Photopatterning of Cross‐Linkable Epoxide‐Functionalized Block Copolymers and Dual‐Tone Nanostructure Development for Fabrication Across the Nano‐ and Microscales

The self‐assembly of block copolymers in thin films provides an attractive approach to patterning 5–100 nm structures. Cross‐linking and photopatterning of the self‐assembled block copolymer morphologies provide further opportunities to structure such materials for lithographic applications, and to also enhance the thermal, chemical, or mechanical stability of such nanostructures to achieve robust templates for subsequent fabrication processes. Here, model lamellar‐forming diblock copolymers of polystyrene and poly(methyl methacrylate) with an epoxide functionality are synthesized by atom transfer radical polymerization. We demonstrate that self‐assembly and cross‐linking of the reactive block copolymer materials in thin films can be decoupled into distinct, controlled process steps using solvent annealing and thermal treatment/ultraviolet exposure, respectively. Conventional optical lithography approaches can also be applied to the cross‐linkable block copolymer materials in thin films and enable simultaneous structure formation across scales—micrometer scale patterns achieved by photolithography and nanostructures via self‐assembly of the block copolymer. Such materials and processes are thus shown to be capable of self‐assembling distinct block copolymers (e.g., lamellae of significantly different periodicity) in adjacent regions of a continuous thin film.     

Combining Bottom‐Up Self‐Assembly with Top‐Down Microfabrication to Create Hierarchical Inverse Opals with High Structural Order

Colloidal particles can assemble into ordered crystals, creating periodically structured materials at the nanoscale without relying on expensive equipment. The combination of small size and high order leads to strong interaction with visible light, which induces macroscopic, iridescent structural coloration. To increase the complexity and functionality, it is important to control the organization of such materials in hierarchical structures with high degrees of order spanning multiple length scales. Here, a bottom‐up assembly of polystyrene particles in the presence of a silica sol–gel precursor material (tetraethylorthosilicate, TEOS), which creates crack‐free inverse opal films with high positional order and uniform crystal alignment along the (110) crystal plane, is combined with top‐down microfabrication techniques. Micrometer scale hierarchical superstructures having a highly regular internal nanostructure with precisely controlled crystal orientation and wall profiles are produced. The ability to combine structural order at the nano‐ and microscale enables the fabrication of materials with complex optical properties resulting from light–matter interactions at different length scales. As an example, a hierarchical diffraction grating, which combines Bragg reflection arising from the nanoscale periodicity of the inverse opal crystal with grating diffraction resulting from a micrometer scale periodicity, is demonstrated.     

Electron‐Tomography Determination of the Packing Structure of Macroporous Ordered Siliceous Foams Assembled From Vesicles

The packing structures of macroporous ordered siliceous foams (MOSFs) are systematically investigated by using a 3D electron tomography technique and the nanostructural characteristics for layered MOSFs are resolved. MOSF materials adopt an ordered 2D hexagonal arrangement in single‐layered areas, regular honeycomb patterns in double‐layered samples, and polyhedric cells similar to a Weaire–Phelan structure in multilayered areas, all following the principle of minimizing surface area, which is well understood in soap foams at the macroscopic scale. In surfactant‐templated materials, liquid‐crystal templating is generally applied, but here it is revealed that the surface‐area‐minimization principle can also be applied, which facilitates the design and synthesis of novel macroporous materials using surfactant molecules as templates.     

Colloidal Self‐Assembly Meets Nanofabrication: From Two‐Dimensional Colloidal Crystals to Nanostructure Arrays

Self‐assembly of colloidal microspheres or nanospheres is an effective strategy for fabrication of ordered nanostructures. By combination of colloidal self‐assembly with nanofabrication techniques, two‐dimensional (2D) colloidal crystals have been employed as masks or templates for evaporation, deposition, etching, and imprinting, etc. These methods are defined as “colloidal lithography”, which is now recognized as a facile, inexpensive, and repeatable nanofabrication technique. This paper presents an overview of 2D colloidal crystals and nanostructure arrays fabricated by colloidal lithography. First, different methods for fabricating self‐assembled 2D colloidal crystals and complex 2D colloidal crystal structures are summarized. After that, according to the nanofabrication strategy employed in colloidal lithography, related works are reviewed as colloidal‐crystal‐assisted evaporation, deposition, etching, imprinting, and dewetting, respectively.     

Temperature‐Enhanced Solvent Vapor Annealing of a C3 Symmetric Hexa‐peri‐Hexabenzocoronene: Controlling the Self‐Assembly from Nano‐ to Macroscale

Temperature‐enhanced solvent vapor annealing (TESVA) is used to self‐assemble functionalized polycyclic aromatic hydrocarbon molecules into ordered macroscopic layers and crystals on solid surfaces. A novel C₃ symmetric hexa‐peri‐hexabenzocoronene functionalized with alternating hydrophilic and hydrophobic side chains is used as a model system since its multivalent character can be expected to offer unique self‐assembly properties and behavior in different solvents. TESVA promotes the molecule's long‐range mobility, as proven by their diffusion on a Si/SiO_x surface on a scale of hundreds of micrometers. This leads to self‐assembly into large, ordered crystals featuring an edge‐on columnar type of arrangement, which differs from the morphologies obtained using conventional solution‐processing methods such as spin‐coating or drop‐casting. The temperature modulation in the TESVA makes it possible to achieve an additional control over the role of hydrodynamic forces in the self‐assembly at surfaces, leading to a macroscopic self‐healing within the adsorbed film notably improved as compared to conventional solvent vapor annealing. This surface re‐organization can be monitored in real time by optical and atomic force microscopy.     

Multiscale Phase Separations for Hierarchically Ordered Macro/Mesostructured Metal Oxides

Porous architectures play an important role in various applications of inorganic materials. Several attempts to develop mesoporous materials with controlled macrostructures have been reported, but they usually require complicated multiple‐step procedures, which limits their versatility and suitability for mass production. Here, a simple approach for controlling the macrostructures of mesoporous materials, without templates for the macropores, is reported. The controlled solvent evaporation induces both macrophase separation via spinodal decomposition and mesophase separation via block copolymer self‐assembly, leading to the formation of hierarchically porous metal oxides with periodic macro/mesostructures. In addition, using this method, macrostructures of mesoporous metal oxides are controlled into spheres and mesoporous powders containing isolated macropores. Nanocomputed tomography, focused ion beam milling, and electron microscopy confirm well‐defined macrostructures containing mesopores. Among the various porous structures, hierarchically macro/mesoporous metal oxide is employed as an anode material in lithium‐ion batteries. The present approach could provide a broad and easily accessible platform for the manufacturing of mesoporous inorganic materials with different macrostructures.     

Wetting‐Induced Climbing for Transferring Interfacially Assembled Large‐Area Ultrathin Pristine Graphene Film

Owing to inherent 2D structure, marvelous mechanical, electrical, and thermal properties, graphene has great potential as a macroscopic thin film for surface coating, composite, flexible electrode, and sensor. Nevertheless, the production of large‐area graphene‐based thin film from pristine graphene dispersion is severely impeded by its poor solution processability. In this study, a robust wetting‐induced climbing strategy is reported for transferring the interfacially assembled large‐area ultrathin pristine graphene film. This strategy can quickly convert solvent‐exfoliated pristine graphene dispersion into ultrathin graphene film on various substrates with different materials (glass, metal, plastics, and cloth), shapes (film, fiber, and bulk), and hydrophobic/hydrophilic patterns. It is also applicable to nanoparticles, nanofibers, and other exfoliated 2D nanomaterials for fabricating large‐area ultrathin films. Alternate climbing of different ultrathin nanomaterial films allows a layer‐by‐layer transfer, forming a well‐ordered layered composite film with the integration of multiple pristine nanomaterials at nanometer scale. This powerful strategy would greatly promote the development of solvent‐exfoliated pristine nanomaterials from dispersions to macroscopic thin film materials.     

Solvent‐Induced Self‐Assembly Strategy to Synthesize Well‐Defined Hierarchically Porous Polymers

Porous polymers with well‐orchestrated nanomorphologies are useful in many fields, but high surface area, hierarchical structure, and ordered pores are difficult to be satisfied in one polymer simultaneously. Herein, a solvent‐induced self‐assembly strategy to synthesize hierarchical porous polymers with tunable morphology, mesoporous structure, and microporous pore wall is reported. The poly(ethylene oxide)‐b‐polystyrene (PEO‐b‐PS) diblock copolymer micelles are cross‐linked via Friedel–Crafts reaction, which is a new way to anchor micelles into porous polymers with well‐defined structure. Varying the polarity of the solvent has a dramatic effect upon the oleophobic/oleophylic interaction, and the self‐assembly structure of PEO‐b‐PS can be tailored from aggregated nanoparticles to hollow spheres even mesoporous bulk. A morphological phase diagram is accomplished to systematically evaluate the influence of the composition of PEO‐b‐PS and the mixed solvent component on the pore structure and morphology of products. The hypercrosslinked hollow polymer spheres provide a confined microenvironment for the in situ reduction of K₂PdCl₄ to ultrasmall Pd nanoparticles, which exhibit excellent catalytic performance in solvent‐free catalytic oxidation of hydrocarbons and alcohols.     

Negative‐Tone Block Copolymer Lithography by In Situ Surface Chemical Modification

Negative‐tone block copolymer (BCP) lithography based on in situ surface chemical modification is introduced as a highly efficient, versatile self‐assembled nanopatterning. BCP blends films consisting of end‐functionalized low molecular weight poly(styrene‐ran‐methyl methacrylate) and polystyrene‐block‐Poly(methyl methacylate) can produce surface vertical BCP nanodomains on various substrates without prior surface chemical treatment. Simple oxygen plasma treatment is employed to activate surface functional group formation at various substrates, where the end‐functionalized polymers can be covalently bonded during the thermal annealing of BCP thin films. The covalently bonded brush layer mediates neutral interfacial condition for vertical BCP nanodomain alignment. This straightforward approach for high aspect ratio, vertical self‐assembled nanodomain formation facilitates single step, site‐specific BCP nanopatterning widely useful for various substrates. Moreover, this approach is compatible with directed self‐assembly approaches to produce device oriented laterally ordered nanopatterns.     

Polymer‐Controlled Crystallization of Unique Mineral Superstructures

The origin of complex superstructures of biomaterials in biological systems and the amazing self‐assembly mechanisms of their emergence have attracted a great deal of attention recently. Mimicking nature, diverse kinds of hydrophilic polymers with different functionalities and organic insoluble matrices have been designed for the morphogenesis of inorganic crystals. In this Research News, emerging new strategies for morphogenesis and controlled crystal growth of minerals, that is, selective adsorption and mesoscale transformation for highly ordered superstructures, the combination of a synthetic hydrophilic polymer with an insoluble matrix, a substrate, or the air/solution interface, and controlled crystallization in a mixed solvent are highlighted. It is shown that these new strategies can be even further extended to morphogenesis and controlled crystallization of diverse inorganic or inorganic–organic hybrid materials with structural complexity, structural specialties, and improved functionalities.     

Monitoring Nanocrystal Self‐Assembly in Real Time Using In Situ Small‐Angle X‐Ray Scattering

Self‐assembled nanocrystal superlattices have attracted large scientific attention due to their potential technological applications. However, the nucleation and growth mechanisms of superlattice assemblies remain largely unresolved due to experimental difficulties to monitor intermediate states. Here, the self‐assembly of colloidal PbS nanocrystals is studied in real time by a combination of controlled solvent evaporation from the bulk solution and in situ small‐angle X‐ray scattering (SAXS) in transmission geometry. For the first time for the investigated system a hexagonal closed‐packed (hcp) superlattice formed in a solvent vapor saturated atmosphere is observed during slow solvent evaporation from a colloidal suspension. The highly ordered hcp superlattice is followed by a transition into the final body‐centered cubic superlattice upon complete drying. Additionally, X‐ray cross‐correlation analysis of Bragg reflections is applied to access information on precursor structures in the assembly process, which is not evident from conventional SAXS analysis. The detailed evolution of the crystal structure with time provides key results for understanding the assembly mechanism and the role of ligand–solvent interactions, which is important both for fundamental research and for fabrication of superlattices with desired properties.     

Self‐Assembly of Ferromagnetic Organic–Inorganic Perovskite‐Like Films

Perovskite‐based organic–inorganic hybrids hold great potential as active layers in electronics or optoelectronics or as components of biosensors. However, many of these applications require thin films grown with good control over structure and thickness—a major challenge that needs to be addressed. The work presented here is an effort towards this goal and concerns the layer‐by‐layer deposition at ambient conditions of ferromagnetic organic–inorganic hybrids consisting of alternating CuCl₄‐octahedra and organic layers. The Langmuir‐Blodgett technique used to assemble these structures provides intrinsic control over the molecular organization and film thickness down to the molecular level. Magnetic characterization reveals that the coercive field for these thin films is larger than that for solution‐grown layered bulk crystals. The strategy presented here suggests a promising cost effective route to facilitate the excellently controlled growth of sophisticated materials on a wide variety of substrates that have properties relevant for the high density storage media and spintronic devices.     

Directed Self‐Assembly of Star‐Block Copolymers by Topographic Nanopatterns through Nucleation and Growth Mechanism

Exploring the ordering mechanism and dynamics of self‐assembled block copolymer (BCP) thin films under confined conditions are highly essential in the application of BCP lithography. In this study, it is aimed to examine the self‐assembling mechanism and kinetics of silicon‐containing 3‐arm star‐block copolymer composed of polystyrene (PS) and poly(dimethylsiloxane) blocks as nanostructured thin films with perpendicular cylinders and controlled lateral ordering by directed self‐assembly using topographically patterned substrates. The ordering process of the star‐block copolymer within fabricated topographic patterns with PS‐functionalized sidewall can be carried out through the type of secondary (i.e., heterogeneous) nucleation for microphase separation initiated from the edge and/or corner of the topographic patterns, and directed to grow as well‐ordered hexagonally packed perpendicular cylinders. The growth rate for the confined microphase separation is highly dependent upon the dimension and also the geometric texture of the preformed pattern. Fast self‐assembly for ordering of BCP thin film can be achieved by lowering the confinement dimension and also increasing the concern number of the preformed pattern, providing a new strategy for the design of BCP lithography from the integration of top‐down and bottom‐up approaches.     

大分子自组装及其应用的研究与进展

综述了化学吸附、分子沉积、旋涂、慢蒸发溶剂和枝接成膜等 5种大分子自组装成膜方法 ,并介绍了其在液晶、非线性光学材料、聚合物表面改性等材料领域的应用及其表征研究。     

In Situ Probing of the Particle‐Mediated Mechanism of WO3‐Networked Structures Grown inside Confined Mesoporous Channels

Nanocasting, using ordered mesoporous silica or carbon as a hard template, has enormous potential for preparing novel mesoporous materials with new structures and compositions. Although a variety of mesoporous materials have been synthesized in recent years, the growth mechanism of nanostructures in a confined space, such as mesoporous channels, is not well understood, which hampers the controlled synthesis and further application of mesoporous materials. Here, the nucleation and growth of WO₃‐networked mesostructures within an ordered mesoporous matrix, using an in situ transmission electron microscopy heating technique and in situ synchrotron small‐angle X‐ray scattering spectroscopy, are probed. It is found that the formation of WO₃ mesostructures involves a particle‐mediated transformation and coalescence mechanism. The liquid‐like particle‐mediated aggregation and mesoscale transformation process can occur in ≈10 nm confined mesoporous channels, which is completely unexpected. The detailed mechanistic study will be of great help for experimental design and to exploit a variety of mesoporous materials for diverse applications, such as catalysis, absorption, separation, energy storage, biomedicine, and nanooptics.     

Core–Shell and Layer‐by‐Layer Assembly of 3D DNA Crystals

A long‐standing goal of DNA nanotechnology has been to assemble 3D crystals to be used as molecular scaffolds. The DNA 13‐mer, BET66, self‐assembles via Crick–Watson and noncanonical base pairs to form crystals. The crystals contain solvent channels that run through them in multiple directions, allowing them to accommodate tethered guest molecules. Here, the first example of biomacromolecular core–shell crystal growth is described, by showing that these crystals can be assembled with two or more discrete layers. This approach leads to structurally identical layers on the DNA level, but with each layer differentiated based on the presence or absence of conjugated guest molecules. The crystal solvent channels also allow layer‐specific postcrystallization covalent attachment of guest molecules. Through controlling the guest‐molecule identity, concentration, and layer thickness, this study opens up a new method for using DNA to create multifunctional periodic biomaterials with tunable optical, chemical, and physical properties.     

Electron Mobility of 24 cm2 V−1 s−1 in PbSe Colloidal‐Quantum‐Dot Superlattices

Colloidal quantum dots (CQDs) are nanoscale building blocks for bottom‐up fabrication of semiconducting solids with tailorable properties beyond the possibilities of bulk materials. Achieving ordered, macroscopic crystal‐like assemblies has been in the focus of researchers for years, since it would allow exploitation of the quantum‐confinement‐based electronic properties with tunable dimensionality. Lead‐chalcogenide CQDs show especially strong tendencies to self‐organize into 2D superlattices with micrometer‐scale order, making the array fabrication fairly simple. However, most studies concentrate on the fundamentals of the assembly process, and none have investigated the electronic properties and their dependence on the nanoscale structure induced by different ligands. Here, it is discussed how different chemical treatments on the initial superlattices affect the nanostructure, the optical, and the electronic‐transport properties. Transistors with average two‐terminal electron mobilities of 13 cm² V^?1 s^?1 and contactless mobility of 24 cm² V^?1 s^?1 are obtained for small‐area superlattice field‐effect transistors. Such mobility values are the highest reported for CQD devices wherein the quantum confinement is substantially present and are comparable to those reported for heavy sintering. The considerable mobility with the simultaneous preservation of the optical bandgap displays the vast potential of colloidal QD superlattices for optoelectronic applications.     

Templated Sub‐100‐nm‐Thick Double‐Gyroid Structure from Si‐Containing Block Copolymer Thin Films

The directed self‐assembly of diblock copolymer chains (poly(1,1‐dimethyl silacyclobutane)‐block‐polystyrene, PDMSB‐b‐PS) into a thin film double gyroid structure is described. A decrease of the kinetics of a typical double‐wave pattern formation is reported within the 3D‐nanostructure when the film thickness on mesas is lower than the gyroid unit cell. However, optimization of the solvent‐vapor annealing process results in very large grains (over 10 µm²) with specific orientation (i.e., parallel to the air substrate) and direction (i.e., along the groove direction) of the characteristic (211) plane, demonstrated by templating sub‐100‐nm‐thick PDMSB‐b‐PS films.     

Self‐Assembled Ag‐MXA Superclusters with Structure‐Dependent Mechanical Properties

The low elastic modulus and time‐consuming formation process represent the major challenges that impede the penetration of nanoparticle superstructures into daily life applications. As observed in the molecular or atomic crystals, more effective interactions between adjacent nanoparticles would introduce beneficial features to assemblies enabling optimized mechanical properties. Here, a straightforward synthetic strategy is showed that allows fast and scalable fabrication of 2D Ag‐mercaptoalkyl acid superclusters of either hexagonal or lamellar topology. Remarkably, these ordered superstructures exhibit a structure‐dependent elastic modulus which is subject to the tether length of straight‐chain mercaptoalkyl acids or the ratio between silver and tether molecules. These superclusters are plastic and moldable against arbitrarily shaped masters of macroscopic dimensions, thereby opening a wealth of possibilities to develop more nanocrystals with practically useful nanoscopic properties.     

Cobalt Nanoparticle Arrays made by Templated Solid‐State Dewetting

Self‐assembled cobalt particle arrays are formed by annealing, which cause agglomeration (dewetting) of thin Co films on oxidized silicon substrates that are topographically prepatterned with an array of 200‐nm‐period pits. The Co nanoparticle size and uniformity are related to the initial film thickness, annealing temperature, and template geometry. One particle per 200‐nm‐period pit is formed from a 15‐nm film annealed at 850 °C; on a smooth substrate, the same annealing process forms particles with an average interparticle distance of 200 nm. Laser annealing enables templated dewetting of 5‐nm‐thick films to give one particle per pit. Although the as‐deposited films exhibit a mixture of hexagonal close‐packed and face‐centered cubic (fcc) phases, the ordered cobalt particles are predominantly twinned fcc crystals with weak magnetic anisotropy. Templated dewetting is shown to provide a method for forming arrays of nanoparticles with well‐controlled sizes and positions.