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CHEMICAL VAPOUR DEPOSITION METHOD FOR SYNTHESIS OF CARBONNANOTUBES.( A sufficient or commercialize method for synthesis)
While the arc discharge method is capable of producing large quantities of unpurified nanotubes, significant effort is being directed towardsproduction processes that offer more controllable routes to the nanotubesynthesis. A class of processes that seems to offer the best chance toobtain a controllable process for the selective production of nanotubeswith predefined properties is chemical vapour deposition (CVD) . Theformation of carbon filaments from the catalytic decomposition of carbon-containing gas over metal surfaces has been known for a long time.However, there was no evidence that this technique could be used tosynthesize carbon nanotubes until Yacamàn
et al
. succeeded. 
© Trisha Banerjee , 2011
 Today, the catalytic chemical vapour deposition (CCVD) method isconsidered as the only economically viable process for large-scale CNTproduction and the integration of CNTs into various devices as it is shownby the large-scale production of quite pure carbon nanotubes by NANOCYLfounded by one of the authors.In principle, chemical vapour deposition is the catalytic decomposition of hydrocarbon or carbon monoxide feedstock with the aid of supportedtransition metal catalysts. Generally, the experiment is carried out in aflow furnace at atmospheric pressure. There are two types of furnacemodality, one is a horizontal configuration, the second is a verticalconfiguration (Figure 11). The application of horizontal furnace is the mostpopular. Here the catalyst is placed in a ceramic or quartz boat which isput into a quartz tube. The reaction mixture containing a source of hydrocarbon and an inert gas is passed over the catalyst bed attemperatures ranging from 500 °C to 1100 °C. The system is then cooleddown to room temperature. The vertical furnace configuration is usuallyemployed for the continuous mass production of carbon fibers/nanotubes. The catalyst and carbon source is injected at the top of the furnace andthe resultant filaments grow during flight and are collected at the bottomof the chamber. Ultrafine metal catalyst particles are either introducedinto the reactor directly or formed
in situ
using precursors such asmetallocenes. The fluidized bed reactor is a variation of the verticalfurnace. Supported catalysts are usually placed in the center of thefurnace and an upward flow of carbon feedstock gases is used. Thefluidization process involves the supported catalysts to remain muchlonger in the furnace than in the vertical floating tehnique. The generalnanotube growth mechanism in the CVD process involves the dissociationof hydrocarbon molecules catalyzed by the transition metal, and thesaturation of carbon atoms in the metal nanoparticle. The precipitation of 
 
carbon from the metal particle leads to the formation of tubular carbonsolids in a sp2 structure. The characteristics of the carbon nanotubesproduced by CVD method depend on the working conditions such as thetemperature and the operation pressure, the kind, volume andconcentration of hydrocarbon, the nature, size and the pretreatment of metallic catalyst, the nature of the support and the reaction time. Byvarying the active particles on the surface of the catalyst, the nanotubediameter can be controlled. The length of the tubes depends on thereaction time; even up to 60 mm long tubes can be produced. 
Figure 11.
Schematic demonstration of CVD method. (a) Horizontalfurnace. (b) Vertical furnace. (c) Fluidized bed reactor. 
©Trisha Banerjee , 2011
Using CVD method, several structural forms of carbon are formedsuch as amorphous carbon layers on the surface of the catalyst, filamentsof amorphous carbon, graphite layers covering metal particles, SWNTsand MWNTs made from well-crystallized graphite layers. This methodallows selective CNT growth in a variety of forms, such as powder andaligned forrest of CNTs . The produced tubes can adopt various shapes;they can be straight, curved, planar-spiral, and helix, often with aremarkably constant pitch. The fibers often have an amorphous carboncoating, and metal particles are sometimes found at their tips. Inparticular, CCVD provides the possibility of growing CNTs from controlledsurface sites by catalyst patterning on a desired substrate. This permitsspecific applications, e.g., field-emission displays, specific architecture of a nanotube device or probe tips of scanning probe microscopes (SPM).Planar arrays of aligned nanotubes over large areas with sufficiently highdensity and order have been also grown on single-crystal substrates of sapphire or quartz, which for instance enable their easy integration intohigh-performance planar devices . In Table 3, the formation of variouskinds of carbonaceous materials is listed regarding to the different CVDmethods and different reaction conditions.
Table 3.
Summary of the articles reporting CVD production of carbonnanoarchitectures.
 
 
©Trisha Banerjee , 2011
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