No abstract

Two terthiophene–isoindigo copolymers (P3TI-O and P3TI-D) were successfully designed and synthesized. Octyl (O) and dodecyl (D) alkyl side chains were appended at the third position of the first and fourth positions of the last thiophene on the terthiophene donor units in P3TI-O and P3TI-D, respectively. The band gaps of these copolymers were less than 1.7 eV. We found intramolecular charge-transfer states in both copolymers, which were generated with time constants of 4.5 and 13 ps for the copolymers with short and long alkyl side chains on their donor units, respectively. These results indicate that an almost 3-fold faster intramolecular charge-transfer process occurs when the alkyl side chains are shortened by four methyl units. Owing to a better interchain charge transfer, P3TI-O exhibits a more efficient exciton diffusion compared to P3TI-D, thus leading to longer exciton lifetimes in the copolymer with shorter alkyl side chains. Consequently, when blended with PC 71 BM in bulk heterojunctions, P3TI-O showed a better exciton dissociation efficiency compared to P3TI-D. These results correlate well with the higher short-circuit current densities observed in P3TI-O:PC 71 BM inverted architecture organic solar cells compared to the P3TI-D:PC 71 BM ones.

Organic solar cells working under continuous light irradiation are prone to photo-induced degradation. Photostabilities of benzodithiophene-alt-2-decyltetradecyl substituted isoindigo (PBDTI-DT) copolymer in solution, and as pristine film, and a PBDTI-DT:PC60BM bulk hetero-junction (BHJ) film were investigated for more than 70 h under simulated AM 1.5 solar irradiation. The photodegradation kinetics studied in standalone polymer chains were found to be fast due to the absence of intermolecular interaction while the inter-chain interaction in the polymer films kept the backbone intact against light-induced degradation. Further addition of PC60BM in the polymer made the BHJ film more stable as PC60BM serves as photoprotective layer and radical scavenger. This conclusion was supported by the similar XRD traces of PBDTIDT: PC60BM fillm during degradation while the traces of the pristine film indicated bleaching and shifted with increasing photon stress. In addition, the absorption of PBDTI-DT:PC60BM and pristine PBDTI-DT films were reduced to 80 and 56%, respectively, after 70 h of photo-degradation.

Three low-band-gap copolymers based on isoindigo acceptor units were designed and successfully synthesized by direct arylation polycondensation method. Two of them were benzodithiophene (BDT)-isoindigo copolymers (PBDTI-OD and PBDTI-DT) with 2-octlydodecyl (OD) and 2-decyltetradecyl (DT) substituted isoindigo units, respectively. Thiophene donor and DT-substituted isoindigo acceptor units were copolymerized to synthesize PTI-DT. The copolymers have a broad absorption range that extends to over 760 nm with a band gap ≈1.5 eV. The photophysical property studies showed that the BDT-based copolymers have non-polar ground states. Their emission exhibited the population of the intramolecular charge transfer (ICT) state in polar solvents and tightly bound excitonic state in non-polar solvents due to self-aggregation. On the contrary, the emission from the thiophene-based copolymers was only from the tightly bound excitonic state. The thermal decomposition temperature of the copolymers was above 380 °C. The X-ray diffraction pattern of the three copolymers showed a halo due to π−π stacking. A second, sharper peak was observed in the BDT-based copolymer with a longer side chain on the isoindigo unit (PBDTI-DT), and the thiophene-based copolymers with PTI-DT, exhibiting a better structural order.