Excitation Dynamics and Losses in Solution Processed Disordered Semiconductors

From a technological point of view, organic semiconductor-based devices are of significant interest due to their light weight, ease of processability, conformal flexibility and potentially low cost and low embodied energy pro-duction. Motivated by these quite unique selling points, the performance of organic semiconductors has been a subject of multi-disciplinary study for more than 60 years with steady progress in applications such as solar cells, transistors, light emitting diodes and various sensors. One of the main characteristics that governs the performance of organic semiconduc-tors is their low dielectric constants, meaning they are excitonic at room temperature. A second main feature that dictates the charge carrier recom-bination and transport properties is the disordered nature of these semicon-ductors causing low charge carrier mobilities. The work described in this thesis focuses on these defining elements, and particularly their implications on photovoltaic devices. The discussion will start with a review into the main electro-optical phenomena in organic solar cells. Subsequently, a new method is presented for measuring exciton diffusion lengths based upon a low-quencher-content device structure. An anomalously large quenching volume is observed that can be assigned to long-range exciton delocaliza-tion prior to thermalization. These ultra-low-impurity content organic so-lar cells are also very useful as model systems to study and engineer trap states. Using this approach, it is found that mid-gap trap states are a universal feature in organic semiconductor donor-acceptor blends and un-expectedly contribute to charge generation and recombination. This has a profound impact on the thermodynamic limit of organic photovoltaic de-vices. Having demonstrated this important new insight it is further shown that a definitive link exists between a reduced recombination rate compared to the Langevin rate in some exceptional, high performance material sys-tems and a significant increase in the dissociation rate of charge transfer states upon post-processing of the active layer. In sum, the work presented in this thesis delivers important new insight as to the underlying dynamics of exciton generation and diffusion, charge transfer state dissociation, and indeed the ultimate fate of photogenerated free carriers.