This conference presentation was prepared for the Physical Chemistry of Semiconductor Materials and Interfaces XXI conference at SPIE Optics + Photonics 2022.
Achieving efficient charge generation has been a challenge in the field of organic photovoltaics (OPVs). Therefore, it is
important to understand the photophysical behaviour of a system in relation to the material properties. In this study,
photophysical properties of a range of conjugated donor-acceptor polymers with varying crystallinity are investigated.
Preliminary study shows a correlation between photophysics and polymer crystallinity.
We focus upon the role of interfacial energetics and morphology in influencing the separation of CT states into dissociated charge carriers. In particular, we undertake transient optical studies of films comprising regioregular poly(3-hexylthiophene) (P3HT) blended with a series of perylene-3,4:9,10-tetracarboxydiimide (PDI) fullerene electron acceptors. For the PDI film series, we observe a close correlation between the PDI electron affinity and the efficiency of charge separation. This correlation is discussed in the context of studies of charge photogeneration for other organic donor/acceptor blend films, including other polymers, blend compositions, and the widely used electron phenyl-C61-butyric acid methyl ester(PCBM). Furthermore, we compare the charge recombination dynamics observed in films comprising P3HT blended with three fullerene derivatives: PCBM and two alternative pyrazolinofullerenes. Transient absorption data indicate that replacement of PCBM with either of the pyrazolinofullerene derivatives results in a transition from nongeminate to monomolecular (geminate) recombination dynamics. We show that this transition cannot be explained by a difference in interfacial energetics. However, this transition does correlate with nanomorphology data that indicate that both pyrazolinofullerenes yield a much finer phase segregation with correspondingly smaller domain sizes than observed with PCBM. Our results therefore provide clear evidence of the role of nanomorphology in determining the nature of recombination dynamics in such donor/acceptor blends.
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