* Patterned Growth:

Focused ion beam milling as a universal template technique for patterned growth of carbon nanotubes
Ying Chen, Hua Chen, Jun Yu, James S. Williams and Vince Craig

APPLIED PHYSICS LETTERS 90, 093126 (2007)

Abstract Focused ion beam (FIB) milling system has been used to create nanosized patterns as the template for patterned growth of carbon nanotubes on Si substrate surface without predeposition of metal catalysts. Carbon nanotubes only nucleate and grow on the template under controlled pyrolysis of iron phthalocyanine at 1000 °C. The size, growth direction, and density of the patterned nanotubes can be controlled under different growth conditions and template sizes. Atomic force microscopy and electron microscopy analyses reveal that the selective growth on the FIB template is due to its
special surface morphology and crystalline structure.

 

Patterned growth of carbon nanotubes on Si substrates without predeposition of metal catalysts
Y. Chen and J. Yu
APPLIED PHYSICS LETTERS 87, 033103 (2005)

Abstract:Aligned carbon nanotubes (CNTs) can be readily synthesized on quartz or silicon-oxide-coated Si substrates using a chemical vapor deposition method, but it is difficult to grow them on pure Si substrates without predeposition of metal catalysts. We report that aligned CNTs were grown by pyrolysis of iron phthalocyanine at 1000 °C on the templates created on Si substrates with simple mechanical scratching. Scanning electron microscopy and x-ray energy spectroscopy analysis revealed that the trenches and patterns created on the surface of Si substrates were preferred nucleation sites for nanotube growth due to a high surface energy, metastable surface structure, and possible capillarity effect. A two-step pyrolysis process maintained Fe as an active catalyst.

* Controlled Growth:

Improved growth of aligned carbon nanotubes by mechanical activation
Y. Chen and L.T. Chadderton
Journal of Materials Research, Vol. 19, No. 10, Oct 2004

Abstract: Straight aligned carbon nanotubes with multiwalled cylindrical structure have been produced by pyrolysis of iron phthalocyanine (FePc) after ball milling treatment. The pre-ball milling treatment prevented the formation of curved nanotubes with bamboo or conelike structures. X-ray diffraction analysis revealed that the milled FePc has an activated and disordered structure, which contributes a lower vaporization temperature determined by thermal gravimetric analysis. The low formation temperature and an increased nanotube growth rate are favorable to the formation of cylindrical structure than bamboo tubes.

* Solid-state Formation:

The nucleation and growth of carbon nanotubes in a mechano-thermal process

Y. Chen, M.J. Conway, J.D. FitzGerald, J.S. Williams, L.T. Chadderton

Carbon, 42 (2004) 1543

Abstract:

Separate nucleation and growth processes of carbon nanotubes were found in a mechano-thermal method in which carbon nanotubes are produced by first mechanical milling of graphite powder at room temperature and subsequent thermal annealing up to 1400 C. The ball-milled graphite contains nucleation structures (nanosized metal particles and deformed (0 0 2) layers containing pentagons), and disordered carbon as a free carbon atom source. The subsequent annealing activates the growth of two types of multi-walled nanotubes in the absence of carbon vapor. Thin nanotubes (diameter <20 nm) are formed via crystallization of the disordered carbon with the preferred formation of the (0 0 2) basal planes. Thick nanotubes (diameter >20 nm) are formed through a metal catalytic solution–precipitation process (solid–liquid–solid). In both cases, carbon nanotubes grew out from disordered carbon particles with closed tips.