Self-assembly Of Block Copolymers Research Articles

FORC analysis of nanopatterned vs unpatterned films: Coercivity and switching mechanisms

We have studied the use of self-assembled block copolymers to pattern multilayers of Co and Pd on silicon wafers. Stacks ranging from four to twelve bilayers of Co (0.3 nm)/Pd (0.8 nm) were sputtered onto Ta/Pd seed layers and capped with 3 nm of Ta and were found to have perpendicular magnetic anisotropy as-deposited. The block copolymer polystyrene-block-poly(ferrocenyl dimethylsilane) (PS-b-PFS) was dissolved in toluene and spun onto the wafers. The polymers were phase-separated by heat treatment, leaving self-assembled PFS spheres embedded in PS, which was removed by oxygen-plasma ashing. The PFS spheres were then used as masks to ion-mill the Co/Pd multilayers into nanopillars. To study the effect of etch time and etch angle on the coercivity distribution, we synthesized samples in a Design of Experiments-(DoE)- in these two factors. Scanning electron micrographs showed nanopillars ranging from 15 to 30 nm in diameter, depending primarily on etch time. M-H loops measured on both patterned and unpatterned wafers showed an increase of up to 130% in overall coercivity upon patterning. First Order Reversal Curves (FORC) were measured, and the resulting FORC distributions displayed using a smoothing program (FORCinel) and one that can display the raw data without smoothing (FORC+). We find that FORC+ reveals information about fine-scale structure and switching mechanism that cannot be seen in the smoothed display.

Block Copolymer Self-Assembly Guided Synthesis of Mesoporous Carbons with In-Plane Holey Pores for Efficient Oxygen Reduction Reaction.

In this paper, a simple approach, using interfacial self-assembly of block copolymers (BCPs) on self-sacrificial templates, for preparing mesoporous carbons with in-plane holey pores, including nitrogen atom-doped carbon nanosheets and nanoflowers (denoted as NHCSs and NHCFs), is reported. The approach employs sheet- or flower-like layered double hydroxide as the templates, P123 copolymer as the pore-directing agent, and m-phenylenediamine as the carbon source. The holey mesopores may shorten the mass transfer distance in the internal active sites of stacked nanosheets, while the 3D packing mode of nanosheets can reduce pore blockage caused by their tight stacking. Profiting from these structural advantages, acting as electrocatalysts for oxygen reduction reaction (ORR), both NHCSs and NHCFs show excellent catalytic performance better than that of carbon nanosheets without holey pores. Particularly, NHCFs exhibit a high half-wave-potential (0.82V) anda limiting current density (5.4mAcm-2 ), close to those of commercial Pt-C catalysts. This study provides valuable clues on building mesoporous materials with in-plane holey pores as well as on the effect of pore structure and stacking mode of 2D materials on their electrocatalytic ORR performance.

Architecture- and Composition-Controlled Self-Assembly of Block Copolymers and Binary Mixtures With Crosslinkable Components: Chain Exchange Between Block Copolymer Nanoparticles.

Chain exchange behaviors in self-assembled block copolymer (BCP) nanoparticles (NPs) at room temperature are investigated through observations of structural differences between parent and binary systems of BCP NPs with and without crosslinked domains. Pairs of linear diblock or triblock, and branched star-like polystyrene-poly(2-vinylpyridine) (PS-PVP) copolymers that self-assemble in a PVP-selective mixed solvent into BCP NPs with definite differences in size and self-assembled morphology are combined by diverse mixing protocols and at different crosslinking densities to reveal the impact of chain exchange between BCP NPs. Clear structural evolution is observed by dynamic light scattering and AFM and TEM imaging, especially in a blend of triblock + star copolymer BCP NPs. The changes are ascribed to the chain motion inherent in the dynamic equilibrium, which drives the system to a new structure, even at room temperature. Chemical crosslinking of PVP corona blocks suppresses chain exchange between the BCP NPs and freezes the nanostructures at a copolymer crosslinking density (CLD) of ∼9%. This investigation of chain exchange behaviors in BCP NPs having architectural and compositional complexity and the ability to moderate chain motion through tailoring the CLD is expected to be valuable for understanding the dynamic nature of BCP self-assemblies and diversifying the self-assembled structures adopted by these systems. These efforts may guide the rational construction of novel polymer NPs for potential use, for example, as drug delivery platforms and nanoreactors.

Polymeric capsules and micelles as promising carriers of anticancer drugs.

Polymeric micelles and capsules are promising candidates for carriers of antineoplastic medications. Biodegradability and broadly defined biocompatibility are the key features that should always characterize polymers intended for medical applications. A well-designed delivery system ought to ensure the safe transport of chemotherapeutic agents to the target area and thus minimize systemic exposure to these drugs, limiting their toxic effect, preferably to the cancer cells. Polymeric micelles are often tailored for encapsulation of water-insoluble drugs. Micellar structures are usually fabricated as a result of self-assembly of various amphiphilic block copolymers in aqueous environment. More advanced methods are used to form capsules with a liquid core and a shell made of fused polymer nanoor microparticles. Such a coating can have homogeneous or heterogeneous composition. Janus and patchy capsules are usually characterized by more useful and advanced properties. Although some polymeric carriers are designed for a sustained release of the cargo, more sophisticated approaches involve payload liberation on demand under the influence of selected chemical or physical stimuli. The variety of available polymers and a wide range of possibilities of forming copolymers from different kind of monomers make polymeric materials ideal for the production of drug delivery systems with the desired properties. The aim of the present review is to sum up selected aspects of the use of polymeric micelles as carriers of cytostatic drugs, taking into account clinical applications. The additional objective is to show the studies on creating alternative systems based on stimuli-responsive capsules with shells made of polymeric particles.

Stimuli-Responsive Liquid Crystal Printheads for Spatial and Temporal Control of Polymerization.

Polymerization reactions triggered by stimuli play a pivotal role in materials science, with applications ranging from lithography to biomedicine to adaptive materials. However, the development of chemically triggered, stimuli-responsive systems that can confer spatial and temporal control on polymerization remains a challenge. Herein, chemical-stimuli-induced polymerization based on a liquid crystal (LC) printhead is presented. The LC responds to a local chemical stimulus at its aqueous interface, resulting in the ejection of initiator into the solution to trigger polymerization. Various LC printhead geometries are designed, allowing programming of: i) bulk solution polymerization, ii) synthesis of a thin surface-confined polymeric coating, iii) polymerization-induced self-assembly of block copolymers to form various nanostructures (sphere, worm-like, and vesicles), and iv) 3D polymeric structures printed according to local solution conditions. The approach is demonstrated using amphiphiles, multivalent ions, and biomolecules as stimuli.

Fabrication of Nanodevices Through Block Copolymer Self-Assembly

Block copolymer (BCP) self-assembly, as a novel bottom-up patterning technique, has received increasing attention in the manufacture of nanodevices because of its significant advantages of high resolution, high throughput, low cost, and simple processing. BCP self-assembly provides a very powerful approach to constructing diverse nanoscale templates and patterns that meet large-scale manufacturing practices. For the past 20 years, the self-assembly of BCPs has been extensively employed to produce a range of nanodevices, such as nonvolatile memory, bit-patterned media (BPM), fin field-effect transistors (FinFETs), photonic nanodevices, solar cells, biological and chemical sensors, and ultrafiltration membranes, providing a variety of configurations for high-density integration and cost-efficient manufacturing. In this review, we summarize the recent progress in the fabrication of nanodevices using the templates of BCP self-assembly, and present current challenges and future opportunities.

Sequential Infiltration Synthesis into Maltoheptaose and Poly(styrene): Implications for Sub-10 nm Pattern Transfer.

Vapor phase infiltration into a self-assembled block copolymer (BCP) to create a hybrid material in one of the constituent blocks can enhance the etch selectivity for pattern transfer. Multiple pulse infiltration into carbohydrate-based high-χ BCP has previously been shown to enable sub-10 nm feature pattern transfer. By optimizing the amount of infiltrated material, the etch selectivity should be further improved. Here, an investigation of semi-static sequential infiltration synthesis of trimethyl aluminum (TMA) and water into maltoheptaose (MH) films, and into hydroxyl-terminated poly(styrene) (PS-OH) films, was performed, by varying the process parameters temperature, precursor pulse duration, and precursor exposure length. It was found that, by decreasing the exposure time from 100 to 20 s, the volumetric percentage on included pure Al2O3 in MH could be increased from 2 to 40 vol% at the expense of a decreased infiltration depth. Furthermore, the degree of infiltration was minimally affected by temperature between 64 and 100 °C. Shorter precursor pulse durations of 10 ms TMA and 5 ms water, as well as longer precursor pulses of 75 ms TMA and 45 ms water, were both shown to promote a higher degree, 40 vol%, of infiltrated alumina in MH. As proof of concept, 12 nm pitch pattern transfer into silicon was demonstrated using the method and can be concluded to be one of few studies showing pattern transfer at such small pitch. These results are expected to be of use for further understanding of the mechanisms involved in sequential infiltration synthesis of TMA/water into MH, and for further optimization of carbohydrate-based etch masks for sub-10 nm pattern transfer. Enabling techniques for high aspect ratio pattern transfer at the single nanometer scale could be of high interest, e.g., in the high-end transistor industry.

Dissipative self-assembly of a dual-responsive block copolymer driven by a chemical oscillator

HypothesisCoupling stimuli-responsive building blocks with an oscillating reaction is an effective strategy to realize and investigate dissipative self-assembly. More importantly, since there is usually more than one component of which concentration periodically changes in a chemical oscillator, it can be expected that this strategy has the advantage of achieving dissipative self-assembly of the building blocks with dual- or even multi-responsiveness. ExperimentsWe realized the dissipative self-assembly of a pH- and iodine-responsive block copolymer, poly(ethylene oxide)-b-poly(2-vinyl pyridine) (PEO-P2VP), by coupling it with the IO3--SO32--Fe(CN)62- (ISF) oscillator, and investigated its rhythmic self-assembly behavior. Furthermore, we proposed a mechanistic model to simulate the kinetics of the ISF oscillator coupling with different amounts of PEO-P2VP. FindingsRhythmic core-shell reversal of the polymer micelles formed by PEO-P2VP was found in the ISF oscillator. The mechanistic model we proposed successfully reproduced the experimental oscillation and provided some data on the kinetics of the dual responsive self-assembly of PEO-P2VP. This line of research provided an example of realizing dissipative self-assembly of dual-responsive building blocks, which was seldom reported previously. It once again suggested that coupling with a suitable chemical oscillator is a promising strategy to have an insight into the kinetics of stimuli-responsive self-assembly.

Separated Micelles Formation of pH-Responsive Random and Block Copolymers Containing Phosphorylcholine Groups.

The self-assembly of pH-responsive random and block copolymers composed of 2-(N,N-diisopropylamino)ethyl methacrylate and 2-methacryloyloxyethyl phosphorylcholine was investigated in aqueous media. Their pH-responsive behaviors were investigated in aqueous media by dynamic light scattering (DLS) and fluorescence measurements using a pyrene hydrophobic fluorescence probe. In an acidic environment, these copolymers existed as single polymer chains that did not interact with each other. In contrast, upon increasing the pH of the solution above the critical value of ~8, separated micelles were formed in the mixture, which was indicated by bimodal distribution in DLS results with radius of 4.5 and 10.4 nm, corresponding to the random and block copolymer micelles, respectively. Fluorescence resonance energy transfer efficiencies were near to zero in the mixture of the donor labeled block and acceptor labeled random copolymers under both acidic and basic pH. These results demonstrated the coexistence of two distinct micelles.

Structure Regulation of Block Copolymer Assemblies in Emulsion Droplets by Adding a Selective Solvent

Generally, nanostructured polymer particles are prepared by 3D confined self-assembly (3D-CSA) of block copolymers (BCPs), while micelles are obtained through self-assembly of BCPs in dilute solutions. Herein, a facile yet robust strategy is developed to regulate the assembled structures of BCP, poly(styrene-block-4-vinylpyridine) (PS-b-P4VP), from nanostructured particles to micelles. The assemblies are prepared by an emulsion-solvent diffusion-induced self-assembly route, which is conducted by dialysis. A key feature of this strategy is that a P4VP-selective solvent (e.g., ethanol) is added to the dialysate to tune the interfacial behavior of the droplets and assembled structures of PS-b-P4VP. The authors' results reveal that in the presence of slight ethanol, the surface and internal structural transitions of nanostructured particles are caused by changes in the interfacial selectivity and packing parameter. Interestingly, interfacial instability, which results in the formation of micelles, is observed when the dialysate contains 50vol% ethanol or more. The reason can be ascribed to the decreased interface tension, which is induced by the increase in ethanol and enhanced solubility of P4VP. This facile strategy provides a new opportunity to bridge the gap between traditional 3D-CSA and solution self-assembly of BCPs, offering a promising route to engineer morphologies and nanostructures of polymeric assemblies.

Facile Achievement of Complementary Resistive Switching in Block Copolymer Micelle-Based Resistive Memories.

Interest in resistive random access memory (RRAM) has grown rapidly in recent years for realizing ultrahigh density data storage devices. However, sneak currents in these devices can result in misreading of the data, thus limiting the applicability of RRAM. Complementary resistive switching (CRS) memory consisting of two antiserial RRAMs can considerably reduce sneak currents; however, complicated device architectures and manufacturing processes still remain as challenges. Herein, an effective and simple approach for fabricating CRS memory devices using self-assembled block copolymer micelles is reported. Cu ions are selectively placed in the core of polystyrene-block-poly(2-vinylpyridine) spherical micelles, and a hexagonally packed micelle monolayer is prepared through spin-coating. The micelle monolayer can be a symmetrical resistive switching layer, because the micelles and Cu act as dielectric and active metals in memory devices, respectively. The locally enhanced electric field and Joule heating achieved by the structured Cu atoms inside the micelles promote metal ionization and ion migration in a controlled manner, thus allowing for position selectivity during resistive switching. The micelle-based memory device exhibits stable and reliable CRS behavior, with a nonoverlapping and narrow distribution of threshold voltages. Therefore, this approach is promising for fabricating CRS memory devices for high-performance and ultrahigh-density RRAM applications.

Block copolymer gyroids for nanophotonics: significance of lattice transformations

Abstract A gyroid crystal possesses a peculiar structural feature that can be conceptualized as a triply periodic surface with a constant mean curvature of zero. The exotic optical properties such as the photonic bandgap and optical chirality can emerge from this three-dimensional (3D) morphological feature. As such, gyroid crystals have been considered as the promising structures for photonic crystals and optical metamaterials. To date, several methods have been proposed to materialize gyroid crystals, including 3D printing, layer-by-layer stacking, two-photon lithography, interference lithography, and self-assembly. Furthermore, the discovery of Weyl points in gyroid crystals has further stimulated these advancements. Among such methods, the self-assembly of block copolymers (BCPs) is unique, because this soft approach can provide an easy-to-craft gyroid, especially at the nanoscale. The unit-cell scale of a gyroid ranging within 30–300 nm can be effectively addressed by BCP self-assembly, whereas other methods would be challenging to achieve this size range. Therefore, a BCP gyroid has provided a material platform for metamaterials and photonic crystals functioning at optical frequencies. Currently, BCP gyroid nanophotonics is ready to take the next step toward topological photonics beyond the conventional photonic crystals and metamaterials. In particular, the intrinsic lattice transformations occurring during the self-assembly of BCP into a gyroid crystal could promise a compelling advantage for advancing Weyl photonics in the optical regime. Lattice transformations are routinely considered as limitations, but in this review, we argue that it is time to widen the scope of the lattice transformations for the future generation of nanophotonics. Thus, our review provides a comprehensive understanding of the gyroid crystal and its lattice transformations, the relevant optical properties, and the recent progress in BCP gyroid self-assembly.

Single Gyroid Self-Assembled by Linear BABAB Pentablock Copolymer.

Although the double-gyroid (DG) structure has been commonly formed from the self-assembly of block copolymers, the single-gyroid (SG) structure is rarely reported. Moreover, the SG structure even shows better performance than DG in some optical applications. How to prepare the SG structure has become an attractive but challenging topic. We speculate that the SG structure can be stabilized by the synergistic effect of released packing frustration and stretched bridging block in AB-type block copolymers. Accordingly, we propose the minimum conditions for the design of architecture that enables the two mechanisms simultaneously. Following these conditions, a simple linear BABAB pentablock copolymer is successfully devised. SCFT calculations confirm that the SG phase can be stabilized by tailoring the architecture. Our work is hopeful to promote relevant experimental studies for engineering the unusual SG structure.

Block copolymer self-assembly assisted fabrication of laterally organized- and stacked- nanoarrays

Block copolymer (BCP) self-assembly processes are often seen as reliable techniques for advanced nanopatterning to achieve functional surfaces and create templates for nanofabrication. By taking advantage of the tunability in pitch, diameter and feature-to-feature separation of the self-assembled BCP features, complex, laterally organized- and stacked- multicomponent nanoarrays comprising of gold and polymer have been fabricated. The approaches not only demonstrate nanopatterning of up to two levels of hierarchy but also investigate how a variation in the feature-to-feature gap at the first hierarchy affects the self-assembly of polymer features at the second. Such BCP self-assembly enabled multicomponent nanoarray configurations are rarely achieved by other nanofabrication approaches and are particularly promising for pushing the boundaries of block copolymer lithography and in creating unique surface architectures and complex morphologies at the nanoscale.

The effects of molecular weight dispersity on block copolymer self-assembly

The influence of dispersity in the molecular weight distributions in the core forming block for block copolymer (BCP) self-assembly is analyzed via an automated flow synthesis approach.

A block copolymer templated approach for the preparation of nanoporous polymer structures and cellulose fiber hybrids by ozone treatment

Porous nanostructures were derived after self-assembly of amphiphilic block copolymers and subsequent ozone-mediated block segment degradation. Highly ordered pores were obtained for BCP films and for coatings at cellulose fibers’ surfaces.

The role of cooling rate in crystallization-driven block copolymer self-assembly.

Self-assembly of crystalline-coil block copolymers (BCPs) in selective solvents is often carried out by heating the mixture until the sample appears to dissolve and then allowing the solution to cool back to room temperature. In self-seeding experiments, some crystallites persist during sample annealing and nucleate the growth of core-crystalline micelles upon cooling. There is evidence in the literature that the nature of the self-assembled structures formed is independent of the annealing time at a particular temperature. There are, however, no systematic studies of how the rate of cooling affects self-assembly. We examine three systems based upon poly(ferrocenyldimethylsilane) BCPs that generated uniform micelles under typical conditions where cooling took pace on the 1–2 h time scale. For example, several of the systems generated elongated 1D micelles of uniform length under these slow cooling conditions. When subjected to rapid cooling (on the time scale of a few minutes or faster), branched structures were obtained. Variation of the cooling rate led to a variation in the size and degree of branching of some of the structures examined. These changes can be explained in terms of the high degree of supersaturation that occurs when unimer solutions at high temperature are suddenly cooled. Enhanced nucleation, seed aggregation, and selective growth of the species of lowest solubility contribute to branching. Cooling rate becomes another tool for manipulating crystallization-driven self-assembly and controlling micelle morphologies.

Si containing block copolymers quickly assemble into sub-6 nm domains

The directed self-assembly (DSA) of block copolymers (BCPs) is a potential patterning technology for sub-7 nm lithography.

Expedient Synthesis and Ring-Opening Metathesis Polymerization of Pyridinonorbornenes.

Pyridine-containing polymers are promising materials for a variety of applications from the capture of contaminants to the self-assembly of block copolymers. However, the innate Lewis basicity of the pyridine motif often hampers living polymerization catalyzed by transition-metal complexes. Herein, we report the expedient synthesis of pyridinonorbornene monomers via a [4+2] cycloaddition between 2,3-pyridynes and cyclopentadiene. Well-controlled ring-opening metathesis polymerization was enabled by careful structural design of the monomer. Polypyridinonorbornenes exhibited high Tg and Td, a promising feature for high-temperature applications. Investigation of the polymerization kinetics and of the reactivity of the chain ends shed light on the influence of nitrogen coordination on the chain-growth mechanism.

Kinetically stable sub-50 nm fluorescent block copolymer nanoparticles via photomediated RAFT dispersion polymerization for cellular imaging.

Self-assembled block copolymer nanoparticles (NPs) have emerged as major potential nanoscale vehicles for fluorescence bioimaging. The preparation of NPs with high yields possessing high kinetic stability to prevent the leakage of fluorophore molecules is crucial to their practical implementation. Here, we report a photomediated RAFT polymerization-induced self-assembly (PISA) yielding uniform and nanosized poly((oligo(ethylene glycol) acrylate)-block-poly(benzyl acrylate) particles (POEGA-b-PBzA) with a concentration of 22 wt%, over 20 times more than with micellization and nanoprecipitation. The spherical diblock copolymer nanoparticles have an average size of 10-50 nm controllable through the degree of polymerization of the stabilizing POEGA block. Subsequent dialysis against water and swelling with Nile red solution led to highly stable fluorescent NPs able to withstand the changes in concentration, ionic strength, pH or temperature. A PBzA/water interfacial tension of 48.6 mN m-1 hinders the exchange between copolymer chains, resulting in the trapping of NPs in a "kinetically frozen" state responsible for high stability. A spectroscopic study combining fluorescence and UV-vis absorption agrees with a preferential distribution of fluorophores in the outer POEGEA shell despite its hydrophobic nature. Nile red-doped POEGA-b-PBzA micelles without initiator residues and unimers but with high structural stability turn out to be noncytotoxic, and can be used for the optical imaging of cells. Real-time confocal fluorescence microscopy shows a fast cellular uptake using C2C12 cell lines in minutes, and a preferential localization in the perinuclear region, in particular in the vesicles.