Universität Stuttgart
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Item Open Access Top‐down approach to study chemical and electronic properties of perovskite solar cells : sputtered depth profiling versus tapered cross‐sectional photoelectron spectroscopies(2021) Das, Chittaranjan; Zia, Waqas; Mortan, Claudiu; Hussain, Navid; Saliba, Michael; Ingo Flege, Jan; Kot, MałgorzataA study of the chemical and electronic properties of various layers across perovskite solar cell (PSC) stacks is challenging. Depth‐profiling photoemission spectroscopy can be used to study the surface, interface, and bulk properties of different layers in PSCs, which influence the overall performance of these devices. Herein, sputter depth profiling (SDP) and tapered cross‐sectional (TCS) photoelectron spectroscopies (PESs) are used to study highly efficient mixed halide PSCs. It is found that the most used SDP‐PES technique degrades the organic and deforms the inorganic materials during sputtering of the PSCs while the TCS‐PES method is less destructive and can determine the chemical and electronic properties of all layers precisely. The SDP‐PES dissociates the chemical bonding in the spiro‐MeOTAD and perovskite layer and reduces the TiO2, which causes the chemical analysis to be unreliable. The TCS‐PES revealed a band bending only at the spiro‐MeOTAD/perovskite interface of about 0.7 eV. Both the TCS and SDP‐PES show that the perovskite layer is inhomogeneous and has a higher amount of bromine at the perovskite/TiO2 interface.Item Open Access Insights into Hildebrand solubility parameters : contributions from cohesive energies or electrophilicity densities?(2023) Miranda‐Quintana, Ramón Alain; Chen, Lexin; Smiatek, JensWe introduce certain concepts and expressions from conceptual density functional theory (DFT) to study the properties of the Hildebrand solubility parameter. The original form of the Hildebrand solubility parameter is used to qualitatively estimate solubilities for various apolar and aprotic substances and solvents and is based on the square root of the cohesive energy density. Our results show that a revised expression allows the replacement of cohesive energy densities by electrophilicity densities, which are numerically accessible by simple DFT calculations. As an extension, the reformulated expression provides a deeper interpretation of the main contributions and, in particular, emphasizes the importance of charge transfer mechanisms. All calculated values of the Hildebrand parameters for a large number of common solvents are compared with experimental values and show good agreement for non‐ or moderately polar aprotic solvents in agreement with the original formulation of the Hildebrand solubility parameters. The observed deviations for more polar and protic solvents define robust limits from the original formulation which remain valid. Likewise, we show that the use of machine learning methods leads to only slightly better predictability.Item Open Access Modeling and simulation of electronic excitation in oxygen-helium discharges and plasma-assisted combustion(2018) Kuntner, Nikolaj; Riedel, Uwe (Prof. Dr. rer. nat.)The present work concerns the generation of electronically excited oxidizers in non-thermal discharges in the context of plasma-assisted hydrogen and methane combustion at atmospheric pressures. These conditions are of practical relevance for the combustion technology. However, as the conversion of electrical power into particular, chosen chemical degrees of freedom is facilitated by low molecular interaction, the atmospheric parameter range is often neglected in the literature. This work provides the design and validation of accurate and efficient computational models for several experiments in this parameter range.Item Open Access Wetting, de-icing and anti-icing behavior of microstructured and plasma-coated polyurethane films(2019) Grimmer, Philipp E. S.; Hirth, Thomas (Prof. Dr. rer. nat.)Ice build-up on surfaces, for example on wings of airplanes or on rotor blades of wind turbines, impairs the functionality of transportation vehicles or technical systems and reduces their safety. Therefore, functional anti-ice surfaces are being researched and developed, which shall enable an easy removal or reduce the amount of ice on the surfaces at risk. The starting hypothesis for this work is that superhydrophobic polyurethane (PU) films with microstructure base diameters of 35 µm or more reduce the wetting by water, show a low ice adhesion for easy removal of ice and reduce or delay icing. Superhydrophobic PU films for passive anti- and de-icing were created by hot embossing and plasma enhanced chemical vapor deposition (PECVD). The hot embossing process as well as the plasma coating and etching processes were analyzed for the dependence of the surface characteristics on different process parameters. The functionalized PU films were characterized for their surface topography, surface chemistry, stability against erosion, wettability, ice adhesion and icing behavior. For comparison, the ice adhesion and icing behavior were examined on relevant technical materials (aluminum, titanium, copper, glass, epoxy resin of carbon fiber reinforced polymer and other fluoropolymers) and on some commercial anti-ice coatings. The PU films were chemically analyzed by IR spectroscopy. As the first process step for functionalization, microstructures of cylindrical, elliptical or linear shape were imprinted in PU films by a hot embossing technique with different ns-pulsed laser-drilled stamps and characterized by several microscopy methods. The microstructures had heights of 15 µm to 140 µm, diameters or widths of 35 µm to 300 µm and distances (pitch values) of 50 µm to 500 µm. The embossing process was analyzed and optimized in terms of the process parameters temperature, pressure, time, PU film release temperature and reproducibility of the microstructures. In a second functionalization step (PECVD) the microstructured surfaces were coated with thin, hydrophobic plasma polymers using different fluorocarbon precursors (CHF3, C3F6 and C4F8) or hexamethyldisiloxane (HMDSO). Different process parameters for plasma coating and etching (Ar or O2 plasmas) were used in order to create various nanoscale roughness values. Electron spectroscopy for chemical analysis (ESCA), spectroscopic ellipsometry and atomic force microscopy (AFM) were used for analysis of the chemical composition, the thickness and the nanoroughness of the plasma polymers. The functionalizations, especially the plasma coatings, were completely worn off by a UV/water weathering test (1000 h, X1a CAM 180 Test, SAE J-2527), but showed sufficient stability against sand erosion (DIN 52348), in a long-term outdoor test for 13.5 months and against fivefold repeated pull-off of ice. The silicone-like plasma coatings were more stable than the fluorocarbon plasma coatings. The wetting behavior of water was determined by static, advancing and receding contact angle measurements. Static contact angle measurements with diiodomethane (DIM) were made for determination of the surface free energies of the relevant surfaces. Advancing contact angles of over 150° and very low contact angle hysteresis values below 10° were reached on some of the cylindrically and elliptically structured PU samples with microstructure base diameters in the range of 35 µm to 50 µm. The measured water advancing contact angles did not reach the theoretical values of the Cassie-Baxter state. Starting from a mixed wetting state near Cassie-Baxter in case of the superhydrophobic PU surfaces, they approached the Wenzel state with an increasing pitch/diameter (P/d) factor. Fluorescence laser scanning microscopy images were taken of some microstructured, uncoated or plasma coated samples during the wetting by a water drop containing a fluorescent dye. These images show the Wenzel state or a mixed wetting state by visualization of the interface between the water droplet and the surface. A new icing test chamber and a test setup were developed for characterization of the ice adhesion and the icing behavior. The tensile ice adhesion was measured at -20 °C by pull-off of ice cylinders (highly purified water, (<0.056 µS/cm, diameter of 4 mm, similar to the diameter of large raindrops) and compared to the theoretical values and the wetting behavior. The technical material surfaces measured for comparison showed a high ice adhesion, which led to cohesive fractures especially on the metal surfaces, whereas some of the commercial anti-ice coatings showed lower ice adhesion values. The flat, plasma coated PU surfaces showed adhesive fractures with a reduced ice adhesion compared to the technical material surfaces and uncoated PU and revealed a good correlation of the ice adhesion with the wetting behavior of water (work of adhesion). On the other hand, the microstructured PU surfaces showed a greatly increased ice adhesion in comparison to the flat PU and technical material surfaces which was enhanced even further by the plasma coatings and did not correlate with the wetting behavior. The reason for this is the wetting transition from the Cassie-Baxter to the Wenzel state during the cooling or freezing process, leading to an increased ice-surface contact area and mechanical interlocking of the ice with the micro- and nanostructures. The freezing of water drops was examined in thermodynamic equilibrium (static experiment) and under quasi-steady conditions (dynamic experiment). In the static experiment, 15 µl water drops (corresponding to medium to large raindrops) at room temperature were dispensed onto a cold surface at a constant temperature of -20 °C. The freezing delay times, the crystallization times and the total freezing times were measured and compared to calculated expected values. On the flat samples, the freezing delay times could be extended by the plasma treatments. On the microstructured samples, the freezing (nucleation) could sometimes be delayed even further, but not always reproducible because of an unstable Cassie-Baxter state. In the dynamic experiment, 25 µl water drops (corresponding to large raindrops) were cooled down in quasi-steady conditions with the surface and the surrounding atmosphere by a constant, low cooling rate of 1 K/min while the water drop temperature was measured by an IR camera for determination of the surface-specific nucleation temperature and crystallization time. A lower nucleation temperature could be measured on the flat, plasma coated PU surfaces compared to uncoated PU and the hydrophilic glass and metal surfaces. The superhydrophobic PU surfaces did not show a further reduction of the nucleation temperature because of an unstable Cassie-Baxter state. The resulting measured nucleation temperatures were compared to the expected values calculated with an enhanced nucleation theory including a quasi-liquid interfacial layer of the ice nucleus and a Poisson process. Overall, it is shown that hot embossing and PECVD are useful processes for creating superhydrophobic PU surfaces with regard to a roll-to-roll process. The flat, plasma coated PU films show a reduced ice adhesion and lowered nucleation temperature compared to the relevant technical material surfaces. The microstructured, plasma coated PU films are far more water repellent than the flat, plasma coated PU surfaces or the other technical materials. However, the microstructures with base diameters of 35 µm or more and the nanoroughness of the plasma coatings cannot stabilize the Cassie-Baxter state of a freezing water drop enough for a low ice adhesion or a significant decrease of the nucleation temperature. These superhydrophobic PU films are therefore not more icephobic than the flat, plasma coated PU films. In the outlook, the reduction of the geometrical parameters of the microstructures (diameter D, distance P) and nanostructures (curvature radius R) of the surface functionalizations for lower ice adhesion values and nucleation temperatures is proposed.Item Open Access Calculation of pure substance and mixture viscosities using PCP-SAFT and entropy scaling(Stuttgart : Universität Stuttgart, Institut für Technische Thermodynamik und Thermische Verfahrenstechnik, 2020) Lötgering-Lin, Oliver; Gross, Joachim (Prof. Dr.-Ing.)Item Open Access Unraveling the impact of acetylation patterns in chitosan oligomers on Cu2+ ion binding : insights from DFT calculations(2023) Singh, Ratna; Smiatek, Jens; Moerschbacher, Bruno M.Chitosans are partially acetylated polymers of glucosamine, structurally characterized by their degree of polymerization as well as their fraction and pattern of acetylation. These parameters strongly influence the physico-chemical properties and biological activities of chitosans, but structure-function relationships are only poorly understood. As an example, we here investigated the influence of acetylation on chitosan-copper complexation using density functional theory. We investigated the electronic structures of completely deacetylated and partially acetylated chitosan oligomers and their copper-bound complexes. Frontier molecular orbital theory revealed bonding orbitals for electrophiles and antibonding orbitals for nucleophiles in fully deacetylated glucosamine oligomers, while partially acetylated oligomers displayed bonding orbitals for both electrophiles and nucleophiles. Our calculations showed that the presence of an acetylated subunit in a chitosan oligomer affects the structural and the electronic properties of the oligomer by generating new intramolecular interactions with the free amino group of neighboring deacetylated subunits, thereby influencing its polarity. Furthermore, the band gap energy calculated from the fully and partially deacetylated oligomers indicates that the mobility of electrons in partially acetylated chitosan oligomers is higher than in fully deacetylated oligomers. In addition, fully deacetylated oligomers form more stable complexes with higher bond dissociation energies with copper than partially acetylated ones. Interestingly, in partially acetylated oligomers, the strength of copper binding was found to be dependent on the pattern of acetylation. Our study provides first insight into the influence of patterns of acetylation on the electronic and ion binding properties of chitosans. Depending on the intended application, the obtained results can serve as a guide for the selection of the optimal chitosan for a specific purpose.Item Open Access Interfacial mechanics and liquid crystal structure of liquid gallium(2021) Yunusa, Muhammad; Sitti, Metin (Prof. Dr.)This dissertation aims to shed light on the fundamental aspects of supercooled liquid gallium. First, the mechanical properties of the oxide skin encapsulating the supercooled liquid gallium droplet is investigated. By leveraging the supercooling behavior of gallium and the formation of its oxide skin, we characterized the emergence of wrinkling at the interface and adhesion energy between the liquid gallium and rigid substrate. An interfacial energy of 0.238 ± 0.008 J m-2 was measured between gallium droplet and flat glass. Second, seed induced crystallization of supercooled liquid gallium on the different substrate materials revealed the dependence of the kinetics of crystallization on thermal behavior of the substrate. Such approach further elucidates on the importance of interface temperature during crystallization with a preferred orientation. The third part of the dissertation reports an unprecedented liquid crystal structure in supercooled liquid gallium. By the use of techniques applied in liquid crystal (LC) research, observation of LC texture in supercooled liquid gallium was realized. Reflective polarized optical microscopy (R-POM) on liquid gallium sandwiched between glasses treated with rubbed polymers reveals the onset of an anisotropic reflection of possible dimer molecules or clusters at 120°C that increases on cooling and persists down to room temperature or below. On the other hand, when gallium is sandwiched between substrates that align conventional liquid crystal molecules normal to the surface, the reflection is isotropic. This observation of LC structure of a highly electrically conductive supercooled liquid gallium provides an unexpected new field of materials science and liquid crystal research.Item Open Access Femtosecond direct laser writing of conductive and electrically witchable PEDOT:PSS optical nanostructures(2025) Ludescher, Dominik; Ruchka, Pavel; Siegle, Leander; Huang, Yanzhe; Flad, Philipp; Ubl, Monika; Ludwigs, Sabine; Hentschel, Mario; Giessen, HaraldMicroscale three‐dimensional (3D)‐printing, with its remarkable precision and ability to create complex structures, has transformed a wide range of applications, from micro‐optics and photonics to endoscopy and quantum technologies. In these fields, miniaturization plays a crucial role in unlocking new capabilities. However, despite these advancements, most 3D‐printed optical structures have remained static, lacking dynamic behavior and tunability. In this study, a novel approach is presented that combines direct laser writing with the electrically switchable optical properties of the conductive polymer poly(3,4‐ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS). This integration facilitates the creation of dynamic structures directly on 3D‐printed objects, marking a significant step toward adaptive optical devices. The fabrication of electrically tunable structures is demonstrated via direct laser writing using PEDOT:PSS on indium tin oxide (ITO)‐coated glass substrates, as well as beneath and atop static 3D‐printed structures. It is found that electrical conductivity as well as the greyscale behavior of PEDOT:PSS remains intact after direct laser writing. The switching speed, durability, and gradual tunability of the material are explored upon complementary metal‐oxide‐semiconductor (CMOS)‐compatible voltages ranging from -3 to +2 V. In the future, this advancement opens exciting possibilities in adaptive micro‐optics, such as switchable apertures printed directly onto micro‐optical lenses.Item Open Access The silicon vacancy centers in SiC : determination of intrinsic spin dynamics for integrated quantum photonics(2024) Liu, Di; Kaiser, Florian; Bushmakin, Vladislav; Hesselmeier, Erik; Steidl, Timo; Ohshima, Takeshi; Son, Nguyen Tien; Ul-Hassan, Jawad; Soykal, Öney O.; Wrachtrup, JörgThe negatively charged silicon vacancy center ( VSi-) in silicon carbide (SiC) is an emerging color center for quantum technology covering quantum sensing, communication, and computing. Yet, limited information currently available on the internal spin-optical dynamics of these color centers prevents us from achieving the optimal operation conditions and reaching the maximum performance especially when integrated within quantum photonics. Here, we establish all the relevant intrinsic spin dynamics of the VSi-center at cubic lattice site (V2) in 4H-SiC by an in-depth electronic fine structure modeling including the intersystem-crossing and deshelving mechanisms. With carefully designed spin-dependent measurements, we obtain all the previously unknown spin-selective radiative and non-radiative decay rates. To showcase the relevance of our work for integrated quantum photonics, we use the obtained rates to propose a realistic implementation of time-bin entangled multi-photon GHZ and cluster state generation. We find that up to three-photon GHZ or cluster states are readily within reach using the existing nanophotonic cavity technology.Item Open Access Ab initio machine-learning unveils strong anharmonicity in non-Arrhenius self-diffusion of tungsten(2025) Zhang, Xi; Divinski, Sergiy V.; Grabowski, BlazejThe knowledge of diffusion mechanisms in materials is crucial for predicting their high-temperature performance and stability, yet accurately capturing the underlying physics like thermal effects remains challenging. In particular, the origin of the experimentally observed non-Arrhenius diffusion behavior has remained elusive, largely due to the lack of effective computational tools. Here we propose an efficient ab initio framework to compute the Gibbs energy of the transition state in vacancy-mediated diffusion including the relevant thermal excitations at the density-functional-theory level. With the aid of a bespoke machine-learning interatomic potential, the temperature-dependent vacancy formation and migration Gibbs energies of the prototype system body-centered cubic (BCC) tungsten are shown to be strongly affected by anharmonicity. This finding explains the physical origin of the experimentally observed non-Arrhenius behavior of tungsten self-diffusion. A remarkable agreement between the calculated and experimental temperature-dependent self-diffusivity and, in particular, its curvature is revealed. The proposed computational framework is robust and broadly applicable, as evidenced by first tests for a hexagonal close-packed (HCP) multicomponent high-entropy alloy. The successful applications underscore the attainability of an accurate ab initio diffusion database.