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Mesoporous thin films are widely used for applications in need of high surface area and good mass and charge transport properties. A well-established fabrication process involves the supramolecular assembly of organic molecules (e.g. block copolymers, and surfactants) with inorganic materials obtained by sol-gel chemistry. Typically, subsequent calcination in air serves to remove the organic template and reveal the pores. A major challenge for such coatings is the anisotropic shrinkage due to the volume contraction related to solvent evaporation, inorganic condensation, and template removal, affecting the final porosity as well as pore shape, size, arrangement and accessibility. Here, we show that a two-step calcination process, composed of high-temperature treatment in argon followed by air calcination, leads to reduced film contraction and enhanced structural control. Crucially, the formation of a transient carbonaceous scaffold enables the inorganic matrix to fully condense before template removal. The resulting mesoporous films retain a higher porosity as well as larger, more uniform pores with extended hexagonally closed-packed order. Such films present favorable characteristics for a variety of applications, such as improved mass transport of large biomolecules. This is demonstrated for the adsorption and desorption of lysozyme into the mesoporous thin films as an example of enzyme storage.

Porous polymeric microspheres are an emerging class of materials, offering stimuli-responsive cargo uptake and release. Herein, we describe a new approach to fabricate porous anisotropic microspheres based on temperature-induced droplet formation and light-induced polymerisation. Anisotropic liquid crystal (LC) microparticles were prepared by exploiting the partial miscibility of a thermotropic LC mixture composed of 4-cyano-4’- pentylbiphenyl (5CB, unreactive mesogens) with 2-methyl- 1,4-phenylene bis4-[3-(acryloyloxy)propoxy] benzoate (RM257, reactive mesogens) in methanol (MeOH). Isotropic 5CB/RM257-rich droplets were generated by cooling below the binodal curve (20°C), and the isotropic-to-nematic transition occurred after cooling below 0°C. The resulting 5CB/RM257-rich droplets with radial configuration were subsequently polymerised under UV light, resulting in nematic microparticles. Upon heating the mixture, the 5CB mesogens underwent a nematic-isotropic transition and eventually became homogeneous with MeOH, while the polymerised RM257 preserved its radial configuration. Repeated cycles of cooling and heating resulted in swelling and shrinking of the porous microparticles. The use of a reversible materials templating approach to obtain porous microparticles provides new insights into binary liquid manipulation and potential for microparticle production.

Mesoporous inorganic thin films are promising materials architectures for a variety of high-value applications, ranging from optical coatings and purification membranes to sensing and energy storage devices. Having precise control over the structural parameters of the porous network is crucial for expanding their applicability. To this end, the use of block copolymers (BCP) as sacrificial structure-directing agents via micelle co-assembly is a particularly attractive route, since the resultant pore size is directly related to scaling laws for the radius of gyration of the pore-forming macromolecule. However, tailoring the molecular weight of the BCP via bespoke synthesis is an elaborate process that requires precise control over highly sensitive reactions conditions. Alternative methods have emerged, based on supramolecular assembly or the addition of different swelling agents, but, to-date, these present a negative impact on the structural order and pore size dispersity of the final inorganic mesoporous films. In this work, we propose a novel and effective method for control over pore size, porosity and structural order, which relies on a synergistic combination of BCP selective swelling via solvent vapor annealing (SVA) and locking of the structure by condensation of the inorganic sol-gel precursors. The results obtained in this work for TiO2 establish SVA as a new, straightforward, simple, and powerful route efor the fabrication of mesoporous thin-film materials with controllable structural characteristics.

International audience; Producing ultrathin light absorber layers is attractive towards the integration of lightweight planar components in electronic, photonic, and sensor devices. In this work, we report the experimental demonstration of a thin gold (Au) metallic metasurface with near-perfect visible absorption (~ 95 %). Au nanoresonators possessing heights from 5-15 nm with sub-50 nm diameters were engineered by block copolymer (BCP) templating. The Au nanoresonators were fabricated on an alumina (Al2O3) spacer layer and a reflecting Au mirror, in a film-coupled nanoparticle design. The BCP nanopatterning strategy to produce desired heights of Au nanoresonators was tailored to achieve nearperfect absorption at ≈ 600 nm. The experimental insight described in this work is a step forward towards realizing large area flat optics applications derived from subwavelengththin metasurfaces.

Enzymatic electrochemical sensors have become the leading glucose detection technology due to their rapid response, affordability, portability, selectivity, and sensitivity. However, the performance of these sensors is highly dependent on the surface properties of the electrode material used to store glucose oxidase and its ability to retain enzymatic activity under variable environmental conditions. Mesoporous thin films have recently attracted considerable attention as promising candidates for storing enzymes while preserving their activity owing. Herein, we systematically compare pathways for the immobilization of glucose oxidase (GOx) and their effectiveness in electrochemical glucose sensing, following modification protocols that lead to electrostatic attraction (amino functionalization), covalent bonding (aldehyde functionalization) and electrostatic repulsion (oxygen plasma treatment) of the ordered porous aluminosilicate-coated electrodes. By direct comparison using a quartz crystal microbalance, we demonstrate that glucose oxidase can be loaded in a nanoarchitecture with a pore size of ~50 nm and pore interconnections of ~35 nm using the native aluminosilicate surface, as well as after amino or aldehyde surface modification, while oxygen plasma exposure of the native surface inhibits glucose oxidase loading. Despite a variety of routes for enzyme loading, quantitative electrochemical glucose sensing between 0-20 mM was only possible when the porous surface was functionalized with amino groups, which we relate to the role of surface chemistry in accessing the underlying substrate. Our results highlight the impact of rational surface modification on electrochemical biosensing performance and demonstrate the potential of tailoring porous nanoarchitecture surfaces for biosensing applications.

Redox flow batteries (RFBs) are promising for large-scale long-duration energy storage owing to their inherent safety, decoupled power and energy, high efficiency, and longevity. Membranes constitute an important component that affects mass transport processes in RFBs, including ion transport, redox-species crossover, and the net volumetric transfer of supporting electrolytes. Hydrophilic microporous polymers, such as polymers of intrinsic microporosity (PIM), are demonstrated as next-generation ion-selective membranes in RFBs. However, the crossover of redox species and water migration through membranes are remaining challenges for battery longevity. Here, a facile strategy is reported for regulating mass transport and enhancing battery cycling stability by employing thin film composite (TFC) membranes prepared from a PIM polymer with optimized selective-layer thickness. Integration of these PIM-based TFC membranes with a variety of redox chemistries allows for the screening of suitable RFB systems that display high compatibility between membrane and redox couples, affording long-life operation with minimal capacity fade. Thickness optimization of TFC membranes further improves cycling performance and significantly restricts water transfer in selected RFB systems.

Extracellular vesicles (EVs) are routinely released from nearly all cell types as transport vehicles and for cell communication. Crucially, they contain biomolecular content for the identification of health and disease states that can be detected from readily accessible physiological fluids, including urine, plasma, or saliva. Despite their clinical utility within noninvasive diagnostic platforms such as liquid biopsies, the currently available portfolio of analytical approaches are challenged by EV heterogeneity in size and composition, as well as the complexity of native biofluids. Quartz crystal microbalance with dissipation monitoring (QCM-D) has recently emerged as a powerful alternative for the phenotypic detection of EVs, offering multiple modes of analyte discrimination by frequency and dissipation. While providing rich data for sensor development, further progress is required to reduce detection limits and fully exploit the technique’s potential within biosensing. Herein, we investigate the impact of nanostructuring the sensor electrode surface for enhancing its detection capabilities. We employ self-assembly of the block copolymer polystyrene-block-poly(4-vinylpyridine) to create well defined 2D gold islands via selective impregnation of the pyridine domain with gold precursors and subsequent removal of the template. When matched to the EV length scale, we find a 4-fold improvement in sensitivity despite a 4-fold reduction in area for analyte and ligand anchoring in comparison to a flat sensor surface. Creation of tailored and confined sensing regions interspersed by non-binding silica provides optimal spatial orientation for EV capture with reduced steric effects and negative cooperativity of grafted antibodies, offering a promising route for enhanced binding efficiency and performance of sensor platforms.

Redox flow batteries (RFBs) have great potential for long-duration grid-scale energy storage. Ion conducting membranes are a crucial component in RFBs, allowing charge-carrying ions to transport while preventing the cross-mixing of redox couples. Commercial Nafion membranes are widely used in RFBs, but their unsatisfactory ionic and molecular selectivity as well as high costs limit the performance and the widespread deployment of this technology. To extend the longevity and reduce the cost of RFB systems, inexpensive ion-selective membranes are highly desired that concurrently deliver low ionic resistance and high selectivity towards redox-active species. In this work, high-performance RFB membranes are fabricated from blends of carboxylate- and amidoxime-functionalized polymers of intrinsic microporosity (PIMs) that exploit the beneficial properties of both polymers. The enthalpy-driven formation of cohesive interchain interactions, including hydrogen bonds and salt bridges, facilitates the microscopic miscibility of the blends, while ionizable functional groups within the sub-nanometer pores allow optimization of membrane ion transport functions. The resulting microporous membranes demonstrate fast cation conduction with low crossover of redox-active molecular species, enabling improved power ratings and reduced capacity fade in aqueous RFBs using anthraquinone and ferrocyanide as redox couples. This article is protected by copyright. All rights reserved.

Mesoporous silica is commonly used as matrix for humidity sensors, which operate on the principle of relative humidity-dependent water uptake and read-out by resistive or capacitive means. Although numerous studies have been dedicated to improving the sensing performance, in particular with conductive additives, the effect of pore structure on sensing behaviour has not been systematically investigated so far. Herein, we showcase the effects of pore size and porosity on resistive sensing behaviour in the 0.5-85% relative humidity (RH) range. We employed evaporation-induced self-assembly (EISA) in combination with sol-gel chemistry to fabricate well-defined mesoporous silica thin films with high degree of structural control. Material architectures with pore sizes of 3 to 15 nm and porosities of 40 to 70% were rationally designed by using structure directing agents (SDAs) with increasing molecular weight and tuning the silica to SDA ratio. We found that a combination of pore size of 15 nm and 70% porosity showcases a particularly high sensitivity (~104 times change in resistance) in the measured range, with quick response and recovery times of 3 and 9 seconds, respectively. Across the various sensors, we identified a clear correlation between the pore size and the linear RH sensing range. Sensors with larger mesopores (~15 nm) exhibited higher sensitivity and linear response in the 65 to 85% RH range than sensors with smaller pores (

Extracellular vesicles (EVs) are routinely released from nearly all cell types as transport vehicles and for cell communication. Crucially, they contain biomolecular content for the identification of health and disease states that can be detected from readily accessible physiological fluids, including urine, plasma, or saliva. Despite their clinical utility within noninvasive diagnostic platforms such as liquid biopsies, the currently available portfolio of analytical approaches are challenged by EV heterogeneity in size and composition, as well as the complexity of native biofluids. Quartz crystal microbalance with dissipation monitoring (QCM-D) has recently emerged as a powerful alternative for the phenotypic detection of EVs, offering multiple modes of analyte discrimination by frequency and dissipation. While providing rich data for sensor development, further progress is required to reduce detection limits and fully exploit the technique’s potential within biosensing. Herein, we investigate the impact of nanostructuring the sensor electrode surface for enhancing its detection capabilities. We employ self-assembly of the block copolymer polystyrene-block-poly(4-vinylpyridine) to create well defined 2D gold islands via selective impregnation of the pyridine domain with gold precursors and subsequent removal of the template. When matched to the EV length scale, we find a 4-fold improvement in sensitivity despite a 4-fold reduction in area for analyte and ligand anchoring in comparison to a flat sensor surface. Creation of tailored and confined sensing regions interspersed by non-binding silica provides optimal spatial orientation for EV capture with reduced steric effects and negative cooperativity of grafted antibodies, offering a promising route for enhanced binding efficiency and performance of sensor platforms.

Extracellular vesicles (EVs) are nanosized circulating assemblies that contain biomarkers considered promising for early diagnosis within neurology, cardiology, and oncology. Recently, acoustic wave biosensors, in particular based on quartz crystal microbalance with dissipation monitoring (QCM-D), have emerged as a sensitive, label-free, and selective EV characterization platform. A rational approach to further improving sensing detection limits relies on the nanostructuration of the sensor surfaces. To this end, inorganic inverse opals (IOs) derived from colloidal self-assembly present a highly tunable and scalable nanoarchitecture of suitable feature sizes and surface chemistry. This work systematically investigates their use in two-dimensional (2D) and three-dimensional (3D) for enhanced QCM-D EV detection. Precise tuning of the architecture parameters delivered improvements in detection performance to sensitivities as low as 6.24 × 10

Exosomes are nanosized circulating vesicles that contain biomarkers considered promising for early diagnosis within neurology, cardiology and oncology. Recently, acoustic wave biosensors, in particular based on quartz crystal microbalance with dissipation monitoring (QCM-D), have emerged as a sensitive, label-free, and selective exosome characterisation platform. A rational approach to further improving sensing detection limits relies on the nanostructuration of the sensor surfaces. To this end, inorganic inverse opals (IOs) derived from colloidal self-assembly present a highly tuneable and scalable nanoarchitecture of suitable feature sizes and surface chemistry. This work systematically investigates their use in 2D and 3D for enhanced QCM-D exosome detection. Precise tuning of the architecture parameters delivered improvements in detection performance to sensitivities as low as 6.24 x 10^7 particles/ml. Our findings emphasise that attempts to enhance acoustic immunosensing via increasing the surface area by 3D nanostructuration need to be carefully analyzed in order to exclude solvent and artefact entrapment effects. Moreover, the use of 2D nanostructured electrodes to compartmentalise analyte anchoring presents a particularly promising design principle.

The use of ferroelectric polarization to promote electron-hole separation has emerged as a promising strategy to improve photocatalytic activity. Although ferroelectric thin films with planar geometry have been largely studied, nanostructured and porous ferroelectric thin films have not been commonly used in photo-electrocatalysis. The inclusion of porosity in ferroelectric thin films would enhance the surface area and reactivity, leading to a potential improvement of the photoelectrochemical (PEC) performance. Herein, the preparation of porous barium titanate (pBTO) thin films by a soft template-assisted sol-gel method is reported, and the control of porosity using different organic/inorganic ratios is verified by the combination of scanning electron microscopy and ellipsometry techniques. Using piezoresponse force microscopy, the switching of ferroelectric domains in pBTO thin films is observed, confirming that the ferroelectric polarization is still retained in the porous structures. In addition, the presence of porosity in pBTO thin films leads to a clear improvement of the PEC response. By electrochemical poling, we also demonstrated the tuning of the PEC performance of pBTO thin films

Mesoporous thin films are widely used for applications in need of high surface area and good mass and charge transport properties. A well-established fabrication process involves the supramolecular assembly of organic molecules (e.g. block copolymers, and surfactants) with inorganic materials obtained by sol-gel chemistry. Typically, subsequent calcination in air serves to remove the organic template and reveal the pores. A major challenge for such coatings is the anisotropic shrinkage due to the volume contraction related to solvent evaporation, inorganic condensation, and template removal, affecting the final porosity as well as pore shape, size, arrangement and accessibility. Here, we show that a two-step calcination process, composed of high-temperature treatment in argon followed by air calcination, leads to reduced film contraction and enhanced structural control. Crucially, the formation of a transient carbonaceous scaffold enables the inorganic matrix to fully condense before template removal. The resulting mesoporous films retain a higher porosity as well as larger, more uniform pores with extended hexagonally closed-packed order. Such films present favorable characteristics for a variety of applications, such as improved mass transport of large biomolecules. This is demonstrated for the adsorption and desorption of lysozyme into the mesoporous thin films as an example of enzyme storage.

Mesoporous coatings are widely used in industries such as optics, display technologies, photovoltaics, and bioengineering, due to their attractive properties such as high surface to volume ratio and excellent mass and electron transport characteristics. While structural parameters and material composition can be routinely tailored to the respective applications, improvements of their mechanical properties and robustness, essential for their long-term performance, remain a challenge. Herein, we provide a comprehensive study on the relationship between the degree of porosity, type of material processing and resulting mechanical properties for the use case of mesoporous aluminosilicate thin films that were co-assembled via a sacrificial block copolymer structure-directing agent. Several routes, including the introduction of chelating agents on the precursor solution, a two-step calcination process, and a variation over the aluminium content were explored with the objective of improving the scratch resistance and mechanical properties of the final mesoporous thin film. Pencil hardness tests were combined with atomic force microscopy analysis to investigate the macroscopic scratch resistance, i.e. plastic deformation. Ellipsometric porosimetry served to determine the elastic deformation of the nanoscopic architecture via measurement of the Young’s modulus. Our comparative investigation highlights the promising role of organic chelating agents to the sol-gel formulation to slow down the hydrolysis of the aluminium precursor, which facilitated improvements of the mechanical performance close to industrial standard.

Mesoporous thin film architectures are an important class of materials that exhibit unique properties, which include high surface area, versatile surface functionalization, and bicontinuous percolation paths through a broad library of pore arrangements on the 10 nm length scale. Although porosimetry of bulk materials via sorption techniques is common practice, the characterization of thin mesoporous films with small sample volumes remains a challenge. A range of techniques are geared toward providing information over pore morphology, pore size distribution, surface area and overall porosity, but none of them offers a holistic evaluation and results are at times inconsistent. In this work, we present a tutorial overview for the reliable structural characterization of mesoporous films. Three model samples with variable pore size and porosity prepared by block copolymer (BCP) coassembly serve for a rational comparison. Various techniques are assessed side-by-side, including scanning electron microscopy (SEM), atomic force microscopy (AFM), grazing incidence small-angle X-ray scattering (GISAXS), and ellipsometric porosimetry (EP). We critically discuss advantages and limitations of each technique and provide guidelines for reliable implementation.

Block copolymers offer the fabrication of mesoporous thin films with distinct nanoscale structural features. In this contribution, we present the use of acetic acid (CH3COOH) as a low‐molecular‐weight guest molecule to tune the supramolecular assembly of poly[styrene‐block‐(4‐vinylpyridine)] (PS‐b‐P4VP), offering a versatile and straightforward method to obtain tailored nanostructured films with controlled topography and pore size. Spin‐coating toluene solutions of PS‐b‐P4VP, with a variable amount of CH3COOH, leads to micellar thin films, where the micelles contain the carboxylic acid as a guest molecule. The size can be conveniently modified in these films (from 48 to 75 nm) by varying the amount of organic acid in the starting solutions. Subsequent surface reconstruction of micellar films using ethanol leads to ring‐shaped copolymer nanoporous films with modulated diameter. Controlling the micelle reconstruction process, cylindrical porous films are also obtained. Interestingly, changing the type of aliphatic carboxylic acid leads to a modification of the observed film morphology from micelles to out‐of‐plane P4VP cylinders (or lamellae) in a PS matrix., This work was supported by Spanish MINECO (grants FIS2013‐45469 and FIS2016‐76058 (AEI/FEDER, EU)).

[Image: see text] The processing of mesoporous inorganic coatings typically requires a high-temperature calcination step to remove organic precursors that are essential during the material assembly. Lowering the fabrication energy costs and cutting back on the necessary resources would provide a greater scope for the deployment in applications such as architectural glass, optical components, photovoltaic cells, and energy storage, as well as further compatibilize substrates with low temperature stability. Organic removal methods based on UV–ozone treatment are increasing in popularity, but concerns remain regarding large-scale ozone generation and usage of mercury-containing UV lamps. To this end, we present a method that relies on non-ozone-generating UV radiation at 254 nm (UV(254)) and incorporation of small amounts of photocatalytic material in the formulation, here demonstrated with TiO(2) nanocrystals. At concentrations as low as 5 wt % relative to the main inorganic aluminosilicate material, the TiO(2) nanocrystals catalyze a “cold combustion” of the organic components under UV(254) irradiation to reveal a porous inorganic network. Using block copolymer-based co-assembly in conjunction with photocatalytic template removal, we produce well-defined mesoporous inorganic thin films with controlled porosity and refractive index values, where the required processing time is governed by the amount of TiO(2) loading. This approach provides an inexpensive, flexible, and environmentally friendly alternative to traditional organic removal techniques, such as UV–ozone degradation and thermal calcination.

International audience; Optical metamaterials are artificially engineered architectures that exhibit desired optical properties not found in nature. Bespoke design requires the ability to define shape, size, orientation and composition of material structures on the nanometre length scale. Bottom-up self-assembly methods, such as block copolymer (BCP) templating, offer unique pathways to tailored features, at spatial resolution not routinely achieved by conventional top-down techniques. In this review, we provide the general readership with basic concepts of the underlying fabrication processes and examine optical phenomena arising from BCP-derived metamaterials and nanoresonators, with both dielectric and plasmonic characteristics.

International audience; Assembling ultra-high molecular weight (UHMW) block copolymers (BCPs) in rapid timescales is perceived as a grand challenge in polymer science due to slow kinetics. Through surface engineering and identifying a non-volatile solvent (propylene glycol methyl ether acetate, PGMEA) we showcase the impressive ability of a series of lamellar poly(styrene)-block-poly(2-vinylpyridine) (PS-b-P2VP) BCPs to self-assemble directly after spin-coating. In particular, we show the formation of large period (≈ 111 nm) lamellar structures from a neat UHMW PS-b-P2VP BCP. The significant influence of solvent-polymer solubility parameters are explored to enhance polymer chain mobility. After optimization using solvent vapor annealing, increased feature order of ultra large period PS-b-P2VP BCP patterns in 1 hr is achieved. The methods described in this article center on industry compatible patterning schemes, solvents and deposition techniques. Isolated metallic and dielectric features are also demonstrated exemplifying the promise that large BCP periods offer for functional applications. Thus, our straightforward UHMW BCP strategy potentially paves a viable and practical path forward for large-scale integration in various sectors, e.g. photonic band gaps, polarizers, and membranes that demand ultra large period sizes.

International audience; In the field of functional nanomaterials, core-satellite nanocluster have recently elicited great interest due to their unique optoelectronic properties. However, core-satellite synthetic routes to date are hampered by delicate and multistep reaction conditions and no practical method has been reported for the ordering of these structures onto a surface monolayer. Herein we show a reproducible and simplified thin film process to fabricate bimetallic raspberry nanoclusters using block copolymer (BCP) lithography. Inorganic raspberry nanoclusters fabricated consisted of a ~ 36 nm alumina core decorated with ~15 nm Au satellites after infusing multilayer BCP nanopatterns. A series of cylindrical BCPs with different molecular weights allowed us to dial in specific nanodot periodicities (from 30 to 80 nm). Highly ordered BCP nanopatterns were then selectively infiltrated with alumina and Au species to develop multi-level bimetallic raspberry features. Microscopy and x-ray reflectivity analysis were used at each fabrication step to gain further mechanistic insights and understand the infiltration process. Furthermore, grazing-incidence small-angle X-ray scattering studies of infiltrated films confirmed the excellent order and vertical orientation over wafer scale areas of Al2O3/Au raspberry nanoclusters. We believe our work demonstrates a robust strategy towards designing hybrid nanoclusters since BCP blocks can be infiltrated with various low cost salt-based precursors. The highly controlled nanocluster strategy disclosed here could have wide ranging uses, in particular for metasurface and optical based sensor applications.

In the field of functional nanomaterials, core-satellite nanoclusters have recently elicited great interest due to their unique optoelectronic properties. However, core-satellite synthetic routes to date are hampered by delicate and multistep reaction conditions and no practical method has been reported for the ordering of these structures onto a surface monolayer. Herein we show a reproducible and simplified thin film process to fabricate bimetallic raspberry nanoclusters using block copolymer (BCP) lithography. The fabricated inorganic raspberry nanoclusters consisted of a ∼36 nm alumina core decorated with ∼15 nm Au satellites after infusing multilayer BCP nanopatterns. A series of cylindrical BCPs with different molecular weights allowed us to dial in specific nanodot periodicities (from 30 to 80 nm). Highly ordered BCP nanopatterns were then selectively infiltrated with alumina and Au species to develop multi-level bimetallic raspberry features. Microscopy and X-ray reflectivity analysis were used at each fabrication step to gain further mechanistic insights and understand the infiltration process. Furthermore, grazing-incidence small-angle X-ray scattering studies of infiltrated films confirmed the excellent order and vertical orientation over wafer scale areas of Al

Mesoporous inorganic thin films are promising materials architectures for a variety of applications, including sensing, catalysis, protective coatings, energy generation and storage. In many cases, precise control over a bicontinuous porous network on the 10-nm length scale is crucial for their operation. A particularly promising route for structure formation utilizes block copolymer (BCP) micelles in solution as sacrificial structure-directing agents for the co-assembly of inorganic precursors. This method offers pore size control via the molecular weight of the pore forming block and is compatible with broad materials library. On the other hand, the molecular weight dependence impedes continuous pore tuning and the intrinsic polymer dispersity presents challenges to the pore size homogeneity. To this end, we demonstrate how chromatographic fractionation of BCPs provides a powerful method to control the pore size and dispersity of the resulting mesoporous thin films. We apply a semi-preparative size exclusion chromatographic fractionation to a polydisperse poly(isobutylene)-block-poly(ethylene oxide) (PIB-b-PEO) BCP obtained from scaled-up synthesis. The isolation of BCP fractions with distinct molecular weight and narrowed dispersity allowed us to not only tune the characteristic pore size from 9.1±1.5 to 14.1±2.1 nm with the identical BCP source material, but also significantly reduce the pore size dispersity compared to the non-fractionated BCP. Our findings offer a route to obtain a library of monodisperse BCPs from a polydisperse feedstock and provide important insights on the direct relationship between macromolecular characteristics and the resulting structure-directed mesopores, in particular related to dispersity.

International audience; Materials with a high and tunable refractive index are attractive for nanophotonic applications. In this contribution, we propose a straightforward fabrication technique of high-refractive index surfaces based on self-assembled nanostructured block copolymer thin films. The selective and customizable metal incorporation within out-of-plane polymer lamellae produces azimuthally isotropic metallic nanostructures of defined geometries, which were analysed using microscopy and small-angle X-ray scattering techniques. Variable-angle spectroscopic ellipsometry was used to relate the geometrical parameters of the metallic features and the resulting refractive index of the patterned surfaces. In particular, nanostructured gold patterns with a high degree of homogeneity and a gold content as low as 16 vol% reach a refractive index value of more than 3 in the visible domain. Our study thus demonstrates a new route for the preparation of high refractive index surfaces with a low metal content for optical applications.

This work was supported by Spanish MINECO (FIS2013-45469 and FIS2016-76058 (AEI/FEDER,EU)).

The authors report here on the optical response and extraction of the morphological properties of three sizes of self-assembled nearly hexagonal arrays of gold (Au) nanoparticles (NPs), deposited on the native oxide on c-Si. The arrays were prepared by templating gold NP growth with self-assembled cylindrically organized block copolymer thin films, with consecutive removal of the polymer matrix by plasma etching. The particle sizes were controlled by using block copolymers of different molecular weights when assembling the templates. The resulting gold nanostructures were characterized by scanning probe microscopy. Spectroscopic ellipsometry was used to record the optical response of the samples, and the modeling of the spectra and the extraction of morphological parameters were performed using a modification of the Bedeaux–Vlieger formalism implemented in GranFilm. The modeling issues upon the introduction of a thin intermediate (oxide) layer between the particle and the substrate are discussed in detail, and a solution to the model procedure is proposed. The particles were modeled as truncated oblate Au spheroids in a hexagonal lattice on the native oxide on c-Si. The model fit converged to a solution indicating that the particles present a low wetting of the native oxide substrate, with parameters describing the particles and lattice in good correspondence with AFM. The extended GranFilm model simulations are also supported by finite element modeling. The authors report here on the optical response and extraction of the morphological properties of three sizes of self-assembled nearly hexagonal arrays of gold (Au) nanoparticles (NPs), deposited on the native oxide on c-Si. The arrays were prepared by templating gold NP growth with self-assembled cylindrically organized block copolymer thin films, with consecutive removal of the polymer matrix by plasma etching. The particle sizes were controlled by using block copolymers of different molecular weights when assembling the templates. The resulting gold nanostructures were characterized by scanning probe microscopy. Spectroscopic ellipsometry was used to record the optical response of the samples, and the modeling of the spectra and the extraction of morphological parameters were performed using a modification of the Bedeaux–Vlieger formalism implemented in GranFilm. The modeling issues upon the introductio...

The functionality and applications of mesoporous inorganic films are closely linked to their mesopore dimensions. For material architectures derived from block copolymer (BCP) micelle co-assembly, the pore size is typically manipulated by changing the molecular weight corresponding to the pore-forming block. However, bespoke BCP synthesis is often a costly and time-consuming process. An alternative method for pore size tuning involves the use of swelling agents, such as homopolymers (HPs), which selectively interact with the core-forming block to increase the micelle size in solution. In this work, poly(isobutylene)-block-poly(ethylene oxide) (PIB-b-PEO) micelles were swollen with poly(isobutylene) HP in solution and co-assembled with aluminosilicate sol with the aim of increasing the resulting pore dimensions. An analytical approach implementing spectroscopic ellipsometry (SE) and ellipsometric porosimetry (EP) alongside the more commonly used atomic force microscopy (AFM) and small angle x-ray scattering in transmission (SAXS) and grazing-incidence (GISAXS) modes enabled to study the material evolution from solution processing through to the manifestation of the mesoporous inorganic film after BCP removal. In-depth SE/EP analysis evidenced an increase of over 40% in mesopore diameter with HP swelling and a consistent scaling of the overall void volume and number of pores. Importantly, our analytical tool-box enabled us to study the effect of swelling on the connecting necks between adjacent pores, with observed increases as high as ≈35%, knowledge of which is crucial to sensing, electrochemical and other mass transfer-dependent applications.

International audience; Nanotemplates derived from the self-assembly of AB-type block copolymers provide an elegant route to achieve well-defined metallic dot arrays, even if the variety of pattern symmetries is restricted due to the limited number of structures offered by microphase separated diblock copolymers. A strategy that relies on the use of complex network structures accessible through the self-assembly of linear ABC-type terpolymers is presented for the formation of metallic nanodots arrays with “outside-the-box” symmetries. Patterned templates formed by the cubic Q214 and orthorhombic O70 network structures are used as excellent platforms to build well-ordered gold nanodot arrays with unique p3m1 and p2 symmetries, respectively. A simple yet efficient blending strategy is used to tune the critical dimensions of the p3m1 pattern while laterally ordered gold nanodot arrays are also demonstrated through a directed self-assembly approach. Such highly ordered gold nanodots with tunable particle dimensions and array periods, enabling the control of their plasmonic responses, are attractive probes for biological imaging.

Redox flow batteries (RFBs) based on aqueous organic electrolytes are a promising technology for safe and cost-effective large-scale electrical energy storage. Membrane separators are a key component in RFBs, allowing fast conduction of charge-carrier ions but minimizing the cross-over of redox-active species. Here, we report the molecular engineering of amidoxime-functionalized polymers of intrinsic microporosity (AO-PIMs) by tuning their polymer chain topology and pore architecture to optimize membrane ion transport selectivity. AO-PIM membranes are integrated with three emerging aqueous organic flow battery chemistries, and the synergetic integration of ion-selective membranes with molecular engineered organic molecules in neutral-pH electrolytes leads to significantly enhanced cycling stability.