Influence of pH on luminescence from water-soluble colloidal Mn-doped ZnSe quantum dots capped with different mercaptoacids

Water-soluble ZnSe/ZnS core–shell quantum dots with ZnSe core doped by manganese ions show different luminescence response to pH changes in aqueous solutions depending on the type of solubilizing agents (thioglycolic acid, mercaptoundecanoic acid, sodium mercaptopropylsulfonate). In the case of long-chain mercaptoundecanoic acid only excitonic emission is affected by pH changes. Short-chain thioglycolic acid brings about equal excitonic/Mn emission variations with pH, while mercaptopropylsulfonate-stabilized quantum dots are insensitive to pH. The mechanism discussed here is based on the competition between different relaxation channels for excited excitons in ZnSe: excitonic radiative recombination, energy transfer to Mn ion and the photogenerated electron trapping due to the presence of protonated carboxyl group. ZnSe:Mn/ZnS quantum dots stabilized with long-chain mercaptoacids may be used as a new type of fluorescence ratiometric pH-sensor or indicator.