Effect of oligothiophene π-bridge length in D-π-A star-shaped small molecules on properties and photovoltaic performance in single-component and bulk-heterojunction organic solar cells and photodetectors

Abstract Donor-acceptor molecules with thiophene fragments as the π-bridge represent a promising class of materials for organic photovoltaics especially in single-component (SC) organic solar cells (OSCs) and other related applications. However, the effect of the oligothiophene π-bridge length on physicochemical properties, photophysics, charge transport and photovoltaic performance of these materials has not been thoroughly addressed. Here we report on the synthesis and comprehensive investigation of the series of star-shaped donor-acceptor molecules (0T–4T) with triphenylamine as a donor core linked through an oligothiophene π-bridge of variable length to the terminal hexyl-dicyanovinyl electron-withdrawing groups. We found that variation of the π-bridge length from 0 to 4 thiophene units strongly impacts their properties such as the solubility, highest occupied molecular orbital energy, optical absorption and photophysics, film morphology, phase behavior and molecular packing as well as the charge-carrier mobility. The performance of the SC and bulk heterojunction organic solar cells and photodetectors are comprehensively studied and compared. The results obtained provide the insight on how to fine-tune and predict properties and photovoltaic performance of small molecules for organic solar cells and photodetectors.