  A high-yield production of high-quality boron-nitride nanotubes (BNNTs) was
reported recently in several publications. A boron-rich material is evaporated
by a laser or plasma in a nitrogen-rich atmosphere to supply precursor gaseous
species for nucleation and growth of BNNTs. Either hydrogen was added or
pressure was increased in the system to achieve high yield and high purity of
the synthesized nanotubes. According to the widely-accepted "root grow"
mechanism, upon the gas cooling, boron droplets form first, then they adsorb
nitrogen from surrounding gas species, and BNNTs grow on their surfaces.
However, what are these precursor species that provide nitrogen for the growth
is still an open question. To answer this question, we performed thermodynamic
calculations of B-N mixture composition considering broad set of gas species.
In enhancement of previous studies, the condensation of boron is now taken into
account and is shown to have drastic effect on the gas chemical composition.
B2N molecules were identified to be a major source of nitrogen for growth of
BNNTs. Presence of B2N molecules in a B-N gas mixture was verified by our
spectroscopic measurements during a laser ablation of boron-rich targets in
nitrogen. It was shown that the increase of pressure has a quantitative effect
on the mixture composition yielding increase of the precursor density. The
hydrogen addition might open an additional channel of nitrogen supply to
support growth of BNNTs. Nitrogen atoms react with abundant H2 molecules to
form NH2 and then NH3 precursor species, instead of just recombining back to
inert N2 molecules, as in the no-hydrogen case. In addition, thermodynamics was
applied in conjunction with agglomeration theory to predict the size of boron
droplets upon growth of BNNTs. Analytical relations for identification of
crucial species densities were derived.
