Polymer solar cells form a promising technology for converting sunlight into electricity, and have reached record efficiencies over 10% and lifetimes of several years. The performance of polymer solar cells depends strongly on the distribution of electron donor and acceptor materials in the active layer. To achieve longer lifetimes, degradation processes in the materials have to be understood. In this thesis, a set of complementary spectroscopy and microscopy techniques, among which soft X-ray techniques have been used to determine the morphology of polymer:fullerene based active layers. We have found that the morphology of TQ1:PC₇₀BM films is strongly influenced by the processing solvent and the use of solvent additives. We have also found, by using soft X-ray techniques, that not only the light-absorbing polymer TQ1, but also the fullerene is susceptible to photo-degradation in air. Moreover, the fullerene degradation is accelerated in the presence of the polymer. Additionally, this thesis addresses the role of the interfacial layers for device performance and stability. The commonly used hole transport material PEDOT:PSS has the advantage of being solution processable at room temperature, but this layer is also known to contribute to the device degradation. We have found that low-temperature processed NiO_x is a promising alternative to PEDOT:PSS, leading to improved device performance. Even for encapsulated polymer solar cells, some photo-induced degradation of the electrical performance is observed and is found to depend on the nature of the hole transport material. We found a better initial stability for solar cells with MoO₃ hole transport layers than with PEDOT:PSS. In the pursuit of understanding the initial decrease in electrical performance of PEDOT:PSS-based devices, simulations were performed, from which a number of degradation sources could be excluded.

With the increasing global demand for energy, solar cells provide a clean method for converting the abundant sunlight to electricity. Polymer solar cells can be made from a large variety of light-harvesting and electrically conducting molecules and are inexpensive to produce. They have additional advantages, like their mechanical flexibility and low weight, which opens opportunities for novel applications. In order for polymer solar cells to be more competitive, however, both the power conversion efficiencies and lifetimes need to further improve. One way to achieve this is to optimize the morphology of the active layer. The active layer of a polymer solar cell consists of electron donating and electron accepting molecules whose distribution in the bulk of the film is a major factor that determines the solar cell performance.

This thesis presents the use of complementary spectroscopy and microscopy methods to probe the local composition in the active layer of polymer solar cells. The stability of the active layer is studied and the interplay between the photo-degradation of the donor and acceptor molecules is investigated. Additionally, this thesis addresses how the interfacial layers between the active layer and the electrodes can influence device performance and stability.