Document Type



Doctor of Philosophy



First Adviser

Biaggio, Ivan

Other advisers/committee members

Dierolf, Volkmar; Fowler, W. Beall; Stavola, Michael J.; Jain, Himanshu


This work discusses the photocurrent and photoluminescence that can be induced by short-pulse illumination in rubrene single crystals. The pulsed illumination excites a rubrene molecule from the ground state to its first optically accessible excited state, resulting in a singlet exciton state. In rubrene, a singlet exciton can transform into two triplet excitons - which together have a spin of zero - by an efficient spin-conserved fission process. On the other hand, two triplet excitons can interact to again form a singlet exciton by a fusion process. Quantitative modeling of the transformation of singlet excitons into triplet excitons and vice-versa shows that both photoconductivity dynamics and photocurrent dynamics after pulsed excitations can be understood within the same framework.The photoluminescence observed after pulsed excitation is only emitted upon radiative recombination of singlet excitons. A simple model of fission and fusion based on rate equations leads to a qualitatively different photoluminescence dynamics depending on the time scale. In particular, it predicts a fast exponential decay corresponding to the initial fission process, later a power-law (quadratic) decay corresponding to a regime when triplet-triplet interaction is dominant, and a final exponential decay with a time-constant which is half the triplet exciton lifetime. This last exponential decay corresponds to the case when only a lower density of triplet excitons is left.The same model can be used to predict the photocurrent dynamics after pulsed excitation. Experimental observations after pulsed illumination show that, for low excitation pulse energies, a large photocurrent grows exponentially with a time constant of the order of 100 microseconds. This photocurrent build-up time then becomes shorter at higher excitation energies, with the peak photocurrent also saturating. One finds that the observed photocurrent dynamics can be reproduced with the same model based on exciton fission and fusion that successfully explained photoluminescence dynamics. The only additional assumption that is required to do so is that triplet excitons be able dissociate and release free holes by direct interaction with a defect state. The 100 microsecond build-up time of the impulsively induced photocurrent then corresponds to the triplet lifetime.

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