Aubrey L. Dyer

Electrochromic organic and polymeric materials for display applications

An electrochromic material is one where a reversible color change takes place upon reduction (gain of electrons) or oxidation (loss of electrons), on passage of electrical current after the application of an appropriate electrode potential. In this review, the general field of electrochromism is introduced, with coverage of the types, applications, and chemical classes of electrochromic materials and the experimental methods that are used in their study. The main classes of electrochromic organic and polymeric materials are then surveyed, with descriptions of representative examples based on the transition metal coordination complexes, viologen systems, and conducting polymers. Examples of the application of such organic and polymeric electrochromic materials in electrochromic displays are given.

Completing the color palette with spray-processable polymer electrochromics.

The field of electrochromic polymers has now reached an important milestone with the availability of a yellow to fully transmissive, cathodically coloring, solution-processable electroactive polymer. This is in addition to previously published electrochromic polymers that have neutral state colors that span from orange, red, magenta, blue, cyan, green, and black, that also attain highly transmissive states upon switching. With this, the full color palette is now complete allowing the largest variety of colors for transmissive and reflective electrochromic display applications. Here, we report on how we have been able to obtain this full color palette through synthetic modifications and color tuning utilizing electron rich and donor-acceptor repeat units, electron-donating substituents, and steric interactions with our 3,4-alkylenedioxythiophene family of polymers. Additionally, using solubilizing pendant groups for both organic and aqueous compatibility, we have been able to create this color palette with fully solution processable materials, paving the way for materials patterning, printing, and incorporation into devices for display and window applications.

Broadly absorbing black to transmissive switching electrochromic polymers.

Non-emissive electrochromic devices (ECDs), which can be operated under a wide range of viewing and lighting conditions, are especially attractive in applications that include smart windows, displays, electronic paper and mirrors. [ 1–4 ] Consequently, the processability, fl exibility, high optical contrast, rapid redox switching and long-term stability of easily oxidized conjugated polymers has made them desired materials for various refl ective/transmissive ECDs. [ 5–7 ] Although many polymeric electrochromes which are colored (red and orange, [ 8 ] green, [ 9–11 ]

Four shades of brown: tuning of electrochromic polymer blends toward high-contrast eyewear.

We report a straightforward strategy of accessing a wide variety of colors through simple predictive color mixing of electrochromic polymers (ECPs). We have created a set of brown ECP blends that can be incorporated as the active material in user-controlled electrochromic eyewear. Color mixing of ECPs proceeds in a subtractive fashion, and we acquire various hues of brown through the mixing of cyan and yellow primaries in combination with orange and periwinkle-blue secondary colors. Upon oxidation, all of the created blends exhibit a change in transmittance from ca. 10 to 70% in a few seconds. We demonstrate the attractiveness of these ECP blends as active materials in electrochromic eyewear by assembling user-controlled, high-contrast, fast-switching, and fully solution-processable electrochromic lenses with colorless transmissive states and colored states that correspond to commercially available sunglasses. The lenses were fabricated using a combination of inkjet printing and blade-coating to illustrate the feasibility of using soluble ECPs for high-throughput and large-scale processing.

Optimization of PEDOT Films in Ionic Liquid Supercapacitors: Demonstration As a Power Source for Polymer Electrochromic Devices

We report on the optimization of the capacitive behavior of poly(3,4-ethylenedioxythiophene) (PEDOT) films as polymeric electrodes in flexible, Type I electrochemical supercapacitors (ESCs) utilizing ionic liquid (IL) and organic gel electrolytes. The device performance was assessed based on figures of merit that are critical to evaluating the practical utility of electroactive polymer ESCs. PEDOT/IL devices were found to be highly stable over hundreds of thousands of cycles and could be reversibly charged/discharged at scan rates between 500 mV/s and 2 V/s depending on the polymer loading. Furthermore, these devices exhibit leakage currents and self-discharge rates that are comparable to state of the art electrochemical double-layer ESCs. Using an IL as device electrolyte allowed an extension of the voltage window of Type I ESCs by 60%, resulting in a 2.5-fold increase in the energy density obtained. The efficacies of tjese PEDOT ESCs were assessed by using them as a power source for a high-contrast and fast-switching electrochromic device, demonstrating their applicability in small organic electronic-based devices.

Tuning the painter's palette: subtle steric effects on spectra and colour in conjugated electrochromic polymers

A series of vibrantly coloured π-conjugated electrochromic polymers (ECPs) were designed and synthesized with the goal of extracting structure–property relationships from subtle changes in steric strain or relaxation. These are soluble all donor, electron rich, alternating polymers based on repeat units of 3,4-ethylenedioxythiophene (EDOT), 3,4-propylenedioxythiophene (ProDOT), and an acyclic dioxythiophene (AcDOT) in varying combinations to tune steric interactions and the subsequent optical absorption for fine colour control. Two families of polymers were formed where ProDOT2–EDOT, ProDOT–EDOT, and ProDOT2–EDOT2 constitute new shades of blues while AcDOT2–ProDOT, AcDOT–ProDOT, and AcDOT–EDOT yield new hues of magentas with the homopolymers of ProDOT and AcDOT and the copolymer AcDOT2–EDOT2 serving as comparisons. The polymers were synthesized using direct (hetero)arylation polymerization. Examinations of the optoelectronic properties via cyclic voltammetry, spectroelectrochemistry, and colorimetry show that by subtly varying the level of steric relaxation or strain in the form of EDOT or AcDOT content, lower or higher energy absorption transitions are produced respectively. This increase in relaxation or strain allows more short or long wavelength light to transmit, giving new shades of blues or magentas respectively. Since these are all donating polymers, they exhibit changes in contrast no less than 70% at the λmax with the exception of AcDOT–EDOT. The most desirable electrochromic properties were achieved with ProDOT2–EDOT2 and AcDOT2–ProDOT, with band gaps (Eg) and neutral state L*a*b* colour values (−a* and +a* correspond to green and red and −b* and +b* correspond to blue and yellow respectively and L* represents the lightness) of 1.74 eV, 37, 12, −63 and 2.01 eV, 56, 59, −16 respectively. The highly transmissive oxidized state colour values for ProDOT2–EDOT2 and AcDOT2–ProDOT are 92, −3, −3 and 91, −2, −1 respectively. These structure–property relationships grant a greater ability to tune light absorption across the visible, with colour properties similar to ECPs made through other methods without using donor–acceptor effects. This all donor steric tuning method leads to considerably higher levels of transparency when the polymers are fully oxidized.

A vertically integrated solar-powered electrochromic window for energy efficient buildings.

A solution-processed self-powered polymer electrochromic/photovoltaic (EC/PV) device is realized by vertically integrating two transparent PV cells with an ECD. The EC/PV cell is a net energy positive dual functional device, which can be reversibly switched between transparent and colored states by PV cells for regulating incoming sunlight through windows. The two PV cells can individually, or in pairs, generate electricity.

Propylenedioxythiophene (ProDOT)–phenylene copolymers allow a yellow-to-transmissive electrochrome

In order to create multicolour displays using electrochromic (EC) technologies, the modulation of the intensity of three primary subtractive colours (red, yellow, blue, or cyan, magenta, yellow) could be used to express any colour in the spectrum. Herein we report the first cathodically colouring yellow-to-transmissive switching EC polymer, which completes a full colour palette and promises to fulfil the requirements necessary to create multicolour EC displays.

Fast switching water processable electrochromic polymers.

This paper describes the synthesis of two new blue to transmissive donor-acceptor electrochromic polymers: a polymer synthesized using an alternating copolymerization route (ECP-Blue-A) and a polymer synthesized using a random copolymerization (ECP-Blue-R) by Stille polymerization. These polymers utilize side chains with four ester groups per donor moiety, allowing organic solubility in the ester form, and water solubility upon saponification to their carboxylate salt form. We demonstrate that the saponified polymer salts of ECP-Blue-A and ECP-Blue-R (WS-ECP-Blue-A and WS-ECP-Blue-R) can be processed from aqueous solutions into thin films by spray-casting. Upon the subsequent neutralization of the thin films, the resulting polymer acid films are solvent resistant and can be electrochemically switched between their colored state and a transmissive state in a KNO(3)/water electrolyte solution. The polymer acids, WS-ECP-Blue-A-acid and WS-ECP-Blue-R-acid, show electrochromic contrast Δ%T of 38% at 655 nm and 39% at 555 nm for a 0.5 s switch, demonstrating the advantage of an aqueous compatible electrochrome switchable in high ionic conductivity aqueous electrolytes. The results of the electrochromic properties study indicate that these polymers are promising candidates for aqueous processable and aqueous switching electrochromic materials and devices as desired for applications where environmental impact is of importance.

Establishing Dual Electrogenerated Chemiluminescence and Multicolor Electrochromism in Functional Ionic Transition-Metal Complexes

A combination of electrochromism and electroluminescence in functional materials could lead to single-layer dual electrochromic/electroluminescent (EC/EL) display devices, capable of simultaneous operation in emissive and reflective modes. Whereas such next generation displays could provide optimal visibility in any ambient lighting situation, materials available that exhibit such characteristics in the active layer are limited due to the required intrinsic multifunctionality (i.e., redox activity, electroluminescence, electrochromism, and ion conductivity) and to date can only be achieved via the rational design of ionic transition-metal complexes. Reported herein is the synthesis and characterization of a new family of acrylate-containing ruthenium (tris)bipyridine-based coordination complexes with multifunctional characteristics. Potential use of the presented compounds in EC/EL devices is established, as they are applied as cross-linked electrochromic films and electrochemiluminescent layers in light-emitting electrochemical cell devices. Electrochromic switching of the polymeric networks between yellow, orange, green, brown and transmissive states is demonstrated, and electrochemiluminescent devices based on the complexes synthesized show red-orange to deep red emission with λ(max) ranging from 680 to 722 nm and luminance up to 135 cd/m(2). Additionally, a dual EC/EL device prototype is presented where light emission and multicolor electrochromism occur from the same pixel comprised of a single active layer, demonstrating a true combination of these properties in ionic transition-metal complexes.