Direct-current plasma-enhanced chemical vapor deposition (CVD) with mixtures of acetylene and ammonia was optimized to synthesize aligned carbon nanotubes (CNTs) on Co- or Ni-covered W wires with regard to wire temperature, wire diameter, gas pressure, and sample bias. A phase diagram of CNT growth was established experimentally in this optimization process. It was revealed by transmission electron microscopy that Co-catalyzed CNTs encapsulated a Co carbide nanoparticle at their tip, disagreeing with a previous report that Co particles were located at the base of CNTs CVD grown on Co-covered Si substrates [C. Bower et al., Appl. Phys. Lett. 77, 2767 (2000)]. This leads to the conclusion that the formation mechanism of aligned CNTs depends significantly on the catalyst support material as well as the catalyst material itself. Since the sample bias strongly affected the morphology of CNTs, the selective supply of positive ions to CNT tips was possibly responsible for the alignment of growing CNTs.
New structural features observed in heat-treated vapor-grown carbon fibers (VGCF's), produced by the thermal decomposition of hydrocarbon vapor, are reported using image analysis of the lattice plane structure observed by transmission electron microscopy (TEM) and atomic force microscopy (AFM). The TEM lattice image of well-ordered graphite fibers (heat-treated VGCF's at 2800 °C) was treated by a two-dimensional fast Fourier transform, showing sharp bright spots associated with the 002 and 100 lattice planes. The heat-treated VGCF's consist of a polygonally shaped shell, and the long and short fringe structures in the TEM lattice image reflect the 002 and 100 lattice planes, respectively. From this analysis, new facts about the lattice structure are obtained visually and quantitatively. The 002 lattice planes remain and are highly parallel to each other along the fiber axis, maintaining a uniform interlayer spacing of 3.36 A. The 100 lattice planes are observed to make several inclined angles with the 002 lattice planes relative to the plane normals, caused by the gliding of adjacent graphene layers. This work visually demonstrates coexistence of the graphitic stacking, as well as the gliding of the adjacent graphene layers, with a gliding angle of about 3-20°. These glide planes are one of the dominant stacking defects in heat-treated VGCF's. On the other hand, turbostratic structural evidence was suggested by AFM observations. The structural model of coexisting graphitic, glide, and turbostratic structures is proposed as a transitional stage to perfect three-dimensional stacking in the graphitization process. These structural features could also occur in common carbons and in carbon nanotubes.
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