Blue phosphorene, a two-dimensional, hexagonal-structured, semiconducting phosphorus, has gained attention as it is considered easier to synthesize on metal surfaces than its allotrope, black phosphorene. Recent studies report different structures of phosphorene, for example, on Cu(111), but the underlying mechanisms of their formation are not known. Here, using a combination of in situ ultrahigh vacuum low-energy electron microscopy and in vacuo scanning tunneling microscopy, we determine the time evolution of the surface structure and morphology during the deposition of phosphorus on single-crystalline Cu(111). We find that during the early stages of deposition phosphorus intermixes with Cu, resulting in copper phosphide structures. With the increasing surface concentration of phosphorus, the phosphide phase disappears, and a blue phosphorene layer forms, followed by the self-assembly of highly ordered phosphorus clusters that eventually grow into multilayer islands. We attribute the unexpected transformation of stable phosphide to a phosphorene layer to the presence of a large concentration of P2 dimers on the surface. Our results constitute direct evidence for a growth mode leading to a flat phosphorene layer via an intermediary phase, which could underpin the growth of other 2D materials on strongly interacting substrates.
- Klíčová slova
- 2D materials, copper phosphide, growth mode, phase transformation, phosphorene,
- Publikační typ
- časopisecké články MeSH
To satisfy the needs of the current technological world that demands high performance and efficiency, a deep understanding of the whole fabrication process of electronic devices based on low-dimensional materials is necessary for rapid prototyping of devices. The fabrication processes of such nanoscale devices often include exposure to an electron beam. A field effect transistor (FET) is a core device in current computation technology, and FET configuration is also commonly used for extraction of electronic properties of low-dimensional materials. In this experimental study, we analyze the effect of electron beam exposure on electrical properties of individual WS2 nanotubes in the FET configuration by in-operando transport measurements inside a scanning electron microscope. Upon exposure to the electron beam, we observed a significant change in the resistance of individual substrate-supported nanotubes (by a factor of 2 to 14) that was generally irreversible. The resistance of each nanotube did not return to its original state even after keeping it under ambient conditions for hours to days. Furthermore, we employed Kelvin probe force microscopy to monitor surface potential and identified that substrate charging is the primary cause of changes in nanotubes' resistance. Hence, extra care should be taken when analyzing nanostructures in contact with insulating oxides that are subject to electron exposure during or after fabrication.
- Publikační typ
- časopisecké články MeSH
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.
- Klíčová slova
- WS2 nanotube, electron microscopy, ex situ, in situ, reaction mechanism, sulfidation,
- Publikační typ
- časopisecké články MeSH
The properties of two-dimensional (2D) van der Waals materials can be tuned through nanostructuring or controlled layer stacking, where interlayer hybridization induces exotic electronic states and transport phenomena. Here we describe a viable approach and underlying mechanism for the assisted self-assembly of twisted layer graphene. The process, which can be implemented in standard chemical vapour deposition growth, is best described by analogy to origami and kirigami with paper. It involves the controlled induction of wrinkle formation in single-layer graphene with subsequent wrinkle folding, tearing and re-growth. Inherent to the process is the formation of intertwined graphene spirals and conversion of the chiral angle of 1D wrinkles into a 2D twist angle of a 3D superlattice. The approach can be extended to other foldable 2D materials and facilitates the production of miniaturized electronic components, including capacitors, resistors, inductors and superconductors.
- Publikační typ
- časopisecké články MeSH
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.
- Klíčová slova
- buckypaper, felt, growth, sulfidation, tungsten disulfide nanotubes, tungsten suboxide nanowhiskers, wet-laying,
- Publikační typ
- časopisecké články MeSH
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).
- Klíčová slova
- chirality, nanoparticle assembly, nanotubes, step edge, tungsten disulfide,
- Publikační typ
- časopisecké články MeSH
We report on the optical properties of a CsPbBr3 polycrystalline thin film on a single grain level. A sample composed of isolated nanocrystals (NCs) mimicking the properties of the polycrystalline thin film grains that can be individually probed by photoluminescence spectroscopy was prepared. These NCs were analyzed using correlative microscopy allowing the examination of structural, chemical, and optical properties from identical sites. Our results show that the stoichiometry of the CsPbBr3 NCs is uniform and independent of the NCs' morphology. The photoluminescence (PL) peak emission wavelength is slightly dependent on the dimensions of NCs, with a blue shift up to 9 nm for the smallest analyzed NCs. The magnitude of the blueshift is smaller than the emission line width, thus detectable only by high-resolution PL mapping. By comparing the emission energies obtained from the experiment and a rigorous effective mass model, we can fully attribute the observed variations to the size-dependent quantum confinement effect.
- Publikační typ
- časopisecké články MeSH
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.
- Klíčová slova
- ZnSe, guided growth, in situ growth, planar nanowires, real-time monitoring,
- Publikační typ
- časopisecké články MeSH
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.
- Publikační typ
- časopisecké články MeSH
Many of graphene's remarkable properties arise from its linear dispersion of the electronic states, forming a Dirac cone at the K points of the Brillouin zone. Silicene, the 2D allotrope of silicon, is also predicted to show a similar electronic band structure, with the addition of a tunable bandgap, induced by spin-orbit coupling. Because of these outstanding electronic properties, silicene is considered as a promising building block for next-generation electronic devices. Recently, it has been shown that silicene grown on Au(111) still possesses a Dirac cone, despite the interaction with the substrate. Here, to fully characterize the structure of this 2D material, we investigate the vibrational spectrum of a monolayer silicene grown on Au(111) by polarized Raman spectroscopy. To enable a detailed ex situ investigation, we passivated the silicene on Au(111) by encapsulating it under few layers hBN or graphene flakes. The observed spectrum is characterized by vibrational modes that are strongly red-shifted with respect to the ones expected for freestanding silicene. By comparing low-energy electron diffraction (LEED) patterns and Raman results with first-principles calculations, we show that the vibrational modes indicate a highly (>7%) biaxially strained silicene phase.
- Publikační typ
- časopisecké články MeSH
