A review of electrochromic (EC) polymers and their applications in absorption/transmission, reflective, and patterned electrochromic devices (ECDs) is presented. Fundamental properties of EC materials such as optical contrast, coloration efficiency, switching speed, and stability are described along with the commonly used characterization methods. The origin of electrochromism in conjugated polymers is explained in terms of the electronic structure changes in the backbone upon doping/dedoping. The ability to tailor the EC properties of conjugated polymers and tune their color states via modification of the polymer structure is demonstrated. Multicolor electrochromic materials can be obtained by substitution of a parent polymer and controlled polymerization of comonomers and with blends and laminates of homopolymers. Absorption/transmission-type ECDs from complementarily colored polymers and reflective-type ECDs on metalized substrates are illustrated with several examples from the literature. Finally, several patterning methods that are promising for ECD applications are discussed. Examples of ECDs constructed from patterned electrodes using line-patterning, screen-printing, and metal vapor deposition techniques are investigated for their possible use in commercial applications.

We report a method to measure the composite coloration efficiency of organic electrochromic polymers at 95% of the total optical density change measured at λmax. This practical method is useful for the comparison of organic polymers as well as inorganic electrochromic oxides and for gaining insights into the reasons for increased efficiencies in organic polymer systems. Three polymers from the family of the poly(3,4-alkylenedioxythiophenes) (PXDOTs) were chosen, due to their well-behaved electrochromic properties, to develop the tandem chronoabsorptometry/chronocoulometry method. Coloration efficiencies were measured by monitoring the amount of injected/ejected charge as a function of the change in optical density of the polymer film. The results of these experiments revealed a significant relationship between structure and coloration efficiency determined at λmax in organic polymers. Poly(3,3-dimethyl-3,4-dihydro-2H-thieno[3,4-b]dioxepine) (PProDOT-Me2) possessed the highest coloration efficiency (375 cm2/C) compared to poly(3,4-ethylenedioxythiophene) (PEDOT) (183 cm2/C) and poly(3,4-propylenedioxythiophene) (PProDOT) (285 cm2/C), due to a combination of larger changes in optical density at λmax and higher doping levels.