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In this study we present an investigation of the bias-enhanced nucleation and early stages of diamond growth on molybdenum. The progression of the different stages of the nucleation and growth was observed using photoelectron spectroscopy with excitation energies in the ultraviolet and x-ray regime. Subsequent to the film deposition the samples were transferred to the analysis chamber without breaking the vacuum. To achieve high nuclei densities methane concentrations in excess of about 20% diluted in hydrogen and a dc bias of -400 V are required. During the bias-enhanced nucleation period a molybdenum carbide interface is formed and the codeposition of a graphitic carbon layer and diamond is observed. The graphitic carbon layer is subsequently removed during the diamond growth step, where deposition conditions conducive of diamond growth are maintained and a continuous diamond film is formed after 40 min. The results are compared with those obtained for the bias-enhanced nucleation on silicon. © 1998 American Institute of Physics.