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International audience; The surface chemistry of gold nanoparticles produced by the pulsed laser ablation in liquids method is investigated by X-ray photoelectron spectroscopy (XPS). The presence of surface oxide expected on these systems is investigated using synchrotron radiation in conditions close to their original state in solvent but free from substrate or solvent effects which could affect the interpretation of spectroscopic observations. For that purpose we performed the experiment on a controlled free-standing nanoparticle beam produced by combination of an atomizer and an aerodynamic lens system. These results are compared with those obtained by the standard situation of deposited nanoparticles on silicon substrate. An accurate analysis based on Bayesian statistics concludes that the existence of oxide in the free-standing conditions cannot be solely confirmed by the recorded core-level 4f spectra. If present, our data indicate an upper limit of 2.15 ± 0.68% of oxide. However, a higher credence to the hypothesis of its existence is brought by the structureless valence profile of the free-standing beam. Moreover, the cross-comparison with the deposited nanoparticles case clearly evidences an important misleading substrate effect. Experiment with free-standing nanoparticles is then demonstrated to be the right way to further investigate oxidation states on Au nanoparticles.

The sub-picosecond response of amorphous germanium telluride thin film to a femtosecond laser excitation is investigated using frequency-domain interferometry and ab initio molecular dynamics. The time-resolved measurement of the surface dynamics reveals a shrinkage of the film with a dielectric properties' response faster than 300 fs. The systematic ab initio molecular dynamics simulations in non-equilibrium conditions allow the atomic configurations to be retrieved for ionic temperature from 300 to 1100 K and width of the electron distribution from 0.001 to 1.0 eV. Local order of the structures is characterized by in-depth analysis of the angle distribution, phonon modes, and pair distribution function, which evidence a transition toward a new amorphous electronic excited state close in bonding/structure to the liquid state. The results shed a new light on the optically highly excited states in chalcogenide materials involved in both important processes: phase-change materials in memory devices and ovonic threshold switching phenomenon induced by a static field.

International audience; Pulsed laser ablation in liquid (PLAL) is a powerful method producing nanoparticle colloids with a long-term stability despite the absence of stabilizing organic agents. The colloid stability involves different reactivities and chemical equilibria with complex ionic-specific effects at the nanoparticle/solvent interface which must be strongly influenced by their chemical composition. In this work, the surface composition of PLAL-produced gold nanoparticles in alkaline and saline (NaBr) water is investigated by X-ray photoelectron spectroscopy on free-flying nanoparticles, exempt from any substrate or radiation damage artifact. The Au 4f photoelectron spectra with a depth profiling investigation are used to evaluate the degree of nanoparticle surface oxidation. In alkaline water, the results preclude any surface oxidation contrary to the case of nanoparticles produced in NaBr solution. In addition, the analysis of Br 3d core-level photoelectron spectra agrees with a clear signature of Br on the nanoparticle surface, which is confirmed by a specific valence band feature. This experimental study is supported by DFT calculations, evaluating the energy balance of halide adsorption on different configurations of gold surfaces including oxidation or adsorbed salts.

In the atmosphere of Titan, Saturn's main satellite, molecular growth is initiated by a chemistry involving charged and free-radical species. However, the respective contribution of these species to the complexification of matter is far from being known. This work presents a chemical analysis by mass spectrometry at relatively low pressure to characterize the formation pathways of the first aromatics, notably benzene, by irradiating a mixture N2/CH4 with EUV photons. Introduction It is now accepted that photochemical processes in the atmosphere of Titan, the largest of Saturn's 62 moons, directly influence the chemical composition of the liquid lakes and the surface hydrological activity. Thus, a detailed understanding of the chemistry of Titan's atmosphere is the way forward to a whole Titan modeling. In the highest atmospheric layers between 700 and 1100 km in altitude, N2 and CH4 are ionized and dissociated mainly by energetic EUV photons from solar radiation, leading to the formation of reactive species like ions and radicals among a diverse range of species hydrocarbons, amines, and imines. In the lower layers of the atmosphere, below 500km, hydrocarbons such as benzene and other aromatics by interaction with lower energy UV photons (>155 nm) are key compounds in the formation of larger and more complex molecules like Polycyclic Aromatic Hydrocarbons (PAHs) and Polycyclic Aromatic Nitrogen Heterocycles (PANHs). These intermediate species between small organic precursor molecules and larger carbonaceous materials, contribute to the production of aerosols which form the opaque photochemical haze layers that obscure the surface of Titan. Thus the identification of the pathways of formation of these species is essential for understanding the chemistry of Titan's atmosphere, but is yet to be fully understood even for the simplest PAH, namely benzene (C6H6). In situ and direct observations are insufficient to constrain photochemical models and understand the molecular complexification pathways of Titan's atmosphere. Thus the way forward is to reproduce the chemistry in the laboratory by irradiating a mixture of gases representative of this environment from a photon-producing energy source. Experimental Method In this study a nonlinear optics approach has been used to generate intense and stable light in the Extreme Ultraviolet (EUV) because energetic photons are absorbed in the upper atmospheric layers and initiate the formation of reactive species in the satellite ionosphere. The EUV light was produced by the high-order harmonic generation of the femtosecond BLASBEAT laser at CELIA in Bordeaux and injected into the closed and removable SURFACAT photoreactor to irradiate for several hours, at a pressure of 0.1mbar, a gas mixture composed of nitrogen and methane (95/5%) at a wavelength of 85.58 nm. This wavelength falls within the energy range of interest between the CH4 dissociation threshold (98 nm) and the N2 ionization threshold (79.4 nm), which allows the production of nitrogen atoms in its ground and excited state that are suspected of playing a fundamental role in the molecular growth of complex but as yet unknown nitrogen species. Results The results presented in Figure 1, show overall a good agreement between the products formed in the photochemical reactor and the data obtained in situ in Titan's atmosphere. Especially, there is good agreement for the peak at mass 78 which has been identified as benzene in Titan's atmosphere. Because of the importance of benzene in Titan's atmosphere, this study is dedicated to analyze its formation pathways in the photochemical reactor and the implications for our understanding of the chemistry of Titan's atmosphere. At the wavelength used in this experiment, photolysis of methane leads mainly to the formation of the CH4+ ion with a branching ratio of 47% and methyl radical ion (CH3+) and methylidyne radical (CH) with branching ratios of 19% and 18% respectively. While the formation of CH4+ leads to a closed cycle of methane formation, CH3+ is a source of C2H5+ ions by reaction with methane. These ions recombine to lead mainly to the formation of highly reactive ethylenyl radicals (C2H3). By reacting with hydrocarbon radicals such as butadienyl (C4H3), they are at the origin of phenyl radicals (C6H5), precursor of benzene by addition of a hydrogen atom. At the wavelength used in this experiment, the other dominant photoproduct of methane photolysis, CH, leads mainly to the formation of C2H4, whose photolysis by energetic photons leads mainly to the formation of hydrocarbon ions C2H2+ and C2H3+. These ions then lead to the formation of propargyl radicals (C3H3) which by recombining give rise to the formation of benzene. Implications for Titan's atmosphere The literature points out that the production of benzene in the upper atmospheric layers of Titan is due to radical-radical reactions but mainly to the chemistry of the ions via the dissociative recombination of aromatic ions such as C6H6+ and C6H7+. In less energetic conditions, such as photons from solar radiation arriving on Titan, the photolysis of methane leads mainly to the formation of hydrocarbon radicals (CH2 and CH3) which will contribute to many small neutral hydrocarbons (C2H2, C2H4) that will form heavy ions and prevent electronic recombinations. However, the troubling overlap between the benzene signal in this EUV-dominated work and that of INMS shows that it is crucial to have a good assessment of the branching ratios of radical-radical reactions at low pressures and low temperatures representative of Titan's atmosphere. Especially, association reactions can be rapid even at low pressures for adducts of significant size. Indeed, the most energetic photons are absorbed in the upper atmospheric layers to initiate molecular growth while the less energetic photons are absorbed lower in the atmosphere. Additionally, the detection of a signal at mass 92 in Figure 1, could be assigned to toluene (C7H8) and signal at mass 91 to its main fragment due to electronic impact by the ionization of the mass spectrometer used in this work. It confirms the importance of a rigorous analysis of neutral reactions, since toluene can be formed by the reaction between phenyl and methyl radicals, which, although poorly understood, involves one of the precursors of benzene whose formation would be favored in an environment with energetic photons.

We reveal the microscopic origin of the ovonic threshold switching mechanism., Fifty years after its discovery, the ovonic threshold switching (OTS) phenomenon, a unique nonlinear conductivity behavior observed in some chalcogenide glasses, has been recently the source of a real technological breakthrough in the field of data storage memories. This breakthrough was achieved because of the successful 3D integration of so-called OTS selector devices with innovative phase-change memories, both based on chalcogenide materials. This paves the way for storage class memories as well as neuromorphic circuits. We elucidate the mechanism behind OTS switching by new state-of-the-art materials using electrical, optical, and x-ray absorption experiments, as well as ab initio molecular dynamics simulations. The model explaining the switching mechanism occurring in amorphous OTS materials under electric field involves the metastable formation of newly introduced metavalent bonds. This model opens the way for design of improved OTS materials and for future types of applications such as brain-inspired computing.

International audience; Laser interaction with solids is routinely used for functionalizing materials' surfaces. In most cases, the generation of patterns/structures is the key feature to endow materials with specific properties like hardening, superhydrophobicity, plasmonic color‐enhancement, or dedicated functions like anti‐counterfeiting tags. A way to generate random patterns, by means of generation of wrinkles on surfaces resulting from laser melting of amorphous Ge‐based chalcogenide thin films, is presented. These patterns, similar to fingerprints, are modulations of the surface height by a few tens of nanometers with a sub‐micrometer periodicity. It is shown that the patterns' spatial frequency depends on the melted layer thickness, which can be tuned by varying the impinging laser fluence. The randomness of these patterns makes them an excellent candidate for the generation of physical unclonable function tags (PUF‐tags) for anti‐counterfeiting applications. Two specific ways are tested to identify the obtained PUF‐tag: cross‐correlation procedure or using a neural network. In both cases, it is demonstrated that the PUF‐tag can be compared to a reference image (PUF‐key) and identified with a high recognition ratio on most real application conditions. This paves the way to straightforward non‐deterministic PUF‐tag generation dedicated to small sensitive parts such as, for example, electronic devices/components, jewelry, or watchmak..

International audience; We present the Aurore platform for ultrafast sciences. This platform is based on a unique 20 W, 1 kHz, 26 fs Ti:Sapphire laser system designed for reliable operation and high intensity temporal contrast. The specific design ensures a high stability in terms of pulse duration, energy and beam pointing necessary for extended experimental campaigns. The laser supplies 5 different beamlines, all dedicated to a specific field: attosecond science (Aurore 1), ultrafast phase transitions in solids (Aurore 2 and 3), ultrafast luminescence in solids (Aurore 4), femtochemistry (Aurore 5). The technical specifications of these five beamlines are described in details and examples of recent results are given.

Synopsis Surface chemistry of gold nanoparticles produced by laser ablation in liquids has been investigated using synchrotron radiation and the X-ray Photoelectron Spectroscopy technique. Thanks to the recorded core-level and valence spectra, combined with a detailed analysis based on Bayesian statistical methods, the oxide presence and its proportion on the nanoparticle surface have been determined.

This work aims to study the lattice structural dynamics of metals under laser femtosecond excitation using time-resolved photoelectron spectroscopy (Tr-PES). When irradiated by short infrared laser pulses, the thermal out-of-equilibrium state established between hot electrons and a cold lattice rises specific dynamics where the thermodynamic properties of matter are still subject to debate. The theoretical description of highly excited materials is difficult and appeals new experimental results to improve the understanding of these physical processes and material properties. Nonetheless, important challenges arise from the use of Tr-PES. When metals are irradiated with strong femtosecond infrared laser pulses, non-linear effects, like multiphoton ionization, can take place and produce photoelectrons with tenths of eV of kinetic energy. This pump photoelectron background can conceal the probe-induced photoelectron spectrum, and perturb the probe spectrum via Coulomb interactions (called space-charge effect). To overcome these challenges three actions were carried out. We designed and built a 100 eV beamline to avoid the superposition between the pump background and the probe photoelectron spectrum. The pump/probe space-charge effect was extensively studied theoretically and experimentally. Finally, the pump photoemission was greatly reduced in our experiments by carefully tuning the experimental parameters. This led us to perform Tr-PES measurements on copper samples of the lattice structural dynamics following the evolution of the photoelectron spectrum. The experiment constituted a proof-of-principle of the Tr-PES technique to study materials under strong excitation.

The in situ exploration of Titan’s atmosphere requires the development of laboratory experiments to understand the molecular growth pathways initiated by photochemistry in the upper layers of the atmosphere. Key species and dominant reaction pathways are used to feed chemical network models that reproduce the chemical and physical processes of this complex environment. Energetic UV photons initiate highly efficient chemistry by forming reactive species in the ionospheres of the satellite. We present here a laboratory experiment based on a new closed and removable photoreactor coupled here to an Extreme Ultraviolet (EUV) irradiation beam produced by the high-order harmonic generation of a femtosecond laser. This type of EUV stable source allow long-term irradiation experiments in which a plethora of individual reactions can take place. In order to demonstrate the validity of our approach, we irradiated for 7 hours at 89.2 nm, a gas mixture based on N2/CH4 (5%). Using only one wavelength, products of the reaction reveal an efficient photochemistry with the formation of large hydrocarbons but especially organic compounds rich in nitrogen similar to Titan. Among these nitrogen compounds, new species had never before been identified in the mass spectra obtained in situ in Titan’s atmosphere. Their production in this experiment, on the opposite, corroborates previous experimental measurements in the literature on the chemical composition of aerosol analogues produced in the laboratory. Diazo-compounds such as dimethyldiazene (C2H6N2), have been observed and are consistent with the large nitrogen incorporation observed by the aerosols collector pyrolysis instrument of the Huygens probe. This work represents an important step forward in the use of a closed cell chamber irradiated by the innovative EUV source for the generation of photochemical analogues of Titan aerosols. This approach allows to better constrain and understand the growth pathways of nitrogen incorporation into organic aerosols in Titan’s atmosphere.

International audience; The chemical and geometrical structure of free-standing carbon dots (Cdots) prepared from the pyrolysis of N-hydroxysuccinimide (NHS) have been characterized using X-ray photoelectron spectroscopy (XPS). An aerodynamic lens system was used to generate a sufficient particle density of monodispersed Cdots for XPS studies at the PLEIADES beamline at the SOLEIL synchrotron facility. Varying the X-ray excitation energy between 315 and 755 eV allows probing of the Cdots from the surface toward their core, owing to the kinetic energy dependence of the photoelectron inelastic mean free path. The C 1s, O 1s, and N 1s core-levels were recorded with high-spectral resolution to identify their main chemical components and branching ratios. While high-resolution transmission electron microscopy (HRTEM) reveals a defective graphitic core, the C 1s spectrum evidence two main peaks similar to those measured from the solid NHS. Their relative abundance as a function of the probing depth is strongly related to the chemical composition of the ligand shell that does not vary substantially over the first 3.4 nm. Combining the depth-resolved XPS and HRTEM studies, it was concluded that the Cdots possess a graphitic core surrounded by a relatively homogeneous shell of at least 3.4 nm thickness with a composition similar to that of the solid NHS.

Chalcogenide Phase-Change Materials (PCMs), mainly GeSbTe-based alloys, have already been widely used for optical data storage in DVD-RAM or CD-RW. Thanks to their unique reversible and very fast amorphous to crystalline phase transition which is characterized by an uncommon huge change in optical and electrical properties, PCMs are now extensively studied aiming at developing innovative emerging non-volatile memories such as phase change random access memory (PCRAM) or storage class memories (SCM) in order to replace current dominant Flash memory technology [1]. The interaction of PCMs with a fs light pulse has attracted significant attention due to fundamental interest since the possible non-thermal amorphous↔crystal phase transition could be used as a process to drive the phase change above the thermal “speed limits” [2]. Our experiments address the investigation of ultra-fast phenomena of fundamentals laser-material interaction. Frequency domain interferometry (FDI) [3] is a pump-probe experiment that gives access to the variation of the refractive index of a material. A pump pulse (25 fs, 800 nm, 1kHz) is used to trigger a phase transition. The probe beam is made of two pulses (120 fs, 532 nm) delayed by 9 ps in our case which are focused on the pump/sample interaction point. The first probe pulse impinges the surface of the sample before the pump pulse, and is thus reflected on the unperturbed material, while the second one that arrives after the pump pulse, is reflected on the pump-heated material. Both pulses are then sent in a spectrometer where they interfere in the frequency domain. The intensity variation and phase shifts in the interference pattern (right image in the fig. 1) can be used to retrieve variations of the optical constant of the heated material. The interference pattern is simultaneously measured for the S ans P polarization independently. The samples are amorphous GeSbTe-based thin film deposited by magnetron sputtering in a 200 mm industrial deposition tool at in the LETI clean-rooms. A 10 nm thick SiN capping layer of hwas been coated deposited on top of the GST films in order to prevent surface oxidation. We will present the results obtained on prototypical PCMs thin films, i.e. Ge2Sb2Te5 and GeTe. Experiments have been conducted in the fluence range (from 17 to 31 mJ/cm2 ) allowing us to trigger the amorphous to crystal phase transition. Dynamics on the sub-ps time scale shows a very rapid switch mainly attributed to the real part of the refractive index. The polarisation resolved FDI permits to foster information on the behaviour of the surface. A clear phase shift is attributed to a contraction, in the nm range, and the sub-ps time scale. The results presented will be discussed and compared to on-going ab-initio simulations. [1] P. Noe et al., “Phase Change Materials for Non-Volatile Memory devices: From Technological Challenges to Materials Science Issues”, Topical Review in Semicond. Sci. Technol., to be published (2017). [2] D. Loke et al. “Breaking the Speed Limits of Phase-Change Memory” Science 336, 1566 (2012) [3] J.P. Geindre et al., “Frequency-domain interferometer for measuring the phase and amplitude of a femtosecond pulse probing a laser-produced plasma” Optics Letters 19, 1997 (1994).

The silicon sample irradiated with femtosecond soft X-ray pulses at the Linac Coherent Light Source has been studied with several synchrotron X-ray diffraction topographic methods at HASYLAB. The irradiations were performed for two different wavelengths combined with various impact energy controlled by means of the gas attenuator. The topographic investigation revealed characteristic images of the created craters included the inner region reflecting the X-rays at lower angle, coming most probably from part of the silicon melted during the irradiation. The melted region was surrounded by strained outer region, similar to those observed in the case of rod-like inclusion but less regular in view of some irregularity of the beam used for generation of the craters. It was observed that the higher impact energy higher dose of the irradiating pulses resulted in increasing diameter of the melted area of the crater and the range of the strained region around it. Some features of the monochromatic and white beam back reflection section images of the craters were reproduced in numerically simulated images approximating the strain field in the crater by a droplet containing uniformly distributed point inclusions.

The use of soft X-rays near the carbon edge of absorption (270–300 eV) greatly enhances studies in various branches of science. However, the choice of reflecting coatings for mirrors operating in free-electron and X-ray free-electron laser (FEL and XFEL) beamlines in this spectral range is not so evident and experimental justifications of the mirror efficiency are rather limited. In the present paper it is demonstrated experimentally that the reflectivity of B4C- and Ni-coated grazing-incidence mirrors is high enough for their operation in FEL or XFEL beamlines near the carbonK-edge of absorption. The minimal reflectivity of both mirrors proves to exceed 80% near the carbon absorption edge at a grazing angle of 0.6°. An in-depth profile of the chemical elements composing the reflecting coatings is reconstructed based on analysis of a set of reflectivity curves measuredversusthe grazing angle at different photon energies in the soft X-ray spectral region. This allows us to predict correctly the mirror reflectivity at any X-ray energy and any grazing angle.

Physical review / B 96(21), 214101 (2017). doi:10.1103/PhysRevB.96.214101, All carbon materials, e.g., amorphous carbon (a-C) coatings and $C_{60}$ fullerene thin films, play an important role in short-wavelength free-electron laser (FEL) research motivated by FEL optics development and prospective nanotechnology applications. Responses of a-C and $C_{60}$ layers to the extreme ultraviolet (SPring-8 Compact SASESource in Japan) and soft x-ray (free-electron laser in Hamburg) free-electron laser radiation are investigated by Raman spectroscopy, differential interference contrast, and atomic force microscopy. A remarkable difference in the behavior of covalent (a-C) and molecular ($C_{60}$) carbonaceous solids is demonstrated under these irradiation conditions. Low thresholds for ablation of a fullerene crystal (estimated to be around 0.15 eV/atom for $C_{60}$ vs 0.9 eV/atom for a-C in terms of the absorbed dose) are caused by a low cohesive energy of fullerene crystals. An efficient mechanism of the removal of intact $C_{60}$ molecules from the irradiated crystal due to Coulomb repulsion of fullerene-cage cation radicals formed by the ionizing radiation is revealed by a detailed modeling., Published by Inst., Woodbury, NY

Interaction of short-wavelength free-electron laser (FEL) beams with matter is undoubtedly a subject to extensive investigation in last decade. During the interaction various exotic states of matter, such as warm dense matter, may exist for a split second. Prior to irreversible damage or ablative removal of the target material, complicated electronic processes at the atomic level occur. As energetic photons impact the target, electrons from inner atomic shells are almost instantly photo-ionized, which may, in some special cases, cause bond weakening, even breaking of the covalent bonds, subsequently result to so-called non-thermal melting. The subject of our research is ablative damage to lead tungstate (PbWO4) induced by focused short-wavelength FEL pulses at different photon energies. Post-mortem analysis of complex damage patterns using the Raman spectroscopy, atomic-force (AFM) and Nomarski (DIC) microscopy confirms an existence of non-thermal melting induced by high-energy photons in the ionic monocrystalline target. Results obtained at Linac Coherent Light Source (LCLS), Free-electron in Hamburg (FLASH), and SPring-8 Compact SASE Source (SCSS) are presented in this Paper.

Silicon crystalline samples were exposed to intense single pulses of XUV radiation ( λ =13.5 nm) what lead to melting and ablation of the surface material. The deformation field around craters along the whole thickness of silicon wafers was observed by means of the synchrotron transmission section topography using the beam perpendicular to the surface of the sample. The geometrical shape and depth extension around craters was evaluated based on numerous, dense series of section topographs spaced by 10 µm. In the topographs we observed the direct image connected with the boundary of the crater associated with some deformation of the Kato fringes. The evaluated depth extension, different for individual craters, was in the range of 30–100 µm. The depth values were confirmed also by evaluations based on the Bragg case section topographs. It was possible to reproduce the contrast of the craters in transmission section topographs by numerical simulation based on integration of the Takagi–Taupin equations. The damage of the crystal defects connected with craters was approximated as droplet-like inclusions.

International audience; We describe a model for the study of the interaction of short X-ray Free-Electron Laser (XFEL) pulses with large finite samples. Hydrodynamics is solved in one-dimensional planar geometry with consideration of the electron-ion energy exchange and of the possible elasto-plastic behavior. From a time-dependent calculation of the complex refractive index and of the underlying atomic physics, XFEL energy deposition is modeled through a calculation of the radiation field in the material. In the case of hard X-ray irradiation, energetic electrons induced by the XFEL absorption can propagate and deposit their energy outside the interaction region. Simulations of the interaction of hard X-ray ultrashort pulses with solid materials Ru and Si at different grazing incidence angles are presented and discussed. The results obtained demonstrate the potential of this approach to predict damage dynamics for materials of interest for X-ray optics.

We report a recent experiment where the first hard x-ray beam line, X-ray Pump Probe (XPP) instrument using the SLAC National Accelerator Laboratory's Linac Coherent Light Source (LCLS) free electron laser, was used to heat thin foils to high energy densities ∼ 107 J/cm 3. An intense 9 keV, 60 fs (FWHM) duration beam with energy of 2 - 4 mJ at the XPP beam line was focused using beryllium lenses to an irradiance approaching 1016 Wcm -2. Targets of 0.5 - 3.5 μm thick foils of Ag and Cu were studied using a suite of diagnostics including Fourier Domain Interferometry, energy calorimetry and grating and crystal spectrometers. The experimental details and spectroscopic results from the campaign will be described. Preliminary results indicate that the target is heated relatively uniformly to a temperature lower than 20 eV. © 2011 SPIE.

An important problem in the experiments performed with the intense fourth generation X-ray sources is the damages of the examined samples caused by the high energy impact. The effect introduced by the beam from the FLASH source in crystalline silicon samples was studied through synchrotron white beam projection and section topography, enabling the evaluation of the strain field associated with the damages. The topographs indicated the existence of deformed field of cylindrical symmetry providing the dark contrast. It was also shown that some of the Bragg-case section images of spots in silicon correspond well to the simulated images of rod-like inclusions.

We develop a theory describing the heating of electrons in crystalline insulators irradiated by high-intensity laser pulses. In agreement with photoelectron yield versus intensity measurements, we assume that electrons are excited into the conduction band from defect layers and traps. The electron dynamics due to direct inter-branch transitions within the conduction band is simulated by solving of time-dependant Schrodinger equation. The set of levels for this equation is supposed to be random with a distribution function equal to the density of states in the conduction band. The influence of different parameters on the electron heating efficiency is studied. The theory is applied for diamond; the theoretical spectrum is in qualitative agreement with the experimental observations.

The structural properties of liquid silica at high pressure and moderate temperature conditions, also referred to as the warm dense matter regime, were investigated using time-resolved $K$-edge x-ray absorption spectroscopy and ab initio calculations. We used a nanosecond laser beam to compress uniformly a solid $\mathrm{Si}{\mathrm{O}}_{2}$ target and a picosecond laser beam to generate a broadband x-ray source. We obtained x-ray absorption spectra at the Si $K$ edge over a large pressure-temperature domain to probe the liquid phase up to 3.6 times the normal solid density. Using ab initio simulations, we are able to interpret the changes in the x-ray absorption near-edge structure with increasing densities as an increase in the coordination number of silicon by oxygen atoms from 4 to 9. This indicates that, up to significant temperatures, the liquid structure becomes akin to what is found in the solid $\mathrm{Si}{\mathrm{O}}_{2}$ phases.

International audience; An irreversible response of inorganic scintillators to intense soft x-ray laser radiation was investigated at the FLASH (Free-electron LASer in Hamburg) facility. Three ionic crystals, namely, Ce:YAG (cerium-doped yttrium aluminum garnet), PbWO4 (lead tungstate), and ZnO (zinc oxide), were exposed to single 4.6 nm ultra-short laser pulses of variable pulse energy (up to 12 μJ) under normal incidence conditions with tight focus. Damaged areas produced with various levels of pulse fluences, were analyzed on the surface of irradiated samples using differential interference contrast (DIC) and atomic force microscopy (AFM). The effective beam area of 22.2 ± 2.2 μm2 was determined by means of the ablation imprints method with the use of poly(methyl methacrylate) - PMMA. Applied to the three inorganic materials, this procedure gave almost the same values of an effective area. The single-shot damage threshold fluence was determined for each of these inorganic materials. The Ce:YAG sample seems to be the most radiation resistant under the given irradiation conditions, its damage threshold was determined to be as high as 660.8 ± 71.2 mJ/cm2. Contrary to that, the PbWO4 sample exhibited the lowest radiation resistance with a threshold fluence of 62.6 ± 11.9 mJ/cm2. The threshold for ZnO was found to be 167.8 ± 30.8 mJ/cm2. Both interaction and material characteristics responsible for the damage threshold difference are discussed in the article.

Nous presentons les resultats d'etudes de luminescence resolue en temps emise par des cristaux sous excitation par des photons VUV issus de la generation d'harmoniques d'ordre eleve. L'utilisation d'un laser Ti-Sa PLFA a Saclay, qui delivre des impulsions d'une energie de 13 mJ et d'une duree de 35 fs a 1 KHz, pour la generation des harmoniques dans l'Argon et la microfocalisation du faisceau VUV nous ont permis de faire varier la densite du rayonnement sur la cible dans une large gamme. Nous avons etudie l'effet de la densite d'excitation VUV sur la luminescence intrinseque de cristaux a large bande interdite (CdWO 4 et BaF 2 ). En fonction de la densite d'excitation VUV nous avons observe les modifications des spectres d'emission et de la cinetique de la luminescence excitonique. Quand la densite d'excitation VUV croit, le rendement de la luminescence diminue et apparaissent dans la cinetique de luminescence des composantes rapides. Le profil de la courbe de declin devient alors complexe avec une forte deviation de la loi exponentielle dans sa partie initiale.

Recemment nous avons debute des series d'experiences sur l'interaction d'impulsions intenses VUV avec les solides luminescents. Le but principal en est l'etude des mecanismes d'interaction et de transfert d'energie entre les excitations electrcniques dans les solides a large bande interdite. L'application directe de ces etudes sera le developpement de materiaux et de methodes de metrologie pour les faisceaux UVX intenses. Nous presentons les resultats obtenus pour CdWO 4 qui montrent que ce cristal pourra servir comme un scintillateur pour le rayonnement VUV intense.

We used high order harmonics of a femtosecond titanium-doped sapphire system (pulse duration 25 fs) to realise Ultraviolet Photoelectron Spectroscopy (UPS) measurements on diamond. The UPS spectra were measured for harmonics in the range 13 to 27. We also made ab initio calculations of the electronic lifetime of conduction electrons in the energy range produced in the UPS experiment. Such calculations show that the lifetime suddenly diminishes when the conduction electron energy reaches the plasmon energy, whereas the UPS spectra show evidence in this range of a strong relaxation mechanism with an increased production of low energy secondary electrons. We propose that in this case the electronic relaxation proceeds in two steps: excitation of a plasmon by the high energy electron, the latter decaying into individual electron-hole pairs, as in the case of metals. This process is observed for the first time in an insulator and, on account of its high efficiency, should be introduced in the models of laser breakdown under high intensity.

We have measured the relaxation of photo-excited carriers in different wide band gap dielectrics by using time resolved two-colour photoemission. Electrons are excited by an ultra-short pulse of VUV photons directly in the conduction band. They are then are re-excited by an IR probe pulse. The evolution of the photoemission spectra as a function of the pump-probe delay gives direct information on the relaxation of the population of excited electron. (© 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)

We measured photoemission spectra for a number of insulators (CsI, Diamond, SiO2, CeF3) excited by femtosecond Ti-Sapphire laser pulses at peak intensities, from 0.5 to 6 TW/cm2, which are at least one order of magnitude below the optical breakdown threshold. An intense and pronounced plateau of high energy electrons appears in the photoelectron spectra in this intensity range, which extends up to 30-40 eV at the highest intensities, which we used. The excitation of electrons at high energies is treated in terms of direct interbranch transitions in the conduction band of insulator. These processes are described using calculations based on numerical solution of time dependant Schrodinger equation (TDSE) for Bloch electrons in electric fields. (© 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)

We investigated relaxation of free charge carriers in pure crystalline diamond exposed to VUV irradiation of high order harmonics of femtosecond Ti:Sa laser in the spectral range 17–32 eV. Electron–hole pairs, possessing a significant kinetic energy, are generated in the material via direct interband transitions, relaxation of which is monitored by means of induced conductivity in the bulk and photoemission from the surface of the material. The experimental data provided by these complementary techniques are compared and discussed in terms of the competition between ionization and conductivity looking for evidences of multiplication of free charge carriers due to impact ionization.

We investigate the photoemission for a set of wide band-gap crystals irradiated by femtosecond Ti-Sapphire laser pulses at intensities varying from 0.5 to 6 TW/cm2 (below the optical breakdown threshold). The measured total electron yield increases linearly with the laser intensity in this intensity range. An intense and wide plateau of high energy electrons appears in the photoelectron spectra at excitation intensities larger than 1 TW/cm2. The exponential cut-off of this plateau reaches 40 eV at maximal applied intensities. In order to explain such a behavior, we propose a mechanism where the heating is due to a sequence of direct interbranch one- and multi-photon transitions in the conduction band.

High-order harmonic generation in polyatomic molecules generally involves multiple channels of ionization. Their relative contribution can be strongly influenced by the presence of resonances, whose assignment remains a major challenge for high-harmonic spectroscopy. Here we present a multi-modal approach for the investigation of unaligned polyatomic molecules, using SF6 as an example. We combine methods from extreme-ultraviolet spectroscopy, above-threshold ionization and attosecond metrology. Fragment-resolved above-threshold ionization measurements reveal that strong-field ionization opens at least three channels. A shape resonance in one of them is found to dominate the signal in the 20–26 eV range. This resonance induces a phase jump in the harmonic emission, a switch in the polarization state and different dynamical responses to molecular vibrations. This study demonstrates a method for extending high-harmonic spectroscopy to polyatomic molecules, where complex attosecond dynamics are expected., Strong-field ionization in molecules is more complex than in atoms with multiple channel dynamics and a coherent superposition of electronic states. Here, Ferré et al. develop multi-modal spectroscopy to measure those dynamics and reveal a resonant to non-resonant high-harmonic generation transition.

International audience; Taking advantage of the new opportunities provided by x-ray free electron laser (FEL) sources when coupled to a long laser pulse as available at the Linear Coherent Light Source (LCLS), we have performed x-ray absorption near-edge spectroscopy (XANES) of laser shock compressed iron up to 420 GPa (±50) and 10 800 K (±1390). Visible diagnostics coupled with hydrodynamic simulations were used to infer the thermodynamical conditions along the Hugoniot and the release adiabat. A modification of the pre-edge feature at 7.12 keV in the XANES spectra is observed above pressures of 260 GPa along the Hugoniot. Comparing with ab initio calculations and with previous laser-heated diamond cell data, we propose that such changes in the XANES pre-edge could be a signature of molten iron. This interpretation then suggests that iron is molten at pressures and temperatures higher than 260 GPa (±29) and 5680 K (±700) along the principal Fe Hugoniot.

X-ray Free Electron Lasers (XFELs) have the potential to contribute to many fields of science and to enable many new avenues of research, in large part due to their orders of magnitude higher peak brilliance than existing and future synchrotrons. To best exploit this peak brilliance, these XFEL beams need to be focused to appropriate spot sizes. However, the survivability of X-ray optical components in these intense, femtosecond radiation conditions is not guaranteed. As mirror optics are routinely used at XFEL facilities, a physical understanding of the interaction between intense X-ray pulses and grazing incidence X-ray optics is desirable. We conducted single shot damage threshold fluence measurements on grazing incidence X-ray optics, with coatings of ruthenium and boron carbide, at the SPring-8 Angstrom compact free electron laser facility using 7 and 12 keV photon energies. The damage threshold dose limits were found to be orders of magnitude higher than would naively be expected. The incorporation of energy transport and dissipation via keV level energetic photoelectrons accounts for the observed damage threshold.

International audience; The time evolution of the electron structure is investigated in a molybdenum foil heated up to the warm dense matter regime by a femtosecond laser pulse, through time-resolved x-ray absorption near-edge spectroscopy. Spectra are measured with independent characterizations of temperature and density. They are successfully compared with ab initio quantum molecular dynamic calculations. We demonstrate that the observed white line in the L-3 edge reveals the time evolution of the electron density of state from the solid to the hot (a few eV) and expanding liquid. The data indicate a highly nonequilibrated state, 5 ps after heating.

Femtosecond lasers are promising tools for micro-machining requiring high surface quality and reliability. One of the many remarkable features in the case of transparent dielectrics is the shallowness of ablated craters, a still unexplained phenomena. We have measured the shape of ablated craters in corundum (α-Al2O3) for various pulse duration (from 60 fs to 14 ps). The evolution of ablated craters depth and shape with laser intensity depends on the pulse duration. Below 1 ps there is a clear threshold above which the depth increases dramatically from 0 to 100 nm, and then slowly increases with laser intensity. For longer pulses, the craters are much more shallow—about 20 nm, and we observe above a second threshold the appearance of a deeper hole in the centre of the first. The fundamental laser–matter interaction mechanisms at work during ablation are discussed. A model aiming to link these microscopic processes and the macroscopic measurements of ablation craters is presented and its results are compared to the experimental data.

We investigate the evolution of the electronic structure of fused silica in a dense plasma regime using time-resolved x-ray absorption spectroscopy. We use a nanosecond (ns) laser beam to generate a strong uniform shock wave in the sample and a picosecond (ps) pulse to produce a broadband x-ray source near the Si $K$ edge. By varying the delay between the two laser beams and the intensity of the ns beam, we explore a large thermodynamical domain with densities varying from 1 to $5\text{ }\text{ }\mathrm{g}/{\mathrm{cm}}^{3}$ and temperatures up to 5 eV. In contrast to normal conditions where silica is a well-known insulator with a wide band gap of 8.9 eV, we find that shocked silica exhibits a pseudogap as a semimetal throughout this thermodynamical domain. This is in quantitative agreement with density functional theory predictions performed using the generalized gradient approximation.

International audience; The rapidly growing ultrafast science with X-ray lasers unveils atomic scale processes with unprecedented time resolution bringing the so called "molecular movie'' within reach. X-ray absorption spectroscopy is one of the most powerful x-ray techniques providing both local atomic order and electronic structure when coupled with ad-hoc theory. Collecting absorption spectra within few x-ray pulses is possible only in a dispersive setup. We demonstrate ultrafast time-resolved measurements of the LIII-edge x-ray absorption near-edge spectra of irreversibly laser excited Molybdenum using an average of only few x-ray pulses with a signal to noise ratio limited only by the saturation level of the detector. The simplicity of the experimental set-up makes this technique versatile and applicable for a wide range of pump-probe experiments, particularly in the case of non-reversible processes.

International audience; We present an overview of some recent theoretical and experimental results obtained on the properties of iron and silica at conditions encountered in planetary interiors. The first part is concerned with the development of x-ray absorption near edge spectroscopy in dynamical experiments using high-energy lasers as a tool to investigate phase transitions and structural changes at extreme pressure-temperature conditions for these two key constituents. The second part focuses on the development of a quasi-isentropic compression technique to achieve the pressure-temperature conditions anticipated in planetary interiors (3-10 Mbar, 5000-8000 K). The experiments were performed using the LULI, LLNL and LIL high-energy lasers' facilities. The experimental results are analyzed using first-principle simulations based on density functional theory.

We studied experimentally and theoretically the structural transition of diamond under an irradiation with an intense femtosecond extreme ultraviolet laser (XUV) pulse of 24–275 eV photon energy provided by free-electron lasers. Experimental results obtained show that the irradiated diamond undergoes a solid-to-solid phase transition to graphite, and not to an amorphous state. Our theoretical findings suggest that the nature of this transition is nonthermal, stimulated by a change of the interatomic potential triggered by the excitation of valence electrons. Ultrashort laser pulse duration enables to identify the subsequent steps of this process: electron excitation, band gap collapse, and the following atomic motion. A good agreement between the experimentally measured and theoretically calculated damage thresholds for the XUV range supports our conclusions.

In this article, we describe the experimental station and procedures for investigating the interaction of short-wavelength free-electron lasers (FELs) pulses with solids. With the advent of these sources, a unique combination of radiation properties (including wavelength range from tens of nanometers down to sub-Angstroms, femtosecond pulse duration, and high pulse energy reaching milli-Joules level) creates new research possibilities for the systematic studies of radiation-induced structural changes in solids. However, the properties of the intense FEL radiation generate, apart from the new experimental opportunities, extreme demands on the experimental set-up (mostly in terms of radiation hardness of detectors and their saturation levels). Thus, radiation-induced phase transitions in solids, beyond the fundamental scientific interest, are of importance for the design of FEL beamlines and instruments which interact with the direct beam. In this report, we focus on the instrumentation and experimental techniques used in the recent studies performed at the FLASH facility in Hamburg.

We present the results of an experiment where amorphous carbon undergoes a phase transition induced by femtosecond 830 eV x-ray free-electron laser pulses. The phase transition threshold fluence is found to be 282 +/- 11 mJ/cm(2). Atomic force microscopy, photoelectron microscopy, and micro-Raman spectroscopy give experimental evidence for the phase transition in terms of a volume expansion, graphitization, and change of local order of the irradiated sample area. The interaction is modeled by an accurate time-dependent treatment of the ionization dynamics coupled to a two-temperature model. At the phase transition fluence threshold the free-electron density N-e is found to be at maximum 9 x 10(20) cm(-3) while the ion (atom) temperature is found to be 1050 K, e.g., above the crystallization activation temperature reported in the literature. This low ionization rate and high atom temperature suggest a thermally activated phase transition.

The interaction of free electron laser pulses with grating structure is investigated using 4.6 +/- 0.1 nm radiation at the FLASH facility in Hamburg. For fluences above 63.7 +/- 8.7 mJ/cm(2), the interaction triggers a damage process starting at the edge of the grating structure as evidenced by optical and atomic force microscopy. Simulations based on solution of the Helmholtz equation demonstrate an enhancement of the electric field intensity distribution at the edge of the grating structure. A procedure is finally deduced to evaluate damage threshold. (C) 2012 Optical Society of America

We characterize the phase shift induced by reflection on a multilayer mirror in the extreme UV range (80-93 eV) using two techniques: one based on high order harmonic generation and attosecond metrology (reconstruction of attosecond beating by interference of two-photon transitions), and a second based on synchrotron radiation and measurements of standing waves (total electron yield). We find an excellent agreement between the results from the two measurements and a flat group delay shift (+/- 40 as) over the main reflectivity peak of the mirror. (C) 2011 Optical Society of America

A laser-based tabletop approach to femtosecond time-resolved photoelectron spectroscopy with photons in the vacuum-ultraviolet (VUV) energy range is described. The femtosecond VUV pulses are produced by high-order harmonic generation (HHG) of an amplified femtosecond Ti:sapphire laser system. Two generations of the same setup and results from photoelectron spectroscopy in the gas phase are discussed. In both generations, a toroidal grating monochromator was used to select one harmonic in the photon energy range of 20-30 eV. The first generation of the setup was used to perform photoelectron spectroscopy in the gas phase to determine the bandwidth of the source. We find that our HHG source has a bandwidth of 140 ± 40 meV. The second and current generation is optimized for femtosecond pump-probe photoelectron spectroscopy with high flux and a small spot size at the sample of the femtosecond probe pulses. The VUV radiation is focused into the interaction region with a toroidal mirror to a spot smaller than 100 × 100 μm(2) and the flux amounts to 10(10) photons/s at the sample at a repetition rate of 1 kHz. The duration of the monochromatized VUV pulses is determined to be 120 fs resulting in an overall pump-probe time resolution of 135 ± 5 fs. We show how this setup can be used to map the transient valence electronic structure in molecular dissociation.

The recent development of intense sources in the XUV range (10-100 nm), such as X-ray laser, Free Electron Laser and High order Harmonics (HoH), allows the study of high flux processes and ultra-fast dynamics in various domains. At the SLIC facility of CEA-Saclay, we have built a gas-harmonic beamline to investigate the interaction of intense XUV pulse with solids. High Harmonics of an IR laser (Ti:Sa at 800 nm, 35 fs, 13 mJ/pulse, 1 kHz) are generated in a rare gas cell (Xe). The useful XUV range (40-60 nm) is selected with metallic filters. The harmonic beam is focused with a parabolic mirror to a 10 μm focal spot on sample, leading to a fluence per shot of up to 1 mJ/cm 2 (within a typical 10 fs pulse duration). Studies aimed at understanding the damaging mechanisms caused by XUV irradiation on surface of various samples by systematically varying of fluence and exposure time. For PMMA irradiated in the desorption regime (fluence/shot ≤ 0.2 mJ/cm2), the surface presents craters whose profile depends on the dose (Grey [Gy] = 1 J/kg). The crater evolution proceeds from the competition between two main degradation processes, that is chain scission and cross linking. Namely, at low dose (≤ 1 GGy) polymer chain scission is followed by the blow up of the volatile, molecular fragments, forming the crater. At high dose (> 10 GGy) the broken chain-ends, in the near-surface layer of the remaining material, recombine by cross-linking, opposing desorption by surface hardening. In a recent experiment at LCLS FEL facility, PMMA was irradiated at high fluence; the cross-linking signature was identified from Raman spectroscopy. A kinetic model could be adapted for interpreting these original and very promising results.

X-ray mirrors are needed for beam steering, beam alignment and monochromatisation at advanced research light sources like 3rd generation synchrotron sources (e.g. PETRA III in Hamburg) or Free-Electron Lasers (for instance FLASH or the European XFEL). At the Helmholtz-Zentrum Geesthacht (formerly GKSS), an in-house designed magnetron sputtering facility for the deposition of single layers and multilayers has been installed for the development of x-ray optics. Earlier results showed that the thin-film fabrication of 1.5 m long amorphous carbon coatings was very successful. These single layers are currently used as total reflection mirrors at FLASH to steer the photon beam to the various beamlines. A major advantage of the sputtering facility is that it is now possible to prepare one, two or more mirrors with similar properties over the whole deposition length. In this contribution we present results for the x-ray optical properties of C, B4C and W coatings and W/C multilayers. The goal of the development of x-ray mirrors is to optimize the deposition conditions in order to control the thickness of a single layer or the lateral period of a multilayer, and to achieve high reflectivity over the whole deposition length according to the application.