Impurity Location-Dependent Relaxation Dynamics of Cu:CdS Quantum Dots

Various types of 2% Cu-incorporated CdS (Cu:CdS) quantum dots (QDs) with very similar sizes have been prepared via a water soluble colloidal method. The locations of Cu impurities in CdS host nanocrystals have been controlled by adopting three different synthetic ways of doping, exchange, and adsorption to understand the impurity location-dependent relaxation dynamics of charge carriers. The oxidation state of incorporated Cu impurities has been found to be +1 and the band-gap energy of Cu:CdS QDs decreases as Cu₂S forms at the surfaces of CdS QDs. Broad and red-shifted emission with a large Stokes shift has been observed for Cu:CdS QDs as newly produced Cu-related defects become luminescent centers. The energetically favored hole trapping of thiol molecules, as well as the local environment, inhibits the radiative recombination processes of Cu:CdS QDs, thus resulting in low photoluminescence. Upon excitation, an electron is promoted to the conduction band, leaving a hole on the valence band. The hole is transferred to the Cu⁺ d-state, changing Cu⁺ into Cu²⁺, which then participates in radiative recombination with an electron. Electrons in the conduction band are ensnared into shallow-trap sites within 52 ns. The electrons can be further captured on the time scale of 260 ns into deep-trap sites, where electrons recombine with holes in 820 ns. Our in-depth analysis of carrier relaxation has shown that the possibilities of both nonradiative recombination and energy transfer to Cu impurities become high when Cu ions are located at the surface of CdS QDs.