arXiv subjects

Christophe Bichara

Publications and source records attributed to Christophe Bichara.

At least 19 recordsLinked to original sources

arXiv2026

Structures of iron and cobalt bimetallic clusters for optimized chemical vapor deposition growth of single-walled carbon nanotubes

We investigate iron-cobalt (Fe-Co) alloys as a representative high-performance catalyst system for SWCNT growth in a systematic manner by combining chemical vapor deposition (CVD) experiments with chirality-resolved spectroscopic analysis, as well as molecular dynamics (MD) simulations based on density functional theory-derived machine learning force fields while varying the Fe-Co ratio. Using zeolite-based SWCNTs prepared by alcohol CVD, absorption and photoluminescence spectroscopy, together with two-dimensional excitation-emission fitting was employed to quantify chirality-specific growth efficiency. Two distinct growth regimes were identified. At a relatively low temperature of 600 C, pure Co exhibits the highest catalytic activity, promoting efficient growth of small-diameter (0.7-0.9 nm) SWCNTs. In contrast, at 850 C, the Fe0.75Co0.25 alloy shows a pronounced enhancement in growth efficiency compared with pure Fe, pure Co, and other Fe-Co compositions, also yielding larger diameter tubes (0.9-1.1nm). Similar growth behavior was observed on SiO2 substrates, enabling detailed transmission electron microscopy analysis of catalyst nanoparticles. Electron microscopy and energy-dispersive X-ray spectroscopy reveal that high SWCNT yields correlate with the formation of small, uniform Fe-Co nanoparticles with Co-enriched surfaces, in excellent agreement with MD simulations. Lastly, MD results are summarized in a composition-diameter phase diagram that rationalizes the experimentally observed growth trends. The exceptional performance of the Fe0.75Co0.25 catalyst at high temperature is attributed to the stabilization of small and uniform catalyst clusters, providing mechanistic insight into the synergistic roles of alloy composition and temperature in SWCNT growth.

cond-mat.mtrl-sci↗

arXiv2025

Advanced structural characterization of single-walled carbon nanotubes with 4D-STEM

Single wall carbon nanotubes (SWCNT) exhibit remarkable optical and electrical properties making them one of the most promising materials for next generation electronic and optoelectronic devices. Their electronic properties strongly depend on their chirality, i.e., their structural configuration, as well as on the presence and nature of atomic defects. Currently, the lack of versatile and efficient structural characterization techniques limits SWCNT applications. Here, we report how four-dimensional scanning transmission electron microscopy (4D-STEM) can address critical challenges in SWCNT structural analysis. Using modern fast pixelated electron detectors, we were able to acquire rapidly a large number of low noise electron diffraction patterns of SWCNTs. The resulting 4D-STEM data allow to precisely determine the local chirality of multiple nanotubes at once, with limited electron dose (down to 1750 e-/{\AA}^2) and nanometric spatial resolution (down to 3.1 nm). We also show how this approach enables to track the chirality along a single nanotube, while giving access to the strain distribution. Then, we report how 4D-STEM data enable to reconstruct high-resolution images with electron ptychography. With this second approach, structural information can be obtained with atomic scale spatial resolution allowing atomic defect imaging. Finally, we investigate how multi-slice electron ptychography could provide even further insight on nanotube defect structures thanks to its close to 3D imaging capabilities at atomic resolution.

cond-mat.mtrl-sci↗

arXiv2025

Analysis of Fe and Co binary catalysts in chemical vapor deposition growth of single-walled carbon nanotubes

Metal catalysts play a pivotal role in the growth of single-walled carbon nanotubes (SWCNTs), with binary metallic catalysts emerging as an efficient SWCNT synthesis strategy. Among these, iron (Fe), cobalt (Co), and their alloys are particularly effective. However, prior studies have predominantly employed Fe--Co alloy catalysts with fixed atomic ratios as well as unchanged chemical vapor deposition (CVD) conditions, leaving the influence of variable Fe--Co compositions and CVD growth parameters on SWCNT synthesis poorly understood. This study focuses on the role of Fe--Co catalyst ratios, with the aim of elucidating the distinct contributions of Fe and Co atoms in the growth of SWCNTs. By systematically exploring a wide range of Fe--Co ratios and growth conditions, we identified Fe$_{0.75}$Co$_{0.25}$ as a highly efficient binary catalyst at 850~$^\circ$C, primarily forming catalyst clusters with diameters of 2.5--6~nm and yielding SWCNTs with diameters ranging from 0.9--1.1~nm. On the other hand, Fe$_{0}$Co$_{1}$ exhibited higher catalytic activity at 600~$^\circ$C, generating smaller catalyst clusters of 1.5--5~nm and producing SWCNTs with reduced diameters of about 0.6--0.9~nm. Transmission electron microscope (TEM) and energy dispersive X-ray spectroscopy (EDS) analyses reveal that high SWCNT yields correlate with the formation of uniformly sized Fe--Co catalyst particles with surface-segregated Co that optimizes carbon solubility. Molecular dynamics (MD) simulations further corroborate these findings, demonstrating that the structure and melting behavior of Fe$_x$Co$_{1-x}$ clusters depend on cluster size and composition.

cond-mat.mtrl-sci↗

arXiv2023

Dynamics of growing carbon nanotube interfaces probed by machine learning-enabled molecular simulations

Carbon nanotubes (CNTs) are currently considered a successor to silicon in future nanoelectronic devices. To realize this, controlled growth of defect-free nanotubes is required. Until now, the understanding of atomic-scale CNT growth mechanisms provided by molecular dynamics simulations has been hampered by their short timescales. Here, we develop an efficient and accurate machine learning force field, DeepCNT-22, to simulate the complete growth of defect-free single-walled CNTs (SWCNTs) on iron catalysts at near-microsecond timescales. We provide atomic-level insight into the nucleation and growth processes of SWCNTs, including the evolution of the tube-catalyst interface and the mechanisms underlying defect formation and healing. Our simulations highlight the maximization of SWCNT-edge configurational entropy during growth and how defect-free CNTs can grow ultralong if carbon supply and temperature are carefully controlled.

cond-mat.mtrl-sci↗

arXiv2023

Swinging Crystal Edge of Growing Carbon Nanotubes

Recent direct measurements of the growth kinetics of individual carbon nanotubes revealed abrupt changes in the growth rate of nanotubes maintaining the same crystal structure. These stochastic switches call into question the possibility of chirality selection based on growth kinetics. Here, we show that a similar average ratio between fast and slow rates of around 1.7 is observed largely independent of the catalyst and growth conditions. A simple model, supported by computer simulations, shows that these switches are caused by tilts of the growing nanotube edge between two main orientations, close-armchair or close-zigzag, inducing different growth mechanisms. The rate ratio of around 1.7 then simply results from an averaging of the number of growth sites and edge configurations in each orientation. Beyond providing new insights on nanotube growth based on classical crystal growth theory, these results point to ways to control the dynamics of nanotube edges, a key requirement for stabilizing growth kinetics and producing arrays of long structurally-selected nanotubes.

cond-mat.mes-hall↗

arXiv2023

Edge Dynamics in Iron-Cluster Catalyzed Growth of Single-Walled Carbon Nanotubes Revealed by Molecular Dynamics Simulations based on a Neural Network Potential

Given the high potential for applications utilizing the unique properties of single-walled carbon nanotubes (SWCNTs), there is considerable enthusiasm for addressing the challenges associated with synthesizing SWCNTs with specific chirality. To elucidate the mechanisms that determine the chirality of SWCNTs during growth, intensive efforts have been devoted to classical molecular dynamics (MD) simulations. However, the mechanism of chirality determination has not been fully clarified, which can partly be attributed to the limited accuracy of empirical interatomic potentials in reproducing the behavior of carbon and metal atoms. In this work, we develop a neural network potential (NNP) for carbon-metal system to accurately describe the SWCNT growth, and perform MD simulations of SWCNT growth using the NNP. The MD simulations illustrate the defect-free, chirality-definable growth of SWCNTs, highlighting the dynamic rearrangement of edge configurations and the consistency between the probability of edge configuration appearance and the entropy-driven edge stability model proposed here. It is also shown that the edge defect formation is induced by vacancy and suppressed by vacancy healing through adatom diffusion on the SWCNT edges. These results provide insights into the edge formation thermodynamics and kinetics of SWCNTs, an important clue to the chirality-controlled synthesis of SWCNTs.

physics.comp-ph↗

arXiv2021

Dynamic instability of individual carbon nanotube growth revealed by in situ homodyne polarization microscopy

Understanding the kinetic selectivity of carbon nanotube growth at the scale of individual nanotubes is essential for the development of high chiral selectivity growth methods. Here we demonstrate that homodyne polarization microscopy can be used for high-throughput imaging of long individual carbon nanotubes under real growth conditions (at ambient pressure, on a substrate), and with sub-second time resolution. Our in situ observations on hundreds of individual nanotubes reveal that about half of them grow at a constant rate all along their lifetime while the other half exhibits stochastic changes in growth rates, and switches between growth, pause and shrinkage. Statistical analysis shows that the growth rate of a given nanotube essentially varies between two values, with similar average ratio (~1.7) regardless of whether the rate change is accompanied by a change in chirality. These switches indicate that the nanotube edge or the catalyst nanoparticle fluctuates between different configurations during growth.

cond-mat.mtrl-sci↗

arXiv2021

A Semi-Grand Canonical Kinetic Monte Carlo study of Single-Walled Carbon Nanotubes growth

Single-walled carbon nanotubes exist in a variety of different geometries, so-called chiralities, that define their electronic properties. Chiral selectivity has been reported in catalytic chemical vapor deposition synthesis experiments, but the underlying mechanisms remain poorly understood. In this contribution, we establish a simple model for the prediction of the growth rates of carbon nanotubes of different chiralities, as a function of energies characterizing the carbon nanotube-catalyst interface and of parameters of the synthesis. The model is sampled efficiently using kinetic Monte Carlo simulations in the semi-grand canonical ensemble, uncovering the interplay of the external experimental conditions and the configuration and energetics of the interface with the catalyst. In particular, the distribution of chiral angle dependent growth rates follows non-monotonic trends as a function of interface energies. We analyze this behavior and use it to identify conditions that lead to high selectivity for a variety of chiral angles.

cond-mat.mes-hall↗

arXiv2018

Tuning bimetallic catalysts for a selective growth of SWCNTs

Recent advances in structural control during the synthesis of SWCNTs have in common the use of bimetallic nanoparticles as catalysts, despite the fact that their exact role is not fully understood. We therefore analyze the effect of the catalyst' s chemical composition on the structure of the resulting SWCNTs by comparing three bimetallic catalysts (FeRu, CoRu and NiRu). A specific synthesis protocol is designed to impede the catalyst nanoparticle coalescence mechanisms and stabilize their diameter distributions throughout the growth. Owing to the ruthenium component which has a limited carbon solubility, tubes grow in tangential mode and their diameter is close to that of their seeding nanoparticle. By using as-synthesized SWCNTs as a channel material in field effect transistors, we show how the chemical composition of the catalysts and temperature can be used as parameters to tune the diameter distribution and semiconducting-to-metallic ratio of SWCNT samples. Finally, a phenomenological model, based on the dependence of the carbon solubility as a function of catalyst nanoparticle size and nature of the alloying elements, is proposed to interpret the results.

physics.app-ph↗

arXiv2018

Entropy driven stability of chiral single-walled carbon nanotubes

Single-walled carbon nanotubes are hollow cylinders, that can grow centimeters long by carbon incorporation at the interface with a catalyst. They display semi-conducting or metallic characteristics, depending on their helicity, that is determined during their growth. To support the quest for a selective synthesis, we develop a thermodynamic model, that relates the tube-catalyst interfacial energies, temperature, and the resulting tube chirality. We show that nanotubes can grow chiral because of the configurational entropy of their nanometer-sized edge, thus explaining experimentally observed temperature evolutions of chiral distributions. Taking the chemical nature of the catalyst into account through interfacial energies, structural maps and phase diagrams are derived, that will guide a rational choice of a catalyst and growth parameters towards a better selectivity.

cond-mat.mtrl-sci↗

arXiv2018

Growth Modes and Chiral Selectivity of Single-Walled Carbon Nanotubes

Chemical vapor deposition synthesis of single-walled carbon nanotubes experiments, using Fe catalyst, and alternating methane and carbon monoxide as carbon feedstocks, lead to the reversible formation of junctions between tubes of different diameters. Combined with an atomistic modeling of the tube / catalyst interface, this shows that the ratio of diameters of the tube and its seeding particle, denoting the growth mode, depends on the carbon fraction inside the catalyst. With carbon monoxide, nanoparticles are strongly carbon enriched, and tend to dewet the tube, in a perpendicular growth mode. Cross-checking our results with available reports from the literature of the last decade strongly suggests that these latter conditions should favor the near armchair chiral selectivity observed empirically.

physics.chem-ph↗

arXiv2017

Incipient Metals: Functional Materials with a Unique Bonding Mechanism

While solid-state materials are commonly classified as covalent, ionic, or metallic, there are cases that defy these iconic bonding mechanisms. A prominent example is given by phase-change materials (PCMs) for data storage or photonics, which have recently been argued to show 'resonant' bonding; a clear definition of this mechanism, however, has been lacking until the present day. Here we show that these solids are clearly different from resonant bonding in the pi-orbital systems of benzene and graphene. Instead, they exhibit a unique mechanism between covalent and metallic bonding, which we call 'metavalent' bonding. The materials are on the verge of electron delocalization, which explains their exceptional property portfolio, and we therefore argue that they represent 'incipient metals'. This yields deeper, fundamental insight into the bonding nature of solid-state materials, and is expected to accelerate the discovery and design of new functional materials including PCMs and thermoelectrics.

cond-mat.mtrl-sci↗

arXiv2017

Probing the role of carbon solubility in transition metal catalyzing Single-Walled Carbon Nanotubes growth

Metal catalysts supporting the growth of Single Wall Carbon Nanotubes display different carbon solubilities and chemical reactivities. In order to specifically assess the role of carbon solubility, we take advantage of the physical transparency of a tight binding model established for Ni-C alloys, to develop metal carbon models where all properties, except carbon solubility, are similar. These models are used to analyze carbon incorporation mechanisms, modifications of metal / carbon wall interfacial properties induced thereby, and the associated nanotube growth mechanisms. Fine tuning carbon solubility is shown to be essential to support sustainable growth, preventing growth termination by either nanoparticle encapsulation or detachment.

cond-mat.mtrl-sci↗

arXiv2015

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 3 nanometers (807 Ni atoms). A tight binding model for interatomic interactions drives the Grand Canonical Monte Carlo 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 be taken into account in our understanding of the nanotube growth mechanisms.

physics.atm-clus↗

arXiv2012

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

Optimized growth of Single Wall Carbon Nanotubes requires a 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 sp2 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 a new light on the growth mechanisms.

cond-mat.mtrl-sci↗

arXiv2012

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.

cond-mat.mtrl-sci↗

arXiv2010

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 healing are thermally activated. We show that in 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.

cond-mat.mtrl-sci↗

arXiv2008

A tight-binding potential for atomistic simulations of carbon interacting with transition metals: Application to the Ni-C system

We present a tight-binding potential for transition metals, carbon, and transition metal carbides, which has been optimized through a systematic fitting procedure. A minimal basis, including the s, p electrons of carbon and the d electrons of the transition metal, is used to obtain a transferable tight-binding model of the carbon-carbon, metal-metal and metal-carbon interactions applicable to binary systems. The Ni-C system is more specifically discussed. The successful validation of the potential for different atomic configurations indicates a good transferability of the model and makes it a good choice for atomistic simulations sampling a large configuration space. This approach appears to be very efficient to describe interactions in systems containing carbon and transition metal elements.

cond-mat.mtrl-sci↗