Two Distinct Transitions in Cu_xInS₂ Quantum Dots. Bandgap versus Sub-Bandgap Excitations in Copper-Deficient Structures

Cu-deficient CuInS₂ quantum dots (QDs) synthesized by varying the [Cu]:[In] ratio allow modulation of optical properties as well as identification of the radiative emission pathways. Absorption and emission spectral features showed a strong dependence on the [Cu]:[In] ratio of Cu_xInS₂ QDs, indicating two independent optical transitions. These effects are pronounced in transient absorption spectra. The bleaching of band edge absorption and broad tail absorption bands in the subpicosecond-nanosecond time scale provide further evidence for the dual optical transitions. The recombination process as monitored by photoemission decay indicated the involvement of surface traps in addition to the bandgap and sub-bandgap transitions. Better understanding of the origin of the optical transitions and their influence on the photodynamics will enable utilization of ternary semiconductor quantum dots in display and photovoltaic devices.