Electrochromic devices having n-doped conductive polymer as transparent conducting layer, ion storage layer, and / or electrochromic layer

Abstract

To provide electrochromic devices / displays containing an n-doped organic conductive polymer.SOLUTION: An electrochromic device comprises: two substrates; and a plurality of areas disposed between the two substrates. Each of the area includes: a first conductive layer; an electrolyte layer on top of the first conductive layer; an electrochromic layer on top of the electrolyte layer; and a second conductive layer on top of the electrochromic layer. The first conductive layer contains an n-doped organic conductive polymer.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to U.S. Application No. 18 / 545,355, filed December 19, 2023, U.S. Application No. 18 / 532,911, filed December 7, 2023, and U.S. Application No. 18 / 099,850, filed January 20, 2023, the entire contents of all of which are incorporated herein by reference.

[0002] The present invention relates to an electrochromic device having an n-doped organic conductive polymer which can serve as a transparent conductive layer or / and an ion storage layer or / and an electrochromic layer. [Background technology]

[0003] An electrochromic device (ECD) typically consists of seven layers, including two non-conductive layers as substrates, one or two transparent conductive (TC) layers, an electrochromic layer as working electrode (WE), an ion storage layer as counter electrode (CE) and an electrolyte layer. The electrochromic layer changes color when an external electrical bias is applied. Meanwhile, in the ion storage layer, the opposite reaction to that in the electrochromic layer occurs, balancing the charge generated in the electrochromic layer. Between the electrochromic layer and the ion storage layer is an electrolyte layer, which acts as an ion source and an ion conducting channel. The electrochromic layer and the ion storage layer are disposed on a transparent conductor, which is a current collector for the device. If two transparent conductive layers are selected, the device functions as a transmissive device. If one transparent conductor is used (e.g., the other conductive layer is a reflective conductive layer), it typically functions as a reflective device. The most used TC layer in ECDs is indium tin oxide (ITO) due to its low sheet resistance, high light transparency and large enough potential window for most EC materials. However, ITO has a small bending radius and bending strain, and is mechanically fragile, limiting its applications in roll-to-roll manufacturing and flexible electronics. In addition, indium is a rare earth metal with scarce mineral reserves. With the increasing demand for ITO, the availability of indium will be highly constrained within 20 years, but has seen a price increase in recent years. Therefore, it is highly desirable to find an ITO substitute that offers high performance while at the same time being low cost, and it would be even more valuable to reduce the number of layers in the ECD to simplify the device structure and further reduce the cost. Furthermore, it is also desirable to combine a solution processable, transparent ion storage material with minimal color change with the electrochromic material to improve performance and durability. Summary of the Invention [Means for solving the problem]

[0004] The present disclosure relates to electrochromic devices / displays comprising n-doped organic conductive polymers.

[0005] In one embodiment, the disclosed electrochromic device includes two substrates and a plurality of regions disposed between the two substrates, each of the regions including a first conductive layer, an electrolyte layer on the first conductive layer, an electrochromic layer on the electrolyte layer, and a second conductive layer on the electrochromic layer. In the disclosed electrochromic device, the first conductive layer is a compound represented by the formula [ka] In this formula, X is O, S or Se, each of m and n is an integer greater than zero, and each of R1 and R2 is independently hydrogen, halogen or C1-C 10 alkyl, M +is an organic or metal cation. In some embodiments, the second conductive layer comprises an n-doped organic conductive polymer. In some embodiments, the thickness of the second conductive layer is less than the thickness of the first conductive layer. In some embodiments, the disclosed electrochromic device further comprises an ion storage layer disposed between the first conductive layer and the electrolyte layer, where the ion storage layer does not comprise an n-doped organic conductive polymer. In some embodiments, each of the electrolyte layer and the electrochromic layer is made of a polymer. In some embodiments, the electrolyte layer is a solid electrolyte layer. In some embodiments, the region comprises a first region and a second region, and the first region comprises a first electrochromic layer that is different from the second electrochromic layer of the second region to display different colors. In some embodiments, at least one of the substrates is flexible. In some embodiments, the first conductive layer or the second conductive layer is transparent or translucent. In some embodiments, the disclosed electrochromic device further comprises a conductive polymer interconnect connecting two adjacent regions. In some embodiments, the conductive polymer interconnect comprises an n-doped organic conductive polymer. In some embodiments, each of the regions in the bleached state is transparent, such that the electrochromic device can be a see-through display. In some embodiments, the n-doped organic conductive polymer has a transmission with minimal color change at wavelengths between 380 nm and 800 nm, and a color saturation change, ΔC, of ​​less than 5 between the oxidized and reduced states of the n-doped organic conductive polymer. *In some embodiments, the disclosed electrochromic device operates at less than 3 volts. In some embodiments, the disclosed electrochromic device has a transmittance decay ΔT of less than 5% during 1000 seconds of operation under open circuit potential at each reductive or oxidative potential bias. In some embodiments, the region includes a first region and a second region, the electrochromic layer and the second conductive layer of the first region are separate from the electrochromic layer and the second conductive layer of the second region, and the second conductive layer of the first region is connected by a first conductive polymer interconnect disposed therebetween. In some embodiments, the electrolyte layer and the first conductive layer of the first region are separate from the electrolyte layer and the first conductive layer of the second region, and the first conductive layer of the first region is connected by a second conductive polymer interconnect disposed therebetween.

[0006] In one embodiment, the disclosed electrochromic device includes two substrates and layers disposed between the two substrates, where the layers include a first conductive layer, an electrolyte layer on the first conductive layer, an electrochromic layer on the electrolyte layer, and a second conductive layer on the electrochromic layer, where the first conductive layer is a compound represented by the formula: [ka] In some embodiments, the electrochromic device includes an n-doped poly(3,7-dihydrobenzo[1,2-b:4,5-b']difuran-2,6-dione) (n-PBDF) of the formula: where m and n are each an integer greater than zero. In some embodiments, the second conductive layer includes n-PBDF. In some embodiments, the thickness of the second conductive layer is less than the thickness of the first conductive layer. In some embodiments, the disclosed electrochromic device includes an ion storage layer disposed between the first conductive layer and the electrolyte layer, the ion storage layer does not include n-PBDF. In some embodiments, each of the electrolyte layer and the electrochromic layer is made of a polymer. In some embodiments, the electrolyte layer is a solid electrolyte layer. In some embodiments, at least one of the substrates is flexible. In some embodiments, the first conductive layer or the second conductive layer is transparent or translucent. In some embodiments, the first conductive layer has a transparency with minimal color change at wavelengths between 380 nm and 800 nm and a color saturation change, ΔC, of ​​less than 5 between the oxidized and reduced states of the first conductive layer. * In some embodiments, the disclosed electrochromic devices operate at less than 3 volts. In some embodiments, the disclosed electrochromic devices have a transmittance decay ΔT of less than 5% during 1000 seconds of operation under open circuit potential at each reductive or oxidative potential bias.

[0007] In one aspect, a method for forming an electrochromic device is disclosed. The method includes coating a first conductive layer on a first substrate, the first conductive layer having a formula: [ka] (In this formula, X is O, S, or Se; each of m and n is an integer greater than zero; and each of R1 and R2 is independently hydrogen or C1-C 10 alkyl, M +wherein x is an organic or metal cation), patterning the first conductive layer to form first regions and first electrical interconnects between adjacent first regions, coating a second conductive layer on a second substrate, patterning the second conductive layer to form second regions and second electrical interconnects between adjacent second regions, and one of the following sets of steps: a) forming a first electrolyte layer on each of the first regions, the first electrolyte layers being separated from each other; forming an electrochromic layer on each of the second regions, the electrochromic layers being separated from each other; forming a second electrolyte layer on each of the electrochromic layers, the second electrolyte layers being separated from each other; or b) forming an electrolyte layer on each of the first regions, the electrolyte layers being separated from one another; forming an electrochromic layer on each of the electrolyte layers, the electrochromic layers being separated from one another; and laminating the first substrate and the second substrate so that the electrochromic layer contacts the second region; or c) forming an electrochromic layer on each of the second regions, the electrochromic layers being separated from one another; forming an electrolyte layer on each of the electrochromic layers, the electrolyte layers being separated from one another; and laminating the first substrate and the second substrate so that the electrolyte layer contacts the first region.

[0008] In another aspect, a method is provided for forming an electrochromic device, the method including forming a first conductive layer on a first substrate, forming a first electrolyte layer on the first conductive layer, forming a second conductive layer on a second substrate, forming an electrochromic layer on the second conductive layer, forming a second electrolyte layer on the electrochromic layer, and laminating the first substrate and the second substrate such that the first electrolyte layer is in contact with the second electrolyte layer.

[0009] In some embodiments, the method further includes patterning the second conductive layer to form second regions and second electrical interconnects between adjacent second regions.

[0010] In some embodiments, forming the electrochromic layer on the second conductive layer includes patterning the electrochromic layer to form an electrochromic film over each of the second regions, wherein the electrochromic films are separated from one another, and forming the second electrolyte layer on the electrochromic layer includes forming the second electrolyte layer over the electrochromic film and each of the second electrical interconnects and in the gaps between adjacent second regions.

[0011] In some embodiments, the first conductive layer has the formula [ka] (wherein X is O, S or Se; each of m and n is an integer greater than zero; each of R1 and R2 is independently hydrogen or C1-C 10 alkyl, M + is an organic or metal cation).

[0012] In some embodiments, forming the electrochromic layer on the second conductive layer includes patterning the electrochromic layer to form an electrochromic film on each of the second regions, where the electrochromic films are separated from one another, and forming the second electrolyte layer on the electrochromic layer includes patterning the second electrolyte layer to form a second electrolyte film on each of the electrochromic films, where the second electrolyte films are separated from one another.

[0013] In some embodiments, the method further includes patterning the first conductive layer to form first regions and first electrical interconnects between adjacent first regions.

[0014] In some embodiments, forming the first electrolyte layer on the first conductive layer includes patterning the first electrolyte layer to form a first electrolyte film on each of the first regions, the first electrolyte films being separated from one another, and laminating the first substrate and the second substrate such that the first electrolyte layer contacts the second electrolyte layer includes laminating the first substrate and the second substrate such that the first electrolyte film contacts the second electrolyte film.

[0015] In some embodiments, the second conductive layer has the formula [ka] (wherein X is O, S or Se; each of m and n is an integer greater than zero; each of R1 and R2 is independently hydrogen or C1-C 10 alkyl, M + is an organic or metal cation).

[0016] In some embodiments, the method further includes forming an ion storage layer between the first conductive layer and the first electrolyte layer.

[0017] In some embodiments, forming an ion storage layer between the first conductive layer and the first electrolyte layer includes patterning the ion storage layer to form an ion storage film on each of the first regions, where the ion storage films are separated from one another. Forming a first electrolyte layer on the first conductive layer includes patterning the first electrolyte layer to form a first electrolyte film on each of the ion storage layers, where the first electrolyte films are separated from one another. Laminating the first substrate and the second substrate such that the first electrolyte layer contacts the second electrolyte layer includes laminating the first substrate and the second substrate such that the first electrolyte film contacts the second electrolyte film.

[0018] In another aspect, a method for forming an electrochromic device is provided, the method comprising coating a first conductive layer on a first substrate, the first conductive layer comprising a compound of the formula: [ka] (wherein X is O, S or Se; each of m and n is an integer greater than zero; each of R1 and R2 is independently hydrogen or C1-C 10 alkyl, M +wherein X is an organic or metal cation; patterning the first conductive layer to form first regions and first electrical interconnects between adjacent first regions; coating a second conductive layer on a second substrate; patterning the second conductive layer to form second regions and second electrical interconnects between adjacent second regions; and one of: a) forming an electrolyte layer on each of the first regions, the electrolyte layers being separated from one another; forming an electrochromic layer on each of the electrolyte layers. and laminating the first substrate and the second substrate such that the electrochromic layers contact the second regions; or b) forming an electrochromic layer on each of the second regions, the electrochromic layers being separated from each other; forming an electrolyte layer on each of the electrochromic layers, the electrolyte layers being separated from each other; and laminating the first substrate and the second substrate such that the electrolyte layer contacts the first regions.

[0019] In another aspect, a method for forming an electrochromic device is provided, the method comprising coating a first conductive layer on a first substrate, the first conductive layer comprising a compound of the formula: [ka] (wherein X is O, S or Se; each of m and n is an integer greater than zero; each of R1 and R2 is independently hydrogen or C1-C 10 alkyl, M +is an organic or metal cation), patterning the first conductive layer to form first regions and first electrical interconnects between adjacent first regions, coating the second conductive layer on a second substrate, and performing one of the following: a) forming an electrochromic layer on each of the first regions, the electrochromic layers being separated from one another; forming an electrolyte layer on the electrochromic layer; and laminating the first substrate and the second substrate such that the electrolyte layer is in contact with the second conductive layer, or b) forming an electrolyte layer on the second conductive layer; forming the electrochromic layer on the electrolyte layer; patterning the electrochromic layer to form a plurality of electrochromic layer regions on the electrolyte layer; and laminating the first substrate and the second substrate such that the electrochromic layer regions are in contact with the first regions.

[0020] In some embodiments, some or all of the above patterning operations may be performed by photolithographic or printing techniques.

[0021] Certain features of various embodiments of the present technology are set forth with particularity in the appended claims. A better understanding of the nature and advantages of the present technology will be obtained by reference to the following detailed description that sets forth illustrative embodiments, which utilize the principles of the present disclosure. The accompanying drawings include: [Brief description of the drawings]

[0022] [Figure 1] FIG. 1 is a cross-sectional view of an electrochromic device including a layer of an n-doped organic conductive polymer of the present disclosure functioning as a transparent conductive layer according to one exemplary embodiment of the present disclosure. [Figure 2(A)] FIG. 13 contains the electrical conductivity of an exemplary n-doped organic conductive polymer, n-PBDF thin film at different thicknesses according to some exemplary embodiments. [Figure 2(B)]FIG. 1 contains a diagram containing the transmittance of an exemplary n-doped organic conductive polymer, n-PBDF thin film at different thicknesses according to some exemplary embodiments. [Figure 2(C)] FIG. 13 contains the sheet resistance and transmittance at 550 nm of an exemplary n-doped organic conductive polymer, n-PBDF, thin film at different thicknesses according to some exemplary embodiments. [Figure 3(A)] 1 shows an exemplary design of a three-electrode electrochromic device including a layer of an exemplary n-doped organic conductive polymer, n-PBDF, which serves as the TC layer of the electrochromic device. FIG 2 shows a schematic diagram of a three-electrode electrochromic device according to one exemplary embodiment. [Figure 3(B)] 3(A) shows an exemplary design of a three-electrode electrochromic device including a layer of an exemplary n-doped organic conductive polymer, n-PBDF, which serves as the TC layer of the electrochromic device. [Figure 4(A)] FIG. 1 contains cyclic voltammograms of electrochromic polymer (ECP)-B on ITO / substrate and on an exemplary n-doped organic conductive polymer, n-PBDF / substrate, as well as cyclic voltammograms of n-PBDF on platinum button electrodes. [Figure 4(B)] FIG. 13. Spectroelectrochemical analysis of ECP-B on n-PBDF / substrate. [Figure 5(A)] Figure 1 shows the charge capacity of an exemplary n-doped organic conductive polymer, n-PBDF.Cyclic voltammograms of 30 nm thick n-BDF thin film on ITO at different rates in 0.2 M tetrabutylammonium-bis-trifluoromethanesulfonimidate (TBA-TFSI) in propylene carbonate (PC). [Figure 5(B)] 1 shows the charge capacity of an exemplary n-doped organic conductive polymer, n-PBDF, and the average current density at 0.3 V (vs. Ag / AgCl) plotted against scan rate. [Figure 6]1A-1C are cross-sectional views of electrochromic devices including a layer of an n-doped organic conductive polymer of the present disclosure that functions as an ion storage layer according to some exemplary embodiments of the present disclosure. [Figure 7(A)] 1 is a diagram of an exemplary ITO / exemplary n-doped organic conductive polymer n-PBDF / ECP-B electrochromic device including a layer of n-PBDF acting as an ion storage layer according to one exemplary embodiment, and a spectroelectrochemical analysis in the colored and bleached states according to one exemplary embodiment. [Figure 7(B)] 1 is a diagram of an exemplary ITO / exemplary n-doped organic conducting polymer n-PBDF / ECP-B electrochromic device including a layer of n-PBDF acting as an ion storage layer according to one exemplary embodiment, and FIG. 2 is a diagram of switching kinetics derived from stepped potential fast chronoamperometry (SPFC) according to one exemplary embodiment. [Figure 8] FIG. 2 is a cross-sectional view of an electrochromic device according to some exemplary embodiments of the present disclosure, comprising a layer of an n-doped organic conductive polymer of the present disclosure simultaneously functioning as both an ion storage layer and a TC layer for a counter electrode, and another layer of an n-doped organic conductive polymer of the present disclosure functioning as a TC layer for a working electrode. [Figure 9(A)] 1 is a diagram of an exemplary n-doped organic conductive polymer n-PBDF / ECP-B electrochromic device including a layer of n-PBDF that simultaneously serves as both an ion storage layer and a TC layer for a counter electrode, and another layer of n-PBDF that serves as a TC layer for a working electrode, according to one exemplary embodiment; and FIG. 2 is a diagram of a spectroelectrochemical analysis in the colored and bleached states, according to one exemplary embodiment. [Figure 9(B)] FIG. 1 is a diagram of an exemplary n-doped organic conductive polymer n-PBDF / ECP-B electrochromic device including a layer of n-PBDF that simultaneously serves as both an ion storage layer and a TC layer for a counter electrode, and another layer of n-PBDF that serves as a TC layer for a working electrode, according to one exemplary embodiment. FIG. 2 is a diagram of an exemplary n-doped organic conductive polymer n-PBDF / ECP-B electrochromic device including a layer of n-PBDF that simultaneously serves as both an ion storage layer and a TC layer for a counter electrode, according to one exemplary embodiment. FIG. 3 is a diagram of an exemplary n-doped organic conductive polymer n-PBDF / ECP-B electrochromic device including a layer of n-PBDF that simultaneously serves as both an ion storage layer and a TC layer for a working electrode, according to one exemplary embodiment. [Figure 10(A)]1 is a diagram of an exemplary n-doped organic conductive polymer n-PBDF / ECP-M electrochromic device including a layer of n-PBDF that simultaneously serves as both an ion storage layer and a TC layer for a counter electrode, and another layer of n-PBDF that serves as a TC layer for a working electrode, according to one exemplary embodiment; and FIG. 2 is a diagram of a spectroelectrochemical analysis in the colored and bleached states, according to one exemplary embodiment. [Figure 10(B)] FIG. 1 is a diagram of an exemplary n-doped organic conductive polymer n-PBDF / ECP-M electrochromic device including a layer of n-PBDF that simultaneously serves as both an ion storage layer and a TC layer for a counter electrode, and another layer of n-PBDF that serves as a TC layer for a working electrode, according to one exemplary embodiment. FIG. 2 is a diagram of an exemplary n-doped organic conductive polymer n-PBDF / ECP-M electrochromic device including a layer of n-PBDF that simultaneously serves as both an ion storage layer and a TC layer for a counter electrode, according to one exemplary embodiment. FIG. 3 is a diagram of an exemplary n-doped organic conductive polymer n-PBDF / ECP-M electrochromic device including a layer of n-PBDF that simultaneously serves as both an ion storage layer and a TC layer for a working electrode, according to one exemplary embodiment. [Figure 11(A)] 1 is a diagram of an exemplary n-doped organic conductive polymer n-PBDF / ECP-BK electrochromic device including a layer of n-PBDF that simultaneously serves as both an ion storage layer and a TC layer for a counter electrode, and another layer of n-PBDF that serves as a TC layer for a working electrode, according to one exemplary embodiment; and FIG. 2 is a diagram of spectroelectrochemical analysis in the colored and bleached states, according to one exemplary embodiment. [Figure 11(B)] FIG. 1 is a diagram of an exemplary n-doped organic conductive polymer n-PBDF / ECP-BK electrochromic device including a layer of n-PBDF that simultaneously serves as both an ion storage layer and a TC layer for a counter electrode, and another layer of n-PBDF that serves as a TC layer for a working electrode, according to one exemplary embodiment. FIG. 2 is a diagram of an exemplary n-doped organic conductive polymer n-PBDF / ECP-BK electrochromic device including a layer of n-PBDF that simultaneously serves as both an ion storage layer and a TC layer for a counter electrode, according to one exemplary embodiment. FIG. 3 is a diagram of an exemplary n-doped organic conductive polymer n-PBDF / ECP-BK electrochromic device including a layer of n-PBDF that simultaneously serves as both an ion storage layer and a TC layer for a working electrode, according to one exemplary embodiment. [Figure 12] FIG. 1 shows the absorbance spectroelectrochemical analysis of an exemplary n-doped organic conducting polymer, n-PBDF, in 0.2 M TBA-TFSI in PC with increasing applied voltage from −0.3 V to 0.9 V. [Figure 13] FIG. 2 is a cross-sectional view of an electrochromic device including a layer of an n-doped organic conductive polymer of the present disclosure that serves as an electrochromic layer for a counter electrode according to one illustrative embodiment. [Figure 14(A)] 1 is a diagram of an exemplary n-doped organic conductive polymer n-PBDF / PEDOT:PSS electrochromic device including a layer of n-PBDF serving as an electrochromic layer for a counter electrode according to one exemplary embodiment, and a spectroelectrochemical analysis in the colored and bleached states according to one exemplary embodiment. [Figure 14(B)] 1 is a diagram of an exemplary n-doped organic conductive polymer n-PBDF / PEDOT:PSS electrochromic device including a layer of n-PBDF serving as an electrochromic layer for the counter electrode according to one exemplary embodiment. FIG. 2 is a diagram of the switching kinetics from a SPFC according to one exemplary embodiment. [Figure 15] FIG. 13 shows cyclic voltammetry results of polymer counter electrodes (n-PBDF and DEPOT:PSS) and ECP-Blue films, and a graph of volumetric capacitance from CV. [Figure 16(A)] 1 is a graph containing data for an exemplary n-doped organic conductive polymer, n-PBDF film, for a working electrode (20 nm), according to one exemplary embodiment. [Figure 16(B)] 16(A) shows the CIE L*, a*, b* color coordinate values ​​estimated from FIG. 16(A) and FIG. 16(B) shows the CIE L*, a*, b* color coordinate values ​​estimated from FIG. 16(A) and FIG. 16(B) show the CIE L*, a*, b* color coordinate values ​​estimated from FIG. 16(A) and FIG. 16(B) show the CIE L*, a*, b* color coordinate values ​​estimated from FIG. 16(B ...B) and FIG. 16(B) show the CIE L*, a*, b* color coordinate values ​​estimated from FIG. 16(B) and FIG. 16(B) show the CIE L*, a*, b* color coordinate values ​​estimated from FIG. 16(B) and FIG. 16(B) show the CIE L*, a*, b* color coordinate values ​​estimated from FIG. 16(B) and FIG. 16(B) show the CIE L*, a*, b* color coordinate values ​​estimated from FIG. 16(B) and FIG. [Figure 17] 1 is a graph showing the CIE L*, a*, b* color coordinate values ​​of two polymer conductors (n-PBDF and PEDOT:PSS) at different thicknesses. [Figure 18(A)] 1 is a graph containing electrochromic behavior data of a transmission-type ECP-B ECD based on an exemplary n-doped organic conductive polymer, n-PBDF film, as both working and counter electrodes according to one exemplary embodiment; [Figure 18(B)]1 is a graph containing electrochromic behavior data of a transmission-type ECP-B ECD based on an exemplary n-doped organic conductive polymer, n-PBDF film, as both a working electrode and a counter electrode according to one exemplary embodiment. [Figure 18(C)] 1 is a graph containing electrochromic behavior data of a transmission-type ECP-B ECD based on an exemplary n-doped organic conductive polymer, n-PBDF film, as both working and counter electrodes according to one exemplary embodiment; [Figure 19(A)] 1 is a graph containing data comparing the electrochromic behavior of transmission ECP-B ECDs using different conductors and ion storage layers, according to some exemplary embodiments. "ITO / VOx" refers to ECDs using Vox as the ion storage layer and ITO as the working electrode. "n-PBDF as C" refers to ECDs using n-PBDF as the ion storage counter electrode and ITO as the working electrode. "n-PBDF as W / C" refers to ECDs using n-PBDF as the ion storage counter electrode and working electrode. Graph showing a comparison of dynamic coloring / fading rates and optical contrast. [Figure 19(B)] 1A-1C are graphs containing data comparing the electrochromic behavior of transmissive ECP-B ECDs using different conductors and ion storage layers according to some example embodiments; [Figure 19(C)] 1 is a graph containing data comparing the electrochromic behavior of a transmission ECP-B ECD using different conductor and ion storage layers according to some example embodiments; [Figure 20] 1 is an exemplary schematic diagram of a fabrication scheme for a patterned electrochromic device, according to one embodiment. [Figure 21] FIG. 1 shows the optical transmittance spectra of ITO, ITO / VOx and n-PBDF films (as working or counter electrodes). [Figure 22(A)] FIG. 1 is a schematic diagram of a method for fabricating a working electrode substrate for a passive matrix based electrochromic device or display using photolithographic patterning, according to some exemplary embodiments. [Figure 22(B)] FIG. 2 is a schematic diagram of a method for fabricating a counter electrode substrate for a passive matrix based electrochromic device or display using photolithographic patterning, according to some exemplary embodiments. [Figure 23(A)] 1 shows an image of an all-polymer passive matrix based electrochromic display with reduced crosstalk. FIG 2 shows an image showing the coloration of target pixel P5. A voltage of -0.8V is applied to the target pixel for 10 seconds. [Figure 23(B)] Image of an all-polymer passive matrix based electrochromic display with reduced crosstalk. Image with two target pixels lit. A voltage of -0.8V is applied to the target pixels for 10 seconds. [Figure 24] FIG. 1 is an illustrative schematic of an all-polymer segmented electrochromic device or display. [Figure 25(A)] 13 is an image of various applications of all-polymer segmented electrochromic displays; [Figure 25(B)] 1 shows images of various applications of all-polymer segmented electrochromic displays. 2 shows images of human skin fitted with ring-shaped structures. [Figure 26] 1 is a flowchart of a method for forming an electrochromic device / display according to one illustrative embodiment. [Figure 27] 4 is a flowchart of a method for forming an electrochromic device / display according to another illustrative embodiment. [Figure 28] 4 is a flowchart of a method for forming an electrochromic device / display according to yet another illustrative embodiment. [Figure 29] 4 is a flowchart of a method for forming an electrochromic device / display according to yet another illustrative embodiment. [Diagram 30] 4 is a flowchart of a method for forming an electrochromic device / display according to yet another illustrative embodiment. [Diagram 31] 4 is a flowchart of a method for forming an electrochromic device / display according to yet another illustrative embodiment. [Diagram 32] 4 is a flowchart of a method for forming an electrochromic device / display according to yet another illustrative embodiment. [Diagram 33] 4 is a flowchart of a method for forming an electrochromic device / display according to yet another illustrative embodiment. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0023] In the following description, certain specific details are set forth to provide a thorough understanding of various embodiments of the present disclosure. However, those skilled in the art will understand that the present disclosure may be practiced without these details. Furthermore, although various embodiments of the present disclosure are disclosed herein, many adjustments and modifications may be made within the scope of the present disclosure, according to the general knowledge commonly held by those skilled in the art. Such modifications include the substitution of known equivalents for any aspect of the present disclosure to achieve the same result in substantially the same way.

[0024] Unless otherwise required by context, throughout this specification and claims, the word "comprise" and variations thereof, such as "comprises" and "comprising," are intended to be construed in an open-ended inclusive sense, i.e., "including, but not limited to." Throughout this specification, the recitation of numerical ranges of values ​​is intended to serve as a shorthand notation to refer individually to each separate value falling within the range, inclusive of the values ​​defining the range, and each separate value is incorporated herein as if it were individually recited therein. Additionally, the singular forms "a," "an," and "the" include plural references unless the context clearly dictates otherwise.

[0025] Throughout this specification, a reference to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with that embodiment is included in at least one embodiment of the present disclosure. Thus, the appearances of the phrases "in one embodiment" or "in an embodiment" in various places throughout this specification do not necessarily all refer to the same embodiment, but in some instances may. Furthermore, in one or more embodiments, particular features, structures, or characteristics may be combined in any suitable manner. "Transparent" means a transmittance of more than 40% in the visible light range, including, for example, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 70% or more. "Semi-transparent" means a transmittance of more than 5% in the visible light range, including, for example, 5%, 10%, 15%, 20%, 25%, 30%, 35%, and less than 40%. "All polymer" or "all-polymer" means that the conductive layer, the ion storage layer, the electrolyte layer, and the electrochromic layer comprise a polymer. In some embodiments, "all polymer" or "all-polymer" may further include a polymer substrate. "Solid electrolyte" includes solid or gelled solid electrolytes.

[0026] Various embodiments described herein are of the formula [ka] In one embodiment, the present invention relates to an electrochromic device comprising an n-doped organic conductive polymer of the formula: wherein X is O, S, or Se, each of m and n is an integer greater than zero, and each of R1 and R2 is independently hydrogen or C1-C 10 alkyl, M + is an organic or metal cation. In some embodiments, X is O, R1 and R2 are each hydrogen, and M + is a proton, and the n-doped organic conductive polymer according to these embodiments has the formula [ka] The n-doped organic conductive polymers of the present disclosure are referred to as n-doped poly(3,7-dihydrobenzo[1,2-b:4,5-b']difuran-2,6-dione) (n-PBDF). A layer comprising the n-doped organic conductive polymers of the present disclosure may function as a transparent conductive (TC) layer, and / or an ion storage layer, and / or an electrochromic layer. Three specific electrochromic polymers are used throughout this specification for illustrative purposes. It should be understood that this disclosure is not limited to these examples. ECP-Magenta (ECP-M) is an exemplary magenta ECP. ECP-Blue (ECP-B) is an exemplary blue ECP. ECP-Black (ECP-BK) is an exemplary black ECP. Exemplary structures of ECP-M, ECP-B, and ECP-BK are shown below, respectively, where n is an integer greater than zero:

[0027] [ka]

[0028] A conventional ECD consists of seven layers including two non-conductive layers as substrates, one or two transparent conductive (TC) layers (one for working electrode and one for counter electrode) disposed on the substrates, an electrochromic layer as working electrode (WE), an ion storage layer as counter electrode (CE), and an electrolyte layer inserted between WE and CE. In the present disclosure, the layer including the n-doped organic conductive polymer of the present disclosure can serve as a TC layer, or / and an ion storage layer, or / and an electrochromic layer. In some embodiments, the n-doped organic conductive polymer of the present disclosure can replace the conventional ITO to be a highly transparent conductor, and the layer including the n-doped organic conductive polymer of the present disclosure can function as at least one layer of the TC layer in the ECD. In some embodiments, the layer including the n-doped organic conductive polymer of the present disclosure can function as an ion storage layer in the ECD. In some embodiments, the layer including the n-doped organic conductive polymer of the present disclosure can function as both a TC layer for the counter electrode and an ion storage layer separately. In some embodiments, the layer comprising the n-doped organic conductive polymer of the present disclosure can function simultaneously (e.g., integrated into one single layer) as both the TC layer and the ion storage layer for the counter electrode, resulting in reduced layers and simplified structure of the electrochromic device. In some embodiments, the layer comprising the n-doped organic conductive polymer of the present disclosure can function separately as the ion storage layer for the counter electrode and the TC layer for the working electrode. In some embodiments, the layer comprising the n-doped organic conductive polymer of the present disclosure can function simultaneously (e.g., integrated into one single layer) as both the TC layer and the ion storage layer for the counter electrode and the TC layer for the working electrode, resulting in reduced layers and simplified structure of the electrochromic device. In some embodiments, the layer comprising the n-doped organic conductive polymer of the present disclosure can function separately as both the TC layer and the ion storage layer for the counter electrode and the TC layer for the working electrode.In some embodiments, the layer comprising the n-doped organic conductive polymer of the present disclosure can undergo an oxidation-reduction reaction to exhibit electrochromic properties and function as an electrochromic layer (replacing a conventional ion storage layer as a counter electrode) and can be combined with an electrochromic layer comprising a p-doped electrochromic material as a working electrode. In some embodiments, the ECD of the present disclosure comprises a layer of the n-doped organic conductive polymer of the present disclosure. The layer comprising the n-doped organic conductive polymer of the present disclosure that functions as a TC layer and / or an ion storage layer can contain, in addition to the n-doped organic conductive polymer of the present disclosure, an electrolyte salt (e.g., Li. + Salt, Sodium + Salt, TBA + (tetrabutylammonium)) or some stabilizers for adjusting mechanical properties (e.g., PEG (polyethylene glycol), polystyrene) may contain other components that do not significantly affect the optical properties and electrical conductivity of the layer. The layer containing the n-doped organic conductive polymer of the present disclosure that functions as an electrochromic layer may contain, in addition to the n-doped organic conductive polymer of the present disclosure, an electrolyte salt (e.g., Li + Salt, Sodium + Salt, TBA + (tetrabutylammonium)), or some stabilizers to adjust the mechanical properties (e.g. PEG (polyethylene glycol), polystyrene), or some other n-doped electrochromic materials, such as WO3, viologens, or n-doped electrochromic polymers. By p-doped electrochromic material, we mean that the electrochromic process occurs when the material is oxidized. By n-doped electrochromic material, we mean that the electrochromic process occurs when the material is reduced.

[0029] In the present disclosure, the n-doped organic conductive polymer of the present disclosure exhibits low sheet resistance, high optical transparency, and large potential window for most EC materials, which makes the n-doped organic conductive polymer of the present disclosure an organic transparent conductor for ECD. In addition, the n-doped organic conductive polymer of the present disclosure is mechanically flexible and can be easily applied to roll-to-roll manufacturing and flexible ECD, competing with the traditional transparent conductor ITO. In the ECD disclosed in the present disclosure, when the layer containing the n-doped organic conductive polymer of the present disclosure simultaneously functions as both the ion storage layer for the counter electrode and the TC layer, the structure of the ECD can be simplified, and therefore can be manufactured at lower cost and improved throughput. Therefore, the technology of the present disclosure can provide high-performance ECD at lower cost.

[0030] In one embodiment, the electrochromic device of the present disclosure includes a layer comprising an n-doped organic conductive polymer of the present disclosure, which does not undergo redox reactions and remains transparent within the potential window of the applied device. There are three main different types of configurations of the electrochromic device of the present disclosure. Exemplary configurations of each type are shown and discussed below.

[0031] A first type of electrochromic device of the present disclosure has at least one TC layer comprising an n-doped organic conductive polymer of the present disclosure. As shown in FIG. 1, such an exemplary configuration may have a first insulating substrate 102, a first conductive layer 104 disposed on the first insulating substrate 102 and comprising an n-doped organic conductive polymer of the present disclosure, an ion storage layer 106 disposed on the first conductive layer 104, an electrolyte layer 108 disposed on the ion storage layer 106, an electrochromic layer 110 disposed on the electrolyte layer 108, a second conductive layer 112 disposed on the electrochromic layer 110, a second insulating substrate 114 disposed on the second conductive layer 112, and circuit wiring 116 for operating the electrochromic device 100. In some embodiments, at least one of the first conductive layer or the second conductive layer is transparent (when the conductive layer is transparent, it is called a TC layer). In some embodiments, both the first conductive layer and the second conductive layer are transparent (for these ECDs of the present disclosure, having two TC layers). In some embodiments, the first conductive layer or the second conductive layer comprises a reflective conductive layer, such as a metal layer, forming a reflective ECD. In some embodiments, the first conductive layer 104 may comprise a transparent conductor (e.g., ITO) that does not comprise the n-doped organic conductive polymer of the present disclosure, and the second conductive layer 112 comprises the n-doped organic conductive polymer of the present disclosure. In some embodiments, both the first conductive layer 104 and the second conductive layer 112 comprise the n-doped organic conductive polymer of the present disclosure. In some embodiments, at least one of the first conductive layer 104 and the second conductive layer 112 is comprised of the n-doped organic conductive polymer of the present disclosure.

[0032] The n-doped organic conductive polymers of the present disclosure can function as high-performance transparent conductors. To demonstrate this, n-PBDF is used as an exemplary n-doped organic conductive polymer to investigate the optical transmittance, electrical conductivity, and sheet resistance at various thicknesses. FIG. 2(A) illustrates the conductivity of thin films with thicknesses ranging from 16 nm to 94 nm. The conductivity of the thin films increases with increasing film thickness. It reaches 6100 S / cm around a thickness of 94 nm. The optical transmittance of n-PBDF thin films is illustrated in FIG. 2(B). As shown in FIG. 2(B), n-PBDF thin films exhibit high transmittance in the visible range (e.g., 400-700 nm). The high conductivity of the thin films and the high transmittance in the visible range indicate that the n-doped organic conductive polymers of the present disclosure are suitable for use as transparent conductors. This is further evident in FIG. 2(C), where sheet resistance and optical transmittance are plotted with film thickness. At the wavelength of 550 nm, where the human eye is most sensitive, the optimized n-PBDF thin film has a low sheet resistance of 45 Ω / sq and a high transmittance (T 550 >80%), which can compete with the conventional transparent conductor ITO. Thus, the n-doped organic conductive polymers of the present disclosure are established as high-performance transparent conductors.

[0033] To simplify the demonstration of the n-doped organic conductive polymer of the present disclosure acting as a TC layer in an ECD, a three-electrode electrochromic device 300 is employed. As shown in the schematic diagram in FIG. 3(A), the ECD 300 disclosed herein includes a counter electrode (e.g., Pt) CE, a reference electrode (e.g., Ag / AgCl) RE, and a working electrode WE. As shown in the cross-sectional view of the working electrode WE in FIG. 3(B), the working electrode WE includes a piece of glass or PET as a substrate, a layer of the n-doped organic conductive polymer of the present disclosure as a transparent conductor, and a layer of electrochromic material (e.g., ECP-B) as an electrochromic layer. In one embodiment, the T 550 (Transmittance at wavelength 550 nm) > 85% and R sA layer of an exemplary n-doped organic conductive polymer, n-PBDF, with (sheet resistance) <80 Ω / sq, is first coated on a bare glass substrate, followed by an electrochromic layer, e.g., ECP-B. The glass slide is then immersed in a liquid electrolyte to prepare a three-electrode electrochromic device. In one embodiment, upon application of a positive potential of up to 0.7 V (vs. Ag / AgCl), ECP-B gradually oxidizes and becomes transparent. This process is captured in a spectroelectrochemical measurement of ECP-B in the n-PBDF / substrate structure, as shown in FIG. 4(B). As the applied voltage increases, the transmittance of ECP-B in the visible range (e.g., 400-700 nm) increases. When the same measurement is performed using ITO as the transparent electrode, a very similar electrochromic response is recorded. CV measurements of ECP-B on ITO / substrate, ECP-B on n-PBDF / substrate, and n-PBDF itself taken on a platinum button working electrode are shown in FIG. 4(A), which shows that the ECP-B electrochromic layer has the same oxidation onset point around −0.2 V (vs. Ag / AgCl) on both ITO and n-PBDF transparent conductors, which is about 0.8 V lower than the oxidation onset point of n-PBDF (0.58 V vs. Ag / AgCl). Thus, when the voltage applied to n-PBDF is lower than 0.58 V, n-PBDF does not undergo redox reaction. Overall, these results demonstrate that the n-doped organic conductive polymers of the present disclosure can be used as TC layers in electrochromic devices without adversely affecting the optical and electrical properties of the electrochromic devices, and can be comparable to inorganic TCs (e.g., ITO).

[0034] In addition to transparency, the n-doped organic conductive polymers of the present disclosure exhibit high charge density. An exemplary n-doped organic conductive polymer, n-PBDF, is used for demonstration. The volumetric capacitance (C) of n-PBDF thin film was measured by recording cyclic voltammograms at different scan rates in 0.2 M TBA-TFSI (PC) electrolyte, as shown in FIG. 5(A). *) was measured. According to the cyclic voltammogram, the non-zero current plateau in the range of -0.2 V to +0.4 V represents the double layer capacitance. The capacitive behavior is also confirmed by the linear increase in current density with the scan rate, as shown in Figure 5(B). Both the high optical transparency and large charge capacity ensure that the n-doped organic conductive polymer of the present disclosure can be used as an ion storage material in ECD.

[0035] A second type of electrochromic device of the present disclosure has a layer comprising an n-doped organic conductive polymer of the present disclosure as an ion storage layer. An exemplary ECD scheme having a layer comprising an n-doped organic conductive polymer of the present disclosure functioning as an ion storage layer is shown in FIG. 6. The ECD includes a first insulating substrate 602, a first conductive layer 604 disposed on the first insulating substrate 602, an ion storage layer 606 comprising an n-doped organic conductive polymer of the present disclosure disposed on the first conductive layer 604, an electrolyte layer 608 disposed on the ion storage layer 606 comprising an n-doped organic conductive polymer of the present disclosure, an electrochromic layer 610 disposed on the electrolyte layer 608, a second conductive layer 612 disposed on the electrochromic layer 610, a second insulating substrate 614 disposed on the second conductive layer 612, and circuit wiring 616 for operating the electrochromic device 600. The n-doped organic conductive polymer layer of the present disclosure functions as an ion storage layer and can work with either inorganic or organic electrochromic materials in the electrochromic layer 610 (working electrode). In some embodiments, the ion storage layer 606 is comprised of an n-doped organic conductive polymer of the present disclosure. In some embodiments, at least one of the first conductive layer or the second conductive layer is transparent. In some embodiments, both the first conductive layer and the second conductive layer are transparent. In some embodiments, the first conductive layer or the second conductive layer includes a reflective conductive layer, such as a metal layer, to form a reflective ECD.

[0036] To demonstrate the performance of a layer including the n-doped organic conductive polymer of the present disclosure as an ion storage layer (counter electrode) for an electrochromic device, the following ECD embodiment uses ECP-B as an exemplary ECP in the electrochromic layer and n-PBDF as an exemplary n-doped organic conductive polymer as the working electrode. 0.2 M TBATFSI in 1:1 PEGDA:PC crosslinked in situ is used as the electrolyte layer 608. The n-PBDF thin film of the present disclosure is used as the ion storage layer 606 for the counter electrode. FIG. 7(A) illustrates the transmittance spectrum of the electrochromic device of the present disclosure. The transmittance spectrum shows a large change during the coloring process, indicating that the electrochromic device successfully switched between the colored and bleached states. The switching kinetics from stepped potential fast chronoamperometry (SPFC) is shown in FIG. 7(B), which shows that the electrochromic device achieves fast switching from 5% to 55% at 612 nm. The results demonstrate that the n-doped organic conductive polymers of the present disclosure perform well as ion storage materials for electrochromic devices.

[0037] A third type of electrochromic device of the present disclosure has a layer comprising an n-doped organic conductive polymer of the present disclosure that functions as both a TC layer and an ion storage layer. One exemplary configuration of an electrochromic device 800 is shown in FIG. 8. The ECD 800 includes a first insulating substrate 802, a layer 804 comprising an n-doped organic conductive polymer of the present disclosure disposed on the first insulating substrate 802, an electrolyte layer 806 disposed on the layer 804 comprising an n-doped organic conductive polymer of the present disclosure, an electrochromic layer 808 disposed on the electrolyte layer 806, a TC layer 810 disposed on the electrochromic layer 808, and a second insulating substrate 812 disposed on the conductive layer 810. The conductive layer 810 may comprise or consist of an n-doped organic conductive polymer of the present disclosure, or may be a TC layer that does not include an n-doped organic conductive polymer of the present disclosure, such as ITO, or may be a reflective conductive layer, such as a metal. The electrochromic device 800 further includes circuit wiring 814 for operating the electrochromic device 800. In this exemplary device 800, a single layer 804 including the n-doped organic conductive polymer of the present disclosure functions simultaneously as both a TC layer for the counter electrode and an ion storage layer, thus simplifying the structure of the device with lower cost and higher throughput. In some embodiments, due to the deformation from other components in each layer, the layer 804 including the n-doped organic conductive polymer of the present disclosure may be divided into two separate layers, one layer including the n-doped organic conductive polymer of the present disclosure functions as a TC layer and the other layer including the n-doped organic conductive polymer of the present disclosure functions as an ion storage layer. The TC layer 810 may also include or consist of the n-doped organic conductive polymer of the present disclosure, or may be a TC layer that does not include the n-doped organic conductive polymer of the present disclosure, such as ITO.In some embodiments, the layer 804 comprising the n-doped organic conductive polymer of the present disclosure may be split into two separate layers, with one layer comprising the n-doped organic conductive polymer of the present disclosure as an ion storage layer and one TC layer, e.g., ITO, that does not comprise the n-doped organic conductive polymer of the present disclosure, and the TC layer 810 may also comprise or consist of the n-doped organic conductive polymer of the present disclosure. In some embodiments, the electrochromic device of the present disclosure has a layer consisting of the n-doped organic conductive polymer of the present disclosure that functions as both a TC layer and an ion storage layer.

[0038] In one embodiment, n-PBDF, an exemplary n-doped organic conductive polymer, is assembled into an electrochromic device using ECP-B as the electrochromic layer 808 (working electrode), 0.2 M TBATFSI in 1:1 PEGDA:PC crosslinked in situ as the electrolyte layer 806, n-PBDF thin film as the transparent conductive layer 810 for the working electrode 808, and n-PBDF layer 804. The n-PBDF layer 804 simultaneously acts as both a transparent conductor and an ion storage layer for the counter electrode. The optical performance of the electrochromic device is shown in Figures 9(A) and 9(B). Figure 9(A) illustrates the transmittance spectrum of the electrochromic device. The transmittance spectrum shows a large change during the coloring process, indicating that the electrochromic device has been successfully switched between the colored and bleached states. The switching kinetics from the SPFC is shown in Figure 9(B), which shows that the electrochromic device achieves fast switching from 18% to 70% at 612 nm. The results demonstrate that the n-doped organic conductive polymers of the present disclosure perform well as transparent conductors and ion storage materials for the counter electrode.

[0039] The above structural configurations can be applied to other types of ECPs. For example, ECP-B in the electrochromic layer 808 can be replaced with ECP-M or ECP-BK. The optical performance of the electrochromic device with ECP-M electrochromic layer 808 is shown in Figures 10(A) and 10(B). Figure 10(A) illustrates the transmittance spectrum of the electrochromic device. The transmittance spectrum shows a large change during the coloring process, indicating that the electrochromic device successfully switches between the colored and bleached states. The switching kinetics from SPFC is shown in Figure 10(B), which shows that the electrochromic device achieves fast switching from 22% to 78% at 550 nm. The results demonstrate that the n-doped organic conductive polymer of the present disclosure works well as a transparent conductor and ion storage material with the ECP-M electrochromic layer 808.

[0040] The optical performance of the electrochromic device with ECP-BK electrochromic layer 808 is shown in Figure 11(A) and Figure 11(B). Figure 11(A) illustrates the transmittance spectrum of the electrochromic device. The transmittance spectrum shows a large change during the coloring process, indicating that the electrochromic device successfully switches between the colored and bleached states. The switching kinetics from SPFC is shown in Figure 11(B), which shows that the electrochromic device achieves fast switching from 7% to 40% at 550 nm. The results demonstrate that the n-doped organic conductive polymer of the present disclosure also works well with ECP-BK electrochromic layer 808 as a transparent conductor and / or ion storage material.

[0041] Both inorganic and organic electrochromic materials may be used in the electrochromic layer in the electrochromic device disclosed herein. In some embodiments, the electrochromic layer in the electrochromic device disclosed herein comprises one or more of electrochromic conjugated polymers including WO3, NiO, IrO2, V2O5, isoindigo, poly(decyl viologen) and its derivatives, polyaniline and its derivatives, polypyrrole and its derivatives, polythiophene and its derivatives, poly(3,4-ethylenedioxythiophene) and its derivatives, poly(propylenedioxythiophene) and its derivatives, polyfluorene and its derivatives, polycarbazole and its derivatives, and copolymers thereof, or copolymers containing acceptor units including benzothiadiazole, benzotriazole, or diketopyrrolopyrrole. Various types of electrolyte materials (e.g., liquid electrolyte, gel electrolyte, or solid electrolyte) may be used in the electrolyte layer in the electrochromic device disclosed herein. In some embodiments, the electrolyte layer in the electrochromic devices disclosed herein comprises a solid electrolyte or a gel electrolyte.

[0042] Both inorganic and organic ion storage materials may be used in the ion storage layer in the electrochromic devices disclosed herein. In some embodiments, when the ion storage layer does not include the n-doped organic conductive polymer of the present disclosure, the ion storage layer in the electrochromic devices disclosed herein comprises one or more oxides of metal elements in Groups 4-12, or a mixture of oxides, or one of the oxides doped with any other metal oxide. The substrates 102 and 114 may be any insulating substrate, such as glass or plastic. The substrates 102 and 114 may be flexible to accommodate roll-to-roll manufacturing processes.

[0043] In another aspect, the present disclosure also relates to the use of the n-doped organic conductive polymer of the present disclosure as an electrochromic layer. The exemplary organic conductive polymer PBDF and the exemplary n-doped organic conductive polymer n-PBDF are a redox couple. Therefore, they can function as electrochromic materials by potential. The spectroelectrochemical characterization of the exemplary n-doped organic conductive polymer n-PBDF is carried out in 0.2M TBA-TFSI in PC. As shown in FIG. 12, n-PBDF can undergo redox reaction and exhibits color with a maximum absorbance around 850 nm, and the absorbance increases with increasing applied voltage. FIG. 13 illustrates the configuration of an electrochromic device 1300 using the n-doped organic conductive polymer of the present disclosure as the electrochromic material for the counter electrode according to one exemplary embodiment. The electrochromic device 1300 includes a first insulating substrate 1302, a first conductive layer 1304 disposed on the first insulating substrate 1302, a first electrochromic layer 1306 disposed on the first conductive layer 1304 and comprising an n-doped organic conductive polymer of the present disclosure, an electrolyte layer 1308 disposed on the first electrochromic layer 1306 comprising an n-doped organic conductive polymer of the present disclosure, a second electrochromic layer 1310 disposed on the electrolyte layer 1308 and comprising a p-doped electrochromic material, a second conductive layer 1312 disposed on the second electrochromic layer 1310 comprising a p-doped electrochromic material, and a second insulating substrate 1314 disposed on the second conductive layer 1312. In some embodiments, one of the first or second conductive layers 1304 and 1312 may comprise an organic or inorganic conductive material (e.g., ITO). In some embodiments, one of the first conductive layer and the second conductive layer comprises a reflective conductive material, such as a metal, forming a reflective ECD. In some embodiments, at least one of the first conductive layer or the second conductive layer is transparent. In some embodiments, both the first conductive layer and the second conductive layer are transparent.In some embodiments, the first conductive layer 1304 and the second conductive layer 1312 do not include an n-doped organic conductive polymer of the present disclosure, as the n-doped organic conductive polymer of the present disclosure may color under the applied potential window for a dual polymer ECD as shown. The n-doped organic conductive polymer of the present disclosure in the first electrochromic layer 1306 functions as an n-doped ECP. The electrochromic device 1300 further includes circuitry 1316 for operating the electrochromic device 1300. In some embodiments, the first electrochromic layer 1306 is comprised of an n-doped organic conductive polymer of the present disclosure.

[0044] Both inorganic and organic p-doped electrochromic materials may be used in the second electrochromic layer 1310. In some embodiments, the p-doped electrochromic material in the second electrochromic layer 1310 includes one or more of electrochromic conjugated polymers including NiO, IrO2, V2O5, isoindigo, poly(decyl viologen) and its derivatives, polyaniline and its derivatives, polypyrrole and its derivatives, polythiophene and its derivatives, poly(3,4-ethylenedioxythiophene) and its derivatives, poly(propylenedioxythiophene) and its derivatives, polyfluorene and its derivatives, polycarbazole and its derivatives, and copolymers thereof, or copolymers containing acceptor units including benzothiadiazole, benzotriazole, or diketopyrrolopyrrole. In some embodiments, the p-doped electrochromic material is a p-doped electrochromic polymer. Various types of electrolyte materials (e.g., liquid electrolytes, gel electrolytes, or solid electrolytes) may be used for the electrolyte layer 1308 in the electrochromic devices disclosed herein. In some embodiments, the electrolyte layer 1308 in the electrochromic devices disclosed herein comprises a solid electrolyte or a gel electrolyte.

[0045] To demonstrate the performance of the n-doped organic conductive polymer of the present disclosure as an EC layer, an exemplary n-doped organic conductive polymer, n-PBDF, is combined with an exemplary p-doped polymer, PEDOT:PSS, to create a dual polymer electrochromic device. In one embodiment, n-PBDF is assembled into an electrochromic device using PEDOT:PSS as the p-doped ECP, 0.2 M TBATFSI in 1:1 in situ crosslinked PEGDA:PC as the electrolyte, and n-PBDF as the n-doped ECP. A schematic diagram is depicted in FIG. 13. As seen in FIG. 14(A), spectroelectrochemical measurements were recorded between −0.5 V and 1.5 V in 0.2 V increments (only a few voltages are shown as examples). At one electrode, n-PBDF loses electrons upon oxidation and returns to a neutral state, accompanied by an increase in the absorbance peak around 850 nm. At the other electrode, the PEDOT:PSS is reduced back to the neutral state, accompanied by an increase in the absorbance peak around 700 nm. The electrochromic device exhibits fast switching kinetics and a high optical contrast of 50%. As shown in Figure 14(B), at an applied voltage of -0.5 V, the bleached state is reached within 0.2 seconds, and at an applied voltage of 1.5 V, the colored state is achieved within 3 seconds. The device exhibits a peak absorbance of 1900 cm 2 This shows a high coloring efficiency of 1.0-1.5 μm / C, the highest value recorded among known electrochromic devices.

[0046] N-doped Capacitive Conductor The disclosed n-doped organic conductive polymer is an n-doped transparent capacitive conductor that can successfully replace traditional ITO in ECDs with its air / water stable high conductivity. More interestingly, the disclosed n-doped organic conductive polymer could directly balance the charge consumed in the electrochromic polymer (ECP) with an efficient capacitor behavior as an ion storage layer due to its high mixed ionic and electronic conductivity. In some embodiments, typical cyclic voltammetry (CV) of the exemplary n-doped organic conductive polymer, n-PBDF film, is recorded at different scan rates. They show similar CV shapes with rectangular-like behavior and clear faradic peaks regardless of thickness. This is due to the combination of pure capacitance due to charge accumulation at the polymer / electrolyte interface depending on the volume and capacitance through reversible redox reaction, which leads to high specific capacitance from pseudocapacitance. In addition, the 100 mVs -1 The n-PBDF film maintained its shape over 1000 s, indicating easy and fast ion insertion / removal into / from the capacitive polymer film. Taking advantage of the highly capacitive property, the n-PBDF film in the counter electrode could directly act as a complementary charge-balancing layer without adding an ion storage layer, and could be bleached and developed together with the cathodically colored ECP. The disclosed n-doped organic conductive polymers can be used as electrodes and / or electrical interconnects in addition to capacitive conductors.

[0047] Figure 15 presents the CV results of two polymer conductors (n-PBDF and PEDOT:PSS) and a typical p-type electrochromic polymer to compare the potential window of the electroresponse. Both polymer conductors exhibit purely capacitive properties with charge accumulation at the bulk polymer / electrolyte interface, a much larger charge reservoir compared to its inorganic counterpart, ITO. This results in a large, potential-independent current that persists even at high oxidizing (for PEDOT:PSS) or reducing (for n-PBDF) potentials. The non-faradaic, electric double layer formed in the polymer domains is the dominant contributor to capacitance at high doping levels. Interestingly, according to the CV curves of unreacted films of the same thickness, n-PBDF exhibits a larger volumetric capacitance (about three times larger than about 72 Fcm for PEDOT:PSS) due to the greater access of ions and charge carriers to the conjugated network and across the polymer / electrolyte interface. -3 In contrast, the n-PBDF has a wavelength of approximately 206 Fcm -3 ). Due to the high mixed ionic and electronic conductivity in the polymer film, the formation of the double layer is not only limited to the polymer / electrolyte interfacial layer, but also extends into the conjugated network of ions and charge carriers. The linear current dependence of the differential anodic / cathodic charge density and scan rate confirms that the ionic diffusion of the electrolyte is excellent and stable. The slope of the line indicates that the high volumetric capacitance is 200-250 Fcm for n-PBDF films at the current plateau due to the electric double layer (EDL). -3 (about 500μFcm -2 The n-PBDF film is estimated to have a capacitance of 170 Fcm2 at 1000 psig (area-specific capacitance), which is higher than that of conventional carbonaceous materials and comparable to that of oxide hybrid materials. The n-PBDF film exhibits a high positive voltage (+0.7 V, 170 Fcm2) due to a faradic redox reaction. -3), showing a well-retained and fairly high capacitance behavior, suggesting excellent capacitive properties in a large field-responsive potential window. Since a large decrease in the faradic capacitance is found during electrochemical cycling, the faradic behavior is examined in fully conditioned n-PBDF films. However, n-PBDF films show stable box-shaped CV behavior from EDL-derived capacitance processes that are independent of electrochemical cycling.

[0048] Transparency with minimal color change In addition to high conductivity and high ionic capacity, the disclosed n-doped organic conductive polymers exhibit transmission with minimal color change throughout the entire range of the electroresponsive potential window when used as conductors and / or ion storage materials. In some embodiments, the disclosed n-doped organic conductive polymers exhibit transmission with minimal color change at wavelengths between 380 nm and 800 nm and a color saturation change ΔC of less than 5 between the oxidized and reduced states of the n-doped organic conductive polymer. * In some embodiments, the disclosed n-doped organic conductive polymers exhibit transparency with minimal color change at wavelengths between 380 nm and 800 nm and a color saturation change, ΔC, of ​​less than 4, or 3, or 2, or 1.5, or 1 between the oxidized and reduced states of the n-doped organic conductive polymer. *The disclosed n-doped organic conductive polymer film may be partially dedoped by oxidation of ECP with positive bias applied at the working electrode, leaving color at the bleached state of ECP. The electrochemical coloring effect of the exemplary n-PBDF film is confirmed in the measurement of absorbance as a function of applied voltage in a three-electrode system. As shown in FIG. 16(A), the n-PBDF film becomes more dedoped and visibly colored as a higher positive bias is applied. When the bias is higher than 0.8 V, the n-PBDF is completely dedoped and the neutral PBDF film shows an absorbance peak at 877 nm with a small shoulder peak around 493 nm, but still has high light transmittance in the visible region. Due to the low coloring efficiency and small absorbance change in the visible region, the n-PBDF electrode shows minimal color change characteristics at both the working and counter electrode positions for ECD. A more detailed color presentation in the human eye is shown in the 1976 CIE L * a * b * The color coordinates are calculated and investigated. Interestingly, the n-PBDF film shows little change in color across redox states. As shown in FIG. 16(B), for the 20 nm n-PBDF film at the working electrode, the color coordinates a * and b * Both and show minimal changes (a * increases by about 0.4, b * increases by about 0.09), chroma C * (C * = (a *2 +b *2 ) 1 / 2 ) also shows small changes (ΔC * A similar trend is observed for the 30 nm n-PBDF film on the counter electrode (a * increases by about 0.8, and b * decreases by about 0.2, and ΔC *is about 0.78), which indicates that there is no color remaining in the bleached state or no color addition in the colored state in the ECD. In transmissive electrochromic display applications, the absence of chromaticity throughout the electrochemical process is very important for both achromatic color display (i.e., the color of the electrochromically active material itself) and high optical contrast. n-PBDFs exhibit a color chroma change ΔC of more than 3 or 5 between 380 nm and 800 nm when fully dedoped under high potential bias. * It should be mentioned that the electrochromic material can be used with much thicker films resulting in

[0049] This property makes our PBDF an excellent candidate as a transparent conductor in various electrochemical device applications, overcoming traditional transparent polymer conductors that suffer from severe color changes during inevitable electrochemical reactions or charge transfer in electronic devices. Indeed, the n-PBDF conductor exhibits minimal color changes over the entire range of electrochemical reactions, compared to PEDOT:PSS, which is the preeminent p-type conductor. As shown in FIG. 17, the color coordinate values ​​of the two polymer conductors (n-PBDF and PEDOT:PSS) are compared. For comparison, a PEDOT:PSS film is fabricated without any additional post-treatment to make the PEDOT:PSS more functional. At the same thickness of polymer film (about 30 nm), the two polymer conductors exhibit similar luminance changes from 98 to 92. However, PEDOT:PSS exhibits a significant color change, with a noticeable blue and moderate greenish shift at a bias of −1.0 V, resulting in a chroma change ΔC *is about 7.1. These changes are detrimental to its use as a transparent conductor, especially when used as a counter electrode with a conventional high-performance p-type electrochromic polymer in the opposite working electrode. When the p-type electrochromic polymer in the working electrode bleaches at positive voltage, it leads to strong oxidation of the counter electrode material. In addition, a coloration effect can occur in the working electrode due to partial dedoping of PEDOT:PSS due to unintentional charge transfer or applied voltage for coloration of p-type EPC. In contrast, n-PBDF shows minimal color change from the oxidized (-0.4V) to reduced (+1.0V) state, regardless of the film thickness, suggesting that it is suitable for use in both working and counter electrodes.

[0050] Lowest unoccupied molecular orbital (LUMO) and low operating voltage The disclosed n-doped organic conductive polymers have a low lowest unoccupied molecular orbital (LUMO) level. In some embodiments, the disclosed n-doped organic conductive polymers have a LUMO level of about -4.5 eV. In some embodiments, the disclosed n-doped organic conductive polymers have a LUMO level of about -4.7 eV, or about -4.9 eV, or about -5.1 eV. A low LUMO allows n-doped conductors to be applied in ambient conditions by avoiding the reduction reaction of water and oxygen. In addition, a low LUMO can result in stable and strong capacitive behavior from the electric double layer (EDL) due to the lack of undesired charge transfer to / from oxygen, small doping changes, or poor charge injection and transport in the strongly dedoped state. In addition, a low LUMO level leads to easy doping or low reduction potential, which results in a wider bleaching state of ECD in the electroactive region. In the case of the exemplary n-PBDF, as shown in FIG. 16(A), it easily retains its doped state and the resulting transparent nature up to a bias of around +0.7 V. At applied voltages higher than +0.8 V, it shows a clear increase in visible absorbance due to a very weak dedoping ability. As shown in FIG. 15, the low onset reduction potential (about +0.7 V) leads to a larger potential window due to the capacitive EDL and an efficient electroresponsiveness that matches the potential window of conventional p-type electrochromic polymers. When conventional n-type transition metal oxides or non-conductive n-type polymers (e.g., PEDOT:PSS shown in FIG. 15) are used as ion storage materials in an unbalanced configuration, the charge balancing voltage applied to the counter electrode is extended to the more negative side. However, the extremely low reduction potential of n-PBDF allows the electroresponsive potential window to be closely matched with p-type polymers, and the voltage applied to the counter electrode becomes much less negative. The low reduction potential and narrow operating voltage prevent electrochemical degradation caused by overoxidation in both the p-type electrochromic polymer and the n-PBDF, resulting in better cycle stability for the ECD. In some embodiments, the disclosed ECD operates below 3 volts. In some embodiments, the disclosed ECD operates below 2 volts, or below 1.5 volts, or below 1 volt.

[0051] Use in all polymer devices The disclosed n-doped organic conductive polymers can be applied to both inorganic and all-polymer electronic devices. Traditionally, inorganic transparent conductive materials are used. However, they suffer from various problems such as poor mechanical flexibility and processing incompatibility. Due to their low cost, flexibility, foldability, light weight, low energy consumption and tunable optoelectronic properties, the emerging all-polymer electronic devices can make a significant advance in the development of advanced wearable and portable electronic devices. For decades, PEDOT:PSS has clearly offered numerous advantages such as high processability, aqueous coating, stability in air and water, and high electrical conductivity, along with optical transparency, making it a special polymer conductor in all-polymer electronic devices. In addition, the high pseudocapacitive properties allow it to be applied in various electrochemical devices, such as supercapacitors and energy converters. However, the challenges for PEDOT:PSS as a transparent, minimally color-shifting electroactive conductor and ion reservoir for all-polymer electrochromic devices are i) transparent in the doped state but clearly switches to a bluish color when dedoped, ii) relatively low conductivity without post-treatment, and iii) difficulty in matching the electroactive voltage to other standard cathodochromic p-type electrochromic polymers. On the other hand, the disclosed n-doped organic conductive polymers have excellent properties such as air / water stability, high compatibility with various substrates / electrolytes / EC materials, high patternability, high conductivity (1000 Scm). -1 The disclosed n-doped organic conductive polymers have been demonstrated to have excellent electrical conductivity, transparency with minimal color change, and high capacitance, thus making them transparent polymer conductors and capacitors in all-polymer electronics. As noted above, the disclosed n-doped organic conductive polymers can be used exclusively as conductive layers or ion storage layers, or both as conductive layers and ion storage layers, and / or as electrical interconnects in circuits.

[0052] In some embodiments, the disclosed n-PBDF is used as a transparent conductor and ion storage layer in electrochromic devices. In the polymerization and ink preparation process, PBDF undergoes immediate reductive doping through water oxidation to produce n-doped PBDF, which leads to highly stable enhanced electrical conductivity and low extinction coefficient in the visible region. In some embodiments, n-PBDF is used to fabricate an all-polymer ECD in combination with photopatternable ECP-B and solid electrolyte. The transparent capacitive n-PBDF polymer conductor can successfully replace the traditional oxide-based ion storage layer and ITO in both the counter and working electrodes. When n-PBDF is introduced, the all-polymer ECD shows obvious absorbance change in a small operating voltage range upon the redox reaction between the p-type electrochromic polymer and the ion storage n-PBDF layer (shown in FIG. 18(A)). Upon reduction of the electrochromic polymer, the ECD shows the pure blue color of ECP-B due to the low absorption of PBDF in the visible region, even though the charge is complementarily balanced by the dedoping of n-PBDF at the counter electrode. In the bleached state of the ECD, the doped n-PBDF contributes to the highly transparent nature, resulting in high optical contrast. In the control device where PBDF replaced only the counter electrode, or the conventional VO x In comparison with those based on ion storage layers and ITO conductors, partial dedoping of n-PBDF is observed in the working electrode of the all-polymer ECD when the device is in the bleached state, resulting in a slight increase in absorbance at 500 nm and a relatively large increase in the NIR range (700-800 nm). However, the shoulder peak at 500 nm from the partially dedoped n-PBDF is a small absorbance, and the remaining dominant absorbance is mainly localized in the near-IR region and does not affect the optical contrast and color display in the visible region. The stable and reversible transmittance change in the DPSC process indicates high optical contrast and facilitated insertion and extraction of ionic liquid into the polymer capacitive conductor in both the working and counter electrodes (as shown in Figure 18(B)).

[0053] In terms of energy efficiency, the coloring and bleaching efficiencies are calculated at 95% change in optical contrast for all-polymer ECDs. The electrochromic efficiencies of all-polymer ECDs are 760 cm for bleaching and coloring at 610 nm, respectively. 2 C -1 and 560cm 2 C -1 Its efficient electrochromic behavior is better than most metal oxide-based electrochromic materials and electrochromic polymers. The low reduction potential of n-PBDF allows many advantages as a counter electrode material, such as transparent nature and low operating voltage throughout the electrochemical range, but on the other hand, it may also cause detrimental self-bleaching phenomenon to maintain overall electrical neutrality under open circuit conditions. Due to the close matching of energy levels between p-type electrochromic polymer and conductive n-PBDF, electrons spontaneously transfer from electrochromic polymer to n-PBDF, resulting in unintentional oxidation of electrochromic polymer at the polymer / electrolyte interface due to additional charge formation. Therefore, when using low LUMO n-type polymer, a dense EDL between polymer and electrolyte is more important to suppress the self-bleaching behavior. Photocrosslinkable solid electrolyte based on fluid ionic liquid can form dense EDL by strong interaction with electrochromic polymer film.

[0054] When using the disclosed n-doped organic conductive polymer as either the working or counter electrode or both the working and counter electrodes in the device, the electrochromic device shows high bistability. In some embodiments, the disclosed device has a transmittance decay ΔT of less than 5% during 1000 seconds of operation under open circuit potential at each reductive or oxidative potential bias. In some embodiments, the disclosed device has a transmittance decay ΔT of less than 4%, or less than 3%, or less than 2%, or less than 1% during 1000 seconds of operation under open circuit potential at each reductive or oxidative potential bias. In some embodiments, when using n-PBDF as both the working and counter electrodes, the all-polymer ECD shows good bistability due to residual charge with a ΔT decay of less than 0.7% during 1000 seconds when the reductive potential is varied from +1V to -0.6V (FIG. 18(C)). However, the transmittance change at the open circuit potential is relatively large (ΔT decay of about 3% in 1000 s) at the high electrochemical reduction potential of -1.2 V. This may be attributed to the slow but not negligible penetration of fluid ions into the thick electrochromic polymer layer and the stronger self-bleaching effect due to the n-PBDF working electrode. In fact, no unstable bistability was observed in the ECD using n-PBDF only as the counter electrode with ITO as the working electrode (ΔT decay of less than 0.3% in 600 s), which is different from the conventional VO x It is similar to ECDs based on ion storage layers.

[0055] Effects resulting from the slow redox behavior at the interface between the electrochromic polymer and the n-PBDF conductor of the working electrode are also observed in the electrochemical kinetics during the coloring and bleaching process. In the DPSC characterization, the coloring and bleaching switching speeds of the all-polymer ECDs were determined as a function of the time to reach 95% of the full optical contrast, t 95% The introduction of n-PBDF into the working electrode reduces the transmittance switching speed, especially during the coloration process. For example, in an ECD with an n-PBDF counter electrode and an ITO working electrode, t B 2.8 seconds, tC is about 4.2 seconds, whereas for an ECD with, for example, n-PBDF as both the working and counter electrodes, t B is about 3.2 seconds, t C The coloring time is about 8.7 seconds. In the coloring process, the doped liquid ions migrate out of the electrochromic polymer layer to adjust the charge neutrality. The redox reaction and charge transfer between n-PBDF and the electrochromic polymer hinder the rapid ion movement, resulting in the slow transmittance difference. A quantitative comparison in the electrochromic performance of the see-through display is shown in Figure 19(A)-Figure 19(B). The ECD using n-PBDF only as the counter electrode is significantly faster than the conventional ITO / VO x Compared with the PBDF-based ECD, the all-polymer ECDs show comparable optical contrast and electrochromic switching times, indicating that the transparent polymer conductor can successfully replace the oxide-based electrodes and ion storage layers. However, the all-polymer ECDs with n-PBDF as both the working and counter electrodes show relatively reduced electrochromic efficiency, especially in the coloring process. As well as the longer switching time in the coloring process, this results from the charge transfer at the working electrode and the additional redox reaction that requires more charges. Despite the redox behavior at the working electrode, the all-polymer ECDs with n-PBDF as both the working and counter electrodes show excellent color display, characterized by minimal color change at both the working and counter electrodes (FIG. 19(C)). They are in the bleached state, with a color coordinate of a * and b * is close to zero, indicating a non-colored state. In addition, from the bleached state to the colored state, a * Small color changes were observed on the axis, indicating a pure color display of ECP-B in the all-polymer platform.

[0056] In some embodiments, to fabricate an ECD, e.g., a non-patterned ECD, an electrochromic polymer (20-40 mg) is dissolved in 1 mL of chloroform and stirred continuously overnight. A PBDF ink is prepared in DMSO solution. The PBDF ink is spin-coated onto a UV-ozone treated glass or PET substrate. The prepared electrochromic polymer solution is spin-coated onto an ITO or PBDF deposition substrate. VO x The system ion storage layer is fabricated on another pre-rinsed ITO substrate. For conventional ECD fabrication without a patternable solid electrolyte, PEGDA, PC with 0.2 M LiTFSI, and HMPP are mixed in a volume ratio of 5:5:1. After stirring for 10 min, the solution is dripped onto the substrate on which the ion storage layer was deposited. The substrate on which the electrochromic polymer was deposited is then turned over and transferred onto it. After waiting a few seconds for the electrolyte precursor solution to become uniform, it is heated under UV light irradiation (approximately 2000 mJ cm -2 , 405 nm) to crosslink the electrolyte. Copper tape is applied to the conductive layers on both sides for electrical contact. For ECD fabrication using patternable solid electrolyte, PEGDA, TT, EMIT-TFSI and HMPP are mixed in a mass ratio of 1:1:2:0.1. After stirring for 10 min, the precursor solution is dropped onto the ion storage layer or onto the electrochromic layer. Under UV light irradiation (approximately 300 mJ cm -2 , 405 nm) to bridge the electrolyte. In some embodiments, separate disclosed n-doped organic conductive polymer films with the same thickness are used for the two conductive (counter and working) electrodes. In some embodiments, a conductive film slightly thicker (e.g., about 30 nm) than the working electrode (e.g., about 20 nm) is used for the counter electrode to balance the charge with the electrochromic polymer film in the electrochemical reaction.

[0057] Use in displays and patterned displays Displays play a central role in the current digital landscape and serve as the primary interface for communication, entertainment, and information transfer. Emitting displays such as LEDs and LCDs are popular due to their vibrant colors, high brightness, and sharp resolution. However, they have drawbacks including high energy consumption and possible eye strain due to prolonged exposure to bright artificial light. In this context, the development of electrochromic displays, which are transmissive non-emissive displays, is essential. These displays offer a promising alternative, such as see-through electrochromic displays. See-through electrochromic displays are characterized by low power consumption, outdoor readability, and reduced eye strain because they do not emit light themselves but adjust to natural light. This technology not only paves the way for a more sustainable and comfortable visual experience, but also paves the way for new innovative applications in smart devices and architectural design that blend functionality with aesthetic appeal. However, the development of see-through transmissive electrochromic displays poses significant challenges, mainly due to the complexity of fabricating multiple layers with conflicting process requirements. The transparent conductor, ion storage material, solid-state electrolyte, and electrochromic layer each require distinct fabrication requirements and materials, making patterning, scaling, and integrating these components into a coherent unit complicated. This complexity often poses technical hurdles, making it difficult to produce large-scale electrochromic displays that perform uniformly and are suitable for commercial use. Methods to reduce crosstalk and response times also pose challenges for electrochromic displays.The disclosed technique allows the fabrication of the very first see-through all-polymer flexible electrochromic display with greatly reduced crosstalk, low power consumption, and high bistability by using the special property of solution processability, which, in conjunction with the patternable solid electrolyte and special fabrication method, allows the disclosed n-doped organic conductive polymer thin film to process n-PBDF in solution, high compatibility with various substrates, electrolytes, and EC materials, high patternability that allows the fabrication of segmented and pixelated EC devices / displays, high conductive layers, large charge storage capacity, low molecular weight, flexibility, and easily tunable properties. The chemical structure of the disclosed n-doped organic conductive polymer is theoretically predicted to be poorly soluble and difficult to solution process, however, the disclosed technique has successfully made it solution processable, which allows compatible processing and is highly desirable for manufacturing. The inventors have found that the disclosed n-doped organic conductive polymer has high compatibility with various substrates, electrolytes, and EC materials. This discovery allows not only the disclosed n-organic conductive polymers to be easily deposited and patterned on various substrates, but also allows electrolytes and electrochromic materials to be easily deposited and patterned on the disclosed conductive layers. Conventionally, electrolyte patterning poses great challenges for electrochromic displays, especially due to the difficulty of forming smooth surfaces with uniform thickness at the microscale. Thus, conventionally, an additional patterned template is required to separate the electrolyte solution, which not only increases the processing complexity but also is cost unfavorable. In addition, electrolytes can be easily swollen by various solvents, making it difficult to use solution-based processing for electrolytes. However, the present inventors are able to successfully pattern electrolytes on n-doped organic conductive polymers. The method of the present invention is solution processable, simple, transferable to manufacture, and cost-effective, all of which are highly desirable for successful commercialization.In the disclosed technique, we have demonstrated conformal patterning of all polymer layers (i.e., conductive layer, ion storage layer, electrolyte layer, electrochromic layer). This method not only allows for the production of high-performance EC devices / displays at low cost, but also greatly reduces the crosstalk problem commonly observed in passive matrix electrochromic displays. We successfully produce the disclosed electrochromic devices / displays with low operating voltages using the high conductivity and capacitance of the disclosed n-doped conjugated polymers along with the passive matrix structure in the circuit and the optical memory effect (i.e., bistability). The disclosed EC devices / displays show promise for applications in energy-saving displays with low information update and even information storage. In addition, due to the fast ion motion and high conductivity in both the electrochromic polymer and the disclosed n-doped organic conductive polymer as the electrode, the disclosed electrochromic displays exhibit fast response times with complete color switching within a few seconds. Based on these findings, the inventors have successfully produced high-performance all-polymer EC devices / displays with or without pixels / segments for the first time. Furthermore, the inventors have successfully produced high-performance see-through all-polymer EC devices / displays with pixels / segments for the first time. Due to their high flexibility and human-friendly nature, transparent polymer components including n-PBDF are utilized for, for example, electrochromic active materials, electrolytes, ion storage layers and electrodes in the demonstration of see-through displays.

[0058] In some embodiments, the disclosed n-doped organic conductive polymers can be fabricated into patterned devices, such as patterned all-polymer electrochromic displays. The patterned electrochromic displays can be segmented or pixelated displays, both of which have been successfully produced by the disclosed techniques. In some embodiments, the patterning of the electrochromic polymer, solid electrolyte, and the disclosed n-doped organic conductive polymer film in the disclosed patterned devices is fabricated using in situ photolithography. In some embodiments, the electrochromic polymer (20-40 mg) and photocrosslinker (5 wt %, e.g., bis(fluorophenylazide (bisFA) crosslinker, which induces significant solvent resistance via photocrosslinking) are dissolved in 1 mL of chloroform and stirred continuously overnight. The electrochromic polymer is then exposed to UV light (approximately 2000 mJ cm ) using a photomask. -2 405 nm) to crosslink the spin-coated film. Toluene is used to remove the unexposed areas. In some embodiments, five color EC polymers based on poly(3,4-propylenedioxythiophene) (PProDOT) are studied for the demonstration of different color rendition in display applications. The electrochromic polymers (ECPs) are designated as ECP-C, ECP-M, ECP-Y, ECP-BK, and ECP-B for cyan, magenta, yellow, black, and blue, respectively. The optical properties of all electrochromic components are investigated for see-through display applications. All ECP films exhibit reversible absorbance changes upon electrochemical reaction. Despite strong photocrosslinking by azide molecules, they show almost unchanged absorbance in the reduced state with a vivid five-color spectral rendition corresponding to the accurate image. They show a large decrease in visible absorbance when a positive bias is applied, resulting in a highly transparent state.

[0059] In some embodiments, the same method is used to prepare the electrolyte precursor solution to fabricate the solid electrolyte layer. The photopolymerization of acrylate groups is accomplished in the presence of ionic liquid and thiol monomer. The thiol monomer enables both chain-growth and step-growth free radical photopolymerization in polyethylene glycol diacrylate (PEGDA), reducing the polymerization time and providing high energy efficiency in the photolithography process. In addition, the use of ionic liquid without additional polar solvent and the addition of thiol molecules enhances the wetting of the precursor solution to various surfaces (e.g., metal oxides, glass, ITO, and polymer layers) in display applications, allowing the fabrication of size-tunable patterned solid electrolyte layers with thicknesses up to tens of nanometers using a simple spin-coating method. The prepared precursor solution is spin-coated or drop-cast onto a substrate deposited with ITO or doped organic conductive polymer, followed by selective UV photocrosslinking using a photomask (approximately 300 mJ cm). -2 , 405 nm). The unexposed area is cleaned with DI water. The transmittance spectra of the patternable solid electrolyte layer according to different blending ratios of thiol molecules, PEGDA, and ionic liquid are investigated for see-through display applications. The blended thiol and ionic liquid do not perturb the optical transparency of the whole polymer matrix system, which results in high transmittance (>98%) in the whole visible region. The photopatternable solid electrolyte with certain ionic conductivity is used to pattern the ECP-B, a conventional metal oxide-based charge-balancing material, VO xECDs are fabricated using ZnO- and ITO-deposited glass. When static absorbance is examined in both colored and bleached states, there is no obvious change in terms of peak shape, intensity, and spectral optical contrast with the solid electrolyte conditions using different blend ratios. Dynamic optical properties are recorded in terms of transmittance change in ECP-B films in double potential step chronoabsorptometry (DPSC) characterization. The electrochromic kinetics based on ECP-B devices can be directly enhanced as the ionic liquid loading increases, with a 75 wt% ionic liquid loading resulting in short bleaching and coloring times of 3.5 and 3.9 seconds, respectively. This indicates that the presence of the polymer network does not have a detrimental effect on the liquid ion motion and the resulting ionic conductivity. Ionic conductivity is also increased by adding thiol monomers to the polymer gel-based solid electrolyte layer, which may be due to the reduced crosslinking of acrylate photopolymerization by chain growth mechanism and the reduced crosslinking power of UV light due to the presence of thiol monomers.

[0060] The disclosed n-doped organic conductive polymers are used as conductors and electrical interconnects to conduct ion storage layers in electrochromic devices. In the polymerization and ink preparation process, the exemplary organic conductive polymer PBDF is readily reductively doped through the oxidation of water to produce n-doped PBDF (n-PBDF), which provides highly stable enhanced electrical conductivity and low extinction coefficient in the visible region. In some embodiments, the patterning of the disclosed n-doped organic conductive polymer film is fabricated using conventional photolithography in combination with a reactive ion etching (RIE) dry process and an etch stop layer. In some embodiments, AZ1518 (Microchemicals) is spin-coated (5000 rpm, 45 s) on the pre-deposited n-PBDF film as an etch stop layer and baked at 110° C. for 2 min to remove residual solvent. The photoresist film is then irradiated with near-UV light (405 nm, 100 mJ cm ) using a maskless aligner (Heidelberg MLA150). -2 ). The film is developed in developer solution (Microposit, MF-26A) for 45 seconds. After rinsing with DI water, the patterned film is exposed to an etching plasma for 30 minutes to remove the unprotected polymer layer. After plasma etching, any remaining photoresist film is removed with acetone. The conductive polymer film is chemically and mechanically robust as a result of thermal treatment and vertical solution processing in the photolithography process, resulting in well-defined microscale patterning with sharp edges.

[0061] To fabricate a patterned electrochromic device or display, a first conductive layer is coated onto a first substrate, the first conductive layer comprising the disclosed n-doped organic conductive polymer, and is patterned to form first regions and first electrical interconnects between adjacent first regions. A second transparent conductive layer is coated onto a second substrate, and the second conductive layer is patterned to form second regions and second electrical interconnects between adjacent second regions. The electrical interconnects provide a pathway for precise activation and control of the regions. Then, one of: a) forming a first electrolyte layer on each of the first regions, the first electrolyte layers being separated from one another; forming an electrochromic layer on each of the second regions, the electrochromic layers being separated from one another; forming a second electrolyte layer on each of the electrochromic layers, the second electrolyte layers being separated from one another; and laminating the first substrate and the second substrate such that the first electrolyte layer is in registration with and in contact with the second electrolyte layer, or b) forming an electrolyte layer on each of the first regions, the electrolyte layers being separated from one another. or c) forming an electrochromic layer on each of the electrolyte layers, the electrochromic layers being separate from one another; and laminating the first substrate and the second substrate such that the electrochromic layer is in registration with and in contact with the second region; or c) forming an electrochromic layer on each of the second regions, the electrochromic layers being separate from one another; forming an electrolyte layer on each of the electrochromic layers, the electrolyte layers being separate from one another; and laminating the first substrate and the second substrate such that the electrolyte layer is in registration with and in contact with the first region. In some embodiments, the patterning is performed by photolithography or printing methods (e.g., ink printing). Similar fabrication methods without patterning can be used to make non-patterned electrochromic devices.A similar fabrication method, without patterning of the electrolyte layer and the second conductive layer, can be used to make a segmented electrochromic device.

[0062] In some embodiments, the disclosed n-doped organic conductive polymer is included in the first and second conductive layers and the above mentioned process is used to make a patterned electrochromic device / display, for example, the all-polymer pixel electrochromic display illustrated in FIG. 20. The disclosed n-doped organic conductive polymer conductor lines are fabricated by patterning the n-doped organic conductive polymer film that serves as the working electrode, the ion storage conductive layer (counter electrode) and the electrical interconnect as mentioned. The electrochromic polymer film is spin-coated on the working electrode and patterned using in situ photolithography. To make a two-color (or four-color) display, the same method is repeated twice (four times) for the conductive layer patterning substrate. The precursor solution is dropped onto both the surfaces of the ion storage conductive layer (counter electrode) and the electrochromic polymer, and then UV photocrosslinking is performed using a photomask on the dropped precursor solution. The unexposed areas are removed using acetone. The two substrates are carefully assembled and vacuumed using a rotary pump for 1 hour. In some embodiments, similar fabrication methods described above and in FIG. 20 are used without patterning to create non-patterned electrochromic devices.

[0063] For capacitive electrode applications in all-polymer ECDs, in some embodiments, transparent n-PBDF films are fabricated using simple spin-coating of polymer dispersions in dimethylsulfoxide (DMSO). A slightly thicker n-PBDF film (~30 nm) than the working electrode (~20 nm) is used as the counter electrode to balance the charge with the electrochromic polymer film in the electrochemical reaction. Both n-PBDF films exhibit highly transparent properties with transmittances higher than 80% in the entire visible range (Figure 21). The optical transparency of n-PBDF films is comparable to ITO and surpasses capacitive metal oxide-deposited ITO films.

[0064] In some embodiments, the disclosed pixelated electrochromic display employs a passive matrix structure. The passive matrix structure is selected to take advantage of the low energy operation through the excellent optical memory effect in the disclosed all-polymer ECD. However, passive matrix driving can cause serious image crosstalk due to unintentional inter-pixel charge transfer through the electrolyte layer. Therefore, for the fabrication of a passive matrix based display with 8x8 matrix pixels, to provide some degree of isolation between individual pixels, a solid electrolyte is patterned for each pixel by in situ photolithography (see Figures 22(A)-22(B)). A solid electrolyte film is successfully deposited on both the photo-patterned electrochromic polymer and the n-PBDF film for the working and counter electrodes, respectively. The first and second substrates are then laminated together to fabricate the device, such that the first electrolyte layer is aligned and in contact with the second electrolyte layer.

[0065] For pixel fabrication of electrochromic passive matrix displays, the solid electrolyte, the disclosed conductor, and the electrochromic polymer layer can all be clearly localized and sharply edged by photolithographic patterning. The techniques of the present invention make the fabrication of EC displays / devices easy and cost-effective, and crosstalk is greatly reduced by using the disclosed techniques, such as solution processability and patterning compatible with layers in electrochromic displays. The disclosed n-doped organic conductive polymers can simultaneously function as a conductive layer, an ion storage layer, and an electronic interconnect in the display circuitry, so that one single step of patterning the disclosed n-doped organic conductive polymers results in one three-function integrated layer, further reducing the process complexity and cost.

[0066] With reference to FIG. 22(A) and FIG. 22(B), an exemplary method for forming an electrochromic device / display is provided. In FIG. 22(A), a conductive film (e.g., n-PBDF film or other suitable conductive film) is deposited on a substrate. The substrate may be rigid (e.g., glass, metal, etc.) or flexible (e.g., plastic). The substrate may be transparent, semi-transparent, or reflective. A patterning process is then performed on the conductive film. The patterning process includes depositing a photoresist film on the conductive film and performing a lithography step including exposing the photoresist film to UV light through a photomask having a desired pattern including regions and pixels, and interconnects between the regions or pixels. The exposed photoresist film is then developed to form a photoresist pattern on the conductive film. An etching process (e.g., dry etching) is performed using the photoresist pattern as a mask to etch the conductive film to form a desired pattern. The remaining photoresist is then removed. The patterning process can separate the conductive layer on different regions (e.g., pixels or segments) and / or different electrical interconnects. In some embodiments, the above method can be used to form segmented devices as well as pixelated devices, and in some embodiments, the above patterning process on the conductive film can be omitted when forming a non-patterned electrochromic device.

[0067] Following the patterning process of the conductive film on the substrate, an electrochromic polymer (EC polymer) layer is coated on the substrate. Then, a lithography process is performed on the PE polymer layer, including UV exposure through a photomask on the EC polymer layer, and removing the uncured EC polymer layer by wet etching after UV exposure, to pattern the EC polymer layer. This patterning process can separate the EC polymer layer on each of the pixels or segments. To make a two-color (or more color) display, the same process is repeated twice (or more times) on the conductive layer patterned substrate. Note that the EC polymer is removed from the interconnects between the regions or pixels, as shown in Figure 22(A). To form a non-patterned electrochromic device, only the coating of the EC polymer layer is performed without the patterning process.

[0068] Next, the electrolyte solution is coated on the substrate to form an electrolyte film. Then, a lithography process (including UV exposure through a photomask on the electrolyte film and removing the uncured electrolyte film by wet etching after UV exposure) is performed on the electrolyte film to pattern the electrolyte film. This patterning process can separate the electrolyte film on each of the pixels or segments. Note that the electrolyte film is removed from the interconnects between the regions or pixels, as shown in FIG. 22(A). To form a segmented or non-patterned electrochromic device, only the coating of the electrolyte solution is performed without the patterning process. This process ends with forming a working electrode for an EC device or display, for example, a passive matrix-based EC device or display in FIG. 22(A).

[0069] Now, referring to FIG. 22(B), a method for forming a counter electrode substrate is illustrated. As shown in FIG. 22(B), a conductive film (e.g., n-PBDF film or other suitable conductive film) is deposited on a substrate. The substrate may be rigid (e.g., glass, metal, etc.) or flexible (e.g., plastic). The substrate may be transparent, semi-transparent, or reflective. A patterning process is then performed on the conductive film. In this patterning process, a photoresist film is deposited on the conductive film, and a lithography process is performed, which includes exposing the photoresist film to UV light through a photomask having a desired pattern including regions and pixels, and interconnections between the regions or pixels. The exposed photoresist film is then developed to form a photoresist pattern on the conductive film. An etching process (e.g., dry etching) is performed using the photoresist pattern as a mask to etch the conductive film to form a desired pattern. The remaining photoresist is then removed. The patterning process can separate the conductive layer on different regions (e.g., pixels or segments) and / or different electrical interconnections. In some embodiments, the above-described patterning process on the conductive film can be omitted when forming a segmented or non-patterned electrochromic device.

[0070] Next, the electrolyte solution is coated on the substrate to form an electrolyte film. Then, a lithography process (including UV exposure through a photomask on the electrolyte film and removing the uncured electrolyte film by wet etching after UV exposure) is performed on the electrolyte film to pattern the electrolyte film. This patterning process can separate the electrolyte film on each of the pixels. Note that the electrolyte film is removed from the interconnects between the regions or pixels, as shown in FIG. 22(B). To form a segmented or non-patterned electrochromic device, only the coating of the electrolyte solution is performed without the patterning process. This process ends with forming a counter electrode for an EC device or display, for example, a passive matrix-based EC device or display in FIG. 22(B).

[0071] After preparing the working electrode substrate and the counter electrode substrate, the two substrates can be laminated such that the electrolyte layer on the working electrode substrate is aligned and in contact with the electrolyte layer on the counter electrode substrate, as shown in FIG. 20. This lamination method forms an electrochromic device by contacting two electrolyte layers together, improving the yield and performance of the EC device since the contact interface is formed by the same electrolyte. This method eliminates potential contamination at many critical interfaces, such as between the conductive layer and the electrolyte or ion storage layer, between the conductive layer and the electrochromic layer, or between the electrolyte layer and the electrochromic layer. In some embodiments, the two electrolyte layers after patterning appear gel-like, which allows for easy assembly using simple vacuum processing. This lamination method also allows for the formation of a uniform electrolyte layer.

[0072] In some embodiments, the electrolyte film / layer and the electrochromic layer can be formed on the same substrate. For example, when the electrolyte film / layer and the electrochromic layer are both formed on a first substrate, the two substrates are laminated together such that the electrochromic layer on the first substrate is aligned with and in contact with the conductive layer on the second substrate. In some embodiments, when the electrolyte film / layer and the electrochromic layer are both formed on a second substrate, the two substrates are laminated together such that the electrolyte layer on the second substrate is aligned with and in contact with the conductive layer on the first substrate.

[0073] To demonstrate the minimization of crosstalk for a passive matrix-based all-polymer electrochromic display using solid electrolyte localization by in situ patterning, we set all pixels to a completely bleached state using a positive voltage (+1.0V) for a few seconds, and then apply a negative voltage (-0.8V) to light up (color) the target pixel at the intersection of a certain row and column electrode line. When the negative voltage is applied for 10 seconds, only the target pixel shows a clear coloration, but there is no clear color change in the neighboring eight pixels, indicating that the signal crosstalk is greatly reduced in our electrolyte-localized passive matrix electrochromic device (Figure 23(A)). On the other hand, very severe crosstalk is observed in the electrochromic display without electrolyte localization. Even though we applied the off voltage (+1.0V) to only the two intersecting electrodes to bleach the target pixel, it affects the surrounding pixels on the working and counter electrode lines, completely bleaching them in 1 second. Significant and rapid crosstalk is also observed in the electrochromic display patterned with electrochromic polymer, indicating that the crosstalk originates from undesired charge transfer in pixels sharing the same row or column electrode through the non-localized electrolyte layer. The suppression of crosstalk in the electrolyte-localized electrochromic display is also confirmed in the multi-pixel coloring and bleaching process shown in FIG. 23(B). When two target pixels spaced by one pixel are biased at −0.8V for 10 seconds, there is no significant crosstalk and a clear blue color is displayed.

[0074] High bistability is also demonstrated. When a bleaching voltage (+1.0V) is applied to four target pixels at 30-second intervals, they show obvious color bleaching in the target pixels and maintain the bleaching transmittance at open circuit potential due to high optical memory. It is noteworthy that our electrochromic display retains the signal without using thin film transistors for active matrix driving, which requires high manufacturing cost, complicated device structure and large space. In some embodiments, the passive matrix-based display shows the same color display when a voltage of -0.8V is applied for 10 seconds and remains unchanged for 1000 seconds at open circuit potential, which means that the display has high bistability. Due to the high bistability, the passive matrix driving can greatly reduce the energy consumption in pixel-type display applications. The outstanding bistability allows for excellent energy-saving display applications. The energy consumption for each coloring or bleaching process is recorded from the current profile in the chronoamperometric response of a single pixel of the passive matrix display. Remarkably, the energy required for one color switch is just 0.71±0.05mJcm -2 In a scenario involving static content, the power consumption is approximately 0.7 μW cm over 1000 seconds if the content is not updated. -2 Compared to reported displays, the all-polymer electrochromic displays demonstrate ultra-low power consumption levels, which is particularly advantageous for applications involving infrequent information updates. This efficiency is due to the fact that energy is consumed only during the switching and updating processes.

[0075] The absorbance spectra are quantitatively recorded for nine pixels, including one target pixel, two working electrode line sharing pixels, two counter electrode line sharing pixels, and four diagonal pixels. For static absorbance measurements, the spectrum is measured after applying a voltage to the target pixel for 30 seconds. As the applied negative voltage increases from -0.6V to -1.0V, the coloring of the target pixel becomes more pronounced. However, in the pixels sharing the working and counter electrode lines, we observe a small increase in absorbance, unlike the diagonal positions. Small color changes are also confirmed in the photographic images. To elucidate the origin of the small crosstalk, we measure the dynamic absorbance changes in the target coloring process in a non-patterned display, a display patterned only with electrochromic polymer, and an electrolyte-localized electrochromic display. When a voltage is applied to the target pixel in a non-patterned electrochromic display, the change in absorbance intensity in the working electrode and counter electrode line sharing pixel reaches around 100% (Δabs) in 1 to 4 seconds compared to the absorbance change in the target pixel. Although the polymer patterning slightly delays the switching speed in adjacent pixels, they show full coloring and bleaching in 5 seconds. Meanwhile, in electrolyte-localized electrochromic displays, the dynamic absorbance change in working and counter electrode line-sharing pixels saturates at about 20% compared to the change in the target pixel, indicating that the remaining crosstalk arises from other mechanisms than charge transfer through the electrolyte layer. The inventors have found another source of crosstalk in electrolyte-patterned displays, originating from the voltages recorded in adjacent pixels. Pixels sharing working or counter electrode lines show small but distinct voltage changes upon application of a bias to the target pixel, resulting from the interaction between pixels through the electrodes associated with the matrix. The voltage transfer effect in the design of electrical circuits can be addressed by introducing semiconductor diodes into integrated circuits or printed circuit boards for further electrical applications.

[0076] The problem in the electrical circuit is relatively small (about 20%) compared to the undesired charge transfer in the delocalized electrolyte, and thus a real-time pixelated image display is demonstrated by sequentially applying voltage to the target pixels along the counter electrode lines using a passive matrix electrochromic display. Although the voltage is applied at intervals of about 10 seconds due to the lack of an advanced processing chip, the all-polymer electrochromic display exhibits pixelated character graphics of "P" and "U" with good resolution using excellent optical memory. The electrochromic display successfully demonstrates desirable graphics with reduced crosstalk and reversible image change. Due to the large optical memory, no additional energy consumption is required to maintain the displayed content. Through efficient energy consumption and pixelated image projection in an all-polymer non-emissive display, our findings open up new possibilities for the realization of compact see-through pixelated displays in an energy-saving on-chip platform.

[0077] In some embodiments, a transmissive display for segmented graphic generation is realized through photolithographic patterning of all-polymer electrochromic components. First, two electrochromic polymers, blue or magenta, are directly patterned by selective UV light exposure for the desired graphic display. After spin-coating ECP-B solution with photocrosslinker, the film is exposed to selective UV light and processed in solution to remove the non-crosslinked polymer layer. The other ECP-M pattern is developed through the same method. Due to the large solvent resistance due to the photocrosslinking of the polymer chains, elaborate patterns can be formed without crosstalk even at the microscale. The patterned electrochromic display shows extraordinary see-through properties due to the light modulation between transparent "long-lasting" graphics and transparent blanks in response to an exogenous electric potential.

[0078] In some embodiments, the fabrication of flexible all-polymer ECDs begins by depositing the polymer conductors onto a plastic substrate. n-PBDF films are easily formed on flexible polyethylene terephthalate (PET) substrates using spin-coating of DMSO solution without additional heat treatment, suggesting high compatibility with flexible plastic substrates. Other electrochromic components are similarly deposited onto the rigid ECD. Flexibility characterization is performed at various bending radii to investigate the mechanical flexibility and operational stability of the all-polymer ECD. Bending tests are performed at five bending radii (i.e., 4.0, 2.5, 2.0, 1.4, and 0.5 cm). Based on the absorbance spectra of the all-polymer ECD in both colored and bleached states at various radii, including the initial state, the all-polymer ECD exhibits highly stable color switching at various bending radii up to 1.4 cm. The electrochemical stability at different bending radii is tested by recording the transient current of the ECD in the redox reaction. They exhibit very stable and relatively enhanced transient currents as the bending radius increases. This may be due to the thinner devices caused by the increased tensile strain, especially the change in electrolyte thickness. The optical density at the smaller bending radius condition could not be recorded because it was difficult to set the bent sample in a straight path between the spectrometer beam and the detector. Instead, we demonstrate color switching at the large bending state, as shown in the photographic images of the all-polymer device with a bending radius of 5 mm. They show stable and reversible color switching with a small electrical bias (-1.2 V for the coloring process and +1.2 V for the bleaching process). Furthermore, bending cycle tests are performed to investigate the mechanical stability of the devices at a bending radius of 5 mm. The absorbance and transient currents of the all-polymer ECD are monitored before, after 100, 1000 and 10,000 bending cycles. Upon oxidation of the electrochromic polymer, a slight reduction in the transient current is demonstrated, but negligible changes in the reduction transient current, switching time, and static absorbance upon both coloring and bleaching of the ECD.The results clearly demonstrate the effectiveness of the all-polymer ECD in flexibility and operational electrochemical stability, even under repetitive and severe bending conditions.

[0079] Considering the advantages of high optical contrast, achromatic color rendition, reliable flexibility and photopatternability properties of all-polymer ECD, paper-like see-through electrochromic displays are carefully fabricated using the all-polymer system developed here. For practical graphic generation, both polymer conductors and electrochromic polymers are patterned with more elaborate designs for flexible all-polymer electrochromic displays. An example of an all-polymer display attached to human skin exhibits a designed transparent electrochromic polymer graphic on a transparent n-PBDF conductor layer. Furthermore, as illustrated in FIG. 24, 15 PBDF conductors and contact lines are first deposited on a plastic substrate and patterned using conventional photolithography to operate two 7-segment displays to represent all numbers, as well as other graphic displays of "heart", alphabet and "1". Two-color ECP is deposited on the patterned n-PBDF conductor lines and directly patterned by selective UV light. The n-PBDF is deposited on the other PET substrate as a common cathode, and then covered with the anode substrate with the electrolyte precursor solution dropped on it, and then UV light is irradiated for cross-linking of the electrolyte. The electrochromic graphics are digitally driven by power supply through the n-PBDF contact lines and the common cathode using an application-specific multi-pixel type multi-channel controller. The all-polymer electrochromic display can successfully display different "numbers" and graphics by selectively driving the segments and update in seconds through redox reactions. To demonstrate practical applicability, the properties of the all-polymer platform are used to utilize flexible see-through displays on watch bands and on human skin using a ring-like structure (Figures 25(A)-25(B)). With reliable flexibility and robust electrochemical stability, the all-polymer display exhibits good resolution real-time transmissive graphic display in bending conditions, even on a human finger using a ring-like structure with a bending radius of 1.5 cm.Flexible all-polymer electronics using transparent / capacitive n-type conductors are expected to be useful for the next generation of optoelectronics that are further developed in composite systems.

[0080] The adoption of the disclosed n-doped organic conductive polymers as capacitive transparent organic conductors represents a new strategy for fabricating flexible electrochromic displays and is expected to advance the development of other electrochemical devices. The disclosed n-doped organic conductive polymers exhibit high conductive and capacitive properties while retaining high light transmittance and minimal color shift transparency in the electrochemical potential window, and serve both as transparent conductors and ion storage materials simultaneously as counter electrodes of electrochromic devices, and as transparent working electrodes and electrical interconnects of the devices. In addition, at low reduction potentials, the potential window is well matched to p-type electrochromic polymers, making operation stable in ambient conditions. In situ photolithographic patterning in ECP and solid electrolytes allows the development of patterned devices (e.g., all-polymer displays) with no apparent crosstalk for both segmented and pixelated applications. These photopatternable electrochromic components are highly transparent, resulting in see-through display applications with excellent outdoor readability, non-emissive eye-friendly modes, and exceptional energy-saving capabilities. In addition, the electrochromic devices exhibit excellent bistability (e.g., optical memory) due to the robust and dense EDL formed by the ionic liquid. Our results demonstrate a successful approach to transparent, conductive polymer conductors and photopatternable electrochromic components that can serve as a commercially viable practical solution for biocompatible flexible optoelectronic devices across an all-polymer platform.

[0081] Reference is now made to FIG. 26. FIG. 26 is a flow chart of a method 260 for forming an electrochromic device / display, according to one exemplary embodiment. At 2602, a first conductive layer is formed on a first substrate. The first conductive layer may be an n-doped organic conductive polymer, including n-PBDF film, or other suitable conductive film, such as ITO. The substrate may be rigid (e.g., glass, metal, etc.) or flexible (e.g., plastic). The substrate may be transparent, semi-transparent, or reflective. At 2604, a first electrolyte layer is formed on the first conductive layer. The first electrolyte layer may be a solid electrolyte, a gelled solid electrolyte, or a gel electrolyte. At 2606, a second conductive layer is formed on a second substrate. The second conductive layer may be the same as or different from the first conductive layer. The second substrate may be the same as or different from the first substrate. At 2608, an electrochromic layer is formed on the second conductive layer. At 2610, a second electrolyte layer is formed on the electrochromic layer. In some embodiments, the second electrolyte layer may include the same material as the first electrolyte or a different material. In some embodiments, the second electrolyte layer may have the same thickness as the first electrolyte or a different thickness. At 2612, the first substrate and the second substrate are laminated such that the first electrolyte layer contacts the second electrolyte layer to form an electrochromic device / display. In some embodiments, the laminating of the first substrate and the second substrate includes applying at least one sealant to the edges of one or both of the substrates. The disclosed technique forms an electrochromic device by contacting two electrolyte layers together, which can improve the yield and performance of the EC device because the contact interface is formed by the same electrolyte. This method eliminates potential contamination at many critical interfaces, such as between the conductive layer and the electrolyte or ion storage layer, between the conductive layer and the electrochromic layer, or between the electrolyte layer and the electrochromic layer. In some embodiments, the two electrolyte layers after patterning appear gel-like, which allows for easy assembly.

[0082] FIG. 27 is a flow chart of a method 270 for forming an electrochromic device / display according to one exemplary embodiment. Operations 2602, 2604, 2606, and 2612 are the same as those described with respect to FIG. 26 and will not be described further for brevity. Following 2606, the second conductive layer is patterned at 2614 to form second regions. In some embodiments, patterning the second conductive layer also forms second electrical interconnects between adjacent second regions. The second regions may be separate from one another except at the second electrical interconnects. Then, forming an electrochromic layer on the second conductive layer, shown in operation 2608 of FIG. 26, may include patterning the electrochromic layer at 2608a to form an electrochromic film on each of the second regions. The electrochromic films are separate from one another. Following operation 2608a, forming a second electrolyte layer on the electrochromic layer, as shown in operation 2610 of FIG. 26, may include forming a second electrolyte layer on each of the electrochromic films and / or second electrical interconnects and / or in the gaps between adjacent second regions, at 2610a.

[0083] FIG. 28 is a flow chart of a method 280 for forming an electrochromic device / display according to one exemplary embodiment. Operations 2602, 2606, 2614, and 2608a are the same as those described with respect to FIG. 27 and will not be described further for brevity. Following operation 2602, the first conductive layer is patterned at 2616 to form first regions. In some embodiments, patterning the first conductive layer forms first electrical interconnects between adjacent first regions. The first regions may be isolated from one another except at the first electrical interconnects. Then, forming a first electrolyte layer on the first conductive layer, shown in operation 2604 of FIG. 27, may include patterning the first electrolyte layer at 2604a to form a first electrolyte film on each of the first regions. The first electrolyte films are isolated from one another. Following operation 2608a, forming a second electrolyte layer on the electrochromic layers, as shown in operation 2610 of FIG. 26, may include patterning the second electrolyte layer to form a second electrolyte film on each of the electrochromic layers, at 2610b. The second electrolyte films are separate from each other. Laminating the first substrate and the second substrate such that the first electrolyte layer contacts the second electrolyte layer, as shown in operation 2612 of FIG. 26, may include laminating the first substrate and the second substrate such that the first electrolyte film contacts the second electrolyte film, at 2612a. In some embodiments, the first electrolyte film is aligned with the second electrolyte film. The first electrolyte film may be aligned with the second electrolyte film in a one-to-one manner such that the first electrolyte film contacts only the corresponding second electrolyte film and the second electrolyte film does not contact an adjacent second electrolyte film.

[0084] 29 is a flow chart of a method 290 for forming an electrochromic device / display according to one exemplary embodiment. Operations 2602, 2604, 2606, 2608, 2610, and 2612 are the same as those described with respect to FIG. 26 and will not be described further for brevity. Between operations 2602 and 2604, the method 290 further includes forming an ion storage layer on the first conductive layer in operation 2618. Thus, forming a first electrolyte layer on the first conductive layer in operation 2604 effectively forms a first electrolyte layer on the ion storage layer. That is, operation 2618 can form an ion storage layer between the first conductive layer and the first electrolyte layer.

[0085] FIG. 30 is a flow chart of a method 300 for forming an electrochromic device / display according to one exemplary embodiment. Operations 2602, 2604, 2606, 2612, and 2618 are the same as those described with respect to FIG. 30 and will not be described further for brevity. Following 2606, at 2614, the second conductive layer is patterned to form second regions. In some embodiments, patterning the second conductive layer also forms second electrical interconnects between adjacent second regions. The second regions may be separate from one another except at the second electrical interconnects. Then, forming an electrochromic layer on the second conductive layer, shown in operation 2608 of FIG. 26, may include patterning the electrochromic layer to form an electrochromic film on each of the second regions at 2608a. The electrochromic films are separate from one another. Following operation 2608a, forming a second electrolyte layer on the electrochromic layer, as shown in operation 2610 of FIG. 26, may include forming a second electrolyte layer on each of the electrochromic films and / or second electrical interconnects and / or in the gaps between adjacent second regions, at 2610a.

[0086] FIG. 31 is a flow chart of a method 310 for forming an electrochromic device / display according to one exemplary embodiment. Operations 2602, 2606, 2614, and 2608a are the same as those described with respect to FIG. 30 and will not be described further for brevity. Following operation 2602, the first conductive layer is patterned at 2616 to form first regions. In some embodiments, patterning the first conductive layer also forms first electrical interconnects between adjacent first regions. The first regions may be separate from one another except at the first electrical interconnects. Then, forming an ion storage layer on the first conductive layer, shown in operation 2618 of FIG. 30, may include patterning the ion storage layer at 2618a to form an ion storage film on each of the first regions. The ion storage films are separate from one another. Then, forming a first electrolyte layer on the first conductive layer, shown in operation 2604 of FIG. 30, may include patterning the first electrolyte layer to form a first electrolyte film on each of the first regions, at 2604a. The first electrolyte films are separate from each other. Following operation 2608a, forming a second electrolyte layer on the electrochromic layers, shown in operation 2610 of FIG. 26, may include patterning the second electrolyte layer to form a second electrolyte film on each of the electrochromic layers, at 2610b. The second electrolyte films are separate from each other. Laminating the first substrate and the second substrate, shown in operation 2612 of FIG. 26, such that the first electrolyte layer contacts the second electrolyte layer, may include laminating the first substrate and the second substrate, at 2612a, such that the first electrolyte film contacts the second electrolyte film. In some embodiments, the first electrolyte film is aligned with the second electrolyte film. The first electrolyte film may be aligned one-to-one with the second electrolyte film such that the first electrolyte film is in contact only with the corresponding second electrolyte film, and the second electrolyte film is not in contact with an adjacent second electrolyte film.

[0087] FIG. 32 is a flow chart of a method 320 for forming an electrochromic device / display according to one exemplary embodiment. At 3202, a first conductive layer is coated on a first substrate. The first conductive layer may be an n-doped organic conductive polymer, including n-PBDF film or other suitable conductive film, such as ITO. The substrate may be rigid (e.g., glass, metal, etc.) or flexible (e.g., plastic). The substrate may be transparent, semi-transparent, or reflective. At 3204, the first conductive layer is patterned to form first regions. In some embodiments, patterning the first conductive layer also forms first electrical interconnects between adjacent first regions. At 3206, a second conductive layer is coated on a second substrate. The second conductive layer may be the same or different than the first conductive layer. The second substrate may be the same or different than the first substrate. At 3208, the second conductive layer is patterned to form second regions. In some embodiments, patterning the second conductive layer also forms second electrical interconnects between adjacent second regions. The method 320 then branches to operations 3210 or 3212. At 3210, the method includes the following operations: forming an electrolyte layer on each of the first regions, the electrolyte layers being separated from one another; forming an electrochromic layer on each of the electrolyte layers, the electrochromic layers being separated from one another; and laminating the first substrate and the second substrate such that the electrochromic layer contacts the second region. At 3212, the method includes the steps of: forming an electrochromic layer on each of the second regions, the electrochromic layers being separated from one another; forming an electrolyte layer on each of the electrochromic layers, the electrolyte layers being separated from one another; and laminating the first substrate and the second substrate such that the electrolyte layer contacts the first regions.

[0088] FIG. 33 is a flow chart of a method 330 for forming an electrochromic device / display according to another exemplary embodiment. At 3302, a first conductive layer is coated on a first substrate. The first conductive layer may be an n-doped organic conductive polymer, including an n-PBDF film or other suitable conductive film, such as ITO. The substrate may be rigid (e.g., glass, metal, etc.) or flexible (e.g., plastic). The substrate may be transparent, semi-transparent, or reflective. At 3304, the first conductive layer is patterned to form first regions. In some embodiments, patterning the first conductive layer also forms first electrical interconnects between adjacent first regions. At 3306, a second conductive layer is coated on a second substrate. The second conductive layer may be the same or different than the first conductive layer. The second substrate may be the same or different than the first substrate. The method 330 then branches to operation 3308 or 3310. At 3308, the method includes the following operations: forming an electrochromic layer on each of the first regions, where the electrochromic layers are separated from one another; forming an electrolyte layer on the electrochromic layer; and laminating the first substrate and the second substrate such that the electrolyte layer contacts the second conductive layer. At 3310, the method includes the following operations: forming an electrolyte layer on the second conductive layer; forming an electrochromic layer on the electrolyte layer; patterning the electrochromic layer to form a plurality of electrochromic layer regions on the electrolyte layer; and laminating the first substrate and the second substrate such that the electrochromic layer regions contact the first regions.

[0089] In some embodiments, one or all of the above patterning operations are performed by photolithography or printing techniques (eg, ink printing).

[0090] The disclosed electrochemical devices include the disclosed n-doped organic conductive polymers that act as transparent conductors, and / or ion storage layers, and / or electrical interconnects in electronic circuits. The disclosed electrochromic devices are selected from the group including energy storage devices, bioelectronics, biosensors, and optoelectronic devices.

[0091] The above description of the disclosure has been provided for purposes of illustration and description. The disclosure is not intended to be exhaustive or to be limited to the precise form disclosed. The breadth and scope of the disclosure should not be limited by any of the above exemplary embodiments. Numerous modifications and variations will be apparent to those skilled in the art. Modifications and variations include any relevant combination of the features of the disclosure. The embodiments have been selected and described in order to best explain the principles of the disclosure and its practical application, so that those skilled in the art can understand the disclosure for various embodiments and with various modifications suitable for the particular use contemplated. It is intended that the scope of the disclosure be defined by the following claims and their equivalents. [Explanation of symbols]

[0092] 100 Electrochromic Device 102 First insulating substrate 104 First conductive layer 106 Ion storage layer 108 Electrolyte layer 110 Electrochromic Layer 112 Second conductive layer 114 Second insulating substrate 116 Circuit wiring CE Counter Electrode RE reference electrode WE working electrode 600 Electrochromic Device 602 First insulating substrate 604 First conductive layer 606 Ion storage layer 608 Electrolyte layer 610 Electrochromic Layer 612 Second conductive layer 614 Second insulating substrate 616 Circuit wiring 800 Electrochromic Device 802 First insulating substrate 804 Layer containing n-doped organic conductive polymer 806 Electrolyte layer 808 Electrochromic Layer 810 Conductive layer 812 Second insulating substrate 814 Circuit wiring 1300 Electrochromic Device 1302 First insulating substrate 1304 First conductive layer 1306 First Electrochromic Layer 1308 Electrolyte layer 1310 Second electrochromic layer 1312 Second conductive layer 1314 Second insulating substrate 1316 Circuit wiring

Claims

1. An electrochromic apparatus comprising two substrates and a plurality of regions disposed between the two substrates, wherein each of the regions is First conductive layer, Electrolyte layer on the first conductive layer, The electrochromic layer above the electrolyte layer, and Second conductive layer on top of the electrochromic layer Includes, The first conductive layer is, 【Chemistry 1】 (In the formula, X is O, S, or Se, and each of m and n is an integer greater than zero, R １ and R ２ Each of these independently consists of hydrogen, halogen, or C １ ~C １０ Selected from one of the alkyl groups, m- is a negative charge that balances mM+, and M ＋ An electrochromic device comprising an n-doped organic conductive polymer (where is an organic cation, a metal cation, or a proton).

2. The electrochromic apparatus according to claim 1, wherein the second conductive layer comprises an n-doped organic conductive polymer.

3. The electrochromic apparatus according to claim 1, wherein the thickness of the second conductive layer is less than the thickness of the first conductive layer.

4. The electrochromic apparatus according to claim 1, further comprising an ion storage layer disposed between a first conductive layer and an electrolyte layer, wherein the ion storage layer does not contain an n-doped organic conductive polymer.

5. The electrochromic apparatus according to claim 1, wherein the electrolyte layer and the electrochromic layer are each made from a polymer.

6. The electrochromic apparatus according to claim 1, wherein the electrolyte layer is a solid electrolyte layer.

7. The electrochromic apparatus according to claim 1, wherein the region comprises a first region and a second region, and the first region comprises a first electrochromic layer different from the second electrochromic layer of the second region in order to display different colors.

8. The electrochromic apparatus according to claim 1, wherein at least one of the substrates is flexible.

9. The electrochromic apparatus according to claim 1, wherein the first conductive layer or the second conductive layer is transparent or translucent.

10. The electrochromic apparatus according to claim 1, further comprising a conductive polymer interconnection connecting two adjacent regions.

11. The electrochromic apparatus according to claim 10, wherein the conductive polymer interconnects include an n-doped organic conductive polymer.

12. The electrochromic apparatus according to claim 1, wherein each region in the faded state is transparent so that the electrochromic apparatus can become a see-through display.

13. The first conductive layer exhibits minimal color change in transmittance at wavelengths between 380 nm and 800 nm, and a color saturation change ΔC of less than 5 between the oxidized and reduced states of the first conductive layer. ＊ The electrochromic apparatus according to claim 1, having the following:

14. The electrochromic device according to claim 1, which operates at less than 3 volts.

15. The electrochromic apparatus according to claim 1, having a transmittance attenuation ΔT of less than 5% during a 1000-second operation under open-circuit potentials in bias conditions for each reduction or oxidation potential.

16. The electrochromic apparatus according to claim 1, wherein the region comprises a first region and a second region, the electrochromic layer and the second conductive layer of the first region are separated from the electrochromic layer and the second conductive layer of the second region, and the second conductive layer of the first region and the second conductive layer of the second region are connected by a first conductive polymer interconnect disposed between them.

17. The electrochromic apparatus according to claim 16, wherein the electrolyte layer and the first conductive layer of the first region are separated from the electrolyte layer and the first conductive layer of the second region, and the first conductive layer of the first region and the first conductive layer of the second region are connected by a second conductive polymer interconnect disposed between them.

18. An electrochromic apparatus comprising two substrates and a layer disposed between the two substrates, wherein the layer is First conductive layer, Electrolyte layer on the first conductive layer, The electrochromic layer above the electrolyte layer, and Second conductive layer on top of the electrochromic layer Includes, The first conductive layer is, 【Chemistry 2】 An electrochromic apparatus comprising n-doped poly(3,7-dihydrobenzo[1,2-b:4,5-b']difuran-2,6-dione) (n-PBDF) (wherein m and n are integers greater than zero).

19. The electrochromic apparatus according to claim 18, wherein the second conductive layer comprises n-PBDF.

20. The electrochromic apparatus according to claim 18, wherein the thickness of the second conductive layer is less than the thickness of the first conductive layer.

21. The electrochromic apparatus according to claim 18, further comprising an ion storage layer disposed between a first conductive layer and an electrolyte layer, wherein the ion storage layer does not contain n-PBDF.

22. The electrochromic apparatus according to claim 18, wherein each of the electrolyte layer and the electrochromic layer is made from a polymer.

23. The electrochromic apparatus according to claim 18, wherein the electrolyte layer is a solid electrolyte layer.

24. The electrochromic apparatus according to claim 18, wherein at least one of the substrates is flexible.

25. The electrochromic apparatus according to claim 18, wherein the first conductive layer or the second conductive layer is transparent or translucent.

26. The first conductive layer exhibits minimal color change in transmittance at wavelengths between 380 nm and 800 nm, and a color saturation change ΔC of less than 5 between the oxidized and reduced states of the first conductive layer. ＊ The electrochromic apparatus according to claim 18, having the following:

27. The electrochromic device according to claim 18, which operates at less than 3 volts.

28. The electrochromic apparatus according to claim 18, having a transmittance attenuation ΔT of less than 5% during a 1000-second operation under open-circuit potentials in bias conditions for each reduction or oxidation potential.

29. A step of forming a first conductive layer on a first substrate, A step of forming a first electrolyte layer on a first conductive layer, A step of forming a second conductive layer on a second substrate, A step of forming an electrochromic layer on a second conductive layer, A step of forming a second electrolyte layer on an electrochromic layer, and A process of laminating a first substrate and a second substrate such that the first electrolyte layer is in contact with the second electrolyte layer. A method for forming an electrochromic apparatus, including the method described above.

30. A process of patterning a second conductive layer to form a second region and a second electrical interconnection between adjacent second regions. The method according to claim 29, further comprising:

31. The step of forming an electrochromic layer on a second conductive layer includes the step of patterning the electrochromic layer to form an electrochromic film on each of the second regions, wherein the electrochromic films are separated from each other. The step of forming a second electrolyte layer on an electrochromic layer includes forming a second electrolyte layer on each of the electrochromic film and the second electrical interconnection, and in the gaps between adjacent second regions. The method according to claim 30.

32. The first conductive layer is, 【Transformation 3】 (wherein X is O, S or Se, each of m and n is an integer greater than zero, R １ and R ２ each is independently selected from hydrogen or one of C １ to C １０ alkyl, m- is a negative charge balanced by mM+, M ＋ is an organic cation, a metal cation or a proton), the method according to claim 31, comprising an n-doped organic conductive polymer.

33. The step of forming an electrochromic layer on a second conductive layer includes the step of patterning the electrochromic layer to form an electrochromic film on each of the second regions, wherein the electrochromic films are separated from each other. The step of forming a second electrolyte layer on an electrochromic layer includes a step of patterning the second electrolyte layer to form a second electrolyte film on each of the electrochromic films, wherein the second electrolyte films are separated from each other. The method according to claim 30.

34. A process of patterning a first conductive layer to form a first region and a first electrical interconnection between adjacent first regions. It further includes, The first conductive layer is, 【Chemistry 4】 (In the formula, X is O, S, or Se, and each of m and n is an integer greater than zero, R １ and R ２ Each of them independently contains hydrogen or C １ ~C １０ Selected from one of the alkyl groups, m- is a negative charge that balances mM+, and M ＋ The method according to claim 33, comprising an n-doped organic conductive polymer (where is an organic cation, a metal cation, or a proton).

35. The step of forming a first electrolyte layer on a first conductive layer is A step of patterning a first electrolyte layer to form a first electrolyte film on each of the first regions, wherein the first electrolyte films are separated from each other. Includes, The process of laminating a first substrate and a second substrate such that the first electrolyte layer is in contact with the second electrolyte layer is as follows: A process of laminating a first substrate and a second substrate such that the first electrolyte film is in contact with the second electrolyte film. The method according to claim 34, including the method described in claim 34.

36. The method according to claim 35, wherein at least one of the patterning operations is performed by photolithography or printing.

37. The second conductive layer is, 【Transformation 5】 (In the formula, X is O, S, or Se, and each of m and n is an integer greater than zero, R １ and R ２ Each of them independently contains hydrogen or C １ ~C １０ Selected from one of the alkyl groups, m- is a negative charge that balances mM+, and M ＋ The method according to claim 29, comprising an n-doped organic conductive polymer (where is an organic cation, a metal cation, or a proton).

38. A step of forming an ion storage layer between the first conductive layer and the first electrolyte layer. The method according to claim 29, further comprising:

39. A process of patterning a second conductive layer to form a second region and a second electrical interconnection between adjacent second regions. The method according to claim 38, further comprising:

40. The step of forming an electrochromic layer on a second conductive layer includes the step of patterning the electrochromic layer to form an electrochromic film on each of the second regions, wherein the electrochromic films are separated from each other. The step of forming a second electrolyte layer on an electrochromic layer includes forming a second electrolyte layer on each of the electrochromic film and the second electrical interconnection, and in the gaps between adjacent second regions. The method according to claim 39.

41. The step of forming an electrochromic layer on a second conductive layer includes the step of patterning the electrochromic layer to form an electrochromic film on each of the second regions, wherein the electrochromic films are separated from each other. The step of forming a second electrolyte layer on an electrochromic layer includes a step of patterning the second electrolyte layer to form a second electrolyte film on each of the electrochromic films, wherein the second electrolyte films are separated from each other. The method according to claim 39.

42. A process of patterning a first conductive layer to form a first region and a first electrical interconnection between adjacent first regions. The method according to claim 41, further comprising:

43. The step of forming an ion storage layer between a first conductive layer and a first electrolyte layer includes a step of patterning the ion storage layer to form an ion storage film on each of the first regions, wherein the ion storage films are separated from each other. The step of forming a first electrolyte layer on a first conductive layer includes the step of patterning the first electrolyte layer to form a first electrolyte film on each of the ion storage films, wherein the first electrolyte films are separated from each other. The step of laminating a first substrate and a second substrate such that the first electrolyte layer is in contact with the second electrolyte layer includes the step of laminating a first substrate and a second substrate such that the first electrolyte film is in contact with the second electrolyte film. The method according to claim 42.

44. The method according to claim 43, wherein at least one of the patterning operations is performed by photolithography or printing.

45. The second conductive layer is, 【Transformation 6】 (In the formula, X is O, S, or Se, and each of m and n is an integer greater than zero, R １ and R ２ Each of them independently contains hydrogen or C １ ~C １０ Selected from one of the alkyl groups, m- is a negative charge that balances mM+, and M ＋ The method according to claim 38, comprising an n-doped organic conductive polymer (where is an organic cation, a metal cation, or a proton).

46. A method for forming an electrochromic apparatus, The process involves coating a first conductive layer onto a first substrate, wherein the first conductive layer is made of a material of the formula 【Transformation 7】 (In the formula, X is O, S, or Se, and each of m and n is an integer greater than zero, R １ and R ２ Each of them independently contains hydrogen or C １ ~C １０ Selected from one of the alkyl groups, m- is a negative charge that balances mM+, and M ＋ The process involves an n-doped organic conductive polymer (which is an organic cation, a metal cation, or a proton), A step of patterning a first conductive layer to form a first region and a first electrical interconnection between adjacent first regions, A step of coating a second conductive layer onto a second substrate, A step of patterning a second conductive layer to form a second region and a second electrical interconnection between adjacent second regions, and One of the following: a) A step of forming an electrolyte layer on each of the first regions, wherein the electrolyte layers are separated from each other; a step of forming an electrochromic layer on each of the electrolyte layers, wherein the electrochromic layers are separated from each other; and a step of laminating the first substrate and the second substrate such that the electrochromic layer is in contact with the second region, or b) A step of forming an electrochromic layer on each of the second regions, wherein the electrochromic layers are separated from each other; a step of forming an electrolyte layer on each of the electrochromic layers, wherein the electrolyte layers are separated from each other; and a step of laminating the first substrate and the second substrate such that the electrolyte layer is in contact with the first region. The process of executing Methods that include...

47. The method according to claim 46, wherein at least one of the patterning operations is performed by photolithography or printing.

48. A method for forming an electrochromic apparatus, The process involves coating a first conductive layer onto a first substrate, wherein the first conductive layer is made of a material of the formula 【Transformation 8】 (In the formula, X is O, S, or Se, and each of m and n is an integer greater than zero, R １ and R ２ Each of them independently contains hydrogen or C １ ~C １０ Selected from one of the alkyl groups, m- is a negative charge that balances mM+, and M ＋ The process involves an n-doped organic conductive polymer (which is an organic cation, a metal cation, or a proton), A step of patterning a first conductive layer to form a first region and a first electrical interconnection between adjacent first regions, A step of coating a second conductive layer onto a second substrate, and One of the following: a) A step of forming an electrochromic layer on each of the first regions, wherein the electrochromic layers are separated from each other; a step of forming an electrolyte layer on the electrochromic layer; and a step of laminating the first substrate and the second substrate such that the electrolyte layer is in contact with the second conductive layer, or b) A step of forming an electrolyte layer on a second conductive layer; a step of forming an electrochromic layer on the electrolyte layer; a step of patterning the electrochromic layer to form a plurality of electrochromic layer regions on the electrolyte layer; and a step of laminating a first substrate and a second substrate such that the electrochromic layer regions are in contact with the first region. A method that includes the step of performing a certain action.

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