posted on 2025-02-21, 13:36authored byPaulius Baronas, Justas Lekavičius, Maciej Majdecki, Jacob Lynge Elholm, Karolis Kazlauskas, Przemysław Gaweł, Kasper Moth-Poulsen
Triplet–triplet
annihilation photon upconversion
(TTA-UC)
systems hold great promise for applications in energy, 3D printing,
and photopharmacology. However, their optimization remains challenging
due to the need for precise tuning of sensitizer and annihilator concentrations
under oxygen-free conditions. This study presents an automated, high-throughput
platform for the discovery and optimization of TTA-UC systems. Capable
of performing 100 concentration scans in just two hours, the platform
generates comprehensive concentration maps of critical parameters,
including quantum yield, triplet energy transfer efficiency, and threshold
intensity. Using this approach, we identify key loss mechanisms in
both the established and novel TTA-UC systems. At high porphyrin-based
sensitizer concentrations, upconversion quantum yield losses are attributed
to sensitizer triplet self-quenching via aggregation and sensitizer
triplet–triplet annihilation (sensitizer-TTA). Additionally,
reverse triplet energy transfer (RTET) at elevated sensitizer levels
increases the upconversion losses and excitation thresholds. Testing
novel sensitizer–annihilator pairs confirms these loss mechanisms,
highlighting opportunities for molecular design improvements. This
automated platform offers a powerful tool for advancing TTA-UC research
and other photochemical studies requiring low oxygen levels, intense
laser excitation, and minimal material use.