Low band-gap benzodithiophene-thienothiophenecopolymers: the effect of dual two-dimensional substitutions on optoelectronic properties

摘要

Two new conjugated copolymers,PBDT-T6-TTF and PBDT-T12-TTF,were derived from a novel 4-fluorobenzoyl thienothiophene(TTF).In addition,two types of benzodithiophene(BDT)units with 2,3-dihexylthienyl(T6)and 2,3-didodecylthienyl(T12)substituents,respectively,were successfully synthesized.The effect of the dual two-dimensional(2D)substitutions of the building blocks upon the optoelectronic properties of the polymers was investigated.Generally,the two polymers exhibited good solubility and broad absorption,showing similar optical band gaps of^1.53 e V.However,PBDT-T6-TTF with its shorter alkyl chain length possessed a larger extinction coefficient in thin solid film.The highest occupied molecular orbital(HOMO)level of PBDT-T6-TTF was located at–5.38 e V while that of PBDT-T12-TTF was at–5.51 e V.In space charge-limitedcurrent(SCLC)measurement,PBDT-T6-TTF and PBDT-T12-TTF displayed respective hole mobilities of 3.0×10–4 and1.6×10–5 cm2 V1 s1.In polymer solar cells,PBDT-T6-TTF and PBDT-T12-TTF showed respective power conversion efficiencies(PCEs)of 2.86%and 1.67%.When 1,8-diiodooctane(DIO)was used as the solvent additive,the PCE of PBDT-T6-TTF was remarkably elevated to 4.85%,but the use of DIO for the PBDT-T12-TTF-blend film resulted in a lower PCE of 0.91%.Atomic force microscopy(AFM)indicated that the superior efficiency of PBDT-T6-TTF with 3%DIO(v/v)should be related to the better continuous phase separation of the blend film.Nevertheless,the morphology of the PBDT-T12-TTF deteriorated when the 3%DIO(v/v)was added.Our results suggest that the alkyl-chain length on the 2D BDT units play an important role in determining the optoelectronic properties of dual 2D BDT-TT-based polymers.