Materials aspects in spin-coated films for polymer photovoltaics
Abstract: Polymer-based photovoltaics have the potential to contribute to boosting photovoltaic energy conversion overall. Besides allowing large-area inexpensive processing, polymeric materials have the added benefit of opening new market applications for photovoltaics due to their low-weight and interesting mechanical properties. The energy conversion efficiency values of polymer photovoltaics have reached new record values over the past years. It is however crucial that stability issues are addressed together with efficiency optimization. Understanding fundamental materials aspects is key in both areas.In the work presented in this thesis, the morphology of polymer:fullerene films and its influence on device performance was studied, as well as the effect of light exposure on the surface of fullerene films. Several polyfluorene copolymers were used for the morphology studies, where the effects of changing spin-coating solvent and of side chain engineering were investigated with dynamic secondary ion mass spectrometry (dSIMS) and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. Polymer-enriched surfaces were found in all blend films, even in the cases with homogeneous distributions in the bulk. Side chain engineering of the polymer led to gradual changes in the compositional variations perpendicular to the surface, and to slight variations in the photocurrent. The electronic structure of the fullerene derivative PCBM was studied in detail and the spectroscopic fingerprint of the materials was analysed by comparison with theoretically simulated spectra. Photo-stability studies done in air showed that the surface of fullerene films underwent severe damages at the molecular level, which is evident from changes in the valence band and X-ray absorption spectra. These changes were explained by transitions from sp2-type to sp3 hybridization of the carbon atoms in the cage that resulted in the destruction of the fullerene cage.
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