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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. [ABSTRACT FROM AUTHOR]

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 (< 0.3 Å-1), 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. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

To optimize the catalytic functionality of cerium oxide it is important to understand the structural modifications associated with reduction and the role of the proximity of metals, which are often coupled with the oxide in the applications. For this purpose, the evolution of the short‐ and long‐range structure of cerium oxide ultrathin epitaxial films and nanostructures supported on Pt(111) is investigated using X‐ray absorption spectroscopy at the Ce L3 edge and surface X‐ray diffraction, during reduction by thermal treatments in vacuum. In epitaxial nanoislands reduction is associated with a contraction of the Ce–O distance and with the appearance of CePt bonds. The formation of a phase with a (2 × 2) periodicity after a thermal treatment at 1023 K is ascribed to the formation of a Pt5Ce alloy. Films of 3 nm thickness do not show, on average, significant structural modifications with the same thermal treatment, consistent with the hypothesis that the reduction involves only the topmost surface layers and it does not influence significantly the bulk structure of the material. This study demonstrates a strong interaction between cerium oxide and platinum, which has implications for the reactivity and stability of catalysts based on metals combined with reducible oxides. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

Absorbing near‐infrared (NIR) photons, with longer wavelengths, in atomically thin monolayer MoS2 presents a significant challenge due to its weak optical absorption and narrow absorption bands. Consequently, MoS2‐based photodetector devices often experience low responsivity and a limited detection window. Herein, a novel InAs@ZnSe core@shell/1L‐MoS2 heterostructure, leveraging InAs@ZnSe as the primary infrared‐absorbing material and exploiting the formation of a type‐II heterostructure is showcased. Steady‐state and time‐resolved spectroscopy, along with optoelectronic characterization, are employed to investigate photo‐induced charge transfer dynamics. The results show efficient hole transfer to InAs@ZnSe upon excitation of both materials. Instead, with selective excitation of InAs@ZnSe, electron transfer is observed from InAs@ZnSe to the 1L‐MoS2. The heterostructure demonstrates a broadband photoresponse spanning the wavelength range of 300 to 850 nm, exhibiting a Responsivity of ≈103 A/W and Detectivity of ≈1011 Jones. The signal‐to‐noise ratio substantially increases by 3 to 4 orders of magnitude for 700 and 850 nm excitation compared to pristine 1L‐MoS2. The enhancement in photoresponse and signal‐to‐noise ratio is attributed to increased absorption, which helps eliminate defect and trap states, thereby promoting the photogating effect. [ABSTRACT FROM AUTHOR]

CsPbBr3 and Cs4PbBr6 perovskite powders have been synthesized through a relatively simple low-temperature and low-cost method. Nanocrystalline films have also been deposited from solutions with four different molar compositions of binary salt precursors. Optical absorption, emission and excitation spectra have been performed in the UV-visible spectral range while X-ray diffraction (XRD) has been recorded to characterize the nanocrystal morphology for the different molar compositions. A preferential orientation of crystallites along the (024) crystalline plane has been observed as a function of the different deposition conditions in films growth. All the crystals show an absorption edge around 530 nm; Tauc plots of the absorption returned bandgaps ranging from 2.29 to 2.35 eV characteristic of CsPbBr3 phase. We attribute the UV absorption band peaked at 324 nm to the fundamental band-to-band transition for Cs4PbBr6. It was observed that the samples with the most ordered Cs4PbBr6 crystals exhibited the most intense emission of light, with a bright green emission at 520 nm, which are however due to the luminescence of the inclusion of CsPbBr3 nanoclusters into the Cs4PbBr6. The latter shows instead an intense UV emission. Differently, the pure CsPbBr3 powder did not show any intense fluorescent emission. The excitation spectra of the green fluorescent emission in all samples closely resemble the CsPbBr3 absorption with the peculiar dip around 324 nm as expected from density of state calculations reported in the literature. [ABSTRACT FROM AUTHOR]

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., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

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 (TaSe 4 ) 2 I, which exhibits a transition into an incommensurate CDW phase when cooled to just below room temperature, namely at T CDW = 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 (TaSe 4 ) 2 I, whose fingerprints are detected along its c -axis only. Our results provide new insights into the symmetry of the ordered phase of (TaSe 4 ) 2 I perturbed by a selective excitation, and suggest a novel approach based on complementary table-top and FEL spectroscopies for the study of complex materials.

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 CeO 2 , 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 CeO 2 film generated by the NPs plasmonic resonance photoexcitation. Ultrafast changes (<200 fs) of the Ce N 4,5 absorption edge allowed us to conclude that the excited Ag NPs transfer electrons to the Ce atoms of the CeO 2 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.

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 CeO 2 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 ( E og = 4 eV), significantly larger than usually reported.