High Contrast Ratio and Fast-Switching Dual Polymer Electrochromic Devices

A series of dual polymer electrochromic devices (ECDs) based on 12 complementary pairs of conducting polymer films have been constructed using 3,4-ethylenedioxythiophene-containing conducting polymers. Poly[3,6-bis(2-(3,4-ethylenedioxythiophene))-N-methylcarbazole] (PBEDOT-NCH3Cz), poly[3,6-bis(2-(3,4-ethylenedioxythiophene))-N-eicosylcarbazole] (PBEDOT-NC20H41Cz), and poly[4,4‘-bis(2-(3,4-ethylenedioxythiophene))biphenyl] (PBEDOT-BP) were utilized as anodically coloring polymers that electrochemically switch between an oxidized deep blue absorptive state and a transmissive (orange or yellow) reduced state. Poly(3,4-ethylenedioxythiophene) (PEDOT) and its alkyl derivatives (PEDOT-C14H29 and PEDOT-C16H33) have been used as high-contrast cathodically coloring polymers that switch between a deep blue absorptive state in the reduced form and a sky blue, highly transmissive state in the oxidized form. The dual polymer ECDs were constructed by separating complementary pairs of EC polymer films, deposited on ITO glass, with a gel electrolyte composed of a lithium salt and plasticized poly(methyl methacrylate) (PMMA). Device contrast ratios, measured as Δ%T, ranged from 27% to 63%, and subsecond switching times for full color change were achieved. These devices were found to exhibit extremely high coloration efficiencies of up to 1400 cm2/C over narrow (ca. 100 nm) wavelength ranges and to retain up to 60% of their optical response after 10 000 deep, double potential steps, rendering them useful for EC applications.