Gold Nanoparticle Superlattices Research Articles

Patterned Gold Nanoparticle Superlattice Film for Wearable Sweat Sensors.

Nanoparticle superlattices are beneficial in terms of providing strong and uniform signals in analysis owing to their closely packed uniform structures. However, nanoparticle superlattices are prone to cracking during physical activities because of stress concentrations, which hinders their detection performance and limits their analytical applications. In this work, template printing methods were used in this study to prepare a patterned gold nanoparticle (AuNP) superlattice film. By adjustment of the size of the AuNP superlattice domain below the critical size of fracture, the mechanical stability of the AuNP superlattice domain is improved. Thus, long-term sustainable high-performance signal output is achieved. The patterned AuNP superlattice film was used to construct a wearable sweat sensor based on surface-enhanced Raman scattering (SERS). The designed sensor showed promise for long-term reliable use in actual scenarios in terms of recommending water replenishment, monitoring hydration states, and tracking the intensity of activity.

Gold Nanoparticle Superlattices: Conditions for Long-Range Order, Moiré Patterns, and Binary Phase from a Single Population

Gold Nanoparticle Superlattices: Conditions for Long-Range Order, Moiré Patterns, and Binary Phase from a Single Population

Tunable Subnanometer Gaps in Self-Assembled Monolayer Gold Nanoparticle Superlattices Enabling Strong Plasmonic Field Confinement.

Nanoparticle superlattices produced with controllable interparticle gap distances down to the subnanometer range are of superior significance for applications in electronic and plasmonic devices as well as in optical metasurfaces. In this work, a method to fabricate large-area (∼1 cm2) gold nanoparticle (GNP) superlattices with a typical size of single domains at several micrometers and high-density nanogaps of tunable distances (from 2.3 to 0.1 nm) as well as variable constituents (from organothiols to inorganic S2-) is demonstrated. Our approach is based on the combination of interfacial nanoparticle self-assembly, subphase exchange, and free-floating ligand exchange. Electrical transport measurements on our GNP superlattices reveal variations in the nanogap conductance of more than 6 orders of magnitude. Meanwhile, nanoscopic modifications in the surface potential landscape of active GNP devices have been observed following engineered nanogaps. In situ optical reflectance measurements during free-floating ligand exchange show a gradual enhancement of plasmonic capacitive coupling with a diminishing average interparticle gap distance down to 0.1 nm, as continuously red-shifted localized surface plasmon resonances with increasing intensity have been observed. Optical metasurfaces consisting of such GNP superlattices exhibit tunable effective refractive index over a broad wavelength range. Maximal real part of the effective refractive index, nmax, reaching 5.4 is obtained as a result of the extreme field confinement in the high-density subnanometer plasmonic gaps.

Cover Feature: The Effect of Mesogenic Coronas on the Type and Anisotropy of Gold Nanoparticle Superlattices: When Can the Tail Wag the Dog? (Chem. Eur. J. 11/2023)

Gold nanoparticles are giants compared to the ligands grafted to their surfaces. The particles weigh several hundred kDa, an organic ligand just 1 kDa. Yet by designing the shape of these small ligands, particularly the length and number of their alkyl tails, they can direct the gold nanoparticles to assemble in a large variety of superlattices. In the Research Article by G. H. Mehl, F. Liu, G. Ungar, and co-workers (DOI: 10.1002/chem.202203673), it is shown by several examples and by detailed geometric analysis how the “tail can wag the dog”.

The Effect of Mesogenic Coronas on the Type and Anisotropy of Gold Nanoparticle Superlattices: When Can the Tail Wag the Dog?

The correlation between the size of nanoparticles, the structure and shape of mesogenic ligands and the ensuing assembly behaviour is not really understood. Closer inspection shows very surprising features. Here, 2- and 4-nm gold nanoparticles (NPs) were synthesized, and grafted with a forked ligand containing two rod-like mesogens in its branches: one cholesterol, the other with azobenzene. The 4-nm NPs also contained n-hexylthiol as co-ligand. They were found to form a FCC cubic superlattice, whereas the 2-nm NPs form hexagonal HCP with weak birefringence, hence with partially oriented ligands. The structures were compared with those of related systems containing a range of different azobenzene-to-cholesterol ratios, all giving body-centred tetragonal superlattices with various degrees of anisotropy. Geometric analysis is presented in terms of the asphericity of the NPs' surroundings, requirement for space-filling and structural anisotropy. Some general rules are derived to help design the soft corona around the NPs in order to obtain superlattices with the desired structure and anisotropy.

Optical Mie Scattering by DNA-Assembled Three-Dimensional Gold Nanoparticle Superlattice Crystals

Programmable assemblies of gold nanoparticles engineered with DNA have intriguing optical properties such as Coulomb-interaction-driven strong coupling, polaritonic response in the visible range, and ultralow dispersion dielectric response in the infrared spectral range. In this work, we demonstrate the optical Mie resonances of individual microcrystals of DNA–gold nanoparticle superlattices. Broadband hyperspectral mapping of both transmission and dark-field scattering reveal a polarization-insensitive optical response with distinct spectral features in the visible and near-infrared ranges. Experimental observations are supported by numerical simulations of the microcrystals under a resonant effective medium approximation in the regime of capacitively coupled nanoparticles. The study identifies a universal characteristic optical response which is defined by a band of multipolar Mie resonances, which only weakly depend on the crystal size and light polarization. The use of gold superlattice microcrystals as scattering materials is of interest for fields such as complex nanophotonics, thermoplasmonics, photocatalysis, sensing, and nonlinear optics.

Binary Superlattices of Gold Nanoparticles in Two Dimensions.

We have created two-dimensional (2D) binary superlattices by cocrystallizing gold nanoparticles (AuNPs) of two distinct sizes into √3 × √3 and 2 × 2 complex binary superlattices, derived from the hexagonal structures of the single components. The building blocks of these binary systems are AuNPs that are functionalized with different chain lengths of poly(ethylene glycol) (PEG). The assembly of these functionalized NPs at the air-water interface is driven by the presence of salt, causing PEG-AuNPs to migrate to the aqueous surface and assemble into a crystalline lattice. We have used liquid surface X-ray reflectivity (XR) and grazing incidence small-angle X-ray scattering (GISAXS) to examine the assembly and crystallization at the liquid interface.

Temperature-Selective Self-Assembled Superlattices of Gold Nanoparticles Driven by Block Copolymer Template Guidance.

Self-assembly of nanoparticles (NPs) into highly ordered structure can enhance their electronic and optical properties that provide great potential applications such as nanoelectronics and nanophotonics. However, the self-assembly of NPs upon external stimuli was still mainly continuous and irreversible, making various potential applications of NPs difficult. Herein, the self-assembled superlattices of gold nanoparticles (AuNPs) with a temperature-selective response had been investigated by using the amphiphilic block copolymer as a template. The AuNPs in the block copolymer template, which has the closed looplike phase behavior upon heating, self-assembled into the highly ordered body centered cubic (BCC) or face centered cubic (FCC) structures at a specific temperature region that means a temperature-selective responsiveness. The formation of highly ordered self-assembled superlattices (BCC or FCC symmetries) of AuNPs with the closed looplike phase behavior was controlled by the additive and temperature. This study is the first demonstration for temperature-selective response of the cooperative self-assembly of AuNPs in the block copolymer template.

Effect of Polymer Chain Length on the Superlattice Assembly of Functionalized Gold Nanoparticles.

We report on the assembly of gold nanoparticle (AuNPs) superlattices at the liquid/vapor interface and in the bulk of their suspensions. Interparticle distances in the assemblies are achieved on multiple length scales by varying chain lengths of surface grafted AuNPs by polyethylene glycol (PEG) with molecular weights in the range 2000-40,000 Da. Crystal structures and lattice constants in both 2D and 3D assemblies are determined by synchrotron-based surface-sensitive and small-angle X-ray scattering. Assuming knowledge of grafting density, we show that experimentally determined interparticle distances are adequately modeled by spherical brushes close to the θ point (Flory-Huggins parameter, ) for 2D superlattices at a liquid interface and a nonsolvent (χ = ∞) for the 3D dry superlattices.

Self-Assembly of 2D Gold Nanoparticle Superlattice in a Polymer Vesicle Layer Driven by Hydrophobic Interaction.

Self-assembly of gold nanoparticles (AuNPs) into highly ordered superstructures provides a promising route toward fabricating materials with new functionalities or enhanced physical properties. Although self-assembly of AuNPs has garnered significant research attention recently, a highly ordered superlattice of AuNPs under a low concentration in a confined geometry formed by nonfunctionalized materials has not been reported. Herein, we investigate the self-assembly of a 2D AuNPs superlattice in a polymer vesicle layer using hydrophobic interactions, which exhibits centered rectangular lattice symmetry. To create the highly ordered AuNPs superlattice, the P(EGx-b-iPGEy) block copolymers that form the thickness of the hydrophobic vesicle layer comparable to the size of the AuNP are used as a template to control the AuNP degree of freedom. To the best of our knowledge, this study provides the first demonstration of a centered rectangular structure formation of AuNPs at the vesicle layer in 2D confined geometry.

Self-assembled 3D free-standing superlattices of gold nanoparticles driven by interfacial instability of emulsion droplets

3D free-standing superlattices self-assembled from polymer tethered gold nanoparticles (AuNPs) are fabricated by carefully tuning the interfacial instability and interfacial tension of emulsion droplets.

Macroscopic Au@PANI Core/Shell Nanoparticle Superlattice Monolayer Film with Dual-Responsive Plasmonic Switches.

The self-assembled gold nanoparticle (NP) superlattice displays unusual but distinctive features such as high mechanical and free-standing performance, electrical conductivity, and plasmonic properties, which are widely employed in various applications especially in biological diagnostics and optoelectronic devices. For a two-dimensional (2D) superlattice monolayer film composed of a given metal nanostructure, it is rather challenging to tune either its plasmonic properties or its optical properties in a reversible way, and it has not been reported. It is therefore of significant value to construct a free-standing 2D superlattice monolayer film of gold nanoparticles with an intelligent response and desired functions. Herein, we developed an easy and efficient approach to construct a gold nanoparticle superlattice film with a dual-responsive plasmonic switch. In this system, gold nanoparticles werecoated by polyaniline (PANI) and then interracially self-assembled into a monolayer film at the air-liquid interface. The PANI shell plays two important roles in the superlattice monolayer film. First, the PANI shell acts as a physical spacer to provide a steric hindrance to counteract the van der Waals (vdW) attraction between densely packed nanoparticles (NPs), resulting in the formation of a superlattice by adjusting the thickness of the PANI shell. Second, the PANI shells provide the superlattice film with multiple stimuli such as electrical potential and pH change, leading to reversible optical and plasmonic responsiveness. The superlattice monolayer film can show a vivid color change from olive green to pink, or from olive green to violet by the change of the corresponding stimuli. Also, the localized surface plasmonic resonance (LSPR) of the superlattice monolayer film can be reversibly modulated by both by changing the local pH and applying an electric potential. Notably, a significant plasmonic shift of 157 nm can be achieved in the superlattice monolayer film when the PANI shell with a thickness of 35 nm and gold nanorods as a core were used. The superlattice monolayer film with dual-responsive plasmonic switches is promising for a range of potential applications in optoelectronic devices, plasmonic and colorimetric sensors, and surface-enhanced Raman scattering (SERS).

Mechanics of Gold Nanoparticle Superlattices at High Hydrostatic Pressures

Pressure-driven assembly of ligand-grafted gold nanoparticle superlattices is a promising approach for fabricating gold nanostructures, such as nanowires and nanosheets. Optimizing this fabrication...

Light-Induced Reversible DNA Ligation of Gold Nanoparticle Superlattices.

DNA-mediated self-assembly of nanoparticles has been of great interest because it enables access to nanoparticle superstructures that cannot be synthesized otherwise. However, the programmability of higher order nanoparticle structures can be easily lost under DNA denaturing conditions. Here, we demonstrate that light can be employed as an external stimulus to master the stability of nanoparticle superlattices (SLs) via the promotion of a reversible photoligation of DNA in SLs. The oligonucleotides attached to the nanoparticles are encoded to ligate using 365 nm light, effectively locking the SLs and rendering them stable under DNA denaturing conditions. The reversible process of unlocking these structures is possible by irradiation with light at 315 nm, recovering the structures to their natural state. Our work inspires an alternative research direction toward postassembly manipulation of nanoparticle superstructures using external stimuli as a tool to enrich the library of additional material forms and their application in different media and environments.

Gold nanoparticle superlattice monolayer with tunable interparticle gap for surface-enhanced Raman spectroscopy.

Taking into account the near-field coupling interaction, non-close-packed two-dimensional nanoparticle (NP) assemblies with centimeter-scale and tunable interparticle gap (d) have attracted considerable attention due to their remarkable physicochemical properties, which show a wide range of potential applications, e.g., surface-enhanced Raman spectroscopy (SERS) active substrates. In the present work, we demonstrate that an Au NP superlattice monolayer (SM) with tunable d, playing a critical role in governing SERS activity, can be created via a rapid liquid-liquid interfacial assembly strategy. We show that the enhancement factor (EF) of SERS has an approximate 1/d2.4 dependence on the gap of Au NP SM assemblies. This work provides a platform for the rational design of plasmon-enhanced spectroscopy active substrates for theoretical studies and for various applications, including SERS-active substrates, photoelectronic devices, biosensors and others.

Non–close-packed nanoparticle arrays

Nanomaterials![Figure][1] Etching out one class of nanoparticles yields an open nanoarray. ILLUSTRATION: ELLA MARUSHCHENKO Films of colloidal nanoparticles usually form dense, close-packed lattices. If binary lattices could be made and one component removed, then a more open array could form, as long as the remaining nanoparticles could be stabilized. Udayabhaskararao et al. formed binary superlattices of gold and magnetite nanoparticles at an air-liquid interface that could then be transferred to carbon-coated surfaces (see the Perspective by Kotov). Selective etching of either of the nanoparticles created non–close-packed arrays with vacancies stabilized by the carbon surface. Science , this issue p. [514][2]; see also p. [448][3] [1]: pending:yes [2]: /lookup/doi/10.1126/science.aan6046 [3]: /lookup/volpage/358/448?iss=6362

Formation of Superlattices of Gold Nanoparticles Using Ostwald Ripening in Emulsions: Transition from fcc to bcc Structure.

An efficient method to form 3D superlattices of gold nanoparticles inside oil emulsion droplets is presented. We demonstrate that this method relies on Ostwald ripening, a well-known phenomenon occurring during the aging of emulsions. The key point is that the nanoparticle concentration inside the smaller droplets is increasing very slowly with time, thus inducing the crystallization of the nanoparticles into superlattices. Using oil-in-water emulsions doped with hydrophobic gold nanoparticles, we demonstrate that this method is efficient for different types of oils (toluene, cyclohexane, dodecane, and hexadecane). 3D superlattices of the nanoparticles are obtained, with dimensions reaching a hundred nanometers. The kinetics of the crystallization depends on the solubility of the oil in water but also on the initial concentration of the gold nanoparticles in oil. This method also provides an innovative way to obtain the complete phase diagram of nanoparticle suspensions with concentration. Indeed, during this slow crystallization process, a transition from a disordered suspension to a fcc structure is observed, followed by a transition toward a bcc structure. This evolution with time provides key results to understand the role played by the ligands located at the surface of the nanoparticles in order to control the type of superlattices which are formed.

Gold nanoparticle superlattices: correlating chemiresistive responses with analyte sorption and swelling

In this study the chemiresistive responses of gold nanoparticle superlattices are investigated by GISAXS and microgravimetry.

Gold nanoparticle superlattices: structure and cavities studied by GISAXS and PALS

In this study the sizes of cavities formed within the ligand matrix of gold nanoparticle superlattices were probed using positron annihilation lifetime spectroscopy.

Evidence for a C14 Frank-Kasper Phase in One-Size Gold Nanoparticle Superlattices.

The Frank-Kasper phases were already known in 1982 when quasi-crystals were discovered, but their complex architectures are now considered as making a link between simple close-packed periodic structures and some quasi-periodic ones. These tetrahedrally close packed structures are observed in many materials from elements to intermetallics as well as self-assembled soft materials like micellar systems, dendritric liquid crystals, star polymers, and more recently block copolymers or heated gold nanocrystal superlattices. We report here the existence of a Frank-Kasper phase with hexagonal symmetry (MgZn2 type, also labeled C14) in superlattices of monodisperse hydrophobically coated gold particles at room temperature obtained from suspensions in various solvents. The existence of such a structure in this system is analyzed in terms of geometrical parameters including gold core diameter, ligand length, and grafting density and an energetic approach based on van der Waals attraction. Hydrophobically coated gold nanoparticles is a new system that exhibits a Frank and Kasper phase built by one-size objects. This result opens a route toward a nanoparticle superlattice with complex structures and thus original physical properties.