Dithieno[3,2-b:2′,3′-d]pyrrole-benzo[c][1,2,5]thiadiazole conjugate small molecule donors: effect of fluorine content on their photovoltaic properties

Abstract

Two new small molecule donors, namely ICT4 and ICT6 with D₁–A–D₂–A–D₁ architecture having 2,4-bis(2-ethylhexyl)-4H-dithieno[3,2-b:2′,3′-d]pyrrole (EHDTP, D₁) and 4,8-bis((2-ethylhexyl)oxy)benzo[1,2-b:4,5-b′]dithiophene (OBDT, D₂) as the terminal and central donor, and benzo[c][1,2,5]thiadiazole (BT for ICT4) and 5,6-difluorobenzo[c][1,2,5]thiadiazole (F2BT for ICT6) as the acceptor (A) moieties, are synthesized and their optical, electronic and photovoltaic properties are investigated. Both ICT4 and ICT6 have considerable solubility in various solvents and possess efficient light absorption ability [ε (×10⁵ mol⁻¹ cm⁻¹) is 0.99 and 1.06, respectively for ICT4 and ICT6] and appropriate frontier molecular orbital energy offsets with [6,6]-phenyl-C₇₁-butyric acid methyl ester (PC₇₁BM). Bulk heterojunction solar cells (BHJSCs) are fabricated using ICT4/ICT6 and PC₇₁BM as donors and acceptors, respectively and BHJSCs with two-step annealed (thermal followed by solvent vapor annealing) active layers of ICT4 and ICT6 show overall power conversion efficiencies (PCEs) of 5.46% and 7.91%, respectively. The superior photovoltaic performance of the ICT6 based BHJSCs is due to the favourable morphology with a nanoscale interpenetrating network in the ICT6:PC₇₁BM active layer induced by the fluorine atoms on the BT acceptor, which significantly enhances the dissociation of excitons, charge transport and the charge collection efficiency, and suppresses bimolecular recombination in the BHJ. The observed higher PCE of 7.91% indicates that ICT6 is one of the best BT based donor material for small molecular BHJSCs.