Dithienylpyrrole- and Tris[4-(2-thienyl)phenyl]amine-Containing Copolymers as Promising Anodic Layers in High-Contrast Electrochromic Devices

Three dithienylpyrrole- and tris[4-(2-thienyl)phenyl]amine-containing copolymers (P(MPS-co-TTPA), P(MPO-co-TTPA), and P(ANIL-co-TTPA)) were deposited on indium tin oxide (ITO) surfaces using electrochemical polymerization. Spectroelectrochemical characterizations of polymer films revealed that P(MPS-co-TTPA) film was light olive green, greyish-green, bluish grey, and grey in neutral state, intermediate state, oxidized state, and highly oxidized state, respectively, whereas P(MPO-co-TTPA) film was green moss, foliage green, dark greyish-green, and bluish-grey in neutral state, intermediate state, oxidized state, and highly oxidized state, respectively. The ΔTmax of P(MPS-co-TTPA) film at 964 nm, P(MPO-co-TTPA) film at 914 nm, and P(ANIL-co-TTPA) film at 960 nm were 67.2%, 60.7%, and 67.1%, respectively, and the coloration efficiency (η) of P(MPS-co-TTPA) film at 964 nm, P(MPO-co-TTPA) film at 914 nm, and P(ANIL-co-TTPA) film at 960 nm were calculated to be 260.3, 176.6, and 230.8 cm2 C−1, respectively. Dual type complementary colored electrochromic devices (ECDs) were constructed using P(MPS-co-TTPA), P(MPO-co-TTPA), or P(ANIL-co-TTPA) as anodic copolymer layer and PProDOT-Et2 as cathodic polymer layer. P(MPO-co-TTPA)/PProDOT-Et2 ECD revealed high ΔT (55.1%) and high η (766.5 cm2 C−1) at 580 nm. Moreover, P(MPS-co-TTPA)/PProDOT-Et2, P(MPO-co-TTPA)/PProDOT-Et2, and P(ANIL-co-TTPA)/PProDOT-Et2 ECDs showed satisfactory long-term cycling stability and optical memory.