Atomic Configuration of Nitrogen Doped Single-Walled Carbon Nanotubes

Having access to the chemical environment at the atomic level of a dopant in a nanostructure is crucial for the understanding of its properties. We have performed atomically-resolved electron energy-loss spectroscopy to detect individual nitrogen dopants in single-walled carbon nanotubes and compared with first principles calculations. We demonstrate that nitrogen doping occurs as single atoms in different bonding configurations: graphitic-like and pyrrolic-like substitutional nitrogen neighbouring local lattice distortion such as Stone-Thrower-Wales defects. The stability under the electron beam of these nanotubes has been studied in two extreme cases of nitrogen incorporation content and configuration. These findings provide key information for the applications of these nanostructures.Comment: 25 pages, 13 figure

Effects of epitaxial strain on the growth mechanism of YBa2Cu3O7-x thin films in [YBa2Cu3O7-x / PrBa2Cu3O7-x] superlattices

We report on the growth mechanism of YBa2Cu3O7-x (YBCO). Our study is based on the analysis of ultrathin, YBa2Cu3O7-x layers in c-axis oriented YBa2Cu3O7-x / PrBa2Cu3O7-x superlattices. We have found that the release of epitaxial strain in very thin YBCO layers triggers a change in the dimensionality of the growth mode. Ultrathin, epitaxially strained, YBCO layers with thickness below 3 unit cells grow in a block by block two dimensional mode coherent over large lateral distances. Meanwhile, when thickness increases, and the strain relaxes, layer growth turns into three dimensional, resulting in rougher layers and interfaces.Comment: 10 pages + 9 figures, accepted in Phys. Rev.

Graphene re-knits its holes

Nano-holes, etched under an electron beam at room temperature in singlelayer graphene sheets as a result of their interaction with metalimpurities, are shown to heal spontaneously by filling up with either non-hexagon, graphene-like, or perfect hexagon 2D structures. Scanning transmission electron microscopy was employed to capture the healing process and study atom-by-atom the re-grown structure. A combination of these nano-scale etching and re-knitting processes could lead to new graphene tailoring approaches.Comment: 11 pages, 4 figure

Position and momentum mapping of vibrations in graphene nanostructures in the electron microscope

Propagating atomic vibrational waves, phonons, rule important thermal, mechanical, optoelectronic and transport characteristics of materials. Thus the knowledge of phonon dispersion, namely the dependence of vibrational energy on momentum is a key ingredient to understand and optimize the material's behavior. However, despite its scientific importance in the last decade, the phonon dispersion of a freestanding monolayer of two dimensional (2D) materials such as graphene and its local variations has still remained elusive because of experimental limitations of vibrational spectroscopy. Even though electron energy loss spectroscopy (EELS) in transmission has recently been shown to probe the local vibrational charge responses, these studies are yet limited to polar materials like boron nitride or oxides, in which huge signals induced by strong dipole moments are present. On the other hand, measurements on graphene performed by inelastic x-ray (neutron) scattering spectroscopy or EELS in reflection do not have any spatial resolution and require large microcrystals. Here we provide a new pathway to determine the phonon dispersions down to the scale of an individual freestanding graphene monolayer by mapping the distinct vibration modes for a large momentum transfer. The measured scattering intensities are accurately reproduced and interpreted with density functional perturbation theory (DFPT). Additionally, a nanometre-scale mapping of selected momentum (q) resolved vibration modes using graphene nanoribbon structures has enabled us to spatially disentangle bulk, edge and surface vibrations

Atomic-resolution spectroscopic imaging of ensembles of nanocatalyst particles across the life of a fuel cell

The thousandfold increase in data-collection speed enabled by aberration-corrected optics allows us to overcome an electron microscopy paradox - how to obtain atomic-resolution chemical structure in individual nanoparticles, yet record a statistically significant sample from an inhomogeneous population. This allowed us to map hundreds of Pt-Co nanoparticles to show atomic-scale elemental distributions across different stages of the catalyst aging in a proton-exchange-membrane fuel cell, and relate Pt-shell thickness to treatment, particle size, surface orientation, and ordering.Comment: 28 pages, 5 figures, accepted, nano letter

Cross-sectional imaging of individual layers and buried interfaces of graphene-based heterostructures and superlattices

By stacking various two-dimensional (2D) atomic crystals [1] on top of each other, it is possible to create multilayer heterostructures and devices with designed electronic properties [2-5]. However, various adsorbates become trapped between layers during their assembly, and this not only affects the resulting quality but also prevents the formation of a true artificial layered crystal upheld by van der Waals interaction, creating instead a laminate glued together by contamination. Transmission electron microscopy (TEM) has shown that graphene and boron nitride monolayers, the two best characterized 2D crystals, are densely covered with hydrocarbons (even after thermal annealing in high vacuum) and exhibit only small clean patches suitable for atomic resolution imaging [6-10]. This observation seems detrimental for any realistic prospect of creating van der Waals materials and heterostructures with atomically sharp interfaces. Here we employ cross sectional TEM to take a side view of several graphene-boron nitride heterostructures. We find that the trapped hydrocarbons segregate into isolated pockets, leaving the interfaces atomically clean. Moreover, we observe a clear correlation between interface roughness and the electronic quality of encapsulated graphene. This work proves the concept of heterostructures assembled with atomic layer precision and provides their first TEM images

Dielectric response of pentagonal defects in multilayer graphene nano-cones

The dielectric response of pentagonal defects in multilayer graphene nano-cones has been studied by electron energy loss spectroscopy and ab initio simulations. At the cone apex, a strong modification of the dielectric response is observed below the energy of the π plasmon resonance. This is attributed to π → π* interband transitions induced by topology-specific resonant π bonding states as well as π*–σ* hybridization. It is concluded that pentagonal defects strongly affect the local electronic structure in such a way that multi-walled graphene nano-cones should show great promise as field emitters

Deciphering chemical order/disorder and material properties at the single-atom level

Correlating 3D arrangements of atoms and defects with material properties and functionality forms the core of several scientific disciplines. Here, we determined the 3D coordinates of 6,569 iron and 16,627 platinum atoms in a model iron-platinum nanoparticle system to correlate 3D atomic arrangements and chemical order/disorder with material properties at the single-atom level. We identified rich structural variety and chemical order/disorder including 3D atomic composition, grain boundaries, anti-phase boundaries, anti-site point defects and swap defects. We show for the first time that experimentally measured 3D atomic coordinates and chemical species with 22 pm precision can be used as direct input for first-principles calculations of material properties such as atomic magnetic moments and local magnetocrystalline anisotropy. This work not only opens the door to determining 3D atomic arrangements and chemical order/disorder of a wide range of nanostructured materials with high precision, but also will transform our understanding of structure-property relationships at the most fundamental level.Comment: 21 pages, 4 figure