摘要： Cu-doped ZnSe/ZnS/L-Cys core–shell QDs are prepared by both nucleation doping and growth doping in an aqueous synthesis method. Transport of photogenerated free charge carriers (FCCs) in these Cu-doped QDs is probed via a combination of surface photovoltaic (SPV), photoacoustic (PA), and electric-field-induced SPV techniques, supplemented by the UV–VIS absorption spectrum and Raman spectrum. The results confirm that the two doping mechanisms result in different doping locations and microelectronic structures of the Cu-doped QDs. The distinctive microelectronic structure of the QDs prepared by nucleation doping, as compared with those prepared by growth doping, results in a number of favorable SPV characteristics. For example, the QDs prepared by nucleation doping exhibit a higher SPV response intensity at 600 nm because of a higher concentration of photogenerated FCCs. The ratio of the strongest SPV response and the strongest PA signal of the QDs prepared by nucleation doping is up to 2.41 times greater than those of the QDs prepared by growth doping. This is because the greater numbers of photogenerated FCCs in the QDs prepared by nucleation doping generate the PV effect rather than the PA effect that is caused by a nonradiative de-excitation process. The position of the shoulder peak of the SPV response at a long wavelength of the QDs prepared by nucleation doping is significantly red-shifted compared with that of the QDs prepared by growth doping, leading to a broader SPV response range in the visible region. The QDs prepared by nucleation doping have a more obvious donor feature than those prepared by growth doping.