Enhancement Mechanism of the Photoluminescence Quantum Yield in Highly Efficient ZnS-AgIn₅S₈ Quantum Dots with Core/Shell Structures

The optical properties of ZnS-AgIn₅S₈ quantum dots (QDs) with core/shell structures are examined to clarify the enhancement mechanism of the photoluminescence (PL) quantum yield (QY). Two types of QDs are synthesized by varying the concentration of zinc precursors, with alloyed-core (ZnS-AgIn₅S₈, ZAIS), inner-shell (ZnIn₂S₄, ZIS), and outer-shell (ZnS) structures, such as ZAIS/ZIS/ZnS and ZAIS/ZnS. Upon alloying/shelling processes from the preformed AgIn₅S₈ QDs, the evolution of the band gap energy indicates the formation of the solid solution of ZAIS. Due to the difference in the degree of alloying between ZAIS/ZIS/ZnS and ZAIS/ZnS QDs, the blue shift of PL, Stokes shift, and QY are different. The alloying/shelling processes improve the QY of the intrinsic defect states more effectively than the QY of the surface defect states, while the time-resolved studies suggest that the enhanced radiative rate of the intrinsic states is responsible for the improvement of the QY, in addition to the reduced nonradiative rate. In ZAIS/ZIS/ZnS QDs, the QY increases to 85%, which is attributed to the existence of the ZIS layer, as well as the reduced nonradiative states and the enhanced radiative states by the alloying/shelling processes. The ZIS layer mitigates the lattice strains and provides the appropriate levels of the electronic structures in the QDs, which further reduces the nonradiative rate and enhances the radiative rate, respectively, leading to the unprecedentedly high PL QY of ZAIS/ZIS/ZnS QDs.