Assembly Of Plasmonic Nanoparticles Research Articles

Beyond the Maxwell Garnett approximation for interacting plasmonic nanoparticles: An analytical and numerical study

We revisit the issue of building a precise mixing formula for the effective permittivity of interacting assemblies of plasmonic nanoparticles. More precisely, we reconsider the analytical expressions rendered by the Maxwell Garnett and Torquato et al. approximation formulas and compare them to each other and to a numerical approach based on the boundary element method applied to interacting assemblies of metallic (gold or silver) nanoparticles. For efficient numerical simulations of interacting assemblies of relatively large sizes, we set up an algorithm with adaptive surface meshing that depends on the particle’s position within the assembly. Next, we derive expressions for the resonance frequency of the assembly from the analytical formulas, which are valid for gold and silver particle assemblies embedded in matrices with large optical indices. We then compare the analytical results with our numerical findings. We find that the Maxwell Garnett approximation formula underestimates the resonance wavelength and that its validity range in terms of inclusion fraction strongly depends on the nature of the metal and the embedding matrix. In the case of silver particles embedded in high-permittivity matrices, the Maxwell Garnett formula should only be used for low particle concentrations. Torquato’s formula, on the other hand, which accounts for multipolar interactions and the assembly spatial arrangement, renders a better agreement with the numerical simulations.

Ultrafast Laser‐Induced Plasmonic Modulation of Optical Properties of Dielectrics at High Resolution

AbstractThe size‐ and shape‐dependent localized surface plasmon properties of metallic nanoparticles (NPs) enable nanoscale‐enhanced near‐field applications in a wide range of fields, including spectroscopy, nonlinear optics, and sensing. Orderly assembled NPs can construct plasmonic metamaterials for light manipulation at a subwavelength scale, exhibiting new collective properties in resonant modes regulated by plasmon coupling between their fundamental components. Despite the recognition of its significant advantages in photonics integration, plasmonic‐based tailored optical responses for practical applications have remained elusive due to limitations in scaling up processes, as neither etching nor assembly can design and fabricate embedded plasmonic devices into functional devices/structures. Here, the assembly of plasmonic NPs is demonstrated by ultrafast laser‐induced writing‐on‐demand inside solids, tailoring their distribution and sizes. By controlling the laser scanning speed, the in situ redistribution of NPs is observed. Plasmon mediated local energy deposition is considered as the main mechanism driving nano‐patterning at a subwavelength range. A direct nano‐printing is realized by utilizing the resonant optical response of laser‐modified NP structures/patterns. This work paves the way for directly induced NP composite structures inside transparent materials at a well‐defined and controlled depth for plasmonic applications.

Chiral Nanoparticle Chains on Inorganic Nanotube Templates.

Fabrication of chiral assemblies of plasmonic nanoparticles is a highly attractive and challenging task, with promising applications in light emission, detection, and sensing. So far, primarily organic chiral templates have been used for chirality inscription. Despite recent progress in using chiral ionic liquids in synthesis, the use of organic templates significantly limits the variety of nanoparticle preparation techniques. Here, we demonstrate the utilization of seemingly achiral inorganic nanotubes as templates for the chiral assembly of nanoparticles. We show that both metallic and dielectric nanoparticles can be attached to scroll-like chiral edges propagating on the surfaces of WS2 nanotubes. Such assembly can be performed at temperatures as high as 550 °C. This large temperature range significantly widens the portfolio of nanoparticle fabrication techniques, allowing us to demonstrate a variety of chiral nanoparticle assemblies, ranging from metals (Au, Ga), semiconductors (Ge), and compound semiconductors (GaAs) to oxides (WO3).

In situ optical spectroscopy for monitoring the assembly of gold nanoparticles for plasmonic applications

Planar assemblies of plasmonic nanoparticles have been extensively used for surface-enhanced Raman scattering (SERS) applications. Understanding the assembly of nanoparticles helps us to fabricate desired sensing substrates. In the current study, we develop a technique for monitoring the assembly of gold nanoparticles (AuNPs) in real-time using optical reflection spectroscopy. The system is integrated with a flow cell enabling the control of the assembly kinetics. The effect of flow velocity on the assembly kinetics is elucidated via monitoring the reflection spectrum. For low AuNP density, the reflection spectrum shows a dip close to 522 nm, whereas for higher densities, a prominent peak is observed close to 550 nm. For a fixed assembly time, the density of particles monotonically increases by increasing the flow rate. The signatures of the particle assembly from the experiments are compared to the computationally derived reflection spectra to understand their underlying origins. The transition from a dip to a peak as a function of density is shown to arise because of destructive and constructive interference from the various interfaces. Furthermore, we demonstrate that the assembly of AuNPs within flow cells is more efficient and rapid as compared to the immersion technique. Finally, the applicability of the in situ prepared substrates for SERS applications was determined using mercapto-benzoic acid as a Raman reporter molecule, and concentrations as low as 0.196 μM could be measured with the fabricated sensor. The proposed real-time tracking method can be used for realizing ultrasensitive SERS-based sensors tailor-made for a specific sensing application.

Large Optical Asymmetry in Silver Nanoparticle Assemblies Enabled by CH-π Interaction-Mediated Chirality Transfer.

Transfer of asymmetry from the molecular system to the other distinct system requires appropriate chemical interactions. Here, we show how the CH-π interaction, one of the weakest hydrogen bonds, can be applied to transfer the asymmetry from π-conjugated chiral molecules to the assemblies of plasmonic Ag nanoparticles, where the aliphatic chains of chiral molecules and the polystyrene chains grafted on Ag nanoparticles are served as the hydrogen donor and acceptor, respectively. The optical asymmetry g-factor of the chiral assemblies of plasmonic nanoparticles is strongly dependent on the molecular weight of the polystyrene ligand, the core structure of the molecule, and the aliphatic chain length of the chiral molecule. Importantly, we explore a molecular mixing strategy to enhance the asymmetry g-factor of chiral molecular assemblies, which consequently promotes the g-factor of chiral plasmonics efficiently, reaching a high value of ∼0.05 under optimal conditions. Overall, we rationalize the chirality transfer from chiral molecules to inorganic nanoparticles, providing the guidance for structural design of chiral nanocomposites with a high g-factor.

Evaporation-induced self-assembly of gold nanorods on a hydrophobic substrate for surface enhanced Raman spectroscopy applications

The controllable assembly of plasmonic nanoparticles has developed as one of the most significant approaches for surface enhanced Raman spectroscopy (SERS) applications. This study developed a simple approach to improve a large-scale ordered assembly of gold nanorods (GNRs) by controlling the droplet evaporation mode on hydrophobic substrates. The hydrophobic substrate was efficiently produced by spin coating the silicone oil onto the glass slides and annealing them. The analyte molecule rhodamine (R6G) was employed as a surface-enhanced Raman scattering probe to demonstrate the potential effects of the synthesized arrays. This hydrophobic platform enables the concentration and delivery of analyte molecules into the surface enhanced Raman spectroscopy sensitive site while suppressing the coffee ring effect generated by the smooth contraction motion of the base contact radius of the droplet without any pinning. Thus, the limit of detection (LOD) of the R6G analyte was lowered to 10−10 M and the homogenous dispersion of surface enhanced Raman spectroscopy hotspots within the self-assembly reproducible surface enhanced Raman spectroscopy signal. This new method enables a broad range of packing patterns and mechanisms by changing the host nanoparticles in the dispersion.

Turning on hotspots: supracolloidal SERS probes made brilliant by an external activation mechanism.

We achieved external activation of local hot-spot sites in supracolloidal assembly structures. The concept was demonstrated by boosting surface-enhanced Raman scattering (SERS) efficiency by one order of magnitude through a heating-induced process. Our approach involves assembling gold nanoparticles with distinct dimensions, i.e. 16 and 80 nm, into well-defined planet-satellite-type arrangement structures using thermoresponsive (poly(N-isopropylacrylamide)) star polymer linkers. Insights into the assembly process were obtained by calculations within the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory framework. We observe one order of magnitude increase in SERS enhancement by a heating-induced volume-phase transition. This magnification aligns with simulations run using the finite-difference time-domain (FDTD) method. The implications of this adaptive supracolloidal concept are twofold: Firstly, our approach bypasses limitations of existing systems that are associated with the limited accessibility of electromagnetic hot-spot sites in strongly coupled, static assemblies of plasmonic nanoparticles, by providing the capability of dynamic hot-spot re-configuration. Second, these externally activated probes offer promising opportunities for the development of messenger materials and associated sensing strategies.

DNA functionalized plasmonic nanoassemblies as SERS sensors for environmental analysis

AbstractSurface‐enhanced Raman scattering (SERS) is among the most widely applied analytical techniques due to its easy execution and extreme sensitivity. Target molecules can be detected and distinguished based upon the fingerprint spectra that arise when absorbed on the SERS substrates surface, particularly on the SERS‐active hotspots. Thus, rational fabricating the enhancing substrates plays a key role in broadening SERS application. Programmable DNA functionalized plasmonic nanoassemblies, where DNA acts as both structure basis and functional unit, combine the specificity of DNA recognition, and modulate the assembly of plasmonic nanoparticles (NPs). Specifically designed DNA not only improves the selectivity to target molecules but also promotes the sensitivity of the optical signals through precisely regulating the distance between the molecule and the substrate. A variety of DNA‐functionalized SERS sensors have been reported and obtained well performance in the analysis of heavy metal ions in water, toxins, pesticide residues, antibiotics, hormones, illicit drugs, or other small molecules. This review places an emphasis on the design and sensing strategies of the DNA‐functionalized plasmonic nanoassemblies, as well as basic principles of Raman enhancement, and recent advances for environmental analysis. The current challenges and potential trends in the development of DNA‐functionalized SERS sensors for environmental pollutant monitoring in complicated scenarios are subsequently discussed.

Controlled assembly of gold nanoparticles in resonant gold nanoapertures for SERS applications

The controlled assembly of plasmonic nanoparticles is vital for realizing low-cost, high efficiency plasmonic substrates with tunable resonances. Here, we present a strategy to assemble gold nanoparticles (AuNPs) in resonant gold nanoapertures (NAs) to enable coupling-mediated near-field enhancement. The NAs templates are fabricated using shadow sphere lithography on polyelectrolyte (PE) coated substrates. Subsequently, AuNPs are assembled in the resonant NA templates via a simple immersion step. The PE layer, AuNP concentration, NaCl concentration, incubation time, and template thickness are used to control the particle number per aperture and the interparticle distance of the AuNP assemblies. The fabricated AuNP-NA substrates are evaluated for their SERS potential using 4-Mercaptobenzoic acid (MBA) as a Raman reporter molecule. The SERS intensity of the AuNP-NA templates can be enhanced by ten times by controlling the AuNP and NA template parameters as compared to the bare NA templates. Numerical simulations show that the coupling between the various plasmonic modes is crucial for this SERS enhancement. The proposed strategy can be used to fabricate hybrid AuNP-NA based SERS substrates with improved sensitivity.

Responsivity of Fractal Nanoparticle Assemblies to Multiple Stimuli: Structural Insights on the Modulation of the Optical Properties.

Multi-responsive nanomaterials based on the self-limited assembly of plasmonic nanoparticles are of great interest due to their widespread employment in sensing applications. We present a thorough investigation of a hybrid nanomaterial based on the protein-mediated aggregation of gold nanoparticles at varying protein concentration, pH and temperature. By combining Small Angle X-ray Scattering with extinction spectroscopy, we are able to frame the morphological features of the formed fractal aggregates in a theoretical model based on patchy interactions. Based on this, we established the main factors that determine the assembly process and their strong correlation with the optical properties of the assemblies. Moreover, the calibration curves that we obtained for each parameter investigated based on the extinction spectra point out to the notable flexibility of this nanomaterial, enabling the selection of different working ranges with high sensitivity. Our study opens for the rational tuning of the morphology and the optical properties of plasmonic assemblies to design colorimetric sensors with improved performances.

Core-satellite assembly of gold nanoshells on solid gold nanoparticles for a color coding plasmonic nanosensor.

We present core-satellite assemblies comprising a solid gold nanoparticle as the core and hollow decahedral gold nanoshells as satellites for tuning the optical properties of the plasmonic structure for sensing. The core-satellite assemblies were fabricated on a substrate via the layer-by-layer assembly of nanoparticles linked by DNA. We used finite-difference time-domain simulations to help guide the geometrical design, and characterized the optical properties and morphology of the solid-shell nanoparticle assemblies using darkfield microscopy, single-nanostructure spectroscopy, and scanning electron microscopy. Plasmon coupling yielded resonant peaks at longer wavelengths in the red to near-infrared range for solid-shell assemblies compared with solid-solid nanoparticle assemblies. We examined sensing with the solid-shell assemblies using adenosine triphosphate (ATP) as a model target and ATP-aptamer as the linker. Binding of ATP induced disassembly and led to a decrease in the scattering intensity and a color change from red to green. The new morphology of the core-satellite assembly enabled plasmonic color-coding of multiplexed sensors. We demonstrate this potential by fabricating two types of assemblies using DNA linkers that target different molecules - ATP and a model nucleic acid. Our work expands the capability of chip-based plasmonic nanoparticle assemblies for the analysis of multiple, different types of biomolecules in small sample sizes including the microenvironment and single cells.

Interparticle gap geometry effects on chiroptical properties of plasmonic nanoparticle assemblies

Chiral linear assemblies of plasmonic nanoparticles with chiral optical activity often show low asymmetry factors. Systematic understanding of the structure-property relationship in these systems must be improved to facilitate rational design of their chiroptical response. Here we study the effect of large area interparticle gaps in chiral linear nanoparticle assemblies on their chiroptical properties using a tetrahelix structure formed by a linear face-to-face assembly of nanoscale Au tetrahedra. Using finite-difference time-domain and finite element methods, we performed in-depth evaluation of the extinction spectra and electric field distribution in the tetrahelix structure and its dependence on various geometric parameters. The reported structure supports various plasmonic modes, one of which shows a strong incident light handedness selectivity that is associated with large face-to-face junctions. This works highlights the importance of gap engineering in chiral plasmonic assemblies to achieve g-factors greater than 1 and produce structures with a handedness-selective optical response.

Engineering Electromagnetic Hot-Spots in Nanoparticle Cluster Arrays on Reflective Substrates for Highly Sensitive Detection of (Bio)molecular Analytes.

Intense electromagnetic (EM) hot-spots arising at the junctions or gaps in plasmonic nanoparticle assemblies can drive ultrahigh sensitivity in molecular detection by surface-enhanced spectroscopies. Harnessing this potential however requires access to the confined physical space at the EM hot-spots, which is a challenge for larger analytes such as biomolecules. Here, we demonstrate self-assembly derived gold nanoparticle cluster arrays (NCAs) on gold substrates exhibiting controlled interparticle (<1 nm wide) and intercluster (<10 nm wide) hot-spots as highly promising in this direction. Sensitivity of the NCAs toward detection of small (<1 nm) or large (protein-receptor interactions) analytes in surface-enhanced Raman and metal-enhanced fluorescence assays is found to be strongly impacted by the size of the cluster and the presence of reflective substrates. Experiments supported by numerical simulations attribute the higher sensitivity to higher EM field enhancements at the hot-spots, as well as greater analyte leverage over EM hot-spots. The best-performing arrays could push the sensitivity down to picomolar detection limits for sub-nanometric organic analytes as well as large protein analytes. The investigation paves the way for rational design of plasmonic biosensors and highlights the unique capabilities of a molecular self-assembly approach toward catering to this objective.

Supramolecular Interactions Induced Chiral Assembly of Plasmonic Nanoparticles with Enhanced Optical Asymmetry

Supramolecular Interactions Induced Chiral Assembly of Plasmonic Nanoparticles with Enhanced Optical Asymmetry

Controlled Assembly of Plasmonic Nanoparticles: From Static to Dynamic Nanostructures.

The spatial arrangement of plasmonic nanoparticles can dramatically affect their interaction with electromagnetic waves, which offers an effective approach to systematically control their optical properties and manifest new phenomena. To this end, significant efforts were made to develop methodologies by which the assembly structure of metal nanoparticles can be controlled with high precision. Herein, recent advances in bottom-up chemical strategies toward the well-controlled assembly of plasmonic nanoparticles, including multicomponent and multifunctional systems are reviewed. Further, it is discussed how the progress in this area has paved the way toward the construction of smart dynamic nanostructures capable of on-demand, reversible structural changes that alter their properties in a predictable and reproducible manner. Finally, this review provides insight into the challenges, future directions, and perspectives in the field of controlled plasmonic assemblies.

Laser-Scanning-Guided Assembly of Quasi-3D Patterned Arrays of Plasmonic Dimers for Information Encryption.

The application of plasmonic dimeric nanostructures in color displays, data storage, and especially metamaterials necessitates the patterning of dimers into ordered arrays, but controllable assembly of plasmonic nanoparticles into patterned dimer arrays on substrates still remains a challenge. Here, a facile laser-scanning-based strategy to fabricate quasi-3D patterned arrays of plasmonic nanoparticle dimers with controlled orientation for plasmonic information encryption is reported. Laser scanning of polymer-covered plasmonic nanoparticle (e.g., gold) arrays selectively exposes the surface of irradiated nanoparticle via localized photothermal heating, guiding the assembly of another type of nanoparticles onto the exposure nanoparticle surface to form dimers on substrates. This combined top-down/bottom-up approach is highly flexible in forming high-resolution patterns of plasmonic dimers from nanoparticles of different sizes and shapes. The z-axis orientation, interparticle spacing, and nanoparticle size and shape of plasmonic dimers can be precisely tuned, enabling the modulation of the coupled resonances of the dimer arrays. Moreover, it is demonstrated that the patterned dimer arrays can be used in information encryption where their plasmonic color can be repeatedly displayed and erased. This work provides an important addition to tools for the fabrication of patterned complex plasmonic nanostructures from as-synthesized nanoparticles with broad applications.

Hierarchically Structured Plasmonic Nanoparticle Assemblies with Dual-Length Scale Electromagnetic Hot Spots for Enhanced Sensitivity in the Detection of (Bio)Molecular Analytes

High sensitivity in plasmon-enhanced spectroscopies results not only from high electromagnetic (EM) field enhancements at the vicinity of nanostructured metal surfaces but also the ability to lever...

Multiplexed and single-cell detection of microRNA with plasmonic nanoparticle assemblies

We present a label-free, low cost, and miniatured biosensing platform based on the disassembly of core-satellite plasmonic nanoparticle assemblies. The rapid and selective detection of an exemplary nucleic acid biomarker, has-miRNA-210-3p, was achieved via the strand displacement nucleic acid reaction. Target binding leads to dehybridization of the DNA linkers and changes in the scattering properties of nanostructures as monitored by darkfield microscopy. We demonstrate the ability to detect microRNA expunged from single cells and the potential to multiplex discrete assemblies to enable diverse biological applicability. The work may help translate the applicability of microRNA as diagnostic biomarkers, quantitate their abundance in the microenvironment, and facilitate the study of their correlation or causation to other biomolecules at the single-cell level.

Near-Infrared Chiral Plasmonic Microwires through Precision Assembly of Gold Nanorods on Soft Biotemplates

Directing the assembly of plasmonic nanoparticles into chiral superstructures has diverse applications including, chiroptical sensing, nonlinear optics, and biomedicine. Though soft template-mediated assemblies of both spherical and nonspherical gold nanoparticles have made significant progress, most approaches require sophisticated chemical synthesis or advanced methodologies. Besides, reports of structurally precise chiral plasmonic assemblies beyond nanoscale are limited. Here, we propose an efficient yet simple strategy to grow such precision assemblies up to mesoscale, which is beneficial for a broader community. Briefly, cationic gold nanorods (AuNRs) are allowed to systematically assemble along atomically precise, chiral, rodlike tobacco mosaic virus (TMV) particles via electrostatic attraction under ambient condition. This leads to spontaneous formation of helical hybrid microwires with high structural precision, as evidenced by cryogenic transmission electron microscopy and tomography. Resulting composite superstructures show a strong circular dichroism response at the plasmon wavelength of the AuNRs, which is supported by simulations using discrete dipole approximation. Further, chirality of the system is investigated at a single-microwire level using polarized dark-field scattering microscopy. An alternative chiral template, negatively charged colloidal cellulose nanocrystals, also arrange AuNRs into similar chiral microstructures. Thus, our report proposes a generic methodology to obtain chiral plasmonic response at the NIR region using inexpensive templates that will encourage the exploration of a wider range of nanoscale templates for creating hybrid mesostructures with emerging optoelectronic properties.

Ligand-Free Fabrication of Ag Nanoassemblies for Highly Sensitive and Reproducible Surface-Enhanced Raman Scattering Sensing of Antibiotics.

The assemblies of plasmonic nanoparticles (NPs) are the universal methods for enhancing their surface-enhanced Raman scattering (SERS) activities. However, the present methods suffer from the problems of poor reproducibility, complicated fabrication, or the adsorption of ligands on the surface, which limit their practical applications. In this work, by using a facile freeze-thaw method, we are able to fabricate the assemblies of Ag NPs with highly reproducible SERS activity without the use of ligands. Moreover, the Ag NPs can be well kept in a frozen state for a long time with few influences on the reproducibility (relative standard deviation, RSD ca. 7%), while those kept in colloid (4 °C) suffer from gradual surface oxidation and aggregation. Such a simple freeze-thaw method does not require the introduction of any ligands (or linkers) with long-term stability and reproducibility, implying its wide applications in practical SERS sensing.