Designer Metasurfaces via Nanocube Assembly at the Air-Water Interface.

The advent of metasurfaces has revolutionized the design of optical instruments, and recent advancements in fabrication techniques are further accelerating their practical applications. However, conventional top-down fabrication of intricate nanostructures proves to be expensive and time-consuming, posing challenges for large-scale production. Here, we propose a cost-effective bottom-up approach to create nanostructure arrays with arbitrarily complex meta-atoms displaying single nanoparticle lateral resolution over submillimeter areas, minimizing the need for advanced and high-cost nanofabrication equipment. By utilizing air/water interface assembly, we transfer nanoparticles onto templated polydimethylsiloxane (PDMS) irrespective of nanopattern density, shape, or size. We demonstrate the robust assembly of nanocubes into meta-atoms with diverse configurations generally unachievable by conventional methods, including U, L, cross, S, T, gammadion, split-ring resonators, and Pancharatnam-Berry metasurfaces with designer optical functionalities. We also show nanocube epitaxy at near ambient temperature to transform the meta-atoms into complex continuous nanostructures that can be swiftly transferred from PDMS to various substrates via contact printing. Our approach potentially offers a large-scale manufacturing alternative to top-down fabrication for metal nanostructuring, unlocking possibilities in the realm of nanophotonics.

Electric-Field-Driven Localization of Molecular Nanowires in Wafer-Scale Nanogap Electrodes.

As integrated circuits continue to scale toward the atomic limit, bottom-up processes, such as epitaxial growth, have come to feature prominently in their fabrication. At the same time, chemistry has developed highly tunable molecular semiconductors that can perform the functions of ultimately scaled circuit components. Hybrid techniques that integrate programmable structures comprising molecular components into devices however are sorely lacking. Here we demonstrate a wafer-scale process that directs the localization of a conductive polymer, Mw = 20 kg mol-1 polyaniline, from dilute solutions into 50 nm vertical nanogap device architectures using electric-field-driven self-assembly. The resulting metal-polymer-metal junctions were characterized by electron microscopy, Raman spectroscopy and transport measurements demonstrating that our technique is highly selective, assembling conductive polymers only in electrically activated nanogaps. Our results represent a step toward scalable hybrid nanoelectronics that seamlessly integrate established lithographic top-down fabrication with bottom-up synthesized molecular functional circuit components.

Nanopipette dynamic microscopy unveils nano coffee ring.

Liquid-phase electron microscopy (LP-EM) imaging has revolutionized our understanding of nanosynthesis and assembly. However, the current closed geometry limits its application for open systems. The ubiquitous physical process of the coffee-ring phenomenon that underpins materials and engineering science remains elusive at the nanoscale due to the lack of experimental tools. We introduce a quartz nanopipette liquid cell with a tunable dimension that requires only standard microscopes. Depending on the imaging condition, the open geometry of the nanopipette allows the imaging of evaporation-induced pattern formation, but it can also function as an ordinary closed-geometry liquid cell where evaporation is negligible despite the nano opening. The nano coffee-ring phenomenon was observed by tracking individual nanoparticles in an evaporating nanodroplet created from a thin liquid film by interfacial instability. Nanoflows drive the assembly and disruption of a ring pattern with the absence of particle-particle correlations. With surface effects, nanoflows override thermal fluctuations at tens of nanometers, in which nanoparticles displayed a "drunken man trajectory" and performed work at a value much smaller than kBT.

All-Solution-Processed Electronics with Sub-Microscale Resolution and Nanoscale Fidelity Fabricated Via a Humidity-Controlled, Surface Energy-Directed Assembly Process.

Solution-based processes have received considerable attention in the fabrication of electronics and sensors owing to their merits of being low-cost, vacuum-free, and simple in equipment. However, the current solution-based processes either lack patterning capability or have low resolution (tens of micrometers) and low pattern fidelity in terms of line edge roughness (LER, several micrometers). Here, we present a surface energy-directed assembly (SEDA) process to fabricate metal oxide patterns with up to 2 orders of magnitude improvement in resolution (800 nm) and LER (16 nm). Experiment results show that high pattern fidelity can be achieved only at low relative humidities of below 30%. The reason for this phenomenon lies in negligible water condensation on the solution droplet. Employing the SEDA process, all-solution-processed metal oxide thin film transistors (TFTs) are fabricated by using indium oxide as channel layers, indium tin oxide as source/drain electrodes and gate electrodes, and aluminum oxide as gate dielectrics. TFT-based logic gate circuits, including NOT, NOR, NAND, and AND are fabricated as well, demonstrating the applicability of the SEDA process in fabricating large area functional electronics.

DNA-Directed Assembly of Hierarchical MOF-Cellulose Nanofiber Microbioreactors with "Branch-Fruit" Structures.

Assembling metal-organic frameworks (MOFs) into ordered multidimensional porous superstructures promises the encapsulation of enzymes for heterogeneous biocatalysts. However, the full potential of this approach has been limited by the poor stability of enzymes and the uncontrolled assembly of MOF nanoparticles onto suitable supports. In this study, a novel and exceptionally robust Ni-imidazole-based MOF was synthesized in water at room temperature, enabling in situ enzyme encapsulation. Based on this MOF platform, we developed a DNA-directed assembly strategy to achieve the uniform placement of MOF nanoparticles onto bacterial cellulose nanofibers, resulting in a distinctive "branch-fruit" structure. The resulting hybrid materials demonstrated remarkable versatility across various catalytic systems, accommodating natural enzymes, nanoenzymes, and multienzyme cascades, thus showcasing enormous potential as universal microbioreactors. Furthermore, the hierarchical composites facilitated rapid diffusion of the bulky substrate while maintaining the enzyme stability, with ∼3.5-fold higher relative activity compared to the traditional enzyme@MOF immobilized in bacterial cellulose nanofibers.

Magnetic field directed assembly of magnetic non-spherical microparticles.

This study reports on the fabrication and assembly of anisotropic microparticles as versatile building blocks for directed magnetic assemblies. Although spherical microparticles have received extensive attention, the assembly of non-spherical magnetic microparticles remains underexplored. Herein, we present a fabrication approach that utilizes photolithography and soft lithography to create prism-shaped magnetic microparticles. In order to investigate their assembly, a switching rotating magnetic field was employed. To support our experimental findings, a numerical model which takes into account the magnetic dipole moments induced by the field of other particles was developed. This model helps in understanding the forces and torques governing particle behavior during assembly. Simulations were conducted using the numerical model to complement our experimental findings. In the two particle experiments, attractive magnetic interactions led to various configurations depending on initial positions. For three particles, a tip-to-tip configuration suggested closed or stable ring-like structures. Our work highlights the feasibility of producing highly responsive, non-spherical magnetic microparticles and their potential for assemblies. The versatile fabrication method, coupled with the added degree of freedom conferred by prismatic shapes, opens promising avenues for applications in biology and material science.

Nanoparticle Assembly: From Self-Organization to Controlled Micropatterning for Enhanced Functionalities.

Nanoparticles form long-range micropatterns via self-assembly or directed self-assembly with superior mechanical, electrical, optical, magnetic, chemical, and other functional properties for broad applications, such as structural supports, thermal exchangers, optoelectronics, microelectronics, and robotics. The precisely defined particle assembly at the nanoscale with simultaneously scalable patterning at the microscale is indispensable for enabling functionality and improving the performance of devices. This article provides a comprehensive review of nanoparticle assembly formed primarily via the balance of forces at the nanoscale (e.g., van der Waals, colloidal, capillary, convection, and chemical forces) and nanoparticle-template interactions (e.g., physical confinement, chemical functionalization, additive layer-upon-layer). The review commences with a general overview of nanoparticle self-assembly, with the state-of-the-art literature review and motivation. It subsequently reviews the recent progress in nanoparticle assembly without the presence of surface templates. Manufacturing techniques for surface template fabrication and their influence on nanoparticle assembly efficiency and effectiveness are then explored. The primary focus is the spatial organization and orientational preference of nanoparticles on non-templated and pre-templated surfaces in a controlled manner. Moreover, the article discusses broad applications of micropatterned surfaces, encompassing various fields. Finally, the review concludes with a summary of manufacturing methods, their limitations, and future trends in nanoparticle assembly.

Controlling Colloidal Crystal Nucleation and Growth with Photolithographically Defined Templates.

Colloidal crystallization provides a means to synthesize hierarchical nanostructures by design and to use these complex structures for nanodevice fabrication. In particular, DNA provides a means to program interactions between particles with high specificity, thereby enabling the formation of particle superlattice crystallites with tailored unit cell geometries and surface faceting. However, while DNA provides precise control of particle-particle bonding interactions, it does not inherently present a means of controlling higher-level structural features such as the size, shape, position, or orientation of a colloidal crystallite. While altering assembly parameters such as temperature or concentration can enable limited control of crystallite size and geometry, integrating colloidal assemblies into nanodevices requires better tools to manipulate higher-order structuring and improved understanding of how these tools control the fundamental kinetics and mechanisms of colloidal crystal growth. In this work, photolithography is used to produce patterned substrates that can manipulate the placement, size, dispersity, and orientation of colloidal crystals. By adjusting aspects of the pattern, such as feature size and separation, we reveal a diffusion-limited mechanism governing crystal nucleation and growth. Leveraging this insight, patterns are designed that can produce wafer-scale substrates with arrays of nanoparticle superlattices of uniform size and shape. These design principles therefore bridge a gap between a fundamental understanding of nanoparticle assembly and the fabrication of nanostructures compatible with functional devices.

Fabrication of Flexible and Transparent Metal Mesh Electrodes Using Surface Energy-Directed Assembly Process for Touch Screen Panels and Heaters.

Transparent conductive electrodes (TCEs) are indispensable components of various optoelectronic devices such as displays, touch screen panels, solar cells, and smart windows. To date, the fabrication processes for metal mesh-based TCEs are either costly or having limited resolution and throughput. Here, a two-step surface energy-directed assembly (SEDA) process to efficiently fabricate high resolution silver meshes is introduced. The two-step SEDA process turns from assembly on a functionalized substrate with hydrophilic mesh patterns into assembly on a functionalized substrate with stripe patterns. During the SEDA process, a three-phase contact line pins on the hydrophilic pattern regions while recedes on the hydrophobic non-pattern regions, ensuring that the assembly process can be achieved with excellent selectivity. The necessity of using the two-step SEDA process rather than a one-step SEDA process is demonstrated by both experimental results and theoretical analysis. Utilizing the two-step SEDA process, silver meshes with a line width down to 2 µm are assembled on both rigid and flexible substrates. The thickness of the silver meshes can be tuned by varying the withdraw speed and the assembly times. The assembled silver meshes exhibit excellent optoelectronic properties (sheet resistance of 1.79 Ω/□, optical transmittance of ≈92%, and a FoM value of 2465) as well as excellent mechanical stability. The applications of the assembled silver meshes in touch screen panels and thermal heaters are demonstrated, implying the potential of using the two-step SEDA process for the fabrication of TCEs for optoelectronic applications.

Ion Diffusion-Directed Assembly of an Artificial Electronic-Ionic Conductor Layer with Zn-Ion Selective Channels for Highly Reversible Zinc Anodes.

Although aqueous zinc-ion batteries have attracted much attention due to their high safety, low cost, and relatively high energy density, their practical applications are severely limited by the uncontrollable dendrite growth and side reactions at the zinc anode. Herein, we design an electronic-ionic conductor artificial layer with Zn-ion selective channels on the Zn surface to regulate the Zn plating/stripping behavior through a one-step ion diffusion-directed assembly strategy using the commercially available conductive polymer poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS). Significantly, the functional PEDOT:PSS-Zn2+ (PPZ) layer with abundant selective Zn-ion channels works as both an electron regulator and an ion regulator that could not only simultaneously uniformize the electrical and Zn2+ concentration field on the Zn surface and accelerate the Zn2+ transport kinetics but also block the access of SO42- and H2O. With such a synergy effect, the PEDOT:PSS-Zn2+-modified Zn anode (2PPZ@Zn) achieves a long lifespan of 2400 h of the symmetrical cell at a current density of 3 mA cm-2 (1 mA h cm-2). Additionally, a long-term lifespan of 500 h is harvested even at a high current of 5 mA cm-2 with a high capacity of 3 mA h cm-2. Furthermore, combined with a manganese dioxide cathode, a full cell similarly provides a cycling stability of over 1500 cycles with 75% capacity retention at a high rate of 10 C (1 C = 308 mA h g-1).

Bubble Printing of Ti3C2TX MXene for Patterning Conductive and Plasmonic Nanostructures.

MXenes represent a novel class of 2D materials with unique properties and have great potential for diverse applications in sensing and electronics; however, their directed assembly at interfaces has not yet been achieved. Herein, the plasmonic heating of MXenes was exploited to achieve the controlled deposition of MXene assemblies via a laser-directed microbubble. The influence of various factors such as solvent composition, substrate surface chemistry, MXene concentration, and laser fluence was investigated, establishing the optimal conditions for rapid patterning with good fidelity. Printed MXene assemblies showed good electrical conductivity and plasmonic sensing capabilities and were able to meet or exceed the state of the art without additional postprocessing steps. This represents the first study of a directed approach for microfabrication using MXenes and lays the foundation for future work in optically directed assembly of MXenes and MXene-based nanocomposites at interfaces toward sensors and devices.

Electric and Magnetic Field-Driven Dynamic Structuring for Smart Functional Devices.

The field of soft matter is rapidly growing and pushing the limits of conventional materials science and engineering. Soft matter refers to materials that are easily deformed by thermal fluctuations and external forces, allowing for better adaptation and interaction with the environment. This has opened up opportunities for applications such as stretchable electronics, soft robotics, and microfluidics. In particular, soft matter plays a crucial role in microfluidics, where viscous forces at the microscale pose a challenge to controlling dynamic material behavior and operating functional devices. Field-driven active colloidal systems are a promising model system for building smart functional devices, where dispersed colloidal particles can be activated and controlled by external fields such as magnetic and electric fields. This review focuses on building smart functional devices from field-driven collective patterns, specifically the dynamic structuring of hierarchically ordered structures. These structures self-organize from colloidal building blocks and exhibit reconfigurable collective patterns that can implement smart functions such as shape shifting and self-healing. The review clarifies the basic mechanisms of field-driven particle dynamic behaviors and how particle-particle interactions determine the collective patterns of dynamic structures. Finally, the review concludes by highlighting representative application areas and future directions.

Probing the Mechanism of Targeted Delivery of Molecular Surfactants Loaded into Nanoparticles after Their Assembly at Oil-Water Interfaces.

A targeted and controlled delivery of molecular surfactants at oil-water interfaces using the directed assembly of nanoparticles, NPs, is reported. The mechanism of NP assembly at the interface and the release of molecular surfactants is followed by laser scanning confocal microscopy and surface force spectroscopy. The assembly of positively charged polystyrene NPs at the oil-water interface was facilitated by the introduction of carboxylic acid groups in the oil phase (e.g., by adding 1 wt % stearic acid to hexadecane to produce a model oil). The presence of positively charged NPs consistently lowers the stiffness of the water-oil interface. The effect is lessened, when the NPs are present in a solution of NaCl or deionized water at pH 2, consistent with a less dense monolayer of NPs at the interface in the last two systems. In addition, the NPs reduce the interfacial adhesion (i.e., the "stickiness" of the interface or, put differently, the pull-off force experienced by the atomic force microscopy (AFM) tip during retraction). After the assembly, the NPs can release a previously loaded cargo of surfactant molecules, which then facilitate the formation of a much finer oil-water emulsion. As a proof of concept, we demonstrate the release of octadecyl amine, ODA, that has been incorporated into the NPs prior to the assembly. The release of ODA causes the NPs to detach from the interface altering the interfacial properties and leads to finer oil droplets. This approach can be exploited in applications in several fields ranging from pharmaceutical and cosmetics to hydrocarbon recovery and oil-spill remediation, where a targeted and controlled release of surfactants is wanted.

On the in situ 3D electrostatic directed assembly of CdSe/CdZnS colloidal quantum nanoplatelets towards display applications.

HYPOTHESIS: Due to their unique quantum yield and photostability performances, quantum nanoplatelets are very promising building blocks for future generations of displays. The directed assembly of such colloidal nano-objects in the shape of micro-pixels is thus the next mandatory step to reach this goal. Selectively trapping them on electrostatically charged patterns by nanoxerography could be a versatile and appealing strategy but requires a full understanding of the assembly mechanisms in order to make the most of their integration. EXPERIMENTS: We propose an experimental platform based on a smart resealable microfluidic chip coupled to an inverted optical fluorescence microscope and a high-speed camera for in situ access of such assembly mechanisms, using CdSe/CdZnS quantum nanoplatelets as model nano-objects. The photoluminescence signal of the nanoplatelet patterns is thus recorded in real time during their assembly and data extracted after image processing. FINDINGS: The coupling of experimental results and numerical simulations evidences the main role of advection at the origin of this directed nanoparticle trapping. Deep understanding of the involved mechanisms and tuning of experimental parameters allow to make high resolution quantum nanoplatelet based micro-pixels with a fine control of their lateral and vertical dimensions.

Electrostatically directed assembly of two-dimensional ultrathin Co2Ni-MOF/Ti3C2Tx nanosheets for electrocatalytic oxygen evolution.

Hydrogen production from water electrolysis is severely restricted by the poor reaction kinetics of oxygen evolution reaction (OER). In this work, a series of two-dimensional (2D) composites MOF/Ti3C2Tx (the MXene phase) were fabricated by electrostatically directed assembly and used as catalysts for OER. The obtained composite materials exhibit enhanced electrocatalytic properties, thanks to the ultrathin 2D/2D heterostructure with abundant active sites in Co2Ni-MOF and the high electronic conductivity of Ti3C2Tx. Among all the catalysts, Co2Ni-MOF@MX-1 achieved the best oxygen evolution performance with the lowest Tafel slope (51.7 mV dec-1) and the lowest overpotential (265 mV on carbon paper) at the current density of 10 mA cm-2. These results demonstrated that the synthesis of 2D composite materials by electrostatically directed assembly could be a feasible and promising method for the preparation of 2D heterostructure catalysts.

Directed Assembly of Nanomaterials for Making Nanoscale Devices and Structures: Mechanisms and Applications.

Nanofabrication has been utilized to manufacture one-, two-, and three-dimensional functional nanostructures for applications such as electronics, sensors, and photonic devices. Although conventional silicon-based nanofabrication (top-down approach) has developed into a technique with extremely high precision and integration density, nanofabrication based on directed assembly (bottom-up approach) is attracting more interest recently owing to its low cost and the advantages of additive manufacturing. Directed assembly is a process that utilizes external fields to directly interact with nanoelements (nanoparticles, 2D nanomaterials, nanotubes, nanowires, etc.) and drive the nanoelements to site-selectively assemble in patterned areas on substrates to form functional structures. Directed assembly processes can be divided into four different categories depending on the external fields: electric field-directed assembly, fluidic flow-directed assembly, magnetic field-directed assembly, and optical field-directed assembly. In this review, we summarize recent progress utilizing these four processes and address how these directed assembly processes harness the external fields, the underlying mechanism of how the external fields interact with the nanoelements, and the advantages and drawbacks of utilizing each method. Finally, we discuss applications made using directed assembly and provide a perspective on the future developments and challenges.

Self-Assembly in water of C60 fullerene into isotropic nanoparticles or nanoplatelets mediated by a cationic amphiphilic polymer.

HYPOTHESIS: To disperse high concentration of C60 fullerene in water, we propose to use an emulsification-evaporation process in the presence of an amphiphilic polymer whose chemical structure has been chosen for inducing specific interaction with fullerene The viscosity enhancement provided by self-assembly of the amphiphilic polymers in water should result in high stability of the suspensions. The organic solvent has also to been chosen so as to maximize the initial fullerene concentration. EXPERIMENTS: The concentrations of polymer and fullerene, the solvent type and the volume fraction of the organic phase have been varied. Their influence on the concentration of the fullerene dispersions and on the size and shape of the resulting nanoparticles have been investigated by UV-Visible spectroscopy, light scattering and cryo-transmission electron microscopy experiments. FINDINGS: The resulting nanoparticles consist of aggregates of C60 fullerene stabilized by the cationic polymer with morphologies/sizes tunable through fullerene and polymer concentration. At high fullerene concentration, nanoplatelets are obtained that consist in thin 2D nanocrystals. Their suspensions are very stable with time due to the viscosity of the dispersing aqueous medium. The concentration of fullerene nanoparticles dispersed in water is as high as 8 g/L which corresponds to an upper limit that has never been reached so far.

Biomimetic and Biologically Compliant Soft Architectures via 3D and 4D Assembly Methods: A Perspective.

Recent progress in soft material chemistry and enabling methods of 3D and 4D fabrication-emerging programmable material designs and associated assembly methods for the construction of complex functional structures-is highlighted. The underlying advances in this science allow the creation of soft material architectures with properties and shapes that programmably vary with time. The ability to control composition from the molecular to the macroscale is highlighted-most notably through examples that focus on biomimetic and biologically compliant soft materials. Such advances, when coupled with the ability to program material structure and properties across multiple scales via microfabrication, 3D printing, or other assembly techniques, give rise to responsive (4D) architectures. The challenges and prospects for progress in this emerging field in terms of its capacities for integrating chemistry, form, and function are described in the context of exemplary soft material systems demonstrating important but heretofore difficult-to-realize biomimetic and biologically compliant behaviors.

Versatile, rapid and robust nano-positioning of single-photon emitters by AFM-nanoxerography.

Atomic force microscopy (AFM) nanoxerography was successfully used to direct the assembly of colloidal nanodiamonds (NDs) containing nitrogen-vacancy (NV) centres on electrostatically patterned surfaces. This study reveals that the number of deposited NDs can be controlled by tuning the surface potentials of positively charged dots on a negatively charged background written by AFM in a thin PMMA electret film, yielding assemblies down to a unique single-photon emitter with very good selectivity. The mechanisms of the ND directed assembly are attested by numerical simulations. This robust deterministic nano-positioning of quantum emitters thus offers great opportunities for ultimate applications in nanophotonics for quantum technologies.

A Single Crystal 2D Hexagonal Array in a Centimeter Scale with a Self-Directed Assembly of Diblock Copolymer Spheres.

The creation of a single-grain two-dimensional (2D) nanoarray over a large area (∼1 cm2) has been only realized with expensive lithographic fabrication involving a complicated multichemical process. In this work, we report the production of a highly aligned single-grain 2D crystalline nanoarray over a centimeter-scale large area with a concept of self-directed assembly (SDA) in block copolymer (BCP) thin films. No lithographic guiding pattern is employed in SDA. A sphere-forming BCP is first transformed to transient-cylinders and aligned with shear. The aligned cylinders act as a guiding pattern to restore the sphere-morphology producing a single-grain 2D crystalline array with the following solvent vapor annealing. The SDA process has two governing parameters: orientational order of guiding patterns in the first step and the lattice matching between the transient guiding cylinders and the restored spheres. The successful application of SDA yields a single-grain of 2D crystalline hexagonal nanoarray with an exceptional long-range order, which is confirmed by employing image treating algorithms and grazing incidence small-angle X-ray scattering (GISAXS) measurements. The suggested SDA strategy is found to be effective for large-scale nanopatterning with no lithographic tools.