Synthesis, molecular and photovoltaic/transistor properties of heptacyclic ladder-type di(thienobenzo)fluorene-based copolymers

Abstract

We present a facile synthesis method to make a new ladder-type heptacyclic dithienobenzofluorene (DTBF) framework, where the central 2,7-fluorene unit is covalently fastened with two external thiophenes via two C=C bridges. A dieneyne-containing precursor undergoes DBU-induced double benzannulation to regiospecifically introduce two solubilizing 2-octyldodecyl side chains at 5,10-positions of DTBF. The rigid and coplanar Br-DTBF monomer with sufficient solubility was copolymerized with 5,6-difluoro-4,7-bis(5-(trimethylstannyl) thiophen-2-yl) benzo[c][1,2,5] thiadiazole (Sn-DTFBT) and 5,10-bis(5-(trimethylstannyl)thiophen-2-yl)naphtho[1,2-c: 5,6-c\'] bis([1,2,5] thiadiazole) (Sn-DTNT) via Stille coupling to furnish two donor-acceptor copolymers, PDTBFFBT and PDTBFNT, respectively. Their thermal, optical, electrochemical, molecular stacking and photovoltaic properties are investigated. PDTBFNT has a higher molecular weight, smaller optical and electrochemical band gaps, and stronger solid-state packing than PDTBFFBT. DFT calculations were carried out to gain insight into the electronic and structural properties of DTBF and its derivatives. Bulk heterojunction solar devices with the ITO/ZnO/polymers: PC71BM/MoO3/Ag configuration were fabricated. By adding 5 vol% diphenyl ether (DPE) as an additive, PDTBFNT: PC71BM and PDTBFFBT: PC71BM devices achieved the power conversion efficiencies of 5.22% and 2.68%, respectively. The superior efficiency of PDTBFNT over PDTBFFBT is attributed to the better LUMO energy alignment between PDTBFNT and PC71BM and the face-on p-stacking of PDTBFNT in the active layer. Moreover, PDTBFNT exhibited a higher field-effect transistor hole mobility of 1.90 x 10(-2) cm(2) V-1 s(-1) than PDTBFFBT with a value of 3.96 x 10(-3) cm(2) V-1 s(-1).