In Situ Heating TEM Study of Onion-like WS2 and MoS2 Nanostructures Obtained via MOCVD

We report on the in situ heating transmission electron microscopy (TEM) study of WS2 and MoS2 nanoparticles obtained from metal–organic chemical vapor deposition (MOCVD). The general behavior of MoS2 and WS2 is similar: Round, amorphous particles in the pristine sample transform to hollow, onion-like particles upon annealing. A second type of particle with straight layers exhibits only minor changes. A significant difference between both compounds could be demonstrated in their crystallization behavior. The results of the in situ heating experiments are compared to those obtained from an ex situ annealing process under Ar.

Formation and transformation of carbon nanoparticles under electron irradiation.

This article reviews the phenomena occurring during irradiation of graphitic nanoparticles with high–energy electrons. A brief introduction to the physics of the interaction between energetic electrons and solids is given with particular emphasis on graphitic materials. Irradiation effects are discussed, starting from microscopic mechanisms that lead to structural alterations of the graphite lattice. It is shown how random displacements of the atoms and their subsequent rearrangements eventually lead to topological changes of the nanoparticles. Examples are the formation of carbon onions, morphological changes of carbon nanotubes, or the coalescence of fullerenes or nanotubes under electron…

The Mobility of Carbon Atoms in Graphitic Nanoparticles Studied by the Relaxation of Strain in Carbon Onions

In situ nucleation of carbon nanotubes by the injection of carbon atoms into metal particles.

The synthesis of carbon nanotubes (CNTs) of desired chiralities and diameters is one of the most important challenges in nanotube science and achieving such selectivity may require a detailed understanding of their growth mechanism. We report the formation of CNTs in an entirely condensed phase process that allows us, for the first time, to monitor the nucleation of a nanotube on the spherical surface of a metal particle. When multiwalled CNTs containing metal particle cores are irradiated with an electron beam, carbon from graphitic shells surrounding the metal particles is ingested into the body of the particle and subsequently emerges as single-walled nanotubes (SWNTs) or multiwalled nan…

The Engineering of Hot Carbon Nanotubes with a Focused Electron Beam

Single-wall and multiwall carbon nanotubes at high temperature are irradiated with the focused electron beam in an electron microscope. Nanotubes can be tailored with monolayer precision, and new morphologies of nanotubes are created. Atoms from layers of multiwall tubes can be removed and the tubes can be bent by a predefined angle. Bundles of single-wall tubes are transformed locally to multiwall tubes with coherent transition between the two modifications.

Electron Irradiation Effects in Carbon Nanostructures: Surface Reconstruction, Extreme Compression, Nanotube Growth and Morphology Manipulation

It will be demonstrated, that irradiation exposure at elevated temperatures, can be used as an effective tool to covalently weld SWNTs in order to create molecular junctions of various geometries [1–3]. We have fabricated Y, X and T-like junctions that are stable [2]. Tight binding molecular dynamics calculations demonstrate that vacancies, formed under the electron beam, trigger the formation of molecular junctions involving seven or eight membered carbon rings. We envisage that these results will pave the way towards controlled fabrication of novel nanotube-based molecular circuits, nanotube fabrics and network architectures. In this context, novel super architectures, using carbon nanotu…

Microstructural evolution of wear-resistant FeCrB and FeCrNiCoB coating alloys during high-energy mechanical attrition

Mechanical milling/attrition provides a convenient scope of simulating the microstructural changes encountered by wear-resistant coating alloys subjected to deformation under high frequency and high-intensity impact loading or accelerated wear condition. In the present study, the microstructural evolution of two commercial coating materials, FeCrB (Armacor M) and FeCrNiCoB (Armacor C), in the course of low- and high-intensity mechanical attrition, was monitored by X-ray diffraction and high-resolution transmission electron microscopy. While low-intensity milling leads to marginal grain refinement but no change in phase-aggregate in FeCrB, similar mechanical attrition causes boride precipita…

Ion irradiation of carbon nanotubes encapsulating cobalt crystals

Abstract The response of multi-walled carbon nanotubes encapsulating Co nanorods to ion irradiation was studied. The irradiation experiments with medium ion energies (40–500 keV) were carried out at high temperatures and combined with transmission electron microscopy and Raman characterization of the irradiated samples. Contrary to electron irradiation and high-energy (100 MeV) ion irradiation, we did not see accumulation of pressure inside irradiated nanotubes. We found that nanotubes with Co nanorods inside were transformed to amorphous carbon rods encapsulating Co clusters with typical diameters of 3–6 nm. As Co is magnetic, such one-dimensional composite systems could be used for variou…

Carbon nanotubes under electron irradiation: Stability of the tubes and their action as pipes for atom transport

The production and migration of carbon interstitials in carbon nanotubes under electron irradiation is studied experimentally and theoretically. It is shown that the threshold for displacing carbon atoms and the defect production rate strongly depend on the diameter of the nanotubes. Multiwalled nanotubes shrink by a loss of atoms and by diffusion of interstitials through the inner hollow in the axial direction. Thus, experimental evidence is given that nanotubes can act as nanoscale pipes for the transport of atoms.

Carbon nanotubes as high-pressure cylinders and nanoextruders.

Closed-shell carbon nanostructures, such as carbon onions, have been shown to act as self-contracting high-pressure cells under electron irradiation. We report that controlled irradiation of multiwalled carbon nanotubes can cause large pressure buildup within the nanotube cores that can plastically deform, extrude, and break solid materials that are encapsulated inside the core. We further showed by atomistic simulations that the internal pressure inside nanotubes can reach values higher than 40 gigapascals. Nanotubes can thus be used as robust nanoscale jigs for extruding and deforming hard nanomaterials and for modifying their properties, as well as templates for the study of individual n…

Synthesis of SWCNT Rings Made by Two Y Junctions and Possible Applications in Electron Interferometry

One- and Two-Dimensional Diffusion of Metal Atoms in Graphene

In the present work, individual Au or Pt atoms in layersconsisting of one or twographene planes have been monitoredin real time at high temperature by high-resolution TEM. Weobtain information about the location of metal atoms ingrapheneandthediffusionmechanisms.Activationenergiesfordiffusion are obtained in a temperature range close to thetemperature of the technically important metal-assisted CVDprocess.Thematerialwassynthesizedinanarcdischarge

Electronic and Magnetic Properties of Ligand-Free FePt Nanoparticles

Ligand-free FePt nanoparticles are prepared in densely packed arrays (see Figure) under ultrahigh vacuum conditions, in which oxygen and hydrogen plasmas are used to remove the organic shells that are present after particle synthesis. The electronic structure and magnetic properties of the “bare”, face-centered-cubic FePt particles are presented. Applications in high-density magnetic data recording are foreseen.

Plastic Deformation of Single Nanometer-Sized Crystals

We report in situ electron microscopy observations of the plastic deformation of individual nanometer-sized Au, Pt, W, and Mo crystals. Specifically designed graphitic cages that contract under electron irradiation are used as nanoscopic deformation cells. The correlation with atomistic simulations shows that the observed slow plastic deformation is due to dislocation activity. Our results also provide evidence that the vacancy concentration in a nanoscale system can be smaller than in the bulk material, an effect which has not been studied experimentally before.

Cutting single-walled carbon nanotubes with an electron beam: evidence for atom migration inside nanotubes.

The diffusion of carbon atoms inside carbon nanotubes

We combine electron irradiation experiments in a transmission electron microscope with kinetic Monte Carlo simulations to determine the mobility of interstitial carbon atoms in single-walled carbon nanotubes. We measure the irradiation dose necessary to cut nanotubes repeatedly with a focused electron beam as a function of the separation between the cuts and at different temperatures. As the cutting speed is related to the migration of displaced carbon atoms trapped inside the tube and to their recombination with vacancies, we obtain information about the mobility of the trapped atoms and estimate their migration barrier to be about 0.25 eV. This is an experimental confirmation of the remar…

The Deformation of Single, Nanometer-Sized Metal Crystals in Graphitic Shells

Engineering of nanostructured carbon materials with electron or ion beams.

Irradiating solids with energetic particles is usually thought to introduce disorder, normally an undesirable phenomenon. But recent experiments on electron or ion irradiation of various nanostructures demonstrate that it can have beneficial effects and that electron or ion beams may be used to tailor the structure and properties of nanosystems with high precision. Moreover, in many cases irradiation can lead to self-organization or self-assembly in nanostructures. In this review we survey recent advances in the rapidly evolving area of irradiation effects in nanostructured materials, with particular emphasis on carbon systems because of their technological importance and the unique ability…

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Stability of carbon nanotubes under electron irradiation: Role of tube diameter and chirality

As recent experiments demonstrate, the inner shells of multiwalled carbon nanotubes are more sensitive to electron irradiation than the outer shells. To understand the origin of such counterintuitive behavior, we employ a density-functional-theory based tight-binding method and calculate the displacement threshold energies for carbon atoms in single-walled nanotubes with different diameters and chiralities. We show that the displacement energy and the defect production rate strongly depend on the diameter of the nanotube and its chirality, with the displacement energy being lower, but saturating towards the value for graphite when the tube diameter increases. This implies that the threshold…