The charge-state control of nitrogen-vacancy (NV) centers in diamond is very important toward its applications because the NV centers undergo stochastic charge-state transitions between the negative charge state (NV) and the neutral charge state (NV0) of the NV center upon illumination. In this letter, engineering of the Fermi level by a nin diamond junction was demonstrated for the control of the charge state of the NV centers in the intrinsic (i) layer region. By changing the size (d) of the i-layer region between the phosphorus-doped n-type layer regions (nin) from 2 μm to 10 μm, we realized the gradual change in the NV charge-state population in the i-layer region from 60% to 80% under 532 nm excitation, which can be attributed to the band bending in the i-layer region. Also, we quantitatively simulated the changes in the Fermi level in the i-layer region depending on d with various concentrations of impurities in the i-layer region.

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