New Roll‐to‐Roll Processable PEDOT‐Based Polymer with Colorless Bleached State for Flexible Electrochromic Devices

Conjugated electrochromic (EC) polymers for flexible EC devices (ECDs) generally lack a fully colorless bleached state. A strategy to overcome this drawback is the implementation of a new sidechain‐modified poly(3,4‐ethylene dioxythiophene) derivative that can be deposited in thin‐film form in a customized high‐throughput and large‐area roll‐to‐roll polymerization process. The sidechain modification provides enhanced EC properties in terms of visible light transmittance change, Δτ_v = 59% (ΔL* = 54.1), contrast ratio (CR = 15.8), coloration efficiency (η = 530 cm² C^?1), and color neutrality (L* = 83.8, a* = ?4.3, b* = ?4.1) in the bleached state. The intense blue‐colored polymer thin films exhibit high cycle stability (10 000 cycles) and fast response times. The design, synthesis, and polymerization of the modified 3,4‐ethylene dioxythiophene derivative are discussed along with a detailed optical, electrochemical, and spectroelectrochemical characterization of the resulting EC thin films. Finally, a flexible see‐through ECD with a visible light transmittance change of Δτ_v = 47% (ΔL* = 51.9) and a neutral‐colored bleached state is developed.     

On‐Substrate Preparation of an Electroactive Conjugated Polyazomethine from Solution‐Processable Monomers and its Application in Electrochromic Devices

An electroactive polyazomethine is prepared from a solution processable 2,5‐diaminothiophene derivative and 4,4′‐triphenylamine dialdehyde by spray‐coating the monomers on substrates, including indium tin oxide (ITO) coated glass and native glass slides. The conjugated polymer was rapidly formed in situ by heating the substrates at 120 °C for 30 min in an acid saturated atmosphere. The resulting immobilized polymer is easily purified by rinsing the substrate with dichloromethane. The on‐substrate polymerization is tolerant towards large stoichiometry imbalances of the comonomers, unlike solution step‐growth polymerization. The resulting polyazomethine is electroactive and it can be switched reversibly between its neutral and oxidized states both electrochemically and chemically without degradation. A transmissive electrochromic device is fabricated from the immobilized polyazomethine on an ITO electrode. The resulting device is successfully cycled between its oxidized (dark blue) and neutral (cyan/light green) states with applied biases of +3.2 and ‐1.5 V under ambient conditions without significant color fatigue or polymer degradation. The coloration efficiency of the oxidized state at 690 nm is 102 cm² C^?1.     

Paper‐Based Electrochromic Devices Enabled by Nanocellulose‐Coated Substrates

As environmental considerations for both the processing and disposal of electronic devices become increasingly important, the ability to replace plastic and glass substrates with bioderived and biodegradable materials remains a major technological goal. Here, the use of cellulose nanofiber‐coated paper is explored as an environmentally benign substrate for preparing low‐resistance (460 Ω sq^?1), colorless (a* = ?2.3, b* = ?2.7) printed poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) electrodes. The PEDOT:PSS/paper electrodes support the reversible oxidation of three electrochromic polymers (ECPs) (cyan, magenta, and yellow), affording the possibility for fully printed, color displays on paper. Lateral electrochromic devices (ECDs) incorporating an ion gel electrolyte are demonstrated where a magenta‐to‐colorless device achieves a color contrast (ΔE*) of 56 owing to a highly color‐neutral bleached state of the ECP (a* = ?0.5, b* = 2.9). Black‐to‐colorless devices achieve ΔE* = 29 and are able to retain 86% of their color contrast after 9000 switches. The switching times of these lateral devices are quantified through colorimetric image analysis which shows comparable performance for devices constructed on paper as devices using ITO/glass electrodes (10 Ω sq^?1). The paper ECDs are then combusted in air leaving 3% of the initial mass at 600 °C, highlighting this approach as a promising route toward disposable displays.     

A Novel Neutral State Green Polymeric Electrochromic with Superior n‐ and p‐Doping Processes: Closer to Red‐Blue‐Green (RGB) Display Realization

Two donor‐acceptor systems, 4,7‐di‐2‐thienyl‐2,1,3‐benzoselenadiazole (TSeT) and 4,7‐di‐2,3‐dihydrothieno[3,4‐b][1,4]dioxin‐5‐yl‐2,1,3‐benzoselenadiazole (ESeE) are synthesized and electropolymerized to give polymers PTSeT and PESeE, respectively. One of the polymers, PTSeT, is blue‐green in the neutral state and soluble, exhibiting a deep‐red emission color. The other, PESeE, is the first 2,1,3‐benzoselenadiazole‐based neutral state green polymer with a narrow bandgap (1.04 eV). Furthermore, PESeE has superior and durable n‐ and p‐doping processes. Beyond the stability and the robustness, both of the polymer films exhibit multi‐electrochromic behavior.     

Development and Manufacture of Polymer‐Based Electrochromic Devices

The field of organic electrochromics is reviewed here, with particular focus on how the “electrochromic” as a functional material can be brought from the current level of accurate laboratory synthesis and characterization to the device and application level through a number of suited roll‐to‐roll methods compatible with upscaling and manufacture. The successful approaches to operational devices are presented in detail, as well as areas where future research would have a high impact and accelerate the development such as highly conducting and transparent substrates, electrolytes adapted for multilayer application and morphologically stable conjugated polymers.     

A Solution‐Processable High‐Coloration‐Efficiency Low‐Switching‐Voltage Electrochromic Polymer Based on Polycyclopentadithiophene

A solution‐processable electrochromic (EC) polymer, poly(4,4‐dioctyl‐cyclopenta[2,1‐b:3,4‐b′]‐dithiophene) (PDOCPDT) is prepared by means of chemical oxidative polymerization of the corresponding monomer. The UV‐vis spectrum of the spin‐coated PDOCPDT film displays an absorption maximum of 580 nm. Although the polymer is deep blue in its neutral state, it turns to transparent bluish after being oxidized. PDOCPDT film (thickness 120 nm) exhibits high coloration efficiency (CE)—as high as 932 C cm^–2 at 580 nm, low response time (0.75 s), high optical density (0.75 at 580 nm), and high‐level stability for long term switch (it switches repetitively 1000 times with less than 8 % contrast loss). The electrochemical stability and redox potentials of PDOCPDT films are independent of film thickness (50–180 nm) and active area (up to 2 cm × 2 cm). Nevertheless, optical contrast increases as the film thickness increases, although the CE and response time changes irregularly with the film thickness. The good EC properties combined with the easy film fabrication process make PDOCPDT a notable candidate for application in EC devices. (ECDs) A simple transmissive‐type ECD with good CE using PDOCPDT film as an active layer is also demonstrated.     

State‐of‐the‐Art Progress in Diverse Heterostructured Photocatalysts toward Promoting Photocatalytic Performance

Semiconductor photocatalysts have received much attention in recent years due to their great potentials for the development of renewable energy technologies, as well as for environmental protection and remediation. The effective harvesting of solar energy and suppression of charge carrier recombination are two key aspects in photocatalysis. The formation of heterostructured photocatalysts is a promising strategy to improve photocatalytic activity, which is superior to that of their single component photocatalysts. This Feature Article concisely summarizes and highlights the state‐of‐the‐art progress of semiconductor/semiconductor heterostructured photocatalysts with diverse models, including type‐I and type‐II heterojunctions, Z‐scheme system, p–n heterojunctions, and homojunction band alignments, which were explored for effective improvement of photocatalytic activity through increase of the visible‐light absorption, promotion of separation, and transportation of the photoinduced charge carries, and enhancement of the photocatalytic stability.     

Perfluoroalkanoate‐Substituted PEDOT for Electrochromic Device Applications

The recent emergence of organic electrochromics on both the scientific and industrial levels has expedited the synthesis of new materials with varied electrochemical and optical properties. The structural versatility and broad usage of poly(3,4‐ethylenedioxythiophene) (PEDOT) has stimulated many research groups to focus on the potential of PEDOT derivatives. Here we report the first synthesis of pentadecafluoro‐octanoic acid 2,3‐dihydro‐thieno(3,4‐b)(1,4)dioxin‐2‐ylmethylester (EDOT‐F), along with its electrochemical polymerization, characterization, and incorporation into electrochromic devices (ECDs). PEDOT‐F is a cathodically coloring polymer that exhibits sub‐second switching time between a dark‐blue neutral state and a transmissive sky‐blue oxidized state, and expresses a 63 % change for both transmittance at λ_max and colorimetrically determined luminance. Hexafluorophosphate‐doped free‐standing films of PEDOT‐F possess conductivities of up to 65 S cm^–1. Variable transmittance ECDs constructed with PEDOT‐F and poly[3,6‐bis(2‐(3,4‐ethylenedioxythienyl))‐N‐methylcarbazole] (PBEDOT‐NMeCz) exhibit an optical contrast of 60 % at λ_max (580 nm) and an overall luminance change of 60 %. Indicating the hydrophobicity of this polymer, doped PEDOT‐F exhibits a water contact angle of 110°, significantly higher than the 30° exhibited for the doped PEDOT parent.     

High‐Conductivity Poly(3,4‐ethylenedioxythiophene):Poly(styrene sulfonate) Film and Its Application in Polymer Optoelectronic Devices

The conductivity of a poly(3,4‐ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) film can be enhanced by more than two orders of magnitude by adding a compound with two or more polar groups, such as ethylene glycol, meso‐erythritol (1,2,3,4‐tetrahydroxybutane), or 2‐nitroenthanol, to an aqueous solution of PEDOT:PSS. The mechanism for this conductivity enhancement is studied, and a new mechanism proposed. Raman spectroscopy indicates an effect of the liquid additive on the chemical structure of the PEDOT chains, which suggests a conformational change of PEDOT chains in the film. Both coil and linear conformations or an expanded‐coil conformation of the PEDOT chains may be present in the untreated PEDOT:PSS film, and the linear or expanded‐coil conformations may become dominant in the treated PEDOT:PSS film. This conformational change results in the enhancement of charge‐carrier mobility in the film and leads to an enhanced conductivity. The high‐conductivity PEDOT:PSS film is ideal as an electrode for polymer optoelectronic devices. Polymer light‐emitting diodes and photovoltaic cells fabricated using such high‐conductivity PEDOT:PSS films as the anode exhibit a high performance, close to that obtained using indium tin oxide as the anode.     

In Search of High‐Performance Platinum(II) Phosphorescent Materials for the Fabrication of Red Electroluminescent Devices

The rational design and syntheses of Pt(iqdz)₂ ( 1 ) and Pt(pydz)₂ ( 2 ) bearing isoquinolinyl indazole (iqdz)H or pyridyl indazole (pydz)H groups on the coordinating ligands are reported. Single‐crystal X‐ray diffraction studies of 1 reveal a square planar geometry, in which two iqdz ligands adopt a trans‐configuration. Short N…H contacts (～2.21 Å) are detected between the ortho‐hydrogen atom of isoquinoline and the adjacent N atom of the indazole fragment, making the overall molecular geometry analogous to that of the platinum(II ) porphyrinato complexes. The lowest absorption bands for both complexes reveal strong state mixings between singlet and triplet (metal‐to‐ligand charge transfer and intra‐ligand) manifolds. This, in combination with the introduction of a camphor‐like structure to avoid the stacking effect, leads to phosphorescence with unprecedented brightness both in solution and in the solid state. Organic light‐emitting diode (OLED) devices fabricated using 1 as a dopant emitter have been achieved in a multilayer configuration. The results constitute the first highly efficient Pt^II‐based red OLED.     

A Unique Processable Green Polymer with a Transmissive Oxidized State for Realization of Potential RGB‐Based Electrochromic Device Applications

Realization of commercial RGB‐based polymer electrochromic‐device applications can only be achieved by processable materials that possess three complementary colors in the reduced state and are transparent in the oxidized state. This report highlights the synthesis of the first processable green polymer with a transmissive oxidized state. The polymer revealed superior optical contrast in the visible region with fast switching times and robust stability. Hence, this material is the outstanding candidate for completion of RGB color space through commercial polymeric electrochromics.     

Highly Efficient Inverted Organic Solar Cells Through Material and Interfacial Engineering of Indacenodithieno[3,2‐b]thiophene‐Based Polymers and Devices

A synergistic approach combining new material design and interfacial engineering of devices is adopted to produce high efficiency inverted solar cells. Two new polymers, based on an indacenodithieno[3,2‐b]thiophene‐difluorobenzothiadiazole (PIDTT‐DFBT) donor–acceptor (D–A) polymer, are produced by incorporating either an alkyl thiophene (PIDTT‐DFBT‐T) or alkyl thieno[3,2‐b]thiophene (PIDTT‐DFBT‐TT) π‐bridge as spacer. Although the PIDTT‐DFBT‐TT polymer exhibits decreased absorption at longer wavelengths and increased absorption at higher energy wavelengths, it shows higher power conversion efficiencies in devices. In contrast, the thiophene bridged PIDTT‐DFBT‐T shows a similar change in its absorption spectrum, but its low molecular weight leads to reduced hole mobilities and performance in photovoltaic cells. Inverted solar cells based on PIDTT‐DFBT‐TT are explored by modifying the electron‐transporting ZnO layer with a fullerene self‐assembled monolayer and the MoO₃ hole‐transporting layer with graphene oxide. This leads to power conversion efficiencies as high as 7.3% in inverted cells. PIDTT‐DFBT‐TT's characteristic strong short wavelength absorption and high efficiency suggests it is a good candidate as a wide band gap material for tandem solar cells.     

Electron‐Rich Alcohol‐Soluble Neutral Conjugated Polymers as Highly Efficient Electron‐Injecting Materials for Polymer Light‐Emitting Diodes

We report the design and synthesis of three alcohol‐soluble neutral conjugated polymers, poly[9,9‐bis(2‐(2‐(2‐diethanolaminoethoxy) ethoxy)ethyl)fluorene] (PF‐OH), poly[9,9‐bis(2‐(2‐(2‐diethanol‐aminoethoxy)ethoxy)ethyl)fluorene‐alt‐4,4′‐phenylether] (PFPE‐OH) and poly[9,9‐bis(2‐(2‐(2‐diethanolaminoethoxy) ethoxy)ethyl)fluorene‐alt‐benzothiadizole] (PFBT‐OH) with different conjugation length and electron affinity as highly efficient electron injecting and transporting materials for polymer light‐emitting diodes (PLEDs). The unique solubility of these polymers in polar solvents renders them as good candidates for multilayer solution processed PLEDs. Both the fluorescent and phosphorescent PLEDs based on these polymers as electron injecting/transporting layer (ETL) were fabricated. It is interesting to find that electron‐deficient polymer (PFBT‐OH) shows very poor electron‐injecting ability compared to polymers with electron‐rich main chain (PF‐OH and PFPE‐OH). This phenomenon is quite different from that obtained from conventional electron‐injecting materials. Moreover, when these polymers were used in the phosphorescent PLEDs, the performance of the devices is highly dependent on the processing conditions of these polymers. The devices with ETL processed from water/methanol mixed solvent showed much better device performance than the devices processed with methanol as solvent. It was found that the erosion of the phosphorescent emission layer could be greatly suppressed by using water/methanol mixed solvent for processing the polymer ETL. The electronic properties of the ETL could also be influenced by the processing conditions. This offers a new avenue to improve the performance of phosphorescent PLEDs through manipulating the processing conditions of these conjugated polymer ETLs.     

Layered,Nanonetwork Composite Cathodes for Flexible,High‐Efficiency,Organic Light Emitting Devices

In this work, the application of an aluminum (Al)/multiwall carbon nanotube (MWCNT)/Al, multilayered electrode to flexible, high‐efficiency, alternating current driven organic electroluminescent devices (AC‐OEL), is reported. The electrode is fabricated by sandwiching a spray‐cast nanonetwork film of MWCNTs between two evaporated layers of Al. The resulting composite film facilitates a uniform charge distribution across a robust crack‐free electrode under various bending angles. It is demonstrated that these composite electrodes stabilize the power efficiency of flexible devices for bending angles up to 120°, with AC‐OEL device power efficiencies of ≈22 lm W^?1 at luminances of ≈4000 cd m^?2 (using no output coupling). Microscopic examination of the Al/MWCNTs/Al electrode after bending of up to 1300 cycles suggests that the nanotubes significantly enhance the mechanical properties of the thin Al layers while providing a moderate modification to the work function of the metal. While the realization of robust, high‐brightness, and high‐efficiency AC‐OEL devices is potentially important in their future lighting applications, it is anticipated that this to also have significant impact in standard organic light emitting diodes lighting applications.     

Mg3+δSbxBi2−x Family: A Promising Substitute for the State‐of‐the‐Art n‐Type Thermoelectric Materials near Room Temperature

The Bi₂Te_3?xSe_x family has constituted n‐type state‐of‐the‐art thermoelectric materials near room temperature (RT) for more than half a century, which dominates the active cooling and novel heat harvesting application near RT. However, the drawbacks of a brittle nature and Te‐content restricts the possibility for exploring potential applications. Here, it is shown that the Mg_3+δSb_xBi_2?x family ((ZT)_avg = 1.05) could be a promising substitute for the Bi₂Te_3?xSe_x family ((ZT)_avg = 0.9–1.0) in the temperature range of 50–250 °C based on the comparable thermoelectric performance through a synergistic effect from the tunable bandgap using the alloy effect and the suppressible Mg‐vacancy formation using an interstitial Mn dopant. The former is to shift the optimal thermoelectric performance to near RT, and the latter is helpful to partially decouple the electrical transport and thermal transport in order to get an optimal RT power factor. The positive temperature dependence of the bandgap suggests this family is also a superior medium‐temperature thermoelectric material for the significantly suppressed bipolar effect. Furthermore, a two times higher mechanical toughness, compared with the Bi₂Te_3?xSe_x family, allows for a promising substitute for state‐of‐the‐art n‐type thermoelectric materials near RT.     

Amino N‐Oxide Functionalized Conjugated Polymers and their Amino‐Functionalized Precursors: New Cathode Interlayers for High‐Performance Optoelectronic Devices

A series of amino N‐oxide functionalized polyfluorene homopolymers and copolymers (PNOs) are synthesized by oxidizing their amino functionalized precursor polymers (PNs) with hydrogen peroxide. Excellent solubility in polar solvents and good electron injection from high work‐function metals make PNOs good candidates for interfacial modification of solution processed multilayer polymer light‐emitting diodes (PLEDs) and polymer solar cells (PSCs). Both PNOs and PNs are used as cathode interlayers in PLEDs and PSCs. It is found that the resulting devices show much better performance than devices based on a bare Al cathode. The effect of side chain and main chain variations on the device performance is investigated. PNOs/Al cathode devices exhibit better performance than PNs/Al cathode devices. Moreover, devices incorporating polymers with para‐linkage of pyridinyl moieties exhibit better performance than those using polymers with meta‐linked counterparts. With a poly[(2,7‐(9,9‐bis(6‐(N,N‐diethylamino)‐hexyl N‐oxide)fluorene))‐alt‐(2,5‐pyridinyl)] (PF6NO25Py) cathode interlayer, the resulting device exhibits a luminance efficiency of 16.9 cd A^?1 and a power conversion efficiency of 6.9% for PLEDs and PSCs, respectively. These results indicate that PNOs are promising new cathode interlayers for modifying a range of optoelectronic devices.     

Large,Switchable Electrochromism in the Visible Through Far‐Infrared in Conducting Polymer Devices

Advanced materials with large and dynamic variation in thermal properties, sought for urgent defense and space applications, have heretofore been elusive. Conducting polymers (CPs) have shown some intrinsic variation of mid‐ to far‐infrared (IR) signature in this respect, but the practical utilization of this has remained elusive. We report herein the first significant IR electrochromism in any material, to our knowledge, in the 0.4 through 45 μm region. This is seen in practical CP devices in the form of thin (<0.5 mm), flexible, entirely solid‐state, variable area (1 cm² to 1 m²) flat panels. Typical properties include: very high reflectance variation; switching times <2 s; cyclabilities of 10⁵ cycles; emittance variation from 0.32 to 0.79; solar absorptance variation from 0.39 to 0.79; operating temperatures of –35 to +85 °C; durability against γ‐radiation to 7.6 Mrad, vacuum to 10^–6 torr, and simulated solar wind (e.g., 6.5 × 10¹⁶ e/cm² @ 10 keV).     

Wood‐Derived Materials for Advanced Electrochemical Energy Storage Devices

Over the past decade, wood‐derived materials have attracted enormous interest for both fundamental research and practical applications in various functional devices. In addition to being renewable, environmentally benign, naturally abundant, and biodegradable, wood‐derived materials have several unique advantages, including hierarchically porous structures, excellent mechanical flexibility and integrity, and tunable multifunctionality, making them ideally suited for efficient energy storage and conversion. In this article, the latest advances in the development of wood‐derived materials are discussed for electrochemical energy storage systems and devices (e.g., supercapacitors and rechargeable batteries), highlighting their micro/nanostructures, strategies for tailoring the structures and morphologies, as well as their impact on electrochemical performance (energy and power density and long‐term durability). Furthermore, the scientific and technical challenges, together with new directions of future research in this exciting field, are also outlined for electrochemical energy storage applications.