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Benzothiadiazole bridged EDOT based donor-acceptor polymers with tunable optical, electrochemical, morphological and electrochromic performance: effects of solvents and electrolytes.

Donor-acceptor (D-A) polymers have been widely studied for their tunable electronic properties, however, it is surprising that systematic studies on the effect of different solvents and electrolytes on their opto-electrochemical, morphological and electrochromic performance have drawn only little attention. In the presented work, nine different D-A polymer films, poly(4,7-di(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)benzo[1,2,5]thiadiazole) (a-i-P1), were electrosynthesised using different polar solvents (PC, MeCN and DCM) and supporting electrolytes (TBAPF6, TBAClO4 and TBABF4). A thorough study of these D-A polymer films using cyclic voltammetry, UV-Vis-NIR spectroscopy, FE-SEM, spectroelectrochemistry and electrochromic techniques has been performed. We found a significant effect of both the supporting electrolytes and solvents on the morphology of polymer films which correlates well with their opto-electronic properties. Films prepared using the TBAClO4/PC system show a smooth morphology with a significantly high coloration efficiency of 264 cm2 C-1 and an optical contrast of 65.3%. Such differences in the optical and electrochemical properties of polymer films were explained by the ion pair formation during polymerisation.