A new series of 2,1,3-benzothiadiazole (BT) acceptors with different conjugated aryl-vinylene side chains have been designed and used to build efficient low-bandgap (LBG) photovoltaic copolymers. Based on benzo[1,2-b:3,4-b']dithiophene and the resulting new BT derivatives, three two-dimensional (2D)-like donor (D)-acceptor (A) conjugated copolymers have been synthesised by Stille coupling polymerisation. These copolymers were characterised by NMR spectroscopy, gel-permeation chromatography, thermogravimetric analysis and differential scanning calorimetry. UV/Vis absorption and cyclic voltammetry measurements indicated that their optical and electrochemical properties can be facilely modified by changing the structures of the conjugated aryl-vinylene side chains. The copolymer with phenyl-vinylene side chains exhibited the best light harvesting and smallest bandgap of the three copolymers. The basic electronic structures of D-A model compounds of these copolymers were also studied by DFT calculations at the B3LYP/6-31G* level of theory. Polymer solar cells (PSCs) with a typical structure of indium tin oxide (ITO)/poly(3,4-ethylenedioxythiophene) (PEDOT):poly(styrenesulfonate) (PSS)/copolymer:[6,6]-phenyl-C(61) (C(71))-butyric acid-methyl ester (PCBM)/calcium (Ca)/aluminum (Al) were fabricated and measured under the illumination of AM1.5G at 100 mW cm(-2). The results showed that the device based on the copolymer with phenyl-vinylene side chains had the highest efficiency of 2.17 % with PC(71)BM as acceptor. The results presented herein indicate that all the prepared copolymers are promising candidates for roll-to-roll manufacturing of efficient PSCs. Suitable electronic, optical and photovoltaic properties of BT-based copolymers can also be achieved by fine-tuning the structures of the aryl-vinylene side chains for photovoltaic application.
Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.