No abstract

A series of poly-3-alkylthiophenes (P3ATs) with butyl (P3BT), hexyl (P3HT), and octyl (P3OT) sidechains and well-defined molecular weights (MWs) were synthesized using Grignard metathesis polymerization. The MWs of P3HTs and P3OTs obtained via gel permeation chromatography agreed well with the calculated MWs ranging from approximately 10 to 70 kDa. Differential scanning calorimetry results showed that the crystalline melting temperature increased with increasing MWs and decreasing alkyl side-chain length, whereas the crystallinity of the P3ATs increased with the growth of MWs. An MW-dependent red shift was observed in the UV–Vis and photoluminiscence spectra of the P3ATs in solution, which might be a strong evidence for the extended effective conjugation occurring in polymers with longer chain lengths. The photoluminescence quantum yields of pristine films in all polymers were lower than those of the diluted solutions, whereas they were higher than those of the phenyl-C61-butyric acid methyl ester-blended films. The UV–Vis spectra of the films showed fine structures with pronounced red shifts, and the interchain interaction-induced features were weakly dependent on the MW but significantly dependent on the alkyl side-chain length. The photovoltaic device performances of the P3BT and P3HT samples significantly improved upon blending with a fullerene derivative and subsequent annealing, whereas those of P3OTs mostly degraded, particularly after annealing. The optimal power conversion efficiencies of P3BT, P3HT, and P3OT were 2.4%, 3.6%, and 1.5%, respectively, after annealing with MWs of ~11, ~39, and ~38 kDa, respectively.

To achieve intrinsically light-weight flexible photovoltaic devices, a bulk-heterojunction-type active layer with a narrow-bandgap polymer is still considered as one of the most important candidates. Therefore, detailed information about the charge transfer efficiency from a photo-excited species on an electron-donating polymer to an electron acceptor is an important factor, given that it is among the most fundamental quantitative measures to understand the solar power conversion efficiency, in particular at the initial stage followed by primary exciton formation. To obtain accurate information in this regard, wide-range acceptor concentration-dependent transient absorption spectroscopy with femtosecond laser pulse excitation was performed using a representative narrow-bandgap polymer, commonly known as PTB7. The investigated acceptor concentration range covered was from 0.01 wt% up to 10 wt%, in addition to a 0 wt% pristine polymer sample and a sample with a conventional acceptor concentration of 60 wt%, which is important for high efficiency. From the kinetic data, an almost two orders of magnitude faster acceptor-induced charge transfer rate constant in addition to the native primary exciton lifetime of about 100 picoseconds could be extracted. These data were used to verify the suggested kinetic model and compare with device properties that show no meaningful loss during the extraction of photo-generated charge carriers.

Efforts to improve the solar power conversion efficiencies of binary bulk heterojunction-type organic photovoltaic devices using an active layer consisting of a poly-(3-alkylthiophene) (P3AT) homopolymer and a suitable fullerene derivative face barriers caused by the intrinsic properties of homopolymers. To overcome such barriers, researchers might be able to chemically tailor homopolymers by means of monomer ratio-balanced block copolymerization to obtain preferable properties. Triblock copolymers consisting of three components—3-hexylthiophene (HT), 3-butylthiophene (BT), and 3-octylthiophene (OT)—were synthesized via Grignard metathesis (GRIM) polymerization. The component ratios of the synthesized block copolymers were virtually the same as the feeding ratios of the monomers, a fact which was verified using 1H-NMR spectra. All the copolymers exhibited comparable crystalline and melting temperatures, which increased when one type of monomer became dominant. In addition, their power conversion efficiencies and photoluminescence properties were governed by the major components of the copolymers. Interestingly, the HT component-dominated block copolymer indicated the highest power conversion efficiency, comparable to that of its homopolymer, although its molecular weight was significantly shorter.