Shell Thickness and Heterogeneity Dependence of Triplet Energy Transfer between Core-Shell Quantum Dots and Adsorbed...

Quantum dot (QD)-sensitized triplet energy transfer (TET) has found promising applications in photon upconversion and photocatalysis. However, the underlying mechanism of TET in the QD-acceptor complex remains unclear despite the well-developed TET theory for the molecular donor-acceptor systems. Herein, the coupling strength of TET from CdSe/CdS core-shell QDs to 9-anthracene carboxylic acid (ACA) was studied by measuring the TET rate as a function of shell thickness with time-resolved photoluminescence. The change of TET-coupling strength with increasing shell thickness was further compared to those of electron and hole transfers from QDs so that we could test whether QD-sensitized TET is mediated by the charge transfer virtual state and can be considered as simultaneous electron and hole transfers as in molecular donor-acceptor systems. The measured coupling strength of TET from the CdSe/CdS QD decreases exponentially with the CdS shell thickness r: |V|(r) = |V|(0)e^-βr, with an exponential decay factor β of 0.19 Å^-1, which is smaller than the sum of the measured decay factors for electron transfer to methyl viologen (0.18 Å^-1) and hole transfer to phenothiazine (0.29 Å^-1) from the same QD. This inconsistency is explained by the broadening of QD shell thicknesses in the distance dependence study, which significantly modifies the TET-coupling strength and driving force, resulting in a shallower distance dependence of the TET rate constants. This study sheds light on the fundamental mechanisms of QD-sensitized TET reactions.