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Short-Range Cooperative Slow-down of Water Solvation Dynamics Around SO42--Mg2+ Ion Pairs
The presence of ions affects the structure and dynamics of water on a multitude of length and time scales. In this context, pairs of Mg2+ and SO42- ions in water constitute a prototypical system for which conflicting pictures of hydration geometries and dynamics have been reported. Key issues are the molecular pair and solvation shell geometries, the spatial range of electric interactions, and their impact on solvation dynamics. Here, we introduce asymmetric SO42- stretching vibrations as new and most specific local probes of solvation dynamics that allow to access ion hydration dynamics at the dilute concentration (0.2 M) of a native electrolyte environment. Highly sensitive heterodyne 2D-IR spectroscopy in the fingerprint region of the SO42- ions around 1100 cm-1 reveals a specific slow-down of solvation dynamics for hydrated MgSO4 and for Na2SO4 in the presence of Mg2+ ions, which manifests as a retardation of spectral diffusion compared to aqueous Na2SO4 solutions in the absence of Mg2+ ions. Extensive molecular dynamics and density functional theory QM/MM simulations provide a microscopic view of the observed ultrafast dephasing and hydration dynamics. They suggest a molecular picture where the slow-down of hydration dynamics arises from the structural peculiarities of solvent-shared SO42--Mg2+ ion pairs.
Engineering Micropatterned Dry Adhesives: From Contact Theory to Handling Applications
Reversible adhesion is the key functionality to grip, place, and release objects nondestructively. Inspired by nature, micropatterned dry adhesives are promising candidates for this purpose and have attracted the attention of research groups worldwide. Their enhanced adhesion compared to nonpatterned surfaces is frequently demonstrated. An important conclusion is that the contact mechanics involved is at least as important as the surface energy and chemistry. In this paper, the roles of the contact geometry and mechanical properties are reviewed. With a focus on applications, the effects of substrate roughness and of temperature variations, and the long-term performance of micropatterned adhesives are discussed. The paper provides a link between the current, detailed understanding of micropatterned adhesives and emerging applications.
Robust Single Molecule Magnet Monolayers on Graphene and Graphite with Magnetic Hysteresis up to 28 K
The chemical functionalization of fullerene single molecule magnet Tb2@C80(CH2Ph) enables the facile preparation of robust monolayers on graphene and highly oriented pyrolytic graphite from solution without impairing their magnetic properties. Monolayers of endohedral fullerene functionalized with pyrene exhibit magnetic bistability up to a temperature of 28 K. The use of pyrene terminated linker molecules opens the way to devise integration of spin carrying units encapsulated by fullerene cages on graphitic substrates, be it single-molecule magnets or qubit candidates. © 2021 The Authors. Advanced Functional Materials published by Wiley-VCH GmbH
Transparent Power-Generating Windows Based on Solar-Thermal-Electric Conversion
Integrating transparent solar-harvesting systems into windows can provide renewable on-site energy supply without altering building aesthetics or imposing further design constraints. Transparent photovoltaics have shown great potential, but the increased transparency comes at the expense of reduced power-conversion efficiency. Here, a new technology that overcomes this limitation by combining solar-thermal-electric conversion with a material's wavelength-selective absorption is presented. A wavelength-selective film consisting of Cs0.33WO3 and resin facilitates high visible-light transmittance (up to 88%) and outstanding ultraviolet and infrared absorbance, thereby converting absorbed light into heat without sacrificing transparency. A prototype that couples the film with thermoelectric power generation produces an extraordinary output voltage of ≈4 V within an area of 0.01 m2 exposed to sunshine. Further optimization design and experimental verification demonstrate high conversion efficiency comparable to state-of-the-art transparent photovoltaics, enriching the library of on-site energy-saving and transparent power generation.
Revealing all states of dewetting of a thin gold layer on a silicon surface by nanosecond laser conditioning
Dewetting is a ubiquitous phenomenon which can be applied to the laser synthesis of nanoparticles. A classical spinodal dewetting process takes place in four successive states, which differ from each other in their morphology. In this study all states are revealed by interaction of pulsed nanosecond UV laser light with thin gold layers with thicknesses between 1 nm and 10 nm on (100) silicon wafers. The specific morphologies of the dewetting states are discussed with particular emphasis on the state boundaries. The main parameter determining which state is formed is not the duration for which the gold remains liquid, but rather the input energy provided by the laser. This shows that each state transition has a separate measurable activation energy. The temperature during the nanosecond pulses and the duration during which the gold remains liquid was determined by simulation using the COMSOL Multiphysics® software package. Using these calculations, an accurate local temperature profile and its development over time was simulated. An analytical study of the morphologies and formed structures was performed using Minkowski measures. With aid of this tool, the laser induced structures were compared with thermally annealed samples, with perfectly ordered structures and with perfectly random structures. The results show that both, structures of the laser induced and the annealed samples, strongly resemble the perfectly ordered structures. This reveals a close relationship between these structures and suggests that the phenomenon under investigation is indeed a spinodal dewetting generated by an internal material wave function. The purposeful generation of these structures and the elucidation of the underlying mechanism of dewetting by short pulse lasers may assist the realisation of various technical elements such as nanowires in science and industry. © 2020
Magnetic Nanoparticle Chains in Gelatin Ferrogels: Bioinspiration from Magnetotactic Bacteria
Inspired by chains of ferrimagnetic nanocrystals (NCs) in magnetotactic bacteria (MTB), the synthesis and detailed characterization of ferrimagnetic magnetite NC chain-like assemblies is reported. An easy green synthesis route in a thermoreversible gelatin hydrogel matrix is used. The structure of these magnetite chains prepared with and without gelatin is characterized by means of transmission electron microscopy, including electron tomography (ET). These structures indeed bear resemblance to the magnetite assemblies found in MTB, known for their mechanical flexibility and outstanding magnetic properties and known to crystallographically align their magnetite NCs along the strongest <111> magnetization easy axis. Using electron holography (EH) and angular dependent magnetic measurements, the magnetic interaction between the NCs and the generation of a magnetically anisotropic material can be shown. The electro- and magnetostatic modeling demonstrates that in order to precisely determine the magnetization (by means of EH) inside chain-like NCs assemblies, their exact shape, arrangement and stray-fields have to be considered (ideally obtained using ET). © 2019 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Perovskite Origami for Programmable Microtube Lasing
Metal halide perovskites are promising materials for optoelectronic and photonic applications ranging from photovoltaics to laser devices. However, current perovskite devices are constrained to simple low-dimensional structures suffering from limited design freedom and holding up performance improvement and functionality upgrades. Here, a micro-origami technique is developed to program 3D perovskite microarchitectures toward a new type of microcavity laser. The design flexibility in 3D supports not only outstanding laser performance such as low threshold, tunable output, and high stability but also yields new functionalities like 3D confined mode lasing and directional emission in, for example, laser “array-in-array” systems. The results represent a significant step forward toward programmable microarchitectures that take perovskite optoelectronics and photonics into the 3D era. © 2021 The Authors. Advanced Functional Materials published by Wiley-VCH GmbH.
Building Hierarchical Martensite
Martensitic materials show a complex, hierarchical microstructure containing structural domains separated by various types of twin boundaries. Several concepts exist to describe this microstructure on each length scale, however, there is no comprehensive approach bridging the whole range from the nano- up to the macroscopic scale. Here, it is described for a Ni-Mn-based Heusler alloy how this hierarchical microstructure is built from scratch with just one key parameter: the tetragonal distortion of the basic building block at the atomic level. Based on this initial block, five successive levels of nested building blocks are introduced. At each level, a larger building block is formed by twinning the preceding one to minimize the relevant energy contributions locally. This naturally explains the coexistence of different types of twin boundaries. The scale-bridging approach of nested building blocks is compared with experiments in real and reciprocal space. The approach of nested building blocks is versatile as it can be applied to the broad class of functional materials exhibiting diffusionless transformations. © 2020 The Authors. Advanced Functional Materials published by Wiley-VCH GmbH
Cell-Instructive Multiphasic Gel-in-Gel Materials
Developing tissue is typically soft, highly hydrated, dynamic, and increasingly heterogeneous matter. Recapitulating such characteristics in engineered cell-instructive materials holds the promise of maximizing the options to direct tissue formation. Accordingly, progress in the design of multiphasic hydrogel materials is expected to expand the therapeutic capabilities of tissue engineering approaches and the relevance of human 3D in vitro tissue and disease models. Recently pioneered methodologies allow for the creation of multiphasic hydrogel systems suitable to template and guide the dynamic formation of tissue- and organ-specific structures across scales, in vitro and in vivo. The related approaches include the assembly of distinct gel phases, the embedding of gels in other gel materials and the patterning of preformed gel materials. Herein, the capabilities and limitations of the respective methods are summarized and discussed and their potential is highlighted with some selected examples of the recent literature. As the modularity of the related methodologies facilitates combinatorial and individualized solutions, it is envisioned that multiphasic gel-in-gel materials will become a versatile morphogenetic toolbox expanding the scope and the power of bioengineering technologies. © 2020 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Semitransparent Perovskite Solar Cells with an Evaporated Ultra-Thin Perovskite Absorber
Metal halide perovskites are of great interest for application in semitransparent solar cells due to their tunable bandgap and high performance. However, fabricating high-efficiency perovskite semitransparent devices with high average visible transmittance (AVT) is challenging because of their high absorption coefficient. Here, a co-evaporation process is adopted to fabricate ultra-thin CsPbI3 perovskite films. The smooth surface and orientated crystal growth of the evaporated perovskite films make it possible to achieve 10 nm thin films with compact and continuous morphology without pinholes. When integrated into a p-i-n device structure of glass/ITO/PTAA/perovskite/PCBM/BCP/Al/Ag with an optimized transparent electrode, these ultra-thin layers result in an impressive open-circuit voltage (VOC) of 1.08 V and a fill factor (FF) of 80%. Consequently, a power conversion efficiency (PCE) of 3.6% with an AVT above 50% is demonstrated, which is the first report for a perovskite device of a 10 nm active layer thickness with high VOC, FF and AVT. These findings demonstrate that deposition by thermal evaporation makes it possible to form compact ultra-thin perovskite films, which are of great interest for future smart windows, light-emitting diodes, and tandem device applications.