Development of an x-ray polarimeter at the SOLEIL synchrotron.

Synchrotron radiation facilities provide highly polarized x-ray beams across a wide energy range. However, the exact type and degree of polarization vary according to the beamline and experimental setup. To accurately determine the angle and degree of linear polarization, a portable x-ray polarimeter has been developed. This setup consists of a silicon drift detector that rotates around a target made of high-density polyethylene. The imprint generated in the angular distribution of scattered photons from the target at a 90-degree angle between the incident x-rays and detector has been exploited to determine the beam polarization. Measurements were conducted at the GALAXIES beamline of the SOLEIL synchrotron. The expected angular distribution of the scattered photons for a given beam polarization was obtained through simulations using the Geant4 simulation toolkit. An excellent agreement between simulations and the collected data has been obtained, validating the setup and enabling a precise determination of the beam polarization.

Exceptionally robust magnetism and structure of SrFeO[Formula: see text] above 100 GPa.

We report the exceptional structural and magnetic stability of SrFeO[Formula: see text] under pressure by X-Ray Magnetic Circular Dichroism (XMCD) and X-ray Diffraction (XRD) up to the Mbar range. The XMCD data confirm the onset of ferromagnetism above 30 GPa and its stability up to 102 GPa while XRD shows that SrFeO[Formula: see text] structure remains unchanged from 30 GPa up to 111 GPa without any sign of structural transition. Our results demonstrate the robustness of Fe properties under extreme conditions in the square planar environment.

Kondo-Induced Giant Isotropic Negative Thermal Expansion.

Negative thermal expansion is an unusual phenomenon appearing in only a handful of materials, but pursuit and mastery of the phenomenon holds great promise for applications across disciplines and industries. Here we report use of x-ray spectroscopy and diffraction to investigate the 4f-electronic properties in Y-doped SmS and employ the Kondo volume collapse model to interpret the results. Our measurements reveal an unparalleled decrease of the bulk Sm valence by over 20% at low temperatures in the mixed-valent golden phase, which we show is caused by a strong coupling between an emergent Kondo lattice state and a large isotropic volume change. The amplitude and temperature range of the negative thermal expansion appear strongly dependent on the Y concentration and the associated chemical disorder, providing control over the observed effect. This finding opens avenues for the design of Kondo lattice materials with tunable, giant, and isotropic negative thermal expansion.

A personally guided tour on some of our data with the Ames assay-A tribute to Professor Bruce Ames.

In contributing to this Special Issue of Mutation Research dedicated to Professor Bruce N. Ames in recognition of his 90th birthday in December 2018, we intend to portray the importance not only of the Ames Salmonella/mammalian-microsome mutagenicity assay in some of our studies over the years, but also the importance of the insight that Bruce Ames brought to the field of genetic toxicology.

Evidence for Collective Nonlinear Interactions in X Ray into Ultraviolet Parametric Down-Conversion.

We present the observation of peculiar nonmonotonic photon energy dependencies of the count rates and of the rocking curves of parametric down-conversion of x rays into ultraviolet far from any atomic resonances. The observations cannot be explained by models that consider only atomic or bond charge responses and suggest that collective phenomena contribute to the effect. We propose an interpretation that includes nonlinear interactions with plasmons, which can explain the existence of peaks in this energy range. Our Letter implies that nonlinear interactions between x rays and either ultraviolet or visible radiation can be utilized as a powerful atomic-scale probe for collective effects in solids.

The GALAXIES inelastic hard X-ray scattering end-station at Synchrotron SOLEIL.

GALAXIES is an in-vacuum undulator hard X-ray micro-focused beamline dedicated to the study of the electronic structure of materials with high energy resolution using both photoelectron spectroscopy and inelastic X-ray scattering and under both non-resonant (NR-IXS) and resonant (RIXS) conditions. Due to the penetrating power of hard X-rays and the `photon-in/photon-out' technique, the sample environment is not a limitation. Materials under extreme conditions, for example in diamond anvil cells or catalysis chambers, thus constitute a major research direction. Here, the design and performance of the inelastic X-ray scattering end-station that operates in the energy range from ∼4 keV up to 12 keV is reported, and its capabilities are highlighted using a selection of data taken from recently performed experiments. The ability to scan `on the fly' the incident and scattered/emitted X-ray energies, and the sample position enables fast data collection and high experimental throughput. A diamond X-ray transmission phase retarder, which can be used to generate circularly polarized light, will also be discussed in the light of the recent RIXS-MCD approach.

Chemistry of resistivity changes in TiTe/Al2O3 conductive-bridge memories.

We report the chemical phenomena involved in the reverse forming (negative bias on top electrode) and reset of a TaN/TiTe/Al2O3/Ta memory stack. Hard X-ray photoelectron spectroscopy was used to conduct a non-destructive investigation of the critical interfaces between the electrolyte (Al2O3) and the TiTe top and Ta bottom electrodes. During reverse forming, Te accumulates at the TiTe/Al2O3 interface, the TiOx layer between the electrolyte and the electrode is reduced and the TaOx at the interface with Al2O3 is oxidized. These interfacial redox processes are related to an oxygen drift toward the bottom electrode under applied bias, which may favour Te transport into the electrolyte. Thus, the forming processes is related to both Te release and also to the probable migration of oxygen vacancies inside the alumina layer. The opposite phenomena are observed during the reset. TiOx is oxidized near Al2O3 and TaOx is reduced at the Al2O3/Ta interface, following the O2- drift towards the top electrode under positive bias while Te is driven back into the TiTe electrode.

Characterization of Pd/Y multilayers with B4C barrier layers using GIXR and X-ray standing wave enhanced HAXPES.

Pd/Y multilayers are high-reflectance mirrors designed to work in the 7.5-11 nm wavelength range. Samples, prepared by magnetron sputtering, are deposited with or without B4C barrier layers located at the interfaces of the Pd and Y layers to reduce interdiffusion, which is expected from calculating the mixing enthalpy of Pd and Y. Grazing-incident X-ray reflectometry is used to characterize these multilayers. B4C barrier layers are found to be effective in reducing Pd-Y interdiffusion. Details of the composition of the multilayers are revealed by hard X-ray photoemission spectroscopy with X-ray standing wave effects. This consists of measuring the photoemission intensity from the samples by performing an angular scan in the region corresponding to the multilayer period and an incident photon energy according to Bragg's law. The experimental results indicate that Pd does not chemically react with B nor C at the Pd-B4C interface while Y does react at the Y-B4C interface. The formation of Y-B or Y-C chemical compounds could be the reason why the interfaces are stabilized. By comparing the experimentally obtained angular variation of the characteristic photoemission with theoretical calculations, the depth distribution of each component element can be interpreted.

Experimental setup for the study of resonant inelastic X-ray scattering of organometallic complexes in gas phase.

A new setup has been designed and built to study organometallic complexes in gas phase at the third-generation Synchrotron radiation sources. This setup consists of a new homemade computer-controlled gas cell that allows us to sublimate solid samples by accurately controlling the temperature. This cell has been developed to be a part of the high-resolution X-ray emission spectrometer permanently installed at the GALAXIES beamline of the French National Synchrotron Facility SOLEIL. To illustrate the capabilities of the setup, the cell has been successfully used to record high-resolution Kα emission spectra of gas-phase ferrocene Fe(C5H5)2 and to characterize their dependence with the excitation energy. This will allow to extend resonant X-ray emission to different organometallic molecules.

Ultrafast evolution and transient phases of a prototype out-of-equilibrium Mott-Hubbard material.

The study of photoexcited strongly correlated materials is attracting growing interest since their rich phase diagram often translates into an equally rich out-of-equilibrium behaviour. With femtosecond optical pulses, electronic and lattice degrees of freedom can be transiently decoupled, giving the opportunity of stabilizing new states inaccessible by quasi-adiabatic pathways. Here we show that the prototype Mott-Hubbard material V2O3 presents a transient non-thermal phase developing immediately after ultrafast photoexcitation and lasting few picoseconds. For both the insulating and the metallic phase, the formation of the transient configuration is triggered by the excitation of electrons into the bonding a1g orbital, and is then stabilized by a lattice distortion characterized by a hardening of the A1g coherent phonon, in stark contrast with the softening observed upon heating. Our results show the importance of selective electron-lattice interplay for the ultrafast control of material parameters, and are relevant for the optical manipulation of strongly correlated systems.

Ultrafast Charge Transfer Processes Accompanying KLL Auger Decay in Aqueous KCl Solution.

X-ray photoelectron and KLL Auger spectra were measured for the K^{+} and Cl^{-} ions in aqueous KCl solution. While the XPS spectra of these ions have similar structures, both exhibiting only weak satellites near the main line, the Auger spectra differ dramatically. Contrary to the chloride case, a very strong extra peak was found in the Auger spectrum of K^{+} at the low kinetic energy side of the ^{1}D state. Using the equivalent core model and ab initio calculations this spectral feature was assigned to electron transfer processes from solvent water molecules to the solvated cation. The observed charge transfer processes are suggested to play an important role in charge redistribution following single and multiple core-hole creation in atoms and molecules placed into environment.

Hybridization-controlled charge transfer and induced magnetism at correlated oxide interfaces.

At interfaces between conventional materials, band bending and alignment are classically controlled by differences in electrochemical potential. Applying this concept to oxides in which interfaces can be polar and cations may adopt a mixed valence has led to the discovery of novel two-dimensional states between simple band insulators such as LaAlO3 and SrTiO3. However, many oxides have a more complex electronic structure, with charge, orbital and/or spin orders arising from strong Coulomb interactions between transition metal and oxygen ions. Such electronic correlations offer a rich playground to engineer functional interfaces but their compatibility with the classical band alignment picture remains an open question. Here we show that beyond differences in electron affinities and polar effects, a key parameter determining charge transfer at correlated oxide interfaces is the energy required to alter the covalence of the metal-oxygen bond. Using the perovskite nickelate (RNiO3) family as a template, we probe charge reconstruction at interfaces with gadolinium titanate GdTiO3. X-ray absorption spectroscopy shows that the charge transfer is thwarted by hybridization effects tuned by the rare-earth (R) size. Charge transfer results in an induced ferromagnetic-like state in the nickelate, exemplifying the potential of correlated interfaces to design novel phases. Further, our work clarifies strategies to engineer two-dimensional systems through the control of both doping and covalence.

Electronic Properties of BaFe2As2 upon Doping and Pressure: The Prominent Role of the As p Orbitals.

Using high-resolution, lifetime removed, x-ray absorption spectroscopy at the As K edge, we evidence the strong sensitivity of the As electronic structure upon electron doping with Co or pressure change in BaFe2As2, at room temperature. Our results unravel the prominent role played by As-4p orbitals in the electronic properties of the Fe pnictide superconductors. We propose a unique picture to describe the overall effect of both external parameter doping and pressure, resolving the apparent contradiction between angle-resolved photoemission spectroscopy, transport, and absorption results, with the As-p states as a key ingredient.

The GALAXIES beamline at the SOLEIL synchrotron: inelastic X-ray scattering and photoelectron spectroscopy in the hard X-ray range.

The GALAXIES beamline at the SOLEIL synchrotron is dedicated to inelastic X-ray scattering (IXS) and photoelectron spectroscopy (HAXPES) in the 2.3-12 keV hard X-ray range. These two techniques offer powerful complementary methods of characterization of materials with bulk sensitivity, chemical and orbital selectivity, resonant enhancement and high resolving power. After a description of the beamline components and endstations, the beamline capabilities are demonstrated through a selection of recent works both in the solid and gas phases and using either IXS or HAXPES approaches. Prospects for studies on liquids are discussed.

La1-xLnxH(O3PCH3)2 (Ln = Tb, Eu; 0 < x ≤ 1): an organic-inorganic hybrid with lanthanide chains and tunable luminescence properties.

The organic/inorganic La1-xLnxH(O3PCH3)2 (Ln = Eu, Tb) hybrids have been synthesized by hydrothermal synthesis. The crystal structure of LaH(O3PCH3)2 consists of chains of edge-sharing LaO8 polyhedra linked through PO3C tetrahedra. Photoluminescence of Eu(3+), Tb(3+) and Eu(3+)/Tb(3+) co-doped materials have been investigated. The Eu and Tb hybrids show no concentration quenching versus doping rate suggesting energy migration through a percolation model. The Eu hybrids exhibit a red emission while the Tb ones exhibit, with the Tb rate increasing, a blue to green emission under a 378 nm excitation wavelength and a cyan to green emission under a 262 nm excitation wavelength. The doping rate dependent red shift results from a cross relaxation phenomenon between closed Tb(3+) ions. The blue to cyan shift observed for the slightly doped materials, when excitation wavelength shifts from 378 nm to 262 nm, is due to different relaxation phenomena, from the (5)D3 level for a 378 nm excitation wavelength and from the (5)D4 level via the 4f5d level for a 262 nm excitation wavelength. Under a 378 nm wavelength, the co-doped La0.93Eu0.03Tb0.04H(O3PCH3)2 hybrid exhibits a white/cyan emission with CIE coordinates equal to x = 0.29, y = 0.37.

Understanding the electronic structure of IrO2 using hard-X-ray photoelectron spectroscopy and density-functional theory.

The electronic structure of IrO2 has been investigated using hard x-ray photoelectron spectroscopy and density-functional theory. Excellent agreement is observed between theory and experiment. We show that the electronic structure of IrO2 involves crystal field splitting of the iridium 5d orbitals in a distorted octahedral field. The behavior of IrO2 closely follows the theoretical predictions of Goodenough for conductive rutile-structured oxides [J. B. Goodenough, J. Solid State Chem. 3, 490 (1971).

Understanding the complex phase diagram of uranium: the role of electron-phonon coupling.

We report an experimental determination of the dispersion of the soft phonon mode along [100] in uranium as a function of pressure. The energies of these phonons increase rapidly, with conventional behavior found by 20 GPa, as predicted by recent theory. New calculations demonstrate the strong pressure (and momentum) dependence of the electron-phonon coupling, whereas the Fermi-surface nesting is surprisingly independent of pressure. This allows a full understanding of the complex phase diagram of uranium and the interplay between the charge-density wave and superconductivity.

Iron under pressure: "Kohn tweezers" and remnant magnetism.

In this work we investigate the magnetic and structural properties of bulk Fe and Fe nanoparticles under pressure with x-ray absorption and emission spectroscopies providing answers to two fundamental questions: (a) the chicken-or-egg problem for the magnetic and structural transitions and (b) magnetism in the high pressure hcp phase. The two transitions, inextricably linked in the bulk, are clearly decoupled in the nanoparticles, with the magnetic collapse preceding the structural transition. Ultrafast x-ray emission spectroscopy detects remnant magnetism, probably antiferromagnetic fluctuations, up to pressures of about 40 GPa in the hcp phase. This could be of direct relevance to the superconductivity in ϵ-Fe [K. Shimizu et al., Nature (London) 412, 316 (2001)] through the existence of a quantum critical point and associated magnetic fluctuations.

Pressure-induced valence crossover in superconducting CeCu2Si2.

Measurement of the Ce valence in the heavy fermion CeCu(2)Si(2) is reported for the first time under pressure and at low temperature (T=14 K) in proximity of the superconducting region. CeCu(2)Si(2) is considered as a strong candidate for a new type of pairing mechanism related to critical valence fluctuations which could set in at high pressure in the vicinity of the second superconducting dome. A quantitative estimate of the valence in this pressure region was achieved from the measurements of the Ce L(3) edge in the high-resolution partial-fluorescence yield mode and subsequent analysis of the spectra within the Anderson impurity model. While a clear increase of the Ce valence is found, the weak electron transfer and the continuous valence change under pressure suggests a crossover regime with the hypothetical valence line terminating at a critical end point T(cr) close to zero.