Individual Au Nanorods Research Articles

Trace detection of chiral J-aggregated molecules adsorbed on single Au nanorods.

Trace detection of chiral molecules, which is of great significance in chemical, biological, medical and pharmaceutical sciences, requires microscopic techniques at the single-particle or single-molecule level. Although ensemble experiments show that the circular dichroism of chiral molecules can be amplified by plasmonic nanocrystals, trace detection of small chiral molecules remains challenging due to weak signals that are far below the detection limit. Herein, we demonstrate trace detection of chiral J-aggregated molecules adsorbed on individual Au nanorods (NRs) using single-particle circular differential scattering (CDS) spectroscopy. Through measuring the single-particle CDS spectra, we identified dip-peak bisignatures and further determined the chirality by matching them with calculations modelled with chiral media. We therefore find that plasmonic nanocrystals can dramatically amplify the circular dichroism of strongly coupled molecules to a detectable level so that the detection limit is as low as 3.9 × 103 molecules on an individual plasmonic nanoparticle, whereas 2.5 × 1012 molecules free in solution are barely detectable using a commercial circular dichroism instrument, suggesting a significant amplification factor of 108. Our method provides a promising strategy with a high amplification factor, shedding light on the trace detection of chiral molecules using optical microscopic methods.

Generation and Detection of Strain-Localized Excitons in WS2 Monolayer by Plasmonic Metal Nanocrystals.

Excitons in a transition-metal dichalcogenide (TMDC) monolayer can be modulated through strain with spatial and spectral control, which offers opportunities for constructing quantum emitters for applications in on-chip quantum communication and information processing. Strain-localized excitons in TMDC monolayers have so far mainly been observed under cryogenic conditions because of their subwavelength emission area, low quantum yield, and thermal-fluctuation-induced delocalization. Herein, we demonstrate both generation and detection of strain-localized excitons in WS2 monolayer through a simple plasmonic structure design, where WS2 monolayer covers individual Au nanodisks or nanorods. Enhanced emission from the strain-localized excitons of the deformed WS2 monolayer near the plasmonic hotspots is observed at room temperature with a photoluminescence energy redshift up to 200 meV. The emission intensity and peak energy of the strain-localized excitons can be adjusted by the nanodisk size. Furthermore, the excitation and emission polarization of the strain-localized excitons are modulated by anisotropic Au nanorods. Our results provide a promising strategy for constructing nonclassical integrated light sources, high-sensitivity strain sensors, or tunable nanolasers for future dense nanophotonic integrated circuits.

Enhanced refractive index sensitivity and SERS performances of individual body-Ag-nanoshell-encapsulated Au nanorods

Individual Au nanorods have been widely investigated in refractive index sensing and surface enhanced Roman spectroscopy (SERS) due to their excitation of localized surface plasmon resonances (LSPRs). It is crucial to unveil the effect of Ag nanoshell encapsulating only the body part of individual Au nanorods to improve their SERS and plasmonic sensing applications, which were investigated numerically by finite element method (FEM) in this paper. We have calculated the extinction spectra of individual body-Ag-nanoshell-encapsulated Au nanorods and optimized their refractive index sensitivity factor S, figure of merit FOM, and enhanced electric fields $$\left| E \right|$$ by controlling Au nanorod aspect ratio AR and Ag nanoshell thickness $$t$$. An effective aspect ratio ARʹ combining both AR and $$t$$ is revealed to control their S, FOM and $$\left| E \right|$$. The optimized FOM and ARʹ for their plasmon sensitivity applications are predicted, both of which are shown to become larger than that of naked Au nanorod. The optimized $$\left| E \right|$$ under three normally adopted excitation laser in experiments are also predicted, which are all ~ 17 times that of naked Au nanorods. This work is helpful to choose the appropriate size of partially encapsulated Au nanorods by Ag to facilitate designing of their LSPR based plasmon sensing and SERS nanodevices from visible to infrared.

Fano resonances from plasmon-exciton coupling in hetero-bilayer WSe2-WS2 on Au nanorod arrays

Plasmon-exciton coupling in hetero-bilayer of WSe2 and WS2 transferred onto Au nanorod arrays is studied. Dark-field scattering measurements reveal that the in-plain dipole moment of excitons in monolayer WS2 allows only the narrow spectral range of 30 nm for the resonant coupling between the localized particle plasmons from Au nanorods and the bright excitons from WS2. We demonstrate that the q-parameter that represents the asymmetry of Fano resonances from plasmon-exciton coupling can be controlled by the polarization states of incident light. Surface lattice resonances in between individual Au nanorods play a role to diminish the damping factor of plasmon-exciton coupling in the arrays.

Probing Electrocatalysis at Individual Au Nanorods via Correlated Optical and Electrochemical Measurements.

A novel analytical methodology based on correlated optical and electroanalytical measurements was developed to probe electrocatalytic reactions at individual nanoparticles (NPs) with well-defined geometries. The developed methodology, Optically Targeted ElectroChemical Cell Microscopy (OTECCM), relies on a combination of optical hyperspectral imaging, to locate individual NPs and provide structural information, and Scanning ElectroChemical Cell Microscopy (SECCM), to provide direct information on the electrochemical behavior of the same NPs. This complementary strategy allows for SECCM measurements to be carried out in a "targeted" fashion, offering significant throughput advantages over conventional, scanning-based approaches. The developed methodology was applied to study the electrocatalytic oxidation of hydrazine at individual Au nanorods (NRs). Correlated electron microscopy investigations were carried out to conclusively demonstrate the ability of the proposed methodology to probe electrochemical reactions at individual NRs. A wide variety in behavior of the individual NRs was observed, with surface reactions at Au playing a prominent role in the observed response. In situ spectroscopic investigations at individual NRs suggest surface restructuring and/or residual ligand desorption leads to significant changes in catalytic activity over time. Results from the correlated electron microscopy investigations as well as the statistical analyses of data obtained for hundreds of individual nanostructures suggest that the gross geometry of a NR is a poor predictor of its electrocatalytic performance.

Glutathione detonated and pH responsive nano-clusters of Au nanorods with a high dose of DOX for treatment of multidrug resistant cancer

Effects of nanosized drug delivery systems on cancer are often compromised due to their low drug loadings, premature drug release and multi-drug resistance (MDR). Herein, we reported a glutathione detonated and pH responsive nano-cluster of Au nanorods (AuNRs) with chemotherapeutic doxorubicin (DOX) and pre-chemosensitizer polycurcumin to treat MCF-7/ADR cells. The nano-cluster was prepared by self-assembling of AuNRs conjugated with DOX and amphiphilic poly(curcumin-co-dithiodipropionic acid)-b-biotinylated poly(ethylene glycol) via an emulsion/solvent evaporation technique, termed AuNR Cluster. The AuNR Cluster had a high drug loading (31.5% DOX), presenting much better aqueous solubility and stability at physiological pH than their individual AuNRs. The AuNR Cluster could be detonated to be their individual AuNRs at an intracellular concentration level of glutathione (GSH) (5 mM) and triggered to release DOX at an acidic pH (pH 6.8 or 5.0), which effectively facilitated cellular uptake of DOX (607 vs 356 a.u. for AuNRs at 12 h) and inhibited DOX efflux (471.33 vs 39.17 a.u. for free DOX at 24 h). The IC50 value of DOX against MCF-7/ADR cells for AuNR Cluster was 4.15 µg/mL, much lower than that for free DOX (90.97 µg/mL). The AuNR Cluster took much more photothermal effects than their corresponding AuNRs and presented enhanced anti-tumor effect (IC50: 2.61 µg/mL) under 808 nm laser irradiation. Statement of SignificanceNano-sized drug delivery systems for anti-MDR cancer is still a challenging task. Herein, AuNR Cluster was self-assembled by individual AuNRs via emulsion/solvent evaporation technique, having a structure consisting of hydrophobic DOX/PCDA-AuNR core and hydrophilic biotin-PEG chain shell. AuNR Cluster is detonated to disintegrate and yield its individual AuNRs at an intracellular concentration level of glutathione (5 mM) and triggered to release DOX at an acidic pH (6.8 or 5.0). In comparison with its individual AuNRs, AuNR Cluster has better water solubility and stability, greater photothermal effects under NIR irradiation, bigger cytotoxicity against MCF-7/ADR cells. AuNR Cluster is expected to be a potential nanomedicine for treatment of MDR cancer.

Correlated Absorption and Scattering Spectroscopy of Individual Platinum-Decorated Gold Nanorods Reveals Strong Excitation Enhancement in the Nonplasmonic Metal.

Bimetallic nanocatalysts have the potential to surmount current limitations in industrial catalysis if their electronic and optical properties can be effectively controlled. However, improving the performance of bimetallic photocatalysts requires a functional understanding of how the intricacies of their morphology and composition dictate every element of their optical response. In this work, we examine Au and Pt-decorated Au nanorods on a single-particle level to ascertain how Pt influences the plasmon resonance of the bimetallic nanostructure. We correlated scattering, photoluminescence, and pure absorption of individual nanostructures separately to expose the impact of Pt on each component. We found that the scattering and absorption spectra of uncoated Au nanorods followed expected trends in peak intensity and shape and were accurately reproduced by finite difference time domain simulations. In contrast, the scattering and absorption spectra of single Pt-decorated Au nanorods exhibited red-shifted, broad features and large deviations in line shape from particle to particle. Simulations using an idealized geometry confirmed that Pt damps the plasmon resonance of individual Au nanorods and that spectral changes after Pt deposition were a consequence of coupling between Au and Pt in the hybrid nanostructure. Simulations also revealed that the Au nanorod acts as an antenna and enhances absorption in the Pt islands. Furthermore, comparing photoluminescence spectra from Au and Pt-decorated Au nanorods illustrated that emission was significantly reduced in the presence of Pt. The reduction in photoluminescence intensity indicates that Pt lowers the number of hot carriers in the Au nanorod available for radiative recombination through either direct production of hot carriers in Pt following enhanced absorption or charge transfer from Au to Pt. Overall, these results confirm that the Pt island morphology and distribution on the nanorod surface contribute to the optical response of individual hybrid nanostructures and that the damping observed in ensemble measurements originates not only from structural heterogeneity but also because of significant damping in single nanostructures.

Momentum Distribution of Electrons Emitted from Resonantly Excited Individual Gold Nanorods.

Electron emission by femtosecond laser pulses from individual Au nanorods is studied with a time-of-flight momentum resolving photoemission electron microscope (ToF k-PEEM). The Au nanorods adhere to a transparent indium-tin oxide substrate, allowing for illumination from the rear side at normal incidence. Localized plasmon polaritons are resonantly excited at 800 nm with 100 fs long pulses. The momentum distribution of emitted electrons reveals two distinct emission mechanisms: a coherent multiphoton photoemission process from the optically heated electron gas leads to an isotropic emission distribution. In contrast, an additional emission process resulting from the optical field enhancement at both ends of the nanorod leads to a strongly directional emission parallel to the nanorod's long axis. The relative intensity of both contributions can be controlled by the peak intensity of the incident light.

Significantly Enhanced Third Harmonic Generation Using Individual Au Nanorods Coated With Gain Materials

We propose a novel design to enhance third harmonic generation (THG) using individual Au nanorods (NRs) coated with gain materials. The present design avoids the use of conventional gap systems, where complicated semiconductor techniques must be used in order to realize the corresponding high-resolution planar structures. As such, this design can contribute to a significant THG enhancement from nanoparticles; this THG is especially favorable for many applications (e.g., photovoltaic devices, bioimaging, and therapy). We perform numerical simulations using a finite-difference time domain (FDTD) in order to identify the origin of the enhanced nonlinear response based on the present system. In addition, we present an effective method to characterize the third harmonics by using Fourier analysis separating them from the excited light. The results show that the THG enhancement of the gain-assisted Au NR with a critical gain coefficient is one to two orders of magnitude greater than the highest values reported for gap THG systems.

Investigation of Au–Hg amalgam formation on substrate-immobilized individual Au nanorods

Investigation of controlled amalgamation of gold nanorods with chemically reduced mercury in aqueous solution leading to dramatic optical and morphological changes in the nanorods.

Multiphoton photoelectron emission microscopy of single Au nanorods: combined experimental and theoretical study of rod morphology and dielectric environment on localized surface plasmon resonances

Multiphoton photoelectron emission from individual Au nanorods deposited on indium tin oxide (ITO) substrates is studied via scanning photoionization microscopy, based on femtosecond laser excitation at frequencies near the rod longitudinal surface plasmon resonance (LSPR). The observed resonances in photoemission correlate strongly with plasmon resonances measured in dark field microscopy (DFM), thus establishing a novel scheme for wavelength-resolved study of plasmons in isolated metallic nanoparticles based on highly sensitive electron counting methods. In this work, we explore experimental and theoretical effects of (i) morphology and (ii) aspect ratio (AR) for longitudinal plasmon resonance behavior in Au nanorods. A quasilinear dependence between LSPR and aspect ratio (AR) is experimentally determined [Δλ≈ +100(10) nm/AR unit] for Au nanorods on ITO, in excellent agreement with the first principles value from finite element computer modeling [Δλ = +108(5) nm/AR unit]. Interestingly, however, LSPR values for larger vs. smaller diameter rods (w≈ 20 nm and 10 nm) are systematically red-shifted [ΔE≈-0.03(1) eV; Δλ≈ +15(5) nm at λ≈ 800 nm], indicating that electromagnetic retardation effects must also be considered for highest accuracy in LSPR position. To augment these results, the influence of the dielectric environment on the rod LSPR has been explored both experimentally and numerically. In particular, detailed finite-element simulations for ITO supported Au nanorods are found to yield plasmon resonances in near quantitative agreement (ΔE≈±0.04 eV) with experiment, with residual differences arising from uncertainty in the refractive index of the ITO thin film. Furthermore, the results indicate that plasmon resonance predictions based on infinitely thick ITO substrates are reliable to a few meV for film thicknesses larger than approximately twice the rod width.

Coherent Multiphoton Photoelectron Emission from Single Au Nanorods: The Critical Role of Plasmonic Electric Near-Field Enhancement

Electron emission from individual Au nanorods deposited on indium-tin-oxide (ITO) following excitation with femtosecond laser pulses near the rod longitudinal plasmon resonance is studied via scanning photoionization microscopy. The measured electron signal is observed to strongly depend on the excitation laser polarization and wavelength. Correlated secondary electron microscopy (SEM) and dark-field microscopy (DFM) studies of the same nanorods unambiguously confirm that maximum electron emission results from (i) laser polarization aligned with the rod long axis and (ii) laser wavelength resonant with the localized surface plasmon resonance. The experimental results are in good agreement with quantitative predictions for a coherent multiphoton photoelectric effect, which is identified as the predominant electron emission mechanism for metal nanoparticles under employed excitation conditions. According to this mechanism, the multiphoton photoemission rate is increased by over 10 orders of magnitude in the vicinity of a localized surface plasmon resonance, due to enhancement of the incident electromagnetic field in the particle near-field. These findings identify multiphoton photoemission as an extremely sensitive metric of local electric fields (i.e., "hot spots") in plasmonic nanoparticles/structures that can potentially be exploited for direct quantitation of local electric field enhancement factors.

Observation of Defocus Images of a Single Metal Nanorod

We examined an emission of light from a single metallic nanoparticle based on surface plasmon (SP) resonance for determination of three-dimensional orientation of nanoparticles as well as their optical properties. The defocused image of individual Au nanorods (Au NRs) is recorded by changing the focus distance under total internal reflection microscopy (TIRM) observations. Numerical and statistical analysis revealed that the observed light distribution patterns of Au NRs defocused images were classified into two groups. One is explained by considering that a single dipole dominates its light emission property. The other is explained by assuming the presence of multidipoles. This result leads us to a consideration that the emission of light coupled with the transverse and the longitudinal SP modes was observed reflecting the optical characteristics of NRs. Additionally, unique multiple ring patterns were also observed by placing Au NRs at the vicinity of nanoscopic structure, reflecting the distance betwee...

Three-Dimensional Orientation Sensors by Defocused Imaging of Gold Nanorods through an Ordinary Wide-Field Microscope

Gold (Au) nanoparticles, particularly nanorods, are actively employed as imaging probes because of their special nonblinking and nonbleaching absorption, scattering, and emitting properties that arise from the excitation of surface plasmons. Herein, we report a novel sensing method that detects feature orientation at the nanoscale via the defocused imaging of individual Au nanorods (AuNRs) with an ordinary wide-field optical microscope. By simultaneously recording defocused images and two-photon luminescence intensities for a large number of individual AuNRs, we correlate their defocused images with their three-dimensional spatial orientations. The spatial orientation of many individual AuNRs can be monitored in situ and in real-time within a single frame, enabling its use as a technique for high-throughput sensing. The probe size can be as small as several nanometers, which is highly desirable for minimization of any potential interference from the probe itself. Furthermore, the sensing property is insensitive to the excitation polarization and the distribution of the probe aspect ratio, which allows AuNRs of any length within a proper regime to be used as orientation sensors without changing the laser frequency and polarization. These unique features make the orientation probes proposed here outstanding candidates for optical imaging and sensing in materials science and biological applications.

Effect of the Dielectric Properties of Substrates on the Scattering Patterns of Gold Nanorods

Understanding the electromagnetic interactions between plasmonic noble metal nanocrystals and different substrates is very important because a number of plasmon-based devices and applications, such as chemical and biological sensing, metamaterials, subwavelength waveguides, plasmon-enhanced photovoltaic cells, plasmon-enhanced spectroscopy, and photoswitches, require the attachment of metal nanocrystals onto various substrates. In this study, we focused on the effect of the dielectric properties of substrates on the far-field scattering patterns of supported Au nanorods. Seven types of substrates, including metals, semiconductors, and insulators, were examined. The far-field scattering patterns from individual Au nanorods were found to exhibit a doughnut shape when the modulus of the dielectric constant of the substrate is above ∼7, while they appear as solid bright spots when the modulus is below ∼7. This finding was validated by numerical electrodynamic calculations. Moreover, the doughnut-shaped scattering patterns are very sensitive to the spacing between the nanorod and substrate. For the nanorods supported on silicon wafers, when the spacing is increased above ∼14 nm, the scattering patterns change from the doughnut shape to the solid bright spot. These results will be useful for the understanding of the plasmonic properties of noble metal nanocrystals supported on substrates and the development of a number of plasmon-based optical and optoelectronic devices at different size scales.

Polarization-Dependent Scanning Photoionization Microscopy: Ultrafast Plasmon-Mediated Electron Ejection Dynamics in Single Au Nanorods

This work investigates plasmon-enhanced multiphoton scanning photoelectron emission microscopy (SPIM) of single gold nanorods under vacuum conditions. Striking differences in their photoemission properties are observed for nanorods deposited either on 2 nm thick Pt films or 10 nm thick indium tin oxide (ITO) films. On a Pt support, the Au nanorods display fourth-order photoionization when excited at 800 nm, a wavelength corresponding to their plasmon resonance in aqueous solution. A cos(8)(θ) dependence of the photoelectron flux on laser polarization implies photoemission mediated by the dipolar plasmon; however, no plasmon resonance signature is exhibited over the 750-880 nm range. Electromagnetic simulations confirm that the resonance is severely broadened compared to aqueous solution, indicative of strong interactions between the Au nanorod and propagating surface plasmon modes in the Pt substrate. On ITO substrates, by way of contrast, sharp plasmon resonances in the photoemission from individual Au nanorods are observed, with widths limited only by fundamental internal electron collision processes. Furthermore, the ensemble-averaged plasmon resonance for Au nanorods on ITO is almost unshifted compared to its frequency in solution. Both findings suggest that plasmonic particle-substrate interactions are suppressed in the Au/ITO system. However, Au nanorods on ITO exhibit a surprising third-order photoemission (observed neither in Au nor ITO by itself), indicating that electrostatic interactions introduce a substantial shift in the work function for this fundamental nanoparticle-substrate system.

Nanoscale characterization of single Au nanorods by confocal microscopy

We analyzed the scattering patterns of individual Au nanorods detected by means of confocal interference scattering microscopy in combination with a higher order laser mode. We placed the Au nanorods at the interface between two dielectric media and examined the influence of different interfaces on the signal amplitude, the signal-to-noise ratio as well as on the precision of topological measurements. Approaching the index matching regime allows for topological measurements with high accuracy minimizing the acquisition time. We were also able to track the position and the orientation of particles embedded in water even when they were not thoroughly sticking to the glass surface. These results underscore the potential of the presented technique for applications in life sciences.

Optical trapping and alignment of single gold nanorods by using plasmon resonances

We demonstrate three-dimensional trapping and orientation of individual Au nanorods by using laser light slightly detuned from their longitudinal plasmon mode. Detuning to the long-wavelength side of the resonance allows stable trapping for several minutes, with an exponential dependence of trapping time on laser power (consistent with a Kramer's escape process). Detuning to the short-wavelength side causes repulsion of the rods from the laser focus. Alignment of the long axis of the rods with the trapping laser polarization is observed as a suppression of rotational diffusion about the short axis.

Ultrafast resonant optical scattering from single gold nanorods: Large nonlinearities and plasmon saturation

We measure nonlinear optical scattering from individual Au nanorods excited by ultrafast laser pulses on resonance with their longitudinal plasmon mode. Isolating single rods removes inhomogeneous broadening and allows the measurement of a large nonlinearity, much greater than that of nanorod ensembles. Surprisingly, the ultrafast nonlinearity can be attributed entirely to heating of conduction electrons and does not exhibit any response associated with coherent plasmon oscillation. This indicates an unanticipated damping of strongly driven plasmons.

Imaging and Manipulation of Gold Nanorods with an Atomic Force Microscope

Designed fabrication of nanostructures requires progress on a number of fronts in research and development. The ability to synthesize, deposit, and position nanometer scale materials is important for the development of this technology. We report here on studies of deposition and manipulation of electrochemically prepared, micelle-capped Au nanorods deposited on silicon dioxide (SiO2) surfaces. A thiol-terminated silane (3-mercaptopropylmethyldimethoxysilane, MPMDMS) was used as an active interface for gold nanorod assembly. A scanning force microscope (SFM) was used to image and manipulate individual Au nanorods. It was found that mechanical movement of the rods depends on the location of the pushing point along the rod.