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The effects of boron doping on the nucleation behavior and the characteristics of nano-crystalline diamond (NCD) films were investigated. NCD films were prepared by microwave plasma enhanced chemical vapor deposition and were grown on mirror-polished p-type Si(100) substrate by bias enhanced growth technique. The morphologies and bonding structures of the films were characterized by field emission scanning electron microscopy, atomic force microscopy, Raman spectroscopy and X-ray diffraction. The increase in proportion of sp2-bonded grain boundaries in finer grain NCD films is assumed to be the main modifying factor in the electron field emission of the film.