Tuning Pore Dimensions of Mesoporous Inorganic Films by Homopolymer Swelling

The functionality and applications of mesoporous inorganic films are closely linked to their mesopore dimensions. For material architectures derived from a block copolymer (BCP) micelle coassembly, 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) micelles were swollen with poly(isobutylene) HP in solution and coassembled with aluminosilicate sol with the aim of increasing the resulting pore dimensions. An analytical approach implementing spectroscopic ellipsometry (SE) and ellipsometric porosimetry (EP) alongside atomic force microscopy (AFM) and small-angle X-ray scattering (SAXS) in transmission and grazing-incidence (GISAXS) modes enabled us to study the material evolution from solution processing through the manifestation of the mesoporous inorganic film after BCP removal. The in-depth SE/EP analysis evidenced an increase of more than 45% in mesopore diameter with HP swelling and a consistent scaling of the overall void volume and number of pores. Importantly, our analytical toolbox enabled us to study the effect of swelling on the connecting necks between adjacent pores, with observed increases as high as ≈35%, offering novel pathways to sensing, electrochemical, and other mass-transfer-dependent applications

Robust Operation of Mesoporous Antireflective Coatings under Variable Ambient Conditions

Generating mesoporous films with adequate film thickness and refractive index is a common method to achieve amplitude and phase matching in low-cost interference-based antireflective coatings (ARCs). For high-surface-energy materials, pores on the 2-50 nm (i.e., on the subwavelength scale) are subject to capillary condensation by surrounding gas phase water molecules, which hampers their functioning. In this work, we examine the effect of relative humidity on mesoporous ARCs and present a simple method for the preparation of ARCs with robust operation under variable conditions. The materials route is based on the generation of well-defined porous aluminosilicate networks by block copolymer co-assembly with poly(isobutylene)- block-poly(ethylene oxide) and postsynthesis grafting of trichloro(octyl)silane molecules to the pore walls. The functionalized films exhibited a maximum transmittance value of 99.8%, with an average transmittance of 99.1% in the visible wavelength range from 400 to 700 nm. Crucially, the antireflection performance was maintained at high humidity values, with an average transmittance decrease of only 0.2% and maximum values maintained at 99.7%. This compared to maximum and average losses of 3.6 and 2.7%, respectively, for nonfunctionalized reference samples. The ARCs were shown to retain their optical properties within 50 humidity cycles, indicating long-term stability against fluctuating environmental conditions

Liquid Crystal-Templated Porous Microparticles via Photopolymerization of Temperature-Induced Droplets in a Binary Liquid Mixture

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 microspheres based on temperature-induced droplet formation and light-induced polymerization. Microparticles were prepared by exploiting the partial miscibility of a thermotropic liquid crystal (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 polymerized 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 polymerized 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

Photocatalytic Template Removal by Non-Ozone-Generating UV Irradiation for the Fabrication of Well-Defined Mesoporous Inorganic Coatings

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 (UV254) and incorporation of small amounts of photocatalytic material in the formulation, here demonstrated with TiO2 nanocrystals. At concentrations as low as 5 wt % relative to the main inorganic aluminosilicate material, the TiO2 nanocrystals catalyze a “cold combustion” of the organic components under UV254 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 TiO2 loading. This approach provides an inexpensive, flexible, and environmentally friendly alternative to traditional organic removal techniques, such as UV–ozone degradation and thermal calcination

Morphology Development in Amorphous Polymer: Fullerene Photovoltaic Blend Films During Solution Casting

The evolution of film structure is reported during solution casting of PCDTBT:PCBM 1:4 wt%, a polymer:fullerene blend system that finds application in an organic photovoltaic device. Using the complimentary techniques of grazing-incidence wide-angle X-ray scattering and spectroscopic ellipsometry, a number of distinct processes that occur during film formation are identified. This includes the growth of fullerene molecules into nanoscale aggregates, the onset of which coincides with the solubility limit of the material in the casting solvent being reached. An apparent delay in Bragg scatter from the PCDTBT-rich phase of the film suggests that, for the film composition studied here, the aggregation of PCBM precedes weak self-organisation of the conjugated polymer. This behaviour is compared with the drying dynamics of a number of different polymer:fullerene blends that each contain a high weight fraction of fullerene molecules, and a range of comparable solid concentrations are identified beyond which the precipitation of fullerene aggregates from solution occurs. These observations provide an insight into the development of structure in relatively amorphous polymer:fullerene blends for organic photovoltaic applications and potentially assists the future optimisation of this category of materials. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Organic photovoltaic devices with enhanced efficiency processed from non-halogenated binary solvent blends

The development of processing routes to fabricate organic photovoltaic devices (OPVs) using non-halogenated solvents is a necessary step towards their eventual commercialisation. To address this issue, we have used Hansen solubility parameter analysis to identify a non-halogenated solvent blend based on a mixture of carbon disulphide and acetone. This solvent blend was then used to deposit a donor–acceptor polymer–fullerene thin-film that was then used as the active layer of bulk-heterojunction OPV. For the benchmark polymer:fullerene system PCDTBT:PC70BM, a power conversion efficiency of 6.75% was achieved; a 20% relative improvement over reference cells processed using the chlorinated-solvent chlorobenzene. Improvements in device efficiency are attributed to an increase in electron and hole conductivity resulting from enhanced fullerene crystallisation; a property that leads to enhanced device efficiency through improved charge extraction

Rapid precipitation : an alternative to solvent casting for organic solar cells

Rapid precipitation, immersion of a liquid formulation into a nonsolvent, is compared with drop casting for fabricating organic solar cells. Blends comprising poly‐3‐hexylthiophene (P3HT), phenyl‐C61‐butyric acid methyl ester (PCBM), and chlorobenzene were processed into bulk samples by using two distinct routes: rapid precipitation and drop casting. The resulting structure, phases, and crystallinity were analyzed by using small‐angle neutron scattering, X‐ray diffraction, differential scanning calorimetry, and muon spin resonance. Rapid precipitation was found to induce a finely structured phase separation between PCBM and P3HT, with 65 wt % crystallinity in the P3HT phase. In contrast, solvent casting resulted in a mixed PCBM/P3HT phase with only 43 wt % P3HT crystallinity. The structural advantages conferred by rapid precipitation were shown to persist following intense thermal treatments

Organic Photovoltaic Cells: From Performance Improvement to Manufacturing Processes

Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/111806/1/smll201402883.pd