The Extremely Brilliant Source storage ring of the European Synchrotron Radiation Facility.

The Extremely Brilliant Source (EBS) is the experimental implementation of the novel Hybrid Multi Bend Achromat (HMBA) storage ring magnetic lattice concept, which has been realised at European Synchrotron Radiation Facility. We present its successful commissioning and first operation. We highlight the strengths of the HMBA design and compare them to the previous designs, on which most operational synchrotron X-ray sources are based. We report on the EBS storage ring's significantly improved horizontal electron beam emittance and other key beam parameters. EBS extends the reach of synchrotron X-ray science confirming the HMBA concept for future facility upgrades and new constructions.

The synchrotron radiation source PETRA III and its future ultra-low-emittance upgrade PETRA IV.

PETRA III at DESY is one of the brightest synchrotron radiation sources worldwide. It serves a broad international multidisciplinary user community from academia to industry at currently 25 specialised beamlines. With a storage-ring energy of 6 GeV, it provides mainly hard to high-energy X-rays for versatile experiments in a very broad range of scientific fields. It is ideally suited for an upgrade to the ultra-low emittance source PETRA IV, owing to its large circumference of 2304 m. With a targeted storage ring emittance of 20 × 5 pm 2 rad 2 , PETRA IV will reach spectral brightnesses two to three orders of magnitude higher than today. The unique beam parameters will make PETRA IV the ultimate in situ 3D microscope for biological, chemical, and physical processes helping to address key questions in health, energy, mobility, information technology, and earth and environment.

The "Historical Materials BAG": A New Facilitated Access to Synchrotron X-ray Diffraction Analyses for Cultural Heritage Materials at the European Synchrotron Radiation Facility.

The European Synchrotron Radiation Facility (ESRF) has recently commissioned the new Extremely Brilliant Source (EBS). The gain in brightness as well as the continuous development of beamline instruments boosts the beamline performances, in particular in terms of accelerated data acquisition. This has motivated the development of new access modes as an alternative to standard proposals for access to beamtime, in particular via the "block allocation group" (BAG) mode. Here, we present the recently implemented "historical materials BAG": a community proposal giving to 10 European institutes the opportunity for guaranteed beamtime at two X-ray powder diffraction (XRPD) beamlines-ID13, for 2D high lateral resolution XRPD mapping, and ID22 for high angular resolution XRPD bulk analyses-with a particular focus on applications to cultural heritage. The capabilities offered by these instruments, the specific hardware and software developments to facilitate and speed-up data acquisition and data processing are detailed, and the first results from this new access are illustrated with recent applications to pigments, paintings, ceramics and wood.

Surface structure evolution in a homologous series of ionic liquids.

Interfaces of room temperature ionic liquids (RTILs) are important for both applications and basic science and are therefore intensely studied. However, the evolution of their interface structure with the cation's alkyl chain length [Formula: see text] from Coulomb to van der Waals interaction domination has not yet been studied for even a single broad homologous RTIL series. We present here such a study of the liquid-air interface for [Formula: see text], using angstrom-resolution X-ray methods. For [Formula: see text], a typical "simple liquid" monotonic surface-normal electron density profile [Formula: see text] is obtained, like those of water and organic solvents. For [Formula: see text], increasingly more pronounced nanoscale self-segregation of the molecules' charged moieties and apolar chains yields surface layering with alternating regions of headgroups and chains. The layering decays into the bulk over a few, to a few tens, of nanometers. The layering periods and decay lengths, their linear [Formula: see text] dependence, and slopes are discussed within two models, one with partial-chain interdigitation and the other with liquid-like chains. No surface-parallel long-range order is found within the surface layer. For [Formula: see text], a different surface phase is observed above melting. Our results also impact general liquid-phase issues like supramolecular self-aggregation and bulk-surface structure relations.

Solid-liquid interfaces of ionic liquid solutions--Interfacial layering and bulk correlations.

The influence of the polar, aprotic solvent propylene carbonate on the interfacial structure of the ionic liquid (IL) 1-butyl-1-methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate on sapphire was investigated by high-energy x-ray reflectivity. Experiments at solvent concentrations between 17 mol. % and 83 mol. % bridge the gap between diluted electrolytes described by the classical Gouy-Chapman theory and pure ionic liquids. Analysis of our experimental data revealed interfacial profiles comprised of alternating anion and cation enriched regions decaying gradually into the bulk liquid. With increasing solvent concentration, we observed a decrease in correlation length of the interfacial layering structure. At high ion concentrations, solvent molecules were found to accumulate laterally within the layers. By separating like-charged ions, they reduce their Coulomb repulsion. The results are compared with the bulk structure of IL/solvent blends probed by x-ray scattering and predictions from fundamental fluid theory.

Chemistry-dependent X-ray-induced surface charging.

Materials science in general, and surface/interface science in particular, have greatly benefited from the development of high energy synchrotron radiation facilities. Irradiation with intense ionizing beams can however influence relevant sample properties. Permanent radiation damage and irradiation-induced sample modifications have been investigated in detail during the last decades. Conversely, reversible sample alterations taking place only during irradiation are still lacking comprehensive in situ characterization. Irradiation-induced surface charging phenomena are particularly relevant for a wide range of interface science investigations, in particular those involving surfaces of solid substrates in contact with gaseous or liquid phases. Here, we demonstrate partially reversible radiation-induced surface charging phenomena, which extend far beyond the spatial dimensions of the X-ray beam mainly as a consequence of the interaction between the surface and ionized ambient molecules. The charging magnitude and sign are found to be surface chemistry specific and dependent on the substrates' bulk conductivity and grounding conditions. These results are obtained by combining a scanning Kelvin probe with a synchrotron surface diffractometer to allow simultaneous in situ work function measurements during precisely controlled hard X-ray micro-beam irradiation.

An X-ray chamber for in situ structural studies of solvent-mediated nanoparticle self-assembly.

Spontaneous ordering of nanoparticles (NPs) occurring as a consequence of solvent evaporation can yield highly ordered and extended NP superlattices bearing both fundamental scientific interest and potential for technological application. A versatile experimental chamber has been developed allowing (i) controlled in situ deposition of NP solutions on solid substrates, (ii) rate-controlled evaporation of the bulk solvent, and (iii) adsorption/desorption of nano-thick solvent films onto preformed NP assemblies. Within this hermetically sealed chamber all the stages of self-assembly, including macroscopic solution evaporation, NP thin-film formation and its subsequent structural transformation induced by nano-thick solvent films, can be characterized in situ by X-ray scattering techniques. Here, technical design and calibration details are provided, as well as three experimental examples highlighting the chamber's performances and potential. Examples include the controlled adsorption of thin toluene films on flat silicon wafers, the observation of transient accumulation of gold NPs near the toluene-vapour interface, and preliminary data on the structural effects of fast macroscopic solvent evaporation followed by nanoscale solvent adsorption/desorption from a vapour phase. By combining bulk evaporation rate control, fine tuning of the thickness of adsorbed solvent films and in situ X-ray characterization capabilities, this cell enables explorations of both near-to-equilibrium and far-from-equilibrium routes to NP self-assembly.

Surface layering and melting in an ionic liquid studied by resonant soft X-ray reflectivity.

The molecular-scale structure of the ionic liquid [C18mim](+)[FAP](-) near its free surface was studied by complementary methods. X-ray absorption spectroscopy and resonant soft X-ray reflectivity revealed a depth-decaying near-surface layering. Element-specific interfacial profiles were extracted with submolecular resolution from energy-dependent soft X-ray reflectivity data. Temperature-dependent hard X-ray reflectivity, small- and wide-angle X-ray scattering, and infrared spectroscopy uncovered an intriguing melting mechanism for the layered region, where alkyl chain melting drove a negative thermal expansion of the surface layer spacing.

A scanning Kelvin probe for synchrotron investigations: the in situ detection of radiation-induced potential changes.

A wide range of high-performance X-ray surface/interface characterization techniques are implemented nowadays at every synchrotron radiation source. However, these techniques are not always `non-destructive' because possible beam-induced electronic or structural changes may occur during X-ray irradiation. As these changes may be at least partially reversible, an in situ technique is required for assessing their extent. Here the integration of a scanning Kelvin probe (SKP) set-up with a synchrotron hard X-ray interface scattering instrument for the in situ detection of work function variations resulting from X-ray irradiation is reported. First results, obtained on bare sapphire and sapphire covered by a room-temperature ionic liquid, are presented. In both cases a potential change was detected, which decayed and vanished after switching off the X-ray beam. This demonstrates the usefulness of a SKP for in situ monitoring of surface/interface potentials during X-ray materials characterization experiments.

Modification of deeply buried hydrophobic interfaces by ionic surfactants.

Hydrophobicity, the spontaneous segregation of oil and water, can be modified by surfactants. The way this modification occurs is studied at the oil-water interface for a range of alkanes and two ionic surfactants. A liquid interfacial monolayer, consisting of a mixture of alkane molecules and surfactant tails, is found. Upon cooling, it freezes at T(s), well above the alkane's bulk freezing temperature, T(b). The monolayer's phase diagram, derived by surface tensiometry, is accounted for by a mixtures-based theory. The monolayer's structure is measured by high-energy X-ray reflectivity above and below T(s). A solid-solid transition in the frozen monolayer, occurring approximately 3 °C below T(s), is discovered and tentatively suggested to be a rotator-to-crystal transition.

A large-volume gas cell for high-energy X-ray reflectivity investigations of interfaces under pressure.

A cell for the investigation of interfaces under pressure is presented. Given the pressure and temperature specifications of the cell, P ≤ 100 bar and 253 K ≤ T ≤ 323 K, respectively, high-energy X-rays are required to penetrate the thick Al(2)O(3) windows. The CH(4)(gas)/H(2)O(liquid) interface has been chosen to test the performance of the new device. The measured dynamic range of the high-energy X-ray reflectivity data exceeds 10(-8), thereby demonstrating the validity of the entire experimental set-up.

On the origin of the hydrophobic water gap: An X-ray reflectivity and MD simulation study.

The density deficit of water at hydrophobic interfaces, frequently called the hydrophobic gap, has been the subject of numerous experimental and theoretical studies in the past decade. Recent experiments give values for the interfacial depletion that consistently correspond to less than a monolayer of water. The main question which remained so far unanswered is its origin and the mechanisms affected by the chemistry and molecular geometry of a particular hydrophobic coating. In this work, we present a combined high-energy X-ray reflectivity and molecular dynamics simulation study of the water depletion at a perfluorinated hydrophobic interface with a spatial resolution on the molecular scale. A comparison of our experimental and computational results elucidates the underlying mechanisms that affect the extent of the interfacial depletion. The complex interplay between surface chemistry and topography precludes the existence of a direct and universal relation between the macroscopic contact angle and the nanoscopic water depletion.

Layering of [BMIM]+-based ionic liquids at a charged sapphire interface.

The structure of two model room temperature ionic liquids, [BMIM](+)[PF(6)](-) and [BMIM](+)[BF(4)](-), near the solid/liquid interface with charged Al(2)O(3)(0001) (sapphire) was determined with subnanometer resolution by high energy (72.5 keV) x-ray reflectivity. [BMIM](+)[PF(6)](-) exhibits alternately charged, exponentially decaying, near-surface layering. By contrast, the smaller-anion compound, [BMIM](+)[BF(4)](-), shows only a single layer of enhanced electron density at the interface. The different layering behaviors, and their characteristic length scales, correspond well to the different bulk diffraction patterns, also measured in this study. Complementary measurements of the surface and interface energies showed no significant different between the two RTILs. The combined bulk-interface results support the conclusion that the interfacial ordering is dominated by the same electrostatic ion-ion interactions dominating the bulk correlations, with hydrogen bonding and dispersion interactions playing only a minor role.

Molecular layering of fluorinated ionic liquids at a charged sapphire (0001) surface.

Room-temperature ionic liquids (RTILs) are promising candidates for a broad range of "green" applications, for which their interaction with solid surfaces plays a crucial role. In this high-energy x-ray reflectivity study, the temperature-dependent structures of three ionic liquids with the tris(pentafluoroethyl)trifluorophosphate anion in contact with a charged sapphire substrate were investigated with submolecular resolution. All three RTILs show strong interfacial layering, starting with a cation layer at the substrate and decaying exponentially into the bulk liquid. The observed decay length and layering period point to an interfacial ordering mechanism, akin to the charge inversion effect, which is suggested to originate from strong correlations between the unscreened ions. The observed layering is expected to be a generic feature of RTILs at charged interfaces.

Water and ice in contact with octadecyl-trichlorosilane functionalized surfaces: a high resolution x-ray reflectivity study.

We present a high energy x-ray reflectivity study of the density profiles of water and ice at hydrophobic and hydrophilic substrates. At the hydrophobic water/octadecyl-trichlorosilane (water-OTS) interface, we find clear evidence for a thin density depletion layer with an integrated density deficit corresponding to approximately 40% of a monolayer of water molecules. We discuss the experimental results in terms of a simple model of hydrophobic/hydrophilic solid-liquid interfaces. Our results also exclude the presence of nanobubbles. A detailed study of possible radiation damage induced by the intense x-ray beam at the dry OTS surface and at the ice-OTS, as well as at water-OTS interfaces, discloses that noticeable damage is only induced at the water-OTS interface, and thus points to the dominant role of highly mobile radicals formed in bulk water close to the interface.

High-resolution in situ x-ray study of the hydrophobic gap at the water-octadecyl-trichlorosilane interface.

The knowledge of the microscopic structure of water at interfaces is essential for the understanding of interfacial phenomena in numerous natural and technological environments. To study deeply buried liquid water-solid interfaces, high-energy x-ray reflectivity measurements have been performed. Silicon wafers, functionalized by a self-assembled monolayer of octadecyl-trichlorosilane, provide strongly hydrophobic substrates. We show interfacial density profiles with angstrom resolution near the solid-liquid interface of water in contact with an octadecyl-trichlorosilane layer. The experimental data provide clear evidence for the existence of a hydrophobic gap on the molecular scale with an integrated density deficit rhod = 1.1 A g cm(-3) at the solid-water interface. In addition, measurements on the influence of gases (Ar, Xe, Kr, N(2), O(2), CO, and CO(2)) and HCl, dissolved in the water, have been performed. No effect on the hydrophobic water gap was found.

Scaling in the time domain: universal dynamics of order fluctuations in Fe3Al.

By focusing a highly brilliant synchrotron x-ray beam to a micrometer spot on a sample, we measured in real time the x-ray intensity fluctuations associated with order fluctuations in crystalline materials. We applied this method to the binary alloy Fe3Al near its continuous A2-B2 phase transformation and determined a specific four-point time correlation function for the order parameter. From a detailed theoretical analysis, dynamical scaling in the time domain with a transition from noncritical to critical dynamics is disclosed.