Ultra-small PbS nanocrystals as sensitizers for red-to-blue triplet-fusion upconversion
Christian J. Imperiale, Philippe B. Green, Minhal Hasham, Mark W. B. Wilson
Abstract
: 637 nm); a demonstration of nanocrystal-sensitized upconversion photochemistry. Time-resolved spectroscopy and kinetic modelling clarify key loss channels, highlighting the benefit of long-lifetime nanocrystal sensitizers, but revealing that many (48%) excitons that reach triplet-extracting carboxyphenylanthracene ligands decay before they can transfer to free-floating acceptors-emphasizing the need to address the reduced lifetimes that we determine for molecular triplets near the nanocrystal surface. Finally, we find that the inferred thermodynamics of triplet sensitization from these ultra-small PbS quantum dots are surprisingly favourable-completing an advantageous suite of properties for upconversion photochemistry-and do not vary significantly across the ensemble, which indicates minimal effects from nanocrystal heterogeneity. Together, our demonstration and study of red-to-blue upconversion using ultra-small PbS nanocrystals in a quasi-equilibrium, mildly endothermic sensitization scheme offer design rules to advance implementations of triplet fusion, especially where large anti-Stokes wavelength shifts are sought.