Film before aggregates: an GISAXS study on electrochemically assisted surfactant assembly.

The process of electrochemically assisted surfactant assembly was followed in real time by grazing incidence small angle X-ray scattering with the aim to deconvolute the formation of mesoporous silica film and unwanted porous particles. The X-ray technique proved to be useful for the characterisation of this process, as it takes place at a very dynamic, solid/liquid interface. This paper shows the electrochemically driven onset and evolution of silica/surfactant structures.

Insights into the kinetics and self-assembly order of small-molecule organic semiconductor/quantum dot blends during blade coating.

Organic-inorganic nanocomposite films formed from blends of small-molecule organic semiconductors and colloidal quantum dots are attractive candidates for high efficiency, low-cost solar energy harvesting devices. Understanding and controlling the self-assembly of the resulting organic-inorganic nanocomposite films is crucial in optimising device performance, not only at a lab-scale but for large-scale, high-throughput printing and coating methods. Here, grazing incidence X-ray scattering (GIXS) gives direct insights into how small-molecule organic semiconductors and colloidal quantum dots self-assemble during blade coating.

Effect of Anionic Lipids on Mammalian Plasma Cell Membrane Properties.

The effect of lipid composition on models of the inner leaflet of mammalian cell membranes has been investigated. Grazing incidence X-ray diffraction and X-ray and neutron reflectivity have been used to characterize lipid packing and solvation, while electrochemical and infrared spectroscopic methods have been employed to probe phase behavior in an applied electric field. Introducing a small quantity of the anionic lipid dimyristoylphosphatidylserine (DMPS) into bilayers of zwitterionic dimyristoylphosphatidylethanolamine (DMPE) results in a significant change in the bilayer response to an applied field: the tilt of the hydrocarbon chains increases before returning to the original tilt angle on detachment of the bilayer.

Influence of the Lipid Backbone on Electrochemical Phase Behavior.

Sphingolipids are an important class of lipids found in mammalian cell membranes with important structural and signaling roles. They differ from another major group of lipids, the glycerophospholipids, in the connection of their hydrocarbon chains to their headgroups. In this study, a combination of electrochemical and structural methods has been used to elucidate the effect of this difference on sphingolipid behavior in an applied electric field.

A smart and responsive crystalline porous organic cage membrane with switchable pore apertures for graded molecular sieving.

Membranes with high selectivity offer an attractive route to molecular separations, where technologies such as distillation and chromatography are energy intensive. However, it remains challenging to fine tune the structure and porosity in membranes, particularly to separate molecules of similar size. Here, we report a process for producing composite membranes that comprise crystalline porous organic cage films fabricated by interfacial synthesis on a polyacrylonitrile support.

Surface-controlled spatially heterogeneous physical properties of a supramolecular gel with homogeneous chemical composition.

Controlling supramolecular self-assembly across multiple length scales to prepare gels with localised properties is challenging. Most strategies concentrate on fabricating gels with heterogeneous components, where localised properties are generated by the stimuli-responsive component. Here, as an alternative approach, we use a spiropyran-modified surface that can be patterned with light.

Structure, Nanomechanical Properties, and Wettability of Organized Erucamide Layers on a Polypropylene Surface.

Understanding the nanostructure and nanomechanical properties of surface layers of erucamide, in particular the molecular orientation of the outermost layer, is important to its widespread use as a slip additive in polymer materials. Extending our recent observations of nanomorphologies of erucamide layers on a , here we evaluate its nanostructure on a . Atomic force microscopy (AFM) imaging revealed the molecular packing, thickness, and surface coverage of the erucamide layers, while peak force quantitative nanomechanical mapping (QNM) showed that erucamide reduced the adhesive response on polypropylene.

Towards a neutron and X-ray reflectometry environment for the study of solid-liquid interfaces under shear.

A novel neutron and X-ray reflectometry sample environment is presented for the study of surface-active molecules at solid-liquid interfaces under shear. Neutron reflectometry was successfully used to characterise the iron oxide-dodecane interface at a shear rate of [Formula: see text] [Formula: see text] using a combination of conventional reflectometry theory coupled with the summation of reflected intensities to describe reflectivity from thicker films. Additionally, the structure adopted by glycerol monooleate (GMO), an Organic Friction Modifier, when adsorbed at the iron oxide-dodecane interface at a shear rate of [Formula: see text] [Formula: see text] was studied.

A Two-Dimensional Polyimide-Graphene Heterostructure with Ultra-fast Interlayer Charge Transfer.

Two-dimensional polymers (2DPs) are a class of atomically/molecularly thin crystalline organic 2D materials. They are intriguing candidates for the development of unprecedented organic-inorganic 2D van der Waals heterostructures (vdWHs) with exotic physicochemical properties. In this work, we demonstrate the on-water surface synthesis of large-area (cm ), monolayer 2D polyimide (2DPI) with 3.

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.

Hydrophobicity of surface-immobilised molecules influences architectures formed via interfacial self-assembly of nucleoside-based gelators.

Surface-mediated self-assembly has potential in biomaterial development but underlying rules governing surface-gelator interactions are poorly understood. Here, we correlate surface properties with structural characterization data of nucleoside-based gels obtained by GISAXS and GIWAXS and find that hydrophobicity descriptors (log P, polar surface area, aromaticity) are key predictors for the gel structures formed.

Molecular structure of the substrate-induced thin-film phase of tetracene.

We present a combined experimental and theoretical study to solve the unit-cell and molecular arrangement of the tetracene thin film (TF) phase. TF phases, also known as substrate induced phases (SIPs), are polymorphs that exist at interfaces and decisively impact the functionality of organic thin films, e.g.

Bottom-Up Fabrication of Semiconductive Metal-Organic Framework Ultrathin Films.

Though generally considered insulating, recent progress on the discovery of conductive porous metal-organic frameworks (MOFs) offers new opportunities for their integration as electroactive components in electronic devices. Compared to classical semiconductors, these metal-organic hybrids combine the crystallinity of inorganic materials with easier chemical functionalization and processability. Still, future development depends on the ability to produce high-quality films with fine control over their orientation, crystallinity, homogeneity, and thickness.

Spectroscopic Ellipsometry of Nanocrystalline Diamond Film Growth.

With the retention of many of the unrivaled properties of bulk diamond but in thin-film form, nanocrystalline diamond (NCD) has applications ranging from micro-/nano-electromechanical systems to tribological coatings. However, with Young's modulus, transparency, and thermal conductivity of films all dependent on the grain size and nondiamond content, compositional and structural analysis of the initial stages of diamond growth is required to optimize growth. Spectroscopic ellipsometry (SE) has therefore been applied to the characterization of 25-75 nm thick NCD samples atop nanodiamond-seeded silicon with a clear distinction between the nucleation and bulk growth regimes discernable.

Structure of the SnO_{2}(110)-(4×1) Surface.

Using surface x-ray diffraction (SXRD), quantitative low-energy electron diffraction (LEED), and density-functional theory (DFT) calculations, we have determined the structure of the (4×1) reconstruction formed by sputtering and annealing of the SnO_{2}(110) surface. We find that the reconstruction consists of an ordered arrangement of Sn_{3}O_{3} clusters bound atop the bulk-terminated SnO_{2}(110) surface. The model was found by application of a DFT-based evolutionary algorithm with surface compositions based on SXRD, and shows excellent agreement with LEED and with previously published scanning tunneling microscopy measurements.

Reversible restructuring of supported Au nanoparticles during butadiene hydrogenation revealed by operando GISAXS/GIWAXS.

Periodically arranged, monodisperse gold nanoparticles supported on flat silicon substrates were studied for the hydrogenation of 1,3-butadiene under operando conditions using Grazing Incidence Small- and Wide-Angle X-ray Scattering (GISAXS/GIWAXS). It was found that the composition and shape of the nanoparticles depends very much on the chemical environment; the particles are shown to be dynamic, undergoing reversible size and shape change particularly during catalytic reaction, highlighting a dynamism often not observed in traditional studies. Specifically, the size of the Au nanoparticles increases during butadiene hydrogenation and this is attributed to the partial removal of a AuO at the metal-oxide interface and consequential shape change of the nanoparticle from a more hemispherical particle to a particle with a larger height to width ratio.

Direct Photoalignment and Optical Patterning of Molecular Thin Films.

A novel strategy for direct photoalignment of molecular materials using optothermal re-orientation is introduced. Photoalignment for molecular materials such as the organic semiconductor tetracene is shown, without relying on additional photoreactive dopants or alignment layers. Patterning and polarized light emission, e.

In situ phase behaviour of a high capacity LiCoPO electrode during constant or pulsed charge of a lithium cell.

The phase changes that occur during lithium extraction from LiCoPO in lithium half-cells were studied using synchrotron X-ray diffraction. The existence of two two-phase regions with an intermediate phase present was observed. Significant variations in the composition of the phases of nominal stoichiometry LiCoPO, LiCoPO and CoPO resulted in unit cell volume variations.

Diamond beamline I07: a beamline for surface and interface diffraction.

Beamline I07 at Diamond Light Source is dedicated to the study of the structure of surfaces and interfaces for a wide range of sample types, from soft matter to ultrahigh vacuum. The beamline operates in the energy range 8-30 keV and has two endstations. The first houses a 2+3 diffractometer, which acts as a versatile platform for grazing-incidence techniques including surface X-ray diffraction, grazing-incidence small- (and wide-) angle X-ray scattering, X-ray reflectivity and grazing-incidence X-ray diffraction.

Water corrosion of spent nuclear fuel: radiolysis driven dissolution at the UO2/water interface.

X-ray diffraction has been used to probe the radiolytic corrosion of uranium dioxide. Single crystal thin films of UO(2) were exposed to an intense X-ray beam at a synchrotron source in the presence of water, in order to simultaneously provide radiation fields required to split the water into highly oxidising radiolytic products, and to probe the crystal structure and composition of the UO(2) layer, and the morphology of the UO(2)/water interface. By modeling the electron density, surface roughness and layer thickness, we have been able to reproduce the observed reflectivity and diffraction profiles and detect changes in oxide composition and rate of dissolution at the Ångström level, over a timescale of several minutes.

Bimodal crystallization at polymer-fullerene interfaces.

The growth-kinetics of [6,6]-phenyl C61-butyric acid methyl ester (PCBM) crystals, on two different length-scales, is shown to be controlled by the thickness of the polymer layer within a PCBM-polymer bilayer. Using a model amorphous polymer we present evidence, from in situ optical microscopy and grazing-incidence X-ray diffraction (GIXD), that an increased growth-rate of nanoscale crystals impedes the growth of micron-sized, needle-like PCBM crystals. A combination of neutron reflectivity and GIXD measurements, also allows us to observe the establishment of a liquid-liquid equilibrium composition-profile between the PCBM layer and a polymer-rich layer, before crystallization occurs.

Atomic diffusion within individual gold nanocrystal.

Due to their excess surface free energy and structural instabilities, nanoparticles exhibit interesting physical and chemical properties. There has been an ever-growing interest in investigating these properties, driven by the desire to further miniaturize electronic devices, develop new functional materials and catalysts. Here, the intriguing question of how diffusion evolves in a single nanoparticle is investigated by measuring the spatial and temporal variations of the diffracted coherent X-ray intensity during copper diffusion into a gold nanocrystal.

Direct Observation of Active Material Concentration Gradients and Crystallinity Breakdown in LiFePO Electrodes During Charge/Discharge Cycling of Lithium Batteries.

The phase changes that occur during discharge of an electrode comprised of LiFePO, carbon, and PTFE binder have been studied in lithium half cells by using X-ray diffraction measurements in reflection geometry. Differences in the state of charge between the front and the back of LiFePO electrodes have been visualized. By modifying the X-ray incident angle the depth of penetration of the X-ray beam into the electrode was altered, allowing for the examination of any concentration gradients that were present within the electrode.

Implementation of a beam deflection system for studies of liquid interfaces on beamline I07 at Diamond.

X-ray optics, based on a double-crystal deflection scheme, that enable reflectivity measurements from liquid surfaces/interfaces have been designed, built and commissioned on beamline I07 at Diamond Light Source. This system is able to deflect the beam onto a fixed sample position located at the centre of a five-circle diffractometer. Thus the incident angle can be easily varied without moving the sample, and the reflected beam is tracked either by a moving Pilatus 100K detector mounted on the diffractometer arm or by a stationary Pilatus 2M detector positioned appropriately for small-angle scattering.