Dry Synthesis of Pure and Ultrathin Nanoporous Metallic Films.

Nanoporous metals possess unique properties attributed to their high surface area and interconnected nanoscale ligaments. They are mostly fabricated by wet synthetic methods that are not universal to various metals and not free from impurities due to solution-based etching processes. Here, we demonstrate that the plasma treatment of metal nanoparticles formed by physical vapor deposition is a general route to form such films with many metals including the non-noble ones. The resultant nanoporous metallic films are free of impurities and possess highly curved ligaments and nanopores. The metal films are ultrathin, yet remarkably robust and very well connected, and thus are highly promising for various applications such as transparent conducting electrodes.

In Situ X-ray Diffraction and Spectro-Microscopic Study of ALD Protected Copper Films.

In many applications of copper in industry and research, copper migration and degradation of metallic copper to its oxides is a common problem. There are numerous ways to overcome this degradation with varying success. Atomic layer deposition (ALD) based encapsulation and passivation of the metallic copper recently emerged as a serious route to success owing to the conformality and density of the ALD films. So far, the majority of the studies have been focused on corrosion protection of copper in a variety of chemical environments, mostly at ambient temperature. An investigation of the stability of the ALD film stacks and copper's interaction with them at elevated temperatures has been lacking. Here, we study the mitigation of copper oxidation and migration in 50 nm thick Al2O3/TiO2 and Al2O3/SiO2 bilayer ALD stacks. First, the corrosion dynamics were investigated via in situ X-ray diffraction (XRD) at 350 °C under atmospheric conditions, and second, the interaction of copper with the passivation layers have been examined post factum using detailed spectro-microscopic investigations. According to the XRD results, both ALD films exhibited excellent oxidation protection. In contrast, bare Cu immediately started to oxidize at 350 °C and transformed entirely to its known oxide phases in 4 h. Spectro-microscopic studies revealed that there are structural and chemical changes on the top surface and within the film stacks. The TiO2 layer was crystallized during annealing, while the SiO2 layer stayed in the amorphous phase, which was analyzed by grazing incidence XRD and transmission electron microscopy. According to scanning electron microscopy and X-ray photoelectron spectroscopy analysis, copper was detected on the surface with a higher amount in Al2O3/TiO2 than Al2O3/SiO2, 5.2 at.% and 0.7 at.%, respectively. Based on the surface and cross-sectional analysis, copper migration was observed on both layers, albeit more substantially in Al2O3/TiO2. In the case of Al2O3/SiO2, the bulk of the copper was captured at the interface of the two oxides.

3D Nanofabrication of High-Resolution Multilayer Fresnel Zone Plates.

Focusing X-rays to single nanometer dimensions is impeded by the lack of high-quality, high-resolution optics. Challenges in fabricating high aspect ratio 3D nanostructures limit the quality and the resolution. Multilayer zone plates target this challenge by offering virtually unlimited and freely selectable aspect ratios. Here, a full-ceramic zone plate is fabricated via atomic layer deposition of multilayers over optical quality glass fibers and subsequent focused ion beam slicing. The quality of the multilayers is confirmed up to an aspect ratio of 500 with zones as thin as 25 nm. Focusing performance of the fabricated zone plate is tested toward the high-energy limit of a soft X-ray scanning transmission microscope, achieving a 15 nm half-pitch cut-off resolution. Sources of adverse influences are identified, and effective routes for improving the zone plate performance are elaborated, paving a clear path toward using multilayer zone plates in high-energy X-ray microscopy. Finally, a new fabrication concept is introduced for making zone plates with precisely tilted zones, targeting even higher resolutions.

Correcting the linear and nonlinear distortions for atomically resolved STEM spectrum and diffraction imaging.

Specimen and stage drift as well as scan distortions can lead to a mismatch between true and desired electron probe positions in scanning transmission electron microscopy (STEM) which can result in both linear and nonlinear distortions in the subsequent experimental images. This problem is intensified in STEM spectrum and diffraction imaging techniques owing to the extended dwell times (pixel exposure time) as compared to conventional STEM imaging. As a consequence, these image distortions become more severe in STEM spectrum/diffraction imaging. This becomes visible as expansion, compression and/or shearing of the crystal lattice, and can even prohibit atomic resolution and thus limits the interpretability of the results. Here, we report a software tool for post-correcting the linear and nonlinear image distortions of atomically resolved 3D spectrum imaging as well as 4D diffraction imaging. This tool improves the interpretability of distorted STEM spectrum/diffraction imaging data.

Towards atomically resolved EELS elemental and fine structure mapping via multi-frame and energy-offset correction spectroscopy.

Electron energy-loss spectroscopy and energy-dispersive X-ray spectroscopy are two of the most common means for chemical analysis in the scanning transmission electron microscope. The marked progress of the instrumentation hardware has made chemical analysis at atomic resolution readily possible nowadays. However, the acquisition and interpretation of atomically resolved spectra can still be problematic due to image distortions and poor signal-to-noise ratio of the spectra, especially for investigation of energy-loss near-edge fine structures. By combining multi-frame spectrum imaging and automatic energy-offset correction, we developed a spectrum imaging technique implemented into customized DigitalMicrograph scripts for suppressing image distortions and improving the signal-to-noise ratio. With practical examples, i.e. SrTiO3 bulk material and Sr-doped La2CuO4 superlattices, we demonstrate the improvement of elemental mapping and the EELS spectrum quality, which opens up new possibilities for atomically resolved EELS fine structure mapping.

Reversed Janus Micro/Nanomotors with Internal Chemical Engine.

Self-motile Janus colloids are important for enabling a wide variety of microtechnology applications as well as for improving our understanding of the mechanisms of motion of artificial micro- and nanoswimmers. We present here micro/nanomotors which possess a reversed Janus structure of an internal catalytic "chemical engine". The catalytic material (here platinum (Pt)) is embedded within the interior of the mesoporous silica (mSiO2)-based hollow particles and triggers the decomposition of H2O2 when suspended in an aqueous peroxide (H2O2) solution. The pores/gaps at the noncatalytic (Pt) hemisphere allow the exchange of chemical species in solution between the exterior and the interior of the particle. By varying the diameter of the particles, we observed size-dependent motile behavior in the form of enhanced diffusion for 500 nm particles, and self-phoretic motion, toward the nonmetallic part, for 1.5 and 3 µm ones. The direction of motion was rationalized by a theoretical model based on self-phoresis. For the 3 µm particles, a change in the morphology of the porous part is observed, which is accompanied by a change in the mechanism of propulsion via bubble nucleation and ejection as well as a change in the direction of motion.

A Lamellar Hybrid Assembled from Metal Disulfide Nanowall Arrays Anchored on a Carbon Layer: In Situ Hybridization and Improved Sodium Storage.

A lamellar hybrid assembled from metal disulfide (MoS2 , WS2 ) nanowall arrays anchored on nitrogen-doped carbon layers is developed via an in situ hybridization strategy through a synergistic pyrolysis reaction of thiourea and oxometalates. Such a hybrid provides adequate electrical and chemical coupling between the active materials and the carbon substrate, thus realizing a high-efficiency electron-conduction/ion-transportation system and exhibiting excellent sodium-storage properties.

Motion Control of Urea-Powered Biocompatible Hollow Microcapsules.

The quest for biocompatible microswimmers powered by compatible fuel and with full motion control over their self-propulsion is a long-standing challenge in the field of active matter and microrobotics. Here, we present an active hybrid microcapsule motor based on Janus hollow mesoporous silica microparticles powered by the biocatalytic decomposition of urea at physiological concentrations. The directional self-propelled motion lasts longer than 10 min with an average velocity of up to 5 body lengths per second. Additionally, we control the velocity of the micromotor by chemically inhibiting and reactivating the enzymatic activity of urease. The incorporation of magnetic material within the Janus structure provides remote magnetic control on the movement direction. Furthermore, the mesoporous/hollow structure can load both small molecules and larger particles up to hundreds of nanometers, making the hybrid micromotor an active and controllable drug delivery microsystem.

Enzyme-Powered Hollow Mesoporous Janus Nanomotors.

The development of synthetic nanomotors for technological applications in particular for life science and nanomedicine is a key focus of current basic research. However, it has been challenging to make active nanosystems based on biocompatible materials consuming nontoxic fuels for providing self-propulsion. Here, we fabricate self-propelled Janus nanomotors based on hollow mesoporous silica nanoparticles (HMSNPs), which are powered by biocatalytic reactions of three different enzymes: catalase, urease, and glucose oxidase (GOx). The active motion is characterized by a mean-square displacement (MSD) analysis of optical video recordings and confirmed by dynamic light scattering (DLS) measurements. We found that the apparent diffusion coefficient was enhanced by up to 83%. In addition, using optical tweezers, we directly measured a holding force of 64 ± 16 fN, which was necessary to counteract the effective self-propulsion force generated by a single nanomotor. The successful demonstration of biocompatible enzyme-powered active nanomotors using biologically benign fuels has a great potential for future biomedical applications.

Catalytic mesoporous Janus nanomotors for active cargo delivery.

We report on the synergy between catalytic propulsion and mesoporous silica nanoparticles (MSNPs) for the design of Janus nanomotors as active cargo delivery systems with sizes <100 nm (40, 65, and 90 nm). The Janus asymmetry of the nanomotors is given by electron beam (e-beam) deposition of a very thin platinum (2 nm) layer on MSNPs. The chemically powered Janus nanomotors present active diffusion at low H2O2 fuel concentration (i.e., <3 wt %). Their apparent diffusion coefficient is enhanced up to 100% compared to their Brownian motion. Due to their mesoporous architecture and small dimensions, they can load cargo molecules in large quantity and serve as active nanocarriers for directed cargo delivery on a chip.

High-performance ZnO nanowire transistors with aluminum top-gate electrodes and naturally formed hybrid self-assembled monolayer/AlO(x) gate dielectric.

A method for the formation of a low-temperature hybrid gate dielectric for high-performance, top-gate ZnO nanowire transistors is reported. The hybrid gate dielectric consists of a self-assembled monolayer (SAM) and an aluminum oxide layer. The thin aluminum oxide layer forms naturally and spontaneously when the aluminum gate electrode is deposited by thermal evaporation onto the SAM-covered ZnO nanowire, and its formation is facilitated by the poor surface wetting of the aluminum on the hydrophobic SAM. The hybrid gate dielectric shows excellent electrical insulation and can sustain voltages up to 6 V. ZnO nanowire transistors utilizing the hybrid gate dielectric feature a large transconductance of 50 µS and large on-state currents of up to 200 µA at gate-source voltages of 3 V. The large on-state current is sufficient to drive organic light-emitting diodes with an active area of 6.7 mm(2) to a brightness of 445 cd/m(2). Inverters based on ZnO nanowire transistors and thin-film carbon load resistors operate with frequencies up to 30 MHz.

Self-propelling nanomotors in the presence of strong Brownian forces.

Motility in living systems is due to an array of complex molecular nanomotors that are essential for the function and survival of cells. These protein nanomotors operate not only despite of but also because of stochastic forces. Artificial means of realizing motility rely on local concentration or temperature gradients that are established across a particle, resulting in slip velocities at the particle surface and thus motion of the particle relative to the fluid. However, it remains unclear if these artificial motors can function at the smallest of scales, where Brownian motion dominates and no actively propelled living organisms can be found. Recently, the first reports have appeared suggesting that the swimming mechanisms of artificial structures may also apply to enzymes that are catalytically active. Here we report a scheme to realize artificial Janus nanoparticles (JNPs) with an overall size that is comparable to that of some enzymes ∼30 nm. Our JNPs can catalyze the decomposition of hydrogen peroxide to water and oxygen and thus actively move by self-electrophoresis. Geometric anisotropy of the Pt-Au Janus nanoparticles permits the simultaneous observation of their translational and rotational motion by dynamic light scattering. While their dynamics is strongly influenced by Brownian rotation, the artificial Janus nanomotors show bursts of linear ballistic motion resulting in enhanced diffusion.

Microstructure, chemistry, and electronic structure of natural hybrid composites in abalone shell.

The crystal structure and chemical composition at the inorganic/inorganic and inorganic/organic interfaces in abalone shell (genus Haliotis) were investigated using advanced analytical transmission electron microscopy (TEM) methods. Electron energy-loss near-edge structures (ELNES) of Ca-M2,3, C-K, Ca-L2,3, O-K and low-loss EEL spectra acquired from aragonite and calcite are distinctly different. When comparing biogenic with inorganic material for aragonite, only minor differences in C-K fine structures could be detected. The crystal structure of the mineral bridges was confirmed by ELNES experiments. ELNES and energy-filtered TEM (EFTEM) experiments of regular and self-healed interfaces between nacreous aragonite and prismatic calcite reveal relatively rough transitions. In this work, the importance of TEM specimen preparation and specimen damage on structural features is discussed.

Electroless synthesis of 3 nm wide alloy nanowires inside Tobacco mosaic virus.

We show that 3 nm wide cobalt-iron alloy nanowires can be synthesized by simple wet chemical electroless deposition inside tubular Tobacco mosaic virus particles. The method is based on adsorption of Pd(II) ions, formation of a Pd catalyst, and autocatalytic deposition of the alloy from dissolved metal salts, reduced by a borane compound. Extensive energy-filtering TEM investigations at the nanoscale revealed that the synthesized wires are alloys of Co, Fe, and Ni. We confirmed by high-resolution TEM that our alloy nanowires are at least partially crystalline, which is compatible with typical Co-rich alloys. Ni traces bestow higher stability, presumably against corrosion, as also known from bulk CoFe. Alloy nanowires, as small as the ones presented here, might be used for a variety of applications including high density data storage, imaging, sensing, and even drug delivery.