Determining Gas Composition for Growth of BNNTs Using Thermodynamic Approach

TL;DR

This study uses thermodynamic calculations and spectroscopic measurements to identify key nitrogen precursor species, especially B2N molecules, in the high-yield production of BNNTs, revealing how pressure and hydrogen influence growth conditions.

Contribution

It provides a comprehensive thermodynamic analysis of B-N gas mixtures, highlighting the role of B2N molecules and the effects of pressure and hydrogen on BNNT growth.

Findings

B2N molecules are major nitrogen sources for BNNT growth

Increased pressure raises precursor density and droplet size

Hydrogen addition facilitates nitrogen supply via NH3 formation

Abstract

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.