Spray coating is proposed as an optional wet method for preparing nano-sized particles suitable for the growth of single-walled carbon nanotubes (SWCNTs). The obtained SWCNT films are characterized by Raman spectroscopy and electron microscopy, and are confirmed to be comparable to SWCNTs produced by the conventional dip-coating process in terms of crystallinity, tube diameter and carbon yield. The mean diameter of SWCNTs can be effectively reduced from 1.85 to 1.35 nm by prolonging the deposition of Mo. In addition, spray coating allows catalyst preparation on supports other than flat wafers, as demonstrated by the synthesis of high-quality SWCNTs on Al2O3 fiber and quartz wool supports.

We propose a unique experimental technique in which isotopically labeled ethanol, e.g., 12CH3–13CH2–OH, is used to trace the carbon atoms during the formation of single-walled carbon nanotubes (SWNTs) by chemical vapor deposition (CVD). The proportion of 13C is determined from Raman spectra of the obtained SWNTs, yielding the respective contribution of ethanol’s two different carbon atoms to SWNT formation. Surprisingly, the carbon away from the hydroxyl group is preferably incorporated into the SWNT structure, and this preference is significantly affected by growth temperature, presence of secondary catalyst metal species such as Mo, and even by the substrate material. These experiments provide solid evidence confirming that the active carbon source is not limited to products of gas-phase decomposition such as ethylene and acetylene, but ethanol itself is arriving at and reacting with the metal catalyst particles. Furthermore, even the substrate or other catalytically inactive species directly influences the formation of SWNTs, possibly by changing the local environment around the catalyst or even the reaction pathway of SWNT formation. These unexpected effects, which are inaccessible by conventional techniques, paint a clearer picture regarding the decomposition and bond breaking process of the ethanol precursor during the entire CVD process and how this might influence the quality of the obtained SWNTs.Keywords: growth mechanism; isotope labeling; precursor decomposition; single-walled carbon nanotube

We demonstrate wide-range diameter modulation of vertically aligned single-walled carbon nanotubes (SWNTs) using a wet chemistry prepared catalyst. In order to ensure compatibility to electronic applications, the current minimum mean diameter of 2 nm for vertically aligned SWNTs is challenged. The mean diameter is decreased to about 1.4 nm by reducing Co catalyst concentrations to 1/100 or by increasing Mo catalyst concentrations by five times. We also propose a novel spectral analysis method that allows one to distinguish absorbance contributions from the upper, middle, and lower parts of a nanotube array. We use this method to quantitatively characterize the slight diameter change observed along the array height. On the basis of further investigation of the array and catalyst particles, we conclude that catalyst aggregation—rather than Ostwald ripening—dominates the growth of metal particles.Keywords: catalyst aggregation; diameter control; single-walled carbon nanotube; vertical alignment