Discriminative detection of bivalent Cu by dual-emission ZnSe quantum dot fluorescence sensing via ratiometric fluorescence measurements

In this work, we showed that 1-thioglycerol (TG)-capped ZnSe quantum dots (QDs) with dual-emission could perform ideal QD fluorescence sensing for ratiometric fluorescence measurements. By comparing the fluorescence ratios at two emission peaks before and after the addition of cations, the discriminative detection of Cu(II) was realized, even in the case of co-existing with large amounts of other sensitive cations, such as Ag(I). The discriminative detection of Cu(II) is accurate with co-existing Ag(I) below 10 mu mol L-1. By a joint investigation of the ionic diffuse dynamics and carrier recombination dynamics, we found that the adsorbed layer of QDs plays a key role in the discriminative detection of Cu(II) from Ag(I) or other sensitive cations. The moderate adsorption capacity with a QD adsorbed layer makes Cu(II) capable of travelling across the QD double-layer structure, following a surface doping process via chemical reactions between Cu(II) and the QD surface atoms. As a result of Cu(II) doping, there were three major carrier recombination channels: the non-radiation recombination between the QD conduction band to the Cu(II) energy level, together with the non-radiation recombination and radiation recombination between the trap state energy levels and the Cu(II) energy level. As for Ag(I) and other sensitive cations, they have a strong adsorption capacity with the QD adsorbed layer, making them mainly present on the adsorbed layer. Due to the blocking of the ligand layer, we only observed weak coupling of the ZnSe conduction band with the Ag(I) energy level via a non-radiation recombination channel.