Study of the catalyst evolution during annealing preceding the growth of carbon nanotubes by microwave plasma-enhanced chemical vapour deposition

A two-step catalyst annealing process is developed in order to control the diameter of nickel catalyst particles for the growth of carbon nanotubes (CNTs) by microwave plasma-enhanced chemical vapour deposition (MW PECVD). Thermal annealing of a continuous nickel film in a hydrogen (H2) environment in a first step is found to be insufficient for the formation of nanometre-size, high-density catalyst particles. In a second step, a H2 MW plasma treatment decreases the catalyst diameter by a factor of two and increases the particle density by a factor of five. An x-ray photoelectron spectroscopy study of the catalyst after each step in the annealing process is presented. It is found that the catalyst particles interact with the substrate during thermal annealing, thereby forming a silicate, even if a buffer layer in between the catalyst and the substrate is intended to prevent silicate formation. The silicate formation and reduction is shown to be directly related to the CNT growth mechanism, determining whether the catalyst particles reside at the base or the tip of the growing CNTs. The catalyst particles are used for the growth of a high-density CNT coating by MW PECVD. CNTs are analysed with electron microscopy and Raman spectroscopy.