The nucleation of carbon caps on small nickel clusters is studied using a tight binding model coupled to grand canonical Monte Carlo simulations. It takes place in a well defined carbon chemical potential range, when a critical concentration of surface carbon atoms is reached. The solubility of carbon in the outermost Ni layers, that depends on the initial, crystalline or disordered, state of the catalyst and on the thermodynamic conditions, is therefore a key quantity to control the nucleation.

Controlling the structure of single-wall carbon nanotubes during their synthesis by chemical vapor deposition remains a challenging issue. Here, using a specific synthesis protocol and ex situ transmission electron microscopy, we perform a statistical analysis of the structure of the tubes and of the catalyst particles from which they grow. We discriminate two nucleation modes, corresponding to different nanotube-particle junctions, that occur independently of the particle size. With the support of tight binding calculations, we show that a direct control of the nanotube diameter by the particle can only be achieved under growth conditions close to thermodynamic equilibrium.