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We report n-type conductivity in phosphorus ion implanted ultrananocrystalline diamond films annealed at 800 °C and above. The amorphous carbon transits to diamond with an increase of stress after 900 °C annealing, which exhibits lower resistivity with Hall mobility of 143 cm2/Vs. After 1000 °C annealing, the diamond transits to amorphous carbon with the stress release, which has higher carrier concentration and lower Hall mobility. Both P+-implanted nano-sized diamond grains and amorphous carbon give contributions to the n-type conductivity in the films. The microstructure evolution and electrical properties are relative to the hydrogen diffusion and desorption under high temperature annealing.