The dynamic underwater chemistry seen in nature is inspiring for the next generation of eco-friendly nanochemistry. In this context, green synthesis of size-tailored nanoparticles in a facile and ...scalable manner via a dynamic process is an interesting challenge. Simulating the volcano-induced dynamic chemistry of the deep ocean, here we demonstrate the Leidenfrost dynamic chemistry occurring in an underwater overheated confined zone as a new tool for customized creation of nanoclusters of zinc peroxide. The hydrodynamic nature of the phenomenon ensures eruption of the nanoclusters towards a much colder region, giving rise to growth of monodisperse, size-tailored nanoclusters. Such nanoparticles are investigated in terms of their cytotoxicity on suspension and adherent cells to prove their applicability as cancer nanotherapeutics. Our research can pave the way for employment of the dynamic green nanochemistry in facile, scalable fabrication of size-tailored nanoparticles for biomedical applications.
Ferroelectric thin films of wurtzite-type aluminum scandium nitride (Al1−xScxN) are promising candidates for non-volatile memory applications and high-temperature sensors due to their outstanding ...functional and thermal stability exceeding most other ferroelectric thin film materials. In this work, the thermal expansion along with the temperature stability and its interrelated effects have been investigated for Al1−xScxN thin films on sapphire Al2O3(0001) with Sc concentrations x (x = 0, 0.09, 0.23, 0.32, 0.40) using in situ X-ray diffraction analyses up to 1100 °C. The selected Al1−xScxN thin films were grown with epitaxial and fiber textured microstructures of high crystal quality, dependent on the choice of growth template, e.g., epitaxial on Al2O3(0001) and fiber texture on Mo(110)/AlN(0001)/Si(100). The presented studies expose an anomalous regime of thermal expansion at high temperatures >~600 °C, which is described as an isotropic expansion of a and c lattice parameters during annealing. The collected high-temperature data suggest differentiation of the observed thermal expansion behavior into defect-coupled intrinsic and oxygen-impurity-coupled extrinsic contributions. In our hypothesis, intrinsic effects are denoted to the thermal activation, migration and curing of defect structures in the material, whereas extrinsic effects describe the interaction of available oxygen species with these activated defect structures. Their interaction is the dominant process at high temperatures >800 °C resulting in the stabilization of larger modifications of the unit cell parameters than under exclusion of oxygen. The described phenomena are relevant for manufacturing and operation of new Al1−xScxN-based devices, e.g., in the fields of high-temperature resistant memory or power electronic applications.
In situ transmission electron microscope (TEM) characterization techniques provide valuable information on structure–property correlations to understand the behavior of materials at the nanoscale. ...However, understanding nanoscale structures and their interaction with the electron beam is pivotal for the reliable interpretation of in situ/ex situ TEM studies. Here, we report that oxides commonly used in nanoelectronic applications, such as transistor gate oxides or memristive devices, are prone to electron beam induced damage that causes small structural changes even under very low dose conditions, eventually changing their electrical properties as examined via in situ measurements. In this work, silicon, titanium, and niobium oxide thin films are used for in situ TEM electrical characterization studies. The electron beam induced reduction of the oxides turns these insulators into conductors. The conductivity change is reversible by exposure to air, supporting the idea of electron beam reduction of oxides as primary damage mechanism. Through these measurements we propose a limit for the critical dose to be considered for in situ scanning electron microscopy and TEM characterization studies.
We report on results of a comprehensive investigation on reaction mechanisms occurring during Li uptake and release of the composite NiFe
2
O
4
/CNT.
Operando
X-ray diffraction (XRD) and X-ray ...absorption spectroscopy (XAS) data collected simultaneously using one
in situ
cell allowed thorough elucidation of structural and electronic alterations happening during Li uptake. From the beginning of Li uptake, the Bragg intensity of the spinel reflections decreases which can be explained by reduction of Fe
3+
ions and simultaneous movement of the Fe
2+
cations from tetrahedral 8a to empty octahedral 16c sites. The reduction of Fe
3+
is clearly evidenced by XAS. The occupation of tetrahedral sites by Li
+
can be excluded based on results of density functional theory calculations. Increasing the Li content leads to formation of a new crystalline phase resembling a monoxide with a NaCl-like structure. The appearance of the new phase is accompanied by a steady decrease of the sizes of coherently scattering domains of the spinel and a growth of the domains of the monoxide phase. After uptake of about 2.5 Li per NiFe
2
O
4
, all Fe
3+
cations are reduced to Fe
2+
and the tetrahedral 8a sites are empty (XAS spectra). Careful Rietveld refinements of X-ray powder patterns demonstrate that the tetrahedral 8a site is successively depleted with increasing Li content. Interestingly, the occupancy of the octahedral 16d site is also slightly reduced. Increasing the Li content beyond 2.5 Li/NiFe
2
O
4
leads to successive reduction of the cations to very small metal particles embedded in a Li
2
O matrix (as evidenced by
7
Li MAS NMR investigations). During Li release metallic Ni and Fe are reoxidized to Ni
2+
resp. Fe
3+
. The cycling stability of NiFe
2
O
4
/CNT is significantly improved compared to pure NiFe
2
O
4
or a mechanical mixture of NiFe
2
O
4
and CNTs.
Transition metal cations on the move: simultaneous
operando
XAS and XRD investigations during Li uptake and release of a NiFe
2
O
4
/CNT composite.
Monolithic integration of permanent micromagnets into MEMS structures offers many advantages in magnetic MEMS applications. A novel technique called PowderMEMS, based on the agglomeration of ...micron-sized powders by atomic layer deposition (ALD), has been used to fabricate permanent micromagnets on 8-inch wafers. In this paper, we report the fabrication and magnetic characterization of PowderMEMS micromagnets prepared from two different NdFeB powder particle sizes. A remanence of 423 mT and intrinsic coercivity of 924 mT is achieved at the low ALD process temperature of 75 °C, making this process compatible with MEMS technology. The magnetic reversible mechanism in the micromagnets is discussed with the help of the Wohlfarth equation. To ensure the operability of such integrated micromagnets in different application environments, we conducted a set of experiments to systematically investigate the thermal and corrosive stability. NdFeB micromagnets with larger powder particle size (d50 = 25 µm) exhibit high thermal stability in air. Furthermore, the corrosion stability of the micromagnets is significantly improved by an additional silicon oxide passivation layer deposited by plasma-enhanced chemical vapor deposition (PECVD). The presented results demonstrate the durability of PowderMEMS micromagnets, enabling their application in various fields, e.g., microfluidics, sensors, actuators, and microelectronics.
Supercapacitors are energy storage devices with the ability to rapidly charge and discharge, making them a valuable complement to battery systems. To maximize their fast‐charging capabilities, ...identifying materials and methods to enhance their energy density is crucial. In this work, we carried out a comprehensive study of an emerging 2D dichalcogenide, CrSe2, as a supercapacitor material. We demonstrate that CrSe2 can be obtained at ambient temperature through deintercalation of a relevant KCrSe2 precursor using a 0.5 M solution of I2 in acetonitrile. Although CrSe2 decomposed in 1 M KOH, it was found to be chemically stable in common electrolytes such as H2SO4, Li2SO4, and Na2SO4. Despite low surface area CrSe2 reached a specific capacitance of 27 F g−1 in 1 M H2SO4 and, thus consistently outperformed high surface carbon black. Computational studies suggested that the metallic conductivity of CrSe2 was likely the primary factor contributing to the superior performance of this 2D chalcogenide over high surface carbon analogues.
The response of individual grain boundaries in polycrystalline ZnO nano‐ and microstructure platelets to visible light illumination is studied using scanning probe microscopy. The grain boundaries ...show enhanced photoconductivity even in the visible range of light below the band gap, suggesting that they can be potentially used as transparent conducting oxide electrodes.
We report the synthesis of alumina/stishovite nano‐nano composite ceramics through a pressure‐induced dissociation in Al2SiO5 at a pressure of 15.6 GPa and temperatures of 1300°C‐1900°C. Stishovite ...is a high‐pressure polymorph of silica and the hardest known oxide at ambient conditions. The grain size of the composites increases with synthesis temperature from ~15 to ~750 nm. The composite is harder than alumina and the hardness increases with reducing grain size down to ~80 nm following a Hall–Petch relation. The maximum hardness with grain size of 81 nm is 23 ± 1 GPa. A softening with reducing grain size was observed below this grain size down to ~15 nm, which is known as inverse Hall–Petch behavior. The grain size dependence of the hardness might be explained by a composite model with a softer grain‐boundary phase.
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