RESUMEN
Spatially resolved x-ray fluorescence (XRF) based analysis employing incident beam sizes in the low micrometer range (µXRF) is widely used to study lateral composition changes of various types of microstructured samples. However, up to now the quantitative analysis of such experimental datasets could only be realized employing adequate calibration or reference specimen. In this work, we extent the applicability of the so-called reference-free XRF approach to enable reference-freeµXRF analysis. Here, no calibration specimen are needed in order to derive a quantitative and position sensitive composition of the sample of interest. The necessary instrumental steps to realize reference-freeµXRF are explained and a validation of ref.-freeµXRF against ref.-free standard XRF is performed employing laterally homogeneous samples. Finally, an application example from semiconductor research is shown, where the lateral sample features require the usage of ref.-freeµXRF for quantitative analysis.
RESUMEN
The investigation of Co oxidation states in pristine LiNixMnyCo1-x-yO2 (NMC) cathodes (NMC111, NMC622, NMC811) has been a subject of ongoing debate, with conflicting findings in the literature. In this study, we present a novel and comprehensive approach to address and clarify this issue using a variety of high energy-resolution X-ray spectroscopy techniques. To shed light on the Co oxidation states in NMC cathodes, we employed independent measurements including X-ray absorption spectrometry in both soft and hard X-ray ranges, as well as resonant X-ray emission spectrometry in the soft X-ray range. The investigation centered on the transition metal (TM) K and L edges, providing a thorough exploration of the electronic structure transitions. The study identified minor shifts in Co oxidation states, and theoretical calculations quantified the ratio of Co atoms undergoing oxidation state changes, which were approximately 2.05% (NMC111 to NMC622) and 3.75% (NMC111 to NMC811). Independent measurements that targeted electronic structure transitions using K-edge and L-edge absorption and emission spectrometry were strategically combined to enhance the reliability of the results. The diverse methodological approach aimed to contribute to a comprehensive understanding of Co oxidation states in NMC cathodes. This study highlights the importance of combining complementary techniques to address intricate scientific debates effectively.
RESUMEN
A methodology based on molecular dynamics simulations is presented to determine the chemical potential of thiol self-assembled monolayers on a gold surface. The thiol de-solvation and then the monolayer formation are described by thermodynamic integration with a gradual decoupling of one molecule from the environment, with the necessary corrections to account for standard state changes. The procedure is applied both to physisorbed undissociated thiol molecules and to chemisorbed dissociated thiyl radicals, considering in the latter case the possible chemical potential of the produced hydrogen. We considered monolayers formed by either 7-mercapto-4-methylcoumarin (MMC) or 3-mercapto-propanoic acid (MPA) on a flat gold surface: the free energy profiles with respect to the monolayer density are consistent with a transition from a very stable lying-down phase at low densities to a standing-up phase at higher densities, as expected. The maximum densities of thermodynamically stable monolayers are compared to experimental measures performed with reference-free grazing-incidence X-ray fluorescence (RF-GIXRF) on the same systems, finding a better agreement in the case of chemisorbed thiyl radicals.