An effect of gas-phase reactions on the vertically aligned CNT growth by temperature gradient chemical vapor deposition

Abstract

Gas-phase reactions among carbon precursors could have a significant effect on the catalytic synthesis of vertically aligned (VA-) carbon nanotubes (CNTs). State-of-the-art adjustment of the gas-phase reaction conditions is done ad hoc with low reproducibility, ascribed partly to an incomplete understanding of the mechanism how the gas-phase reaction influences the growth kinetics of VA-CNTs. Here, we investigate this mechanism and propose that in the presence of prominent gas-phase reaction, the growth kinetics characterization shifts from a single rate-limiting reaction to a multi-route reaction with each pathway having its own rate-limiting step. The rate of the gas-phase reaction could be tailored by the partial pressure and thermal history of a carbon feedstock (e.g., acetylene). According to in-situ mass spectrometry and numerical simulation, a rich set of thermally rearranged secondary species (e.g., C4H4 and C6H6) are found above the catalyst surface. It appears that these secondary species, along with a chief precursor (C2H2), can give variation to a yield of CNTs through various reaction pathways with altering the overall growth rate of VA-CNTs. Our findings would further the current understanding of the VA-CNT growth from thermally rearranged precursors, instrumental to applications such as diameter-controlled growth and CMOS-compatible low-temperature growth.