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    Auger- and X-ray Photoelectron Spectroscopy at Metallic Li Material: Chemical Shifts Related to Sample Preparation, Gas Atmosphere, and Ion and Electron Beam Effects
    (Basel : MDPI, 2022) Oswald, Steffen
    Li-based batteries are a key element in reaching a sustainable energy economy in the near future. The understanding of the very complex electrochemical processes is necessary for the optimization of their performance. X-ray photoelectron spectroscopy (XPS) is an accepted method used to improve understanding around the chemical processes at the electrode surfaces. Nevertheless, its application is limited because the surfaces under investigation are mostly rough and inhomogeneous. Local elemental analysis, such as Auger electron spectroscopy (AES), could assist XPS to gain more insight into the chemical processes at the surfaces. In this paper, some challenges in using electron spectroscopy are discussed, such as binding energy (BE) referencing for the quantitative study of chemical shifts, gas atmospheric influences, or beam damage (including both AE and XP spectroscopy). Carefully prepared and surface-modified metallic lithium material is used as model surface, considering that Li is the key element for most battery applications.
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    Evaluation of surface cleaning procedures for CTGS substrates for SAW technology with XPS
    (Basel : MDPI, 2017) Brachmann, Erik; Seifert, Marietta; Oswald, Steffen; Menzel, Siegfried B.; Gemming, Thomas
    A highly efficient and reproducible cleaning procedure of piezoelectric substrates is essential in surface acoustic waves (SAW) technology to fabricate high-quality SAW devices, especially for new applications such SAW sensors wherein new materials for piezoelectric substrates and interdigital transducers are used. Therefore, the development and critical evaluation of cleaning procedures for each material system that is under consideration becomes crucial. Contaminants like particles or the presence of organic/inorganic material on the substrate can dramatically influence and alter the properties of the thin film substrate composite, such as wettability, film adhesion, film texture, and so on. In this article, focus is given to different cleaning processes like SC-1 and SC-2, UV-ozone treatment, as well as cleaning by first-contact polymer Opticlean, which are applied for removal of contaminants from the piezoelectric substrate Ca 3 TaGa 3 Si 2 O 14 . By means of X-ray photoelectron spectroscopy, the presence of the most critical contaminants such as carbon, sodium, and iron removed through different cleaning procedures were studied and significant differences were observed between the outcomes of these procedures. Based on these results, a two-step cleaning process, combining SC-1 at a reduced temperature at 30 ∘ C instead of 80 ∘ C and a subsequent UV-ozone cleaning directly prior to deposition of the metallization, is suggested to achieve the lowest residual contamination level.
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    Impact of atomic defects in the electronic states of FeSe1-x Sx superconducting crystals
    (Bristol : IOP Publishing, 2022) Aragón Sánchez, Jazmín; Amigó, María Lourdes; Belussi, Cristian Horacio; Ale Crivillero, María Victoria; Suárez, Sergio; Guimpel, Julio; Nieva, Gladys; Gayone, Julio Esteban; Fasano, Yanina
    The electronic properties of Fe-based superconductors are drastically affected by deformations on their crystal structure introduced by doping and pressure. Here we study single crystals of FeSe 1 − x Sx and reveal that local crystal deformations such as atomic-scale defects impact the spectral shape of the electronic core level states of the material. By means of scanning tunneling microscopy we image S-doping induced defects as well as diluted dumbbell defects associated with Fe vacancies. We have access to the electronic structure of the samples by means of x-ray photoemission spectroscopy (XPS) and show that the spectral shape of the Se core levels can only be adequately described by considering a principal plus a minor component of the electronic states. We find this result for both pure and S-doped samples, irrespective that in the latter case the material presents extra crystal defects associated to doping with S atoms. We argue that the second component in our XPS spectra is associated with the ubiquitous dumbbell defects in FeSe that are known to entail a significant modification of the electronic clouds of surrounding atoms.
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    Binding energy referencing for XPS in Alkali metal-based battery materials research (II): Application to complex composite electrodes
    (Basel : MDPI AG, 2018) Oswald, S.; Thoss, F.; Zier, M.; Hoffmann, M.; Jaumann, T.; Herklotz, M.; Nikolowski, K.; Scheiba, F.; Kohl, M.; Giebeler, L.; Mikhailova, D.; Ehrenberg, H.
    X-ray photoelectron spectroscopy (XPS) is a key method for studying (electro-)chemical changes in metal-ion battery electrode materials. In a recent publication, we pointed out a conflict in binding energy (BE) scale referencing at alkali metal samples, which is manifested in systematic deviations of the BEs up to several eV due to a specific interaction between the highly reactive alkali metal in contact with non-conducting surrounding species. The consequences of this phenomenon for XPS data interpretation are discussed in the present manuscript. Investigations of phenomena at surface-electrolyte interphase regions for a wide range of materials for both lithium and sodium-based applications are explained, ranging from oxide-based cathode materials via alloys and carbon-based anodes including appropriate reference chemicals. Depending on material class and alkaline content, specific solutions are proposed for choosing the correct reference BE to accurately define the BE scale. In conclusion, the different approaches for the use of reference elements, such as aliphatic carbon, implanted noble gas or surface metals, partially lack practicability and can lead to misinterpretation for application in battery materials. Thus, this manuscript provides exemplary alternative solutions.
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    XPS chemical state analysis of sputter depth profiling measurements for annealed TiAl-SiO2 and TiAl-W layer stacks
    (Chichester [u.a.] : Wiley, 2020) Oswald, Steffen; Lattner, Eric; Seifert, Marietta
    For the application of surface acoustic wave sensors at high temperatures, both a high-temperature stable piezoelectric substrate and a suitable metallization for the electrodes are needed. Our current attempt is to use TiAl thin films as metallization because this material is also known to be high temperature stable. In this study, Ti/Al multilayers and Ti-Al alloy layers were prepared in combination with an SiO2 cover layer or a W barrier layer at the interface to the substrate (thermally oxidized Si or Ca3TaGa3Si2O14) as an oxidation protection. To form the high-temperature stable γ-TiAl phase and to test the thermal stability of the layer systems, thermal treatments were done in vacuum at several temperatures. We used X-ray photoelectron spectroscopy (XPS) sputter depth-profiling to investigate the film composition and oxidation behavior. In this paper, we demonstrate how the semiautomatic peak fitting can help to extract beside the elemental information also the chemical information from the measured depth profiles. © 2020 The Authors. Surface and Interface Analysis published by John Wiley & Sons Ltd