Akinari Kozawa

Unveiling the Evolutions of Nanotube Diameter Distribution during the Growth of Single-Walled Carbon Nanotubes

In situ and ex situ Raman measurements were used to study the dynamics of the populations of single-walled carbon nanotubes (SWCNTs) during their catalytic growth by chemical vapor deposition. Our study reveals that the nanotube diameter distribution strongly evolves during SWCNT growth but in dissimilar ways depending on the growth conditions. We notably show that high selectivity can be obtained using short or moderate growth times. High-resolution transmission electron microscopy observations support that Ostwald ripening is the key process driving these seemingly contradictory results by regulating the size distribution and lifetime of the active catalyst particles. Ostwald ripening appears as the main termination mechanism for the smallest diameter tubes, whereas carbon poisoning dominates for the largest ones. By unveiling the key concept of dynamic competition between nanotube growth and catalyst ripening, we show that time can be used as an active parameter to control the growth selectivity of carbon nanotubes and other 1D systems.

Synthesis of single-walled carbon nanotubes from Pd catalysts by gas source method using ethanol in high vacuum

We carried out single-walled carbon nanotube (SWCNT) growth at 600 °C using Pd catalysts by the alcohol gas source method. When Pd catalysts deposited on SiO2/Si substrates were used, the G band in the Raman spectra was broad and weak RBM peaks were observed at ethanol pressures between 1 × 10−3 and 1 × 10−1 Pa. On the other hand, using Al2Ox buffer layers, a sharp G band with a shoulder peak (G− peak) and several radial breathing mode (RBM) peaks were observed, which indicates the growth of SWCNTs. Scanning electron microscopy (SEM) observation showed that dense web like SWCNTs were formed, and the diameters of SWCNTs estimated from the wavenumbers of RBM peaks were 1.3–2.9 nm, which were larger than those from Pt catalysts. Transmission electron microscopy (TEM) observation showed that the larger migration distance of Pd caused an enlargement of catalyst particle sizes, resulting in the larger diameters of SWCNTs from Pd catalysts.

Low-temperature growth of single-walled carbon nanotube using Al2O3/Pd/Al2O3 multilayer catalyst by alcohol gas source method at high vacuum

We carried out single-walled carbon nanotube (SWCNT) growth at 500 and 600 °C using Al2O3/Pd/Al2O3 multilayer catalysts on SiO2/Si substrates by the alcohol gas source method. When the ethanol pressures were 1 × 10−4 and 1 × 10−3 Pa, radial-breathing-mode (RBM) peaks and sharp G band peaks appeared in Raman spectra, indicating the growth of SWCNTs even at 500 °C. When the growth temperature and ethanol pressure were 500 °C and 1 × 10−4 Pa, respectively, the growth rate decreased gradually with the growth time, but the SWCNT growth continued for more than 4 h and the diameter distribution changed as the growth proceeded. X-ray photoelectron spectroscopy measurements showed that oxidized Pd catalyst particles were reduced to metallic states after the SWCNT growth started.