Mechanism of WS2 Nanotube Formation Revealed by in Situ/ex Situ Imaging.

Multiwall WS2 nanotubes have been synthesized from W18O49 nanowhiskers in substantial amounts for more than a decade. The established growth model is based on the "surface-inward" mechanism, whereby the high-temperature reaction with H2S starts on the nanowhisker surface, and the oxide-to-sulfide conversion progresses inward until hollow-core multiwall WS2 nanotubes are obtained. In the present work, an upgraded in situ SEM µReactor with H2 and H2S sources has been conceived to study the growth mechanism in detail. A hitherto undescribed growth mechanism, named "receding oxide core", which complements the "surface-inward" model, is observed and kinetically evaluated. Initially, the nanowhisker is passivated by several WS2 layers via the surface-inward reaction. At this point, the diffusion of H2S through the already existing outer layers becomes exceedingly sluggish, and the surface-inward reaction is slowed down appreciably. Subsequently, the tungsten suboxide core is anisotropically volatilized within the core close to its tips. The oxide vapors within the core lead to its partial out-diffusion, partially forming a cavity that expands with reaction time. Additionally, the oxide vapors react with the internalized H2S gas, forming fresh WS2 layers in the cavity of the nascent nanotube. The rate of the receding oxide core mode increases with temperatures above 900 °C. The growth of nanotubes in the atmospheric pressure flow reactor is carried out as well, showing that the proposed growth model (receding oxide core) is also relevant under regular reaction parameters. The current study comprehensively explains the WS2 nanotube growth mechanism, combining the known model with contemporary insight.

W18O49 Nanowhiskers Decorating SiO2 Nanofibers: Lessons from In Situ SEM/TEM Growth to Large Scale Synthesis and Fundamental Structural Understanding.

Tungsten suboxide W18O49 nanowhiskers are a material of great interest due to their potential high-end applications in electronics, near-infrared light shielding, catalysis, and gas sensing. The present study introduces three main approaches for the fundamental understanding of W18O49 nanowhisker growth and structure. First, W18O49 nanowhiskers were grown from γ-WO3/a-SiO2 nanofibers in situ in a scanning electron microscope (SEM) utilizing a specially designed microreactor (µReactor). It was found that irradiation by the electron beam slows the growth kinetics of the W18O49 nanowhisker, markedly. Following this, an in situ TEM study led to some new fundamental understanding of the growth mode of the crystal shear planes in the W18O49 nanowhisker and the formation of a domain (bundle) structure. High-resolution scanning transmission electron microscopy analysis of a cross-sectioned W18O49 nanowhisker revealed the well-documented pentagonal Magnéli columns and hexagonal channel characteristics for this phase. Furthermore, a highly crystalline and oriented domain structure and previously unreported mixed structural arrangement of tungsten oxide polyhedrons were analyzed. The tungsten oxide phases found in the cross section of the W18O49 nanowhisker were analyzed by nanodiffraction and electron energy loss spectroscopy (EELS), which were discussed and compared in light of theoretical calculations based on the density functional theory method. Finally, the knowledge gained from the in situ SEM and TEM experiments was valorized in developing a multigram synthesis of W18O49/a-SiO2 urchin-like nanofibers in a flow reactor.

Submillimeter-Long WS2 Nanotubes: The Pathway to Inorganic Buckypaper.

WS2 nanotubes present many new technologies under development, including reinforced biocompatible polymers, membranes, photovoltaic-based memories, ferroelectric devices, etc. These technologies depend on the aspect ratio (length/diameter) of the nanotubes, which was limited to 100 or so. A new synthetic technique is presented, resulting in WS2 nanotubes a few hundred micrometers long and diameters below 50 nm (aspect ratios of 2000-5000) in high yields. Preliminary investigation into the mechanistic aspects of the two-step synthesis reveals that W5O14 nanowhisker intermediates are formed in the first step of the reaction instead of the ubiquitous W18O49 nanowhiskers used in the previous syntheses. The electrical and photoluminescence properties of the long nanotubes were studied. WS2 nanotube-based paper-like material was prepared via a wet-laying process, which could not be realized with the 10 µm long WS2 nanotubes. Ultrafiltration of gold nanoparticles using the nanotube-paper membrane was demonstrated.

Superflux of an organic adlayer towards its local reactive immobilization.

On-surface mass transport is the key process determining the kinetics and dynamics of on-surface reactions, including the formation of nanostructures, catalysis, or surface cleaning. Volatile organic compounds (VOC) localized on a majority of surfaces dramatically change their properties and act as reactants in many surface reactions. However, the fundamental question "How far and how fast can the molecules travel on the surface to react?" remains open. Here we show that isoprene, the natural VOC, can travel ~1 µm s-1, i.e., centimeters per day, quickly filling low-concentration areas if they become locally depleted. We show that VOC have high surface adhesion on ceramic surfaces and simultaneously high mobility providing a steady flow of resource material for focused electron beam synthesis, which is applicable also on rough or porous surfaces. Our work established the mass transport of reactants on solid surfaces and explored a route for nanofabrication using the natural VOC layer.

Chiral Nanoparticle Chains on Inorganic Nanotube Templates.

Fabrication of chiral assemblies of plasmonic nanoparticles is a highly attractive and challenging task, with promising applications in light emission, detection, and sensing. So far, primarily organic chiral templates have been used for chirality inscription. Despite recent progress in using chiral ionic liquids in synthesis, the use of organic templates significantly limits the variety of nanoparticle preparation techniques. Here, we demonstrate the utilization of seemingly achiral inorganic nanotubes as templates for the chiral assembly of nanoparticles. We show that both metallic and dielectric nanoparticles can be attached to scroll-like chiral edges propagating on the surfaces of WS2 nanotubes. Such assembly can be performed at temperatures as high as 550 °C. This large temperature range significantly widens the portfolio of nanoparticle fabrication techniques, allowing us to demonstrate a variety of chiral nanoparticle assemblies, ranging from metals (Au, Ga), semiconductors (Ge), and compound semiconductors (GaAs) to oxides (WO3).

Real-Time Study of Surface-Guided Nanowire Growth by In Situ Scanning Electron Microscopy.

Surface-guided growth has proven to be an efficient approach for the production of nanowire arrays with controlled orientations and their large-scale integration into electronic and optoelectronic devices. Much has been learned about the different mechanisms of guided nanowire growth by epitaxy, graphoepitaxy, and artificial epitaxy. A model describing the kinetics of surface-guided nanowire growth has been recently reported. Yet, many aspects of the surface-guided growth process remain unclear due to a lack of its observation in real time. Here we observe how surface-guided nanowires grow in real time by in situ scanning electron microscopy (SEM). Movies of ZnSe surface-guided nanowires growing on periodically faceted substrates of annealed M-plane sapphire clearly show how the nanowires elongate along the substrate nanogrooves while pushing the catalytic Au nanodroplet forward at the tip of the nanowire. The movies reveal the timing between competing processes, such as planar vs nonplanar growth, catalyst-selective vapor-liquid-solid elongation vs nonselective vapor-solid thickening, and the effect of topographic discontinuities of the substrate on the growth direction, leading to the formation of kinks and loops. Contrary to some observations for nonplanar nanowire growth, planar nanowires are shown to elongate at a constant rate and not by jumps. A decrease in precursor concentration as it is consumed after long reaction time causes the nanowires to shrink back instead of growing, thus indicating that the process is reversible and takes place near equilibrium. This real-time study of surface-guided growth, enabled by in situ SEM, enables a better understanding of the formation of nanostructures on surfaces.

Nanotubes from the Misfit Layered Compound (SmS)1.19TaS2: Atomic Structure, Charge Transfer, and Electrical Properties.

Misfit layered compounds (MLCs) MX-TX2, where M, T = metal atoms and X = S, Se, or Te, and their nanotubes are of significant interest due to their rich chemistry and unique quasi-1D structure. In particular, LnX-TX2 (Ln = rare-earth atom) constitute a relatively large family of MLCs, from which nanotubes have been synthesized. The properties of MLCs can be tuned by the chemical and structural interplay between LnX and TX2 sublayers and alloying of each of the Ln, T, and X elements. In order to engineer them to gain desirable performance, a detailed understanding of their complex structure is indispensable. MLC nanotubes are a relative newcomer and offer new opportunities. In particular, like WS2 nanotubes before, the confinement of the free carriers in these quasi-1D nanostructures and their chiral nature offer intriguing physical behavior. High-resolution transmission electron microscopy in conjunction with a focused ion beam are engaged to study SmS-TaS2 nanotubes and their cross-sections at the atomic scale. The atomic resolution images distinctly reveal that Ta is in trigonal prismatic coordination with S atoms in a hexagonal structure. Furthermore, the position of the sulfur atoms in both the SmS and the TaS2 sublattices is revealed. X-ray photoelectron spectroscopy, electron energy loss spectroscopy, and X-ray absorption spectroscopy are carried out. These analyses conclude that charge transfer from the Sm to the Ta atoms leads to filling of the Ta 5d z 2 level, which is confirmed by density functional theory (DFT) calculations. Transport measurements show that the nanotubes are semimetallic with resistivities in the range of 10-4 Ω·cm at room temperature, and magnetic susceptibility measurements show a superconducting transition at 4 K.

Coherent light emission in cathodoluminescence when using GaAs in a scanning (transmission) electron microscope.

For most materials science oriented applications incoherent cathodoluminescence (CL) is of main interest, for which the recombination of electron-hole pairs yields the emission of light. However, the incoherent signal is superimposed by coherently excited photons, similar to the situation for X-rays in Energy-Dispersive X-ray spectra (EDX). In EDX two very different processes superimpose in each spectrum: Bremsstrahlung and characteristic X-ray radiation. Both processes yield X-rays, however, their origin is substantially different. Therefore, in the present CL study we focus on the coherent emission of light, in particular Cerenkov radiation. We use a 200µm thick GaAs sample, not electron transparent and therefore not acting as a light guide, and investigate the radiation emitted from the top surface of the sample generated by back-scattered electrons on their way out of the specimen. The CL spectra revealed a pronounced peak corresponding to the expected interband transition. This peak was at 892 nm at room temperature and shifted to 845 nm at 80 K. The coherent light emission significantly modifies the shape of CL spectra at elevated beam energies. For the first time, by the systematic variation of current and energy of primary electrons we could distinguish the coherent and incoherent light superimposed in CL spectra. These findings are essential for the correct interpretation of CL spectra in STEM. The Cerenkov intensity as well as the total intensity in a spectrum scales linearly with the beam current. Additionally, we investigate the influence of asymmetric mirrors on the spectral shapes, collecting roughly only half of the whole solid angle. Different emission behaviour of different physical causes thus lead to changes in the overall spectral shape.

Using Cˇerenkov radiation for measuring the refractive index in thick samples by interferometric cathodoluminescence.

Cathodoluminescence (CL) has evolved into a standard analytical technique in (scanning) transmission electron microscopy. CL utilizes light excited due to the interactions between the electron-beam and the sample. In the present study we focus on Cˇerenkov radiation. We make use of the fact that the electron transparent specimen acts as a Fabry-Pérot interferometer for coherently emitted radiation. From the wavelength dependent interference pattern of thickness dependent measurements we calculate the refractive index of the studied material. We describe the limits of this approach and compare it with the determination of the refractive index by using valence electron energy loss spectrometry (VEELS).

Electroforming in Metal-Oxide Memristive Synapses.

Memristors have shown an extraordinary potential to emulate the plastic and dynamic electrical behaviors of biological synapses and have been already used to construct neuromorphic systems with in-memory computing and unsupervised learning capabilities; moreover, the small size and simple fabrication process of memristors make them ideal candidates for ultradense configurations. So far, the properties of memristive electronic synapses (i.e., potentiation/depression, relaxation, linearity) have been extensively analyzed by several groups. However, the dynamics of electroforming in memristive devices, which defines the position, size, shape, and chemical composition of the conductive nanofilaments across the device, has not been analyzed in depth. By applying ramped voltage stress (RVS), constant voltage stress (CVS), and pulsed voltage stress (PVS), we found that electroforming is highly affected by the biasing methods applied. We also found that the technique used to deposit the oxide, the chemical composition of the adjacent metal electrodes, and the polarity of the electrical stimuli applied have important effects on the dynamics of the electroforming process and in subsequent post-electroforming bipolar resistive switching. This work should be of interest to designers of memristive neuromorphic systems and could open the door for the implementation of new bioinspired functionalities into memristive neuromorphic systems.

Fundamentals of cathodoluminescence in a STEM: The impact of sample geometry and electron beam energy on light emission of semiconductors.

Cathodoluminescence has attracted interest in scanning transmission electron microscopy since the advent of commercial available detection systems with high efficiency, like the Gatan Vulcan or the Attolight Mönch system. In this work we discuss light emission caused by high-energy electron beams when traversing a semiconducting specimen. We find that it is impossible to directly interpret the spectrum of the emitted light to the inter-band transitions excited by the electron beam, because the Cerenkov effect and the related light guiding modes as well as transition radiation is altering the spectra. Total inner reflection and subsequent interference effects are changing the spectral shape dependent on the sample shape and geometry, sample thickness, and beam energy, respectively. A detailed study on these parameters is given using silicon and GaAs as test materials.

Comparative study of plasmonic antennas fabricated by electron beam and focused ion beam lithography.

We present a comparative study of plasmonic antennas fabricated by electron beam lithography and direct focused ion beam milling. We have investigated optical and structural properties and chemical composition of gold disc-shaped plasmonic antennas on a silicon nitride membrane fabricated by both methods to identify their advantages and disadvantages. Plasmonic antennas were characterized using transmission electron microscopy including electron energy loss spectroscopy and energy dispersive X-ray spectroscopy, and atomic force microscopy. We have found stronger plasmonic response with better field confinement in the antennas fabricated by electron beam lithography, which is attributed to their better structural quality, homogeneous thickness, and only moderate contamination mostly of organic nature. Plasmonic antennas fabricated by focused ion beam lithography feature weaker plasmonic response, lower structural quality with pronounced thickness fluctuations, and strong contamination, both organic and inorganic, including implanted ions from the focused beam. While both techniques are suitable for the fabrication of plasmonic antennas, electron beam lithography shall be prioritized over focused ion beam lithography due to better quality and performance of its products.