Search Results (71)

Despite intense interest in the catalytic potential of transition metal oxide heterostructures, originating from their large surface area and tunable chemistry, the fabrication of well-defined multicomponent oxide coatings with controlled architectures remains challenging. Here, we demonstrate a simple and effective swelling-assisted sequential infiltration synthesis (SIS) strategy to fabricate hierarchically porous multicomponent metal-oxide electrocatalysts with tunable bimetallic composition. A combination of solution-based infiltration (SBI) of transition metals, iron (Fe), nickel (Ni), and cobalt (Co), into a block copolymer (PS73-b-P4VP28) template, followed by vapor-phase infiltration of alumina using sequential infiltration synthesis (SIS), was employed to synthesize porous, robust, conformal and transparent multicomponent metal-oxide coatings like Fe/AlO_x, Fe+Ni/AlO_x, and Fe+Co/AlO_x. Electrochemical assessments for the oxygen evolution reaction (OER) in a 0.1 M KOH electrolyte demonstrated that the Fe+Ni/AlO_x composite exhibited markedly superior catalytic activity, achieving an impressive onset potential of 1.41 V and a peak current density of 3.29 mA/cm². This superior activity reflects the well-known synergistic effect of alloying transition metals with a trace of Fe, which facilitates OER kinetics. Overall, our approach offers a versatile and scalable path towards the design of stable and efficient catalysts with tunable nanostructures, opening new possibilities for a wide range of electrochemical energy applications. Full article

Graphoepitaxial directed self-assembly (DSA) of block copolymers (BCPs) has emerged as a promising strategy for sub-30 nm line spacing patterning in semiconductor nanofabrication. Among the available BCP systems, polystyrene-block-poly (methyl methacrylate) (PS-b-PMMA) has been extensively utilized due to its well-characterized phase behavior and compatibility with standard lithographic processes. However, achieving a high-fidelity pattern with PS-b-PMMA remains challenging, owing to its limited etch contrast and reliance on UV-assisted degradation for PMMA removal. In this study, we report the synthesis of an acid-cleavable lamellar BCP, PS-N=CH-PMMA, incorporating a dynamic Schiff base (-N=CH-) linkage at the junction. This functional design enables UV-free wet etching, allowing selective removal of PMMA domains using glacial acetic acid. The synthesized copolymers retain the self-assembly characteristics of PS-b-PMMA and form vertically aligned lamellar nanostructures, with domain spacings tunable from 36.1 to 40.2 nm by varying the PMMA block length. When confined within 193i-defined trench templates with a critical dimension (CD) of 55 nm (trench width), these materials produced well-ordered one-space-per-trench patterns with interline spacings tunable from 15 to 25 nm, demonstrating significant line spacing shrinkage relative to the original template CD. SEM and FIB-TEM analyses confirmed that PS-N=CH-PMMA exhibits markedly improved vertical etch profiles and reduced PMMA residue compared to PS-b-PMMA, even without UV exposure. Furthermore, Ohta–Kawasaki simulations revealed that trench sidewall angle critically influences PS distribution and residual morphology. Collectively, this work demonstrates the potential of dynamic covalent chemistry to enhance the wet development fidelity of BCP lithography and offers a thermally compatible, UV-free strategy for sub-30 nm nanopatterning. Full article

Directed self-assembly (DSA) lithography, a cutting-edge technology based on the self-assembly of block copolymers (BCPs), has received significant attention in recent years. Combining DSA with established lithography technologies, such as extreme ultraviolet (EUV), deep ultraviolet (DUV), electron beam lithography, and nanoimprint lithography, significantly enhances the resolution of target patterns and device density. Currently, there are two commonly used methods in DSA: graphoepitaxy, employing lithographically defined topographic templates to guide BCP assembly, and chemoepitaxy, utilizing chemically patterned surfaces with precisely controlled interfacial energies to direct nanoscale phase segregation. Through novel DSA lithography technology, nanoscale patterns with smaller feature sizes and higher densities can be obtained, realizing the miniaturization of hole and line patterns and pitch multiplication and improving the roughness and local critical dimension uniformity (LCDU). It is gradually becoming one of the most promising and advanced lithography techniques. DSA lithography technology has been applied in logic, memory, and optoelectronic device fabrications. Full article

In this review work, the different routes and methods for preparing hybrid materials based on nanostructured block copolymers (BCPs) and magnetic nanoparticles (MNPs) are analyzed, as they can be potentially employed in different sectors like biomedicine, electronic or optoelectronic devices, data storing devices, etc. The first procedure for their preparation consists of the nanostructuring of BCPs in the presence of previously synthesized NPs by modifying their surface for increasing compatibility with the matrix or employing magnetic fields for NP orientation, which can also promote the orientation of nanodomains. Surface modification with surfactants led to the selective confinement of NPs depending on the interaction (mainly hydrogen bonding) degree and their intensity. Surface modification with brushes can be performed by three methods, including grafting from, grafting to, or grafting through. Those methods are compared in terms of success for the positioning and confinement of NPs in the desired domains, showing the crucial importance of brush length and grafting density, as well as of NP amount and modification degree in the self-assembled morphology. Regarding the use of external magnetic fields, the importance of relative amounts of MNPs and BCPs employed and that of the magnetic field intensity for the orientation of the NPs and the nearby BCP domains is shown. The second procedure, consisting of the in situ synthesis of NPs inside the nanodomains by a reduction in the respective metallic ions or employing metal-containing BCPs for the generation of MNP patterns or arrays, is also shown. In all cases, the transference of magnetic properties to the nanocomposite was successful. Finally, a brief summary of some aspects about the use of BCPs for the synthesis, encapsulation, and release of MNPs is shown, as they present potential biomedical applications such as cancer treatment, among others. Full article

Diblock copolymers (BCP) consisting of poly(methyl methacrylate) (PMMA) and poly(1H,1H,2H,2H-perfluorodecyl methacrylate) (PsfMA) blocks are employed as templates for controlled dispersion and localization of multi-walled carbon nanotubes (MWCNT). Short MWCNT are modified with perfluoroalkyl groups to increase the compatibility between MWCNT and the semifluorinated (PsfMA) phase and to promote a defined arrangement of MWCNT in the BCP morphology. Thin BCP and BCP/MWCNT composite films are prepared by dip-coating using tetrahydrofuran as solvent with dispersed MWCNT. Atomic force microscopy, scanning and transmission electron microscopy reveal a strong tendency of the BCP to form micelle-like domains consisting of a PMMA shell and a semifluorinated PsfMA core, embedded in a soft phase, containing also semifluorinated blocks. MWCNT preferentially localized in the embedding phase outside the micelles. Perfluoroalkyl-modification leads to significant improvement in the dispersion of MWCNT, both in the polymer solution and the resulting nanocomposite film due to increased interaction of MWCNT with the semifluorinated side chains in the soft phase outside the micelle domains. As a result, reliable electrical conductivity is observed in contrast to films with non-modified MWCNT. Thus, well-dispersed, modified MWCNT provide a defined electrical conduction path at the micrometer level, which is interesting for applications in electronics and vapor sensing. Full article

Designing bifunctional catalysts for efficient hydroisomerization of phenanthrene to alkyl-adamantane is a great challenge for producing high-density fuels. Herein, a bifunctional Pt catalyst was fabricated by developing hierarchical H-MSY-T zeolites with an NOA-co strategy. The influence of different mesopore template agents on the hierarchical structure of H-MSY-T zeolite was investigated. Effective regulation of pore structure and acid distribution of zeolites was achieved by adjusting the templating agents. The block copolymer P123 promoted the formation of mesoporous structures via self-assembly with a large mesopore centered at 8 nm. Large mesoporous structure and suitable distribution of Bronsted acid boosted the hydroisomerization of phenanthrene. The highest alkyl-adamantane yield of 45.9 wt% was achieved on the Pt/MSY-P1 catalyst and a reaction network of hydroisomerization was proposed. This work provides guidance to design highly selective bifunctional catalysts for the one-step hydroconversion of tricyclic aromatic hydrocarbons into high-density fuels. Full article

The development of photo-/electro-chemical and flexible electronics has stimulated research in catalysis, informatics, biomedicine, energy conversion, and storage applications. Gels (e.g., aerogel, hydrogel) comprise a range of polymers with three-dimensional (3D) network structures, where hydrophilic polyacrylamide, polyvinyl alcohol, copolymers, and hydroxides are the most widely studied for hydrogels, whereas 3D graphene, carbon, organic, and inorganic networks are widely studied for aerogels. Encapsulation of functional species with hydrogel building blocks can modify the optoelectronic, physicochemical, and mechanical properties. In addition, aerogels are a set of nanoporous or microporous 3D networks that bridge the macro- and nano-world. Different architectures modulate properties and have been adopted as a backbone substrate, enriching active sites and surface areas for photo-/electro-chemical energy conversion and storage applications. Fabrication via sol–gel processes, module assembly, and template routes have responded to professionalized features and enhanced performance. This review presents the most studied hydrogel materials, the classification of aerogel materials, and their applications in flexible sensors, batteries, supercapacitors, catalysis, biomedical, thermal insulation, etc. Full article

Starting from poly(4-vinylpyridine) ((P4VP)_n), poly(2-vinylpyridine) ((P2VP)_n), and [N=P(O₂CH₂CF₃)]_m-b-P2VP₂₀ block copolymers, a series of metal-containing homopolymers, (P4VP)_n⊕MX_m, (P2VP)_n⊕MX_m, and [N=P(O₂CH₂CF₃)]_m-b-P2VP₂₀]⊕MX_m MX_m = PtCl₂, ZnCl₂, and Eu(NO₃)₃, have been successfully prepared by using a direct and simple solution methodology. Solid-state pyrolysis of the prepared metal-containing polymeric precursors led to the formation of a variety of different metallic and metal oxide nanoparticles (Pt, ZnO, Eu₂O₃, and EuPO₄) depending on the composition and nature of the polymeric template precursor. Thus, whereas Eu₂O₃ nanostructures were obtained from europium-containing homopolymers ((P4VP)_n⊕MX_m and (P2VP)_n⊕MX_m), EuPO₄ nanostructures were achieved using phosphorus-containing block copolymer precursors, [N=P(O₂CH₂CF₃)]_m-b-P2VP₂₀]⊕MX_m with MX_m = Eu(NO₃)₃. Importantly, and although both Eu₂O₃ and EuPO₄ nanostructures exhibited a strong luminescence emission, these were strongly influenced by the nature and composition of the macromolecular metal-containing polymer template. Thus, for P2VP europium-containing homopolymers ((P4VP)_n⊕MX_m and (P2VP)_n⊕MX_m), the highest emission intensity corresponded to the lowest-molecular-weight homopolymer template, [P4VP(Eu(NO₃)₃]₆₀₀₀, whereas the opposite behavior was observed when block copolymer precursors, [N=P(O₂CH₂CF₃)]_m-b-P2VP₂₀]⊕MX_m MX_m= Eu(NO₃)₃, were used (highest emission intensity corresponded to [N=P(O₂CH₂CF₃)]₁₀₀-b-[P2VP(Eu(NO₃)₃)_x]₂₀). The intensity ratio of the emission transitions: ⁵D₀ → ⁷F₂/⁵D₀ → ⁷F₁, suggested a different symmetry around the Eu³⁺ ions depending on the nature of the polymeric precursor, which also influenced the sizes of the prepared Pt°, ZnO, Eu₂O₃, and EuPO₄ nanostructures. Full article

The microphase separation of high-molecular-weight block copolymers into nanostructured films is strongly dependent on the surface fields. Both, the chain mobility and the effective interaction parameters can lead to deviations from the bulk morphologies in the structures adjacent to the substrate. Resolving frustrated morphologies with domain period L₀ above 100 nm is an experimental challenge. Here, solvothermal annealing was used to assess the contribution of elevated temperatures of the vapor T_v and of the substrate T_s on the evolution of the microphase-separated structures in thin films symmetric of polystyrene-b-poly(2vinylpyridine) block copolymer (PS-PVP) with L₀ about 120 nm. Pronounced topographic mesh-like and stripe patterns develop on a time scale of min and are attributed to the perforated lamella (PL) and up-standing lamella phases. By setting T_v/T_s combinations it is possible to tune the sizes of the resulting PL patterns by almost 10%. Resolving chemical periodicity using selective metallization of the structures revealed multiplication of the topographic stripes, i.e., complex segregation of the component within the topographic pattern, presumably as a result of morphological phase transition from initial non-equilibrium spherical morphology. Reported results reveal approaches to tune the topographical and chemical periodicity of microphase separation of high-molecular-weight block copolymers under strong confinement, which is essential for exploiting these structures as functional templates. Full article

Nanopatterning methods utilizing block copolymer (BCP) self-assembly are attractive for semiconductor fabrication due to their molecular precision and high resolution. Grafted polymer brushes play a crucial role in providing a neutral surface conducive for the orientational control of BCPs. These brushes create a non-preferential substrate, allowing wetting of the distinct chemistries from each block of the BCP. This vertically aligns the BCP self-assembled lattice to create patterns that are useful for semiconductor nanofabrication. In this review, we aim to explore various methods used to tune the substrate and BCP interface toward a neutral template. This review takes a historical perspective on the polymer brush methods developed to achieve substrate neutrality. We divide the approaches into copolymer and blended homopolymer methods. Early attempts to obtain neutral substrates utilized end-grafted random copolymers that consisted of monomers from each block. This evolved into side-group-grafted chains, cross-linked mats, and block cooligomer brushes. Amidst the augmentation of the chain architecture, homopolymer blends were developed as a facile method where polymer chains with each chemistry were mixed and grafted onto the substrate. This was largely believed to be challenging due to the macrophase separation of the chemically incompatible chains. However, innovative methods such as sequential grafting and BCP compatibilizers were utilized to circumvent this problem. The advantages and challenges of each method are discussed in the context of neutrality and feasibility. Full article

The porous architectures of oxygen cathodes are highly desired for high-capacity lithium–oxygen batteries (LOBs) to support cathodic catalysts and provide accommodation for discharge products. However, controllable porosity is still a challenge for laminated cathodes with cathode materials and binders, since polymer binders usually shield the active sites of catalysts and block the pores of cathodes. In addition, polymer binders such as poly(vinylidene fluoride) (PVDF) are not stable under the nucleophilic attack of intermediate product superoxide radicals in the oxygen electrochemical environment. The parasitic reactions and blocking effect of binders deteriorate and then quickly shut down the operation of LOBs. Herein, the present work proposes a binder-free three-dimensional (3D) porous graphene (PG) cathode for LOBs, which is prepared by the self-assembly and the chemical reduction of GO with triblock copolymer soft templates (Pluronic F127). The interconnected mesoporous architecture of resultant 3D PG cathodes achieved an ultrahigh capacity of 10,300 mAh g⁻¹ for LOBs. Further, the cathodic catalysts ruthenium (Ru) and manganese dioxide (MnO₂) were, respectively, loaded onto the inner surface of PG cathodes to lower the polarization and enhance the cycling performance of LOBs. This work provides an effective way to fabricate free-standing 3D porous oxygen cathodes for high-performance LOBs. Full article

Photocatalytic self-cleaning coatings with a high surface area are important for a wide range of applications, including optical coatings, solar panels, mirrors, etc. Here, we designed a highly porous TiO₂ coating with photoinduced self-cleaning characteristics and very high hydrophilicity. This was achieved using the swelling-assisted sequential infiltration synthesis (SIS) of a block copolymer (BCP) template, which was followed by polymer removal via oxidative thermal annealing. The quartz crystal microbalance (QCM) was employed to optimize the infiltration process by estimating the mass of material infiltrated into the polymer template as a function of the number of SIS cycles. This adopted swelling-assisted SIS approach resulted in a smooth uniform TiO₂ film with an interconnected network of pores. The synthesized film exhibited good crystallinity in the anatase phase. The resulting nanoporous TiO₂ coatings were tested for their functional characteristics. Exposure to UV irradiation for 1 h induced an improvement in the hydrophilicity of coatings with wetting angle reducing to unmeasurable values upon contact with water droplets. Furthermore, their self-cleaning characteristics were tested by measuring the photocatalytic degradation of methylene blue (MB). The synthesized porous TiO₂ nanostructures displayed promising photocatalytic activity, demonstrating the degradation of approximately 92% of MB after 180 min under ultraviolet (UV) light irradiation. Thus, the level of performance was comparable to the photoactivity of commercial anatase TiO₂ nanoparticles of the same quantity. Our results highlight a new robust approach for designing hydrophilic self-cleaning coatings with controlled porosity and composition. Full article

A series of polyacrylonitrile (PAN)-based block copolymers with poly(methyl methacrylate) (PMMA) as sacrificial bock were synthesized by atom transfer radical polymerization and used as precursors for the synthesis of porous carbons. The carbons enriched with O- and S-containing groups, introduced by controlled oxidation and sulfuration, respectively, were characterized by Raman spectroscopy, scanning electron microscopy, and X-ray photoelectron spectrometry, and their surface textural properties were measured by a volumetric analyzer. We observed that the presence of sulfur tends to modify the structure of the carbons, from microporous to mesoporous, while the use of copolymers with a range of molar composition PAN/PMMA between 10/90 and 47/53 allows the obtainment of carbons with different degrees of porosity. The amount of sacrificial block only affects the morphology of carbons stabilized in oxygen, inducing their nanostructuration, but has no effect on their chemical composition. We also demonstrated their suitability for separating a typical N₂/CO₂ post-combustion stream. Full article

Block copolymers, known for their capacity to undergo microphase separation, spontaneously yield various periodic nanostructures. These precisely controlled nanostructures have attracted considerable interest due to their potential applications in microfabrication templates, conducting films, filter membranes, and other areas. However, it is crucial to acknowledge that microphase-separated structures typically exhibit random alignment, making alignment control a pivotal factor in functional material development. To address this challenge, researchers have explored the use of block copolymers containing liquid-crystalline (LC) polymers, which offer a promising technique for alignment control. The molecular structure and LC behavior of these polymers significantly impact the morphology and alignment of microphase-separated structures. In this study, we synthesized LC diblock copolymers with cyano-terminated phenyl benzoate moieties and evaluated the microphase-separated structures and molecular alignment behaviors. The LC diblock copolymers with a narrow molecular weight distribution were synthesized by atom transfer radical polymerization. Small angle X-ray scattering measurements revealed that the block copolymers exhibit smectic LC phases and form cylinder structures with a lattice period of about 18 nm by microphase separation. The examination of block copolymer films using polarized optical microscopy and polarized UV-visible absorption spectroscopy corroborated that the LC moieties were uniaxially aligned along the alignment treatment direction. Full article

This review article emphasizes the current enlargements in the formation and properties of the various nanostructured aggregates resulting from the self-assembly of a variety of block copolymers (BCPs) in an aqueous solution. The development of the different polymerization techniques which produce polymers with a desired predetermined molecular weight and low polydispersity is investigated with regard to their technological and biomedical applications; in particular, their applications as vehicles for drug delivery systems are considered. The solution behavior of amphiphilic BCPs and double-hydrophilic block copolymers (DHBCs), with one or both blocks being responsive to any stimulus, is discussed. Polyion complex micelles (PICMs)/polymersomes obtained from the electrostatic interaction of a polyelectrolyte-neutral BCP with oppositely charged species are also detailed. Lastly, polymerization-induced self-assembly (PISA), which forms nanoscale micellar aggregates with controlled size/shape/surface functionality, and the crystallization-driven self-assembly of semicrystalline BCPs facilitated when one block of the BCP is crystallizable, are also revealed. The scalability of the copolymeric micelles in the drug delivery systems and pharmaceutical formations that are currently being used in clinical trials, research, or preclinical testing is emphasized as these micelles could be used in the future to create novel nanomedicines. The updated literature and the future perspectives of BCP self-assembly are considered. Full article