Control of Energy Flow Dynamics between Tetracene Ligands and PbS Quantum Dots by Size Tuning and Ligand Coverage

We have prepared a series of samples with the ligand 6,13-bistri(iso-propyqsilylethynyl tetracene 2-carboxylic acid (TIPS-Tc-COOH) attached to PbS quantum dot (QD) samples of three different sizes in order to monitor and control the extent and time scales of energy. low after photoexcitation. Fast energy transfer (similar to 1 ps) to the PbS QD occurs upon direct excitation of the ligand for all sainples. The largest size QD maintains the microsecond exciton lifetime characteristic of the as-prepared oleate terminated PbS QDs. However, two smaller QD sizes with lowest exciton energies similar to or larger than the TIPS-Tc-OOOO- triplet energy transfer between QD core and ligand triplet on nanosecond to microsecond timescales. For the intermediate size QDs in particular, energy can be recycled many times,between ligand and core, but the triplet remains the dominant excited species at long times, living for similar to 3 mu s for fully exchanged QDs and up to 30 mu s for partial ligand exchange, which is revealed as a method for controlling the triplet lifetime. A unique upconverted luminescence spectrum is observed that results from annihilation of triplets after exclusive excitation of the QD core.