Structural Study of Diketopyrrolopyrrole Derivative Thin Films: Influence of Deposition Method, Substrate Surface, and Aging.

We report the morphology and microstructure of n-dialkyl side-chain-substituted thiophene DPP end-capped with phenyl groups (Ph-TDPP-Ph) thin films and compare the influence of deposition method and substrate surface using thermally oxidized Si and graphene substrates as well as monolayer graphene surfaces with an underlying self-assembled octadecyltrichlorosilane monolayer, complemented by an aging study of spin-coated films over a 2 weeks aging period. A distinct difference in morphology was observed between spin-coated and vacuum-deposited thin films, which formed a fiber-like morphology and a continuous layer of terraced grains, respectively. After an initial film evolution, all combinations of deposition method and substrate type result in well-ordered thin films with almost identical crystalline phases with slight variations in crystallinity and mosaicity. These findings point toward strong intermolecular forces dominating during growth, and the templating effect observed for other oligomer films formed on graphene is consequently ineffective for this material type. Upon aging of spin-coated films, a noticeable evolution involving two different morphologies and crystalline phases were observed. After several days, the thin film evolved into a more stable crystal phase and a fiber-like morphology. Moreover, slight variation in optical spectra were elucidated on the basis on density functional theory calculations. These results demonstrate that thin-film properties of DPP derivatives can be tailored by manipulating the film formation process.

Substrate Protection with Corrosion Scales: Can We Depend on Iron Carbonate?

Controlling corrosion with naturally occurring corrosion scales is potentially a more environmentally sustainable alternative to current approaches, including dosing of organic corrosion inhibitors. We report operando grazing incidence X-ray diffractograms correlated with electrochemical measurements to elucidate the growth and corrosion protection properties of a corrosion scale composed of FeCO3 crystallites, which is encountered in various key energy industry applications. Data, acquired as a function of time from high-purity iron immersed in CO2-saturated deionized H2O at pH 6.8 and T = 80 °C, show that the FeCO3 scale not only prevents corrosion of the covered substrate but also acts as a significant interfacial diffusion barrier for corrosion reagents and/or products once sufficient coverage is achieved. Most notably, from a corrosion engineering perspective, however, it is determined that corrosion occurring in gaps between scale crystallites remains appreciable; this important insight is gained through the analysis of electrochemical impedance spectra to estimate the variation in electrochemically active surface area as scale coverage increases. These results indicate that naturally occurring FeCO3 scales are not a tenable solution for corrosion protection, as even in their intact state they are highly likely to be, at best, semiprotective.

On Compton scattering as a source of background in coherent diffraction imaging experiments.

Compton scattering is generally neglected in diffraction experiments because the incoherent radiation it generates does not give rise to interference effects and therefore is negligible at Bragg peaks. However, as the scattering volume is reduced, the difference between the Rayleigh (coherent) and Compton (incoherent) contributions at Bragg peaks diminishes and the incoherent part may become substantial. The consequences can be significant for coherent diffraction imaging at high scattering angles: the incoherent radiation produces background that smears out the secondary interference fringes, affecting thus the achievable resolution of the technique. Here, a criterion that relates the object shape and the resolution is introduced. The Compton contribution for several object shapes is quantified, and it is shown that the maximum achievable resolution along different directions has a strong dependence on the crystal shape and size.

Interactions between PAMAM dendrimers and DOPC lipid multilayers: Membrane thinning and structural disorder.

BACKGROUND: Understanding the structure of hybrid nanoparticle-lipid multilayers is of fundamental importance to their bioanalytical applications and nanotoxicity, where nanoparticle-membrane interactions play an important role. Poly(amidoamine) (PAMAM) dendrimers are branched polymeric nanoparticles with potential biomedical applications due to precise tunability of their physicochemical properties. Here, the effect of PAMAM dendrimers (2.9-4.5 nm) with either a hydrophilic amine (NH2) or a hydrophobic C12 chain surface termination on the 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) multilayers has been studied for the first time. METHODS: DOPC multilayers were created by the liposome-rupture method via drop-casting dendrimer-liposome dispersions with the dendrimers added at different concentrations and at three different stages. The multilayer structure was evaluated via the analysis of the synchrotron X-ray reflectivity (XRR) curves, obtaining the bilayer d-spacing, the coherence length from the Scherrer (Ls) analysis of the Bragg peaks, and the paracrystalline disorder parameter (g). RESULTS: Dendrimer addition led to lipid bilayer thinning and more disordered multilayer structures. Larger hydrophobic dendrimers caused greater structural disruption to the multilayers compared to the smaller dendrimers. The smallest, positively charged dendrimers at their highest concentration caused the most pronounced bilayer thinning. The dendrimer-liposome mixing method also affected the multilayer structure due to different dendrimer aggregation involved. CONCLUSIONS: These results show the complexity of the effect of dendrimer physicochemical properties and the addition method of dendrimers on the structure of mixed dendrimer-DOPC multilayers. GENERAL SIGNIFICANCE: These insights are useful for fundamental understanding of nanotoxicity and future biomedical application of nanocomposite multilayer materials in which nanoparticles are added for enhanced properties and functionality.

Structural evolution of supported lipid bilayers intercalated with quantum dots.

HYPOTHESIS: Supported lipid bilayers (SLBs) embedded with hydrophobic quantum dots (QDs) undergo temporal structural rearrangement. EXPERIMENTS: Synchrotron X-ray reflectivity (XRR) was applied to monitor the temporal structural changes over a period of 24 h of mixed SLBs of 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) / 1-palmitoyl-2-oleoyl-sn-glycero-3-phospho-ethanolamine (POPE) intercalated with 4.9 nm hydrophobic cadmium sulphide quantum dots (CdS QDs). The QD-embedded SLBs (QD-SLBs) were formed via rupture of the mixed liposomes on a positively charged polyethylene imine (PEI) monolayer. Atomic force microscopy (AFM) imaging provided complementary characterization of the bilayer morphology. FINDINGS: Our results show time-dependent perturbations in the SLB structure due to the interaction upon QD incorporation. Compared to the SLB without QDs, at 3 h incubation time, there was a measurable decrease in the bilayer thickness and a concurrent increase in the scattering length density (SLD) of the QD-SLB. The QD-SLB then became progressively thicker with increasing incubation time, which - along with the fitted SLD profile - was attributed to the structural rearrangement due to the QDs being expelled from the inner leaflet to the outer leaflet of the bilayer. Our results give unprecedented mechanistic insights into the structural evolution of QD-SLBs on a polymer cushion, important to their potential biomedical and biosensing applications.

Water-Induced Reversal of the TiO2(011)-(2 × 1) Surface Reconstruction: Observed with in Situ Surface X-ray Diffraction.

The (011) termination of rutile TiO2 is reported to be particularly effective for photocatalysis. Here, the structure of the interface formed between this substrate and water is revealed using surface X-ray diffraction. While the TiO2(011) surface exhibits a (2 × 1) reconstruction in ultra-high vacuum (UHV), this is lifted in the presence of a multilayer of water at room temperature. This change is driven by the formation of Ti-OH at the interface, which has a bond distance of 1.93 ± 0.02 Å. The experimental solution is in good agreement with density functional theory and first-principles molecular dynamics calculations. These results point to the important differences that can arise between the structure of oxide surfaces in UHV and technical environments and will ultimately lead to an atomistic understanding of the photocatalytic process of water splitting on TiO2 surfaces.

XMaS @ the ESRF.

This paper describes the motivation for the design and construction of a beamline at the European Synchrotron Radiation Facility (ESRF) for the use of UK material scientists. Although originally focused on the study of magnetic materials, the beamline has been running for 20 years and currently supports a very broad range of science as evidenced by the research topics highlighted in this article. We describe how the beamline will adapt to align with the ESRF's upgrade to a diffraction limited storage ring. This article is part of the theme issue 'Fifty years of synchrotron science: achievements and opportunities'.

Pristine and hydrated fluoroapatite (0001).

The surface structure of fluoroapatite (0001) (FAp0001) under quasi-dry and humid conditions has been probed with surface X-ray diffraction (SXRD). Lateral and perpendicular atomic relaxations corresponding to the FAp0001 termination before and after H2O exposure and the location of the adsorbed water molecules have been determined from experimental analysis of the crystal truncation rod (CTR) intensities. The surface under dry conditions exhibits a bulk termination with relaxations in the outermost atomic layers. The hydrated surface is formed by a disordered partially occupied H2O layer containing one water molecule (33% surface coverage) adsorbed at each of the three surface Ca atoms, and is coupled with one OH group randomly bonded to each of the three topmost P atoms with a 33% surface coverage.

Correlating Charge Transport with Structure in Deconstructed Diketopyrrolopyrrole Oligomers: A Case Study of a Monomer in Field-Effect Transistors.

Copolymers based on diketopyrrolopyrrole (DPP) cores have attracted a lot of attention because of their high p-type as well as n-type carrier mobilities in organic field-effect transistors (FETs) and high power conversion efficiencies in solar cell structures. We report the structural and charge transport properties of n-dialkyl side-chain-substituted thiophene DPP end-capped with a phenyl group (Ph-TDPP-Ph) monomer in FETs which were fabricated by vacuum deposition and solvent coating. Grazing-incidence X-ray diffraction (GIXRD) from bottom-gate, bottom-contact FET architectures was measured with and without biasing. Ph-TDPP-Ph reveals a polymorphic structure with π-conjugated stacking direction oriented in-plane. The unit cell comprises either one monomer with a = 20.89 Å, b = 13.02 Å, c = 5.85 Å, α = 101.4°, ß = 90.6°, and γ = 94.7° for one phase (TR1) or two monomers with a = 24.92 Å, b = 25.59 Å, c = 5.42 Å, α = 80.3°, ß = 83.5°, and γ = 111.8° for the second phase (TR2). The TR2 phase thus signals a shift from a coplanar to herringbone orientation of the molecules. The device performance is sensitive to the ratio of the two triclinic phases found in the film. Some of the best FET performances with p-type carrier mobilities of 0.1 cm2/V s and an on/off ratio of 106 are for films that comprise mainly the TR1 phase. GIXRD from in operando FETs demonstrates the crystalline stability of Ph-TDPP-Ph.

Structural Evaluation of 5,5'-Bis(naphth-2-yl)-2,2'-bithiophene in Organic Field-Effect Transistors with n-Octadecyltrichlorosilane Coated SiO2 Gate Dielectric.

We report on the structure and morphology of 5,5'-bis(naphth-2-yl)-2,2'-bithiophene (NaT2) films in bottom-contact organic field-effect transistors (OFETs) with octadecyltrichlorosilane (OTS) coated SiO2 gate dielectric, characterized by atomic force microscopy (AFM), grazing-incidence X-ray diffraction (GIXRD), and electrical transport measurements. Three types of devices were investigated with the NaT2 thin-film deposited either on (1) pristine SiO2 (corresponding to higher surface energy, 47 mJ/m2) or on OTS deposited on SiO2 under (2) anhydrous or (3) humid conditions (corresponding to lower surface energies, 20-25 mJ/m2). NaT2 films grown on pristine SiO2 form nearly featureless three-dimensional islands. NaT2 films grown on OTS/SiO2 deposited under anhydrous conditions form staggered pyramid islands where the interlayer spacing corresponds to the size of the NaT2 unit cell. At the same time, the grain size measured by AFM increases from hundreds of nanometers to micrometers and the crystal size measured by GIXRD from 30 nm to more than 100 nm. NaT2 on OTS/SiO2 deposited under humid conditions also promotes staggered pyramids but with smaller crystals 30-80 nm. The NaT2 unit cell parameters in OFETs differ 1-2% from those in bulk. Carrier mobilities tend to be higher for NaT2 layers on SiO2 (2-3 × 10-4 cm2/(V s)) compared to NaT2 on OTS (2 × 10-5-1 × 10-4 cm2/(V s)). An applied voltage does not influence the unit cell parameters when probed by GIXRD in operando.

Water Dissociates at the Aqueous Interface with Reduced Anatase TiO2 (101).

Elucidating the structure of the interface between natural (reduced) anatase TiO2 (101) and water is an essential step toward understanding the associated photoassisted water splitting mechanism. Here we present surface X-ray diffraction results for the room temperature interface with ultrathin and bulk water, which we explain by reference to density functional theory calculations. We find that both interfaces contain a 25:75 mixture of molecular H2O and terminal OH bound to titanium atoms along with bridging OH species in the contact layer. This is in complete contrast to the inert character of room temperature anatase TiO2 (101) in ultrahigh vacuum. A key difference between the ultrathin and bulk water interfaces is that in the latter water in the second layer is also ordered. These molecules are hydrogen bonded to the contact layer, modifying the bond angles.

On the use of two-time correlation functions for X-ray photon correlation spectroscopy data analysis.

Multi-time correlation functions are especially well suited to study non-equilibrium processes. In particular, two-time correlation functions are widely used in X-ray photon correlation experiments on systems out of equilibrium. One-time correlations are often extracted from two-time correlation functions at different sample ages. However, this way of analysing two-time correlation functions is not unique. Here, two methods to analyse two-time correlation functions are scrutinized, and three illustrative examples are used to discuss the implications for the evaluation of the correlation times and functional shape of the correlations.

Quantitative Structure of an Acetate Dye Molecule Analogue at the TiO2-Acetic Acid Interface.

The positions of atoms in and around acetate molecules at the rutile TiO2(110) interface with 0.1 M acetic acid have been determined with a precision of ±0.05 Å. Acetate is used as a surrogate for the carboxylate groups typically employed to anchor monocarboxylate dye molecules to TiO2 in dye-sensitized solar cells (DSSC). Structural analysis reveals small domains of ordered (2 × 1) acetate molecules, with substrate atoms closer to their bulk terminated positions compared to the clean UHV surface. Acetate is found in a bidentate bridge position, binding through both oxygen atoms to two 5-fold titanium atoms such that the molecular plane is along the [001] azimuth. Density functional theory calculations provide adsorption geometries in excellent agreement with experiment. The availability of these structural data will improve the accuracy of charge transport models for DSSC.

Structure of lipid multilayers via drop casting of aqueous liposome dispersions.

Understanding the structure of solid supported lipid multilayers is crucial to their application as a platform for novel materials. Conventionally, they are prepared from drop casting or spin coating of lipids dissolved in organic solvents, and lipid multilayers prepared from aqueous media and their structural characterisation have not been reported previously, due to their extremely low lipid solubility (i.e.∼10(-9) M) in water. Herein, using X-ray reflectivity (XRR) facilitated by a "bending mica" method, we have studied the structural characteristics of dioleoylphosphatidylcholine (DOPC) multilayers prepared via drop casting aqueous small unilamellar and multilamellar vesicle or liposome (i.e. SUV and MLV) dispersions on different surfaces, including mica, positively charged polyethylenimine (PEI) coated mica, and stearic trimethylammonium iodide (STAI) coated mica which exposes a monolayer of hydrocarbon tails. We suggest that DOPC liposomes served both as a delivery matrix where an appreciable lipid concentration in water (∼25 mg mL(-1) or 14 mM) was feasible, and as a structural precursor where the lamellar structure was readily retained on the rupture of the vesicles at the solid surface upon solvent evaporation to facilitate rapid multilayer formation. We find that multilayers on mica from MLVs exhibited polymorphism, whereas the SUV multilayers were well ordered and showed stronger stability against water. The influence of substrate chemistry (i.e. polymer coating, charge and hydrophobicity) on the multilayer structure is discussed in terms of lipid-substrate molecular interactions determining the bilayer packing proximal to the solid-liquid interface, which then had a templating effect on the structure of the bilayers distal from the interface, resulting in the overall different multilayer structural characteristics on different substrates. Such a fundamental understanding of the correlation between the physical parameters that characterise liposomes and substrate chemistry, and the structure of lipid multilayers underpins the potential development of a simple method via an aqueous liposome dispersion route for the inclusion of hydrophilic functional additives (e.g. drugs or nanoparticles) into lipid multilayer based hybrid materials, where tailored structural characteristics are an important consideration.

X-ray spectroscopy for chemistry in the 2-4 keV energy regime at the XMaS beamline: ionic liquids, Rh and Pd catalysts in gas and liquid environments, and Cl contamination in γ-Al2O3.

The 2-4 keV energy range provides a rich window into many facets of materials science and chemistry. Within this window, P, S, Cl, K and Ca K-edges may be found along with the L-edges of industrially important elements from Y through to Sn. Yet, compared with those that cater for energies above ca. 4-5 keV, there are relatively few resources available for X-ray spectroscopy below these energies. In addition, in situ or operando studies become to varying degrees more challenging than at higher X-ray energies due to restrictions imposed by the lower energies of the X-rays upon the design and construction of appropriate sample environments. The XMaS beamline at the ESRF has recently made efforts to extend its operational energy range to include this softer end of the X-ray spectrum. In this report the resulting performance of this resource for X-ray spectroscopy is detailed with specific attention drawn to: understanding electrostatic and charge transfer effects at the S K-edge in ionic liquids; quantification of dilution limits at the Cl K- and Rh L3-edges and structural equilibria in solution; in vacuum deposition and reduction of [Rh(I)(CO)2Cl]2 to γ-Al2O3; contamination of γ-Al2O3 by Cl and its potential role in determining the chemical character of supported Rh catalysts; and the development of chlorinated Pd catalysts in `green' solvent systems. Sample environments thus far developed are also presented, characterized and their overall performance evaluated.

Absence of Structural Impact of Noble Nanoparticles on P3HT:PCBM Blends for Plasmon-Enhanced Bulk-Heterojunction Organic Solar Cells Probed by Synchrotron GI-XRD.

The incorporation of noble metal nanoparticles, displaying localized surface plasmon resonance, in the active area of donor-acceptor bulk-heterojunction organic photovoltaic devices is an industrially compatible light trapping strategy, able to guarantee better absorption of the incident photons and give an efficiency improvement between 12% and 38%. In the present work, we investigate the effect of Au and Ag nanoparticles blended with P3HT: PCBM on the P3HT crystallization dynamics by synchrotron grazing incidence X-ray diffraction. We conclude that the presence of (1) 80 nm Au, (2) mix of 5 nm, 50 nm, 80 nm Au, (3) 40 nm Ag, and (4) 10 nm, 40 nm, 60 nm Ag colloidal nanoparticles, at different concentrations below 0.3 wt% for Au and below 0.1% for Ag in P3HT: PCBM blends, does not affect the behaviour of the blends themselves.

Ageing dynamics of ion bombardment induced self-organization processes.

Instabilities caused during the erosion of a surface by an ion beam can lead to the formation of self-organized patterns of nanostructures. Understanding the self-organization process requires not only the in-situ characterization of ensemble averaged properties but also probing the dynamics. This can be done with the use of coherent X-rays and analyzing the temporal correlations of the scattered intensity. Here, we show that the dynamics of a semiconductor surface nanopatterned by normal incidence ion beam sputtering are age-dependent and slow down with sputtering time. This work provides a novel insight into the erosion dynamics and opens new perspectives for the understanding of self-organization mechanisms.

Ion beam sputtered surface dynamics investigated with two-time correlation functions: a model study.

Ion beam sputtering is a widely used technique to obtain patterned surfaces. Despite the wide use of this approach on different materials to create surface nanostructures, the theoretical model to explain the time evolution of the erosion process is still debated. We show, with the help of simulations, that two-time correlation functions can serve to assess the validity of different models. These functions can be measured experimentally with the x-ray photon correlation spectroscopy technique.

Versatile vacuum chamber for in situ surface X-ray scattering studies.

A compact portable vacuum-compatible chamber designed for surface X-ray scattering measurements on beamline ID01 of the European Synchrotron Radiation Facility, Grenoble, is described. The chamber is versatile and can be used for in situ investigation of various systems, such as surfaces, nanostructures, thin films etc., using a variety of X-ray-based techniques such as reflectivity, grazing-incidence small-angle scattering and diffraction. It has been conceived for the study of morphology and structure of semiconductor surfaces during ion beam erosion, but it is also used for the study of surface oxidation or thin film growth under ultra-high-vacuum conditions. Coherent X-ray beam experiments are also possible. The chamber is described in detail, and examples of its use are given.