Nanoparticle Superlattices Research Articles

Phase Diagram and Structure Map of Binary Nanoparticle Superlattices from a Lennard-Jones Model.

A first-principles prediction of the binary nanoparticle phase diagram assembled by solvent evaporation has eluded theoretical approaches. In this paper, we show that a binary system interacting through the Lennard-Jones (LJ) potential contains all experimental phases in which nanoparticles are effectively described as quasi hard spheres. We report a phase diagram consisting of 53 equilibrium phases, whose stability is quite insensitive to the microscopic details of the potentials, thus giving rise to some type of universality. Furthermore, we show that binary lattices may be understood as consisting of certain particle clusters, i.e., motifs, that provide a generalization of the four conventional Frank-Kasper polyhedral units. Our results show that metastable phases share the very same motifs as equilibrium phases. We discuss the connection with packing models, phase diagrams with repulsive potentials, and the prediction of likely experimental superlattices.

Electron microscopy of nanoparticle superlattice formation at a solid-liquid interface in nonpolar liquids.

Nanoparticle superlattice films form at the solid-liquid interface and are important for mesoscale materials, but are notoriously difficult to analyze before they are fully dried. Here, the early stages of nanoparticle assembly were studied at solid-liquid interfaces using liquid-phase electron microscopy. Oleylamine-stabilized gold nanoparticles spontaneously formed thin layers on a silicon nitride (SiN) membrane window of the liquid enclosure. Dense packings of hexagonal symmetry were obtained for the first monolayer independent of the nonpolar solvent type. The second layer, however, exhibited geometries ranging from dense packing in a hexagonal honeycomb structure to quasi-crystalline particle arrangements depending on the dielectric constant of the liquid. The complex structures formed by the weaker interactions in the second particle layer were preserved, while the surface remained immersed in liquid. Fine-tuning the properties of the involved materials can thus be used to control the three-dimensional geometry of a superlattice including quasi-crystals.

Coupled Dynamics of Colloidal Nanoparticle Spreading and Self-Assembly at a Fluid-Fluid Interface.

We investigated the physicochemical and transport phenomena governing the self-assembly of colloidal nanoparticles at the interface of two immiscible fluids. By combining in situ grazing-incidence small-angle X-ray scattering (GISAXS) with a temporal resolution of 200 ms and electron microscopy measurements, we gained new insights into the coupled effects of solvent spreading, nanoparticle assembly, and recession of the vapor-liquid interface on the morphology of the self-assembled thin films. We focus on oleate-passivated PbSe nanoparticles dispersed across an ethylene glycol subphase as a model system and demonstrate how solvent parameters such as surface tension, nanoparticle solubility, aromaticity, and polarity influence the mesoscale morphology of the nanoparticle superlattice. We discovered that a nanoparticle precursor monolayer film spreads in front of the bulk solution and influences the fluid spreading across the subphase. Improved understanding of the impact of kinetic phenomena (i.e., solvent spreading and evaporation) on the superlattice morphology is important to describe the formation mechanism and ultimately enable the assembly of high-quality superlattices with long-range order.

Epitaxial-assembled monolayer superlattices for efficient micromotor propulsion

Exploring micromotors with outstanding propulsion efficiency is of great importance for aspects ranging from enhancement of performance to realization of applications. Improvements in propulsion efficiency lead to a lower fuel requirementand broadens the potential application areas for higher environment compatibility. In this article, a tubular micromotor with catalytic nanoparticle superlattices is fabricated through a simple epitaxial assembly method. A high surface-to-volume ratio due to the use of catalytic nanoparticles, a carbon outer layer and cooperative propulsion of multitubes enables the micromotor to move in biocompatible environment with a low concentration of fuel. In addition, magnetic nanoparticles are integrated into the micromotor to offer effective control of the direction of movement by using a magnetic field. This work provides a simple and low-cost fabrication method for a micromotor with high performance, which is expected to meet practical demands.

Ionic solids from common colloids.

From rock salt to nanoparticle superlattices, complex structure can emerge from simple building blocks that attract each other through Coulombic forces1-4. On the micrometre scale, however, colloids in water defy the intuitively simple idea of forming crystals from oppositely charged partners, instead forming non-equilibrium structures such as clusters and gels5-7. Although various systems have been engineered to grow binary crystals8-11, native surface charge in aqueous conditions has not been used to assemble crystalline materials. Here we form ionic colloidal crystals in water through an approach that we refer to as polymer-attenuated Coulombic self-assembly. The key to crystallization is the use of a neutral polymer to keep particles separated by well defined distances, allowing us to tune the attractive overlap of electrical double layers, directing particles to disperse, crystallize or become permanently fixed on demand. The nucleation and growth of macroscopic single crystals is demonstrated by using the Debye screening length to fine-tune assembly. Using a variety of colloidal particles and commercial polymers, ionic colloidal crystals isostructural to caesium chloride, sodium chloride, aluminium diboride and K4C60 are selected according to particle size ratios. Once fixed by simply diluting out solution salts, crystals are pulled out of the water for further manipulation, demonstrating an accurate translation from solution-phase assembly to dried solid structures. In contrast to other assembly approaches, in which particles must be carefully engineered to encode binding information12-18, polymer-attenuated Coulombic self-assembly enables conventional colloids to be used as model colloidal ions, primed for crystallization.

The Phase Behavior of Nanoparticle Superlattices in the Presence of a Solvent.

Superlattices of nanoparticles coated by alkyl-chain ligands are usually prepared from a stable solution by evaporation, therefore the pathway of superlattice self-assembly critically depends on the amount of solvent present within it. This work addresses the role of the solvent on the structure and the relative stability of the different supercrystalline phases of single-component superlattices (simple cubic, body-centered cubic (BCC), face-centered cubic (FCC), and hexagonal close-packed). The study is performed with a molecular theory for nanoparticle superlattices introduced in this work, which predicts the structure and thermodynamics of the supercrystals explicitly treating the presence and molecular details of the solvent and the ligands. The theory predicts a FCC-BCC transition with decreasing solvent content due to the competition between the translational entropy of the solvent and the entropy and internal energy of the ligands. This result provides an explanation for recent experimental observations by in situ X-ray scattering, which reported a FCC-BCC transition during solvent evaporation. The theory also predicts the effects of the length and surface coverage of the ligands and the radius of the core on the phase behavior in agreement with experimental evidence and previous molecular dynamics simulations. These results validate the use of the dimensionless softness parameter λ (ratio of ligand length to core radius) to predict the phase behavior of wet superlattices. Our results stress the importance of explicitly considering the presence of the solvent in order to reach a complete picture of the mechanisms that mediate the self-assembly of nanoparticle superlattices.

How to Become a Protein Crystallographer in a Nanoscience Lab

Download : Download high-res image (240KB) Download : Download full-size image Peter H. Winegar obtained his BS in chemistry at Michigan Technological University in 2017 under the mentorship of Prof. Loredana Valenzano. Currently, he is a PhD candidate in chemistry at Northwestern University and is advised by Prof. Chad A. Mirkin. Peter’s current research includes the directed crystallization and oligomerization of proteins using DNA interactions. He serves on the board of Northwestern’s Phi Lambda Upsilon Chemistry Honor Society and participates in science outreach to elementary students through Northwestern’s Science in the Classroom program.

Single-crystal Winterbottom constructions of nanoparticle superlattices.

Colloidal nanoparticle assembly methods can serve as ideal models to explore the fundamentals of homogeneous crystallization phenomena, as interparticle interactions can be readily tuned to modify crystal nucleation and growth. However, heterogeneous crystallization at interfaces is often more challenging to control, as it requires that both interparticle and particle-surface interactions be manipulated simultaneously. Here, we demonstrate how programmable DNA hybridization enables the formation of single-crystal Winterbottom constructions of substrate-bound nanoparticle superlattices with defined sizes, shapes, orientations and degrees of anisotropy. Additionally, we show that some crystals exhibit deviations from their predicted Winterbottom structures due to an additional growth pathway that is not typically observed in atomic crystals, providing insight into the differences between this model system and other atomic or molecular crystals. By precisely tailoring both interparticle and particle-surface potentials, we therefore can use this model to both understand and rationally control the complex process of interfacial crystallization.

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).

Primary growth of binary nanoparticle superlattices with distinct systems contingent on synergy: softness and crystalline anisotropy

Binary nanoparticle superlattices (BNSLs), which are studied for developing multicomponent materials and multifunctional nanodevices, are distinguished by their outstanding synergetic properties. Owing to complex factors that might influence the formation of BNSLs, it is necessary to comprehensively explore the self-assembly of nanocrystals. A variety of BNSL structural configurations, such as NaZn13, Cu3Au, NaCl, AlB2, CaCu5-type structures, were obtained by cocrystallizing Au–Ni and Ag–Ni nanocrystals of different sizes. Specifically, at a similar effective size ratio, the supercrystal structures formed by the Au–Ni and Ag–Ni systems coated with different organic ligands are not essentially the same. We attribute this diversity to the different softness of effective entities and facet-dependent interdigitation between the ligands tethered on the nanoparticle surface. Inherent crystallinity directed formation of the final BNSL structures is likely driven by anisotropic or isotropic cocrystallization. The synergistic effect of the coating agent and crystallinity directed assembly process is reasonably believed to be the important factor affecting the growth of BNSLs, which provides a new idea for the study of kinetics during the self-assembly of supercrystals.

Chain-length effect on binary superlattices of polymer-tethered nanoparticles

The co-assembly behavior of polymer-tethered NPs is determined by the chain-length of the polymer ligand on the two sized NPs, and exhibits three different models, where each one has its own key factor that determines the crystalline structure.

Molecular Control of Charge Carrier and Seebeck Coefficient in Hybrid Two-Dimensional Nanoparticle Superlattices

The development of high efficiency thermoelectric materials would revolutionize energy harvesting capabilities and be useful for a large number of applications. Hybrid organic–inorganic nanostructu...

Electron properties of 13-atom nanoparticle superlattices

A density functional theory (DFT) study of electronic properties and Seebeck coefficient S of d-metal (Au, Ag, Pt, Pd, Ta) 13-atom nanoparticle superlattices is presented. The geometry optimization, calculations of electronic structure and density of electron states (DOS) was performed in DFT generalized gradient approximation in Perdiew-Burke-Ernzerhoff form (GGA-PBE) with full relativistic pseudopotentials. From the band structure S values are calculated using semi-classical Boltzmann equation in τ approximation. A size-dependent appearance of features in DOS near Fermi level is shown. The influence of these features on S is discussed. Potential usage of such model materials with strong DOS features near Fermi level as a source of varied energy monochromatic photons in metal insulator semiconductor structures for resonant excitation of long-lived forbidden states, including nuclear ones is discussed.

Refocusing in Situ Electron Microscopy: Moving beyond Visualization of Nanoparticle Self-Assembly To Gain Practical Insights into Advanced Material Fabrication.

Despite incredible progress in preparing extended nanoparticle superlattices by self-assembly, theoretically predicted collective properties of extended nanoparticle superlattices are rarely correlated to observations due to the presence of defects. Enhanced fundamental understanding of the kinetics involved in nanoparticle superlattice self-assembly, specifically defect formation and annealing kinetics and mechanisms, is needed to prepare defect-free nanoparticle superlattices. In situ transmission electron microscopy (TEM) enables direct visualization of nanoparticle self-assembly phenomena in real time and at atomic spatial resolution; however, effective translation of in situ TEM data into new predictive models and material synthesis design rules remains a persistent challenge. Recent work by Ondry et al. in this issue of ACS Nano utilized atomic resolution in situ TEM to establish defect removal kinetics in epitaxially attached CdSe nanocrystal pairs, revealing a set of practical guidelines for minimizing defect formation in extended nanoparticle solids. Motivated by this work, in this Perspective, I explore and discuss the most effective and impactful uses of in situ TEM for nanoscience research and the associated technical barriers for performing in situ TEM measurements that are meaningful to bulk-scale self-assembly experiments.

Influence of Softness on the Stability of Binary Colloidal Crystals.

Mixtures of two types of nanoparticles can self-assemble into a wide variety of binary colloidal crystals (also called binary nanoparticle superlattices), which are interesting for their structural diversity and potential applications. Although so-called packing models-which usually treat the particles as "hard" with only excluded volume interactions-seem to explain many reported dense crystalline phases, these models often fail to predict the right structure. Here, we examine the role of soft repulsive interparticle interactions on binary colloidal crystals comprising two sizes of spherical particles; such "softness" can arise due to ligand shells or screened electrostatics. We determine the ground state phase diagram of binary systems of particles interacting with an additive inverse power law potential using a basin hopping algorithm to calculate the enthalpy of an extremely large pool of candidate structures. We find that a surprisingly small amount of softness can destabilize dense packings in favor of less densely packed structures, which provides further evidence that considerations beyond packing are necessary for describing many of the observed phases of binary colloidal crystals. Importantly, we find that several of the phases stabilized by softness, which are characterized by relatively few interparticle contacts and a tendency for local icosahedral order, are more likely to be observed experimentally than those predicted by packing models. We also report a previously unknown dense AB4 phase and conduct free energy calculations to examine how the stability of several crystals will vary with temperature. Our results further our understanding of why particular binary colloidal crystals form and will be useful as a reference for experimentalists working with softly repulsive colloids.

Self-assembly and characterization of 2D plasmene nanosheets

Freestanding plasmonic nanoparticle (NP) superlattice sheets are novel 2D nanomaterials with tailorable properties that enable their use for broad applications in sensing, anticounterfeit measures, ionic gating, nanophotonics and flat lenses. We recently developed a robust, yet general, two-step drying-mediated approach to produce freestanding monolayer, plasmonic NP superlattice sheets, which are typically held together by holey grids with minimal solid support. Within these superlattices, NP building blocks are closely packed and have strong plasmonic coupling interactions; hence, we termed such freestanding materials 'plasmene nanosheets'. Using the desired NP building blocks as starting material, we describe the detailed fabrication protocol, including NP surface functionalization by thiolated polystyrene and the self-assembly of NPs at the air-water interface. We also discuss various characterization approaches for checking the quality and optical properties of the as-obtained plasmene nanosheets: optical microscopy, spectrophotometry, transmission/scanning electron microscopy (TEM/SEM) and atomic force microscopy (AFM). With regard to different constituent building blocks, the key experimental parameters, including NP concentration and volume, are summarized to guide the successful fabrication of specific types of plasmene nanosheets. This protocol, from initial NP synthesis to the final fabrication and characterization, takes ~33.5 h.

Hydration‐Driven Superlattices: Interplay between Short‐ and Long‐Ranged Forces Leading to the Formation of Ag Nanoparticle Superlattice (Small 33/2019)

Hydration‐Driven Superlattices: Interplay between Short‐ and Long‐Ranged Forces Leading to the Formation of Ag Nanoparticle Superlattice (Small 33/2019)

Local orientational order in self-assembled nanoparticle films: the role of ligand composition and salt

An X-ray cross-correlation study of the local orientational order in self-assembled films made from PEGylated gold nanoparticles is presented. The local structure of this model system is dominated by four- and sixfold order. Coadsorption of shorter ligands in the particle's ligand layer and variation of salt concentration in the suspension prior to self-assembly result in a change of local orientational order. The degree of sixfold order is reduced after salt addition. This decrease of order is less pronounced for the fourfold symmetry. The results presented here suggest complex symmetry-selective order formation upon ligand exchange and salt addition and demonstrate the versatility of X-ray cross-correlation methods for nanoparticle superlattices.

Interplay between Short- and Long-Ranged Forces Leading to the Formation of Ag Nanoparticle Superlattice.

Nanoparticle (NP) superlattices have attracted increasing attention due to their unique physicochemical properties. However, key questions persist regarding the correlation between short- and long-range driving forces for nanoparticle assembly and resultant capability to predict the transient and final superlattice structure. Here the self-assembly of Ag NPs in aqueous solutions is investigated by employing in situ liquid cell transmission electron microscopy, combined with atomic force microscopy-based force measurements, and theoretical calculations. Despite the NPs exhibiting instantaneous Brownian motion, it is found that the dynamic behavior of NPs is correlated with the van der Waals force, sometimes unexpectedly over relatively large particle separations. After the NPs assemble into clusters, a delicate balance between the hydration and van der Waals forces results in a distinct distribution of particle separation, which is ascribed to layers of hydrated ions adsorbed on the NP surface. The study demonstrates pivotal roles of the complicated correlation between interparticle forces; potentially enabling the control of particle separation, which is critical for tailoring the properties of NP superlattices.

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...