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Institute
Perovskite semiconductors differ from most inorganic and organic semiconductors due to the presence of mobile ions in the material. Although the phenomenon is intensively investigated, important questions such as the exact impact of the mobile ions on the steady-state power conversion efficiency (PCE) and stability remain. Herein, a simple method is proposed to estimate the efficiency loss due to mobile ions via "fast-hysteresis" measurements by preventing the perturbation of mobile ions out of their equilibrium position at fast scan speeds (approximate to 1000 V s(-1)). The "ion-free" PCE is between 1% and 3% higher than the steady-state PCE, demonstrating the importance of ion-induced losses, even in cells with low levels of hysteresis at typical scan speeds (approximate to 100mv s(-1)). The hysteresis over many orders of magnitude in scan speed provides important information on the effective ion diffusion constant from the peak hysteresis position. The fast-hysteresis measurements are corroborated by transient charge extraction and capacitance measurements and numerical simulations, which confirm the experimental findings and provide important insights into the charge carrier dynamics. The proposed method to quantify PCE losses due to field screening induced by mobile ions clarifies several important experimental observations and opens up a large range of future experiments.
Organic solar cells offer an efficient and cost-effective alternative for solar energy harvesting. This type of photovoltaic cell typically consists of a blend of two organic semiconductors, an electron donating polymer and a low molecular weight electron acceptor to create what is known as a bulk heterojunction (BHJ) morphology. Traditionally, fullerene-based acceptors have been used for this purpose. In recent years, the development of new acceptor molecules, so-called non-fullerene acceptors (NFA), has breathed new life into organic solar cell research, enabling record efficiencies close to 19%. Today, NFA-based solar cells are approaching their inorganic competitors in terms of photocurrent generation, but lag in terms of open circuit voltage (V_OC). Interestingly, the V_OC of these cells benefits from small offsets of orbital energies at the donor-NFA interface, although previous knowledge considered large energy offsets to be critical for efficient charge carrier generation. In addition, there are several other electronic and structural features that distinguish NFAs from fullerenes.
My thesis focuses on understanding the interplay between the unique attributes of NFAs and the physical processes occurring in solar cells. By combining various experimental techniques with drift-diffusion simulations, the generation of free charge carriers as well as their recombination in state-of-the-art NFA-based solar cells is characterized. For this purpose, solar cells based on the donor polymer PM6 and the NFA Y6 have been investigated. The generation of free charge carriers in PM6:Y6 is efficient and independent of electric field and excitation energy. Temperature-dependent measurements show a very low activation energy for photocurrent generation (about 6 meV), indicating barrierless charge carrier separation. Theoretical modeling suggests that Y6 molecules have large quadrupole moments, leading to band bending at the donor-acceptor interface and thereby reducing the electrostatic Coulomb dissociation barrier. In this regard, this work identifies poor extraction of free charges in competition with nongeminate recombination as a dominant loss process in PM6:Y6 devices. Subsequently, the spectral characteristics of PM6:Y6 solar cells were investigated with respect to the dominant process of charge carrier recombination. It was found that the photon emission under open-circuit conditions can be almost entirely attributed to the occupation and recombination of Y6 singlet excitons. Nevertheless, the recombination pathway via the singlet state contributes only 1% to the total recombination, which is dominated by the charge transfer state (CT-state) at the donor-acceptor interface. Further V_OC gains can therefore only be expected if the density and/or recombination rate of these CT-states can be significantly reduced. Finally, the role of energetic disorder in NFA solar cells is investigated by comparing Y6 with a structurally related derivative, named N4. Layer morphology studies combined with temperature-dependent charge transport experiments show significantly lower structural and energetic disorder in the case of the PM6:Y6 blend. For both PM6:Y6 and PM6:N4, disorder determines the maximum achievable V_OC, with PM6:Y6 benefiting from improved morphological order. Overall, the obtained findings point to avenues for the realization of NFA-based solar cells with even smaller V_OC losses. Further reduction of nongeminate recombination and energetic disorder should result in organic solar cells with efficiencies above 20% in the future.