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We present a detailed study of the growth mechanism of single-walled boron nitride nanotubes synthesized by laser vaporization, which is the unique route known to the synthesis of this kind of tube in high quantities. We have performed a nanometric chemical and structural characterization by transmission electron microscopy (high-resolution mode (HRTEM) and electron energy loss spectroscopy) of the synthesis products. Different boron-based compounds and other impurities were identified in the raw synthesis products. The results obtained by the TEM analysis and from the synthesis parameters (temperature, boron, and nitrogen sources) combined with phase diagram analysis to provide identification of the fundamental factors determining the nanotube growth mechanism. Our experiments strongly support a root-growth model that involves the presence of a droplet of boron. This phenomenological model considers the solubility, solidification, and segregation phenomena of the elements present in this boron droplet. In this model, we distinguish three different steps as a function of the temperature: (1) formation of the liquid boron droplet from the decomposition of different boron compounds existing in the hexagonal boron nitride target, (2) reaction of these boron droplets with nitrogen gas present in the vaporization chamber and recombination of these elements to form boron nitride, and (3) incorporation of the nitrogen atoms at the root of the boron particle at active reacting sites that achieves the growth of the tube.

We report on the synthesis of C-BN single-walled nanotubes made of BN nanodomains embedded into a graphene layer. The synthesis process consists of vaporizing, by a continuous CO2 laser, a target made of carbon and boron mixed with a Co/Ni catalyst under N2 atmosphere. High-resolution transmission electron microscopy (HRTEM) and nanoelectron energy loss spectroscopy (nanoEELS) provide direct evidence that boron and nitrogen co-segregate with respect to carbon and form nanodomains within the hexagonal lattice of the graphene layer in a sequential manner. A growth model is proposed to account for the observed C-BN self-organization and to explain how kinetics and local energetics at intermediate states can tailor ultimate single layer BN-C heterojunctions.

We have fabricated electronic devices based on single-walled boron nitride nanotubes (BNNTs). Our measurements indicate that all BNNTs are semiconducting, and p-doped. Temperature dependence of two terminal transport experiments suggests that at low drain fields, transport is dominated by thermionic emission over 250–300 meV Schottky contact barriers. Gate-induced barrier modulation was observed in vertically scaled devices, resulting in field-effect transistor operation.

A reactor has been developed at ONERA to investigate the gas phase during carbon nanotube formation by laser-induced fluorescence (LIF), Laser-induced incandescence (LII), coherent anti-Stokes Raman Scattering (CARS), and emission spectroscopy. Continuous vaporization is achieved with a continuous wave CO2 laser. Optimized conditions are used for single-walled nanotube growth, that is, a graphite target doped with 2 atom % Ni and 2 atom % Co, helium as buffer gas at a flow rate of 50 ml/s, and a pressure of 300 hPa. Temperature profiles are measured by CARS on H2, and soot images are obtained by LII in the hot carbonaceous flow. LIF and spontaneous emission of the C2 radical and Ni and Co atoms are presented. Spectral investigations are conducted at 3100 and 3200 K to have an optimized pair of excitation/detection wavelengths. Spatial investigations of the relative concentrations in the hot carbonaceous flow are performed up to 3500 K. The concentrations are measured as a function of target temperature. Two regimes of vaporization are observed. Vaporization is slow up to 3350 K and becomes much faster above this temperature. The fast regime in the 3350-3500 K range corresponds to the observed spatial extent of the metal vapors region. At 3500 K, the C2 profiles obtained with and without catalysts are very different as a result of carbon coalescence as well as carbon dissolution into the metal nanoparticles when these are present in the gas phase. The shape of the C2 profile can be related to nanotube formation and growth at a target temperature of 3500 K.

Multiwalled boron-and nitrogen-doped carbon nanotubes (C x B y N z ) have been synthesized using both low and high temperature synthesis methods namely an aerosol-assisted chemical vapor deposition process and a laser vaporization process, respectively. Degrees of purity, homogeneity, and yield have been estimated from a systematic inspection of the sample by scanning electron microscopy (SEM) and high resolution transmission electron microscopy (HRTEM). Spatially resolved electron energy loss spectroscopy (EELS) measurements in a dedicated scanning transmission electron microscope (STEM) have been performed in order to correlate spectroscopic information with structural features at a nanometer scale on nanotubes and nanoparticles that originates their growth. As a result, spatially resolved analyses have shown a clearly defined segregation of BN-regions from CN-rich regions, indicating that separate nanodomains of boron nitride and carbon nitride may exist with different arrangements in carbon nanotubes as a function of the synthesis method.

Gas-phase production of carbon nanotubes in presence of a metal catalyst with a continuous wave CO 2 laser is investigated by combining coherent anti-Stokes Raman scattering ͑CARS͒, laser-induced fluorescence ͑LIF͒, and laser-induced incandescence ͑LII͒. These in situ techniques provide a unique investigation of the different transformation processes of the primarily carbon and metal vapors issued from the vaporization of the target by the laser and the temperature at which these processes occur. Continuous-wave laser provides with stable continuous vaporization conditions very well suited for such in situ investigations. Temperature profiles inside the reactor are known from CARS measurements and flow calculations. Carbon soot, density, and size of carbon aggregates are determined by LII measurements. LIF measurements are used to study the gas phases, namely, C 2 and C 3 radicals which are the very first steps of carbon recombination, and metal catalysts gas phase. Spectral investigations allow us to discriminate the signal from each species by selecting the correct pair of excitation/detection wavelengths. Spatial distributions of the different species are measured as a function of target composition and temperature. The comparison of LIF and LII signals allow us to correlate the spatial evolution of gas and soot in the scope of the different steps of the nanotube growth already proposed in the literature and to identify the impact of the chemical nature of the catalyst on carbon condensation and nanotube nucleation. Our study presents the first direct evidence of the nanotube onset and that the nucleation proceeds from a dissolution-segregation process from metal particles as assumed in the well-known vapor-liquid-solid model. Comparison of different catalysts reveals that this process is strongly favored when Ni is present.

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