We present a simple approach for patterning metal nanoparticles into periodic superstructures on flat films spanning centimeter-square areas. Our approach is based on capillary force lithography, a soft lithography method that is used to impart topography to molten polymer films, and applies it to block copolymer films to obtain substrates featuring both topographic and chemical contrasts that can serve as templates for the selective deposition of nanoparticles. Here we show that flattening the films by exposure to solvent vapour prior to nanoparticle deposition not only retains chemical heterogeneity but also provides access to unique hierarchically-organized nanoparticle superstructures that are unattainable by other methods. Such structures could be useful for optical, sensor, and catalytic applications.

Directed self-assembly of block copolymers is evolving toward applications that are more defect-tolerant but still require high morphological control and could benefit from simple, inexpensive fabrication processes. Previously, we demonstrated that simply casting ultra-thin block copolymer films on topographically defined substrates leads to hierarchical structures with dual patterns in a controlled manner and unraveled the dependence of the local morphology on the topographic feature dimensions. In this article, we discuss the extreme of the ultraconfined thickness regime at the border of film dewetting. Additional non-bulk morphologies are observed at this extreme, which further elaborate the arsenal of dual patterns that could be obtained in coexistence with full placement control. It is shown that as the thickness confinement approaches its limit, lateral confinement imposed by the width of the plateaus becomes a critical factor influencing the local morphology.

Soft lithography techniques have become leading mesoscale approaches for replicating topographic features in polymer films. So far, the modified polymer films formed by soft lithography only featured topographic heterogeneity. Here we demonstrate the application of soft lithography techniques to block copolymer films, and show that the preferential affinity of one of the blocks to the stamping material leads to chemical heterogeneity that corresponds to the topographic features. Detailed surface and structural characterization of the patterned films provided information on its three-dimensional structure, revealing insights on the domain reorganization that takes place in the block copolymer film concomitantly with topography formation. The formed structures were utilized for selective assembly of gold nanoparticles into hierarchical structures. The versatility of this combined nanofabrication/self-assembly approach was demonstrated by the assembly of two types of metallic nanoparticles into two different arrangements with full control over the location of each type of nanoparticles.

The ability to create mixed morphologies using easily controlled parameters is crucial for the integration of block copolymers in advanced technologies. We have previously shown that casting an ultrathin block copolymer film on a topographically patterned substrate results in different deposited thicknesses on the plateaus and in the trenches, which leads to the co-existence of two patterns. In this work, we highlight the dependence of the dual patterns on the film profile. We suggest that the steepness of the film profile formed across the plateau edge affects the nucleation of microphase-separated domains near the plateau edges, which influences the morphology that develops on the plateau regions. An analysis of the local film thicknesses in multiple samples exhibiting various combinations of plateau and trench widths for different trench depths enabled the construction of phase diagrams, which unraveled the intricate dependence of the formed patterns not only on the curvature of the film profile but also on the fraction of the film that resides in the trenches. Our analysis facilitates the prediction of the patterns that would develop in the trenches and on the plateaus for a given block copolymer film of known thickness from the dimensions of the topographic features.

The olefin metathesis reaction is among the most widely applicable catalytic reactions for carbon–carbon double bond formation. Currently, Mo– and Ru–carbene catalysts are the most common choices for this reaction. It has been suggested that an iron-based catalyst would be a desirable economical and biocompatible substitute of the Ru catalysts; however, practical solutions in this regard are still lacking. Here, we report the discovery and mechanistic studies of three-coordinate iron(II) catalysts for ring-opening metathesis polymerization of olefins. Remarkably, their reactivity enabled the formation of polynorbornene with stereoregularity and high molecular weight (>10⁷ g mol^–1). The polymerization in the presence of styrene revealed cross metathesis reactivity with iron catalysts. Mechanistic studies suggest the possible role of metal–ligand cooperation in formation of the productive catalyst. This work opens the door to the development of iron complexes that can be economical and biocompatible catalysts for olefin metathesis reactions.

The collective properties of ordered ensembles of anisotropically shaped nanoparticles depend on the morphology of organization. Here, we describe the utilization of block copolymer micelles to bias the natural packing tendency of semiconductor nanorods and organize them into circularly arranged superstructures. These structures are formed as a result of competition between the segregation tendency of the nanorods in solution and in the polymer melt; when the nanorods are highly compatible with the solvent but prefer to segregate in the melt to the core-forming block, they migrate during annealing toward the core–corona interface, and their superstructure is, thus, templated by the shape of the micelle. The nanorods, in turn, exhibit surfactant-like behavior and protect the micelles from coalescence during annealing. Lastly, the influence of the attributes of the micelles on nanorod organization is also studied. The circular nanorod arrangements and the insights gained in this study add to a growing list of possibilities for organizing metal and semiconductor nanorods that can be achieved using rational design.

Controlling complexity in assemblies of metal and semiconductor nanoparticles has the potential to expand the utilization of photonic devices into wavelength regimes that are currently inaccessible. Here we show that casting ultrathin films of asymmetric block copolymers on topographically defined substrates affords four types of mixed patterns through fine control of film thickness. Analysis of top-view and cross-sectional images revealed different morphological behavior of the film in the trench and on the plateau, which was explained by the difference in the type of boundary imposed by each topographic feature. Exposed domains were chemically modified and selectively decorated with gold nanoparticles, giving rise to nanoparticle superstructures with mixed patterns in a controlled fashion. We envisage utilization of such hierarchical superstructures as plasmon waveguides and metasurfaces.

Supramolecular polymers are based on noncovalent interactions, which impart unique properties such as dynamic behavior, concentration-dependent degree of polymerization, and environmental responsiveness. While linear supramolecular polymers are ubiquitous and have been extensively studied, branched polymers that are based exclusively on supramolecular interactions are much less abundant, and a fundamental understanding of their molecular-level structure is still lacking. We report on the preparation of branched, all-supramolecular polymers based on a combination of a bisureidotoluene building block [N,N′-2,4-bis((2-ethylhexyl)ureido)toluene (EHUT)], which is associated with four-point hydrogen bonding, and three anionic co-monomers featuring one, two, or three sulfonate groups. The co-monomers were designed to serve as a chain stopper, a bifunctional linear comonomer, and a branch point. Whereas combination of EHUT with the singly functionalized co-monomer led to linear supramolecular chains, diffusion and viscosity data indicate that branched supramolecular polymers were obtained when EHUT was combined not only with the triply functionalized molecules but also with the doubly functionalized molecules. Theoretical analysis based on an adaptation of Flory’s theory of branched polymers suggests that in both cases, the interaction of certain EHUT units
with the multiply functionalized co-monomers converted these EHUT units into branch points, which led to substantially reduced viscosities in these systems. The insights gained from this study enable tuning the properties of supramolecular polymers not only by
concentration and temperature but also by introducing appropriately designed molecular additives. This may lead to the development of sophisticated smart materials.

Arrays of alternating metallic nanostructures present hybrid properties, which are useful for applications in photonics and catalysis. Block copolymer films provide versatile templates for fabricating periodic arrays of nanowires. Yet, creating arrays with alternating compositions or structures requires different modifications of domains of the same kind. By controlling the penetration depth of metal precursors into the film we were able to impregnate different layers of copolymer cylinders with different metals. Capitalizing on the hexagonal packing of the cylinders led to simultaneous formation of nanowires with alternating compositions and periodic arrangement on the substrate after plasma etching. Selective deposition of nanoparticles on the film enabled creating alternating bare and decorated nanowires, as well as trimetallic nanowire arrays.

Bottlebrush block copolymers offer unique advantages for polymer-nanoparticle assembly, arising from the stiffness of their backbones and the compositional tunability afforded by the lengths of the grafts in each block independently. The morphologies of ultrathin bottlebrush block copolymer films are extremely sensitive to the chemistry of the substrate. Modifying the substrate with a polymer brush that corresponds to one of the blocks of the bottlebrush copolymer leads to different, often non-bulk morphologies that relate to the interaction of the copolymer with the substrate, which is dictated by the bottlebrush polymer composition. In this work, we investigate the assembly of bottlebrush block copolymers of different compositions with gold nanoparticles, which are modified with polymeric ligands that correspond to one of the blocks. Our results show that the net interaction of the copolymer with the substrate influences the self-assembly process, leading to two types of routes: the co-assembly route, in which the nanoparticles are organized by the polymer into periodic structures, or macrophase separation. In the co-assembly route, selective substrates slightly distort the shape of the domains. The nanoparticles, in turn, influence the kinetics of the process by their interaction with the substrate.

Ultraconfined block copolymer films present non-bulk structures that are highly sensitive to film thickness and are strongly influenced by the wetting properties of the substrate. Here we describe the self-assembly of bottlebrush block copolymers with varying side-chain lengths on different types of substrates. Our results show a pronounced influence of the nature of the substrate on the self-assembled morphology and the surface patterns that evolve during solvent-vapor annealing. In particular, we observe by experiments and simulations a transient, substrate-driven morphology of cylinder-like structures obtained in films of doubly symmetric (i.e., backbone and side-chains) bottlebrush block copolymer despite the general tendency of these polymers to form lamellar structures. The insights gained from this study highlight the ability to use the substrate chemistry for inducing the formation of unique morphologies in bottlebrush block copolymer films.

Simulations and experiments of nanorods (NRs) show that co-assembly with block copolymer (BCP) melts leads to the formation of a superstructure of side-to-side NRs perpendicular to the lamellar axis. A mesoscopic model is validated against scanning electron microscopy (SEM) images of CdSe NRs mixed with polystyrene-block-poly(methyl methacrylate). It is then used to study the co-assembly of anisotropic nanoparticles (NPs) with a length in the same order of magnitude as the lamellar spacing. The phase diagram of BCP/NP is explored as well as the time evolution of the NR. NRs that are slightly larger than the lamellar spacing are found to rotate and organize side-to-side with a tilted orientation with respect to the interface. Strongly interacting NPs are found to dominate the co-assembly, while weakly interacting nanoparticles are less prone to form aggregates and tend to form well-ordered configurations.

Various types of devices require hierarchically nano-patterned substrates, where spacing between patterned domains is controlled. Ultra-confined films exhibit extreme morphological sensitivity to slight variations in film thickness when the substrate is highly selective toward one of the blocks. Here, it is shown that using the substrate’s topography as a thickness differentiating tool enables the creation of domains with different surface patterns in a fully controlled fashion from a single, unblended block copolymer. This approach is applicable to block copolymers of different compositions and to different topographical patterns, and thus opens numerous possibilities for hierarchical construction of multifunctional devices.

Polyelectrolyte multilayers (PEMs) assembled layer-by-layer have emerged as functional polymer films that are both stable and capable of containing drug molecules for controlled release applications. Most of these applications concentrate on sustained release, where the concentration of the released molecules remains rather constant with time. However, high-efficiency delivery requires obtaining high local concentrations at the vicinity of the cells, which is achieved by triggered release. Here, we show that a nanopatterned PEM platform demonstrates superior properties with respect to drug retention and triggered delivery. A chemically modified block copolymer film was used as a template for the selective deposition of poly(ethylene imine) and a charged derivative of the electroactive poly(3,4-ethylenedioxythiophene) together with a drug molecule. This nanopatterned PEM shows the following advantages: (1) high drug loading; (2) enhanced retention of the bioactive molecule; (3) release triggered by an electrochemical stimulus; (4) high efficacy of drug delivery to cells adsorbed on the surface compared to the delivery efficacy of a similar concentration of drug to cells suspended in a solution.

Block copolymer guided assembly of nanoparticles leads to the formation of nanocomposites with periodic arrangement of nanoparticles, which are important for applications such as photonic devices and sensors. However, linear block copolymers offer limited control over the internal arrangement of nanoparticles inside their hosting domains. In contrast, bottlebrush block copolymers possess unique architectural attributes that enable additional ways to control the local organization of nanoparticles. In this work, we studied the coassembly of 8 and 13 nm gold nanoparticles with three bottlebrush block copolymers differing in the asymmetry of their graft lengths. Assembly was performed in ultraconfined films, where it occurs quasi-two-dimensionally. Our results indicate that graft asymmetry could be used as an additional tool to enhance nanoparticle ordering by forcing them to localize at the center of the domain regardless of their size. This behavior is analyzed in terms of the influence of the graft asymmetry on the average conformations of the blocks.

Exploiting the full potential of metal and semiconductor nanoparticles for advanced nanotechnological applications requires their organization into predefined structures with high orientational control. Nanofabrication approaches that combine high resolution lithography and self-assembly afford the advantages of accurate placement, compositional diversity, and reduced production costs. This review concentrates on the creation of organized nanoparticle superstructures assisted by recent developments in the directed self-assembly of block copolymers, and delineates possible applications. Copyright (C) 2016 John Wiley & Sons, Ltd.

Polyelectrolyte multilayers gain their importance from their applicability to a wide variety of functional building blocks. The ability to create these multilayers as laterally nano-patterned films, which has only been scarcely investigated so far, augments the functionality of the multilayer and makes it valuable for applications that require nanoscale features or periodic arrangement, such as photonic devices, catalytic surfaces, and biomedical applications. In this study we reveal how the lateral confinement imposed by block copolymer nano-domains in thin film templates affects the assembly of the deposited poly electrolyte layers at different ionic strengths, and how the combined effects of nano-confinement and ionic strength dictate the final structure of the multilayer. These fundamental insights provide the basis for successful construction of nano-patterned, functional coatings. (C) 2017 Elsevier Ltd. All rights reserved.

The construction of nano-sized, two-dimensionally ordered nanoparticle (NP) superstructures is important for various advanced applications such as photonics, sensing, catalysis, or nano-circuitry. Currently, such structures are fabricated using the templated organization approach, in which the templates are mainly created by photo-lithography or laser-lithography and other invasive top-down etching procedures. In this work, we present an alternative bottom-up preparation method for the controlled deposition of NPs into hierarchical structures. Lamellar polystyrene-block-poly(2-vinylpyridinium) thin films featuring alternating stripes of neutral PS and positively charged P2VP domains serve as templates, allowing for the selective adsorption of negatively charged gold NPs. Dense NP assembly is achieved by a simple immersion process, whereas two-dimensionally ordered arrays of NPs are realized by microcontact printing (mu CP), utilizing periodic polydimethylsiloxane wrinkle grooves loaded with gold NPs. This approach enables the facile construction of hierarchical NP arrays with variable geometries. Copyright (C) 2016 John Wiley & Sons, Ltd.

ITO electrodes modified with a nanopatterned film of polystyrene-block-poly(2-vinylpyridine), PS-b-P2VP, where the P2VP domains are quaternized with iodomethane, are used for selective deposition of redox-active materials. Electrochemical studies (cyclic voltammetry, Faradaic impedance measurements) indicate that the PS domains insulate the conductive surface toward redox labels in solution. In turn, the quaternized P2VP domains electrostatically attract negatively charged redox labels solubilized in the electrolyte solution, resulting in an effective electron transfer between the electrode and the redox label. This phenomenon is implemented for the selective deposition of the electroactive Prussian blue on the nanopatterned surface and for the electrochemical deposition of Au nanoparticles, modified with a monolayer of p-aminothiophenol/2-mercaptoethanesulfonic acid, on the quaternized P2VP domains. The patterned Prussian blue-modified surface enables controlling the wettability properties by the content of the electrochemically deposited Prussian blue. Controlled wettability is unattainable with the homopolymer-modified surface, attesting to the role of the nanopattern.