Colloidal Building Research Articles

A Dirty Story: Improving Colloidal Monolayer Formation by Understanding the Effect of Impurities at the Air/Water Interface.

Colloidal monolayers are important tools to fabricate surface structures at the nanoscale. A typical monolayer fabrication strategy involves the self-assembly of colloidal building blocks at liquid interfaces, which are subsequently deposited on a solid substrate. Even though this process is well established, the resulting order of the particles within the colloidal monolayer differs between batches of colloidal particles and can even change with the age of the dispersion. In this study, we investigate the origins of this variation of monolayer quality for polystyrene particles synthesized by surfactant-free emulsion polymerization. We correlate the interfacial behavior of the colloidal particles at the air/water interface on a Langmuir trough with the resulting quality of the monolayer after transfer to a solid substrate. We identify surface-active impurities as a major cause for a disturbed self-assembly of the colloidal particles. These impurities form during the particle synthesis and consist of copolymers of styrene, the comonomer acrylic acid, and sulfonate species from the initiator. We show that they can be removed by cleaning protocols to increase the monolayer quality. However, our experiments demonstrate that the impurities reappear over time even for cleaned dispersions, indicating desorption from the surface of the colloidal particles. We identify strategies to avoid the presence of the impurities at the air/water interface or to inhibit their effect on the self-assembly process. These simple guidelines improve the quality of the resulting colloidal monolayer, which is a prerequisite for the reliable fabrication of high-quality surface nanostructures from colloidal templates.

Sustainable Barrier System via Self-Assembly of Colloidal Montmorillonite and Cross-linking Resins on Nanocellulose Interfaces.

Cellulose nanofibrils (CNFs) are able to form strong oxygen-barrier films suitable for food packaging but lack the needed water resistance in comparison to plastics. Desired water barrier quality can be achieved by applying mineral additives within the nanofibrils network. In current contribution, a sustainable hybrid system with an improved water barrier function is proposed by incorporating colloidal montmorillonite nanoclay (MMT) and two cross-linking agents, namely, polyamidoamine epichlorohydrin (PAE) and Acrodur thermoset acrylic resin (ACR) into CNF interfaces. Continuous matrices were produced via evaporation-induced self-assembly of colloidal building blocks followed by appropriate heat-curing regime to impart internal cross-linking. The development of chromophore functionalities and formation of ester motifs on the hybrid matrix (with no evidence of degradation) were detected by Fourier-transform infrared (FT-IR) spectroscopy. Intercalation of clay, solely, reduced the water vapor transmission rate (WVTR) to some extent; however, a more remarkable decline (by 60%) was observed upon the curing and cross-linking process. In fact, combination of clay platelets and cross-linkers contributed to a denser film structure and restricted water passage. Also, an excellent resistance to oil and grease was observed in all the studied films (Kit number of 11). A reduction in tensile strengths and resistance to cracking at fold was noted and ascribed to MMT interference in cellulose interchain hydrogen bonds. This however was counteracted by the introduction of cross-linkers, apparently by aiding stress transfer within the matrix. MMT imparted a limited elevation in the surface free energy, pointing out to an induced hydrophilicity; however, surface energy values declined markedly upon using cross-linkers. Finally, thermal stability of hybrids was adversely affected, compared to neat CNFs. Our study suggests the potential utilization of low-cost, sustainable biobarrier films for application in food/drug packaging, where low permeation of moisture is highly desirable.

Self-faceting of emulsion droplets as a route to solid icosahedra and other polyhedra

HypothesisTemperature-controlled self-faceting of liquid droplets has been recently discovered in surfactant-stabilized alkane-in-water emulsions. We hypothesize that similar self-faceting may occur in emulsion droplets of UV-polymerizable linear hydrocarbons. We further hypothesize that the faceted droplet shapes can be fixed by UV-initiated polymerization, thus providing a new route towards the production of solid polyhedra. ExperimentsTemperature-induced shape variations were studied by optical microscopy in micron-size emulsion droplets of UV-polymerizable alkyl acrylate. When polymerized, the resultant solid particles’ 3D shape and internal structure were determined by combined scanning electron microscopy (SEM) and focused ion beam (FIB) slicing. The SEM and FIB nanoscale resolution provided a far greater detail imaging than that achievable for the liquid droplets, which could only be studied by optical microscopy, severely limiting their 3D shape determination. FindingsWe demonstrate the formation of solid icosahedra, polyhedral platelets, and rods of hitherto-unreported sizes, well below the 3D-printing resolution (∼20μm). The presence of icosahedral shapes and the absence of any resolvable internal structure at sub-μm length scales, are in line with the surface-freezing-driven mechanism proposed for the faceting phenomenon. Further development of the method presented here may allow large-quantity production of shaped micron- to nano- sized colloidal building blocks for 3D metamaterials and other applications.

Electrostatic Stabilization of Carbon Nitride Colloids in Organic Solvents Enables Stable Dispersions and Transparent Homogeneous CN Films for Optoelectronics.

Covalent modification of phenyl-modified carbon nitride with vinylthiazole groups via visible light induced grafting is reported. Modified structures express negative charge migration to the thiazole edges while the carbon nitride sheet remains positively charged in organic solutions. Such a phenomenon provides electrostatic stabilization of modified carbon nitride particles in organic media leading to highly organodispersible and colloidally stable carbon nitrides. The resulting structures can be homogeneously dispersed in organic solvents and can be cast to transparent films. The usefulness of such a processable colloidal carbon nitride building block is exemplified here by its high luminescence and inkjet printing of films.

Pyrochlore lattice, self-assembly and photonic band gap optimizations.

Non-spherical colloidal building blocks introduce new design principles for self-assembly, making it possible to realize optical structures that could not be assembled previously. With this added complexity, the phase space expands enormously so that computer simulation becomes a valuable tool to design and assemble structures with useful optical properties. We recently demonstrated that tetrahedral clusters and spheres, interacting through a DNA-mediated short-range attractive interaction, self-assemble into a superlattice of interpenetrating diamond and pyrochlore sublattices, but only if the clusters consist of partially overlapping spheres. Here we show how the domain of crystallization can be extended by implementing a longer range potential and consider how the resultant structures affect the photonic band gaps of the underlying pyrochlore sublattice. We show that with the proper design, using clusters of overlapping spheres lead to larger photonic band gaps that open up at lower optical contrast.

Colloidal Self‐Assembly Concepts for Plasmonic Metasurfaces

AbstractMetallic nanostructures exhibit strong interactions with electromagnetic radiation, known as the localized surface plasmon resonance. In recent years, there is significant interest and growth in the area of coupled metallic nanostructures. In such assemblies, short‐ and long‐range coupling effects can be tailored and emergent properties, e.g., metamaterial effects, can be realized. The term “plasmonic metasurfaces” is used for this novel class of assemblies deposited on planar surfaces. Herein, the focus is on plasmonic metasurfaces formed from colloidal particles. These are formed by self‐assembly and can meet the demands of low‐cost manufacturing of large‐area, flexible, and ultrathin devices. The advances in high optical quality of the colloidal building blocks and methods for controlling their self‐assembly on surfaces will lead to novel functional devices for dynamic light modulators, pulse sharpening, subwavelength imaging, sensing, and quantum devices. This progress report focuses on predicting optical properties of single colloidal building blocks and their assemblies, wet‐chemical synthesis, and directed self‐assembly of colloidal particles. The report concludes with a discussion of the perspectives toward expanding the colloidal plasmonic metasurfaces concept by integrating them with quantum emitters (gain materials) or mechanically responsive structures.

Direct-Write Freeform Colloidal Assembly.

Colloidal assembly is an attractive means to control material properties via hierarchy of particle composition, size, ordering, and macroscopic form. However, despite well-established methods for assembling colloidal crystals as films and patterns on substrates, and within microscale confinements such as droplets or microwells, it has not been possible to build freeform colloidal crystal structures. Direct-write colloidal assembly, a process combining the bottom-up principle of colloidal self-assembly with the versatility of direct-write 3D printing, is introduced in the present study. By this method, centimeter-scale, free-standing colloidal structures are built from a variety of materials. A scaling law that governs the rate of assembly is derived; macroscale structural color is tailored via the size and crystalline ordering of polystyrene particles, and several freestanding structures are built from silica and gold particles. Owing to the diversity of colloidal building blocks and the means to control their interactions, direct-write colloidal assembly could therefore enable novel composites, photonics, electronics, and other materials and devices.

A Brownian quasi-crystal of pre-assembled colloidal Penrose tiles

Penrose's pentagonal P2 quasi-crystal1-4 is a beautiful, hierarchically organized multiscale structure in which kite- and dart-shaped tiles are arranged into local motifs, such as pentagonal stars, which are in turn arranged into various close-packed superstructural patterns that become increasingly complex at larger length scales. Although certain types of quasi-periodic structure have been observed in hard and soft matter, such structures are difficult to engineer, especially over large areas, because generating the necessary, highly specific interactions between constituent building blocks is challenging. Previously reported soft-matter quasi-crystals of dendrimers5, triblock copolymers6, nanoparticles7 and polymeric micelles8 have been limited to 12- or 18-fold symmetries. Because routes for self-assembling complex colloidal building blocks9-11 into low-defect dynamic superstructures remain limited12, alternative methods, such as using optical and directed assembly, are being explored13,14. Holographic laser tweezers15 and optical standing waves16 have been used to hold microspheres in local quasi-crystalline arrangements, and magnetic microspheres of two different sizes have been assembled into local five-fold-symmetric quasi-crystalline arrangements in two dimensions17. But a Penrose quasi-crystal of mobile colloidal tiles has hitherto not been fabricated over large areas. Here we report such a quasi-crystal in two dimensions, created using a highly parallelizable method of lithographic printing and subsequent release of pre-assembled kite- and dart-shaped tiles into a solution-dispersion containing a depletion agent. After release, the positions and orientations of the tiles within the quasi-crystal can fluctuate, and these tiles undergo random, Brownian motion in the monolayer owing to frequent collisions between neighbouring tiles, even after the system reaches equilibrium. Using optical microscopy, we study both the equilibrium fluctuations of the system at high tile densities and alsothe 'melting' of the pattern as the tile density is lowered. At high tile densities we find signatures of a five-fold pentatic liquid quasi-crystalline phase, analogous to a six-fold hexatic liquid crystal. Our fabrication approach is applicable to tiles of different sizes and shapes, and with different initial positions and orientations, enabling the creation of two-dimensional quasi-crystalline systems (and other systems that possess multiscale complexity at high tile densities) beyond those of current self- or directed-assembly methods18-20. We anticipate that our approach for generating lithographically pre-assembled monolayers could be extended to create three-dimensional Brownian systems of fluctuating particles with custom-designed shapes through holographic lithography21,22 or stereolithography23.

Colloidal Assembly Approaches to Micro/Nanostructures of Complex Morphologies

The ability to programmatically assemble colloidal micro/nanostructures into highly ordered superstructures is of great importance in both fundamental studies and practical applications. In addition to the sophisticated manipulation of the short-range and long-range interactions imposed on the colloidal building blocks, the intrinsic shape elements including face, edge, corner, concave, convex, and curvature also play very important roles in solving the "jigsaw puzzle" of the superstructures. Here, the recent progress in the development of colloidal assembly strategies for the formation of complex superstructures is reviewed, with a primary focus on the unique effects of the morphology of the building blocks to the assembly processes and the final structures. Overall, this Review aims to shed light on the fundamental understanding of the colloidal behaviors of complex micro/nanostructures and promote the continued development of effective strategies for the creation of functional materials with complex compositions and morphologies.

Supraparticles: Functionality from Uniform Structural Motifs.

Under the right process conditions, nanoparticles can cluster together to form defined, dispersed structures, which can be termed supraparticles. Controlling the size, shape, and morphology of such entities is a central step in various fields of science and technology, ranging from colloid chemistry and soft matter physics to powder technology and pharmaceutical and food sciences. These diverse scientific communities have been investigating formation processes and structure/property relations of such supraparticles under completely different boundary conditions. On the fundamental side, the field is driven by the desire to gain maximum control of the assembly structures using very defined and tailored colloidal building blocks, whereas more applied disciplines focus on optimizing the functional properties from rather ill-defined starting materials. With this review article, we aim to provide a connecting perspective by outlining fundamental principles that govern the formation and functionality of supraparticles. We discuss the formation of supraparticles as a result of colloidal properties interplaying with external process parameters. We then outline how the structure of the supraparticles gives rise to diverse functional properties. They can be a result of the structure itself (emergent properties), of the colocalization of different, functional building blocks, or of coupling between individual particles in close proximity. Taken together, we aim to establish structure-property and process-structure relationships that provide unifying guidelines for the rational design of functional supraparticles with optimized properties. Finally, we aspire to connect the different disciplines by providing a categorized overview of the existing, diverging nomenclature of seemingly similar supraparticle structures.

Emulsions Stabilized by Chitosan-Modified Silica Nanoparticles: pH Control of Structure-Property Relations.

In food-grade emulsions, particles with an appropriate surface modification can be used to replace surfactants and potentially enhance the stability of emulsions. During the life cycle of products based on such emulsions, they can be exposed to a broad range of pH conditions and hence it is crucial to understand how pH changes affect stability of emulsions stabilized by particles. Here, we report on a comprehensive study of the stability, microstructure, and macroscopic behavior of pH-controlled oil-in-water emulsions containing silica nanoparticles modified with chitosan, a food-grade polycation. We found that the modified colloidal particles used as stabilizers behave differently depending on the pH, resulting in unique emulsion structures at multiple length scales. Our findings are rationalized in terms of the different emulsion stabilization mechanisms involved, which are determined by the pH-dependent charges and interactions between the colloidal building blocks of the system. At pH 4, the silica particles are partially hydrophobized through chitosan modification, favoring their adsorption at the oil-water interface and the formation of Pickering emulsions. At pH 5.5, the particles become attractive and the emulsion is stabilized by a network of agglomerated particles formed between the droplets. Finally, chitosan aggregates form at pH 9 and these act as the emulsion stabilizers under alkaline conditions. These insights have important implications for the processing and use of particle-stabilized emulsions. On one hand, changes in pH can lead to undesired macroscopic phase separation or coalescence of oil droplets. On the other hand, the pH effect on emulsion behavior can be harnessed in industrial processing, either to tune their flow response by altering the pH between processing stages or to produce pH-responsive emulsions that enhance the functionality of the emulsified end products.

Influence of Geometries on the Assembly of Snowman-Shaped Janus Nanoparticles

The self-assembly of micro/nanoparticles into suprastructures is a promising way to develop reconfigurable materials and to gain insights into the fundamental question of how matter organizes itself. The geometry of particles, especially those deviating from perfectly spherical shapes, is of significant importance in colloidal assembly because it influences the particle "recognition", determines the particle packing, and ultimately dictates the formation of assembled suprastructures. In order to organize particles into desired structures, it is of vital importance to understand the relationship between the shape of the colloidal building blocks and the assembled suprastructures. This fundamental issue is an enduring topic in the assembly of molecular surfactants, but it remained elusive in colloidal assembly. To address this issue, we use snowman-shaped Janus nanoparticles (JNPs) as a model to systematically study the effect of colloidal geometries on their assembled suprastructures. Ten types of JNPs with identical chemical compositions but with different geometries were synthesized. Specifically, the synthesized JNPs differ in their lobe size ratios, phase separation degrees, and overall sizes. We show that by altering these parameters, both finite suprastructures, such as capsules with different curvatures, and nonfinite suprastructures, including free-standing single-layered or double-layered JNPs sheets, can be obtained via self-assembly. All these different types of suprastructures are constituted by highly oriented and hexagonally packed JNPs. These findings demonstrate the significance of geometries in colloidal assembly, such that slightly changing the building block geometries could result in a large variety of very different assembled structures, without altering the chemistry of the particles.

Shape‐Tunable Colloids from Structured Liquid Droplet Templates

AbstractShaping colloidal building units is of paramount importance for their self‐assembly into complex objects. Continuous tuning of colloidal shapes is highly desired for understanding self‐assembly, but it still remains a challenge. Herein, we report a new template strategy for the shape‐tunable synthesis of anisotropic colloids with shapes that can be continuously tuned from discs (oblate spheroids) to spheres to theta shapes to dumbbells. This was realized by creating structured shape‐tunable droplets from patchy colloidal discs and using these droplets as templates. In particular, we found that a controlled dumbbell‐to‐eyeball droplet transformation can be used for the synthesis of eyeball‐shaped colloids. We also demonstrated the droplet transformation pathways and applied the method to the synthesis of colloidal molecules. These colloids provide possibilities for exploring their ordered packing structures, and the method based on the use of structured droplets can be adapted for the synthesis of other functional colloidal particles.

Shape-Tunable Colloids from Structured Liquid Droplet Templates.

Shaping colloidal building units is of paramount importance for their self-assembly into complex objects. Continuous tuning of colloidal shapes is highly desired for understanding self-assembly, but it still remains a challenge. Herein, we report a new template strategy for the shape-tunable synthesis of anisotropic colloids with shapes that can be continuously tuned from discs (oblate spheroids) to spheres to theta shapes to dumbbells. This was realized by creating structured shape-tunable droplets from patchy colloidal discs and using these droplets as templates. In particular, we found that a controlled dumbbell-to-eyeball droplet transformation can be used for the synthesis of eyeball-shaped colloids. We also demonstrated the droplet transformation pathways and applied the method to the synthesis of colloidal molecules. These colloids provide possibilities for exploring their ordered packing structures, and the method based on the use of structured droplets can be adapted for the synthesis of other functional colloidal particles.

Cysteamine-modified ZIF-8 colloidal building blocks: Direct assembly of nanoparticulate MOF films on gold surfaces via thiol chemistry

Chemical modification of metal organic framework (MOF) nanocrystal colloids was used to endow them with chemical affinity for gold substrates. Modified nanocrystals were then used as building blocks for rapid and selective self-assembly of porous films. Cysteamine (Cys, 2-aminoetanethiol) was chosen as both chemical modulator and functionalizing agent of Zeolite Imidazolate Framework-8 (ZIF-8) MOF nanocrystals. Important parameters such as the impact of the modulator on the range of nanocrystals stability, size, polydispersity, morphology, and crystalline structure were assessed via both, small and wide angle x-ray scattering (SAXS and WAXS). Cysteamine modified ZIF-8 nanocrystals were assembled into films over conductive Au substrates and film growth was followed in-situ with Quartz Crystal Microbalance (QCM). Thiol moieties exposed out of the ZIF-8 surface after cysteamine modification, results in the formation of thiol bonds with Au conductive substrates as shown via Cyclic Voltammetry experiments. The strategy here presented allows for the synthesis of pre-designed building blocks for MOF films on metal surfaces.

Programming Hierarchical Self-Assembly of Patchy Particles into Colloidal Crystals via Colloidal Molecules.

Colloidal self-assembly is a promising bottom-up route to a wide variety of three-dimensional structures, from clusters to crystals. Programming hierarchical self-assembly of colloidal building blocks, which can give rise to structures ordered at multiple levels to rival biological complexity, poses a multiscale design problem. Here we explore a generic design principle that exploits a hierarchy of interaction strengths and employ this design principle in computer simulations to demonstrate the hierarchical self-assembly of triblock patchy colloidal particles into two distinct colloidal crystals. We obtain cubic diamond and body-centered cubic crystals via distinct clusters of uniform size and shape, namely, tetrahedra and octahedra, respectively. Such a conceptual design framework has the potential to reliably encode hierarchical self-assembly of colloidal particles into a high level of sophistication. Moreover, the design framework underpins a bottom-up route to cubic diamond colloidal crystals, which have remained elusive despite being much sought after for their attractive photonic applications.

Anisotropic Self-Assembly from Isotropic Colloidal Building Blocks.

Spherical colloidal particles generally self-assemble into hexagonal lattices in two dimensions. However, more complex, non-hexagonal phases have been predicted theoretically for isotropic particles with a soft repulsive shoulder but have not been experimentally realized. We study the phase behavior of microspheres in the presence of poly(N-isopropylacrylamide) (PNiPAm) microgels at the air/water interface. We observe a complex phase diagram, including phases with chain and square arrangements, which exclusively form in the presence of the microgels. Our experimental data suggests that the microgels form a corona around the microspheres and induce a soft repulsive shoulder that governs the self-assembly in this system. The observed structures are fully reproduced by both minimum energy calculations and finite temperature Monte Carlo simulations of hard core-soft shoulder particles with experimentally realistic interaction parameters. Our results demonstrate how complex, anisotropic assembly patterns can be realized from entirely isotropic building blocks by control of the interaction potential.

Hydrogen Bonding Directed Colloidal Self‐Assembly of Nanoparticles into 2D Crystals, Capsids, and Supracolloidal Assemblies

AbstractSelf‐assembly of colloidal building blocks, like metal nanoparticles, is a rapidly progressing research area toward new functional materials. However, in‐depth control of the colloidal self‐assembly and especially hierarchical self‐assembly is difficult due to challenges in controlling the size dispersities, shape/morphology, directionalities, and aggregation tendencies. Using either polydispersed or narrow‐size dispersed nanoparticles, considerable progress has been achieved over the past few years. However, absolutely monodisperse nanoparticles could allow new options for rational designs of self‐assemblies. Therein, atomically precise monolayer protected nanoclusters (d < 3 nm) have recently been synthesized with well‐defined metal cores and surface ligands. Their dispersion behavior is commonly tuned by surfactant‐like ligands. Beyond that, this study deals with approaches based on ligand‐driven supramolecular interactions and colloidal monodispersity until atomic precision to tune the colloidal self‐assembly and hierarchy from nanoscale to mesoscopic scale. Therein colloidal packing to self‐assembled 2D crystals and closed virus capsid‐inspired shells provide relevant research goals due to ever increasing potential of 2D materials and encapsulation. This study addresses the hydrogen bonding (H‐bonding) directed self‐assembly of atomically precise gold and silver nanoparticles and narrow size dispersed cobalt nanoparticles to free‐standing 2D colloidal nanosheets, nanowire assemblies, capsid‐like colloidal closed shells, as well as higher order structures.

An Active Approach to Colloidal Self-Assembly.

In this review, we discuss recent advances in the self-assembly of self-propelled colloidal particles and highlight some of the most exciting results in this field, with a specific focus on dry active matter. We explore this phenomenology through the lens of the complexity of the colloidal building blocks. We begin by considering the behavior of isotropic spherical particles. We then discuss the case of amphiphilic and dipolar Janus particles. Finally, we show how the geometry of the colloids and/or the directionality of their interactions can be used to control the physical properties of the assembled active aggregates, and we suggest possible strategies for how to exploit activity as a tunable driving force for self-assembly. The unique properties of active colloids lend promise to the design of the next generation of functional, environment-sensing microstructures able to perform specific tasks in an autonomous and targeted manner.

Colloidal Rings by Site-Selective Growth on Patchy Colloidal Disc Templates.

Anisotropic colloidal building blocks are quite attractive as they enable the self-assembly towards new materials with designated hierarchical structures. Although many advances have been achieved in colloidal synthetic methodology, synthesis of colloidal rings with low polydispersity and on a large scale remains a challenge. To address this issue we introduce a new site-selective growth strategy, which relies on using patchy particles. For example, by using patchy discs as templates, silica can selectively be grown on only side surfaces, resulting in formation of silica rings. We demonstrate that shape parameters are tunable and find that these silica rings can be used as secondary template to synthesize other types of rings. This method for synthesizing ring-like colloids provides possibilities for studying their self-assembly and associated phase transitions, and this patchy particles template strategy paves a new route for fabricating other new colloidal particles.