A simple combinatorial method aiding research on single-walled carbon nanotube growth on substrates

Establishing fabrication methods of carbon nanotubes (CNTs) is essential to realize many applications expected for CNTs. Catalytic growth of CNTs on substrates by chemical vapor deposition (CVD) is promising for direct fabrication of CNT devices, and catalyst nanoparticles play a crucial role in such growth. We have developed a simple method called "combinatorial masked deposition (CMD)", in which catalyst particles of a given series of sizes and compositions are formed on a single substrate by annealing gradient catalyst layers formed by sputtering through a mask. CMD enables preparation of hundreds of catalysts on a wafer, growth of single-walled CNTs (SWCNTs), and evaluation of SWCNT diameter distributions by automated Raman mapping in a single day. CMD helps determinations of the CVD and catalyst windows realizing millimeter-tall SWCNT forest growth in 10 min, and of growth curves for a series of catalysts in a single measurement when combined with realtime monitoring. A catalyst library prepared using CMD yields various CNTs, ranging from individuals, networks, spikes, and to forests of both SWCNTs and multi-walled CNTs, and thus can be used to efficiently evaluate self-organized CNT field emitters, for example. The CMD method is simple yet effective for research of CNT growth methods. © 2010 The Japan Society of Applied Physics.

The role of the catalytic particle in the growth of carbon nanotubes by plasma enhanced chemical vapor deposition

Vertically aligned carbon nanotubes were synthesized by plasma enhanced chemical vapor deposition using nickel as a metal catalyst. High resolution transmission electron microscopy analysis of the particle found at the tip of the tubes reveals the presence of a metastable carbide Ni3C. Since the carbide is found to decompose upon annealing at 600 degreesC, we suggest that Ni3C is formed after the growth is stopped due to the rapid cooling of the Ni-C interstitial solid solution. A detailed description of the tip growth mechanism is given, that accounts for the composite structure of the tube walls. The shape and size of the catalytic particle determine the concentration gradient that drives the diffusion of C atoms across and though the metal. (C) 2004 American Institute of Physics.

Twin plane re-entrant mechanism for catalytic nanowire growth.

A twin-plane based nanowire growth mechanism is established using Au catalyzed Ge nanowire growth as a model system. Video-rate lattice-resolved environmental transmission electron microscopy shows a convex, V-shaped liquid catalyst-nanowire growth interface for a ⟨112⟩ growth direction that is composed of two Ge {111} planes that meet at a twin boundary. Unlike bulk crystals, the nanowire geometry allows steady-state growth with a single twin boundary at the nanowire center. We suggest that the nucleation barrier at the twin-plane re-entrant groove is effectively reduced by the line energy, and hence the twin acts as a preferential nucleation site that dictates the lateral step flow cycle which constitutes nanowire growth.

Growth of highly-quality single-wall carbon nanotubes without amorphous carbon formation

A simple way to deposit single-wall carbon nanotubes by CVD without the co-deposition of unwanted a-C was demonstrated. It was found that the catalytic deposition of SWCNTs occurs at a substantial rate compared to the self-pyrolysis of the hydrocarbon gas used.

Direct growth of horizontally aligned carbon nanotubes between electrodes and its application to field-effect transistors

This paper presents direct growth of horizontally aligned carbon nanotubes (CNTs) between two predefined various inter-spacing up to tens of microns of electrodes (pads) and its use as CNT field-effect transistors (CNT-FETs). The catalytic metals were prepared, consisting of iron (Fe), aluminum (Al) and platinum (Pt) triple layers, on the thermal silicon oxide substrate (Pt/Al/Fe/SiO2). Scanning electron microscopy measurements of CNT-FETs from the as-grown samples showed that over 80% of the nanotubes are grown across the catalytic electrodes. Moreover, the number of CNTs across the catalytic electrodes is roughly controllable by adjusting the growth condition. The Al, as the upper layer on Fe electrode, not only plays a role as a barrier to prevent vertical growth but also serves as a porous medium that helps in forming smaller nano-sized Fe particles which would be necessary for lateral growth of CNTs. Back-gate field effect transistors were demonstrated with the laterally aligned CNTs. The on/off ratios in all the measured devices are lower than 100 due to the drain leakage current. ©2010 IEEE.

Kinetic control of catalytic CVD for high-quality graphene at low temperatures.

Low-temperature (∼600 °C), scalable chemical vapor deposition of high-quality, uniform monolayer graphene is demonstrated with a mapped Raman 2D/G ratio of >3.2, D/G ratio ≤0.08, and carrier mobilities of ≥3000 cm(2) V(-1) s(-1) on SiO(2) support. A kinetic growth model for graphene CVD based on flux balances is established, which is well supported by a systematic study of Ni-based polycrystalline catalysts. A finite carbon solubility of the catalyst is thereby a key advantage, as it allows the catalyst bulk to act as a mediating carbon sink while optimized graphene growth occurs by only locally saturating the catalyst surface with carbon. This also enables a route to the controlled formation of Bernal stacked bi- and few-layered graphene. The model is relevant to all catalyst materials and can readily serve as a general process rationale for optimized graphene CVD.

Introducing carbon diffusion barriers for uniform, high-quality graphene growth from solid sources.

Carbon diffusion barriers are introduced as a general and simple method to prevent premature carbon dissolution and thereby to significantly improve graphene formation from the catalytic transformation of solid carbon sources. A thin Al2O3 barrier inserted into an amorphous-C/Ni bilayer stack is demonstrated to enable growth of uniform monolayer graphene at 600 °C with domain sizes exceeding 50 μm, and an average Raman D/G ratio of <0.07. A detailed growth rationale is established via in situ measurements, relevant to solid-state growth of a wide range of layered materials, as well as layer-by-layer control in these systems.

Growth kinetics and uniform scaling-up of graphene synthesis

Chemical vapor deposition on copper is the most widely used method to synthesize graphene at large scale. However, the clear understanding of the fundamental mechanisms that govern this synthesis is lacking. Using a vertical-flow, cold-wall reactor with short gas residence time we observe the early growths to study the kinetics of chemical vapor deposition of graphene on copper foils and demonstrate uniform synthesis at wafer scale. Our results indicate that the growth is limited by the catalytic dissociative dehydrogenation on the surface and copper sublimation hinders the graphene growth. We report an activation energy of 3.1 eV for ethylene-based graphene synthesis. © The Electrochemical Society.

Evaluation of bimetallic catalysts for the growth of carbon nanotube forests

We systematically study the growth of carbon nanotube forests by chemical vapor deposition using evaporated monometallic or bimetallic Ni, Co, or Fe films supported on alumina. Our results show two regimes of catalytic activity. When the total thickness of catalyst is larger than nominally 1nm, bimetallic catalysts tend to outperform the equivalent layers of a single metal, yielding taller forests of multi-walled carbon nanotubes (CNTs). In contrast, for layers thinner than ~1nm, bimetallic catalysts are notably less active than individually. However, the amount of small diameter and single-walled CNTs is significantly increased. This possible transition at ~1nm might be related to different catalyst composition after annealing, depending whether or not the films overlap during evaporation and alloy during catalyst formation. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Co-catalytic absorption layers for controlled laser-induced chemical vapor deposition of carbon nanotubes.

The concept of co-catalytic layer structures for controlled laser-induced chemical vapor deposition of carbon nanotubes is established, in which a thin Ta support layer chemically aids the initial Fe catalyst reduction. This enables a significant reduction in laser power, preventing detrimental positive optical feedback and allowing improved growth control. Systematic study of experimental parameters combined with simple thermostatic modeling establishes general guidelines for the effective design of such catalyst/absorption layer combinations. Local growth of vertically aligned carbon nanotube forests directly on flexible polyimide substrates is demonstrated, opening up new routes for nanodevice design and fabrication.