Imaging mechanism and contrast separation in low-voltage scanning electron microscopy imaging of carbon nanotube arrays on SiO2/Si substrate

Polymer-sorted high-density carbon nanotube (CNT) arrays have shown great potential to extend the silicon-based Moore's law. Imaging the CNT arrays on insulators like SiO2/Si using low-voltage scanning electron microscopy (LVSEM) to acquire array information like the alignment, density, and distribution of residual polymers is necessary. Such a task remains challenging due to the nanoscale CNT body (1-2 nm in diameter), nanoscale tube-to-tube separation (1-10 nm), the broadening of the apparent diameter, and the complex image contrast caused by the insulating substrate and polymer residues. In this study, the imaging mechanism for this system is investigated. Two methods are developed to separate the three dominant contrasts, i.e. topographic contrast, charge contrast, and material contrast, by selecting the take-off angle and energy of the emitted electrons as enabled by changing the working distance or the deceleration voltage. The contrast formation and separation mechanism is further confirmed by the dynamic contrast evolution due to the electron-beam-induced deposition of amorphous carbon. The contrast separation method is further applied to an individual CNT, reducing its apparent diameter from 36 nm to 6 nm. This result hints at the potential for LVSEM to count the density exceeding 150 CNTs/um of CNT arrays. Finally, a comparative study of LVSEM and transmission electron microscopy confirms the failure of LVSEM to resolve CNTs in a bundle. The results suggest that the density of CNT arrays may be underestimated in reported SEM data. The proposed method can serve as a useful tool for further study and application of arrayed CNTs.Comment: 25 pages, 9 figures main text. 5 pages, 6 figures supplementary material

Three-Leaf Dart-Shaped Single-Crystal BN Formation Promoted by Surface Oxygen

Two-dimensional hexagonal boron nitride (h-BN) single crystals with various shapes have been synthesized by chemical vapor deposition over the past several years. Here we report the formation of three-leaf dart (3LD)-shaped single crystals of h-BN on Cu foil by atmospheric-pressure chemical vapor deposition. The leaves of the 3LD-shaped h-BN are as long as 18 {\mu}m and their edges are smooth armchair on one side and stepped armchair on the other. Careful analysis revealed that surface oxygen plays an important role in the formation of the 3LD shape. Oxygen suppressed h-BN nucleation by passivating Cu surface active sites and lowered the edge attachment energy, which caused the growth kinetics to change to a diffusion-controlled mode.Comment: 7 pages,6 figure

Layer-dependent anisotropic electronic structure of freestanding quasi-two dimensional MoS2

The anisotropy of the electronic transition is an important physical property not only determining the materials' optical property, but also revealing the underlying character of the electronic states involved. Here we used momentum-resolved electron energy-loss spectroscopy to study the evolution of the anisotropy of the electronic transition involving the low energy valence electrons in the free-standing MoS2 systems as the layer thickness was reduced to monolayer. We used the orientation and the spectral-density analysis to show that indirect to direct band-gap transition is accompanied by a three- to two-dimensional anisotropy cross-over. The result provides a logical explanation for the large sensitivity of indirect transition to the change of thickness compared with that for direct transition. By tracking the energy of indirect transition, we also revealed the asymmetric response of the valence band and conduction band to the quantum confinement effect. Our results have implication for future optoelectronic applications of atomic thin MoS2

Atomic Defects in Two-Dimensioal Materials: From Single-Atom Spectroscopy to Functionalities in Opto-/Electronics, Nanomagnetism, and Catalysis

Two-dimensional layered graphene-like crystals including transition metal dichalcogenides (TMDs) have received extensive research interest due to their diverse electronic, valleytronic and chemical properties, with the corresponding optoelectronics and catalysis application being actively explored. However, the recent surge in two-dimensional materials science is accompanied by equally great challenges such as defects engineering in the large-scale sample synthesis. It is necessary to elucidate the effect of structural defects on the electronic properties, in order to develop an application-specific strategy for the defect engineering. Here in this paper, we review the two aspects of the existing knowledge of native defects in two-dimensional crystals. One is the point defects emerging in graphene and hexagonal boron nitride as probed by atomically resolved electron microscopy and their local electronic properties as measured by single-atom electron energy-loss spectroscopy. The other will focus on the point defects in TMDs and their influence on the electronic structure, photoluminescence and electric transport properties. Our review of atomic defects in two-dimensional materials will offer a clear picture of the defect physics involved to demonstrate the local modulation of the electronic properties and possibly benefit in potential applications in magnetism and catalysis

Direct Imaging of Kinetic Pathways of Atomic Diffusion in Monolayer Molybdenum Disulfide

Direct observation of atomic migration both on and below surfaces is a long-standing but important challenge in materials science as diffusion is one of the most elementary processes essential to many vital material behaviors. Probing the kinetic pathways, including metastable or even transition states involved down to atomic scale, holds the key to the underlying physical mechanisms. Here, we applied aberration-corrected transmission electron microscopy (TEM) to demonstrate direct atomic-scale imaging and quasi-real-time tracking of diffusion of Mo adatoms and vacancies in monolayer MoS 2, an important two-dimensional transition metal dichalcogenide (TMD) system. Preferred kinetic pathways and the migration potential-energy landscape are determined experimentally and confirmed theoretically. The resulting three-dimensional knowledge of the atomic configuration evolution reveals the different microscopic mechanisms responsible for the contrasting intrinsic diffusion rates for Mo adatoms and vacancies. The new insight will benefit our understanding of material processes such as phase transformation and heterogeneous catalysis