Universität Stuttgart

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    Designing covalent organic framework‐based light‐driven microswimmers toward therapeutic applications
    (2023) Sridhar, Varun; Yildiz, Erdost; Rodríguez‐Camargo, Andrés; Lyu, Xianglong; Yao, Liang; Wrede, Paul; Aghakhani, Amirreza; Akolpoglu, Birgul M.; Podjaski, Filip; Lotsch, Bettina V.; Sitti, Metin
    While micromachines with tailored functionalities enable therapeutic applications in biological environments, their controlled motion and targeted drug delivery in biological media require sophisticated designs for practical applications. Covalent organic frameworks (COFs), a new generation of crystalline and nanoporous polymers, offer new perspectives for light‐driven microswimmers in heterogeneous biological environments including intraocular fluids, thus setting the stage for biomedical applications such as retinal drug delivery. Two different types of COFs, uniformly spherical TABP‐PDA‐COF sub‐micrometer particles and texturally nanoporous, micrometer‐sized TpAzo‐COF particles are described and compared as light‐driven microrobots. They can be used as highly efficient visible‐light‐driven drug carriers in aqueous ionic and cellular media. Their absorption ranging down to red light enables phototaxis even in deeper and viscous biological media, while the organic nature of COFs ensures their biocompatibility. Their inherently porous structures with ≈2.6  and ≈3.4 nm pores, and large surface areas allow for targeted and efficient drug loading even for insoluble drugs, which can be released on demand. Additionally, indocyanine green (ICG) dye loading in the pores enables photoacoustic imaging, optical coherence tomography, and hyperthermia in operando conditions. This real‐time visualization of the drug‐loaded COF microswimmers enables unique insights into the action of photoactive porous drug carriers for therapeutic applications.
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    Exploring the growth of refractory metal and sapphire films by thermal laser epitaxy
    (2024) Majer, Lena N.; Mannhart, Jochen (Prof. Dr.)
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    Confirmation of siderazot, Fe3N1.33, the only terrestrial nitride mineral
    (2021) Bette, Sebastian; Theye, Thomas; Bernhardt, Heinz-Jürgen; Clark, William P.; Niewa, Rainer
    Siderazot, the only terrestrial nitride mineral, was reported only once in 1876 to occur as coating on volcanic rocks in a fumarolic environment from Mt. Etna and, to date, has been neither confirmed nor structurally characterized. We have studied the holotype sample from the Natural History Museum, London, UK, originally collected by O. Silvestri in 1874, and present siderazot with epsilon-Fe3N-type crystal structure and composition of Fe3N1.33(7) according to crystal structure Rietveld refinements, in good agreement with electron microprobe analyses. Crystal structure data, chemical composition, and Raman and reflectance measurements are reported. Possible formation conditions are derived from composition and phase stability data according to synthetic samples.
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    Polarized neutron reflectometry study of complex magnetism and hydrogen incorporation in thin-film structures
    (2022) Guasco, Laura; Keimer, Bernhard (Prof. Dr.)
    In this thesis, we present the study of the structural and magnetic properties of simple metals and complex oxide thin films by means of polarized neutron reflectometry. The nuclear and electronic properties of thin films were modified via two routes, namely via hydrogen incorporation, in the case of niobium systems and complex oxide layers, and via depth modulated hole doping, in the case of manganite heterostructures.
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    Real-space spectroscopy of interacting quasiparticles in exotic semimetals
    (2022) He, Qingyu; Takagi, Hidenori (Prof. Dr.)
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    High quality graphene for magnetic sensing
    (2022) Herlinger, Patrick; Smet, Jurgen (Dr.)
    In this thesis, we investigated the reliable fabrication of high quality graphene and its use as Hall transducer material. Charged impurities and random strain fluctuations were identified as main culprits that deteriorate the electrical properties of graphene devices. It was shown that these extrinsic sources of disorder can be reduced through optimized device processing steps as well as the use of a proper substrate material for graphene such as hexagonal boron nitride (hBN). This insulating material is atomically flat and possesses a very low intrinsic density of charged impurities. By performing Raman spectroscopy and electrical transport measurements, both without and with applied magnetic field, on a large number of different types of graphene devices, it was demonstrated that the encapsulation of graphene between hexagonal boron nitride thin films is the best way to obtain high quality graphene devices. However, even for these hBN-encapsulated devices, we still observed a notable sample-to-sample variation of the electrical properties. Therefore, we developed a post-processing technique that allows us to improve the electrical properties of such devices both significantly and reliably. Since our technique is applied after device fabrication, we could also demonstrate its beneficial effect by comparing one and the same device before and after treatment. We then assessed the application of such high quality graphene as Hall transducer material. The dependencies on and between all relevant operating parameters were explored. This allowed us to develop a deep understanding and empirical model for graphene Hall elements, including the interplay between thermal and 1/f noise in these devices. All key performance indicators for Hall sensors were measured and their typical values reported. For comparable device dimensions, hBN-encapsulated graphene Hall elements were found to have the potential to become a strong competitor to existing materials that are used in today's commercial Hall sensors. Unfortunately, the large-scale fabrication of hBN thin films still remains an unresolved challenge for the industrialization of large area, high quality graphene Hall elements. Also, the Si CMOS integration demands further development. Even though the application of graphene in Hall devices is promising, as shown in this work, this use case alone does likely not justify the significant efforts and investments we expect to be necessary to industrialize the fabrication of high quality graphene devices. Instead, these efforts and costs must be shared by developing a common technology platform for 2D materials that can address several commercially attractive applications where graphene or another 2D material offers superior performance as well. We hope that the insights provided in this work can help to accelerate this process.
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    On the thermal dimorphy of the strontium perrhenate Sr[ReO4]2
    (2024) Conrad, Maurice; Bette, Sebastian; Dinnebier, Robert E.; Schleid, Thomas
    Hygroscopic single crystals of a new hexagonal high‐temperature modification of Sr[ReO4]2 were prepared from a melt of Sr[ReO4]2 ⋅ H2O and SrCl2 ⋅ 6 H2O. The structure analysis of the obtained crystals by X‐ray diffraction revealed that the title compound crystallizes in the ThCd[MoO4]3‐type structure with the hexagonal space group P63/m and the lattice parameters a=1023.81(7) pm and c=646.92(4) pm (c/a=0.632) for Z=2 in its quenchable high‐temperature form. Two crystallographically independent Sr2+ cations are coordinated by oxygen atoms forming either octahedra or tricapped trigonal prisms, whereas the Re7+ cations are found in the centers of discrete tetrahedral meta‐perrhenate units [ReO4]-. Temperature‐dependent in‐situ PXRD studies of dry powder samples of Sr[ReO4]2 exhibited its thermal dimorphy with a phase‐transition temperature at 500-550 °C from literature‐known m‐Sr[ReO4]2 into the newly discovered h‐Sr[ReO4]2 (hexagonal).
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    Heterodyne sensing of microwaves with a quantum sensor
    (2021) Meinel, Jonas; Vorobyov, Vadim; Yavkin, Boris; Dasari, Durga; Sumiya, Hitoshi; Onoda, Shinobu; Isoya, Junichi; Wrachtrup, Jörg
    Diamond quantum sensors are sensitive to weak microwave magnetic fields resonant to the spin transitions. However, the spectral resolution in such protocols is ultimately limited by the sensor lifetime. Here, we demonstrate a heterodyne detection method for microwaves (MW) leading to a lifetime independent spectral resolution in the GHz range. We reference the MW signal to a local oscillator by generating the initial superposition state from a coherent source. Experimentally, we achieve a spectral resolution below 1 Hz for a 4 GHz signal far below the sensor lifetime limit of kilohertz. Furthermore, we show control over the interaction of the MW-field with the two-level system by applying dressing fields, pulsed Mollow absorption and Floquet dynamics under strong longitudinal radio frequency drive. While pulsed Mollow absorption leads to improved sensitivity, the Floquet dynamics allow robust control, independent from the system’s resonance frequency. Our work is important for future studies in sensing weak microwave signals in a wide frequency range with high spectral resolution.
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    High‐performance magnesium‐sulfur batteries based on a sulfurated poly(acrylonitrile) cathode, a borohydride electrolyte, and a high‐surface area magnesium anode
    (2020) Wang, Peiwen; Trück, Janina; Niesen, Stefan; Kappler, Julian; Küster, Kathrin; Starke, Ulrich; Ziegler, Felix; Hintennach, Andreas; Buchmeiser, Michael R.
    Post‐lithium‐ion battery technology is considered a key element of future energy storage and management. Apart from high gravimetric and volumetric energy densities, economic, ecologic and safety issues become increasingly important. In that regards, both the anode and cathode materials must be easily available, recyclable, non‐toxic and safe, which renders magnesium‐sulfur (Mg-S) batteries a promising choice. Herein, we present Mg-S cells based on a sulfurated poly(acrylonitrile) composite cathode (SPAN), together with a halogen‐free electrolyte containing both Mg[BH4]2 and Li[BH4] in diglyme and a high‐specific surface area magnesium anode based on Rieke magnesium powder. These cells deliver discharge capacities of 1400 and 800 mAh/gsulfur with >99 % Coulombic efficiency at 0.1 C and 0.5 C, respectively, and are stable over at least 300 cycles. Energy densities are 470 and 400 Wh/kgsulfur at 0.1 C and 0.5 C, respectively. Rate tests carried out between 0.1 C and 2 C demonstrate good rate capability of the cells. Detailed mechanistic studies based on X‐ray photoelectron spectroscopy and electric impedance spectroscopy are presented.