Fundamental understanding of photocarrier generation, transport and recombination under a steady-state photoexcitation has been an important goal of organic electronics and photonics, since these processes govern such electronic properties of organic semiconductors as, for instance, photoconductivity. Here, we discovered that photoconductivity of a highly ordered organic semiconductor rubrene exhibits several distinct regimes, in which photocurrent as a function of cw (continuous wave) excitation intensity is described by a power law with exponents sequentially taking values 1, 1/3 and 1/4. We show that in pristine crystals this photocurrent is generated at the very surface of the crystals, while the bulk photocurrent is drastically smaller and follows a different sequence of exponents, 1 and 1/2. We describe a simple experimental procedure, based on an application of "gauge effect" in high vacuum, that allows to disentangle the surface and bulk contributions to photoconductivity. A model based on singlet exciton fission, triplet fusion and triplet-charge quenching that can describe these non-trivial effects in photoconductivity of highly ordered organic semiconductors is proposed. Observation of these effects in photoconductivity and modeling of the underlying microscopic mechanisms described in this work represent a significant step forward in our understanding of electronic properties of organic semiconductors.
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