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Potassium hydroxide (KOH) aqueous solutions can effectively etch germanium. Etch rates were determined in an electrolytic etch cell. Electrically isolated Ge wafers were subject to an etch rate of 1.45 ± 0.07 nm min−1, increasing to 12.6 ± 0.2 nm min−1 when grounded, 97 ± 2 nm min−1 when biased at −0.9 V, and 138 ± 2 nm min−1 with periodic biasing. Results suggest that the previously reported limited etching in KOH is associated with the recombination of holes with electrons injected from the surface reaction. The results of this study demonstrate that changing the hole concentration through biasing is an effective tool to control electrolytic etch rates, enabling future selective etching processes for germanium.

Highlights Confirmation of 2-electron model for anodic dissolution of Ge in H2O2 Etching mechanism for Ge is significantly different compared to silicon Etch processing techniques cannot be transferred between silicon and germanium Addition of alcohol to H2O2 and agitation improves specularity and etch quality

During thermal annealing at 1425 °C nominal electric field strengths of 50 V/mm and 150 V/mm were applied along the grain boundary planes of a near 45° (100) twist grain boundary in SrTiO3. Electron microscopy characterization revealed interface expansions near the positive electrode around 0.8 nm for either field strength. While the interface width decreased to roughly 0.4 nm after annealing at 50 V/mm, the higher field strength caused decomposition of the boundary structure close to the negative electrode. Electron energy-loss and X-ray photoelectron spectroscopies demonstrated an increased degree of oxygen sublattice distortion at the negative electrode side, and enhanced concentrations of Ti3+ and Ti2+ compared to bulk for both single crystals and bicrystals annealed with an external electric field, respectively. Oxygen migration due to the applied electric field causes the observed alteration of grain boundary structures. At sufficiently high field strength the agglomeration of anion vacancies may lead to the decomposition of the grain boundary.

The reduction reactions and densification of nanochains assembled from γ-Fe2O3 nanoparticles were investigated using in situ transmission electron microscopy (TEM). Morphological changes and reduction of the metal oxide nanochains were observed during in situ TEM annealing through simultaneous imaging and quantitative analysis of the near-edge fine structures of Fe L2,3 absorption edges acquired by spatially resolved electron energy loss spectroscopy. A change in the oxidation states during annealing of the iron oxide nanochains was observed with phase transformations due to continuous reduction from Fe2O3 over Fe3O4, FeO to metallic Fe. Phase transitions during the in situ heating experiments were accompanied with morphological changes in the nanochains, specifically rough-to-smooth surface transitions below 500 °C, neck formation between adjacent particles around 500 °C, and subsequent neck growth. At higher temperatures, coalescence of FeO particles was observed, representing densification.

A spark plasma sintering apparatus was used as a novel method for diffusion bonding of two single crystals of strontium titanate to form bicrystals with one twist grain boundary. This apparatus utilizes high uniaxial pressure and a pulsed direct current for rapid consolidation of material. Diffusion bonding of strontium titanate bicrystals without fracture, in a spark plasma sintering apparatus, is possible at high pressures due to the unusual temperature dependent plasticity behavior of strontium titanate. We demonstrate a method for the successful formation of bicrystals at accelerated time scales and lower temperatures in a spark plasma sintering apparatus compared to bicrystals formed by conventional diffusion bonding parameters. Bond quality was verified by scanning electron microscopy. A clean and atomically abrupt interface containing no secondary phases was observed using transmission electron microscopy techniques. Local changes in bonding across the boundary was characterized by simultaneous scanning transmission electron microscopy and spatially resolved electron energy-loss spectroscopy.

Obliteration of matter by pulsed laser beams is not only prevalent in science fiction movies, but finds numerous technological applications ranging from additive manufacturing over machining of micro- and nanostructured features to health care. Pulse lengths ranging from femtoseconds to nanoseconds are utilized at varying laser beam energies and pulse lengths, and enable the removal of nanometric volumes of material. While the mechanisms for removal of material by laser irradiation, i.e., laser ablation, are well understood on the micrometer length scale, it was previously impossible to directly observe obliteration processes on smaller scales due to experimental limitations for the combination of nanometer spatial and nanosecond temporal resolution. Here, we report the direct observation of metal thin film ablation from a solid substrate through dynamic transmission electron microscopy. Quantitative analysis reveals liquid-phase dewetting of the thin-film, followed by hydrodynamic sputtering of nano- to submicron sized metal droplets. We discovered unexpected fracturing of the substrate due to evolving thermal stresses. This study confirms that hydrodynamic sputtering remains a valid mechanism for droplet expulsion on the nanoscale, while irradiation induced stress fields represent limit laser processing of nanostructured materials. Our results allow for improved safety during laser ablation in manufacturing and medical applications.

The contamination of drinking water with naturally occurring arsenic is a global health threat. Filters that are packed with adsorbent media with a high affinity for arsenic have been used to de-contaminate water - generally iron or aluminium oxides are favored materials. Recently, nanoparticles have been introduced as adsorbent media due to their superior efficiency compared to their bulk counter-parts. An efficient nanoadsorbent should ideally possess high surface area, be easy to synthesize, and most importantly offer a high arsenic removal capacity. Achieving all the key features in a single step synthesis is an engineering challenge. We have successfully engineered such a material in the form of nanochains synthesized via a one step flame synthesis. The ultra-long γ-Fe2O3 nanochains possess high surface area (151.12 m2 g-1), large saturation magnetization (77.1 emu g-1) that aids in their gas phase self-assembly into long chains in an external magnetic field, along with an extraordinary arsenic removal capacity (162 mg.g-1). A filter made with this material exhibited a relatively low-pressure drop and very little break-through of the iron oxide across the filter.

Ultrathin films of nickel deposited onto (100) Si substrates were found to form kinetically constrained multilayered interface structures characterized by structural and compositional gradients. The presence of a native SiO2 on the substrate surface in tandem with thickness-dependent intrinsic stress of the metal film limits the solid-state reaction between Ni and Si. A roughly 6.5 nm thick Ni film on top of the native oxide was observed regardless of the initial nominal film thickness of either 5 or 15 nm. The thickness of the silicide layer that formed by Ni diffusion into the Si substrate, however, scales with the nominal film thickness. Cross-sectional in situ annealing experiments in the transmission electron microscope elucidate the kinetics of interface transformation towards thermodynamic equilibrium. Two competing mechanisms are active during thermal annealing: thermally activated diffusion of Ni through the native oxide layer and subsequent transformation of the observed compositional gradient into a thick reaction layer of NiSi2 with an epitaxial orientation relationship to the Si substrate; and, secondly, metal film dispersion and subsequent formation of faceted Ni islands on top of the native oxide layer.

The agglomeration of thin films on substrates is driven by minimization of the free surface and film/substrate interface energies and has been studied extensively for single component metal films. Only a few studies have investigated the agglomeration of kinetically constrained metal bilayer films, for which unusual long-range edge retraction was recently reported. This study has explored the agglomeration of kinetically constrained thin films of Au and Ni that were subsequently deposited on SiO2/Si substrates and annealed under high vacuum conditions at 545, 675, and 730 °C. Long-range edge retraction of the metal bilayer films revealed seven regions across the receding edge that are microstructurally distinct. The absolute and relative widths of the regions depend on the deposition sequence of the two metal films and annealing temperature. Arrhenius analysis of growth rates for different regions was used to identify energy barriers for mass transport mechanisms. The presence of native nickel oxide was found to have a significant effect on the kinetics of long-range edge retraction. The experimental results suggest that the formation of multiple regions across the receding edge is part of the kinetic evolution of long-range edge retraction of metal bilayer films. [ABSTRACT FROM AUTHOR]

Anisotropic growth of nanostructures from individual nickel nanoparticles was observed during in situ heating experiments in an environmental scanning electron microscope (ESEM) at 800°C under water vapor atmosphere. The morphology of nanostructures exhibited one directional growth with rates ranging below 1.8 nm/s. Energy dispersive X‐ray spectroscopy and selected area electron diffraction confirmed NiO stoichiometry of the growing nanostructures. Variations of the oxygen partial pressure during ex situ annealing and in situ ESEM heating experiments elucidate that anisotropic NiO growth is energetically favored in areas where the local surface energy density is relatively high. Growth of NiO nanostructures was absent in dry air and dry nitrogen environments and required the presence of water vapor. The results of this study suggest that the manipulation of surface energy prior to exposure to water vapor at elevated temperatures can prevent unwanted oxide nanostructure growth. [ABSTRACT FROM AUTHOR]

The dewetting of thin films can occur in either the solid or the liquid state for which different mass transport mechanisms are expected to control morphological changes. Traditionally, dewetting dynamics have been examined on time scales between several seconds to hours, and length scales ranging between nanometers and millimeters. The determination of mass transport mechanisms on the nanoscale, however, requires nanoscale spatial resolution and much shorter time scales. This study reports the high-speed observation of dewetting phenomena for kinetically constrained Ni thin films on crystalline SrTiO3 substrates. Movie-mode Dynamic Transmission Electron Microscopy (DTEM) was used for high-speed image acquisition during thin film dewetting at different temperatures. DTEM imaging confirmed that the initial stages of film agglomeration include edge retraction, hole formation, and growth. Finite element modeling was used to simulate temperature distributions within the DTEM samples after laser irradiation with different energies. For pulsed laser irradiation at 18 μJ, experimentally observed hole growth suggests that Marangoni flow dominates hole formation in the liquid nickel film. After irradiation with 13.8 μJ, however, the observations suggest that dewetting was initiated by nucleation of voids followed by hole growth through solid-state surface diffusion. [ABSTRACT FROM AUTHOR]

Recent interest in spintronic applications has necessitated the study of magnetic materials in contact with semiconductor substrates; importantly, the structure and composition of these interfaces can influence both device functionality and the magnetic properties. Nanoscale ferromagnet/semiconductor structures are of particular interest. In this study, the interface structure between a monolayer of ferromagnetic magnetite (Fe3O4) nanoparticles and a GaAs substrate was studied using cross-sectional transmission electron microscopy techniques. It was found that a continuous amorphous oxide interface layer separates the nanoparticles from the GaAs substrate, and that iron diffused into the interface layer forming a compositional gradient. Electron energy-loss near-edge fine structures of the O K absorption edge revealed that the amorphous oxide is composed of c-Fe3O3 directly underneath the Fe3O4 nanoparticles, followed by a solid solution of Ga2O3 and FeO and mostly Ga2O3 when approaching the buckled oxide/substrate interface. Realspace density functional theory calculations of the dynamical form factor confirmed the experimental observations. The implication of the findings on the optimization of these structures for spin injection is discussed. [ABSTRACT FROM AUTHOR]

Increasing surface-to-volume ratios for nanoscale materials may cause metal(II)oxides phases to be thermodynamically unstable compared to their bulk counterparts. For instance, previous studies have found FeO to be unstable for nanoparticles with dimensions below 100 nm. In this study in-situ TEM was used to gradually reduce nanoparticles and nanochains of Fe2O3. Electron energy-loss spectroscopy and selected area diffraction at different temperatures not only confirm earlier predictions, but also reveal the unexpected stabilization of the FeO phase for nanochains with a minimal critical length. Hence, dimensionally constrained phases were stabilized on length-scales that were previously considered unattainable. This study provides direct experimental evidence for the previously unanticipated stabilization of metal(II)oxides with dimensions well below 100 nm, which has exciting potential for catalyst technologies and next generation memory devices. [ABSTRACT FROM AUTHOR]