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Non-destructive reference-free grazing incidence X-ray fluorescence (RF-GIXRF) is proposed as a highly effective analytical technique for extracting molecular arrangement density in self-assembled monolayers. The establishment of surface density standards through RF-GIXRF impacts various applications, from calibrating laboratory XRF setups to expanding its applicability in materials science, particularly in surface coating scenarios with molecular assemblies. Accurate determination of coverage density is crucial for proper functionalization and interaction, such as in assessing the surface concentration of probes on plasmonic nanostructures. However, limited synchrotron radiation access hinders widespread use, prompting the need for molecular surface density standards, especially for benchmarking substrates for surface-enhanced Raman and infrared absorption spectroscopies (SERS and SEIRA) as well as associated surface-enhanced techniques. Using reproducible densities on gold ensures a solid evaluation of the number of molecules contributing to enhanced signals, facilitating comparability across substrates. The research discusses the importance of employing molecular surface density standards for advancing the field of surface-enhanced spectroscopies, encouraging collaborative efforts in protocol development and benchmarking in surface science.

In order to understand the role of foraging habitat quality on fecundity parameters we measured habitat use, breeding parameters, and body condition of chicks in six colonies of Little Egrets in southern France. The foraging habitat available differed between colonies; it was mainly natural marshes around the Carrelet colony, agricultural lands (rice fields and dry crops) around the Agon colony, a mix of agricultural and natural lands around the Redon and Fiélouse colonies, a mix of natural and urbanised/industrial lands around the Palissade colony, and mainly cultivated and urbanised lands around the Chaumont colony. The habitat attractiveness to adult Little Egret breeding was higher for natural marshes than for other habitat types. Agricultural marshes (rice fields) came next. Other human¿made habitats came last. Clutch size and body condition index of chicks did not differ between colonies. Brood size was influenced by both the association of the proportion of natural marshes in the foraging area and clutch size, and the association of clutch size and the total number of heron pairs in the colony. The effect of the proportion of natural marshes could not be distinguished from the effects of the colony size. The potential influence of other parameters not taken into account in this study is discussed.

This paper introduces a novel slit‐less wavelength‐dispersive spectrometer design that incorporates a single‐bounce monocapillary with the goal of positioning the sample directly on the Rowland circle, thereby eliminating the need for a traditional entrance slit. This configuration enhances photon throughput while preserving energy resolution, demonstrated in comparative measurements on boron nitride and different lithium nickel manganese cobalt oxide cathodes. A common alternative to an entrance slit for limiting the source size on the Rowland circle is a customized design of the beamline involving a focusing optics unit consisting of two Kirkpatrick–Baez mirrors close to the end station. The new slit‐less design does not rely on specialized beamlines and can be considered, thanks to the increased efficiency, for spectrometers using laboratory based sources equipped with equivalent optics. The comparative measurements found that the resolving power achieved was E/ΔE = 1085 at 401.5 eV incident energy, and the enhancement in detection efficiency was a factor of 3.7 due to more effective utilization of the X‐ray beam. [ABSTRACT FROM AUTHOR]

A novel double full-cylinder crystal x-ray spectrometer for x-ray emission spectroscopy (XES) has been realized based on a modified von Hamos geometry. The spectrometer is characterized by its compact dimensions, its versatility with respect to the number of crystals used in series in the detection path, and the option to perform calibrated XES measurements. The full-cylinder crystals used are based on highly annealed pyrolytic graphite with a thickness of 40 μm, which was bent to a radius of curvature of 50 mm. The flexible design of the spectrometer allows for an easy change—within the same setup—between measurements with one crystal for maximized efficiency or two crystals for increased spectral resolving power. The spectrometer realized can be used at different end-stations of synchrotron radiation beamlines or can be laboratory-based. The main application focus of the spectrometer is the determination of x-ray fundamental atomic parameters in the photon energy range from 2.4 to 18 keV. The evaluation of chemical speciation is also an area of application, as demonstrated in the example of battery electrodes using resonant inelastic x-ray scattering. [ABSTRACT FROM AUTHOR]

We report on the application of synchrotron radiation based high-resolution grazing-emission x-ray fluorescence (GEXRF) method to measure low-level impurities on silicon wafers. The presented high-resolution GEXRF technique leads to direct detection limits of about 1012 atoms/cm2. The latter can be presumably further improved down to 107 atoms/cm2 by combining the synchrotron radiation-based GEXRF method with the vapor phase decomposition preconcentration technique. The capability of the high-resolution GEXRF method to perform surface-sensitive elemental mappings with a lateral resolution of several tens of micrometers was probed. [ABSTRACT FROM AUTHOR]

"Probe-before-destroy" methodology permitted diffraction and imaging measurements of intact specimens using ultrabright but highly destructive X-ray free-electron laser (XFEL) pulses. The methodology takes advantage of XFEL pulses ultrashort duration to outrun the destructive nature of the X-rays. Atomic movement, generally on the order of >50 fs, regulates the maximum pulse duration for intact specimen measurements. In this contribution, we report the electronic structure damage of a molecule with ultrashort X-ray pulses under preservation of the atoms' positions. A detailed investigation of the X-ray induced processes revealed that X-ray absorption events in the solvent produce a significant number of solvated electrons within attosecond and femtosecond timescales that are capable of coulombic interactions with the probed molecules. The presented findings show a strong influence on the experimental spectra coming from ionization of the probed atoms' surroundings leading to electronic structure modification much faster than direct absorption of photons. This work calls for consideration of this phenomenon in cases focused on samples embedded in, e.g., solutions or in matrices, which in fact concerns most of the experimental studies. [ABSTRACT FROM AUTHOR]

The potential of valence to core Al X-ray emission spectroscopy to determine aluminum distribution in ferrierite zeolites was investigated. The recorded emission spectra of four samples prepared with different structure directing agents exhibit slight variations in the position of the main emission peak and the intensity of its low energy shoulder. Theoretical calculations indicate that an increased intensity of the Kβx shoulder in the Al emission spectra can be linked to a predominant occupation of the T3 site by a single aluminum atom. This study thus suggests that valence to core X-ray emission spectroscopy can be applied to help determine the occupation of aluminum at crystallographic T-sites in zeolites. [ABSTRACT FROM AUTHOR]

The two novel manganese(II) complexes with 2-hydroxymethylpyridine (2-CH2OHpy) {[Mn2(μ-Cl)2-(2-CH2OHpy)4]Cl2·2H2O (1)} and 2-hydroxyethylpyridine (2-(CH2)2OHpy) {[Mn(2-(CH2)2OHpy)2(NCS)2] (2)} were synthesized and characterized by means of X-ray diffraction, IR, EPR, HF EPR spectroscopy, magnetic and TG/DTG data. The complexes show catalase-like activity in neutral aqueous solution since they were able to disproportionate H2O2 to harmless H2O and O2. Both complexes act as true catalysts since they reverted to their original form after depleting all the H2O2, as suggested by the operando resonant inelastic X-ray spectroscopy (RIXS) measurements. [ABSTRACT FROM AUTHOR]

The high-resolution von Hamos bent crystal spectrometer of the University of Fribourg was upgraded with a focused X-ray beam source with the aim of performing micro-sized X-ray fluorescence (XRF) measurements in the laboratory. The focused X-ray beam source integrates a collimating optics mounted on a low-power micro-spot X-ray tube and a focusing polycapillary half-lens placed in front of the sample. The performances of the setup were probed in terms of spatial and energy resolution. In particular, the fluorescence intensity and energy resolution of the von Hamos spectrometer equipped with the novel micro-focused X-ray source and a standard high-power water-cooled X-ray tube were compared. The XRF analysis capability of the new setup was assessed by measuring the dopant distribution within the core of Er-doped SiO2 optical fibers. [ABSTRACT FROM AUTHOR]

Physical, biological, and chemical transformations are initiated by changes in the electronic configuration of the species involved. These electronic changes occur on the timescales of attoseconds (10-18 s) to femtoseconds (10-15 s) and drive all subsequent electronic reorganization as the system moves to a new equilibrium or quasi-equilibrium state. The ability to detect the dynamics of these electronic changes is crucial for understanding the potential energy surfaces upon which chemical and biological reactions take place. Here, we report on the determination of the electronic structure of matter using a single self-seeded femtosecond x-ray pulse from the Linac Coherent Light Source hard x-ray free electron laser. By measuring the high energy resolution off-resonant spectrum (HEROS), we were able to obtain information about the electronic density of states with a single femtosecond x-ray pulse. We show that the unoccupied electronic states of the scattering atom may be determined on a shot-to-shot basis and that the measured spectral shape is independent of the large intensity fluctuations of the incoming x-ray beam. Moreover, we demonstrate the chemical sensitivity and single-shot capability and limitations of HEROS, which enables the technique to track the electronic structural dynamics in matter on femtosecond time scales, making it an ideal probe technique for time-resolved X-ray experiments. [ABSTRACT FROM AUTHOR]

We report on the application of a two-dimensional position-sensitive area detector towards grazing emission x-ray fluorescence (GEXRF) spectroscopy. GEXRF allows for surface-sensitive studies with nanometer-scale accuracy in the depth direction by measuring the intensity variation of an x-ray fluorescence line with the grazing emission angle. The presented experimental setup is based on a fixed sample-detector arrangement and does not require any moving components. We show that the dispersion of the grazing emission angle along a position-sensitive detector allows to acquire with an excellent angular resolution a full GEXRF profile in a single measurement. Moreover, the use of a two-dimensional detector allows to perform experiments with an increased solid angle of detection per emission angle. This results in combination with the nonsequential and simultaneous acquisition of the GEXRF profiles of different emission lines in considerably reduced acquisition times. The realization, the demands, and the main characteristics of the scanning-free GEXRF setup will be presented. A few experimental examples will serve to illustrate the analytical possibilities offered by the presented setup. [ABSTRACT FROM AUTHOR]

Abstract: The grazing emission X-ray fluorescence (GEXRF) technique was applied to the analysis of different Al films, with nominal thicknesses in the range of 1nm to 150nm, on Si wafers. In GEXRF the sample volume from which the fluorescence intensity is detected is restricted to a near-surface region whose thickness can be tuned by varying the observation angle. This is possible because of the refraction of the fluorescence X-rays and the quite long emission paths within the probed sample. By recording the X-ray fluorescence signal for different shallow emission angles, defined relatively to the flat, smooth sample surface, the deposited Al surface layers of the different samples could be well characterized in terms of layer thickness, layer density, oxidation and surface roughness. The advantages offered by synchrotron radiation and the employed wavelength-dispersive detection setup were profited from. The GEXRF results retrieved were confirmed by complementary measurements. The experimental setup, the principles and advantages of GEXRF and the analysis of the recorded angular intensity profiles will be discussed in details. [Copyright &y& Elsevier]

In this work two synchrotron radiation-based depth-sensitive X-ray fluorescence techniques, grazing incidence X-ray fluorescence (GIXRF) and grazing emission X-ray fluorescence (GEXRF), are compared and their potential for non-destructive depth-profiling applications is investigated. The depth-profiling capabilities of the two methods are illustrated for five aluminum-implanted silicon wafers all having the same implantation dose of 1016 atoms per cm2 but with different implantation energies ranging from 1 keV up to 50 keV. The work was motivated by the ongoing downscaling effort of the microelectronics industry and the resulting need for more sensitive methods for the impurity and dopant depth-profile control. The principles of GIXRF and GEXRF, both based on the refraction of X-rays at the sample surface to enhance the surface-to-bulk ratio of the detected fluorescence signal, are explained. The complementary experimental setups employed at the Physikalisch-Technische Bundesanstalt (PTB) for GIXRF and the University of Fribourg for GEXRF are presented in detail. In particular, for each technique it is shown how the dopant depth profile can be derived from the angular intensity dependence of the Al Kα fluorescence line. The results are compared to theoretical predictions and, for two samples, crosschecked with values obtained from secondary ion mass spectroscopy (SIMS) measurements. A good agreement between the different approaches is found proving that the GIXRF and GEXRF methods can be efficiently employed to extract the dopant depth distribution of ion-implanted samples with good accuracy and over a wide range of implantation energies. [ABSTRACT FROM AUTHOR]

Abstract: The synchrotron radiation based high-resolution grazing emission X-ray fluorescence (GEXRF) technique was used to extract the distribution of Al ions implanted with a dose of 1016 atoms/cm2 in Si wafers with energies ranging between 1 and 100keV. The depth distributions of the implanted ions were deduced from the measured angular profiles of the Al-Kα X-ray fluorescence line with nanometer-scale precision. The experimental results were compared to theoretical predictions of the depth distributions resulting from ion implantation. A good agreement between experiment and theory was found which proved that the presented high-resolution grazing emission X-ray fluorescence technique is well suited to perform depth profiling measurements of impurities located within the extinction depth, provided the overall shape of the distribution can be assumed a priori. [Copyright &y& Elsevier]

Domestic cats (Felis earns) have been introduced on many islands in the world and are responsible for much damage to native insular faunas. The worldwide success and spread of this opportunistic predator is generally associated with its trophic adaptability. We examined the diet of a long-established feral cat population on a small Mediterranean island through the analysis of 1,219 scats collected during a 4-year period. Our results confirm that feral cats are generalist predators, able to feed on a wide range of prey. However, only a few prey species formed the major part of its diet. Two introduced mammals and a Mediterranean endemic seabird provided 93% of the yearly biomass consumed by cats (ship rats, 70%: wild rabbits, 7%; and yelkouan shearwaters, 6%). Ship rats remained by far the staple prey for cats throughout the year, but the diet of feral cats was more diversified in spring and early summer, frequently including insects, reptiles, and migrant birds. Endemic yelknouan shearwaters were preyed upon most frequently in autumn and winter, that is, during the shearwaters' prelaying period. Because rats provide the majority of the food of cats, they could help to maintain or inflate this alien predator population with deleterious consequences to the endemic shearwater. A cat eradication campaign would help protect the population of shearwaters on this island. [ABSTRACT FROM AUTHOR]

X-ray Free Electron Lasers (FELs) can produce extremely intense and very short pulses, down to below 10 femtoseconds (fs). Among the key applications are ultrafast time-resolved studies of dynamics of matter by observing responses to fast excitation pulses in a pump-probe manner. Detectors with sufficient time resolution for observing these processes are not available. Therefore, such experiments typically measure a sample's full dynamics by repeating multiple pump-probe cycles at different delay times. This conventional method assumes that the sample returns to an identical or very similar state after each cycle. Here we describe a novel approach that can provide a time trace of responses following a single excitation pulse, jitter-free, with fs timing precision. We demonstrate, in an X-ray diffraction experiment, how it can be applied to the investigation of ultrafast irreversible processes. [ABSTRACT FROM AUTHOR]

We report on the design and performance of a wavelength-dispersive type spectrometer based on the von Hamos geometry. The spectrometer is equipped with a segmented-type crystal for x-ray diffraction and provides an energy resolution in the order of 0.25 eV and 1 eV over an energy range of 8000 eV-9600 eV. The use of a segmented crystal results in a simple and straightforward crystal preparation that allows to preserve the spectrometer resolution and spectrometer efficiency. Application of the spectrometer for time-resolved resonant inelastic x-ray scattering and single-shot x-ray emission spectroscopy is demonstrated. [ABSTRACT FROM AUTHOR]

Various 3-dimensional nano-scaled periodic structures with different configurations and periods deposited on the surface of silicon and silica substrates were investigated by means of the grazing incidence and grazing emission X-ray fluorescence techniques. Apart from the characteristics which are typical for particle- and layer-like samples, the measured angular intensity profiles show additional periodicity-related features. The latter could be explained by a novel theoretical approach based on simple geometrical optics (GO) considerations. The new GO-based calculations were found to yield results in good agreement with experiment, also in cases where other theoretical approaches are not valid, e.g., periodic particle distributions with an increased surface coverage. [ABSTRACT FROM AUTHOR]

X-ray emission spectra recorded in the off-resonant regime carry information on the density of unoccupied states. It is known that by employing the Kramers-Heisenberg formalism, the high energy resolution off-resonant spectroscopy (HEROS) is equivalent to the x-ray absorption spectroscopy (XAS) technique and provides the same electronic state information. Moreover, in the present Letter we demonstrate that the shape of HEROS spectra is not modified by self-absorption effects. Therefore, in contrast to the fluorescence-based XAS techniques, the recorded shape of the spectra is independent of the sample concentration or thickness. The HEROS may thus be used as an experimental technique when precise information about specific absorption features and their strengths is crucial for chemical speciation or theoretical evaluation. [ABSTRACT FROM AUTHOR]