Gold Nanoparticle Arrays Research Articles

Laser Controlled Manipulation of Microbubbles on a Surface with Silica-Coated Gold Nanoparticle Array.

Microbubble generation and manipulation play critical roles in diverse applications such as microfluidic mixing, pumping, and microrobot propulsion. However, existing methods are typically limited to lateral movements on customized substrates or rely on specific liquids with particular properties or designed concentration gradients, thereby hindering their practical applications. To address this challenge, this paperpresents a method that enables robust vertical manipulation of microbubbles. By focusing a resonant laser on hydrophilic silica-coated gold nanoparticle arrays immersed in water, plasmonic microbubbles are generated and detach from the substrates immediately upon cessation of laser irradiation. Using simple laser pulse control, it can achieve an adjustable size and frequency of bubble bouncing, which is governed by the movement of the three-phase contact line during surface wetting. Furthermore, it demonstrates that rising bubbles can be pulled back by laser irradiation induced thermal Marangoni flow, which is verified by particle image velocimetry measurements and numerical simulations. This study provides novel insights into flexible bubble manipulation and integration in microfluidics, with significant implications for various applications including mixing, drug delivery, and the development of soft actuators.

Charge-transfer complexation: A highly effective way towards chiral nanoparticles endowed by intrinsically chiral helicene and enantioselective SERS detection

An ordered chiral gold nanoparticle (AuNPs) array was prepared by the treatment of achiral sphere-shaped gold nanoparticles endowed with electron-accepting dinitro-phenyl (DNP) groups complexing with enantiomers of [6]helicene representing electron donors with strong chiroptical properties. Such surface-functionalization utilizes the principles of charge-transfer (CT) interaction. The incorporation of [6]helicene molecules with unique electronic and optical properties and subsequent arrangement of AuNPs caused chirality induction to intrinsically non-chiral plasmon-active nanostructures. The created nanostructures enabled the excitation of chiral plasmon and its application in highly sensitive enantioselective detection of small chiral molecules by surface-enhanced Raman spectroscopy (SERS). The chiral plasmonic response of such a system was shown to be fully controlled via the helicity of the parent [6]helicene. Upon calibration, it allowed us to directly determine the enantiomeric composition of non-racemic mixtures of (R)/(S)− 1-phenylethanol and (R)/(S)− 2-butanol.

Molecular-Induced Chirality Transfer to Plasmonic Lattice Modes.

Molecular chirality plays fundamental roles in biology. The chiral response of a molecule occurs at a specific spectral position, determined by its molecular structure. This fingerprint can be transferred to other spectral regions via the interaction with localized surface plasmon resonances of gold nanoparticles. Here, we demonstrate that molecular chirality transfer occurs also for plasmonic lattice modes, providing a very effective and tunable means to control chirality. We use colloidal self-assembly to fabricate non-close packed, periodic arrays of achiral gold nanoparticles, which are embedded in a polymer film containing chiral molecules. In the presence of the chiral molecules, the surface lattice resonances (SLRs) become optically active, i.e., showing handedness-dependent excitation. Numerical simulations with varying lattice parameters show circular dichroism peaks shifting along with the spectral positions of the lattice modes, corroborating the chirality transfer to these collective modes. A semi-analytical model based on the coupling of single-molecular and plasmonic resonances rationalizes this chirality transfer.

Thiol-End-Group Dendrons Decorated with Gold Nanoparticles Immobilized on Amino-Functionalized Graphene Oxide for SERS Detection

Surface-enhanced Raman scattering (SERS) has abundant chemical fingerprint information to analyze complex analytes under aqueous conditions. However, SERS requires uniform metal particles to generate a hotspot effect and improve sensitivity and enhancement by localized surface plasmon resonance. Therefore, in this study, SERS detection chips have been developed using uniform gold nanoparticle (AuNP) arrays embedded on thiol-end-group dendritic polymers immobilized on amino-functionalized graphene oxide (AGO) thin films of transmission electron microscopy (TEM) grids. The graphene oxide (GO) thin film was fabricated by low-damage plasma with mixed gas (O2/H2) and then further functionalized by diethylenetriamine to form AGO substrates. Based on the efficient building block of dual-functional 4-isocyanato-4′-(3,3-dimethyl-2,4-dioxo-azetidino)-diphenylmethane (IDD), the 0.5 and 1.5 generations of thiol-end-functionalized poly(urea/malonamide) dendrons (DG0.5-SH and DG1.5-SH) were precisely synthesized and grafted onto AGO substrates. The interparticle gap of AuNPs could be well controlled and decorated on these thiol-end-group dendrons to achieve the optimal SERS enhancement effect by manipulating the sizes of AuNPs and generating dendrons. The results indicate that 31 nm AuNPs immobilized on the DG0.5-SH@AGO substrate exhibited reproducible and strong SERS enhancement compared with free AuNPs. Graphene-based SERS substrates provide rapid and stable SERS detection in solutions, which offers great potential for practical applications in detecting biomolecules and environmental pollutants.

Poly‐N‐isopropylacrylamide Colloidal Arrays as Templates for Droplet‐Assisted Fabrication of Plasmonic Nanostructure Patterns

AbstractThe homogeneous and ordered coverage of substrate surfaces with nanostructures is still a challenge and is often tackled today, for example, by inkjet printing. In this case, drying effects in printed liquid droplets can lead to undesired pattern formation. Herein, colloidal arrays of poly‐N‐isopropylacrylamide are used for site‐selective self‐assembly of gold nanoparticles on large areas. The soft colloids support the drying process of gold nanoparticle dispersion droplets and leave room for capillary convection and Marangoni convection flow. This results in homogenous gold nanoparticle arrays with different shapes after drying, which can be converted into solid gold nanostructures by thermal treatment, paving the way for a simple bottom‐up fabrication strategy for highly ordered nanostructure arrays on large areas.

One hour road to high-quality arrays of gold nanoparticles coated with organic ligands

A fast and simple approach to assemble 2D and 3D gold nanoparticle-organic ligand arrays with versatile applications.

Sol-Gel Synthesis of Uniform Arrays of Ag and Au Nanoparticles

The obtaining of uniform arrays of silver and gold nanoparticles with a surface density up to 3.3∙109 cm–2 on the zinc oxide buffer layers by sol-gel method is described. The variations of the solution composition and synthesis mode, layers coating and subsequent heat treatment were carried out. The absorption spectra of the obtained samples had a peak near 400–570 nm corresponding to the plasmon resonance in the Ag and Au nanoparticles. Wavelength and shape of Ag and Au nanoparticles plasmon peak varied depending on the synthesis mode: the use of ZnO buffer layers leads to an increase in the intensity of the nanoparticles plasmon peak, the annealing leads to a gradual decrease and broadening of the absorption peak of Ag and mixed Ag and Au nanoparticles arrays, but does not affect the peak of Au nanoparticles.

Ordered arrays of gold nanoparticles crosslinked by dithioacetate linkers for molecular devices

Enhanced electrical conductance of the self-assembled monolayers upon molecular exchange with dithioacetate-terminating molecules.

Electroactive substrates for surface-enhanced Raman spectroscopy based on overgrown gold-nanoparticle arrays by electrodeposition on indium tin oxide

Highly homogeneous and robust SERS conductive surfaces with large gold coverages and small inter-particle distances for a combined electrochemical-SERS investigation to monitor switchable redox molecules and electroactivated interfacial reactions.

Formation and Characterization of 2D Closely Packed Arrays of Bare Gold Nanoparticles without Aggregation.

Uniform 2D arrays of metal nanoparticles (NPs) have received significant attention in the field of molecular sensing using localized surface plasmon resonance. Generally, metal NPs bear organic surface-modifying molecules to prevent aggregation and form 2D metal NP arrays. However, surface-modifying molecules negatively affect molecular sensing. Previously, we developed a technique for forming a 2D bare metal NP array, denoted the sandwich (SW) technique. However, the formation mechanism of these 2D metal NP arrays remains unknown and therefore the experimental conditions of the SW technique are not optimized. Here, we observed the formation of a 2D Au NP (d: 60 nm) array using the SW technique with an optical microscope. Moderate drying conditions of the colloidal droplets sandwiched between two parallel substrates were necessary for forming 2D Au NP arrays. We then optimized the drying conditions and obtained a 2D Au NP array. This array was uniform, and the Au NPs were arranged at distances of 4.5 nm with hexagonal periodicity, without aggregation. Further, the 2D Au NP arrays exhibited excellent spot-to-spot reproducibility in surface-enhanced Raman scattering.

Surface lattice resonance in three-dimensional plasmonic arrays fabricated via self-assembly of silica-coated gold nanoparticles

HypothesisThree-dimensional plasmonic nanoparticle arrays in which the nanoparticles are assembled with a certain distance apart are expected to exhibit unique optical properties attributed to surface lattice resonances because of the interactions between the nanoparticle layers. ExperimentsMulti-layered gold nanoparticle arrays were created to experimentally prove surface lattice resonances from three-dimensional arrays. Silica-coated gold nanoparticles were employed as building blocks for the array because the distance between the nanoparticles can be tuned by adjusting the thickness of the silica coating. Employing highly monodisperse building blocks enabled to fabricate both single-layered and multi-layered plasmonic arrays via a confined convective assembly method. FindingsMulti-layering of monodisperse building blocks brought about some additional peaks corresponded to Bragg diffraction of gold nanoparticle periodic array and the interactions between layers in a hexagonal close-packed structure of the nanoparticles, respectively. Most importantly, the multi-layered arrays exhibited a distinctive extinction peak at the same wavelength as that observed from the single-layered array, proving the realization of surface lattice resonances from the three-dimensional plasmonic array.

Optimization of Colloidal Gold Nanoparticles on Porous Anodic Aluminum Oxide Substrates for Refractometric Sensing.

A new composite metal-insulator-metal (MIM) system consisting of exceptionally dense non-close-packed (NCP) arrays of gold or silver nanoparticles, porous anodic aluminum oxide (PAAO), and bulk aluminum substrate interacts strongly with visible light and may become a very useful component for optical applications. The proposed MIM structure can be synthesized using accessible lithography-free chemical and physical processes (anodization and capillary force assisted colloidal particle deposition) that are suitable for the low-cost production of specialized devices. Here, we present a systematic study to determine the essential MIM structure parameters (nanoparticle size and PAAO layer thickness) for localized surface plasmon resonance (LSPR) refractometric sensing. A performance comparison was done by recording the spectra of scattered light upon angled illumination in media with different refractive indices. A clear advantage for maximizing the signal to background ratio was observed in the case of 60 and 80 nm Au nanoparticles with a PAAO thickness in a narrow range between 300 and 375 nm. Sensitivity exceeding a 200 nm peak wavelength shift per refractive index unit was found for 60 nm Au nanoparticles on approximately 500-nm-thick PAAO. The experimental observations were supported by finite-difference time-domain (FDTD) simulations.

Effect of the Combination of Gold Nanoparticles and Polyelectrolyte Layers on SERS Measurements

In this study, polyelectrolyte (PE) layers are deposited on substrates made by glass covered with an array of gold nanoparticles (GNPs). In particular, the samples studied have 0 PE layers (GGPE), 3 PE layers (GGPE), 11 PE layers (GGPE), and 21 PE layers (GGPE). All samples have been studied by micro-Raman spectroscopy. An acetic acid solution (10% v/v) has been used as a standard solution in order to investigate the SERS effect induced by different numbers of PE layers in each sample. The Surface Enhancement Raman Spectroscopy (SERS) effect correlating to the number of PE layers deposited on the samples has been shown. This effect is explained in terms of an increase in the interaction between the photon of the laser source and the plasmonic band of the GNPs due to a change of the permittivity of the surrounding medium around the GNPs. The trends of the ratios of the intensities of the Raman bands of the acetic acid solution (acetic acid and water molecules) on the band at 1098 cm ascribed to the substrates increase, and the number of PE layers increases.

Tuning the Packing Density of Gold Nanoparticles in Peptoid Nanosheets Prepared at the Oil-Water Interface.

Two-dimensional (2D) arrays of gold nanoparticles that can freely float in water are promising materials for solution-based plasmonic applications like sensing. To be effective sensors, it is critical to control the interparticle gap distance and thus the plasmonic properties of the 2D arrays. Here, we demonstrate excellent control over the interparticle gap distance in a family of freely floating gold nanoparticle-embedded peptoid nanosheets. Nanosheets are made via monolayer assembly and collapse at the oil-water interface, allowing for fine control over the solution nanoparticle concentration during assembly. We used surface pressure measurements to monitor the assembly of the peptoid, nanoparticle, and combined system at the oil-water interface to determine a workable range of nanosheet assembly conditions suitable for controlling the interparticle gap distances within the nanosheets. These measurements revealed that the extent of nanoparticle adsorption to the peptoid monolayer can be tuned by varying the bulk nanoparticle concentration, but the ability for the monolayer to collapse into nanosheets is compromised at high nanoparticle concentrations. Peptoid nanosheets were synthesized with varying bulk nanoparticle concentrations and analyzed using light microscopy and UV-visible spectroscopy. Based on the spectral shift of the localized surface plasmon resonance peaks for the nanoparticles in the nanosheets relative to those well dispersed in toluene, we estimate that we can access interparticle gap distances within the nanosheet interior between 2.9 ± 0.5 and 9 ± 2 nm. Our results suggest that the minimum interparticle distance achievable by this method is limited by the nanoparticle ligand length, and so has the potential to be further tuned by varying the ligand chemical structure. The ability to quantitatively control and monitor the assembly conditions by this method provide an opportunity to readily tune the optoelectronic properties of this new class of 2D nanomaterial, making it a promising platform for plasmonic-based sensing applications.

Plasmon resonance of gold and silver nanoparticle arrays in the Kretschmann (attenuated total reflectance) vs. direct incidence configuration

While the behaviour of plasmonic solid thin films in the Kretschmann (also known as Attenuated Total Reflection, ATR) configuration is well-understood, the use of discrete nanoparticle arrays in this optical configuration is not thoroughly explored. It is important to do so, since close packed plasmonic nanoparticle arrays exhibit exceptionally strong light-matter interactions by plasmonic coupling. The present work elucidates the optical properties of plasmonic Au and Ag nanoparticle arrays in both the direct normal incidence and Kretschmann configuration by numerical models, that are validated experimentally. First, hexagonal close packed Au and Ag nanoparticle films/arrays are obtained by air–liquid interfacial assembly. The numerical models for the rigorous solution of the Maxwell’s equations are validated using experimental optical spectra of these films before systematically investigating various parameters. The individual far-field/near-field optical properties, as well as the plasmon relaxation mechanism of the nanoparticles, vary strongly as the packing density of the array increases. In the Kretschmann configuration, the evanescent fields arising from p- and s-polarized (or TM and TE polarized) incidence have different directional components. The local evanescent field intensity and direction depends on the polarization, angle of incidence and the wavelength of incidence. These factors in the Kretschmann configuration give rise to interesting far-field as well as near-field optical properties. Overall, it is shown that plasmonic nanoparticle arrays in the Kretschmann configuration facilitate strong broadband absorptance without transmission losses, and strong near-field enhancement. The results reported herein elucidate the optical properties of self-assembled nanoparticle films, pinpointing the ideal conditions under which the normal and the Kretschmann configuration can be exploited in multiple light-driven applications.

A Novel Fabrication of Single Electron Transistor from Patterned Gold Nanoparticle Array Template-Prepared by Polystyrene Nanospheres.

In this paper, polystyrene microspheres were firstly prepared by seeded emulsion polymerization, and the uniform monolayer of polystyrene microspheres was prepared on the substrate by the dipping method. Then, polystyrene monolayer film was used as a mask and a low dimensional array structure of gold was prepared by bottom-up self-assembly process. After that, the method of solution etching and annealing was used, and the gold nanoparticle array was post-processed. As a result, gold nanoparticles were recrystallized, with an average diameter of about 50 nm. Subsequently, the semiconductor process was adopted, with focused ion beams induced deposition and electron beam evaporation, and single electron transistors were fabricated, based on self-assembled gold nanoparticles. Finally, the devices were fixed in a liquid helium cryostat and Coulomb blockade was observed at 320 mK. It is a novel fabrication of a single electron transistor based on gold nanoparticle array template and prepared with polystyrene nanospheres.

Large emergent optoelectronic enhancement in molecularly cross-linked gold nanoparticle nanosheets

A central goal in molecular electronics and optoelectronics is to translate tailorable molecular properties to larger materials and to the device level. Here, we present a method to fabricate molecularly cross-linked, self-assembled 2D nanoparticle sheets (X-NS). Our method extends a Langmuir approach of self-assembling gold nanoparticle (NP) arrays at an air-water interface by replacing the liquid sub-phase to an organic solvent to enable cross-linking with organic molecules, and then draining the sub-phase to deposit films. Remarkably, X-NS comprising conjugated oligophenylene dithiol cross-linkers (HS-(C6H4)n-SH, 1 ≤ n ≤ 3) exhibit increasing conductance with molecule length, ~6 orders of magnitude enhancement in UV-Vis extinction coefficients, and photoconductivity with molecule vs. NP contributions varying depending on the excitation wavelength. Finite difference time domain (FDTD) analyses and control measurements indicate that these effects can be modeled provided the local complex dielectric constant is strongly modified upon cross-linking. This suggests quantum hybridization at a molecule–band (q-MB) level. Given the vast number of molecules and nano-building blocks available, X-NS have potential to significantly increase the range of available 2D nanosheets and associated quantum properties.

Nano meets macro: Furnishing the surface of polymer molds with gold‐nanoparticle arrays

AbstractThe formation of well‐defined, functional surfaces that incorporate the unique properties of inorganic nanoparticles (NPs) requires robust and scalable fabrication strategies. Herein, we report a methodology for the decoration of polymer molds with plasmonic (gold) nanoparticle arrays. Wrinkled soft templates were used to assemble gold NPs (74 nm) into line arrays. These pre‐formed nanoparticle arrays were transferred in a subsequent step onto polycarbonate molds via an injection molding process. Scanning electron microscopy analysis revealed the structural fidelity of the pattern structure upon transfer. The preservation of the optical functionality of the gold nanoparticle line arrays was proven by surface‐enhanced Raman scattering (SERS) experiments. The reported strategy of nanoparticle pattern transfer to polymer bodies by this robust process is expected to prove useful for the fabrication of polymer surfaces with tailored optical functionality.

An LSPR Sensor Integrated with VCSEL and Microfluidic Chip.

The work introduces a localized surface plasmon resonance (LSPR) sensor chip integrated with vertical-cavity surface-emitting lasers (VCSELs). Using VCSEL as the light source, the hexagonal gold nanoparticle array was integrated with anodic aluminum oxide (AAO) as the mask on the light-emitting end face. The sensitivity sensing test of the refractive index solution was realized, combined with microfluidic technology. At the same time, the finite-difference time- domain (FDTD) algorithm was applied to model and simulate the gold nanostructures. The experimental results showed that the output power of the sensor was related to the refractive index of the sucrose solution. The maximum sensitivity of the sensor was 1.65 × 106 nW/RIU, which gives it great application potential in the field of biomolecular detection.

Submolecular Ligand Size and Spacing for Cell Adhesion.

Cell adhesion occurs when integrin recognizes and binds to Arg-Gly-Asp (RGD) ligands present in fibronectin. In this work, submolecular ligand size and spacing are tuned via template-mediated in situ growth of nanoparticles for dynamic macrophage modulation. To tune liganded gold nanoparticle (GNP) size and spacing from 3 to 20nm, in situ localized assemblies of GNP arrays on nanomagnetite templates are engineered. 3nm-spaced ligands stimulate the binding of integrin, which mediates macrophage-adhesion-assisted pro-regenerative polarization as compared to 20nm-spaced ligands, which can be dynamically anchored to the substrate for stabilizing integrin binding and facilitating dynamic macrophage adhesion. Increasing the ligand size from 7 to 20nm only slightly promotes macrophage adhesion, not observed with 13nm-sized ligands. Increasing the ligand spacing from 3 to 17nm significantly hinders macrophage adhesion that induces inflammatory polarization. Submolecular tuning of ligand spacing can dominantly modulate host macrophages.