Large stokes shift of Ag doped CdSe quantum dots via aqueous route

Monodispersed and luminescent Ag-doped CdSe semiconductor quantum dots (d-dots) were synthesized by an aqueous route assisted with electrochemical preparation of Se source with 3-mercaptopropionic acid as stabilizer. The silver dopants were incorporated into the host crystals via cation-exchange mechanism. X-ray diffraction patterns revealed that the as-synthesized CdSe:Ag d-dots were well retained in the zinc blende structure. The CdSe:Ag d-dots that exhibited uniform size distribution and good crystallnity could be observed by High-resolution transmission electron microscopy (HRTEM), with average diameter of 2.7 nm. Successful doping was confirmed by X-ray photoelectron spectroscopy survey spectra. The peculiar Ag-related photoluminescence showed strong intensity, and at the same time, intrinsic band-edge exciton emission of CdSe QDs was suppressed. The dopant emission exhibited larger Stockes shift of - 0.51 eV than that of the band-gap emission, and varied from 546 to 583 nm by changing electrolytic time. Possible radiative recombination mechanism of the aqueous Ag-doped CdSe d-dots was discussed. The results demonstrated that doping can be an effective way to manipulate the optical properties of semiconductor nanocrystals.