Engineering vertically aligned carbon nanotube growth by decoupled thermal treatment of precursor and catalyst.

We study synthesis of vertically aligned carbon nanotube (CNT) "forests" by a decoupled method that facilitates control of the mean diameter and structural quality of the CNTs and enables tuning of the kinetics for efficient growth to forest heights of several millimeters. The growth substrate temperature (T(s)) primarily determines the CNT diameter, whereas independent and rapid thermal treatment (T(p)) of the C(2)H(4)/H(2) reactant mixture significantly changes the growth rate and terminal forest height but does not change the CNT diameter. Synchrotron X-ray scattering is utilized for precise, nondestructive measurement of CNT diameter in large numbers of samples. CNT structural quality monotonically increases with T(s) yet decreases with T(p), and forests grown by this decoupled method have significantly higher quality than those grown using a conventional single-zone tube furnace. Chemical analysis reveals that the thermal treatment generates a broad population of hydrocarbon species, and a nonmonotonic relationship between catalyst lifetime and T(p) suggests that certain carbon species either enhance or inhibit CNT growth. However, the forest height kinetics, as measured in real-time during growth, are self-similar, thereby indicating that a common mechanism of growth termination may be present over a wide range of process conditions.