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    Current Advances in TiO2-Based Nanostructure Electrodes for High Performance Lithium Ion Batteries
    (Basel : MDPI, 2018-2-6) Madian, Mahmoud; Eychmüller, Alexander; Giebeler, Lars
    The lithium ion battery (LIB) has proven to be a very reliably used system to store electrical energy, for either mobile or stationary applications. Among others, TiO2-based anodes are the most attractive candidates for building safe and durable lithium ion batteries with high energy density. A variety of TiO2 nanostructures has been thoroughly investigated as anodes in LIBs, e.g., nanoparticles, nanorods, nanoneedles, nanowires, and nanotubes discussed either in their pure form or in composites. In this review, we present the recent developments and breakthroughs demonstrated to synthesize safe, high power, and low cost nanostructured titania-based anodes. The reader is provided with an in-depth review of well-oriented TiO2-based nanotubes fabricated by anodic oxidation. Other strategies for modification of TiO2-based anodes with other elements or materials are also highlighted in this report.
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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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    Low-Temperature Magnetothermodynamics Performance of Tb1-xErxNi2 Laves-Phases Compounds for Designing Composite Refrigerants
    (Basel : MDPI, 2022) Ćwik, Jacek; Koshkid’ko, Yurii; Nenkov, Konstantin; Tereshina-Chitrova, Evgenia; Weise, Bruno; Kowalska, Karolina
    In this paper, the results of heat capacity measurements performed on the polycrystalline Tb1-xErxNi2 intermetallic compounds with x = 0.25, 0.5 and 0.75 are presented. The Debye temperatures and lattice contributions as well as the magnetic part of the heat capacity were determined and analyzed. The heat capacity measurements reveal that the substitution of Tb atoms for Er atoms leads to a linear reduction of the Curie temperatures in the investigated compounds. The ordering temperatures decrease from 28.3 K for Tb0.25Er0.75Ni2 to 12.9 K for Tb0.75Er0.25Ni2. Heat capacity measurements enabled us to calculate with good approximation the isothermal magnetic entropy ΔSmag and adiabatic temperature changes ΔTad for Tb1-xErxNi2, for the magnetic field value equal to 1 T and 2 T. The optimal molar ratios of individual Tb0.75Er0.25Ni2, Tb0.5Er0.5Ni2 and Tb0.25Er0.75Ni2 components in the final composite were theoretically determined. According to the obtained results, the investigated composites make promising candidates that can find their application as an active body in a magnetic refrigerator performing an Ericsson cycle at low temperatures. Moreover, for the Tb0.5Er0.5Ni2 compound, direct measurements of adiabatic temperature change in the vicinity of the Curie temperature in the magnetic field up to 14 T were performed. The obtained high-field results are compared to the data for the parent TbNi2 and ErNi2 compounds, and their magnetocaloric properties near the Curie temperature are analyzed in the framework of the Landau theory for the second-order phase transitions.
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    Polaron-Mediated Luminescence in Lithium Niobate and Lithium Tantalate and Its Domain Contrast
    (Basel : MDPI, 2018-5-15) Reichenbach, Philipp; Kämpfe, Thomas; Haußmann, Alexander; Thiessen, Andreas; Woike, Theo; Steudtner, Robin; Kocsor, Laura; Szaller, Zsuzsanna; Kovács, László; Eng, Lukas M.
    In this review article, we discuss photoluminescence phenomena mediated by polarons in lithium niobate (LNO). At first we present the fundamentals on polaron states in LNO and their energy levels, i.e., on free and bound electron polarons, on hole polarons as well as on bipolarons. We discuss the absorption measurements on reduced as well as on doped LNO that made the characterization of the formed polaron states possible by their absorption bands. Next, we proceed by reporting on the two polaron-mediated photoluminescence bands that have been observed in LNO: (1) A near-infrared luminescence band in the range of 1.5 eV shows a mono-exponential decay and a strong dependence on iron doping. This luminescence is emitted by bound polarons returning from an excited state to the ground state. (2) A luminescence band at visible wavelengths with a maximum at 2.6 eV shows a stretched-exponential decay and is strongly enhanced by optical damage resistant doping around the doping threshold. This luminescence stems from the recombination of free electron and hole polarons. The next major topic of this review are domain contrasts of the visible photoluminescence that have been observed after electrical poling of the substrate, as singly inverted domains show a slightly reduced and faster decaying luminescence. Subsequent annealing results in an exponential decrease of that domain contrast. We show that this contrast decay is strongly related to the mobility of lithium ions, thus confirming the role of polar defect complexes, including lithium vacancies, for these domain contrasts. Finally we discuss the extension of our investigations to lithium tantalate (LTO) samples. While the results on the domain contrast and its decay are similar to LNO, there are remarkable differences in their luminescence spectra.
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    Core–Shell Structures Prepared by Atomic Layer Deposition on GaAs Nanowires
    (Basel : MDPI, 2022) Ursaki, Veaceslav V.; Lehmann, Sebastian; Zalamai, Victor V.; Morari, Vadim; Nielsch, Kornelius; Tiginyanu, Ion M.; Monaico, Eduard V.
    GaAs nanowire arrays have been prepared by anodization of GaAs substrates. The nanowires produced on (111)B GaAs substrates were found to be oriented predominantly perpendicular to the substrate surface. The prepared nanowire arrays have been coated with thin ZnO or TiO2 layers by means of thermal atomic layer deposition (ALD), thus coaxial core–shell hybrid structures are being fabricated. The hybrid structures have been characterized by scanning electron microscopy (SEM) for the morphology investigations, by Energy Dispersive X-ray (EDX) and X-ray diffraction (XRD) analysis for the composition and crystal structure assessment, and by photoluminescence (PL) spectroscopy for obtaining an insight on emission polarization related to different recombination channels in the prepared core–shell structures.
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    Aero-TiO2 Prepared on the Basis of Networks of ZnO Tetrapods
    (Basel : MDPI, 2022) Ciobanu, Vladimir; Ursaki, Veaceslav V.; Lehmann, Sebastian; Braniste, Tudor; Raevschi, Simion; Zalamai, Victor V.; Monaico, Eduard V.; Colpo, Pascal; Nielsch, Kornelius; Tiginyanu, Ion M.
    In this paper, new aeromaterials are proposed on the basis of titania thin films deposited using atomic layer deposition (ALD) on a sacrificial network of ZnO microtetrapods. The technology consists of two technological steps applied after ALD, namely, thermal treatment at different temperatures and etching of the sacrificial template. Two procedures are applied for etching, one of which is wet etching in a citric acid aqua solution, while the other one is etching in a hydride vapor phase epitaxy (HVPE) system with HCl and hydrogen chemicals. The morphology, composition, and crystal structure of the produced aeromaterials are investigated depending on the temperature of annealing and the sequence of the technological steps. The performed photoluminescence analysis suggests that the developed aeromaterials are potential candidates for photocatalytic applications.
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    TSFZ Growth of Eu-Substituted Large-Size LSCO Crystals
    (Basel : MDPI, 2022) Voloshyna, Olesia; Romaka, Vitaliy V.; Karmakar, Koushik ;Seiro, Silvia; Maljuk, Andrey; Büchner, Bernd
    The travelling solvent floating zone (TSFZ) growth of Eu-substituted LSCO (La1.81−xEuxSr0.19CuO4, with nominal x = 0 ÷ 0.4) single crystals was systematically explored for the first time. The substitution of La with Eu considerably decreased the decomposition temperature. Optimal growth parameters were found to be: oxygen pressure 9.0–9.5 bars; Eu-free CuO-poor solvent (66 mol% CuO) with a molar ratio of La2O3:SrCO3:CuO = 4:4.5:16.5 and growth rate 0.6 mm/hour. The obtained single crystals were characterized with optical polarized microscopy, X-ray diffraction and energy-dispersive X-ray spectroscopy analysis. The solubility of Eu in LSCO appeared to be limited to x~0.36–0.38 under the used conditions. The substitution of La3+ with smaller Eu3+ ions led to a structural transition from tetragonal with space group I4/mmm for La1.81Sr0.19CuO4 (x = 0) to orthorhombic with space group Fmmm for La1.81−xSr0.19EuxCuO4 (x = 0.2, 0.3, 0.4), and to a substantial shrinking of the c-axis from 13.2446 Å (x = 0.0) to 13.1257 Å (x = 0.4). Such structural changes were accompanied by a dramatic decrease in the superconducting critical temperature, Tc, from 29.5 K for x = 0 to 13.8 K for 0.2. For x ≥ 0.3, no superconductivity was detected down to 4 K.
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    Phase Diagram of a Strained Ferroelectric Nanowire
    (Basel : MDPI, 2022) Pavlenko, Maksim A.; Di Rino, Franco; Boron, Leo; Kondovych, Svitlana; Sené, Anaïs; Tikhonov, Yuri A.; Razumnaya, Anna G.; Vinokur, Valerii M.; Sepliarsky, Marcelo; Lukyanchuk, Igor A.
    Ferroelectric materials manifest unique dielectric, ferroelastic, and piezoelectric properties. A targeted design of ferroelectrics at the nanoscale is not only of fundamental appeal but holds the highest potential for applications. Compared to two-dimensional nanostructures such as thin films and superlattices, one-dimensional ferroelectric nanowires are investigated to a much lesser extent. Here, we reveal a variety of the topological polarization states, particularly the vortex and helical chiral phases, in loaded ferroelectric nanowires, which enable us to complete the strain–temperature phase diagram of the one-dimensional ferroelectrics. These phases are of prime importance for optoelectronics and quantum communication technologies
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    Effect of Silver Doping on the Superconducting and Structural Properties of YBCO Films Grown by PLD on Different Templates
    (Basel : MDPI, 2022) Shipulin, Ilya A.; Thomas, Aleena Anna; Holleis, Sigrid; Eisterer, Michael; Nielsch, Kornelius; Hühne, Ruben
    We report the local structural and superconducting properties of undoped and Ag-doped YBa2Cu3O6+x (YBCO) films with a thickness of up to 1 µm prepared by pulsed laser deposition on SrTiO3 (STO) single crystals and on ion-beam-assisted deposition (IBAD) and rolling-assisted biaxially textured substrate (RABiTS)-based metal templates. X-ray diffraction demonstrates the high crystalline quality of the films on both single crystalline substrates and metal-based templates, respectively. Although there was only a slight decrease in Tc of up to 1.5 K for the Ag-doped YBCO films on all substrates, we found significant changes in their transport characteristics. The effect of the silver doping mainly depended on the concentration of silver, the type of substrate, and the temperature and magnetic field. In general, the greatest improvement in Jc over a wide range of magnetic fields and temperatures was observed for the 5%Ag-doped YBCO films on STO substrates, showing a significant increase compared to undoped films. Furthermore, a slight Jc improvement was observed for the 2%Ag-doped YBCO films on the RABiTS templates at temperatures below 65 K, whereas Jc decreased for the Ag-doped films on IBAD-MgO-based templates compared to undoped YBCO films. Using detailed electron microscopy studies, small changes in the local microstructure of the Ag-doped YBCO films were revealed; however, no clear correlation was found with the transport properties of the films.
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    The Influence of the Composition of Ru100−xAlx (x = 50, 55, 60, 67) Thin Films on Their Thermal Stability
    (Basel : MDPI, 2017-3-10) Seifert, Marietta; Rane, Gayatri K.; Oswald, Steffen; Menzel, Siegfried B.; Gemming, Thomas
    RuAl thin films possess a high potential as a high temperature stable metallization for surface acoustic wave devices. During the annealing process of the Ru-Al films, Al2O3 is formed at the surface of the films even under high vacuum conditions, so that the composition of a deposited Ru50Al50 film is shifted to a Ru-rich alloy. To compensate for this effect, the Al content is systematically increased during the deposition of the Ru-Al films. Three Al-rich alloys—Ru45Al55, Ru40Al60 and Ru33Al67—were analyzed concerning their behavior after high temperature treatment under high vacuum and air conditions in comparison to the initial Ru50Al50 sample. Although the films’ cross sections show a more homogeneous structure in the case of the Al-rich films, the RuAl phase formation is reduced with increasing Al content.