series of boron-and phosphorus-doped silicon wafers are used to prepare a series of doped silicon nanocrystals (nc-Si) by high-energy ball milling with carboxylic acid-terminated surface.The sizes of the nc-Si samples are demonstrated to be ＜5nm.The doping levels of the nc-Si are found to be nonlinearly dependent on the original doping level of the wafers by x-ray photoelectron spectroscopy measurement.It is found that the nonlinear doping process will lead to the nonlinear chemical passivation and photoluminescence (PL) intensity evolution.The doping,chemical passivation and PL mechanisms of the doped nc-Si samples prepared by mechanochemical synthesis are analyzed in detail.