Eliminating the Trade‐Off between the Throughput and Pattern Quality of Sub‐15 nm Directed Self‐Assembly via Warm Solvent Annealing

The directed self‐assembly (DSA) of block copolymers (BCPs) has been suggested as a promising nanofabrication solution. However, further improvements of both the pattern quality and manufacturability remain as critical challenges. Although the use of BCPs with a high Flory‐Huggins interaction parameter (χ) has been suggested as a potential solution, this practical self‐assembly route has yet to be developed due to their extremely slow self‐assembly kinetics. In this study, it is reported that warm solvent annealing (WSA) in a controlled environment can markedly improve both the self‐assembly kinetics and pattern quality. A means of avoiding the undesirable trade‐off between the quality and formation throughput of the self‐assembled patterns, which is a dilemma which arises when using the conventional solvent vapor treatment, is suggested. As a demonstration, the formation of well‐defined 13‐nm‐wide self‐assembled patterns (3σ line edge roughness of ≈2.50 nm) in treatment times of 0.5 min (for 360‐nm‐wide templates) is shown. Self‐consistent field theory (SCFT) simulation results are provided to elucidate the mechanism of the pattern quality improvement realized by WSA.     

Fibrillar Constructs from Multilevel Hierarchical Self‐Assembly of Discotic and Calamitic Supramolecular Motifs

We here report on polymeric solid‐state self‐assembly leading to organization over six length scales, ranging from the molecular scale up to the macroscopic length scale. We combine several concepts, i.e., rod‐like helical and disc‐like liquid crystallinity, block copolymer self‐assembly, DNA‐like interactions to form an ionic polypeptide–nucleotide complex and packing frustration to construct mesoscale fibrils. Ionic complexation of anionic deoxyguanosine monophosphate (dGMP) and triblock coil–rod–coil copolypeptides is used with cationic end blocks and a helical rod‐like midblock. The guanines undergo Hoogsteen pairing to form supramolecular discs, they π‐stack into columns that self‐assemble into hexagonal arrays that are controlled by the end blocks. Packing frustration between the helical rods from the block copolymer midblock and the discotic motif limits the lateral growth of the assembly thus affording mesoscale fibrils, which in turn, form an open fibrillar network. The concepts suggest new rational methodologies to construct structures on multiple length scales in order to tune polymer properties.     

Thermodynamic and Kinetic Tuning of Block Copolymer Based on Random Copolymerization for High‐Quality Sub‐6 nm Pattern Formation

The precisely controllable self‐assembly phenomenon of block copolymers (BCPs) has garnered much attention because it yields well‐defined periodic nanostructures with a periodicity of 5–50 nm. However, from both thermodynamic and kinetic viewpoints, it still remains a challenge to develop a BCP material that can provide sub‐10 nm resolution, high pattern quality, fast pattern formation, and sufficient etch selectivity. To address these challenges, this study reports a BCP system containing a random‐copolymerized block (poly(2‐vinylpyridine‐co‐4‐vinylpyridne)‐b‐poly(dimethylsiloxane) (P(2VP‐co‐4VP)‐b‐PDMS)) that can provide sub‐6 nm resolution, 3σ line edge roughness of 0.89 nm, sub‐1‐min assembly time, and a high etch selectivity over 10. Calculation of the Flory–Huggins interaction parameter (χ) based on Leibler's mean‐field theory and small‐angle X‐ray scattering measurement data confirms the gradual tunability of χ with the controlled addition of 4VP fraction in the P(2VP‐co‐4VP) block. While guaranteeing kinetically fast self‐assembly within one minute using microwave annealing, the best pattern quality resulting from the thermodynamic suppression of line edge fluctuation is achieved with a 4VP weight fraction of 33% in the random‐copolymerized block. This approach enables systematical control of sub‐6 nm scale BCP self‐assembly and will provide a practical patterning solution for diverse nanostructures and devices.     

Solid‐State Light Emission Controlled by Tuning the Hierarchical Superstructure of Self‐Assembled Luminogens

Solid‐state luminescence is an important strategy for color generation via molecular self‐assembly. Here, a new luminogen (AT₃EMIS) containing both a rigid chromophore and a flexible dendron is designed and synthesized for multicolor emission. The emission energy of the target material is precisely controlled by adjusting three different columnar arrays through thermal and mechanical stimulation. With well‐defined supramolecular organizations in different length scales, the luminescent properties of the light switch can be tuned.     

Sub‐5 nm Dendrimer Directed Self‐Assembly with Large‐Area Uniform Alignment by Graphoepitaxy

Directed self‐assembly (DSA) using soft materials is an important method for producing periodic nanostructures because it is a simple, cost‐effective process for fabricating high‐resolution patterns. Most of the previously reported DSA methods exploit the self‐assembly of block copolymers, which generates a wide range of nanostructures. In this study, cylinders obtained from supramolecular dendrimer films with a high resolution (<5 nm) exhibit planar ordering over a macroscopic area via guiding topographical templates with a high aspect ratio (>10) and high spatial resolution (≈20 nm) of guiding line patterns. Theoretical and experimental studies reveal that this property is related to geometrical anchoring on the meniscus region and physical surface anchoring on the sidewall. Furthermore, this DSA of dendrimer cylinders is demonstrated by the non‐regular geometry of the patterned template. The macroscopic planar alignment of the dendrimer nanostructure reveals an extremely small feature size (≈4.7 nm) on the wafer scale (>16 cm²). This study is expected to open avenues for the production of a large family of supramolecular dendrimers with different phases and feature dimensions oriented by the DSA approach.     

Controlled Assembly of Poly(3‐hexylthiophene): Managing the Disorder to Order Transition on the Nano‐ through Meso‐Scales

Self‐assembly of conjugated organic semiconductors into ordered, larger scale entities is a critical process to achieve efficient charge transport at the nano‐ through macro‐scales, and various methodologies aimed at enhancing molecular ordering have been introduced. However, mechanistic understanding is limited. Here, a mechanistic elucidation of poly(3‐hexylthiophene) (P3HT) molecular self‐assembly is proposed based on experimental demonstration of controlled, solution‐based P3HT self‐assembly into rod‐like polycrystalline nanostructures. The synergistic combination of nonsolvent addition and ultrasonication facilitates rod‐like P3HT nanostructure formation in solution. Importantly, through sequential application of both treatments, nanostructure length can be easily modulated, and the assembly process is shown to follow a simple 2‐step crystallization model, which depends upon nucleation followed by growth. Through arrays of experimental results, the validity of 2‐step crystallization is confirmed and is proposed as a comprehensive platform to understand self‐assembly processes of conjugated polymers into larger, ordered mesoscale entities.     

Non‐Covalent Functionalization of Graphene Using Self‐Assembly of Alkane‐Amines

A simple, versatile method for non‐covalent functionalization of graphene based on solution‐phase assembly of alkane‐amine layers is presented. Second‐order Møller–Plesset (MP2) perturbation theory on a cluster model (methylamine on pyrene) yields a binding energy of ≈220 meV for the amine–graphene interaction, which is strong enough to enable formation of a stable aminodecane layer at room temperature. Atomistic molecular dynamics simulations on an assembly of 1‐aminodecane molecules indicate that a self‐assembled monolayer can form, with the alkane chains oriented perpendicular to the graphene basal plane. The calculated monolayer height (≈1.7 nm) is in good agreement with atomic force microscopy data acquired for graphene functionalized with 1‐aminodecane, which yield a continuous layer with mean thickness ≈1.7 nm, albeit with some island defects. Raman data also confirm that self‐assembly of alkane‐amines is a non‐covalent process, i.e., it does not perturb the sp² hybridization of the graphene. Passivation and adsorbate n‐doping of graphene field‐effect devices using 1‐aminodecane, as well as high‐density binding of plasmonic metal nanoparticles and seeded atomic layer deposition of inorganic dielectrics using 1,10‐diaminodecane are also reported.     

A General Approach to Semimetallic,Ultra‐High‐Resolution,Electron‐Beam Resists

Commercial electron‐beam resists are modified into semimetallic resists by doping with 1–3 nm metal nanoparticles, which improve the resolution, contrast, strength, dry‐etching resistance, and other properties of the resist. With the modified resists, fine resist nanopatterns from electron‐beam lithography are readily converted into 5–50 nm, high‐quality multilayers for metallic nanosensors or nanopatterns via ion‐beam etching. This method solves the problem of the fabrication of fine (<50 nm) metallic nanodevices via pattern transferring.     

Co‐Assembled and Microfabricated Bioactive Membranes

The fabrication of hierarchical and bioactive self‐supporting membranes, which integrate physical and biomolecular elements, using a single‐step process that combines molecular self‐assembly with soft lithography is reported. A positively charged multidomain peptide (with or without the cell‐adhesive sequence arginine‐glycine‐aspartic acid‐serine (RGDS)) self‐assembles with hyaluronic acid (HA), an anionic biopolymer. Optimization of the assembling conditions enables the realization of membranes with well‐controlled and easily tunable features at multiple size scales including peptide sequence, building‐block co‐assembly, membrane thickness, bioactive epitope availability, and topographical pattern morphology. Membrane structure, morphology, and bioactivity are investigated according to temperature, assembly time, and variations in the experimental setup. Furthermore, to evaluate the physical and biomolecular signaling of the self‐assembled microfabricated membranes, rat mesenchymal stem cells are cultured on membranes exhibiting various densities of RGDS and different topographical patterns. Cell adhesion, spreading, and morphology are significantly affected by the surface topographical patterns and the different concentrations of RGDS. The versatility of the combined bottom‐up and top‐down fabrication processes described may permit the development of hierarchical macrostructures with precise biomolecular and physical properties and the opportunity to fine tune them with spatiotemporal control.     

Hierarchical Self‐Assembly of Peptide‐Coated Carbon Nanotubes

Numerous applications, from molecular electronics to super‐strong composites, have been suggested for carbon nanotubes. Despite this promise, difficulty in assembling raw carbon nanotubes into functional structures is a deterrent for applications. In contrast, biological materials have evolved to self‐assemble, and the lessons of their self‐assembly can be applied to synthetic materials such as carbon nanotubes. Here we show that single‐walled carbon nanotubes, coated with a designed amphiphilic peptide, can be assembled into ordered hierarchical structures. This novel methodology offers a new route for controlling the physical properties of nanotube systems at all length scales from the nano‐ to the macroscale. Moreover, this technique is not limited to assembling carbon nanotubes, and could be modified to serve as a general procedure for controllably assembling other nanostructures into functional materials.     

Reversible Electroaddressing of Self‐assembling Amino‐Acid Conjugates

The triggered assembly of organic and biological materials in response to imposed electrical signals (i.e., electroaddressing) provides interesting opportunities for applications in molecular electronics, biosensing and nanobiotechnology. Recent studies have shown that the conjugation of aromatic moieties to short peptides often yields hydrogelator compounds that can be triggered to self‐assemble over a hierarchy of length scales in response to a reduction in pH. Here, we examined the capabilities of fluorenyl‐9‐methoxycarbonyl‐phenylalanine (Fmoc‐Phe) to electrodeposit in response to an electrochemically‐induced pH gradient generated at the anode surface. We report that the electrodeposition of Fmoc‐Phe; is rapid (minutes), can be spatially controlled in normal and lateral directions, and can be reversed by applying a brief cathodic current. Further more, we show that Fmoc‐Phe can be simultaneously deposited on one electrode address (anode) while it is being cathodically stripped from a separate electrode address of the same chip. Finally, we demonstrate that these capabilities can be extended for electroaddressing within microfluidic channels. The reversible assembly/disassembly of molecular gelators (Fmoc‐amino acids and Fmoc‐peptides) in response to spatiotemporally imposed electrical signals offers unique opportunities for electroaddressing that should be especially valuable for lab‐on‐a‐chip applications.     

Self‐Assembly of Atomically Thin Chiral Copper Heterostructures Templated by Black Phosphorus

The fabrication of 2D systems for electronic devices is not straightforward, with top‐down low‐yield methods often employed leading to irregular nanostructures and lower quality devices. Here, a simple and reproducible method to trigger self‐assembly of arrays of high aspect‐ratio chiral copper heterostructures templated by the structural anisotropy in black phosphorus (BP) nanosheets is presented. Using quantitative atomic resolution aberration‐corrected scanning transmission electron microscopy imaging, in situ heating transmission electron microscopy and electron energy‐loss spectroscopy arrays of heterostructures forming at speeds exceeding 100 nm s^?1 and displaying long‐range order over micrometers are observed. The controlled instigation of the self‐assembly of the Cu heterostructures embedded in BP is achieved using conventional electron beam lithography combined with site specific placement of Cu nanoparticles. Density functional theory calculations are used to investigate the atomic structure and suggest a metallic nature of the Cu heterostructures grown in BP. The findings of this new hybrid material with unique dimensionality, chirality, and metallic nature and its triggered self‐assembly open new and exciting opportunities for next generation, self‐assembling devices.     

Soft Graphoepitaxy for Large Area Directed Self‐Assembly of Polystyrene‐block‐Poly(dimethylsiloxane) Block Copolymer on Nanopatterned POSS Substrates Fabricated by Nanoimprint Lithography

Polyhedral oligomeric silsequioxane (POSS) derivatives have been successfully employed as substrates for graphoepitaxial directed self‐assembly (DSA) of block copolymers (BCPs). Tailored POSS materials of tuned surface chemistry are subject to nanoimprint lithography (NIL) resulting in topographically patterned substrates with dimensions commensurate with the BCP block length. A cylinder forming polystyrene‐block‐polydimethylsiloxane (PS‐b‐PDMS) BCP is synthesized by sequential living anionic polymerization of styrene and hexamethylcyclotrisiloxane. The patterned POSS materials provide a surface chemistry and topography for DSA of this BCP and after solvent annealing the BCP shows well‐ordered microphase segregation. The orientation of the PDMS cylinders to the substrate plane could be controlled within the trench walls by the choice of the POSS materials. The BCP patterns are successfully used as on‐chip etch mask to transfer the pattern to underlying silicon substrate. This soft graphoepitaxy method shows highly promising results as a means to generate lithographic quality patterns by nonconventional methods and could be applied to both hard and soft substrates. The methodology might have application in several fields including device and interconnect fabrication, nanoimprint lithography stamp production, nanofluidic devices, lab‐on‐chip, or in other technologies requiring simple nanodimensional patterns.     

DNA Origami‐Guided Assembly of the Roundest 60–100 nm Gold Nanospheres into Plasmonic Metamolecules

DNA origami can provide programmed information to guide the self‐assembly of gold nanospheres (Au NSs) into higher‐order supracolloids. Molecularly precise and truly 2D/3D integration of Au NSs is possible using DNA origami‐enabled assembly, and the resulting assemblies have potential applications in plasmonics and metamaterials. However, the relatively small size (<60 nm) and randomly faceted Au NSs that have been used thus far in DNA origami‐enabled assembly have limited their nanophotonic applications. Here, the robust self‐assembly of the 60–100 nm roundest Au NSs into metamolecular assemblies using 3D DNA origami is described. These Au NSs are successfully conjugated with DNA oligonucleotides and are therefore stable at high salt concentrations even without backfilling using organic ligands. The roundest Au NSs are successfully assembled into supracolloidal metamolecules and chains via 3D DNA origami. These plasmonic metamolecules and chains display strong electric and unnatural magnetic resonances that can be deterministically controlled.     

Surface‐Shielding Nanostructures Derived from Self‐Assembled Block Copolymers Enable Reliable Plasma Doping for Few‐Layer Transition Metal Dichalcogenides

Precise modulation of electrical and optical properties of 2D transition metal dichalcogenides (TMDs) is required for their application to high‐performance devices. Although conventional plasma‐based doping methods have provided excellent controllability and reproducibility for bulk or relatively thick TMDs, the application of plasma doping for ultrathin few‐layer TMDs has been hindered by serious degradation of their properties. Herein, a reliable and universal doping route is reported for few‐layer TMDs by employing surface‐shielding nanostructures during a plasma‐doping process. It is shown that the surface‐protection oxidized polydimethylsiloxane nanostructures obtained from the sub‐20 nm self‐assembly of Si‐containing block copolymers can preserve the integrity of 2D TMDs and maintain high mobility while affording extensive control over the doping level. For example, the self‐assembled nanostructures form periodically arranged plasma‐blocking and plasma‐accepting nanoscale regions for realizing modulated plasma doping on few‐layer MoS₂, controlling the n‐doping level of few‐layer MoS₂ from 1.9 × 10¹¹ cm^?2 to 8.1 × 10¹¹ cm^?2 via the local generation of extra sulfur vacancies without compromising the carrier mobility.     

Room‐Temperature Ion‐Exchange‐Mediated Self‐Assembly toward Formamidinium Perovskite Nanoplates with Finely Tunable,Ultrapure Green Emissions for Achieving Rec. 2020 Displays

Delicate engineering of chromaticity is required to faithfully reproduce colors in a backlit display, this is extremely difficult for green downconverters because the human eye is highly sensitive to green colors. The central challenge is to achieve finely tunable green emissions in the narrow range of 525–535 nm while keeping the full width at half maximum (FWHM) <25 nm at the same time. Here, a room‐temperature ion‐exchange‐mediated self‐assembly strategy for preparing FAPbBr₃ (FA = CH(NH₂)₂⁺) nanoplates (NPs) to fulfill this goal is introduced. 2D layered OA₂PbBr₄ (OA is octadecylamine) NPs are first synthesized by spontaneous reprecipitation, and are then transformed into FAPbBr₃ NPs through a OA⁺‐to‐FA⁺ exchange induced self‐assembly of HP monolayers. A c‐axis contraction in this process makes a relative large thickness variation in OA₂PbBr₄ NPs, which can be realized by simply varying the precursor concentration, only result in a small thickness change in subsequent FAPbBr₃ NPs, thereby enabling finely tunable emissions in the range of 525–535 nm along with FWHM <25 nm and a quantum yield up to 85%. As a downconverter, the FAPbBr₃ NPs realize an ultrapure green backlight that covers ≈95% Rec. 2020 standard in the CIE 1931 color space.     

Nucleation‐Governed Reversible Self‐Assembly of an Organic Semiconductor at Surfaces: Long‐Range Mass Transport Forming Giant Functional Fibers

The use of solvent‐vapor annealing (SVA) to form millimeter‐long crystalline fibers, having a sub‐micrometer cross section, on various solid substrates is described. Thin films of a perylene‐bis(dicarboximide) (PDI) derivative, with branched alkyl chains, prepared from solution exhibit hundreds of nanometer‐sized PDI needles. Upon exposure to the vapors of a chosen solvent, tetrahydrofuran (THF), the needles re‐organize into long fibers that have a remarkably high aspect ratio, exceeding 10³. Time‐ and space‐resolved mapping with optical microscopy allows the self‐assembly mechanism to be unravelled; the mechanism is found to be a nucleation‐governed growth, which complies with an Avrami‐type of mechanism. SVA is found to lead to self‐assembly featuring i) long‐range order (up to the millimeter scale), ii) reversible characteristics, as demonstrated through a series of assembly and disassembly steps, obtained by cycling between THF and CHCl₃ as solvents, iii) remarkably high mass transport because the PDI molecular motion is found to occur at least over hundreds of micrometers. Such a detailed understanding of the growth process is fundamental to control the formation of self‐assembled architectures with pre‐programmed structures and physical properties. The versatility of the SVA approach is proved by its successful application using different substrates and solvents. Kelvin probe force microscopy reveals that the highly regular and thermodynamically stable fibers of PDI obtained by SVA exhibit a greater electron‐accepting character than the smaller needles of the drop‐cast films. The giant fibers can be grown in situ in the gap between microscopic electrodes supported on SiO_x, paving the way towards the application of SVA in micro‐ and nanoelectronics.     

Evaporation‐Induced Coating and Self‐Assembly of Ordered Mesoporous Carbon‐Silica Composite Monoliths with Macroporous Architecture on Polyurethane Foams

A facile approach of solvent‐evaporation‐induced coating and self‐assembly is demonstrated for the mass preparation of ordered mesoporous carbon‐silica composite monoliths by using a polyether polyol‐based polyurethane (PU) foam as a sacrificial scaffold. The preparation is carried out using resol as a carbon precursor, tetraethyl orthosilicate (TEOS) as a silica source and Pluronic F127 triblock copolymer as a template. The PU foam with its macrostructure provides a large, 3D, interconnecting interface for evaporation‐induced coating of the phenolic resin‐silica block‐copolymer composites and self‐assembly of the mesostructure, and endows the composite monoliths with a diversity of macroporous architectures. Small‐angle X‐ray scattering, X‐ray diffraction and transmission electron microscopy results indicate that the obtained composite monoliths have an ordered mesostructure with 2D hexagonal symmetry (p6m) and good thermal stability. By simply changing the mass ratio of the resol to TEOS over a wide range (10–90%), a series of ordered, mesoporous composite foams with different compositions can be obtained. The composite monoliths with hierarchical macro/mesopores exhibit large pore volumes (0.3–0.8 cm³ g^?1), uniform pore sizes (4.2–9.0 nm), and surface areas (230–610 m² g^?1). A formation process for the hierarchical porous composite monoliths on the struts of the PU foam through the evaporation‐induced coating and self‐assembly method is described in detail. This simple strategy performed on commercial PU foam is a good candidate for mass production of interface‐assembly materials.     

Self‐Assembly and Metallization of Resorcinarene Microtubes in Water

Amphiphilic resorcinarene‐based multiwalled microtubes, millimetres in diameter and centimetres in length, are generated in water. The thickness of the tube wall approaches 300 nm. Their self‐assembly properties are investigated using transmission electron microscopy, scanning electron microscopy, atomic‐force microscopy, dynamic light scattering, X‐ray diffraction, UV‐vis spectra, and Fourier transform IR techniques. From these studies, the structures critical for the self‐assembly of resorcinarene into microtubes in aqueous media are determined. Furthermore, the study manifests a feasible method that aims to completely change the structure from a microtube to a sheet‐like morphology by selectively eliminating key groups. Subsequently, resorcinarene‐capped water‐soluble gold nanoparticles (AuNPs) are fabricated. By utilizing the obtained microtubes as a template, a gold/organic microtubular composite is successfully prepared.     

Individual Confinement of Block Copolymer Microdomains in Nanoscale Crossbar Templates

Highly ordered pattern formation of block copolymers (BCPs) within nanoscale templates is of great interest for generating diverse ordered nanostructures. Here, introduced is a combined methodology of nanotransfer printing (nTP) and BCP self‐assembly to guide the formation of spherical nanodots within a printed crossbar nanotemplate. By successfully accommodating poly(styrene‐b‐dimethylsiloxane) (PS‐b‐PDMS) BCPs in the guiding metallic crossbar nanotemplate (≈30 × 30 nm²), a well‐organized array of single‐domain PDMS spheres (≈10 nm) with a square symmetry is successfully obtained in an extremely short annealing time (<5 s). The self‐consistent field theory simulation results theoretically explain the spontaneous one‐to‐one accommodation of PDMS spheres in the confined area of the crossbar template. This approach can potentially be extended to the many other BCP materials and morphologies to diversify the geometry of self‐assembled BCP and/or transfer‐printed nanopatterns for various types of nanodevice applications.