By controlling the timing and duration of hydrogen exposure in a fixed thermal process, we tuned the diameters of carbon nanotubes (CNTs) within a vertically aligned film by a factor of 2, and tuned the areal densities by an order of magnitude. The CNT structure is correlated with the catalyst morphology, suggesting that while chemical reduction of the catalyst layer is required for growth, prolonged H2 exposure not only reduces the iron oxide and enables agglomeration of the Fe film, but also leads to catalyst coarsening. Control of this coarsening process allows tuning of CNT characteristics.

Carbon nanotubes (CNTs) have been extensively investigated in the last decade because their superior properties could benefit many applications. However, CNTs have not yet made a major leap into industry, especially for electronic devices, because of fabrication challenges. This review provides an overview of state-of-the-art of CNT synthesis techniques and illustrates their major technical difficulties. It also charts possible in situ analyses and new reactor designs that might enable commercialization. After a brief description of the CNT properties and of the various techniques used to synthesize substrate-free CNTs, the bulk of this review analyzes chemical vapor deposition (CVD). This technique receives special attention since it allows CNTs to be grown in predefined locations, provides a certain degree of control of the types of CNTs grown, and may have the highest chance to succeed commercially. Understanding the primary growth mechanisms at play during CVD is critical for controlling the properties of the CNTs grown and remains the major hurdle to overcome. Various factors that influence CNT growth receive a special focus: choice of catalyst and substrate materials, source gases, and process parameters. This review illustrates important considerations for in situ characterization and new reactor designs that may enable researchers to better understand the physical growth mechanisms and to optimize the synthesis of CNTs, thus contributing to make carbon nanotubes a manufacturing reality.

Growth of vertically aligned carbon nanotube (CNT) carpets on metallic substrates at low temperatures was achieved by controlled thermal treatment of ethylene and hydrogen at a temperature higher than the substrate temperature. High-resolution transmission electron microscopy showed that nanotubes were crystalline for a preheating temperature of 770 degrees C and a substrate temperature of 500 degrees C. Conductive atomic force microscopy measurements indicated electrical contact through the CNT carpet to the metallic substrate with an approximate resistance of 35 kOmega for multiwall carpets taller than two micrometers. An analysis of the activation energies indicated that thermal decomposition of the hydrocarbon/hydrogen gas mixture was the rate-limiting step for low-temperature chemical vapor deposition growth of CNTs. These results represent a significant advance toward the goal of replacing copper interconnects with nanotubes using CMOS-compatible processes.