Multiple population-period transient spectroscopy (MUPPETS) of CdSe/ZnS nanoparticles. I. Exciton and biexciton dynamics.

The nonradiative relaxation of both the exciton and biexciton in CdSe/ZnS core-shell nanoparticles have complicated, nonexponential kinetics. This paper presents data on this system from multiple population-period transient spectroscopy (MUPPETS), a method for two-dimensional kinetics. An initial report of a dispersed (nonexponential) biexciton decay [J. Am. Chem. Soc. 2013, 135, 1002] is confirmed in a more rigorous analysis. Additional transient-grating data allow a quantitative treatment of the full, complex MUPPETS data set. The MUPPETS signal has a strong fluence dependence. With extrapolation to the low fluence limit, the ratio of cross sections for ground-to-exciton and exciton-to-biexciton absorption is found to be close to the predictions of the uncorrelated-electron model. The full two-dimensional MUPPETS data set is reported for the first time and is analyzed to detect heterogeneity in the exciton decay. The exciton has a substantial (>40%) nonradiative decay, but it is not due to a subset of defective particles. A surface relaxation in response to formation of the exciton is suggested. This data set is the first capable of detecting correlations between the biexciton and exciton decay mechanism. None is found.