Vincent Jourdain

Magnetic interactions in carbon nanostructures

A review is given of local and non-local magnetic interactions in carbon nanotubes as observed by NMR and EPR. Since reference to graphite and graphene is compulsory, an extended review of the NMR and EPR of graphite and related materials, including GIC, is given. Then EPR, and either static or high-resolution NMR experimental results, both in pure and intercalated MWNT or SWNT, are then reviewed. From high-resolution 13C-NMR in association with a theoretical modelization, it is shown how conducting and semiconducting carbon nanotubes might be discriminated. The benefits of high-resolution NMR for the characterization of carbon nanotube functionalization are described. The strong interdependence of all carbon material studies is clearly highlighted throughout the paper.

Self-Deactivation of Single-Walled Carbon Nanotube Growth Studied by in Situ Raman Measurements

In situ Raman measurements were used to investigate the kinetics and the self-deactivation of the growth of single-walled carbon nanotubes during catalytic chemical vapor deposition. The kinetics appear controlled by the mass-transport of the gaseous precursor at low precursor pressure and high temperature and by the catalytic decomposition of the precursor at high precursor pressure and low temperature. The initial growth rate and the lifetime display inversely correlated evolutions with the growth parameters. In addition, we measured the activation energy for the healing of defects during the growth and discuss it in comparison to the apparent activation energies measured for the initial growth rate and the lifetime. Our results support that the healing of the edge defects controls both the crystalline order and the growth lifetime.

Processes Controlling the Diameter Distribution of Single-Walled Carbon Nanotubes during Catalytic Chemical Vapor Deposition

Single-walled carbon nanotubes are grown by catalytic chemical vapor deposition in various conditions of temperature and carbon precursor pressure. Systematic analyses of the Raman radial breathing modes at two laser wavelengths are used to monitor the evolution of the diameter distribution. Two distinct domains with opposite influences of the temperature and the precursor pressure on the diameter distribution are evidenced. Thanks to specially designed experiments made of two successive growths, three processes are identified to influence the diameter distribution during the nanotube growth: (i) at too low precursor pressure, nanotube nucleation cannot occur on the smallest catalyst particles; (ii) at low temperature and high precursor pressure, small catalyst particles are preferably encapsulated by disordered carbon structures; (iii) at high temperature, catalyst coarsening causes the disappearance of the smallest catalyst particles.

Experimental evidence of a mechanical coupling between layers in an individual double-walled carbon nanotube.

We perform transmission electron microscopy, electron diffraction, and Raman scattering experiments on an individual suspended double-walled carbon nanotube (DWCNT). The first two techniques allow the unambiguous determination of the DWCNT structure: (12,8)@(16,14). However, the low-frequency features in the Raman spectra cannot be connected to the derived layer diameters d by means of the 1/d power law, widely used for the diameter dependence of the radial-breathing mode of single-walled nanotubes. We discuss this disagreement in terms of mechanical coupling between the layers of the DWCNT, which results in collective vibrational modes. Theoretical predictions for the breathing-like modes of the DWCNT, originating from the radial-breathing modes of the layers, are in a very good agreement with the observed Raman spectra. Moreover, the mechanical coupling qualitatively explains the observation of Raman lines of breathing-like modes, whenever only one of the layers is in resonance with the laser energy.

Gold contact to individual metallic carbon nanotubes: A sensitive nanosensor for high-pressure

A strong and universal piezoresistive effect is evidenced for individual metallic carbon nanotubes contacted to gold electrodes through high contact resistances. The effect is well explained through a pressure modulation of the tunnel barrier width at the contact. The pressure dependence (−16%/GPa) is much stronger than for standard resistive high pressure gauges, and it depends neither on the initial resistance nor on the pressure transmitting medium.

Synthesis of individual ultra-long carbon nanotubes and transfer to other substrates

In this article, we report the synthesis of ultra-long carbon nanotubes (CNTs) by thermal chemical vapour deposition method. Ultra-long, individual and aligned CNTs were directly grown on a flat silicon substrate. The orientation of the nanotubes was found parallel to the gas flow direction. The ultra-long CNTs were grown with different transition metallic salts, such as nickel chloride, iron (III) chloride, cobalt acetate and ruthenium acetate, as the catalysts. The influence of the growth conditions, such as growth temperature, reactive gas flow on the length and alignment of the CNTs was studied in detail. By using different catalysts, ultra-long single-walled carbon nanotubes (SWCNTs) or multi-walled carbon nanotubes (MWCNTs) were successfully grown. These ultra-long CNTs were transferred to other substrates by two methods. (1) The first method is to use polydimethylsiloxane as a stamp. (2) The second method is to use KOH as an etching agent. The diameter and length of the CNTs were characterised by transmission electron microscope, scanning electron microscope, atomic force microscope and Raman spectroscopy. The results indicate that the length of the CNTs can reach up to 4 mm. The diameter of the SWCNTs is in the range of 0.7–2.1 nm and the diameter of the MWCNTs is approximately 150 nm.

Unveiling the Evolutions of Nanotube Diameter Distribution during the Growth of Single-Walled Carbon Nanotubes

In situ and ex situ Raman measurements were used to study the dynamics of the populations of single-walled carbon nanotubes (SWCNTs) during their catalytic growth by chemical vapor deposition. Our study reveals that the nanotube diameter distribution strongly evolves during SWCNT growth but in dissimilar ways depending on the growth conditions. We notably show that high selectivity can be obtained using short or moderate growth times. High-resolution transmission electron microscopy observations support that Ostwald ripening is the key process driving these seemingly contradictory results by regulating the size distribution and lifetime of the active catalyst particles. Ostwald ripening appears as the main termination mechanism for the smallest diameter tubes, whereas carbon poisoning dominates for the largest ones. By unveiling the key concept of dynamic competition between nanotube growth and catalyst ripening, we show that time can be used as an active parameter to control the growth selectivity of carbon nanotubes and other 1D systems.

Increased chemical reactivity of single-walled carbon nanotubes on oxide substrates: In situ imaging and effect of electron and laser irradiations

We studied the oxygen etching of individual single-walled carbon nanotubes on silicon oxide substrates using atomic force microscopy and high-temperature environmental scanning electron microscopy. Our in situ observations show that carbon nanotubes are not progressively etched from their ends, as frequently assumed, but disappear segment by segment. Atomic force microscopy, before and after oxidation, reveals that the oxidation of carbon nanotubes on substrates proceeds through a local cutting that is followed by a rapid etching of the disconnected nanotube segment. Unexpectedly, semiconducting nanotubes appear more reactive under these conditions than metallic ones. We also show that exposure to electron and laser beams locally increases the chemical reactivity of carbon nanotubes on such substrates. These results are rationalized by considering the effect of substrate-trapped charges on the nanotube density of states close to the Fermi level, which is impacted by the substrate type and the exposure to electron and laser beams.

Macroscopic fibers of carbon nanotubes produced by electric arc discharge

Macroscopic fibers of single-wall carbon nanotube bundles were generated in an electric arc experiment in carbon monoxide helium mixtures. The fibers have diameters between 0.1 and 0.5 mm and reached lengths up to 2.5 cm. Scanning and transmission electron microscopy showed that the fibers consist predominantly of bundles of single-wall carbon nanotubes and metal particles but very little contamination of other carbon products. X-ray diffraction measurements suggest a preferable orientation of the nanotubes along the fiber axis.

In situ study of single-walled carbon nanotube growth in an environmental scanning electron microscope

Monitoring individual single-walled carbon nanotubes (SWCNTs) during their growth is a highly sought-after goal in view of understanding the processes involved in the nucleation, elongation and termination which ultimately control the diameter and chiral selectivity. Here, we report on the first truly in situ observations of SWCNT growth in an environmental scanning electron microscope (ESEM). The CNT growth from lithographically patterned catalysts was investigated as a function of the catalyst type (Fe, Co or Ni), temperature, type of precursor (ethanol or acetylene), gas phase composition and pressure, and pretreatment conditions, and we report on the most appropriate conditions for SWCNT growth in ESEM conditions. We show that this approach allows the observation at the submicron scale of the different steps of the nanotube synthesis including the catalyst reduction, the growth and percolation of the nanotube network, and the deposition of individual nanotubes grown in the gas phase on the substrate. Despite these obvious advantages, we identified a few limitations which will need to be tackled for fully taking advantage of the approach, for instance for monitoring the growth of individual SWCNTs by ESEM, including the short lifetime of the catalyst nanoparticles, the preference for kite growth (by opposition to surface growth) and the influence of the electron beam on the nanotube growth.