In this study the charge dissociation at the donor/acceptor heterointerface of thermally evaporated planar heterojunction merocyanine/C 60 organic solar cells is investigated. Deposition of the donor material on a heated substrate as well as post-annealing of the complete devices at temperatures above the glass transition temperature of the donor material results in a twofold increase of the fill factor. An analytical model employing an electric-fielddependent exciton dissociation mechanism reveals that geminate recombination is limiting the performance of as-deposited cells. Fourier-transform infrared ellipsometry shows that, at temperatures above the glass transition temperature of the donor material, the orientation of the dye molecules in the donor films undergoes changes upon annealing. Based on this finding, the influence of the dye molecules' orientations on the charge-transfer state energies is calculated by quantum mechanical/molecular mechanics methods. The results of these detailed studies provide new insight into the exciton dissociation process in organic photovoltaic devices, and thus valuable guidelines for designing new donor materials.

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In organic heterojunction solar cells, the generation of free charge carriers takes place in a multistep process which involves charge transfer (CT) states, that is, bound electron-hole pairs at the interface between donor and acceptor molecules. Past efforts to model the CT-state dissociation during solar cell operation were not able to consistently reproduce the experimentally observed field and temperature dependence. This discrepancy between model and experiment was partly due to the field-dependent free charge carrier collection process, which plays an important role in the widely used bulk heterojunction cell configuration and superimposes a possible field-dependent charge carrier generation process. In order to distinguish between generation and collection of free charge carriers, we propose the planar heterojunction cell configuration as a model system to study the field-dependent charge carrier generation process in organic heterojunction solar cells. We apply this model system to check current CT-state dissociation models against experimental data. Although the models can quantitatively account for the photocurrent's dependence on the applied voltage and the device thickness, they fail to account for the virtually negligible temperature dependence of the field-dependent charge-generation process. This discrepancy is traced back to a common feature of the models: an Arrhenius-like temperature dependence, distinctive of all processes involving a thermally activated jump over an energy barrier. As a solution to the problem, we introduce an exciton dissociation model based on a field-dependent tunnel process and demonstrate its consistency with the experimental observations. Our results indicate that the current microscopic picture of the charge-generation process in organic heterojunction solar cells being limited by the CT-state dissociation process needs to be reconsidered.

Thermal co-evaporation of C(60) fullerene and two merocyanine dyes affords bulk heterojunction solar cells with improved short-circuit currents and power conversion efficiencies in comparison with the respective single donor cells. These results are rationalized by the formation of three distinct subphases driven by differences in molecular shape and electrostatic interactions.

The polymorphism and solvate formation of thiophanate-ethyl (TE), a fungicidal active, were investigated by solvent crystallization and compared to a close analogue, thiophanate-methyl (TM). Four polymorphs and seven solvates of TE were found and structurally compared with the previously found two polymorphs and fourteen solvates of TM by analyzing the hydrogen bonding patterns and using fingerprint plots, packing coefficients and lattice energies. TE and TM have the same functional groups that can build identical supramolecular synthons. Despite the strong similarities, the polymorphs and solvates of the two actives show significant differences in hydrogen bonding and packing. The results demonstrate the challenges in using a supramolecular synthon approach, and promote the importance in finding methods to also make use of packing effects and lipophilic interactions in crystal engineering.Scheme 1 Molecular structures of thiophanate-methyl (TM) and thiophanate-ethyl (TE).

The growth of a thermally deposited merocyanine (HB364) thin film can be modified through insertion of a transition metal oxide layer between an indium tin oxide (ITO) covered glass substrate and the dye film. Pure or V 2 O 5 modified ITO substrates result in highly crystalline HB364 films where the dye molecules adopt an edge-on orientation. Changing the transition metal oxide layer to WO 3 or MoO 3 results in a less ordered dye film with a mixed growth of edge-on and face-on orientations. Planar HB364/C 60 heterojunction (PHJ) solar cells are fabricated using the different transition metal oxides as the anode buffer layers. The devices with a pure ITO or a V 2 O 5 modified anode demonstrate the highest power conversion efficiencies up to 2.7% that also outperform HB364:C 60 bulk heterojunction (BHJ) devices (2.5%). Finally, HB364/HB364:C 60 hybrid heterojunction (HHJ) cells are fabricated showing the highest power conversion efficiency of 2.9%.

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