Twisted Alkylthiothien‐2‐yl Flanks and Extended Conjugation Length Synergistically Enhanced Photovoltaic Performance by Boosting Dielectric Constant and Carriers Kinetic Characteristics

Alternating conjugated polymers (CPs), derived from 2-ethylhexylthiothiophen-2-yl (TS) or 2-ethylhexylthiophen-2-yl (T) flanked dithieno[3,2-d:3,2-d ']benzo[1,2-b:4,5-b ']dithiophene (DTBDT) and diketopyrrolo-pyrrole (DPP) termed as PDTBDT-TS-DPP and PDTBDT-T-DPP, are prepared and characterized. It is found that the PDTBDT-TS-DPP not only exhibits slightly deepening the highest occupied molecular orbital energy levels, and similar absorption, etc., but also presents higher dielectric constant (epsilon(r)) of 6.7 at 1 kHz in contrast to 3.2 for PDTBDT-T-DPP, which are even higher than those of 4.3 and 3.0 for PBDT-TS-DPP/PBDT-T-DPP generated from TS and T flanked benzo[1,2-b:4,5-bMODIFIER LETTER PRIME]dithiophene and DPP. Beyond that, the power conversion efficiency of 8.17% for the inverted photovoltaic devices from DPP-based CPs, is achieved from PDTBDT-TS-DPP. The alkylthio side chains are used in the DTBDT of the larger twisting angles of TS flanks and longer conjugation length, synergistically contribute to the highest dipole moments, and then lead to the enhancement of epsilon(r), thus devoted the modification exciton dissociation and charge carriers kinetic characteristics. To the authors' knowledge, it is the first time to report that epsilon(r) of the CPs is connected with the twisting angle of flanks and conjugation length of the building blocks, besides the use of functional side chains and atoms.