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We describe a versatile and scalable strategy toward long-range and periodically ordered mesoporous alumina (Al2O3) structures by evaporation-induced self-assembly of a structure-directing ABA triblock copolymer (F127) mixed with aluminum tri-sec-butoxide-derived sol additive. We found that the separate preparation of the alkoxide sol-gel reaction before mixing with the block copolymer enabled access to a relatively unexplored parameter space of copolymer-to-additive composition, acid-to-metal molar ratio, and solvent, yielding ordered mesophases of two-dimensional (2D) lamellar, hexagonal cylinder, and 3D cage-like cubic lattices, as well as multiscale hierarchical ordered structures from spinodal decomposition-induced macro- and mesophase separation. Thermal annealing in air at 900 °C yielded well-ordered mesoporous crystalline γ-Al2O3 structures and hierarchically porous γ-Al2O3 with 3D interconnected macroscale and ordered mesoscale pore networks. The ordered Al2O3 structures exhibited tunable pore sizes in three different length scales

Two-dimensional (2D) nanomaterials (NM) have emerged as promising platforms for antibacterial applications. However, the inherent “flatness” of 2D NM often limits the loading of antimicrobial components needed for synergistic bactericidal actions. Here, inspired by the highly ornamented siliceous frustules of diatoms, we prepared 2D ultrathin (

This Communication describes a facile strategy coupling block copolymer-directed self-assembly with high-power Joule heating to form highly crystalline and long-range ordered mesoporous oxide and carbon nanostructures in just a few seconds. The combined approach is compatible with various self-assembled hybrid systems, generating mesoporous composites of γ-Al2O3-carbon, γ-Al2O3/MgO-carbon and anatase-TiO2-carbon with p6mm symmetry, as well as mesoporous non-close-packed carbon structures. Removing the polymer/carbon gives well-defined mesoporous all-γ-Al2O3 and all-anatase-TiO2 structures. Impregnation of chloroplatinic acid followed by Joule heating yields platinum nanoparticles decorated on the channel walls of mesoporous γ-Al2O3-carbon structures. The rapid formation of thermally stable and periodically ordered crystalline oxide, carbon and oxide-carbon structures.

This report describes a simple one-pot soft-templating and ammonolysis-free approach to synthesize mesoporous crystalline titanium oxynitride by combining block copolymer-directed self-assembly with metal sol and urea precursors. The Pluronic F127 triblock copolymer was employed to structure-direct titanium-oxo-acetate sol nanoparticles and urea-formaldehyde into ordered hybrid mesostructured monoliths. The hybrid composites were directly converted into mesoporous crystalline titanium oxynitride and retained macroscale monolithic integrity up to 800 °C under nitrogen. Notably, the urea-formaldehyde additive provided nitrogen and rigid support to the inorganic mesostructure during crystallization. The resultant mesoporous titanium oxynitride exhibited good electrochemical catalytic activity toward hydrogen evolution reaction in 1 M KOH aqueous medium under applied bias. Our results suggest an inexpensive and safe pathway to generate ordered mesoporous crystalline metal oxynitride structures suitable for catalyst and energy-storage applications. National Research Foundation (NRF) Accepted version This work was supported by a startup grant from Nanyang Technological University, Singapore. S.M. and W.M.Jr. wish to acknowledge financial support from the National Research Foundation of Singapore (NRF) Investigatorship Award (NRFI 2017-08). This work made use of research facilities at the Facility for Analysis, Characterization, Testing and Simulation (FACTS), Nanyang Technological University, Singapore. The authors gratefully acknowledge J. C. Kuan, R. Lee, T. Salim, G. L. Seah and Y. Y. Tay for kind experimental assistance and discussion.

Despite extensive studies on mesoporous silica since the early 1990s, the synthesis of two‐dimensional (2D) silica nanostructures remains challenging. Here, mesoporous silica is synthesized at an interface between two immiscible solvents under conditions leading to the formation of 2D superstructures of silica cages, the thinnest mesoporous silica films synthesized to date. Orientational correlations between cage units increase with increasing layer number controlled via pH, while swelling with oil and mixed surfactants increase micelle size dispersity, leading to complex clathrate type structures in multilayer superstructures. The results suggest that a three‐dimensional (3D) crystallographic registry within cage‐like superstructures emerges as a result of the concerted 3D co‐assembly of the organic and inorganic components. Mesoporous 2D superstructures can be fabricated over macroscopic film dimensions and stacked on top of each other. The realization of previously inaccessible mesoporous silica heterostructures with separation or catalytic properties unachievable via conventional bulk syntheses is envisioned. MOE (Min. of Education, S’pore) Accepted version

Hierarchically porous structured materials with multifunctional properties and higher order complexities are highly desirable for many applications such as separation and energy storage. Here we describe the generation of hierarchically porous organic and inorganic structures coupling block copolymer self-assembly with spatially- and temporally controlled laser irradiation. A simple and rapid laser irradiation of block copolymer-directed hybrid films with a continuous wave laser in the sub-millisecond timescales enabled synthesis of 3D mesoporous polymer structures and shapes. Backfilling the polymer template with amorphous silicon followed by pulsed laser annealing enabled transient melt transformation of amorphous precursors into 3D mesoporous crystalline silicon nanostructures. Mechanistic studies on laser-induced crystalline silicon nanostructure formation during the nanosecond silicon melt-crystallization process and polymer template stability at temperatures above 1250 degrees Celsius are highlighted. Ministry of Education (MOE) Accepted version Singapore Ministry of Education AcRF Tier 1 grant (2018-T1-001-084)

We highlight two recent approaches operating far from equilibrium for the synthesis of hierarchical porous thin film materials by coupling block copolymer-directed self-assembly with transient laser heating. In first block copolymer-induced writing by transient heating experiments, or B-WRITE, an all-organic block copolymer-resols hybrid film is heated by submillisecond carbon dioxide laser irradiation, directly generating 3D mesoporous continuous resin structures and shapes. Harnessing the highly unique resin materials properties under laser heating conditions, in the second approach block copolymer-directed resin templating is coupled with nanosecond pulsed excimer laser annealing to generate complementary crystalline silicon nanostructures. The underlying structure formation mechanisms for such laser-induced organic and inorganic nanostructured materials are discussed, emphasizing that the nonequilibrium nature of these transient laser annealing approaches opens up vast and new processing windows beyond traditional stability limits of organic polymer materials. Finally, we highlight opportunities and challenges for possible future research directions and applications of laser-induced block copolymer-directed hierarchical porous materials formation including structure control, materials diversification, scale-up, on-chip applications, and additive manufacturing, which may provide solutions in areas as diverse as catalysis, sensing, and energy storage and conversion. MOE (Min. of Education, S’pore) Published version

Evaporation-induced asymmetric triblock terpolymer membrane formation from polyisoprene-block-polystyrene-block-poly(4-vinylpyridine) (ISV) that relies on self-assembly of doctor bladed solutions was studied using in situ grazing incidence small-angle X-ray scattering (GISAXS). Transient ordered structures were observed for two ISV terpolymers at intermediate evaporation times in the top surface layers of the films as a function of molar mass and solution concentration. Analysis of the GISAXS patterns revealed the evolution from disordered to ordered structures including a transition from body-centered cubic (BCC) to simple cubic (SC) lattices and finally to an amorphous mesoscale structure. The BCC to SC transition solves an apparent structural puzzle resulting from comparisons of, on one side, earlier quiescent solution SAXS studies suggesting BCC terpolymer micelle structures at higher concentrations and, on the other side, electron microscopy studies consistent with SC lattices originating from polyme...

Stimuli-responsive materials have attracted great interest in catalysis, sensing, and drug delivery applications and are typically constituted by soft components. We present a one-pot synthetic method for a type of inorganic silica-based shape change material that is responsive to water vapor exposure. After the wetting treatment, the cross-sectional shape of aminated mesoporous silica nanoparticles (MSNs) with hexagonal pore lattice changed from hexagonal to six-angle-star, accompanied by the loss of periodic mesostructural order. Nitrogen sorption measurements suggested that the wetting treatment induced a shrinkage of mesopores resulting in a broad size distribution and decreased mesopore volume. Solid-state (29)Si nuclear magnetic resonance (NMR) spectroscopy of samples after wetting treatment displayed a higher degree of silica condensation, indicating that the shape change was associated with the formation of more siloxane bonds within the silica matrix. On the basis of material characterization results, a mechanism for the observed anisotropic shrinkage is suggested based on a buckling deformation induced by capillary forces in the presence of a threshold amount of water vapor available beyond a humidity of about 50%. The work presented here may open a path toward novel stimuli-responsive materials based on inorganic components.

Three-dimensional (3D) mesoporous thin films with sub-100 nm periodic lattices are of increasing interest as templates for a number of nanotechnology applications, yet are hard to achieve with conventional top-down fabrication methods. Block copolymer self-assembly derived mesoscale structures provide a toolbox for such 3D template formation. In this work, single (alternating) gyroidal and double gyroidal mesoporous thin-film structures are achieved via solvent vapor annealing assisted co-assembly of poly(isoprene-block-styrene-block-ethylene oxide) (PI-b-PS-b-PEO, ISO) and resorcinol/phenol formaldehyde resols. In particular, the alternating gyroid thin-film morphology is highly desirable for potential template backfilling processes as a result of the large pore volume fraction. In situ grazing-incidence small-angle X-ray scattering during solvent annealing is employed as a tool to elucidate and navigate the pathway complexity of the structure formation processes. The resulting network structures are resistant to high temperatures provided an inert atmosphere. The thin films have tunable hydrophilicity from pyrolysis at different temperatures, while pore sizes can be tailored by varying ISO molar mass. A transfer technique between substrates is demonstrated for alternating gyroidal mesoporous thin films, circumventing the need to re-optimize film formation protocols for different substrates. Increased conductivity after pyrolysis at high temperatures demonstrates that these gyroidal mesoporous resin/carbon thin films have potential as functional 3D templates for a number of nanomaterials applications. Accepted version

This report describes the generation of three-dimensional (3D) crystalline silicon continuous network nanostructures by coupling all-organic block copolymer self-assembly-directed resin templates with low-temperature silicon chemical vapor deposition and pulsed excimer laser annealing. Organic 3D mesoporous continuous-network resin templates were synthesized from the all-organic self-assembly of an ABC triblock terpolymer and resorcinol–formaldehyde resols. Nanosecond pulsed excimer laser irradiation induced the transient melt transformation of amorphous silicon precursors backfilled in the organic template into complementary 3D mesoporous crystalline silicon nanostructures with high pattern fidelity. Mechanistic studies on laser-induced crystalline silicon nanostructure formation revealed that the resin template was carbonized during transient laser-induced heating on the milli- to nanosecond timescales, thereby imparting enhanced thermal and structural stability to support the silicon melt–crystallization process at temperatures above 1250 °C. Photoablation of the resin material under pulsed excimer laser irradiation was mitigated by depositing an amorphous silicon overlayer on the resin template. This approach represents a potential pathway from organic block copolymer self-assembly to alternative functional hard materials with well-ordered 3D morphologies for potential hybrid photovoltaics, photonic, and energy storage applications. MOE (Min. of Education, S’pore) Accepted version

Laser patterning polymer membranes Porous materials are useful for membranes, filters, energy conversion, and catalysis. Their utility often depends on the ability to finely control both the pore sizes and their connectivity. Tan et al. prepared porous thin films of block copolymers mixed with phenol-formaldehyde resins (resols) on silicon substrates using a simple laser process. On exposure to ultraviolet light, rapid heating of the substrate causes polymerization of the resols and decomposition of the block copolymer. This method allows direct patterning of the films on a local scale, with tunable pore sizes and size distributions. Science , this issue p. 54

Selective degradation of block copolymer templates and backfilling the open mesopores is an effective strategy for the synthesis of nanostructured hybrid and inorganic materials. Incorporation of more than one type of inorganic material in orthogonal ways enables the synthesis of multicomponent nanomaterials with complex yet well-controlled architectures; however, developments in this field have been limited by the availability of appropriate orthogonally degradable block copolymers for use as templates. We report the synthesis and self-assembly into cocontinuous network structures of polyisoprene-block-polystyrene-block-poly(propylene carbonate) where the polyisoprene and poly(propylene carbonate) blocks can be orthogonally removed from the polymer film. Through sequential block etching and backfilling the resulting mesopores with different metals, we demonstrate first steps toward the preparation of three-component polymer-inorganic hybrid materials with two distinct metal networks. Multiblock copolymers in which two blocks can be degraded and backfilled independently of each other, without interference from the other, may be used in a wide range of applications requiring periodically ordered complex multicomponent nanoarchitectures.

A one-pot synthesis approach is described to generate ordered mesoporous crystalline γ-alumina–carbon composites and ordered mesoporous crystalline γ-alumina materials via the combination of soft and hard-templating chemistries using block copolymers as soft structure-directing agents. Periodically ordered alumina hybrid mesostructures were generated by self-assembly of a poly(isoprene)-block-poly(styrene)-block-poly(ethylene oxide) terpolymer, n-butanol and aluminum tri-sec-butoxide derived sols in organic solvents. The triblock terpolymer was converted into a rigid carbon framework during thermal annealing under nitrogen to support and preserve the ordered mesoporous crystalline γ-alumina–carbon composite structures up to 1200 °C. The carbon matrix was subsequently removed in a second heat treatment in air to obtain ordered mesoporous crystalline γ-alumina structures. Such thermally stable, highly crystalline, and periodically ordered mesoporous ceramic and ceramic–carbon composite materials may be promising candidates for various high temperature catalysis, separation, and energy-related applications.

We investigate the thermally induced morphological and crystalline development of methylammonium lead mixed halide perovskite (CH 3NH3PbI3-xClx) thin films and photovoltaic device performance with meso-superstructured and planar heterojunction architectures. We observe that a short rapid thermal annealing at 130 °C leads to the growth of large micron-sized textured perovskite domains and improved the short circuit currents and power conversion efficiencies up to 13.5% for the planar heterojunction perovskite solar cells. This work highlights the criticality of controlling the thin film crystallization mechanism of hybrid perovskite materials for high-performing photovoltaic applications. © 2014 American Chemical Society.

A novel strategy for fabrication of ordered ceramic–metal nanocomposites was demonstrated by multifunctional block copolymer/metal nanoparticle self-assembly. Hybrid organic–inorganic block copolymer poly(3-methacryloxypropyl-T8-heptaisobutyl-polyhedral oligomeric silsesquioxane-block-N,N-dimethylaminoethyl methacrylate) was synthesized and used as a bi-functional structure directing agent for ligand-stabilized platinum nanoparticles to form ordered organic–inorganic nanocomposites with dense loading of inorganic species in both microphase separated domains. Subsequently, thin films of the hybrid material were converted to ordered silica (ceramic)–platinum (metal) nanocomposites via UV-assisted ozonolysis. This is the first time ordered ceramic–metal nanocomposites were achieved through a bottom-up approach, opening up opportunities for the design and synthesis of a broad range of ordered inorganic–inorganic nanocomposites.

In the colloidal self-assembly of charged particles on surfaces with opposite polarity, disorder often dominates. In this report, we show that ionic strength, volume fraction, and solvent evaporation temperature can be optimized in the vertical deposition method to yield hexagonal close-packed monolayer arrays with positively charged colloids on negatively charged bare glass. We further extend our study to form well-defined binary two-dimensional superlattices with oppositely charged monolayers grown layer-by-layer. Our results suggest that the lack of particulate mobility in oppositely charged systems is the main cause of disorder, and maximum mobility is attained when all three growth parameters are finely adjusted to increase the time scale for the particles to stabilize and order during crystal growth in these attractive systems. A clear understanding and control of the collective behavior of highly mobile colloids could lead to the creation of greater diversity of nanoarchitectures.

We investigate the two-dimensional (2D) colloidal structures formed by oppositely charged polystyrene monolayers grown layer-by-layer, where the electrostatic forces are recruited to assist in the packing of the layers. Our results show a transition through several 2D-superlattices to more close-packed structures with increasing ionic strength. The observed geometrical packing constraints of the 2D-superlattice structures agree well with the estimated Debye screening length of the electric double layer. By tuning interaction forces between charged colloids, electrostatic interactions could enhance the template-directed self-assembly process to achieve more complex and diverse structures.

Block copolymer self-assembly is used to synthesize three-dimensionally continuous gyroidal mesoporous superconductors of niobium nitride., Superconductors with periodically ordered mesoporous structures are expected to have properties very different from those of their bulk counterparts. Systematic studies of such phenomena to date are sparse, however, because of a lack of versatile synthetic approaches to such materials. We demonstrate the formation of three-dimensionally continuous gyroidal mesoporous niobium nitride (NbN) superconductors from chiral ABC triblock terpolymer self-assembly–directed sol-gel–derived niobium oxide with subsequent thermal processing in air and ammonia gas. Superconducting materials exhibit a critical temperature (Tc) of about 7 to 8 K, a flux exclusion of about 5% compared to a dense NbN solid, and an estimated critical current density (Jc) of 440 A cm−2 at 100 Oe and 2.5 K. We expect block copolymer self-assembly–directed mesoporous superconductors to provide interesting subjects for mesostructure-superconductivity correlation studies.

Development of rapid processes combining hierarchical self-assembly with mesoscopic shape control has remained a challenge. This is particularly true for high-surface-area porous materials essential for applications including separation and detection, catalysis, and energy conversion and storage. We introduce a simple and rapid laser writing method compatible with semiconductor processing technology to control three-dimensionally continuous hierarchically porous polymer network structures and shapes. Combining self-assembly of mixtures of block copolymers and resols with spatially localized transient laser heating enables pore size and pore size distribution control in all-organic and highly conducting inorganic carbon films with variable thickness. The method provides all-laser-controlled pathways to complex high-surface-area structures, including fabrication of microfluidic devices with high-surface-area channels and complex porous crystalline semiconductor nanostructures.

Methylammonium lead halide perovskite solar cells continue to excite the research community due to their rapidly increasing performance which, in large part, is due to improvements in film morphology. The next step in this progression is control of the crystal morphology which requires a better fundamental understanding of the crystal growth. In this study we use in situ X-ray scattering data to study isothermal transformations of perovskite films derived from chloride, iodide, nitrate, and acetate lead salts. Using established models we determine the activation energy for crystallization and find that it changes as a function of the lead salt. Further analysis enabled determination of the precursor composition and showed that the primary step in perovskite formation is removal of excess organic salt from the precursor. This understanding suggests that careful choice of the lead salt will aid in controlling crystal growth, leading to superior films and better performing solar cells.

Structure control in solution-processed hybrid perovskites is crucial to design and fabricate highly efficient solar cells. Here, we utilize in situ grazing incidence wide-angle X-ray scattering and scanning electron microscopy to investigate the structural evolution and film morphologies of methylammonium lead tri-iodide/chloride (CH3NH3PbI(3-x)Cl(x)) in mesoporous block copolymer derived alumina superstructures during thermal annealing. We show the CH3NH3PbI(3-x)Cl(x) material evolution to be characterized by three distinct structures: a crystalline precursor structure not described previously, a 3D perovskite structure, and a mixture of compounds resulting from degradation. Finally, we demonstrate how understanding the processing parameters provides the foundation needed for optimal perovskite film morphology and coverage, leading to enhanced block copolymer-directed perovskite solar cell performance.

A Complicated Scaffold, Simply Materials with tailored pore structures can be useful as catalysis supports and for lightweight materials. When preparing medical scaffolds, restrictive preparation conditions have to be met, which can prohibit multistep preparation procedures. Sai et al. (p. 530 ) describe a method for making porous polymers containing both relatively large (several microns) interconnecting pores and a second population of ∼ tens of nanometer pores. The process exploits spinodal decomposition of a block copolymer blended with small-molecule additives and requires a simple washing step with water, methanol, or ethanol.

Polymer Templating for Metals Polymer templating has been used to fabricate a wide range of ordered materials, both due to the ability to pattern the polymers easily over a large area and their facile removal. However, the process is somewhat limited to the incorporation of materials that will flow easily into the templated areas. Arora et al. (p. 214 ) show that current techniques can be extended to the patterning of metals, through guided epitaxial growth. An excimer laser was used to control the flow of material into patterned templates formed from block copolymers.

The methylammonium lead halide perovskites have shown significant promise as a low-cost, second generation, photovoltaic material. Despite recent advances, however, there are still a number of fundamental aspects of their formation as well as their physical and electronic behavior that are not well understood. In this letter we explore the mechanism by which these materials crystallize by testing the outcome of each of the reagent halide salts. We find that components of both salts, lead halide and methylammonium halide, are relatively mobile and can be readily exchanged during the crystallization process when the reaction is carried out in solution or in the solid state. We exploit this fact by showing that the perovskite structure is formed even when the lead salt's anion is a non-halide, leading to lower annealing temperature and time requirements for film formation. Studies into these behaviors may ultimately lead to improved processing conditions for photovoltaic films.