Excited state dynamics of metalloporphyrins utilized in optoelectronic devices

Abstract

Energy consumption in the world is currently dominated by fossil fuels (85%) which include coal, gas, and oil while photovoltaics constitute a small portion (0.1%). The hotovoltaic market is primarily comprised of silicon based photovoltaics which are currently unable to compete with fossil fuels in cost per kilowatt hour. However, emerging organic photovoltaics (OPVs) have shown potential to be surpass silicon based photovoltaics and be cost competitive with fossil fuels. One of the limitations in OPVs is the short diffusion length (10 nm) relative to the absorbing layer thickness (100-200 nm). Porphyrins, of which chlorophylls are derivatives, remain at the forefront of OPV investigation due to their success in natural photosynthesis and potential in photovoltaic devices. Furthermore, platinum octaethyl porphyrin (PtOEP) has been estimated to have a diusion length between 18-30 nm and long triplet lifetime (100 microsecondss). This long diffusion length indicates that platinum porphyrins are able to efficiently funnel excitons to the interface, showing promise as suitable donor materials. Other porphyrins, such as nickel, palladium, tin, and indium show similar properties including strong absorption, enhanced excited state lifetimes, and charge separated states. This thesis investigates the excited state properties of porphyrin materials. Ultrafast pump probe spectroscopy allows for investigation of excited state dynamics including intramolecular energy transfer observed in nickel porphyrins. Femtosecond dynamics of palladium and platinum porphyrins are explored as well as triplet fusion in PtOEP neat films, providing a unique way to study energy transfer and amorphous films. Finally, pump probe studies aim to explain photoluminescent quenching behavior in tin and indium porphyrins through observation of charge separated states. Investigation of these porphyrins is crucial to improving device efficiency through fundamental understanding of the excited state dynamics in films and neat films.