Drying-mediated Self-assembly Research Articles

Plasmonic Superlattice Membranes Based on Bimetallic Nano-Sea Urchins as High-Performance Label-Free Surface-Enhanced Raman Spectroscopy Platforms.

On the basis of an abundance of elemental plasmonic nanocrystals identifiable by their unique morphology and intrinsic optoelectronic properties, it is necessary to rationally tailor the structural parameters to optimize the functionalities of nanoassemblies for application as plasmonic circuits/devices. Among them, the plasmonic superlattice membrane has emerged as a novel optically active metamaterial, which is constructed by nanocrystals at a two-dimensional (2D) plane with a highly ordered structure and strong plasmonic coupling interactions. Here, we report on the fabrication of a novel plasmonic superlattice membrane using bimetallic core-shell nano-sea urchins (Nano-SEUs) as meta-atoms. Under the guidance of soft-ligand balancing in conjugation with drying-mediated self-assembly at the air/water interface, well-defined giant 2D superlattices with total lateral dimensions of up to 5 mm wide and 80 nm thick have been synthesized, corresponding to an aspect ratio of 62 500. Programmable morphology control over the Nano-SEUs has been achieved in high yield by rationally tuning the spiky branches as well as the thickness of the silver shell, allowing systematic variation of the plasmonic properties of the membrane. Such superlattice membranes exhibited a strong and reproducible surface-enhanced Raman spectroscopy (SERS) signal that originates from interparticle coupling and electric (E)-field enhancement, enabling an enhancement factor of up to 106. We also demonstrated that the fabricated membrane allows the label-free SERS detection of dopamine from 0.1 nM to 1 μM. Thus, this giant Nano-SEU assembled superlattice membrane can be used as a SERS substrate for on-spot biomarker detection, which paves a robust and inexpensive avenue for highly sensitive and reliable biomedical sensing and diagnostics.

Hierarchical Fabrication of Plasmonic Superlattice Membrane by Aspect-Ratio Controllable Nanobricks for Label-Free Protein Detection.

Plasmonic superlattice membrane exhibits remarkable functional properties that are emerging from engineered assemblies of well-defined “meta-atoms,” which is featured as a conceptual new category of two-dimensional optical metamaterials. The ability to build plasmonic membranes over macroscopic surfaces but with nanoscale ordering is crucial for systematically controlling the light-matter interactions and represents considerable advances for the bottom-up fabrication of soft optoelectronic devices and circuits. Through rational design, novel nanocrystals, and by engineering the packing orders, the hybridized plasmon signature can be customized, promoting controllable near-field confinement for surface-enhanced Raman scattering (SERS) based detection. However, building such 2D architectures has proven to be remarkably challenging due to the complicated interparticle forces and multiscale interactions during self-assembly. Here, we report on the fabrication of ultralong-nanobrick-based giant plasmonic superlattice membranes as high-performance SERS substrates for ultrasensitive and label-free protein detection. Using aspect-ratio controllable short-to-ultralong nanobricks as building blocks, we construct three distinctive plasmonic membranes by polymer-ligand-based strategy in drying-mediated self-assembly at the air/water interfaces. The plasmonic membranes exhibit monolayered morphology with nanoscale assembled ordering but macroscopic lateral dimensions, inducing enhanced near-field confinement and uniform hot-spot distribution. By choosing 4-aminothiophenol and bovine serum albumin (BSA) as a model analyte, we establish an ultrasensitive assay for label-free SERS detection. The detection limit of BSA can reach 15 nM, and the enhancement factor reached 4.3 × 105, enabling a promising avenue for its clinical application in ultrasensitive biodiagnostics.

Drying-Mediated Self-Assembly of Graphene for Inkjet Printing of High-Rate Micro-supercapacitors

HighlightsBased on the drying-mediated self-assembly behavior of passivated graphene, a new kind of 2D micro-flake inks is developed to directly print high-resolution patterns with multiscale porous microstructure.The new ink allows to directly print complex 3D structures comprising multiple layers of heterogeneous materials.High-rate all-solid-state 3D micro-supercapacitors have been fully inkjet-printed with an areal capacitance surpassing 10 mF cm−2 at a high scan rate of 1 V s−1.

Lead Halide Perovskite Nanocrystals: From Discovery to Self-assembly and Applications.

Lead halide perovskites (LHPs) of the general formula APbX3 (A=Cs+, CH3NH3+, or CH(NH2)2+; X=Cl, Br, or I) have recently emerged as a unique class of low-cost, versatile semiconductors of high optoelectronic quality. These materials offer exceptionally facile solution-based engineerability in the form of bulk single crystals, thin films, or supported and unsupported nanostructures. The lattermost form, especially as colloidal nanocrystals (NCs), holds great promise as a versatile photonic source, operated via bright photoluminescence (PL) in displays or lighting (energy down-conversion of blue light into green and red), or via electroluminescence in light-emitting diodes. In this article we discuss the recent history of the development of highly-luminescent NCs of LHPs, the current state-of-the-art of this class of materials, and the future prospects of this highly active research field. We also report the demonstration of long-range ordered, self-organized superlattice structures obtained from cube-shaped colloidal CsPbBr3NCs using drying-mediated self-assembly.

Liquid Cell Electron Microscopy of Nanoparticle Self-Assembly Driven by Solvent Drying.

Drying a colloidal solution of nanoparticles is a versatile method to construct self-assembled structures of nanoparticles. However, mechanistic understanding has mostly relied on empirical knowledge obtained from the final structures of self-assembly as relevant processes during solvent drying are likely kinetic and far from equilibrium. Here, we present in situ TEM studies of nanoparticle self-assembly under various conditions, including the concentrations of the initial solution and the types of nanoparticles and substrates. The capability of tracking trajectories of individual nanoparticles enables us to understand the mechanisms of drying-mediated self-assembly at the single-nanoparticle level. Our results consistently show that a solvent boundary primarily affects nanoparticle motions and the resulting self-assembly processes regardless of different conditions. The solvent boundary drives nanoparticles to form two-dimensional assembly mainly through two pathways, transporting scattered nanoparticles by lateral dragging and flattening aggregated nanoparticles by vertical pressing.

Two-Dimensional Bipyramid Plasmonic Nanoparticle Liquid Crystalline Superstructure with Four Distinct Orientational Packing Orders.

Anisotropic plasmonic nanoparticles have been successfully used as constituent elements for growing ordered nanoparticle arrays. However, orientational control over their spatial ordering remains challenging. Here, we report on a self-assembled two-dimensional (2D) nanoparticle liquid crystalline superstructure (NLCS) from bipyramid gold nanoparticles (BNPs), which showed four distinct orientational packing orders, corresponding to horizontal alignment (H-NLCS), circular arrangement (C-NLCS), slanted alignment (S-NLCS), and vertical alignment (V-NLCS) of constituent particle building elements. These packing orders are characteristic of the unique shape of BNPs because all four packing modes were observed for particles with various sizes. Nevertheless, only H-NLCS and V-NLCS packing orders were observed for the free-standing ordered array nanosheets formed from a drying-mediated self-assembly at the air/water interface of a sessile droplet. This is due to strong surface tension and the absence of particle-substrate interaction. In addition, we found the collective plasmonic coupling properties mainly depend on the packing type, and characteristic coupling peak locations depend on particle sizes. Interestingly, surface-enhanced Raman scattering (SERS) enhancements were heavily dependent on the orientational packing ordering. In particular, V-NLCS showed the highest Raman enhancement factor, which was about 77-fold greater than the H-NLCS and about 19-fold greater than C-NLCS. The results presented here reveal the nature and significance of orientational ordering in controlling plasmonic coupling and SERS enhancements of ordered plasmonic nanoparticle arrays.

Free-Standing Bilayered Nanoparticle Superlattice Nanosheets with Asymmetric Ionic Transport Behaviors.

Natural cell membranes can directionally and selectively regulate the ion transport, which is critical for the functioning of living cells. Here, we report on the fabrication of an artificial membrane based on an asymmetric nanoparticle superlattice bilayered nanosheet, which exhibits similar ion transport characteristics. The superlattice nanosheets were fabricated via a drying-mediated self-assembly of polystyrene-capped gold nanoparticles at the liquid-air interface. By adopting a layer-by-layer assembly process, an asymmetric nanomembrane could be obtained consisting of two nanosheets with different nanoparticle size. The resulting nanomembranes exhibit an asymmetric ion transport behavior, and diode-like current-voltage curves were observed. The asymmetric ion transport is attributed to the cone-like nanochannels formed within the membranes, upon which a simulation map was established to illustrate the relationship between the channel structure and the ionic selectivity, in consistency with our experimental results. Our superlattice nanosheet-based design presents a promising strategy for the fabrication of next-generation smart nanomembranes for rationally and selectively regulating the ion transport even at a large ion flux, with potential applications in a wide range of fields, including biosensor devices, energy conversion, biophotonics, and bioelectronics.

Functional silicon nanostructures derived from drying-mediated self-assembly of gold nanoparticles

Self-assembly of nanoparticles is an efficient technique where nanobuilding blocks spontaneously organize into ordered structures by thermodynamic and other constraints. We demonstrate that multifunctional Silicon (Si) nanostructures with unique morphologies like sheets, plates and flakes can be etched chemically by taking an advantage of natural self-assembly of gold nanoparticles (AuNPs) characterized with drying kinetics under external stimuli. We further demonstrated antireflection properties of the as-synthesized Si nanostructures.

Simulation Modelling Study of Self-Assembled Nanoparticle Coatings for Retinal Implants

The electrode resolution of current retinal prostheses is still far from matching the densities of retinal neurons. Decreasing electrode diameter increases impedance levels thus deterring effective stimulation of neurons. One solution is to increase the surface roughness of electrodes, which can be done via nanoparticle coatings. This paper explores a Lattice Gas Model of the drying-mediated self-assembly of nanoparticle mixtures. The model includes representations for different types of nanoparticles, solvent, vapour, substrate and the energetic relationships between these elements. The dynamical aspect of the model is determined by energy minimization, stochastic fluctuations and physical constraints. The model attempts to unravel the relationships between different experimental conditions (e.g. evaporation rate, substrate characteristics and solvent viscosity) and the surface roughness of resulting assemblies. Some of the main results include the facts that the assemblies formed by nanoparticles of different sizes can boost roughness in specific circumstances and that the optimized assemblies can exhibit walled or stalagmite structures. This study provides a set of simulation modelling experiments that if confirmed in the laboratory may result in new and useful materials.

Lattice Gas Model for the Drying-Mediated Self-Assembly of Nanorods

A coarse-grained lattice gas model is developed to study drying-mediated self-assembly of nanorods. Out-of-equilibrium simulations of the model provide insight into the dynamics of solvent evaporation and the formation of ordered arrays of nanorods. Two different initial depositions of the nanorods on the substrate are studied: a random deposition and a prealigned deposition. We show that an initial random alignment of the nanorods in a thin liquid layer typical of drop casting experiments leads to local order only on time scales relevant for experiments. On the other hand, long-range order can be achieved when external forces are used to prealign the nanorods before evaporation. The effects of nanorod coverage, aspect ratio, spatial and orientational diffusion, and evaporation schemes are discussed.

Self-Assembly of Hierarchical Microstructures and Their Ring Patterns in Evaporating Droplets

Urchin-like and tree-shaped hierarchical microstructures were prepared within a solution droplet through drying-mediated self-assembly of organic molecules. The hierarchical architectures inside the droplet can orderly arrange into irregular ring patterns. The morphology evolvement of the hierarchical microstructures and the formation of the ring patterns were captured and studies with the assistance of optical microscopy. Their formation mechanisms were discussed on the basis of the results of time-dependent experiments. The amount of organic molecules in the solution had an obvious effect on the size and morphology of hierarchical microstructures and ring pattern formation. The optical properties of the hierarchical microstructures were investigated in detail and the formation of self-assembled structures resulted in significant changes in optical properties. The formation of the complex superstructures and generation of the ring patterns not only enriched synthesis science but also provided new blocks in future architectures of functional devices.

Device-Scale Perpendicular Alignment of Colloidal Nanorods

The self-assembly of nanocrystals enables new classes of materials whose properties are controlled by the periodicities of the assembly, as well as by the size, shape, and composition of the nanocrystals. While self-assembly of spherical nanoparticles has advanced significantly in the past decade, assembly of rod-shaped nanocrystals has seen limited progress due to the requirement of orientational order. Here, the parameters relevant to self-assembly are systematically quantified using a combination of diffraction and theoretical modeling; these highlight the importance of kinetics on orientational order. Through drying-mediated self-assembly, we achieve unprecedented control over orientational order (up to 96% vertically oriented rods on 1 cm(2) areas) on a wide range of substrates (ITO, PEDOT:PSS, Si(3)N(4)). This opens new avenues for nanocrystal-based devices competitive with thin film devices, as problems of granularity can be tackled through crystallographic orientational control over macroscopic areas.

Coarse-grained lattice models for drying-mediated self-assembly of nanoparticles

We present a coarse-grained lattice gas approach applicable for modelling the drying-mediated self-assembly of nanoparticles. The approach is exemplified for self-assembly of binary superlattices and for the hierarchical self-assembly of nanoparticles over patterned templates. The theory predicts many observed superstructures along with novel morphologies yet to be explored. The role of solvent evaporation, nanoparticle diffusion mechanisms, surface patterning, and the relevant time and length scales are discussed.

Synthesis of Copper Dendrite Nanostructures by a Sonoelectrochemical Method

Copper dendrites have been prepared by a sonoelectrochemical process from an aqueous solution of Cu(2+) in the presence of polyvinyl alcohol. A SEM image of the morpholohy of the copper formed on the electrode after one electric pulse is presented. A subsequent sonic pulse removes the copper from the electrode surface, cleaning it for the next step. The formation of the dendrites is accounted for by the "drying-mediated self-assembly of nanoparticles" theory.

Drying-Mediated Hierarchical Self-Assembly of Nanoparticles: A Dynamical Coarse-Grained Approach

A coarse-grained lattice gas model is developed to study the drying-mediated self-assembly of nanoparticles on diblock copolymer substrates. The model describes the nanoparticles, the solvent and the diblock copolymer on length scales that are typical to the solvent bulk correlation length. Monte Carlo simulation techniques are used to delineate the various mechanisms of this out-of-equilibrium hierarchical self-assembly. Several different assembly scenarios corresponding to different selectivity of the nanoparticles/liquid/substrate are discussed. The role of surface tension, evaporation rate, diffusion rate, nanoparticle coverage, and diblock copolymer periodicity is explored. Optimal conditions to form a stripe phase of nanoparticles along with predictions of novel 3D structures resulting from high nanoparticle and solvent selectivity are described.

Magnetic field-induced assembly of oriented superlattices from maghemite nanocubes.

Tailoring the structure of nanocrystal superlattices is an important step toward controlled design of novel nanostructured materials and devices. We demonstrate how the long-range order and macroscopic dimensions of magnetic nanoparticle arrays can be controlled by the use of a modulated magnetic field. Inducing a dipolar attraction during the initial stage of the drying-mediated self-assembly process was sufficient to assemble the superparamagnetic oleate-capped maghemite nanocubes into large and defect-free superstructures with both translational and orientational order. The characteristic dimensions of the superlattice are controlled by the particle concentration as well as the duration of the applied magnetic field. The superparamagnetic maghemite nanocubes assemble into large and highly oriented thin arrays by applying the magnetic field perpendicular to the substrate surface only during the initial phase of drying-mediated self-assembly. Micrometer-sized and thick three-dimensional mesocrystals are obtained when the drying dispersion is subjected to an external magnetic field of moderate strength for the entire duration of the assembly process. The discovery of how translational and orientation order of nanocrystal superlattices can be induced by a temporal modulation of an anisotropic interparticle force offers new insight on the importance of the initial nucleation stage in the self-assembly process and suggests new routes for controlled self-assembly of dipolar nanocrystals.

Out‐of‐Equilibrium Self‐Assembly of Binary Mixtures of Nanoparticles

A coarse-grained lattice-gas model is developed to study the drying-mediated self-assembly of binary mixtures of nanoparticles (NPs). Three model systems are considered, corresponding to equilibrium phase separation between two NPs (A and B), to an amorphous state, and to an ordered, checkerboard-like superstructure (see Figure; red: NPA; green: NPB; blue: solvent). The mechanism for self-ordering depends on the nature of the equilibrium superstructure and on the dynamic coupling to the evaporating solvent.

A distribution kinetics model of self-assembly: Effects of coalescence and solvent evaporation

Self-assembly from a metastable state often occurs by nucleation accompanied by nanoparticle growth and eventually by Ostwald coarsening. By developing a population balance model for growth and coarsening, we here determine the dynamics of self-assembled cluster size distributions (CSDs) in two or three dimensions. The governing equations are solved numerically and the asymptotic coarsening stage reveals a power-law increase in average particle mass as the CSD evolves to a (minimum) polydispersity index of unity for both 2-D and 3-D phase transitions. By incorporating solvent evaporation to simulate drying-mediated self-assembly of nanoparticles, the model yields a temporal power law relationship with exponent 1/4 for the average 2-D domain radius, in agreement with experimentally observed behavior. The power law relationships can also be obtained by varying the coalescence rate and the power on mass in rate coefficient expressions.

Self-Assembly of Nanoparticles in Three-Dimensions: Formation of Stalagmites

We develop a coarse-grained lattice gas model to describe drying-mediated self-assembly of nanoparticles in three dimensions. Our model is an extension of the model developed by Rabani et al. [Nature 2003, 426, 271] in two dimensions. We show that when liquid evaporation occurs layer by layer and solvation forces are strong, the resulting morphologies agree well with the predictions of the 2D model. We discuss scenarios in which the full 3D treatment is necessary and predict the formation of nanostalagmites.

Drying-mediated self-assembly of nanoparticles.

Systems far from equilibrium can exhibit complex transitory structures, even when equilibrium fluctuations are mundane. A dramatic example of this phenomenon has recently been demonstrated for thin-film solutions of passivated nanocrystals during the irreversible evaporation of the solvent. The relatively weak attractions between nanocrystals, which are efficiently screened in solution, become manifest as the solvent evaporates, initiating assembly of intricate, slowly evolving structures. Although certain aspects of this aggregation process can be explained using thermodynamic arguments alone, it is in principle a non-equilibrium process. A representation of this process as arising from the phase separation between a dense nanocrystal 'liquid' and dilute nanocrystal 'vapour' captures some of the behaviour observed in experiments, but neglects entirely the role of solvent fluctuations, which can be considerable on the nanometre length scale. Here we present a coarse-grained model of nanoparticle self-assembly that explicitly includes the dynamics of the evaporating solvent. Simulations using this model not only account for all observed spatial and temporal patterns, but also predict network structures that have yet to be explored. Two distinct mechanisms of ordering emerge, corresponding to the homogeneous and heterogeneous limits of evaporation dynamics. Our calculations show how different choices of solvent, nanoparticle size (and identity) and thermodynamic state give rise to the various morphologies of the final structures. The resulting guide for designing statistically patterned arrays of nanoparticles suggests the possibility of fabricating spontaneously organized nanoscale devices.