triplet-fusion-upconversion-nanocapsule-synthesis

Triplet Fusion Upconversion Nanocapsule Synthesis

Triplet fusion upconversion (UC) allows for the generation of one high energy photon from two low energy input photons. This well-studied process has ...

Harvard University

Optical upconversion is a net process by which two low energy photons are converted into one higher energy photon. There is vast potential to exploit upconversion in applications ranging from solar energy and biological imaging to data storage and photocatalysis. Here, we link two upconverting chromophores together to synthesize a series of novel tetracene dimers for use as annihilators. When compared with the monomer annihilator, TIPS-tetracene, the dimers yield a strong enhancement in the triplet fusion process, also known as triplet-triplet annihilation, as demonstrated  a large increase in upconversion efficiency and an order of magnitude reduction of the threshold power for maximum yield. Along with the ongoing rapid improvements to sensitizer materials, the dimerization improvements demonstrated here open the way to a wide variety of emerging upconversion applications.

Annihilator dimers enhance triplet fusion upconversion.

Triplet-triplet annihilation upconversion (TTA-UC) is an unconventional photophysical process that yields high-energy photons from low-energy incident light and offers pathways for innovation across many technologies, including solar energy harvesting, photochemistry, and optogenetics. Within aromatic organic chromophores, TTA-UC is achieved through several consecutive energy conversion events that ultimately fuse two triplet excitons into a singlet exciton. In chromophores where the singlet exciton is roughly isoergic with two triplet excitons, the limiting step is the triplet-triplet annihilation pathway, where the kinetics and yield depend sensitively on the energies of the lowest singlet and triplet excited states. Herein we report up to 40-fold improvements in upconversion quantum yields using molecular engineering to selectively tailor the relative energies of the lowest singlet and triplet excited states, enhancing the yield of triplet-triplet annihilation and promoting radiative decay of the resulting singlet exciton. Using this general and effective strategy, we obtain upconversion yields with red emission that are among the highest reported, with remarkable chemical stability under ambient conditions.

Molecular Engineering of Chromophores to Enable Triplet-Triplet Annihilation Upconversion.

Three-dimensional (3D) printing has exploded in interest as new technologies have opened up a multitude of applications, with stereolithography a particularly successful approach. However, owing to the linear absorption of light, this technique requires photopolymerization to occur at the surface of the printing volume, imparting fundamental limitations on resin choice and shape gamut. One promising way to circumvent this interfacial paradigm is to move beyond linear processes, with many groups using two-photon absorption to print in a truly volumetric fashion. Using two-photon absorption, many groups and companies have been able to create remarkable nanoscale structures, but the laser power required to drive this process has limited print size and speed, preventing widespread application beyond the nanoscale. Here we use triplet fusion upconversion to print volumetrically with less than 4 milliwatt continuous-wave excitation. Upconversion is introduced to the resin by means of encapsulation with a silica shell and solubilizing ligands. We further introduce an excitonic strategy to systematically control the upconversion threshold to support either monovoxel or parallelized printing schemes, printing at power densities several orders of magnitude lower than the power densities required for two-photon-based 3D printing.

Article	Year
Annihilator dimers enhance triplet fusion upconversion. Chemical science\| PubMed ID: 31015937	2019
Molecular Engineering of Chromophores to Enable Triplet-Triplet Annihilation Upconversion. Journal of the American Chemical Society\| PubMed ID: 33174728	2020
Triplet fusion upconversion nanocapsules for volumetric 3D printing. Nature\| PubMed ID: 35444324	2022

Samuel N. Sanders

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