Christophe Bichara

Understanding the nucleation mechanisms of carbon nanotubes in catalytic chemical vapor deposition

The nucleation of carbon caps on small nickel clusters is studied using a tight binding model coupled to grand canonical Monte Carlo simulations. It takes place in a well defined carbon chemical potential range, when a critical concentration of surface carbon atoms is reached. The solubility of carbon in the outermost Ni layers, that depends on the initial, crystalline or disordered, state of the catalyst and on the thermodynamic conditions, is therefore a key quantity to control the nucleation.

Early Stages in the Nucleation Process of Carbon Nanotubes

The early stages of carbon nanotube nucleation are investigated using field ion/electron microscopy along with in situ local chemical probing of a single nanosized nickel crystal. To go beyond experiments, tight-binding Monte Carlo simulations are performed on oriented Ni slabs. Real-time field electron imaging demonstrates a carbon-induced increase of the number density of steps in the truncated vertices of a polyhedral Ni nanoparticle. The necessary diffusion and step-site trapping of adsorbed carbon atoms are observed in the simulations and precede the nucleation of graphene-based sheets in these steps. Chemical probing of selected nanofacets of the Ni crystal reveals the occurrence of Cn (n=1-4) surface species. Kinetic studies prove C2+ species are formed from C1 with a delay time of several milliseconds at 623 K. Carbon dimers, C2, must not necessarily be formed on the Ni surface. Tight-binding Monte Carlo simulations reveal the high stability of such dimers in the first layer beneath the surface.

Aging mechanisms in amorphous phase-change materials

Aging is a ubiquitous phenomenon in glasses. In the case of phase-change materials, it leads to a drift in the electrical resistance, which hinders the development of ultrahigh density storage devices. Here we elucidate the aging process in amorphous GeTe, a prototypical phase-change material, by advanced numerical simulations, photothermal deflection spectroscopy and impedance spectroscopy experiments. We show that aging is accompanied by a progressive change of the local chemical order towards the crystalline one. Yet, the glass evolves towards a covalent amorphous network with increasing Peierls distortion, whose structural and electronic properties drift away from those of the resonantly bonded crystal. This behaviour sets phase-change materials apart from conventional glass-forming systems, which display the same local structure and bonding in both phases.

Importance of carbon solubility and wetting properties of nickel nanoparticles for single wall nanotube growth

Optimized growth of single wall carbon nanotubes requires full knowledge of the actual state of the catalyst nanoparticle and its interface with the tube. Using tight binding based atomistic computer simulations, we calculate carbon adsorption isotherms on nanoparticles of nickel, a typical catalyst, and show that carbon solubility increases for smaller nanoparticles that are either molten or surface molten under experimental conditions. Increasing carbon content favors the dewetting of Ni nanoparticles with respect to sp(2) carbon walls, a necessary property to limit catalyst encapsulation and deactivation. Grand canonical Monte Carlo simulations of the growth of tube embryos show that wetting properties of the nanoparticles, controlled by carbon solubility, are of fundamental importance to enable the growth, shedding new light on the growth mechanisms.

Nickel-assisted healing of defective graphene.

The healing of graphene grown from a metallic substrate is investigated using tight-binding Monte Carlo simulations. At temperatures (ranging from 1000 to 2500 K), an isolated graphene sheet can anneal a large number of defects suggesting that their healings are thermally activated. We show that in the presence of a nickel substrate we obtain a perfect graphene layer. The nickel-carbon chemical bonds keep breaking and reforming around defected carbon zones, providing a direct interaction, necessary for the healing. Thus, the action of Ni atoms is found to play a key role in the reconstruction of the graphene sheet by annealing defects.

Interdependency of Subsurface Carbon Distribution and Graphene–Catalyst Interaction

The dynamics of the graphene–catalyst interaction during chemical vapor deposition are investigated using in situ, time- and depth-resolved X-ray photoelectron spectroscopy, and complementary grand canonical Monte Carlo simulations coupled to a tight-binding model. We thereby reveal the interdependency of the distribution of carbon close to the catalyst surface and the strength of the graphene–catalyst interaction. The strong interaction of epitaxial graphene with Ni(111) causes a depletion of dissolved carbon close to the catalyst surface, which prevents additional layer formation leading to a self-limiting graphene growth behavior for low exposure pressures (10–6–10–3 mbar). A further hydrocarbon pressure increase (to ∼10–1 mbar) leads to weakening of the graphene–Ni(111) interaction accompanied by additional graphene layer formation, mediated by an increased concentration of near-surface dissolved carbon. We show that growth of more weakly adhered, rotated graphene on Ni(111) is linked to an initially higher level of near-surface carbon compared to the case of epitaxial graphene growth. The key implications of these results for graphene growth control and their relevance to carbon nanotube growth are highlighted in the context of existing literature.

Atomic structure of amorphous and crystallized Ge15Sb85

Ge15Sb85 is a promising material for phase-change memory applications owing to its very short crystallization times. As deposited amorphous samples of sputter deposited Ge15Sb85 have been investigated by extended x-ray absorption fine structure (EXAFS) measurements on both, Sb and Geu2009K absorption edges. After crystallizing the specimen, x-ray diffraction (XRD) and EXAFS measurements have been performed to analyze the atomic structure at different annealing conditions. Thus, experimental techniques focusing on the long range order as well as on the local order have been combined. Sb atoms have on average 3.2(2) nearest neighbors, while Ge atoms have 4.0(3). The Ge–Ge and Ge–Sb bond lengths are determined to 2.46(2) and 2.66(1) A, respectively and agree well with those observed in the amorphous phase of the common phase-change material Ge2Sb2Te5. After crystallizing the sample at 250u2009°C, very different EXAFS spectra with modified Ge–Sb bond lengths are observed. The higher concentration of Ge neighbors at the Ge edge as compared to the as-deposited sample is indicative for phase separation. For the corresponding sample, XRD does not show reflections of Ge, which indicates that the agglomeration of Ge is amorphous or below the coherence length of the x-radiation. The EXAFS spectrum shows a superposition of two phases: one with bond lengths which agree with sp3-hybridized Ge [2.43(1) A] and another one with longer Ge–Ge bond lengths [2.79(8) A]. This result can be explained by phase separation in the material.Ge15Sb85 is a promising material for phase-change memory applications owing to its very short crystallization times. As deposited amorphous samples of sputter deposited Ge15Sb85 have been investigated by extended x-ray absorption fine structure (EXAFS) measurements on both, Sb and Geu2009K absorption edges. After crystallizing the specimen, x-ray diffraction (XRD) and EXAFS measurements have been performed to analyze the atomic structure at different annealing conditions. Thus, experimental techniques focusing on the long range order as well as on the local order have been combined. Sb atoms have on average 3.2(2) nearest neighbors, while Ge atoms have 4.0(3). The Ge–Ge and Ge–Sb bond lengths are determined to 2.46(2) and 2.66(1) A, respectively and agree well with those observed in the amorphous phase of the common phase-change material Ge2Sb2Te5. After crystallizing the sample at 250u2009°C, very different EXAFS spectra with modified Ge–Sb bond lengths are observed. The higher concentration of Ge neighbors at t...

Computational studies of metal-carbon nanotube interfaces for regrowth and electronic transport.

First principles and tight binding Monte Carlo simulations show that junctions between single-walled carbon nanotubes (SWNTs) and nickel clusters are on the cluster surface, and not at subsurface sites, irrespective of the nanotube chirality, temperature, and whether the docking is gentle or forced. Gentle docking helps to preserve the pristine structure of the SWNT at the metal interface, whereas forced docking may partially dissolve the SWNT in the cluster. This is important for SWNT-based electronics and SWNT-seeded regrowth.

Size Dependent Phase Diagrams of Nickel-Carbon Nanoparticles.

The carbon rich phase diagrams of nickel-carbon nanoparticles, relevant to catalysis and catalytic chemical vapor deposition synthesis of carbon nanotubes, are calculated for system sizes up to about 3xa0nm (807 Ni atoms). A tight binding model for interatomic interactions drives the grand canonical Montexa0Carlo simulations used to locate solid, core shell and liquid stability domains, as a function of size, temperature, and carbon chemical potential or concentration. Melting is favored by carbon incorporation from the nanoparticle surface, resulting in a strong relative lowering of the eutectic temperature and a phase diagram topology different from the bulk one. This should lead to a better understanding of the nanotube growth mechanisms.

Role of defect healing on the chirality of single-wall carbon nanotubes

Although significant efforts have been directed towards a selective single wall carbon nanotube synthesis, the resulting diameter and chirality distributions are still too broad and their control remains a challenge. Progress in this direction requires an understanding of the mechanisms leading to the chiral selectivity reported by some authors. Here, we focus on one possible such mechanism and investigate the healing processes of defective tubes, at the atomic scale. We use tight-binding Monte Carlo simulations to perform a statistical analysis of the healing of a number of defective tubes. We study the role of temperature as a primary factor to overcome the energy barriers involved by healing, as well as the role of the metal catalyst. Using both electron diffraction patterns and local characterizations, we show that the healing proceeds first along the tube axis, before spreading laterally, and observe the competition between two or more chiralities. The resulting picture is that no chirality seems to be favored by the healing mechanisms, implying that the reported chiral preference should result from other sources.