Investigations into inward positioned 3,3′-Dihexylditheinylbenzothiadiazole (DTBTh)-Benzodithiophene (BDT) based polymer solar cells by controlling molecular weight and alkyl side chain

Abstract In previous studies, PSCs based on polymers with an inward alkyl positioned DTBT unit showed poor power conversion efficiency mainly due to the greatly distorted polymer backbone structure caused by severe steric hindrance between the alkyl groups on the flanking thiophene of DTBT and the BT unit. In this study, PSCs based on polymers with an inward alkyl positioned DTBT unit are markedly improved by controlling the molecular weight and alkyl chain length. Two BDT-DTBTs and one BDT-BT polymers were synthesized by engineering alkylthienyl chains on BDT and by installing these with a short alkyl chain on the inward alkyl positioned DTBT. Extraordinary bathochromic shifts in the absorption maxima at 146 nm for PA and 165 nm for PB were observed going from solution to a solid film state, suggesting great differences in the polymer structures of the two states. Optical and electrochemical measurements were taken, and the HOMO levels of PA, PB, and PC were determined to be −5.76, −5.66, and −5.71 eV, respectively, indicating very low-lying HOMO energy levels. The optimized PSCs based on PA, PB, and PC exhibit power conversion efficiencies (PCEs) of 3.75%, 2.42%, and 2.30%, respectively, with Voc (0.77–0.86 V), Jsc (6.9–8.7 mA/cm2), and FF (38–52%). We believe that the highest PCE for the PSCs based on PA may be attributed to the high molecular weight and improved processability relative to those of PB and PC. A theoretical study suggests that the polymer backbones of PA and PB are highly distorted between the donor unit and the acceptor unit, by as much as 49°, possibly by the steric hindrance between BT and the inward positioned methyl group on the flanking thiophene. Therefore, the conjugations for the HOMO p-orbitals of PA and PB are highly localized throughout the backbone while the conjugations for the HOMO p-orbitals of PC are well delocalized. The AFM study revealed that DIO additive greatly changed the morphology of the polymer blend from an amorphous state into distinct nanoscale phase separated states, leading to a great improvement in PCEs. The XRD study revealed that all polymers are amorphous.