The deposition of boron nitride nanomaterials and ultrathin films in high vacuum conditions (1×10-1×10 Torr) using molecular borazine as well as pre-dissociated borazine has been investigated with the motivation of studying the nucleation efficiency of BN under high vacuum conditions. Molecular borazine displays negligible sticking probability on Si(1 1 1) 7×7 at room temperature. Pre-adsorbing the borazine on silicon at 140 K and subsequent annealing is effective in forming ultrathin hexagonal films on the sample. It is possible to nucleate BN nanomaterials on nickel-sputtered silicon with high efficiency if the borazine is first discharged in a radio-frequency plasma to form reactive radicals. High quality crystalline h-BN thin films, as well as BN nanotubes can be formed on nickel via this approach. © 2002 Elsevier Science B.V. All rights reserved.