Single-Particle Dynamics of ZnS Shelling Induced Replenishment of Carrier Diffusion for Individual Emission Centers in CuInS2 Quantum Dots

Insights into blinking and photoactivation of aqueous copper indium sulfide (CIS) quantum dots have been obtained using fluorescence correlation spectroscopy (FCS) and fluorescence lifetime correlation spectroscopy (FLCS). An unusual excitation wavelength-dependence of photoactivation/photocorrosion is manifested in an increase in the initial correlation amplitude G(0) for λex = 532 nm, but a decrease for λex = 405 nm. This has been rationalized in terms of different contributions from surface-assisted recombination in the two cases. Blinking times obtained from the autocorrelation functions (ACFs) of the 100-200 ns lifetime component (core Cu-mediated recombination) are almost unaffected by shelling, but those from the ACF for the 10-30 ns lifetime (surface states) increase significantly. Absence of cross-correlation between the two recombinative states of bare CIS QDs and the emergence of an anticorrelation with the introduction of the ZnS shell are observed, indicating the diffusive nature of the two states for CIS-ZnS. The diffusion is inhibited in bare CIS QDs due to the preponderance of surface states.