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.

Silica Inverse Opal Nanostructured Sensors for Enhanced Immunodetection of Extracellular Vesicles by Quartz Crystal Microbalance with Dissipation Monitoring.

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 × 107 particles/mL. Our findings emphasize 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 artifact entrapment effects. Moreover, the use of 2D nanostructured electrodes to compartmentalize analyte anchoring presents a particularly promising design principle.

Supramolecular packing of alkyl substituted Janus face all-cis 2,3,4,5,6-pentafluorocyclohexyl motifs.

This study uses X-ray crystallography, theory and Langmuir isotherm analysis to explore the conformations and molecular packing of alkyl all-cis 2,3,4,5,6-pentafluorocyclohexyl motifs, which are prepared by direct aryl hydrogenations from alkyl- or vinyl-pentafluoroaryl benzenes. Favoured conformations retain the more polar triaxial C-F bond arrangement of the all-cis 2,3,4,5,6-pentafluorocyclohexyl ring systems with the alkyl substituent adopting an equatorial orientation, and accommodating strong supramolecular interactions between rings. Langmuir isotherm analysis on a water subphase of a long chain fatty acid and alcohol carrying terminal all-cis 2,3,4,5,6-pentafluorocyclohexyl rings do not show any indication of monolayer assembly relative to their cyclohexane analogues, instead the molecules appear to aggregate and form higher molecular assemblies prior to compression. The study indicates the power and potential of this ring system as a motif for ordering supramolecular assembly.

Charge Transport Phenomena in Heterojunction Photocatalysts: The WO3/TiO2 System as an Archetypical Model.

Recent studies have demonstrated the high efficiency through which nanostructured core-shell WO3/TiO2 (WT) heterojunctions can photocatalytically degrade model organic pollutants (stearic acid, QE ≈ 18% @ λ = 365 nm), and as such, has varied potential environmental and antimicrobial applications. The key motivation herein is to connect theoretical calculations of charge transport phenomena, with experimental measures of charge carrier behavior using transient absorption spectroscopy (TAS), to develop a fundamental understanding of how such WT heterojunctions achieve high photocatalytic efficiency (in comparison to standalone WO3 and TiO2 photocatalysts). This work reveals an order of magnitude enhancement in electron and hole recombination lifetimes, respectively located in the TiO2 and WO3 sides, when an optimally designed WT heterojunction photocatalyst operates under UV excitation. This observation is further supported by our computationally captured details of conduction band and valence band processes, identified as (i) dominant electron transfer from WO3 to TiO2 via the diffusion of excess electrons; and (ii) dominant hole transfer from TiO2 to WO3 via thermionic emission over the valence band edge. Simultaneously, our combined theoretical and experimental study offers a time-resolved understanding of what occurs on the micro- to milliseconds (µs-ms) time scale in this archetypical photocatalytic heterojunction. At the microsecond time scale, a portion of the accumulated holes in WO3 contribute to the depopulation of W5+ polaronic states, whereas the remaining accumulated holes in WO3 are separated from adjacent electrons in TiO2 up to 3 ms after photoexcitation. The presence of these exceptionally long-lived photogenerated carriers, dynamically separated by the WT heterojunction, is the origin of the superior photocatalytic efficiency displayed by this system (in the degradation of stearic acid). Consequently, our combined computational and experimental approach delivers a robust understanding of the direction of charge separation along with critical time-resolved insights into the evolution of charge transport phenomena in this model heterojunction photocatalyst.

Chemical vapour deposition (CVD) of nickel oxide using the novel nickel dialkylaminoalkoxide precursor [Ni(dmamp')2] (dmamp' = 2-dimethylamino-2-methyl-1-propanolate).

Nickel oxide (NiO) has good optical transparency and wide band-gap, and due to the particular alignment of valence and conduction band energies with typical current collector materials has been used in solar cells as an efficient hole transport-electron blocking layer, where it is most commonly deposited via sol-gel or directly deposited as nanoparticles. An attractive alternative approach is via vapour deposition. This paper describes the chemical vapour deposition of p-type nickel oxide (NiO) thin films using the new nickel CVD precursor [Ni(dmamp')2], which unlike previous examples in literature is synthesised using the readily commercially available dialkylaminoalkoxide ligand dmamp' (2-dimethylamino-2-methyl-1-propanolate). The use of vapour deposited NiO as a blocking layer in a solar-cell device is presented, including benchmarking of performance and potential routes to improving performance to viable levels.

Humidity-Tolerant Ultrathin NiO Gas-Sensing Films.

When the gas sensor active layer film thickness is decreased, increased sensitivity to changes in the adsorbate concentration is expected when measuring the resistance of the layer, in particular when this thickness is on the order of the Debye length of the material (one-tens of nanometers); however, this is demonstrated only for a limited number of materials. Herein, ultrathin NiO films of different thicknesses (8-21 nm) have been deposited via chemical vapor deposition to fabricate gas sensor devices. Sensor performance for a range of NO2 concentrations (800 part-per-billion to 7 part-per-million) was evaluated and an optimum operating temperature of 125 °C determined. The dependence of the potential relative changes with respect to the NO2 concentration and of the sensor signal with respect to the geometrical parameters was qualitatively evaluated to derive a transduction model capable of fitting the experimental results. The selective sensitivity toward NO2 was confirmed by the limited response for different reducing gases, CO, CH4, NH3, and SO2, under optimum operating conditions, and the sensor signal toward NO2 increased with decreasing thickness, demonstrating that the concept of a Debye length dependence of sensitivity is applicable for the p-type semiconductor NiO. In addition, these NiO sensors were exposed to different relative levels of humidity over a wide range of operating temperatures and were found to display humidity tolerance far superior to those in previous reports on SnO2 materials.

Structural Characterization of Mesoporous Thin Film Architectures: A Tutorial Overview.

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.

Use of a New Non-Pyrophoric Liquid Aluminum Precursor for Atomic Layer Deposition.

An Al2O3 thin film has been grown by vapor deposition using different Al precursors. The most commonly used precursor is trimethylaluminum, which is highly reactive and pyrophoric. In the purpose of searching for a more ideal Al source, the non-pyrophoric aluminum tri-sec-butoxide ([Al(OsBu)3], ATSB) was introduced as a novel precursor for atomic layer deposition (ALD). After demonstrating the deposition of Al2O3 via chemical vapor deposition (CVD) and 'pulsed CVD' routes, the use of ATSB in an atomic layer deposition (ALD)-like process was investigated and optimized to achieve self-limiting growth. The films were characterized using spectral reflectance, ellipsometry and UV-Vis before their composition was studied. The growth rate of Al2O3 via the ALD-like process was consistently 0.12 nm/cycle on glass, silicon and quartz substrates under the optimized conditions. Scanning electron microscopy and transmission electron microscopy images of the ALD-deposited Al2O3 films deposited on complex nanostructures demonstrated the conformity, uniformity and good thickness control of these films, suggesting a potential of being used as the protection layer in photoelectrochemical water splitting.

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.

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.

Single step route to highly transparent, conductive and hazy aluminium doped zinc oxide films.

Light scattering yet transparent electrodes are important for photovoltaics as they increase device efficiency by prolonging light path lengths. Here, we present a novel single step route to highly textured Al doped ZnO thin films on glass substrates that show a minimum resistivity of ∼3 × 10-3 Ω cm and high visible light transmittance of 83% while still maintaining high haze factor of 63%. Roughness was imparted into the ZnO films during the synthetic process using acetylacetone and deionized water as additives. The highly hazy yet visible and near infrared transparent nature of the conductive ZnO:Al films allow it to be potentially used as an electrode material in amorphous and microcrystalline silicon solar cells.

Flexible and fluorophore-doped luminescent solar concentrators based on polydimethylsiloxane.

We demonstrate a simple and inexpensive method to fabricate flexible and fluorophore-doped luminescent solar concentrators (LSCs). Polydimethylsiloxane (PDMS) serves as a host material which additionally offers the potential to cast LSCs in arbitrary shapes. The laser dye Pyrromethene 567 is used as a prototype fluorophore, and it is shown that it has a high quantum yield of 93% over the concentration range investigated. The optical efficiency and loss channels of the flexible LSCs are investigated; it is also demonstrated that the efficiency remains high while bending the LSC which is essential for flexible LSCs to make an impact on solar energy.

Copper-based water repellent and antibacterial coatings by aerosol assisted chemical vapour deposition.

The adhesion and proliferation of bacteria on solid surfaces presents a major challenge in both healthcare and industrial applications. In response to this problem, an effective and simple method is reported to fabricate superhydrophobic antibacterial copper coated polymer films via aerosol assisted chemical vapor deposition (AACVD). The material is characterized using a range of techniques including electron microscopy, water contact angle measurement and elemental mapping. The antibacterial activity of the modified film is tested against the Gram-negative bacterium, Escherichia coli, and the Gram-positive bacterium, Staphylococcus aureus and the film shows highly significant antibacterial activity against both bacteria (>4 log reduction in bacterial numbers) in 15 min and 60 min, respectively. In addition, all the CVD modified samples results in a significant reduction in bacterial cell adhesion compared to the control materials. Thus, we report a new film type that has dual mode of action-the superhydrophobicity helps limit cell adhesion combined with a cytotoxic copper induced bacteria kill.

Influence of depth of interaction upon the performance of scintillator detectors.

The uncertainty in time of particle detection within a scintillator detector, characterised by the coincidence time resolution (CTR), is explored with respect to the interaction position within the scintillator crystal itself. Electronic collimation between two scintillator detectors is utilised to determine the CTR with depth of interaction (DOI) for different materials, geometries and wrappings. Significantly, no relationship between the CTR and DOI is observed within experimental error. Confinement of the interaction position is seen to degrade the CTR in long scintillator crystals by 10%.

Efficiency and loss mechanisms of plasmonic Luminescent Solar Concentrators.

Using a hybrid nanoscale/macroscale model, we simulate the efficiency of a luminescent solar concentrator (LSC) which employs silver nanoparticles to enhance the dye absorption and scatter the incoming light. We show that the normalized optical efficiency can be increased from 10.4% for a single dye LSC to 32.6% for a plasmonic LSC with silver spheres immersed inside a thin dye layer. Most of the efficiency enhancement is due to scattering of the particles and not due to dye absorption/re-emission.

A bioinspired solution for spectrally selective thermochromic VO2 coated intelligent glazing.

We present a novel approach towards achieving high visible transmittance for vanadium dioxide (VO(2)) coated surfaces whilst maintaining the solar energy transmittance modulation required for smart-window applications. Our method deviates from conventional approaches and utilizes subwavelength surface structures, based upon those present on the eyeballs of moths, that are engineered to exhibit broadband, polarization insensitive and wide-angle antireflection properties. The moth-eye functionalised surface is expected to benefit from simultaneous super-hydrophobic properties that enable the window to self-clean. We develop a set of design rules for the moth-eye surface nanostructures and, following this, numerically optimize their dimensions using parameter search algorithms implemented through a series of Finite Difference Time Domain (FDTD) simulations. We select six high-performing cases for presentation, all of which have a periodicity of 130 nm and aspect ratios between 1.9 and 8.8. Based upon our calculations the selected cases modulate the solar energy transmittance by as much as 23.1% whilst maintaining high visible transmittance of up to 70.3%. The performance metrics of the windows presented in this paper are the highest calculated for VO(2) based smart-windows.