Ultrafast photophysics of pi-conjugated polymers and polythiophene/fullerene blends for organic photovoltaic applications.

摘要

The present work reports studies of the ultrafast photoexcitations in various pristine n-conjugated polymers as well as compounds of polythiophene/fullerene blends, which act as the active layer of donor/acceptor in organic photovoltaic applications. The main technique used is the ultrafast (∼150 fs) transient photomodulation (PM) spectroscopy in the range of 0.25 to 2.5 eV using two different laser systems. In addition, two-photon-absorption and electroabsorption have also been complementary used.;The transient PM measurement of poly(phenylene-vinylene) (PPV) derivatives show that in 2-methoxy-5-(2'-ethylhexyloxy) PPV (MEH-PPV) film there are two kinds of primary photoexcitations, namely, intrachain exciton and excimer, but only intra-chain exciton in other PPV derivative polymers. Furthermore the high-pressure study of MEHPPV film shows two kinds of polymer chain orders: isolated-chains and closely packed-chains. The high pressure mainly affects photoexcited excimers in the closely packed-chains. In contrast there is no pressure effect on the photogenerated intrachain excitons in the isolated-chains.;The other pi-conjugated polymers investigated in this dissertation are platinum(Pt)-containing conjugated polymers. The different parity excited states of these Pt-polymers are studied by electroabsorption and two-photon-absorption spectroscopies. These results show that, even after the incorporation of Pt atoms into the backbone of conjugated polymer, the behavior of the excited states is similar to regular pi-conjugated polymers.;In organic photovoltaic studies, two different donor polymers namely, Regio-Regular-poly(3-hexylthiophene) (RR-P3HT) that forms lamellae, and Regio-Random-poly(3-hexylthiophene) (RRa-P3HT) that forms lamellae with lesser extent have been compared. The transient PM measurement of the most efficient RR-P3HT/fullerene blend shows that the decay of exciton does not result in the generation of polarons in the donor and acceptor materials, as assumed by the present model of charge dissociation in photovoltaic devices. On the contrary, the decay of exciton fits very well to the build-up of charge-transfer (CT) state in the fullerene phase, which indicates the migration of the photoexcited exciton in the polymer phase to the fullerene nano-domains. The transient PM measurement of RRa-P3HT/fullerene blend, which does not form phase-separated nano-domains, shows the formation of a CT state at the interface following by ultrafast geminate recombination.