Perovskite Crystallization Dynamics during Spin-Casting: An Wide-Angle X-ray Scattering Study.

wide-angle X-ray scattering (WAXS) has been measured during the spin coating process used to make the precursor films required for the formation of thin films of perovskite. A customized hollow axis spin coater was developed to permit the scattered X-rays to be collected in transmission geometry during the deposition process. Spin coating is the technique most commonly used in laboratories to make thin perovskite films.

The influence of structure and morphology on ion permeation in commercial silicone hydrogel contact lenses.

The importance of the microstzructure of silicone hydrogels is widely appreciated but is poorly understood and minimally investigated. To ensure comfort and eye health, these materials must simultaneously exhibit both high oxygen and high water permeability. In contrast with most conventional hydrogels, the water content and water structuring within silicone hydrogels cannot be solely used to predict permeability.

Does 1,8-diiodooctane affect the aggregation state of PCBM in solution?

1,8-Diiodooctane (DIO) is an additive used in the processing of organic photovoltaics and has previously been reported, on the basis of small-angle X-ray scattering (SAXS) measurements, to deflocculate nano-aggregates of [6,6]-phenyl-C71-butyric acid methyl ester (PCBM) in chlorobenzene. We have critically re-examined this finding in a series of scattering measurements using both X-rays and neutrons. With SAXS, we find that the form of the background solvent scattering is influenced by the presence of DIO, that there is substantial attenuation of the X-rays by the background solvent and that there appears to be beam-induced aggregation.

Efficient long-range electron transfer processes in polyfluorene-perylene diimide blends.

In bulk heterojunction donor-acceptor (D-A) blends, high photovoltaic yields require charge carrier separation to outcompete geminate recombination. Recently, evidence for long-range electron transfer mechanisms has been presented, avoiding strongly-bound interfacial charge transfer (CT) states. However, due to the lack of specific optical probes at the D-A interface, a detailed quantification of the long-range processes has not been feasible, until now.

A Pickering Emulsion Route to Swimming Active Janus Colloids.

The field of active colloids is attracting significant interest to both enable applications and allow investigations of new collective colloidal phenomena. One convenient active colloidal system that has been much studied is spherical Janus particles, where a hemispherical coating of platinum decomposes hydrogen peroxide to produce rapid motion. However, at present producing these active colloids relies on a physical vapor deposition (PVD) process, which is difficult to scale and requires access to expensive equipment.

Gravimetric and density profiling using the combination of surface acoustic waves and neutron reflectivity.

A new approach is described herein, where neutron reflectivity measurements that probe changes in the density profile of thin films as they absorb material from the gas phase have been combined with a Love wave based gravimetric assay that measures the mass of absorbed material. This combination of techniques not only determines the spatial distribution of absorbed molecules, but also reveals the amount of void space within the thin film (a quantity that can be difficult to assess using neutron reflectivity measurements alone). The uptake of organic solvent vapours into spun cast films of polystyrene has been used as a model system with a view to this method having the potential for extension to the study of other systems.

Development of an optical microscopy system for automated bubble cloud analysis: publisher's note.

This note reports changes to the author list and additional funding sources for [Appl. Opt.55, 6102 (2016)].

Influence of Surface Wettability on Microbubble Formation.

The production and utilization of microbubbles are rapidly becoming of major importance in a number of global applications, from biofuel production to medical imaging contrast agents. Many aspects of bubble formation have been studied, with diffuser characteristics (such as pore size, pore orientation) and gas flow rate all being shown to influence the bubble formation process. However, very little attention has been paid to the influence of surface wettability of the diffuser and the detailed role it plays at the triple interface of gas-liquid-diffuser.

On the mechanisms of colloidal self-assembly during spin-coating.

Spin-coating offers a facile fabrication route for the production of high quality colloidal crystals, which have potential as photonic band-gap materials. This paper presents the results of direct observations of the self-assembly of latex colloids during spin-coating through the use of stroboscopic microscopy. We have been able to identify several mechanisms by which self-assembly occurs, depending upon the dispersion properties, such as particle weight fraction, solvent volatility and viscosity.

Reduced curvilinear velocity of boar sperm on substrates with increased hydrophobicity.

The curvilinear velocity (VCL) of boar spermatozoa between standard microscopy glassware decreases when the slides are coated with the hydrophobic polymer polystyrene (PS) compared with the less hydrophobic poly(methyl methacrylate) (PMMA) coating. Sperm from three boars were observed and analyzed using particle tracking software. The VCL did not differ significantly between coatings of different thickness, indicating no penetration of the sperm into the coating and that only the surface layer of the polymer film interacts with the sperm and buffer medium.

In situ studies of phase separation and crystallization directed by Marangoni instabilities during spin-coating.

Results of a pioneering study are presented in which for the first time, crystallization, phase separation and Marangoni instabilities occurring during the spin-coating of polymer blends are directly visualized, in real-space and real-time. The results provide exciting new insights into the process of self-assembly, taking place during spin-coating, paving the way for the rational design of processing conditions, to allow desired morphologies to be obtained.

The relationship between charge density and polyelectrolyte brush profile using simultaneous neutron reflectivity and in situ attenuated total internal reflection FTIR.

We report on a novel experimental study of a pH-responsive polyelectrolyte brush at the silicon/D2O interface. A poly[2-(diethylamino)ethyl methacrylate] brush was grown on a large silicon crystal which acted as both a substrate for a neutron reflectivity solid/liquid experiment but also as an FTIR-ATR spectroscopy crystal. This arrangement has allowed for both neutron reflectivities and FTIR spectroscopic information to be measured in parallel.

Size dependence of the propulsion velocity for catalytic Janus-sphere swimmers.

The propulsion velocity of active colloids that asymmetrically catalyze a chemical reaction is probed experimentally as a function of their sizes. It is found that over the experimentally accessible range, the velocity decays as a function of size, with a rate that is compatible with an inverse size dependence. A diffusion-reaction model for the concentrations of the fuel and waste molecules that takes into account a two-step process for the asymmetric catalytic activity on the surface of the colloid is shown to predict a similar behavior for colloids at the large size limit, with a saturation for smaller sizes.

Direct observation of the direction of motion for spherical catalytic swimmers.

Nonconductive Janus particle swimmers made by coating fluorescent polymer beads with hemispheres of platinum have been fully characterized using video microscopy to reveal that they undergo propulsion in hydrogen peroxide fuel away from the catalytic platinum patch. The platinum coating shadows the fluorescence signal from half of each swimmer to allow the orientation to be observed directly and correlated quantitatively with the resulting swimming direction. The observed swimmer direction is consistent with both the bubble release and diffusiophoretic propulsion mechanisms.

Controlling the motion and placement of micrometer-sized metal particles using patterned polymer brush surfaces.

In this paper, we show that silicon surfaces patterned with poly(methacrylic acid) brushes are able to control the Brownian motion of 2-3 μm iron particles, which sediment onto the surface in aqueous solution and experience differences in repulsive force depending upon their position. Differences in repulsion lead to different gravitational potential energies across the surface, which gives bias to the Brownian motion taking place. Three regimes have been identified depending upon the brush height: (i) no control of Brownian motion when the brush height is small, (ii) Brownian motion that is influenced by the polymer brush when the brush 17 height is intermediate, (iii) Brownian motion that is confined by polymer brush barriers when the brush height is greatest.

In situ imaging and height reconstruction of phase separation processes in polymer blends during spin coating.

Spin coating polymer blend thin films provides a method to produce multiphase functional layers of high uniformity covering large surface areas. Applications for such layers include photovoltaics and light-emitting diodes where performance relies upon the nanoscale phase separation morphology of the spun film. Furthermore, at micrometer scales, phase separation provides a route to produce self-organized structures for templating applications.

Shear ordered diblock copolymers with tuneable optical properties.

A series of high molecular weight poly(styrene-b-isoprene) block copolymers with optical properties defined by composition in a non-selective solvent were studied using simultaneous ultra small angle X-ray scattering (USAXS) and optical spectrometry. A small magnitude shear produces ordered and oriented states in the copolymer solutions that persist for extended periods of time, and also have superior optical properties that are directly attributable to the mesoscopic block copolymer (BCP) morphology. We have demonstrated that the optical transmission of these materials can be tuned by the addition of low molecular weight poly(isoprene) and poly(styrene) to swell their respective domains within the diblock copolymer.

Self-assembled autonomous runners and tumblers.

A class of artificial microswimmers with combined translational and rotational self-propulsion is studied experimentally. The chemically fueled microswimmers are made of doublets of Janus colloidal beads with catalytic patches that are positioned at a fixed angle relative to one another. The mean-square displacement and the mean-square angular displacement of the active doublets are analyzed in the context of a simple Langevin description, using which the physical characteristics of the microswimmers such as the spontaneous translational and rotational velocities are extracted.

Effect of the Hofmeister anions upon the swelling of a self-assembled pH-responsive hydrogel.

We report the effect of a range of monovalent sodium salts on the molecular equilibrium swelling of a simple synthetic microphase separated poly(methyl methacrylate)-block-poly(2-(diethylamino)ethyl methacrylate)-block-poly(methyl methacrylate) (PMMA(88)-b-PDEA(223)-b-PMMA(88)) pH-responsive hydrogel. Sodium acetate, sodium chloride, sodium bromide, sodium iodide, sodium nitrate and sodium thiocyanate were selected for study at controlled ionic strength and pH; all salts are taken from the Hofmeister series (HS). The influence of the anions on the expansion of the hydrogel was found to follow the reverse order of the classical HS.

Homopolymer induced aggregation of poly(ethylene oxide)n-b-poly(butylene oxide)m polymersomes.

We have studied the addition of poly(ethylene oxide) homopolymer (PEO) to a range of polymersome dispersions composed of amphiphilic di- and triblock copolymers. A number of E(n)B(m) E(n)B(m)E(n) and B(m)E(n)B(m) (E = poly(ethylene oxide) B = poly(butylene oxide)) block copolymers of varying molecular weights that spontaneously form polymersomes in water were investigated. This resulted in the aggregation of the dispersed polymersomes by two mechanisms, PEO adsorption or depletion interactions, and is shown to be dependent on PEO concentration.

Templated formation of giant polymer vesicles with controlled size distributions.

Unilamellar polymer vesicles are formed when a block copolymer self-assembles to form a single bilayer structure, with a hydrophobic core and hydrophilic surfaces, and the resulting membrane folds over and rearranges by connecting its edges to enclose a space. The physics of self-assembly tightly specifies the wall thickness of the resulting vesicle, but, both for polymer vesicles and phospholipids, no mechanism strongly selects for the overall size, so the size distribution of vesicles tends to be very polydisperse. We report a method for the production of controlled size distributions of micrometre-sized (that is, giant) vesicles combining the 'top-down' control of micrometre-sized features (vesicle diameter) by photolithography and dewetting with the 'bottom-up' control of nanometre-sized features (membrane thickness) by molecular self-assembly.

Floating lipid bilayers deposited on chemically grafted phosphatidylcholine surfaces.

Floating supported bilayers (FSBs) are new systems which have emerged over the past few years to produce supported membrane mimics, where the bilayers remain associated with the substrate, but are cushioned from the substrates constraining influence by a large hydration layer. In this paper we describe a new approach to fabricating FSBs using a chemically grafted phospholipid layer as the support for the floating membrane. The grafted lipid layer was produced using a Langmuir-Schaeffer transfer of acryloyl-functionalized lipid onto a pre-prepared substrate, with AIBN-induced cross-polymerization to permanently bind the lipids in place.

The performance of poly(styrene)-block-poly(2-vinyl pyridine)-block-poly(styrene) triblock copolymers as pH-driven actuators.

Poly(styrene)--poly(2-vinyl pyridine)--poly(styrene) (PS--P2VP--PS) triblock copolymers were synthesised by anionic polymerisation. Thick films were cast from solution and their structure analysed by small angle X-ray scattering (SAXS). Longer annealing times led to more ordered structures whereas short evaporation times effectively "lock" the polymer chains in a disordered state by vitrification.

Self-motile colloidal particles: from directed propulsion to random walk.

The motion of an artificial microscale swimmer that uses a chemical reaction catalyzed on its own surface to achieve autonomous propulsion is fully characterized experimentally. It is shown that at short times it has a substantial component of directed motion, with a velocity that depends on the concentration of fuel molecules. At longer times, the motion reverts to a random walk with a substantially enhanced diffusion coefficient.