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Shockley Equation Parameters of Organic Solar Cells derived by Transient Techniques

The Shockley equation (SE), originally derived to describe a p--n junction, was frequently used in the past to simulate current--voltage (j/V) characteristics of organic solar cells (OSC). In order to gain a more detailed understanding of recombination losses, we determined the SE parameters, i.e. the ideality factor and the dark saturation current, from temperature dependent static j/V-measurements on poly(3-hexylthiophene-2,5-diyl)(P3HT):[6,6]-phenyl-C$_{61}$ butyric acid methyl ester (PCBM) bulk heterojunction solar cells. As we show here, these parameters are directly related to charge carrier recombination and become also accessible by transient photovoltage and photocurrent methods in the case of field-independent charge carrier generation. Although determined in very different ways, both SE parameters were found to be identical. The good agreement of static and transient approaches over a wide temperature range demonstrates the validity of the Shockley model for OSC based on material systems satisfying the requirement of field-independent polaron-pair dissociation. In particular, we were able to reproduce the photocurrent at various light intensities and temperatures from the respective nongeminate recombination rates. Furthermore, the temperature dependence of the dark saturation current $j_0$ allowed determining the effective band gap of the photoactive blend perfectly agreeing with the literature values of the energy onset of the photocurrent due to charge transfer absorption. We also present a consistent model directly relating the ideality factor to recombination of free with trapped charge carriers in an exponential density of tail states. We verify this finding by data from thermally stimulated current measurements.