Synthesis and characterization of novel donor-acceptor isoindigo-based conjugated copolymers and small molecules and their integration in organic photovoltaics

Abstract

The conversion of solar energy into electricity is an environmentally friendly, safe and low-cost way of renewable energy production. Among the different photovoltaic technologies, organic photovoltaics (OPV) have particular assets in terms of aesthetics, flexibility and low-cost large area coverage. Nevertheless, the moderate OPV efficiencies (˞11%) and lack of durability (< 10 years) strongly limit their large-scale exploitation in particular consumer goods. The main goal of this thesis is to deal with these two drawbacks by designing novel conjugated polymers and small molecules with broad absorption in the visible range (i.e. low band gap), and by setting up strategies to improve the (thermal) stability of the photovoltaic cells. To this extent, novel push-pull type organic semiconducting materials have been synthesized, with different architectures and composed of electron-poor isoindigo building blocks alternating with electron-rich moieties, presenting a favorable spectral overlap with the solar emission. The optical properties of the novel materials were generally investigated by UV-visible absorption spectroscopy, while cyclic voltammetry was implemented to estimate the frontier orbital (HOMO/LUMO) energy levels. Relationships between the chemical nature and architecture of the push-pull systems and their absorption spectra and HOMO-LUMO energy levels have been pursued. Finally, the photovoltaic performances of the new materials have been evaluated in conventional bulk heterojunction organic solar cells using methanofullerene acceptor materials. Correlations between the molecular and photovoltaic parameters have been established. Ultimately, cross-linkable diblock copolymers based on poly(3-hexylthiophene) (P3HT) have been synthesized to improve the long-term stability of P3HT/PC60BM photovoltaic cells. Bulk heterojunction polymer solar cells have been prepared and their stability has been evaluated by accelerated ageing experiments and compared with standard P3HT-based devices.