Nanoparticle Dimers Research Articles

Novel analysis tool for the distance of gold dimers controlled by the DNA strand length on the DNA origami.

Metallic nanoparticle dimers have been used to enhance the excitation rate of single-quantum emitters. The interparticle distance (d) of the dimers has a crucial influence on the signal enhancement. Therefore, precise control of d is desired for optimal performance. However, statistical analysis of d has been often restricted to a small number of dimers due to the lack of reliable automatic software tools. For this reason, we developed a novel analysis tool for automatic dimer analysis. Our approach combines particle detection by circle Hough transformation (CHT) with custom classification routines optimised for distinct types of particles. We applied our tool to scanning electron microscopy (SEM) images and achieved great agreement in dimer detection, reaching an agreement of around 97% between automatic analysis and manual inspection for more than 3000 metallic nanoparticle dimers on DNA origami controlled by a combination of multiple DNA strands. Our study revealed the effects of the strand length (L) on the distribution of d. Based on geometric consideration, we expected a strong correlation between L and the standard deviation (σ) of d. We could verify this correlation by characterising four dimer designs with different L while analysing more than 1000 dimers per specimen.

Optomechanical motions of gold dimer’s spin, rotation and revolution manipulated by bessel beam

The optomechanical motion of a gold nanoparticle (GNP) dimer—a pair of optically bound GNPs—in fluid, manipulated by a Bessel beam, is theoretically studied using the multiple multipole (MMP) method. Since a Bessel beam possesses orbital angular momentum (OAM) and spin angular momentum (SAM) simultaneously, complicated rigid-body motions of the dimer can be induced. The mechanism involves the equilibrium between the optical force with the reactive drag force exerted by the fluid. Our results demonstrate that the dimer rotates around its center of mass (COM), while the COM performs an orbital revolution around the optical axis. Additionally, each individual GNP undergoes spinning. The directions of the GNPs’ spin and the orbital revolution of COM depend on the handedness and the order (topological charge) of Bessel beam, respectively. Nevertheless, the rotation direction of the dimer depends on the size of GNP. In the case of a smaller dimer, the direction of dimer’s rotation with respect to the COM is consistent with the handedness of the light. Conversely, a larger dimer performs a reverse rotation, accompanied by a precession during the orbital revolution. There are multiple turning points in the radius of the GNP for the alternating rotation of the dimer caused by positive or negative optical torque. Our finding may provide an insight to the optomechanical manipulation of optical vortexes on the motions of GNP clusters.

Achiral Plasmonic Antennas Enhance Differential Absorption To Increase Preferential Detection of Chiral Single Molecules.

Plasmonic antennas increase the photon flux in their vicinity, which can lead to plasmon-enhanced fluorescence for molecules near these nanostructures. Here, we combine plasmon-coupled fluorescence and fluorescence-detected circular dichroism to build a specific and sensitive detection strategy for chiral single molecules. Electromagnetic simulations indicate that a two-dimensional gold nanoparticle dimer antenna enhances the electric field and optical chirality of a plane wave in its near field. Furthermore, this optical chirality enhancement can be tuned based on the polarization of the incident electric field, such that enhancing the optical chirality via these antennas will increase the differential absorption of parity-inverted fields. We measured the fluorescence from single molecules of chiral absorbers-Cy5 J-dimers assembled in double-stranded DNA backbones-and achieved increased detectability of these right-handed molecules near achiral gold nanoparticle dimer antennas under right circularly polarized illumination. This strategy offers a new approach to distinguishing weakly fluorescent enantiomers.

Influence of atomistic features in plasmon-exciton coupling and charge transfer driven by a single molecule in a metallic nanocavity.

When an organic molecule is placed inside a plasmonic cavity formed by two metallic nanoparticles (MNP) under illumination, the electronic excitations of the molecule couple to the plasmonic electromagnetic modes of the cavity, inducing new hybrid light-matter states called polaritons. Atomistic abinitio methods accurately describe the coupling between MNPs and molecules at the nanometer scale and allow us to analyze how atomistic features influence the interaction. In this work, we study the optical response of a porphine molecule coupled to a silver nanoparticle dimer from first principles, within the linear-response time-dependent density functional theory framework, using the recently developed Python Numeric Atomic Orbitals implementation to compute the optical excitations. The optical spectra show the splitting of the resonances of the plasmonic dimer and the molecule into two distinct polaritons, a characteristic feature of the strong light-matter coupling regime. Our results stress the importance of atomistic features, such as the gap configuration in determining the plasmon-exciton coupling strength and in the emergence of molecule-mediated charge-transfer plasmon (CTP) resonances at lower frequencies. Moreover, we show that the strength of the CTP resonance can be tuned by shifting the alignment of the molecular energy levels with respect to the Fermi level of the MNPs.

Dual-spectral narrow bandwidth surface lattice resonance sensors

Dual-spectral narrow bandwidth surface lattice resonance (SLR) sensors consisting of semiconductor/SiO2 nanoparticle dimer arrays are proposed to achieve two high figures of merit (FOM). We demonstrate that FOM can be optimized by the change of semiconductor nanoparticles’ shape. The best shape of Si nanoparticles with high FOM is pillar because of the narrowest FWHM of SLR. The FOM of Si/SiO2 nanopillar dimer array can reach a value of 180 due to the high sensitivity and narrow bandwidth. Besides, the influences of different structural parameters (such as the gap of the Si nanopillars in each dimer, Si nanopillars’ diameter and height) on FOM of Si/SiO2 nanopillar dimer arrays are investigated. In the trade-off between the strong SLR and the high FOM, the gap of 50[Formula: see text]nm, the Si nanopillars’ diameter of 80[Formula: see text]nm, and the Si nanopillars’ height of 100[Formula: see text]nm, are chosen as suitable values. Furthermore, a comparison of FOM between Si, Ge, GaAs nanopillars with fixed sizes is implemented to select the appropriate materials. The best semiconductor material to obtain a high FOM is Si because of a narrower FWHM and higher sensitivity. This work is of great significance for the design of multi-spectral SLR sensors.

Hyperspectral dark-field optical microscopy correlated to atomic force microscopy for the analysis of single plasmonic nanoparticles: tutorial

Plasmonic nanostructures are actively investigated for their optical properties and for a wide range of applications in nanophotonics, biosensing, photocatalysis, hot carrier physics, and advanced cancer therapies. The localized surface plasmon resonance (LSPR) can be excited in gold or silver nanoparticles or in more complex nanostructures and gives rise to a wide range of unique optical properties. It is often critical to be able to localize individual plasmonic nanoparticles and simultaneously measure their spectrum. This is known as hyperspectral microscopy. In this tutorial, we describe and carefully explain how to achieve this goal with an optical microscope equipped with a dark-field objective and an optical spectrometer. The images and the scattering spectra of spherical gold nanoparticles with diameters of 90, 70, 50, and 25 nm are recorded. We compare them with the scattering spectra predicted with the Mie formula (LSPR peaks measured at 553, 541, 535, and 534 nm, respectively). The optical images are limited by the diffraction, and this is discussed in the framework of the Abbe equation. We also describe a strategy to easily correlate the optical images with atomic force microscope images of the samples. This allows us to precisely relate the morphology of the nanoparticles with their optical images, their color, and their optical spectrum. The case of non-spherical nanostructures, namely, dimers of nanoparticles, is also discussed. This approach allows a relatively low-cost setup and efficient characterization method that will be helpful for teachers who want to introduce their students to the wide topics of plasmonics. This will also be useful for labs seeking an affordable method to investigate the plasmonic properties of single nanostructures.

Real-Time Simulation of Ultrafast Electronic Dynamics of Nanoscale Systems Involving an Organic Molecule and a Nanoparticle Dimer.

Understanding and predicting the behavior of nanomaterials composed of plasmons interacting with quantum emitters at ultrafast timescales is crucial for the better manipulation of light at the nanoscale and advancing technologies like ultrafast communication and computing. Here we perform a simulation of the "real-time" electronic dynamics of a coupled molecule-metal nanoparticle dimer interacting with an ultrashort resonant laser pulse by combining the real-time time-dependent density functional theory (RT-TDDFT) approach with the time-domain frequency-dependent fluctuating charge (TD-ωFQ) model, an atomistic electromagnetic (AEM) model for the dynamic plasmonic response of nanoparticles. It is shown that the induced dipoles evolve from an exponential decay pattern to a beat pattern with an increase in coupling strength, which is altered by changing the molecular orientation relative to the dimer axis. It is further shown that in the strong coupling regime, both the excited molecule and the plasmon relax rapidly due to the molecule-plasmon interaction, and the efficient coherent energy exchange between the interacting molecule and plasmon modes occurs on a femtosecond (fs) timescale. This work provides guidance on manipulating light-matter interaction and studying molecular plasmonics at extremely fast timescales.

Symmetry-breaking-induced off-resonance second-harmonic generation enhancement in asymmetric plasmonic nanoparticle dimers

Abstract The linear and nonlinear optical properties of metallic nanoparticles have attracted considerable experimental and theoretical research interest. To date, most researchers have focused primarily on exploiting their plasmon excitation enhanced near-field and far-field responses and related applications in sensing, imaging, energy harvesting, conversion, and storage. Among numerous plasmonic structures, nanoparticle dimers, being a structurally simple and easy-to-prepare system, hold significant importance in the field of nanoplasmonics. In highly symmetric plasmonic nanostructures, although the odd-order optical nonlinearity of the near-surface region will be improved because of the enhanced near-fields, even-order nonlinear processes such as second-harmonic generation (SHG) will still be quenched and thus optically forbidden. Under this premise, it is imperative to introduce structural symmetry breaking to realize plasmon-enhanced even-order optical nonlinearity. Here, we fabricate a series of nanoparticle dimers each composed of two gold nanospheres with different diameters and subsequently investigate their structural asymmetry dependent linear and nonlinear optical properties. We find that the SHG intensities of gold nanosphere dimers are significantly enhanced by structural asymmetry under off-resonance excitation while the plasmonic near-field enhancement mainly affects SHG under on-resonance excitation. Our results reveal that symmetry breaking will play an indispensable role when designing novel coupled plasmonic nanostructures with enhanced nonlinear optical properties.

A quick paster type of soluble nanoparticle microneedle patch for the treatment of obesity

Obesity is a major public burden on the working population and induces chronic diseases. Its treatment often requires long-term medication, which makes patient compliance difficult. In this study, we reported the value of HORN-MN, which comprised a fast-soluble hyaluronic acid microneedle matrix and a weak acid-degradable oleanolic acid dimer of rosiglitazone nanoparticles. The results showed that the microneedles easily punctured the stratum corneum and dissolved in the dermis of the abdominal wall within 5 min, followed by the release of rosiglitazone nanoparticles. Thereafter, the nanoparticles were endocytosed by macrophages and white adipocytes, then degraded to oleanolic acid in the lysosomes, thereby, releasing rosiglitazone. Oleanolic acid significantly improved the inflammatory status of obese adipose tissue and promoted white adipocyte browning, and rosiglitazone significantly potentiated WAC browning. Accordingly, the patch demonstrated a remarkable obesity-reducing efficacy in mice. In conclusion, this study developed a quick paster type of soluble rosiglitazone nanoparticle microneedle for the treatment of obesity. This patch can be suitable for working people, with an evident obesity-reducing efficacy but no effect on skin integrity despite multiple administrations.

Singular and Nonsingular Transitions in the Infrared Plasmons of Nearly Touching Nanocube Dimers.

Narrow gaps between plasmon-supporting materials can confine infrared electromagnetic energy at the nanoscale, thus enabling applications in areas such as optical sensing. However, in nanoparticle dimers, the nature of the transition between touching (zero gap) and nearly nontouching (nonzero gap ≲15 nm) regimes is still a subject of debate. Here, we observe both singular and nonsingular transitions in infrared plasmons confined to dimers of fluorine-doped indium oxide nanocubes when moving from touching to nontouching configurations depending on the dimensionality of the contact region. Through spatially resolved electron energy-loss spectroscopy, we find a continuous spectral evolution of the lowest-order plasmon mode across the transition for finite touching areas, in excellent agreement with the simulations. This behavior challenges the widely accepted idea that a singular transition always emerges in the near-touching regime of plasmonic particle dimers. The apparent contradiction is resolved by theoretically examining different types of gap morphologies, revealing that the presence of a finite touching area renders the transition nonsingular, while one-dimensional and point-like contacts produce a singular behavior in which the lowest-order dipolar mode in the touching configuration, characterized by a net induced charge in each of the particles, becomes unphysical as soon as they are separated. Our results provide valuable insights into the nature of dimer plasmons in highly doped semiconductors.

Tunable Plasmonic Properties of Spatially Overlapping Asymmetric Nanoparticle Dimers

Tunable Plasmonic Properties of Spatially Overlapping Asymmetric Nanoparticle Dimers

Numerical investigation of SERS effects of silver dimers based on homo and hybrid nanoparticles

In this study, we examine Surface-enhanced Raman Scattering effects of silver nanoparticle dimers made of sphere-sphere, sphere-cube, and sphere-cylinder topologies by utilizing the Finite-Difference-Time-domain method. We aim to elucidate the complex effects of morphology, size, and interstitial distance on the absorbance and electric field enhancement associated with localized surface plasmon resonance. Our findings show that the sphere-cube hybrid dimer gives a better possibility for enhanced field strength at the hot spot and also offers an improved absorption coefficient with a reduced full-with at half maximum.

Intense charge transfer plasmons in golden nanoparticle dimers connected by conductive molecular linkers.

Golden nanoparticle dimers connected by conjugated molecular linkers 1,2-bis(2-pyridyl)ethylene are produced. The formation of stable dimers with 22nm diameter nanoparticles is confirmed by transmission electron microphotography. The possibility of charge transfer through the linkers between the particles in the dimers is shown by the density functional theory calculations. In addition to localized plasmon resonance of solitary nanoparticles with a wavelength of 530nm, the optical spectra exhibit a new intense absorption peak in the near-infrared range with a wavelength of ∼780nm. The emergent absorption peak is attributed to the charge-transfer plasmon (CTP) mode; the spectra simulated within the CTP developed model agree with the experimental ones. This resonant absorption may be of interest to biomedical applications due to its position in the so-called transmission window of biological tissues. The invitro heating of CTP dimer solution by a laser diode with a wavelength of 792nm proved the efficiency of CTP dimers for achieving a temperature increase of ΔT = 6 °C, which is sufficient for hyperthermia treatment of malignant tumors. This indicates the possibility of using hyperthermia to treat malignant tumors using the material we synthesized.

Two-color interferometric scattering (iSCAT) microscopy reveals structural dynamics in discrete plasmonic molecules.

Plasmonic molecules are discrete assemblies of noble metal nanoparticles (NPs) that are of interest as transducers in optical nanosensors. So far, NPs with diameters of ∼40 nm have been the preferred building blocks for plasmonic molecules intended as optical single molecule sensors due to difficulties associated with detecting smaller NPs through elastic scattering in conventional darkfield microscopy. Here, we apply 405 nm, 445 nm two-color interferometric scattering (iSCAT) microscopy to characterize polyethylene glycol (PEG) tethered dimers of 10 nm and 20 nm Ag NPs and their monomers. Dimers of both NP sizes can be discerned from their respective monomers through changes in the average iSCAT contrast. In the case of 20 nm Ag NPs, dimer formation induces a change in the sign of the iSCAT contrast, providing a characteristic signal for detecting binding events. 20 nm Ag NP dimers with 0.4 kDa and 3.4 kDa polyethylene glycol (PEG) spacers show iSCAT contrast distributions with significantly different averages on both wavelength channels. The iSCAT contrast measured for individual PEG-tethered 10 nm or 20 nm NP dimers as a function of time shows contrast fluctuations indicative of a rich structural dynamics in the assembled plasmonic molecules, which provides an additional metric to discern dimers from monomers and paves the path to a new class of interferometric plasmon rulers.

Refractometric sensing with plasmon resonances in dimer, trimer and quadrumer ensembles of gold nanoparticles

We studied by FDTD computer simulations the dependence of the surface plasmon resonances in linearly arranged gold nanospheres on incident light polarization, spheres number and diameter, and interparticle gap. The observed scattering spectra of large particles show a particularly interesting behaviour, with coupled plasmon resonances that can be either red or blue shifting with the modification of the interparticle gap. The sensitivity of the various observed coupled plasmon modes to refractive index variations is then evaluated.

The impact of analyte size on SERS enhancement location, enhancement factor, excitation wavelength, and spectrum

The study systematically explores the connection between analyte particle size and the hotspot in Au nanoparticle dimer systems, highlighting the need for different design strategies for optimal SERS substrates tailored to accommodate analyte size.

Hot carrier creation in a nanoparticle dimer-molecule composite.

Light-matter interactions have garnered considerable interest owing to their burgeoning applications in quantum optics and plasmonics. Utilizing first principles calculations, this work explores the hot carrier (HC) generation and distribution within a composite system made up of a plasmonic nanoparticle dimer and linear polycyclic aromatic hydrocarbon (PAH) molecules. We examine the spatial and energetic distributions of HCs by initiating photoexcitation and allowing localized surface plasmon dephasing. By positioning PAH molecules within the plasmonic nanodimer's gap region, our investigation uncovers HC tuning. Notably, depending on the size of the PAH molecules, there are significant alterations in the HC distribution. Hot electrons (HEs) are distributed across both the nanodimer and the PAH molecule, while hot holes (HHs) become entirely localized on the PAH as the PAH grows larger. These findings improve our understanding of plasmon-molecule coupled states and provide guidance on how to customize HC distributions through the creation of hybrid plasmonic materials.

Deep-learning-augmented microscopy for super-resolution imaging of nanoparticles.

Conventional optical microscopes generally provide blurry and indistinguishable images for subwavelength nanostructures. However, a wealth of intensity and phase information is hidden in the corresponding diffraction-limited optical patterns and can be used for the recognition of structural features, such as size, shape, and spatial arrangement. Here, we apply a deep-learning framework to improve the spatial resolution of optical imaging for metal nanostructures with regular shapes yet varied arrangement. A convolutional neural network (CNN) is constructed and pre-trained by the optical images of randomly distributed gold nanoparticles as input and the corresponding scanning-electron microscopy images as ground truth. The CNN is then learned to recover reversely the non-diffracted super-resolution images of both regularly arranged nanoparticle dimers and randomly clustered nanoparticle multimers from their blurry optical images. The profiles and orientations of these structures can also be reconstructed accurately. Moreover, the same network is extended to deblur the optical images of randomly cross-linked silver nanowires. Most sections of these intricate nanowire nets are recovered well with a slight discrepancy near their intersections. This deep-learning augmented framework opens new opportunities for computational super-resolution optical microscopy with many potential applications in the fields of bioimaging and nanoscale fabrication and characterization. It could also be applied to significantly enhance the resolving capability of low-magnification scanning-electron microscopy.

DNA Origami-Based Letterpress Printing of Gold Nanostructures with Predesigned Morphologies.

Creating customizable metallic nanostructures in a simple and controllable manner has been a long-standing goal in nanoscience. In this study, we use DNA origami as a letterpress printing plate and gold nanoparticles as ink to produce predesigned gold nanostructures. The letterpress plate is reusable, enabling the repetitive production of predesigned gold nanostructures. Furthermore, by modifying the DNA origami letterpress plate on magnetic beads, we can simplify the printing processes. We have successfully printed gold nanoparticle dimers, trimers, straight and quadrilateral tetramers, and other nanostructures. Our approach improves the flexibility and stability of metallic nanostructures, simplifying both their design and their operation. It promises universal applicability in the fabrication of metamaterials, biosensors, and surface plasma nanooptics.

Polarization Z-Scan Studies Revealing Plasmon Coupling Enhancement Due to Dimer Formation of Gold Nanoparticles in Nematic Liquid Crystals.

We investigate the plasmon coupling of gold nanoparticle (AuNP) dimers dispersed in a nematic liquid crystal matrix using the polarization z-scan technique. Our experimental setup includes the precise control of incident light polarization through polarization angles of 0°, 45°, and 90°. Two distinct cell orientations are examined: parallel and twisted nematic cells. In parallel-oriented cells, where liquid crystal molecules and AuNPs align with the rubbing direction, we observe a remarkable 2-3-fold increase in the nonlinear absorption coefficient when the polarization of the incident light is parallel to the rubbing direction. Additionally, a linear decrease in the third-order nonlinear absorption coefficient is noted as the polarization angle varies from 0° to 90°. In the case of twisted nematic cells, the NPs do not have any preferred orientation, and the enhancement remains consistent across all polarization angles. These findings conclusively establish that the observed enhancement in the nonlinear absorption coefficient is a direct consequence of plasmon coupling, shedding light on the intricate interplay between plasmonic nanostructures and liquid crystal matrices.