Electrochromic Polymers Based on 1,4-Bis((9H-carbazol-9-yl)methyl)benzene and 3,4-Ethylenedioxythiophene Derivatives as Promising Electrodes for Flexible Electrochromic Devices

A 1,4-bis((9H-carbazol-9-yl)methyl)benzene (DCB)-containing homopolymer (P(DCB)) and four DCB- and ED-derivative (3,4-ethylenedioxythiophene (EDOT) and 3,4-ethylenedioxythiophene-methanol (EDm))-containing copolymers (P(DCB-co-ED), P(2DCB-co-ED), P(DCB-co-EDm), and P(2DCB-co-EDm)) were electropolymerized on ITO-polyethylene terephthalate (PET) substrates and their electrochromic performances were studied. DCB displays a lower E-onset than that of EDOT and EDm, conjecturing that the biscarbazole-containing DCB group shows a stronger electron-donating property than that of the ED derivatives. The P(2DCB-co-ED) film presents slate grey, dark khaki, and dark olive green at 0.0, 1.0, and 1.2 V. Bleaching-to-coloring switching studies of polymers show that P(2DCB-co-EDm) shows a high Delta T (31.0% at 725 nm) in solutions. Five dual-layer flexible electrochromic devices (ECDs) based on P(DCB), P(DCB-co-ED), P(2DCB-co-ED), P(DCB-co-EDm), and P(2DCB-co-EDm) as the anodic materials and PEDOT-PSS as the cathodic material are constructed. The P(2DCB-co-ED)/PEDOT-PSS flexible ECD shows a high Delta T (40.3% at 690 nm) and long-term electrochemical cycling stability, while the P(DCB-co-EDm)/PEDOT-PSS ECD shows a high Delta T (39.1% at 640 nm) and short response time (<= 1.5 s). These findings offer us a new structural insight for the valuable design of conjugated polymers in high-contrast, flexible ECDs.