A sub-100†nm thickness flat jet for extreme ultraviolet to soft X-ray absorption spectroscopy.

Experimental characterization of the structural, electronic and dynamic properties of dilute systems in aqueous solvents, such as nanoparticles, molecules and proteins, are nowadays an open challenge. X-ray absorption spectroscopy (XAS) is probably one of the most established approaches to this aim as it is element-specific. However, typical dilute systems of interest are often composed of light elements that require extreme-ultraviolet to soft X-ray photons. In this spectral regime, water and other solvents are rather opaque, thus demanding radical reduction of the solvent volume and removal of the liquid to minimize background absorption. Here, we present an experimental endstation designed to operate a liquid flat jet of sub-micrometre thickness in a vacuum environment compatible with extreme ultraviolet/soft XAS measurements in transmission geometry. The apparatus developed can be easily connected to synchrotron and free-electron-laser user-facility beamlines dedicated to XAS experiments. The conditions for stable generation and control of the liquid flat jet are analyzed and discussed. Preliminary soft XAS measurements on some test solutions are shown.

Superradiant Thomson scattering from graphite in the extreme ultraviolet.

We study the Thomson scattering from highly oriented pyrolitic graphite excited by the extreme ultraviolet, coherent pulses of FERMI free electron laser (FEL). An apparent nonlinear behavior is observed and fully described in terms of the coherent nature of both exciting FEL beam and scattered radiation, producing an intensity-dependent enhancement of the Thomson scattering cross-section. The process resembles Dicke's superradiant phenomenon and is thus interpreted as the observation of superradiant Thomson scattering. The process also triggers the creation of coherent, low-q ([Formula: see text] 0.3 Å[Formula: see text]), low energy phonons. The experimental data and analysis provide quantitative information on the sample characteristics, absorption, scattering factor, and coherent phonon energies and populations and open the route for the investigation of the deep nature of complex materials.

Injecting Electrons into CeO2 via Photoexcitation of Embedded Au Nanoparticles.

The electron injection efficiency and the steady state absorptance at different photon energies for a composite system made of Au NPs embedded in a cerium oxide matrix are reported. Cerium oxide can be coupled with plasmonic nanoparticles (NPs) to improve its catalytic properties by visible-light absorption. The present work is a study of the ultrafast dynamics of excited states induced by ultraviolet and visible-light excitation in Au NPs combined with cerium oxide, aimed at understanding the excitation pathways. The data, obtained by femtosecond transient absorption spectroscopy, show that the excitation of localized surface plasmon resonances (LSPRs) in the Au NPs leads to an ultrafast injection of electrons into the empty 4f states of the surrounding cerium oxide. Within the first few picoseconds, the injected electrons couple with the lattice distortion forming a polaronic excited state, with similar properties to that formed after direct band gap excitation of the oxide. At sub-picosecond delay times, we observed relevant differences in the energetics and the time dynamics as compared to the case of band gap excitation of the oxide. Using different pump energies across the LSPR-related absorption band, the efficiency of the electron injection from the NPs into the oxide was found to be rather high, with a maximum above 30%. The injection efficiency has a different trend in energy as compared to the LSPR-related static optical absorptance, showing a significant decrease in low energies. This behavior is explained considering different deexcitation pathways with variable weight across the LSPR band. The results are important for the design of materials with high overall solar catalytic efficiency.

Ultrafast dynamics in (TaSe4)2I triggered by valence and core-level excitation.

Dimensionality plays a key role in the emergence of ordered phases, such as charge density-waves (CDW), which can couple to, and modulate, the topological properties of matter. In this work, we study the out-of-equilibrium dynamics of the paradigmatic quasi-one-dimensional material (TaSe4)2I, which exhibits a transition into an incommensurate CDW phase when cooled to just below room temperature, namely at TCDW = 263 K. We make use of both optical laser and free-electron laser (FEL) based time-resolved spectroscopies in order to study the effect of a selective excitation on the normal-state and on the CDW phases by probing the near-infrared/visible optical properties both along and perpendicularly to the direction of the CDW, where the system is metallic and insulating, respectively. Excitation of the core-levels by ultrashort X-ray FEL pulses at 47 eV and 119 eV induces reflectivity transients resembling those recorded when only exciting the valence band of the compound - by near-infrared pulses at 1.55 eV - in the case of the insulating sub-system. Conversely, the metallic sub-system displays relaxation dynamics which depend on the energy of photo-excitation. Moreover, excitation of the CDW amplitude mode is recorded only for excitation at a low-photon-energy. This fact suggests that the coupling of light to ordered states of matter can predominantly be achieved when directly injecting delocalized carriers in the valence band, rather than localized excitations in the core levels. Complementing this, table-top experiments allow us to prove the quasi-unidirectional nature of the CDW phase in (TaSe4)2I, whose fingerprints are detected along its c-axis only. Our results provide new insights into the symmetry of the ordered phase of (TaSe4)2I perturbed by a selective excitation, and suggest a novel approach based on complementary table-top and FEL spectroscopies for the study of complex materials.

Ultrafast Dynamics of Plasmon-Mediated Charge Transfer in Ag@CeO2 Studied by Free Electron Laser Time-Resolved X-ray Absorption Spectroscopy.

Expanding the activity of wide bandgap semiconductors from the UV into the visible range has become a central goal for their application in green solar photocatalysis. The hybrid plasmonic/semiconductor system, based on silver nanoparticles (Ag NPs) embedded in a film of CeO2, is an example of a functional material developed with this aim. In this work, we take advantage of the chemical sensitivity of free electron laser (FEL) time-resolved soft X-ray absorption spectroscopy (TRXAS) to investigate the electron transfer process from the Ag NPs to the CeO2 film generated by the NPs plasmonic resonance photoexcitation. Ultrafast changes (<200 fs) of the Ce N4,5 absorption edge allowed us to conclude that the excited Ag NPs transfer electrons to the Ce atoms of the CeO2 film through a highly efficient electron-based mechanism. These results demonstrate the potential of FEL-based TRXAS measurements for the characterization of energy transfer in novel hybrid plasmonic/semiconductor materials.

Ultrafast Formation of Small Polarons and the Optical Gap in CeO2.

The ultrafast dynamics of excited states in cerium oxide are investigated to access the early moments of polaron formation, which can influence the photocatalytic functionality of the material. UV transient absorbance spectra of photoexcited CeO2 exhibit a bleaching of the band edge absorbance induced by the pump and a photoinduced absorbance feature assigned to Ce 4f → Ce 5d transitions. A blue shift of the spectral response of the photoinduced absorbance signal in the first picosecond after the pump excitation is attributed to the dynamical formation of small polarons with a characteristic time of 330 fs. A further important result of our work is that the combined use of steady-state and ultrafast transient absorption allows us to propose a revised value for the optical gap for ceria (Eog = 4 eV), significantly larger than usually reported.

Optical and electronic properties of silver nanoparticles embedded in cerium oxide.

Wide bandgap oxides can be sensitized to visible light by coupling them with plasmonic nanoparticles (NPs). We investigate the optical and electronic properties of composite materials made of Ag NPs embedded within cerium oxide layers of different thickness. The electronic properties of the materials are investigated by x-ray and ultraviolet photoemission spectroscopy, which demonstrates the occurrence of static charge transfers between the metal and the oxide and its dependence on the NP size. Ultraviolet-visible spectrophotometry measurements show that the materials have a strong absorption in the visible range induced by the excitation of localized surface plasmon resonances. The plasmonic absorption band can be modified in shape and intensity by changing the NP aspect ratio and density and the thickness of the cerium oxide film.

Highly efficient plasmon-mediated electron injection into cerium oxide from embedded silver nanoparticles.

The coupling with plasmonic metal nanoparticles (NPs) represents a promising opportunity to sensitize wide band gap oxides to visible light. The processes which come into play after the excitation of localized surface plasmon resonances (LSPRs) in the NPs largely determine the efficiency of the charge/energy transfer from the metal NP to the oxide. We report a study of plasmon-mediated energy transfer from mass-selected silver NPs into the cerium oxide matrix in which they are embedded. Femtosecond transient absorption spectroscopy is used to probe the dynamics of charge carrier relaxation after the excitation of the LSPR of the silver nanoparticles and to evaluate the plasmon-mediated electron transfer efficiency from the silver nanoparticles to the cerium oxide. High injection efficiencies in the 6-16% range have been identified for excitation between 400 and 600 nm. These high values have been explained in terms of plasmon-mediated direct electron injection as well as indirect hot electron injection from the NPs to the oxide. The information obtained provides an important contribution towards a knowledge-driven design of efficient cerium oxide based nanostructured materials for solar to chemical energy conversion.

Role of cerium oxide in bioactive glasses during catalytic dissociation of hydrogen peroxide.

The addition of cerium oxide to bioactive glasses, important materials for bone tissue regeneration, has been shown to induce multifunctionality, combining a significant bioactivity with antioxidant properties. We provide a real time investigation of the evolution of the electronic properties of highly diluted cerium ions in a liquid environment containing hydrogen peroxide - the most abundant reactive oxygen species in living cells. This challenging task is undertaken by means of high-energy resolution fluorescence detected by X-ray absorption near-edge spectroscopy at the Ce L3 edge. We investigate samples with variable compositions and different morphologies. We relate the observed spectroscopic changes not only to variations in the concentration of the two Ce oxidation states in the samples, but also to changes in the local atomic environment of Ce ions, providing a clear picture of the role of cerium ions in the dissociation of hydrogen peroxide. The obtained results contribute to the understanding of the mechanisms that come into play in the process and provide a basis for the optimization of the functionalities of this class of materials.