This review describes figures of merit, challenges and strategies during the development of solution-processable electrochromic materials and devices for large-area smart window applications.
The repetitive size change of the electrode over cycles, termed as mechanical breathing, is a crucial issue limiting the quality and lifetime of organic electrochromic devices. The mechanical deformation originates from the electron transport and ion intercalation in the redox active material. The dynamics of the state of charge induces drastic changes of the microstructure and properties of the host, and ultimately leads to structural disintegration at the interfaces. We quantify the breathing strain and the evolution of the mechanical properties of poly(3,4-propylenedioxythiophene) thin films in-situ using customized environmental nanoindentation. Upon oxidation, the film expands nearly 30% in volume, and the elastic modulus and hardness decrease by a factor of two. We perform theoretical modeling to understand thin film delamination from an indium tin oxide (ITO) current collector under cyclic load. We show that toughening the interface with roughened or silica-nanoparticle coated ITO surface significantly improves the cyclic performance.
A scalable and green approach to manufacture semiconducting microfibers from polymer melts has been demonstrated. The polymer chains are highly aligned along the microfiber's long axis direction and exhibit highly anisotropic optical properties. In addition, the polymer microfibers show good flexibility and stretchability with a yield point around 10% under a reversible stress and can be stretched up to 180% without breaking. These features are desired for future flexible, stretchable, and conformable electronics. The origin of this stretchability is studied with diketopyrrolopyrrole derivatives using different conjugation break spacers and side chains. In addition, stretchable conducting microfibers can be obtained by doping with FeCl 3 , which are further evaluated as organic conductors and source/drain electrodes in organic field-effect transistors.
Camouflage is often seen in animals, and it presents in both passive and active forms. For instance, the wings of Closterocerus coffeellae exhibit distinct appearances against different backgrounds, while the chameleon actively changes its skin colors to morph into the environment. Herein, we report an artificial skin-like optoelectronic device that enables actively changing appearances and passively morphing into the environment by manipulating light–matter interactions with electrochromic polymers and photonic colloid nanocrystals. To construct the new electrochromic device, highly reflective, yet transmissive photonic nanocrystals are introduced into the gel electrolyte and sandwiched between the layers of electrochromic polymers and ion storage materials. Through voltage-controlled color switching of electrochromic polymers from colored state to bleached state, the degree of light absorbance, transmittance, and reflectance can be finely balanced and precisely modulated with the device. A broad synthesized color gamut and angle-dependent visual effects can be realized on this electronic skin-like device.
The limited availability of solution-processable ion storage materials, both inorganic and organic, hinders the adoption of roll-to-roll manufacturing for polymer electrochromic devices (ECDs). The n-type transition metal oxides are known for their ion storage properties. However, the fabrication methods of their amorphous metal oxide thin films typically involve sputtering, thermal deposition, electrical deposition, or sol−gel deposition followed by high-temperature thermal annealing (>300 °C), thus making them incompatible for low-cost roll-to-roll manufacturing on flexible substrates. In this study, we report the synthesis of amorphous niobium oxide(a-Nb 2 O 5 ) thin films from sol−gel precursors through the combination of photoactivation and low-temperature thermal annealing (150 °C). Coupled with p-type electrochromic polymers (ECPs), solution-processed a-Nb 2 O 5 thin films were evaluated as a minimally color changing counter electrode (MCC-CE) material for electrochromic devices. We found that ultraviolet ozone (UVO) treated and 150 °C thermally annealed (UVO-150 °C) a-Nb 2 O 5 thin films show excellent electrochemical properties and cycling stability. Notably, a-Nb 2 O 5 /ECP-magenta ECD has a high optical contrast of ∼70% and a fast switching time (bleaching and coloring time of 1.6 and 0.5 s for reaching 95% of optical contrast). In addition, the ECD demonstrates a high coloration efficiency of ∼849.5 mC cm −2 and a long cycling stability without a noticeable decay up to 3000 cycles.
Semiconductors with electrically tunable band gaps are of great interest in controlling transparency to electromagnetic radiation. Thin films of perovskite nickelate NdNiO3 (NNO), a class of correlated oxides, were deposited on single-crystal (LaAlO3 (LAO)) and polycrystalline (fluorine-doped tin oxide-coated glass (FTO)) substrates by magnetron sputtering, chemical solution deposition (CSD), and atomic layer deposition (ALD). Their electrochromic behaviors were investigated using a three-electrode setup in basic (KOH solution, pH = 12) electrolyte. During bleaching/coloration process, the proton intercalation/deintercalation and simultaneous electron compensation in the NNO lattice under electrical bias led to crossover of the material between the pristine-conducting phase (Ni3+) and the strongly correlated insulating phase (Ni2+), which serves as the working principle for electrochromic (tunable opacity in the visible range) behavior. Cyclic voltammetry (CV) scans demonstrate that NNO films are electrochemically stable in basic solutions for all three film deposition methods explored here. CV scans at varying rates enabled the extraction of diffusion coefficient of protons in thin film NNO, which is ∼10–7 cm2 s–1 among all films studied. Large light transmittance modulation by bleaching and coloration was observed on films grown on both LAO and FTO substrates, suggesting its potential as an electrochromic material candidate for smart windows and optical shutter applications. Porous NNO films obtained by chemical solution deposition tend to demonstrate stronger electrochromic activity than dense films grown by sputtering or ALD.
A highly transparent crosslinkable thin film made of the radical polymer poly(2,2,6,6-tetramethyl-4-piperidinyloxy methacrylate)- co-(4-benzoylphenyl methacrylate) (PTMA- co-BP) has been developed as the ion storage layer in electrochromic devices (ECDs). After photo-crosslinking, the dissolution of PTMA- co-BP in electrolytes was mitigated, which results in an enhanced electrochemical stability compared with the homopolymer PTMA thin film. Moreover, the redox capacity of PTMA- co-BP increased because of the formation of a crosslinked network. By matching the redox capacity of the PTMA- co-BP thin film and bis(alkoxy)-substituted poly(propylenedioxythiophene), the ECD achieved an optical contrast of 72% in a small potential window of 2.55 V (i.e., switching between +1.2 and -1.35 V), and it was cycled up to 1800 cycles. The ECD showed an excellent optical memory as its transmittance decayed by less than 3% in both the colored and bleached states while operating for over 30 min under open-circuit conditions. Use of crosslinkable radical polymers as the transparent ion storage layer opens up a new venue for the fabrication of transmissive-mode organic ECDs.
Three types of macroanion-countercation interactions in dilute solution, decided by the strength of electrostatic attraction and the change of hydration shells are reported: minor interaction between macroanions [MO Pd (SeO ) ] (M=Zn or Ni ) and monovalent cations (Na , K , Rb , Cs ), leaving their hydration shells intact (solvent-separated ion-pairs); strong binding between macroanions and divalent cations (Sr , Ba ) to form solvent-shared ion-pairs with partial dehydration; very strong electrostatic attraction between macroanions and Y ion with contact ion-pairs formation by severely breaking their original hydration shells and forming new ones. In addition, divalent cations can help the macroanions self-assemble into hollow spherical blackberry structures through counterion-mediated attraction, whereas macroanions with mono- or trivalent cations only stay as discrete ions due to either weak interaction or a small number of bound countercations.
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