Effects of Annealing Parameters on Nickel Catalyst Nanoparticle Size for Carbon Nanotube Synthesis Applications

Abstract

The properties of carbon nanotubes are dependent, in part, on the size of the catalyst metal nanoparticles from which the carbon nanotubes are grown. Annealing is a common technique for forming the catalyst nanoparticles from deposited films. While there is ample work connecting catalyst film properties or catalyst nanoparticle properties to carbon nanotube growth outcomes, the control of catalyst nanoparticle size by means other than the variation of initial film thickness is less explored. This work develops an empirical correlation for the control of nickel nanoparticle equivalent diameter by modification of anneal plateau temperature and anneal plateau time, thereby providing an additional avenue of control for catalyst properties. It has been hypothesized that the size of catalyst nanoparticles can be predetermined by appropriate selection of the initial catalyst film thickness, plateau temperature, and plateau time of the annealing process. To this end, buffer layers of 50 nm titanium, followed by 20 nm aluminum, were deposited onto silicon substrates via electron beam evaporation. Nickel catalyst layers were then deposited with thicknesses of either 5, 10, or 20 nm. Samples of each of the three nickel layer thicknesses were annealed in an ambient air environment at different combinations of 500, 600, 700, 800, and 900 °C plateau temperature and 5, 10, and 15 minute plateau time. Representative time-temperature curves corresponding to each plateau temperature were also acquired. The end result was a set of 45 samples, each with a unique combination of initial nickel film thickness, anneal plateau temperature, and anneal plateau time. Resulting nanoparticles were characterized by atomic force microscopy, and distributions of nanoparticle equivalent diameter were collected via a watershed algorithm implemented by the Gwyddion software package. Comparison of the 45 parameter combinations revealed a wide range of nanoparticle sizes. In most cases, comparable equivalent diameters were obtained from a variety of parameter combinations. Thus, results provide multiple options for achieving the same nanoparticle diameter, for use in cases where additional restraints are present. To facilitate such decisions, a correlation was developed that connected catalyst nanoparticle diameter to the three process parameters of initial catalyst film thickness, anneal plateau temperature, and anneal plateau time. For example, a given initial Ni film thickness can be annealed to a specified nanoparticle size by selecting anneal plateau temperature and plateau time per the correlation, provided that comparable buffer layers were chosen. This correlation provides a more robust array of options for specification of catalyst nanoparticle size and final carbon nanotube properties for a specific application.