We assess bithiophene (C8H6S2) as a novel sulfur-based promotor for the growth of single-walled carbon nanotubes (SWCNTs) in the aerosol (floating catalyst) CVD method. Technologically suitable equilibrium vapor pressure and an excess of hydrocarbon residuals formed under its decomposition make bithiophene an attractive promoter for the production of carbon nanotubes in general and specifically for ferrocene-based SWCNT growth. Indeed, we detect a moderate enhancement in the carbon nanotube yield and a decrease in the equivalent sheet resistance of the films at a low bithiophene content, indicating the improvement of the product properties. Moreover, the relatively high concentrations and low temperature stability of bithiophene result in non-catalytical decomposition, leading to the formation of pyrolytic carbon deposits; the deposits appear as few-layer graphene structures. Thus, bithiophene pyrolysis opens a route for the cheap production of hierarchical composite thin films comprising carbon nanotubes and few-layer graphene, which might be of practical use for hierarchical adsorbents, protective membranes, or electrocatalysis.
We examined the effect of hydrogen on the growth of single-walled carbon nanotubes in the aerosol (a specific case of the floating catalyst) chemical vapor deposition process using ethylene as a carbon source and ferrocene as a precursor for a Fe-based catalyst. With a comprehensive set of physical methods (UV-vis-NIR and Raman spectroscopies, transmission electron microscopy, scanning electron microscopy, differential mobility analysis, and four-probe sheet resistance measurements), we showed hydrogen to inhibit ethylene pyrolysis extending the window of synthesis parameters. Moreover, the detailed study at different temperatures allowed us to distinguish three different regimes for the hydrogen effect: pyrolysis suppression at low concentrations (I) followed by surface cleaning/activation promotion (II), and surface blockage/nanotube etching (III) at the highest concentrations. We believe that such a detailed study will help to reveal the complex role of hydrogen and contribute toward the synthesis of single-walled carbon nanotubes with detailed characteristics.
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