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    Model-based autofocus for near-field phase retrieval
    (Optica Publishing Group, 2025-02-24) ; ; ; ;
    The phase problem is a well known ill-posed reconstruction problem of coherent lens-less microscopic imaging, where only the intensities of a complex wave-field are measured by the detector and the phase information is lost. For the reconstruction of sharp images from holograms in a near-field experimental setting, it is crucial to solve the autofocus problem, i.e., to precisely estimate the Fresnel number of the forward model. Otherwise, blurred out-of focus images that also can contain artifacts are the result. In general, a simple distance measurement at the experiment is not sufficiently accurate, thus the fine-tuning of the Fresnel number has to be done prior to the actual reconstructions. This can be done manually or automatically by an estimation algorithm. To automatize the process, as needed, e.g., for in-situ/operando experiments, different focus criteria have been widely studied in literature but are subjected to certain restrictions. The methods often rely on image analysis of the reconstructed image, making them sensitive to image noise and also neglecting algorithmic properties of the applied phase retrieval. In this paper, we propose a novel criterion, based on a model-matching approach, which improves autofocusing by also taking the underlying reconstruction algorithm, the forward model and the measured hologram into account. We derive a common autofocusing framework, based on a recent phase-retrieval approach and a downhill-simplex method for the automatic optimization of the Fresnel number. We further demonstrate the robustness of the framework on different data sets obtained at the nano imaging endstation of P05 at PETRA III (DESY, Hamburg) operated by Helmholtz-Zentrum Hereon.
    Publicationtype: Journal Article
      20  49
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    Wafer-scale fabrication of hierarchically porous silicon and silica by active nanoparticle-assisted chemical etching and pseudomorphic thermal oxidation
    Many biological materials exhibit a multiscale porosity with small, mostly nanoscale pores as well as large, macroscopic capillaries to simultaneously achieve optimized mass transport capabilities and lightweight structures with large inner surfaces. Realizing such a hierarchical porosity in artificial materials necessitates often sophisticated and expensive top-down processing that limits scalability. Here, an approach that combines self-organized porosity based on metal-assisted chemical etching (MACE) with photolithographically induced macroporosity for the synthesis of single-crystalline silicon with a bimodal pore-size distribution is presented, i.e., hexagonally arranged cylindrical macropores with 1 µm diameter separated by walls that are traversed by pores 60 nm across. The MACE process is mainly guided by a metal-catalyzed reduction–oxidation reaction, where silver nanoparticles (AgNPs) serve as the catalyst. In this process, the AgNPs act as self-propelled particles that are constantly removing silicon along their trajectories. High-resolution X-ray imaging and electron tomography reveal a resulting large open porosity and inner surface for potential applications in high-performance energy storage, harvesting and conversion or for on-chip sensorics and actuorics. Finally, the hierarchically porous silicon membranes can be transformed structure-conserving by thermal oxidation into hierarchically porous amorphous silica, a material that could be of particular interest for opto-fluidic and (bio-)photonic applications due to its multiscale artificial vascularization.
    Publicationtype: Journal Article
    Scopus© Citations 1  70  83
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    How nanoporous silicon-polypyrrole hybrids flex their muscles in aqueous electrolytes: in operando high-resolution x-ray diffraction and electron tomography-based micromechanical computer simulations
    (American Physical Society (APS), 2022-11-28) ; ; ; ;
    Macroscopic strain experiments have revealed that silicon crystals traversed by parallel, channel-like nanopores functionalized with the artificial muscle polymer polypyrrole (PPy) exhibit large and reversible electrochemomechanical actuation in aqueous electrolytes. On a macroscopic scale these actuation properties are well understood. However, on the microscopical level this system still bears open questions, as to how the electrochemical expansion and contraction of PPy acts on to np-Si pore walls and how the collective motorics of the pore array emerges from the single-nanopore behavior. Here we present synchrotron-based, in operando x-ray diffraction on the evolving electrostrains in epilayers of this material grown on bulk silicon. An analysis of these experiments with micromechanical finite-element simulations, that are based on a full three-dimensional reconstruction of the nanoporous medium by transmission electron microscopy (TEM) tomography, shows that the in-plane mechanical response is dominantly isotropic despite the anisotropic elasticity of the single-crystalline host matrix. However, the structural anisotropy originating from the parallel alignment of the nanopores led to significant differences between the in- and out-of-plane electromechanical response. This response is not describable by a simple two-dimensional arrangement of parallel cylindrical channels. Rather, the simulations highlight that the dendritic shape of the silicon pore walls, including pore connections between the main channels, causes complex, highly inhomogeneous stress-strain fields in the crystalline host. Time-dependent x-ray scattering experiments on the dynamics of the actuator properties hint towards the importance of diffusion limitations, plastic deformation, and creep in the nanoconfined polymer upon (counter)ion adsorption and desorption, the very pore-scale processes causing the macroscopic electroactuation. From a more general perspective, our study demonstrates that the combination of TEM tomography-based micromechanical modeling with high-resolution x-ray scattering experiments provides a powerful approach for in operando analysis of nanoporous composites from the single nanopore up to the porous-medium scale.
    Publicationtype: Journal Article
    Scopus© Citations 5  54  55
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    Deformation behavior of cross-linked supercrystalline nanocomposites: an in situ SAXS/WAXS study during uniaxial compression
    (American Chemical Society (ACS), 2021-03-22) ; ; ; ;
    With the ever-expanding functional applications of supercrystalline nanocomposites (a relatively new category of materials consisting of organically functionalized nanoparticles arranged into periodic structures), it becomes necessary to ensure their structural stability and understand their deformation and failure mechanisms. Inducing the cross-linking of the functionalizing organic ligands, for instance, leads to a remarkable enhancement of the nanocomposites' mechanical properties. It is however still unknown how the cross-linked organic phase redistributes applied loads, how the supercrystalline lattice accommodates the imposed deformations, and thus in general what phenomena govern the overall material's mechanical response. This work elucidates these aspects for cross-linked supercrystalline nanocomposites through an in situ small- and wide-angle X-ray scattering study combined with uniaxial pressing. Because of this loading condition, it emerges that the cross-linked ligands effectively carry and distribute loads homogeneously throughout the nanocomposites, while the superlattice deforms via rotation, slip, and local defects generation.
    Publicationtype: Journal Article
    Scopus© Citations 12  181  314
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    Elasticity of cross-linked titania nanocrystal assemblies probed by AFM-bulge tests
    (Multidisciplinary Digital Publishing Institute (MDPI), 2019-08-29) ; ; ; ;
    In order to enable advanced technological applications of nanocrystal composites, e.g., as functional coatings and layers in flexible optics and electronics, it is necessary to understand and control their mechanical properties. The objective of this study was to show how the elasticity of such composites depends on the nanocrystals’ dimensionality. To this end, thin films of titania nanodots (TNDs; diameter: ~3–7 nm), nanorods (TNRs; diameter: ~3.4 nm; length: ~29 nm), and nanoplates (TNPs; thickness: ~6 nm; edge length: ~34 nm) were assembled via layer-by-layer spin-coating. 1,12-dodecanedioic acid (12DAC) was added to cross-link the nanocrystals and to enable regular film deposition. The optical attenuation coefficients of the films were determined by ultraviolet/visible (UV/vis) absorbance measurements, revealing much lower values than those known for titania films prepared via chemical vapor deposition (CVD). Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) images showed a homogeneous coverage of the substrates on the µm-scale but a highly disordered arrangement of nanocrystals on the nm-scale. X-ray photoelectron spectroscopy (XPS) analyses confirmed the presence of the 12DAC cross-linker after film fabrication. After transferring the films onto silicon substrates featuring circular apertures (diameter: 32–111 µm), freestanding membranes (thickness: 20–42 nm) were obtained and subjected to atomic force microscopy bulge tests (AFM-bulge tests). These measurements revealed increasing elastic moduli with increasing dimensionality of the nanocrystals, i.e., 2.57 ± 0.18 GPa for the TND films, 5.22 ± 0.39 GPa for the TNR films, and 7.21 ± 1.04 GPa for the TNP films.
    Publicationtype: Journal Article
    Scopus© Citations 6  431  476
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    Iron oxide-based nanostructured ceramics with tailored magnetic and mechanical properties: Development of mechanically robust, bulk superparamagnetic materials
    (Royal Society of Chemistry (RSC), 2019-07-02) ; ; ; ;
    Nanostructured iron-oxide based materials with tailored mechanical and magnetic behavior are produced in bulk form. By applying ultra-fast heating routines via spark plasma sintering (SPS) to supercrystalline pellets, materials with an enhanced combination of elastic modulus, hardness and saturation magnetization are achieved. Supercrystallinity-namely the arrangement of the constituent nanoparticles into periodic structures-is achieved through self-assembly of the organically-functionalized iron oxide nanoparticles. The optimization of the following SPS regime allows the control of organics' removal, necking, iron oxide phase transformations and nano-grain size retention, and thus the fine-tuning of both mechanical properties and magnetic response, up until the production of bulk mm-size superparamagnetic materials.
    Publicationtype: Journal Article
    Scopus© Citations 28  416  389
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    Porous gold with a nested-network architecture and ultrafine structure
    © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. A preparation strategy is developed for monolithic samples of nanoporous gold with a hierarchical structure comprising two nested networks of solid "ligaments" on distinctly different structural length scales. The electrochemical dealloying protocol achieves a large retention of less noble element in a first corrosion step, thereby allowing an extra corrosion step which forms a separate structural hierarchy level. The beneficial impact of adding Pt to the Ag-Au master alloys that are more conventionally used in dealloying approaches to nanoporous gold is demonstrated. At ≈6 nm, the lower hierarchy level ligament size emerges extremely small. Furthermore, Pt favors the retention of Ag during the first dealloying step even when the master alloy has a high Au content. The high Au content reduces the corrosion-induced shrinkage, mitigating crack formation during preparation and favoring the formation of high-quality macroscopic (mm-sized) samples. The corrosion effectively carves out the nanoscale hierarchical ligament structure from the parent crystals tens of micrometers in size. This is revealed by X-ray as well as electron backscatter diffraction, which shows that the porous crystallites inherit the highly ordered, macroscopic crystal lattice structure of the master alloy.
    Publicationtype: Journal Article
    Scopus© Citations 65  309  347