10–501.00μM and low detection limit (S/N=3) of 0.02μM with ultra-high sensitivity, revealing the improved electroanalytical performance for hydrazine determination.

Kinetic study of nanorods self-assembly process based on logistic function model

Understanding the complicated kinetic process involved in nanoparticle self-assembly is of considerable importance for designing and fabricating functional nanostructures with desired properties. In this work, using the stopped-flow absorption technique, we investigate kinetic behaviors involved in gold nanorod assembly mediated by cysteine molecules. Further combining with SEM microstructural analyses of the assembly structure of gold nanorods, we establish the correlations between the kinetic parameter and the assembled structure. The dynamical surface plasmonic absorptions of gold nanorods are monitored during the formation of GNRs chains with different assembly rates. And the acquired kinetic data are analyzed in the frame of the second-order theoretical model, which has been widely used in the literature for linear assembly of gold nanorods. We find that the second-order theoretical model for describing the kinetic behaviors is merely limited to the case of slow assembly process of gold nanorods, but shows large deviation when the assembly process is relatively fast. We, therefore, propose in this work a new kinetic model on the basis of the logistic function, to make kinetic analyses for the different assembly rates of gold nanorods. Compared with the second-order theoretical model, this new logistic function model possesses an extended validity in describing the kinetic behaviors of both the slow and relatively fast nanorods assembly. Particularly, due to introduction of a new parameter, i.e., the exponential parameter p, the logistic function model enables a more accurate description of the kinetic behavior at a very earlier assembly stage (e.g., on a millisecond scale), in addition to quantifying the assembly rate T0. More importantly, the value of p derived from the new logistic function model allows us to establish the kinetics-structure relationship. The slow assembly process that produces mainly the one-dimensional linear chains of nanorods, is featured by the value of kinetic parameter p close to 1. By contrast, for the relatively fast assembly process that results in the formations of irregular zigzag chains even two-dimensional assembled structures of nanorods, the value of kinetic parameter approaches to 2. Furthermore, in the present study, the kinetic parameter p based on the logistic model might be related to the fractal dimension (Df) of the aggregated structures of the gold nanorods self-assembly processes. These results suggest that the logistic function model could provide the kinetic features for directly quantifying the fractal structures of the nanorods assembly. We believe that the new kinetic analysis method presented in this work could be helpful for an in-depth understanding of the kinetics-structure-property relationship in self-assembled plasmonic nanostructures.

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.

Gold nanorod linking to control plasmonic properties in solution and polymer nanocomposites.

A novel, solution-based method is presented to prepare bifunctional gold nanorods (B-NRs), assemble B-NRs end-to-end in various solvents, and disperse linked B-NRs in a polymer matrix. The B-NRs have poly(ethylene glycol) grafted along its long axis and cysteine adsorbed to its ends. By controlling cysteine coverage, bifunctional ligands or polymer can be end-grafted to the AuNRs. Here, two dithiol ligands (C6DT and C9DT) are used to link the B-NRs in organic solvents. With increasing incubation time, the nanorod chain length increases linearly as the longitudinal surface plasmon resonance shifts toward lower adsorption wavelengths (i.e., red shift). Analogous to step-growth polymerization, the polydispersity in chain length also increases. Upon adding poly(ethylene glycol) or poly(methyl methacrylate) to chloroform solution with linked B-NR, the nanorod chains are shown to retain end-to-end linking upon spin-casting into PEO or PMMA films. Using quartz crystal microbalance with dissipation (QCM-D), the mechanism of nanorod linking is investigated on planar gold surfaces. At submonolayer coverage of cysteine, C6DT molecules can insert between cysteines and reach an areal density of 3.4 molecules per nm2. To mimic the linking of Au NRs, this planar surface is exposed to cysteine-coated Au nanoparticles, which graft at 7 NPs per μm2. This solution-based method to prepare, assemble, and disperse Au nanorods is applicable to other nanorod systems (e.g., CdSe) and presents a new strategy to assemble anisotropic particles in organic solvents and polymer coatings.

Optical total reflection and transmission with mode control in a dielectric subwavelength nanorod chain

We report a polarization dependent reflection phenomenon beyond the normal incidence with a subwavelength nanorod chain. Light waves of the transverse electric mode will be totally reflected while those of the transverse magnetic mode will transmit through. The total reflection or transmission phenomenon can be seen as a constructive or destructive interference of the incident field with the transverse mode field of the chain. With the low-loss feature and the ultra-compact characteristic, this structure may find applications in photonic circuits.

In SituPlasmonic Counter for Polymerization of Chains of Gold Nanorods in Solution

Self-assembly of gold nanorods (NRs) in linear, polymer-like chains offers the ability to test and validate theoretical models of molecular polymerization. Practically, NR chains show multiple promising applications in sensing of chemical and biological species. Both areas of research can strongly benefit from the development of a quantitative tool for characterization of the structure of NR chains in the course of self-assembly, based on the change in ensemble-averaged optical properties of plasmonic polymers; however, quantitative correlation between the extinction spectra and the structural characteristics of NR chains has not been reported. Here, we report such a tool by a quantitatively correlating the red shift of the longitudinal surface plasmon band of gold NRs and the average aggregation number of NR chains. The generality of the method is demonstrated for NRs with different aspect ratios, for varying inter-rod distances in the chains, and for varying initial concentrations of NRs in solution. We modeled the extinction spectra of the NR chains by combining the theory of step-growth polymerization with finite-difference time-domain simulations and a resistor-inductor-capacitor model, and obtained agreement between the theoretical and experimental results. In addition to capturing quantitatively the ensemble physics of the polymerization, the proposed 'plasmonic counter' approach provides a real-time cost- and labor-efficient method for the characterization of self-assembly of plasmonic polymers.

Electrical contacts to nanorod networks at different length scales: From macroscale ensembles to single nanorod chains

The nature of metal–semiconductor interfaces at the nanoscale is an important issue in micro- and nano-electronic engineering. The study of charge transport through chains of CdSe semiconductor nanorods linked by Au particles represents an ideal model system for this matter, because the metal semiconductor interface is an intrinsic feature of the nanosystem. Here we show the controlled fabrication of all-inorganic hybrid metal–semiconductor networks with different size, in which the semiconductor nanorods are linked by Au domains at their tips. We demonstrate different approaches to selectively contact the networks and single nanorod chains with planar electrodes, and we investigate their charge transport at room temperature.

Deterministic assembly of linear gold nanorod chains as a platform for nanoscale applications

We demonstrate a method to assemble gold nanorods highly deterministically into a chain formation by means of directed capillary assembly. This way we achieved straight chains consisting of end-to-end aligned gold nanorods assembled in one specific direction with well-controlled gaps of ∼6 nm between the individual constituents. We determined the conditions for optimum quality and yield of nanorod chain assembly by investigating the influence of template dimensions and assembly temperature. In addition, we transferred the gold nanorod chains from the assembly template onto a Si/SiO2 target substrate, thus establishing a platform for a variety of nanoscale electronic and optical applications ranging from molecular electronics to optical and plasmonic devices. As a first example, electrical measurements are performed on contacted gold nanorod chains before and after their immersion in a solution of thiol end-capped oligophenylenevinylene molecules showing an increase in the conductance by three orders of magnitude, indicating molecular-mediated transport.

Giant optical activity from the radiative electromagnetic interactions in plasmonic nanoantennas

We fabricate the linear chains of twisted gold nanorods by a facile chiral molecular templating method. In such a chiral plasmonic system, particle-particle separation distances are in the order of the light wavelength and are much larger than the sizes of individual particles. As a result, the inter-particle interactions in this chiral system are mediated mainly by a relatively weak far-field plasmonic coupling, rather than a strong near-field coupling. However, such a chiral system of twisted gold nanorods show a huge surface plasmon based circular dichroism response, with the highest anisotropy factor around 0.027. This is in contrast to the previous studies in which near-field plasmonic coupling is an indispensable prerequisite to obtain strong optical activity from a chiral plasmonic nanostructure. Our study demonstrates here an alternative strategy for achieving huge chiroptical response of a chiral plasmonic nanostructure based on far-field, radiative electromagnetic interactions of metallic nanoparticles. Theoretical simulations show a satisfactory agreement with the experimental results. This study may provide more flexible ways to design chiral plasmon nanostructures with strong CD responses for various applications.

Energy transportation in a subwavelength waveguide composed of a pair of comb-shape nanorod chains

A subwavelength plasmonic waveguide composed of a pair of comb-shape nanorod chains is proposed. The electromagnetic energy can be transported in the waveguide via the interaction strength of magnetoinductive coupling as well as conduction current exchange. Finite Element Method simulation results reveal that for such a waveguide composed of 50 pairs of 400 nm-long-nanorods, a passband ranging from zero to cutoff frequency 156.2 THz, and an effective propagation length of 20.87 μm can be achieved simultaneously. The proposed mechanism of energy transport in the nanoscale has potential applications in subwavelength transmission lines for a wide range of integrated optical devices.

Calculation of waveguide modes in linear chains of metallic nanorods

We report on the calculation of the fundamental plasmon waveguide modes in linear periodic chains of finite silver nanorods, aligned perpendicular to the chain. The results of rigorous full-electrodynamic calculations by the layer-multiple-scattering method are discussed in conjunction with the results of the widely used coupled-dipole model and a critical evaluation of the latter is provided. More specifically, it is shown that both diameter and height of the nanorods must be much smaller than the interparticle distance; otherwise, for relatively long nanorods close to each other, the coupled-dipole model can fail completely to predict the waveguide dispersion diagram. Moreover, the model systematically underestimates the effect of dissipative losses and cannot describe the effect of a supporting substrate, which is always present in realistic cases and induces considerable changes in the waveguide dispersion diagram.

Charge Transport in Nanoscale “All-Inorganic” Networks of Semiconductor Nanorods Linked by Metal Domains

Charge transport across metal-semiconductor interfaces at the nanoscale is a crucial issue in nanoelectronics. Chains of semiconductor nanorods linked by Au particles represent an ideal model system in this respect, because the metal-semiconductor interface is an intrinsic feature of the nanosystem and does not manifest solely as the contact to the macroscopic external electrodes. Here we investigate charge transport mechanisms in all-inorganic hybrid metal-semiconductor networks fabricated via self-assembly in solution, in which CdSe nanorods were linked to each other by Au nanoparticles. Thermal annealing of our devices changed the morphology of the networks and resulted in the removal of small Au domains that were present on the lateral nanorod facets, and in ripening of the Au nanoparticles in the nanorod junctions with more homogeneous metal-semiconductor interfaces. In such thermally annealed devices the voltage dependence of the current at room temperature can be well described by a Schottky barrier lowering at a metal semiconductor contact under reverse bias, if the spherical shape of the gold nanoparticles is considered. In this case the natural logarithm of the current does not follow the square-root dependence of the voltage as in the bulk, but that of V(2/3). From our fitting with this model we extract the effective permittivity that agrees well with theoretical predictions for the permittivity near the surface of CdSe nanorods. Furthermore, the annealing improved the network conductance at cryogenic temperatures, which could be related to the reduction of the number of trap states.

Freezing the self-assembly process of gold nanocrystals

The ability to stop the self-assembly of gold nanocrystals at a desired stage of the process provides new leverage to understand and control the dynamics of self-assembly. Herein, competitive ligands are used to unfavor the interaction of the cross-linker with the gold surface and terminate the growth reaction of gold nanoparticles and nanorod chains.

Gold nanorodassembly based approach to toxin detection by SERS

A novel, rapid and ultrasensitive surface-enhanced Raman scattering (SERS) immunoassay for the detection of microcystin LR was developed based on the assembly of gold nanorods (GNRs). GNRs were assembled into nanorod chains through the bio-recognition. The SERS signal of the probe molecule modified to the end of the NRs could be enhanced due to the hot spot between the NRs. Meanwhile, the finite integration technique simulation revealed that the electrical field of nanorods was increased obviously depending on the degree of end to end assembled structures. The research results demonstrated that the linear detection range was from 0.01 ng mL−1 to 5 ng mL−1, the limit of detection was 5 pg mL−1, and the time necessary for the analysis was only 15 min.