Mechanistic Understanding and Rational Design of Quantum Dot/Mediator Interfaces for Efficient Photon Upconversion.

The semiconductor-nanocrystal-sensitized, three-component upconversion system has made great strides over the past 5 years. The three components (i.e., triplet photosensitizer, mediator, and emitter) each play critical roles in determining the input and output photon energy and overall quantum efficiency (QE). The nanocrystal photosensitizer converts the absorbed photon into singlet excitons and then triplet excitons via intersystem crossing. The mediator accepts the triplet exciton via either direct Dexter-type triplet energy transfer (TET) or sequential charge transfer (CT) while extending the exciton lifetime. Through a second triplet energy-transfer step from the mediator to the emitter, the latter is populated in its lowest excited triplet state. Triplet-triplet annihilation (TTA) between two triplet emitters generates the emitter in its bright singlet state, which then emits the upconverted photon. Quantum dots (QD) have a tunable band gap, large extinction coefficient, and small singlet-triplet energy losses compared to metal-ligand charge-transfer complexes. This high triplet exciton yield makes QDs good candidates for photosensitizers. In terms of driving triplet energy transfer, the triplet energy of the mediator should be slightly lower than the triplet exciton energy of the QD sensitizer for a downhill energy landscape with minimal energy loss. The same energy cascade is also required for the transfer from the mediator to the emitter. Finally, the triplet energy of the emitter must be slightly larger than one-half of its singlet energy to ensure that TTA is exothermic. Optimization of the sensitizer, mediator, and emitter will lead to an increase in the anti-Stokes shift and the total quantum efficiency. Evaluating each individual step's efficiency and kinetics is necessary for the understanding of the limiting factors in existing systems.This review summarizes chalcogenide QD-based photon upconversion systems with a focus on the mechanistic aspects of triplet energy transfer conducted by the Tang and Lian groups. Via time-resolved spectroscopy, the rates and major loss pathways associated with the two triplet energy-transfer steps were identified. The studies are focused on the near-infrared (NIR) to visible (VIS) PbS-tetracene-based systems as they allow systematic control of the QD, mediator, and emitter. Our results show that the mediator triplet state is mostly formed by direct TET from the QD and the transfer rate is influenced by the density of bound mediator molecules. Charge transfer, a loss pathway, does not produce triplet excitons and can be minimized by adding an inert shell to the QD. This transfer rate decreases exponentially with the distance between the QD and mediator molecule. The second TET rate was found to be much slower than the diffusion-limited collision rate, which results in the triplet lifetime of the mediator being the main factor limiting its efficiency. Finally, the total quantum efficiency can be calculated using these measured quantities including the TET1 and TET2 efficiencies. The agreement between calculated and measured quantum efficiencies suggests a firm understanding of QD-sensitized photon upconversion. We believe the above conclusions are general and should be widely applicable to similar systems, including singlet fission in hybrid organic-nanocrystal materials.