CN117991555A

CN117991555A - Electrochromic device having n-doped conductive polymer as transparent conductive layer, ion storage layer and/or electrochromic layer

Info

Publication number: CN117991555A
Application number: CN202410057636.3A
Authority: CN
Inventors: 梅建国; 宋仁浩; 阿什坎阿布塔希
Original assignee: An Bilaite
Current assignee: An Bilaite
Priority date: 2023-01-20
Filing date: 2024-01-15
Publication date: 2024-05-07

Abstract

A method for forming an electrochromic device, comprising: forming a first conductive layer over a first substrate; forming a first electrolyte layer over the first conductive layer; forming a second conductive layer over the second substrate; forming an electrochromic layer over the second conductive layer; forming a second electrolyte layer over 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.

Description

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

Cross Reference to Related Applications

The present application is a partially continued application of U.S. application Ser. No. 18/532,911, filed on 7 of 12 months of 2023, which is a partially continued application of U.S. application Ser. No. 18/099,850, filed on 20 of 1 month of 2023, which is a partially continued application of International application Ser. No. PCT/US2022/048711, filed on 2 of 11 months of 2022. The entire contents of all of the above applications are incorporated herein by reference in their entirety.

Technical Field

The present invention relates to electrochromic devices comprising n-doped organic conductive polymers that can be used in transparent conductive layers or/and ion storage layers or/and electrochromic layers.

Background

Electrochromic devices (Electrochromic Device, ECD) are typically composed of seven layers, including two non-conductive layers as substrates, one or two transparent conductive (TRANSPARENT CONDUCTING, TC) layers, an electrochromic layer as a working electrode (Working Electrode, WE), an ion storage layer as a counter electrode (Counter Electrode, CE), and an electrolyte layer. When an external electrical bias is applied, the electrochromic layer undergoes a color change. At the same time, the ion storage layer undergoes a reaction opposite to that in the electrochromic layer to balance the charge generated at the electrochromic layer. Between the electrochromic layer and the ion storage layer is an electrolyte layer, which serves as an ion source and ion conduction channel. The electrochromic layer and the ion storage layer are disposed on a transparent conductor, which is the current collector of the device. When two transparent conductor layers are selected, the device functions as a transmissive device. When only one transparent conductor is used (e.g., the other conductive layer is a reflective conductive layer), it is typically used as a reflective device. The TC layer most commonly used in ECDs is Indium Tin Oxide (ITO) because of its low sheet resistance, high optical transparency, and sufficiently large voltage window for most EC materials. However, ITO is mechanically fragile, has small bending radii and strains, which limit its use in roll-to-roll manufacturing and flexible electronics. In addition, indium is a rare earth mineral with a scarce mineral reserve. With the increasing demand for ITO, the availability of indium will be highly limited for twenty years, and the price has been proven to be rising in recent years. Therefore, it is highly desirable to find an ITO substitute that provides high performance and low cost, and it is desirable to reduce the number of layers ECDs to simplify the device structure, thereby further reducing cost. Further, it is also desirable that the least color-changing transmissive ion storage material be solution processable with electrochromic materials to improve performance and durability.

Disclosure of Invention

The present invention relates to electrochromic devices/displays comprising n-doped organic conductive polymers.

In one aspect, the disclosed electrochromic device includes: two substrates and a plurality of regions disposed between the two substrates, and each region includes: a first conductive layer; an electrolyte layer over the first conductive layer; an electrochromic layer over the electrolyte layer; and a second conductive layer over the electrochromic layer. In the disclosed electrochromic device, the first conductive layer includes a compound having the formulaN-doped organic conductive polymers of (a). In the formula, X is O, S or Se; each of m and n is an integer greater than zero; each of R ₁ and R ₂ is independently selected from one of hydrogen, halogen, or C ₁-C₁₀ 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 includes an ion storage layer disposed between the first conductive layer and the electrolyte layer, and where the ion storage layer does not include 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 regions comprise a first region and a second region, wherein the first region comprises a first electrochromic layer different from a second electrochromic layer of the second region for displaying a different color. 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 region in the fade state is transparent to enable the electrochromic device to become a see-through display. In some embodiments, the n-doped organic conductive polymer has a minimum color-shifting transparency in a wavelength range of 380nm to 800nm, wherein the chromaticity change Δc between the oxidized and reduced states of the n-doped organic conductive polymer is less than 5. 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 < 5% at each reduction or oxidation potential bias operating at an open circuit potential for 1000 seconds. In some embodiments, the regions comprise a first region and a second region, wherein 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 and the second conductive layer of the second region are 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 separated from the electrolyte layer and the first conductive layer of the second region, wherein 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 therebetween.

In one aspect, the disclosed electrochromic device includes: two substrates and a plurality of layers disposed between the two substrates. Here, the plurality of layers includes: a first conductive layer; an electrolyte layer over the first conductive layer; an electrochromic layer over the electrolyte layer; and a second conductive layer over the electrochromic layer, wherein the first conductive layer comprises a compound of formulaN-doped poly (3, 7-dihydrobenzo [1,2-b:4,5-b' ] difuran-2, 6-dione) (n-PBDF). In this formula, each of m and n is an integer greater than zero. In some embodiments, the second conductive layer comprises an 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, and the ion storage layer does not include an 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 minimum color-shifting transparency in a wavelength between 380nm and 800nm, wherein a chromaticity shift Δc between an oxidized state and a reduced state of the first conductive layer is less than 5. 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 < 5% at each reduction or oxidation potential bias operating at an open circuit potential for 1000 seconds.

In one aspect, a method of forming an electrochromic device is disclosed. The method comprises the following steps: coating a first conductive layer over the first substrate, wherein the first conductive layer comprises a compound having the formulaN-doped organic conductive polymer of (c), and in the formula, X is O, S or Se; each of m and n is an integer greater than zero; each of R ₁ and R ₂ is independently selected from one of hydrogen or C ₁-C₁₀ 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 a second conductive layer over the second substrate; patterning the second conductive layer to form second regions and second electrical interconnects between adjacent second regions; and performing one of the following steps: a) Forming a first electrolyte layer over each first region, wherein the first electrolyte layers are separated from each other; forming an electrochromic layer over each second area, wherein the electrochromic layers are separated from each other; forming a second electrolyte layer over each electrochromic layer, wherein the second electrolyte layers are separated from each other; and laminating the first substrate and the second substrate such that the first electrolyte layer is in contact with the second electrolyte layer; or b) forming an electrolyte layer over each first region, wherein the electrolyte layers are separated from each other; forming an electrochromic layer over each electrolyte layer, wherein the electrochromic layers are separated from each other; and laminating the first substrate and the second substrate such that the electrochromic layer is in contact with the second region; or c) forming an electrochromic layer over each of the second areas, wherein the electrochromic layers are separated from each other; forming an electrolyte layer over each electrochromic layer, wherein the electrolyte layers are separated from each other; and laminating the first substrate and the second substrate such that the electrolyte layer is in contact with the first region.

In another aspect, a method for forming an electrochromic device is provided. The method comprises the following steps: forming a first conductive layer over a first substrate; forming a first electrolyte layer over the first conductive layer; forming a second conductive layer over the second substrate; forming an electrochromic layer over the second conductive layer; forming a second electrolyte layer over 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.

In some embodiments, the method further comprises: the second conductive layer is patterned to form second regions and second electrical interconnects between adjacent second regions.

In some embodiments, forming the electrochromic layer over the second conductive layer includes: patterning the electrochromic layer to form an electrochromic film over each of the second areas, wherein the electrochromic films are separated from each other; and forming a second electrolyte layer over the electrochromic layer includes: the second electrolyte layer is formed in the gap over each electrochromic film and the second electrical interconnect and between adjacent second regions.

In some embodiments, the first conductive layer includes a compound having the formulaWherein X is O, S or Se; each of m and n is an integer greater than zero; each of R ₁ and R ₂ is independently selected from one of hydrogen or C ₁-C₁₀ alkyl; m ⁺ is an organic or metal cation.

In some embodiments, forming the electrochromic layer over the second conductive layer includes: patterning the electrochromic layer to form an electrochromic film over each of the second areas, wherein the electrochromic films are separated from each other; and forming a second electrolyte layer over the electrochromic layer includes: the second electrolyte layer is patterned to form a second electrolyte membrane over each electrochromic film, wherein the second electrolyte membranes are separated from each other.

In some embodiments, the method further comprises: the first conductive layer is patterned to form first regions and first electrical interconnects between adjacent first regions.

In some embodiments, forming the first electrolyte layer over the first conductive layer includes: the first electrolyte layer is patterned to form a first electrolyte membrane over each first region, wherein the first electrolyte membranes are separated from each other. Laminating the first substrate and the second substrate such that the first electrolyte layer is in contact with the second electrolyte layer includes: the first substrate and the second substrate are laminated such that the first electrolyte membrane is in contact with the second electrolyte membrane.

In some embodiments, the second conductive layer includes a compound having the formulaWherein X is O, S or Se; each of m and n is an integer greater than zero; each of R ₁ and R ₂ is independently selected from one of hydrogen or C ₁-C₁₀ alkyl; m ⁺ is an organic or metal cation.

In some embodiments, the method further comprises: an ion storage layer is formed between the first conductive layer and the first electrolyte layer.

In some embodiments, forming an ion storage layer between the first conductive layer and the first electrolyte layer includes: the ion storage layer is patterned to form ion storage films over each of the first regions, wherein the ion storage films are separated from each other. Forming a first electrolyte layer over the first conductive layer includes: the first electrolyte layer is patterned to form a first electrolyte membrane over each ion storage membrane, wherein the first electrolyte membranes are separated from each other. Laminating the first substrate and the second substrate such that the first electrolyte layer is in contact with the second electrolyte layer includes: the first substrate and the second substrate are laminated such that the first electrolyte membrane is in contact with the second electrolyte membrane.

In another aspect, a method for forming an electrochromic device is provided. The method comprises the following steps: coating a first conductive layer over the first substrate, wherein the first conductive layer comprises a compound having the formulaWherein X is O, S or Se; each of m and n is an integer greater than zero; each of R ₁ and R ₂ is independently selected from one of hydrogen or C ₁-C₁₀ 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 a second conductive layer over the second substrate; patterning the second conductive layer to form second regions and second electrical interconnects between adjacent second regions; and performing one of the following operations: a) Forming an electrolyte layer over each first region, wherein the electrolyte layers are separated from each other; forming an electrochromic layer over each electrolyte layer, wherein the electrochromic layers are separated from each other; and laminating the first substrate and the second substrate such that the electrochromic layer is in contact with the second region; or b) forming an electrochromic layer over each of the second areas, wherein the electrochromic layers are separated from each other; forming an electrolyte layer over each electrochromic layer, wherein the electrolyte layers are separated from each other; and laminating the first substrate and the second substrate such that the electrolyte layer is in contact with the first region.

In another aspect, a method for forming an electrochromic device is provided. The method comprises the following steps: coating a first conductive layer over the first substrate, wherein the first conductive layer comprises a compound having the formulaWherein X is O, S or Se; each of m and n is an integer greater than zero; each of R ₁ and R ₂ is independently selected from one of hydrogen or C ₁-C₁₀ 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 a second conductive layer over the second substrate; and performing one of the following operations: a) Forming an electrochromic layer over each first region, wherein the electrochromic layers are separated from each other; forming an electrolyte layer over 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 over the second conductive layer; forming an electrochromic layer over the electrolyte layer; patterning the electrochromic layer to form a plurality of electrochromic layer regions over the electrolyte layer; and laminating the first substrate and the second substrate such that the electrochromic layer area is in contact with the first area.

In some embodiments, some or all of the above patterning operations may be performed by photolithography or printing methods.

Drawings

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

Fig. 1 depicts a cross-sectional view of an electrochromic device comprising a layer of the disclosed n-doped organic conductive polymer used as a transparent conductive layer, according to one example embodiment of the invention.

Fig. 2 (a) - (C) are graphs of electrical conductivity (fig. 2 (a)), transmittance (fig. 2 (B)), as well as sheet resistance and 550nm transmittance (fig. 2 (C)) of an example n-doped organic conductive polymer n-PBDF film comprising different thicknesses according to some example embodiments.

Fig. 3 (a) - (B) depict an example design of a 3-electrode electrochromic device comprising a layer of an example n-doped organic conductive polymer n-PBDF acting as a TC layer for the electrochromic device. Fig. 3 (a) is a schematic diagram of a 3-electrode electrochromic device according to an example embodiment. Fig. 3 (B) is a cross-sectional view of the working electrode in fig. 3 (a).

Fig. 4 (a) - (B) are graphs of cyclic voltammograms of electrochromic polymer (ECP) -B contained on ITO/substrate and on example n-doped organic conductive polymer n-PBDF/substrate and cyclic voltammograms of n-PBDF on platinum button electrode (fig. 4 (a)) and spectro-electrochemical of ECP-B on n-PBDF/substrate (fig. 4 (B)).

Fig. 5 (a) - (B) are graphs illustrating charge capacities of example n-doped organic conductive polymers n-PBDF. FIG. 5 (A) is a cyclic voltammogram of a 30nm thick n-BDF film formed at different rates on ITO in 0.2M tetrabutylammonium bistrifluoromethane sulfonimide (TBA-TFSI) in Propylene Carbonate (PC). Fig. 5 (B) illustrates the average current density at 0.3V (vs Ag/AgCl) plotted against scan rate.

Fig. 6 is a cross-sectional view of an electrochromic device including a layer of the disclosed n-doped organic conductive polymer used as an ion storage layer, according to some example embodiments of the invention.

Fig. 7 (a) - (B) are diagrams of an example ITO/example n-doped organic conductive polymer n-PBDF/ECP-B electrochromic device including a layer of n-PBDF serving as an ion storage layer, according to one example embodiment. Fig. 7 (a) is a spectroelectrochemical in colored and faded states according to an example embodiment, and fig. 7 (B) depicts conversion kinetics from a step potential rapid chronoamperometry (SPFC) according to an example embodiment.

Fig. 8 is a cross-sectional view of an electrochromic device including one layer of the disclosed n-doped organic conductive polymer acting as both an ion storage layer and a TC layer for a counter electrode and another layer of the disclosed n-doped organic conductive polymer acting as a TC layer for a working electrode, according to some example embodiments of the invention.

Fig. 9 (a) - (B) are diagrams of an example n-doped organic conductive polymer n-PBDF/ECP-B electrochromic device comprising one layer of n-PBDF serving as both an ion storage layer and a TC layer for a counter electrode and another layer of n-PBDF serving as a TC layer for a working electrode, according to one example embodiment. Fig. 9 (a) is a spectroelectrochemical in colored and faded states according to an example embodiment, and fig. 9 (B) depicts conversion kinetics from SPFC according to an example embodiment.

Fig. 10 (a) - (B) are diagrams of an example n-doped organic conductive polymer n-PBDF/ECP-M electrochromic device including a layer of n-PBDF serving as both an ion storage layer and a TC layer for a counter electrode and a layer of another n-PBDF serving as a TC layer for a working electrode, according to one example embodiment. Fig. 10 (a) is a spectroelectrochemical in colored and faded states according to an example embodiment, and fig. 10 (B) depicts conversion kinetics from SPFC according to an example embodiment.

Fig. 11 (a) - (B) are diagrams of an example n-doped organic conductive polymer n-PBDF/ECP-BK electrochromic device including one layer of n-PBDF serving as both an ion storage layer and a TC layer for a counter electrode and another layer of n-PBDF serving as a TC layer for a working electrode, according to an example embodiment. Fig. 11 (a) is a spectroelectrochemical in colored and faded states according to an example embodiment, and fig. 11 (B) depicts conversion kinetics from SPFC according to an example embodiment.

Fig. 12 is an absorption spectroelectrochemical of an example n-doped organic conductive polymer n-PBDF in 0.2M TBA-TFSI in PC with an increase in applied voltage from-0.3V to 0.9V.

Fig. 13 is a cross-sectional view of an electrochromic device including a layer of the disclosed n-doped organic conductive polymer used as an electrochromic layer for a counter electrode, according to one example embodiment.

Fig. 14 (a) - (B) contain diagrams of an example 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 example embodiment. Fig. 14 (a) is a spectroelectrochemical in colored and faded states according to an example embodiment, and fig. 14 (B) depicts conversion kinetics from SPFC according to an example embodiment.

FIG. 15 is cyclic voltammetry results and specific volume capacitance for CVs from polymer counter electrodes (n-PBDF and PEDOT: PSS) and ECP-blue films.

Fig. 16 (a) - (B) contain data for an example n-doped organic conductive polymer n-PBDF film for a working electrode (20 nm) according to one example embodiment. Fig. 16 (a) shows an optical absorption spectrum. Fig. 16 (B) shows CIE L, a, B color coordinate values estimated from fig. 16 (a).

Fig. 17 shows CIE L, a, b color coordinate values for two polymer conductors of different thickness (n-PBDF and PEDOT: PSS).

Fig. 18 (a) - (C) contain data based on electrochromic behavior of an exemplary n-doped organic conductive polymer n-PBDF film as a transmissive ECP-B ECD for a working electrode and a counter electrode according to one exemplary embodiment. Fig. 18 (a) shows an optical absorption spectrum; fig. 18 (B) shows a dynamic transmittance change; fig. 18 (C) shows optical memory.

Fig. 19 (a) - (C) contain data for electrochromic behavior comparisons of transmissive ECP-B ECDs using different conductors and ion storage layers, according to some example embodiments. "ITO/VO _x" refers to an ECD that uses VO _x as the ion storage layer and ITO as the working electrode. "n-PBDF as C" refers to an ECD using n-PBDF as the ion storage counter electrode and ITO as the working electrode. "n-PBDF as W/C" refers to ECDs that use n-PBDF as the ion storage counter electrode and working electrode. FIG. 19 (A) shows a comparison of dynamic coloring/fading rate with optical contrast; fig. 19 (B) shows a comparison of electrochromic efficiencies; fig. 19 (C) shows a comparison of CIE a and b color coordinate value changes.

Fig. 20 is an example schematic diagram of a fabrication concept of a patterned electrochromic device according to one embodiment.

FIG. 21 shows the optical transmission spectra of ITO, ITO/VO _x, and n-PBDF films (as either the working or counter electrodes).

Fig. 22 (a) - (B) illustrate schematic diagrams of a fabrication process for working electrode substrates (fig. 22 (a)) and counter electrode substrates (fig. 22 (B)) of passive matrix electrochromic devices or displays patterned using photolithography, according to some example embodiments.

Fig. 23 (a) - (B) contain images of an all-polymer passive matrix electrochromic display with cross-talk reduction. Fig. 23 (a) shows coloring of the target pixel P5. Fig. 23 (B) shows an image when two target pixels are turned on. A voltage of-0.8V is applied at the target pixel for 10 seconds.

Fig. 24 is an exemplary schematic of an electrochromic device or display of an all-polymer segment.

Fig. 25 (a) - (B) contain images of various applications of an all-polymer segmented electrochromic display. Fig. 25 (a) is an image of a wristband. Fig. 25 (B) is an image of human skin having a ring structure.

Fig. 26 is a flowchart of a method for forming an electrochromic device/display according to an example embodiment.

Fig. 27 is a flowchart of a method for forming an electrochromic device/display according to another example embodiment.

Fig. 28 is a flowchart of a method for forming an electrochromic device/display according to yet another example embodiment.

Fig. 29 is a flowchart of a method for forming an electrochromic device/display according to yet another example embodiment.

Fig. 30 is a flowchart of a method for forming an electrochromic device/display according to yet another example embodiment.

Fig. 31 is a flowchart of a method for forming an electrochromic device/display according to yet another example embodiment.

Fig. 32 is a flowchart of a method for forming an electrochromic device/display according to yet another example embodiment.

Fig. 33 is a flowchart of a method for forming an electrochromic device/display according to yet another example embodiment.

Detailed Description

In the following description, certain specific details are set forth in order to provide a thorough understanding of various embodiments of the invention. However, it will be understood by those skilled in the art that the present invention may be practiced without these details. Moreover, although various embodiments of the invention are disclosed herein, many adaptations and modifications may be made within the scope of the invention, as would be apparent to one skilled in the art based on the common general knowledge. Such modifications include the substitution of known equivalents for any aspect of the invention in order to achieve the same result in substantially the same way.

In the present specification and claims, unless the context requires otherwise, the word "comprise" and variations such as "comprises" and "comprising" are to be construed in an open, inclusive sense, i.e. "including but not limited to. References to numerical ranges of values are intended to be used as shorthand notations, respectively referring to each individual value falling within the range including the value of the defined range, and each individual value is incorporated into the specification as if it were individually recited. In addition, the singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise.

Reference in the specification to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment of the invention. Thus, the appearances of the phrases "in one embodiment" or "in an embodiment" in various places throughout this specification are not necessarily all referring to the same embodiment, but may in some cases be. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments. By "transparent" is meant a transmittance of greater than 40% in the visible light range, including, for example, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75% and above. "translucent" means a transmission in the visible region of greater than 5%, including, for example, 5%, 10%, 15%, 20%, 25%, 30%, 35% and less than 40%. "all-polymer" or "all-polymer" means that the conductive layer, ion storage layer, electrolyte layer, and electrochromic layer include polymers. In some embodiments, "all-polymer" or "all-polymer" may also include polymeric substrates. "solid electrolyte" includes solid or gel-like solid electrolytes.

Various embodiments described herein relate to electrochromic devices including a compound having the formulaN-doped organic conductive polymers of (a). In the formula, X is O, S or Se; each of m and n is an integer greater than zero; each of R ₁ and R ₂ is independently selected from one of hydrogen or C ₁-C₁₀ alkyl; m+ is an organic cation or a metal cation. In some embodiments, X is O, each of R ₁ and R ₂ is hydrogen, m+ is a proton, and the n-doped organic conductive polymer according to these embodiments is referred to as having the formula/>N-doped poly (3, 7-dihydrobenzo [1,2-b:4,5-b' ] difuran-2, 6-dione) (n-PBDF). The layers comprising the disclosed n-doped organic conductive polymers may be used as Transparent Conductive (TC) layers and/or ion storage layers and/or electrochromic layers. In this specification, three specific electrochromic polymers are used for purposes of illustration. It should be understood that the invention is not limited to these examples. ECP-magenta (ECP-M) is an example magenta ECP. ECP-blue (ECP-B) is an example blue ECP. ECP-Black (ECP-BK) is an example black ECP. The structures of the example ECP-M, ECP-B and ECP-BK are shown below, respectively, where n is an integer greater than zero.

The existing ECD is composed of seven layers including two non-conductive layers as a substrate, one or two Transparent Conductive (TC) layers (one for a working electrode and one for a counter electrode) respectively disposed over the substrate, an electrochromic layer as a Working Electrode (WE), an ion storage layer as a Counter Electrode (CE), and an electrolyte layer interposed between WE and CE. In the present invention, a layer comprising the disclosed n-doped organic conductive polymer may be used as a TC layer or/and an ion storage layer or/and an electrochromic layer. In some embodiments, the disclosed n-doped organic conductive polymer can replace conventional ITO as an excellent transparent conductor, and a layer comprising the disclosed n-doped organic conductive polymer can be used as at least one TC layer in an ECD. In some embodiments, a layer comprising the disclosed n-doped organic conductive polymer may be used as an ion storage layer in an ECD. In some embodiments, layers comprising the disclosed n-doped organic conductive polymers may be used as a TC layer and an ion storage layer for the counter electrode, respectively. In some embodiments, a layer comprising the disclosed n-doped organic conductive polymer may be used as both a TC layer and an ion storage layer for a counter electrode (e.g., integrated as a single layer), such that the number of layers is reduced, thereby simplifying the electrochromic device structure. In some embodiments, layers comprising the disclosed n-doped organic conductive polymers may be used as an ion storage layer for the counter electrode and a TC layer for the working electrode, respectively. In some embodiments, layers comprising the disclosed n-doped organic conductive polymers may be used as both a TC layer for the counter electrode and an ion storage layer (e.g., integrated as a single layer) as well as a TC layer for the working electrode, such that the number of layers is reduced, thereby simplifying the electrochromic device structure. In some embodiments, layers comprising the disclosed n-doped organic conductive polymers may be used as TC layers for the counter electrode and ion storage layer, respectively, and for the working electrode. In some embodiments, a layer comprising the disclosed n-doped organic conductive polymer may undergo a redox reaction to exhibit electrochromic properties, thereby acting as an electrochromic layer (as a counter electrode, instead of a conventional ion storage layer) paired with an electrochromic layer comprising a p-doped electrochromic material as a working electrode. In some embodiments, the disclosed ECD includes a layer composed of the disclosed n-doped organic conductive polymer. When a layer comprising the disclosed n-doped organic conductive polymer is used as the TC layer and/or ion storage layer, in addition to the disclosed n-doped organic conductive polymer, other components may be included that do not significantly affect the optical properties and conductivity of the layer, such as electrolyte salts (e.g., li ⁺ salt, na ⁺ salt, TBA ⁺ (tetrabutylammonium)) or some stabilizers (e.g., PEG (polyethylene glycol), polystyrene) that adjust its mechanical properties. When a layer comprising the disclosed n-doped organic conductive polymer is used as electrochromic layer, in addition to the disclosed n-doped organic conductive polymer, other components may be included that do not significantly affect the optical properties and conductivity of the layer, such as electrolyte salts (e.g. Li ⁺ salt, na ⁺ salt, TBA ⁺ (tetrabutylammonium)) or some stabilizers (e.g. PEG (polyethylene glycol), polystyrene) or some other n-doped electrochromic material that adjusts its mechanical properties, e.g. WO ₃, viologen or n-doped electrochromic polymer. By p-doped electrochromic material is meant a material that undergoes an electrochromic process when oxidized. An n-doped electrochromic material means a material that undergoes an electrochromic process when reduced.

In the present invention, for most EC materials, the disclosed n-doped organic conductive polymers show low sheet resistance, high optical transparency and large voltage window, which makes the disclosed n-doped organic conductive polymers organic transparent conductors for ECD. In addition, the disclosed n-doped organic conductive polymers are mechanically flexible and can be readily applied to roll-to-roll fabrication and flexibility ECDs, which is comparable to conventional transparent conductor ITO. In the ECD disclosed in the present invention, when a layer including the disclosed n-doped organic conductive polymer is used as both an ion storage layer and a TC layer for a counter electrode, the ECD structure can be simplified, and thus the ECD can be manufactured at lower cost and with improved throughput. Thus, the disclosed techniques may provide high performance ECDs at a lower cost.

In one aspect, the disclosed electrochromic device includes a layer comprising the disclosed n-doped organic conductive polymer that does not undergo a redox reaction and remains transparent in the applied device voltage window. The disclosed electrochromic device is configured with three main different types. Various example constructions from various types are shown and discussed below.

The first type of electrochromic device disclosed has at least one TC layer comprising the disclosed n-doped organic conductive polymer. As shown in fig. 1, such an example configuration may have: a first insulating substrate 102; a first conductive layer 104 comprising the disclosed n-doped organic conductive polymer disposed over the first insulating substrate 102; an ion storage layer 106 disposed over the first conductive layer 104; an electrolyte layer 108 disposed over the ion storage layer 106; an electrochromic layer 110 disposed over the electrolyte layer 108; a second conductive layer 112 disposed over the electrochromic layer 110; a second insulating substrate 114 disposed over the second conductive layer 112; and circuitry 116 that manipulates 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 referred to as a TC layer). In some embodiments, both the first conductive layer and the second conductive layer are transparent (for these disclosures ECDs, they have 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, to form a reflective ECD. In some embodiments, the first conductive layer 104 may include a transparent conductor (such as ITO) without the disclosed n-doped organic conductive polymer, while the second conductive layer 112 includes the disclosed n-doped organic conductive polymer. In some embodiments, both the first conductive layer 104 and the second conductive layer 112 comprise the disclosed n-doped organic conductive polymers. In some embodiments, at least one of the first conductive layer 104 and the second conductive layer 112 is comprised of the disclosed n-doped organic conductive polymers.

The disclosed n-doped organic conductive polymers can be used as high performance transparent conductors. To demonstrate this, n-PBDF was used as an example n-doped organic conductive polymer and its optical transmittance, conductivity and sheet resistance at various thicknesses were studied. Fig. 2 (a) is a graph showing the conductivity of a thin film having a thickness of 16nm to 94 nm. The conductivity of the thin film increases with increasing film thickness. When the thickness is about 94nm, the conductivity can reach 6100S/cm. The optical transmittance of the n-PBDF film is depicted in FIG. 2 (B). As shown in fig. 2 (B), the n-PBDF film shows high transmittance in the visible light region (e.g., 400-700 nm). The high conductivity of the film and high transmittance in the visible region indicate that the disclosed n-doped organic conductive polymers are suitable for use as transparent conductors. This is more evident in fig. 2 (C), where sheet resistance and optical transmittance are plotted with film thickness. At the 550nm wavelength, which is most sensitive to the human eye, the optimized n-PBDF film exhibits a low sheet resistance of 45 Ω/sq and a high transmittance (T ₅₅₀ > 80%), which is comparable to conventional transparent conductor ITO. Thus, the disclosed n-doped organic conductive polymers are established as high performance transparent conductors.

To simplify the presentation of the disclosed n-doped organic conductive polymer for use as a TC layer in an ECD, a 3-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 sheet of glass or PET as a substrate, a layer of the disclosed n-doped organic conductive polymer as a transparent conductor, and a layer of electrochromic material (e.g., ECP-B) as an electrochromic layer. In one embodiment, an exemplary n-doped organic conductive polymer n-PBDF layer with T ₅₅₀ (transmittance at wavelength 550 nm) > 85% and R _s (sheet resistance) < 80 Ω/sq is first coated over a bare glass substrate, followed by an electrochromic layer, such as ECP-B. The slide was then immersed in a liquid electrolyte to create a 3-electrode electrochromic device. In one embodiment, ECP-B is gradually oxidized and becomes transmissive when a positive potential (relative to Ag/AgCl) of up to 0.7V is applied. As shown in fig. 4 (B), this process was captured in the spectroelectrochemical measurement of ECP-B on an n-PBDF/substrate structure. As the applied voltage increases, the transmittance of ECP-B in the visible region (e.g., 400-700 nm) increases. The same measurements were performed when ITO was used as the transparent electrode, and very similar electrochromic responses were recorded. The CV measurements of ECP-B, n-PBDF on ITO/substrate and of n-PBDF itself on platinum button working electrode are shown in FIG. 4 (A), the ECP-B electrochromic layer shows that ECP-B has the same oxidation onset on ITO and n-PBDF transparent conductors, about-0.2V (vs. Ag/AgCl), about 0.8V lower than the oxidation onset of n-PBDF (0.58V vs. Ag/AgCl). Therefore, when the voltage applied to the n-PBDF is lower than 0.58V, the n-PBDF does not undergo the oxidation-reduction reaction. Taken together, these results demonstrate that the disclosed n-doped organic conductive polymers can be used as TC layers in electrochromic devices without adversely affecting the optical and electrical properties of the electrochromic device, comparable to inorganic TCs (e.g., ITO).

In addition to transparency, the disclosed n-doped organic conductive polymers also exhibit high charge densities. The demonstration was performed using an example n-doped organic conductive polymer n-PBDF. As shown in fig. 5 (a), the specific volumetric capacitance (C) of the n-PBDF film was measured by recording cyclic voltammograms at different scan rates in a 0.2M TBA-TFSI (PC) electrolyte. According to cyclic voltammograms, a non-zero current plateau in the range of-0.2V to +0.4v represents a double layer capacitance. As shown in fig. 5 (B), the linear increase of the current density with the scan rate also confirms the capacitive behavior. Both high light transmittance and large charge capacity ensure that the disclosed n-doped organic conductive polymers can be used as ion storage materials in ECDs.

The second type of electrochromic device disclosed has a layer comprising the disclosed n-doped organic conductive polymer as an ion storage layer. An example ECD scheme with a layer comprising the disclosed n-doped organic conductive polymer as an ion storage layer is shown in fig. 6. The ECD includes: a first insulating substrate 602; a first conductive layer 604 disposed over the first insulating substrate 602; an ion storage layer 606 comprising the disclosed n-doped organic conductive polymer disposed over the first conductive layer 604; an electrolyte layer 608 disposed over the ion storage layer 606 comprising the disclosed n-doped organic conductive polymer; an electrochromic layer 610 disposed over the electrolyte layer 608; a second conductive layer 612 disposed over the electrochromic layer 610; a second insulating substrate 614 disposed over the second conductive layer 612; and circuitry 616 that manipulates electrochromic device 600. The disclosed n-doped organic conductive polymer layer serves as an ion storage layer and can work with inorganic or organic electrochromic materials in the electrochromic layer 610 (working electrode). In some embodiments, ion storage layer 606 is comprised of the disclosed n-doped organic conductive polymers. 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 comprises a reflective conductive layer, such as a metal layer, to form a reflective ECD.

To demonstrate the performance of a layer comprising the disclosed n-doped organic conductive polymer as an ion storage layer (counter electrode) in an electrochromic device, ECP-B was used as an example ECP as a working electrode at the electrochromic layer, and an example n-doped organic conductive polymer n-PBDF was used in the following ECD examples. 0.2MTBATFSI in an in situ crosslinked 1:1pegda:pc was used as the electrolyte layer 608. The disclosed n-PBDF thin films are used as the ion storage layer 606 for the counter electrode. Fig. 7 (a) is a graph depicting the transmission spectrum of the disclosed electrochromic device. The transmission spectrum showed a large change during the coloring process, indicating that the electrochromic device successfully switched between the colored state and the fade state. The switching kinetics from the Step Potential Fast Chronoamperometry (SPFC) are shown in fig. 7 (B), which shows that the electrochromic device achieves a fast switching from 5% to 55% at 612 nm. These results demonstrate that the disclosed n-doped organic conductive polymers perform well as ion storage materials for electrochromic devices.

A third type of the disclosed electrochromic device has a layer comprising the disclosed n-doped organic conductive polymer that serves as both a TC layer and an ion storage layer. An example configuration of an electrochromic device 800 is shown in fig. 8. The ECD 800 includes: a first insulating substrate 802; a layer 804 comprising the disclosed n-doped organic conductive polymer disposed over the first insulating substrate 802; an electrolyte layer 806 disposed over the layer 804 comprising the disclosed n-doped organic conductive polymer; an electrochromic layer 808 disposed over the electrolyte layer 806; a TC layer 810 disposed over the electrochromic layer 808; and a second insulating substrate 812 disposed over the conductive layer 810. The conductive layer 810 may include or consist of the disclosed n-doped organic conductive polymer, or may be a TC layer without the disclosed n-doped organic conductive polymer, such as ITO, or may be a reflective conductive layer, such as metal. Electrochromic device 800 also includes circuitry 814 that manipulates electrochromic device 800. In this example device 800, a monolayer 804 comprising the disclosed n-doped organic conductive polymer serves as both a TC layer and an ion storage layer for the counter electrode, thus simplifying the device structure, being lower cost and higher throughput. In some embodiments, the layer 804 comprising the disclosed n-doped organic conductive polymer may be separated into two separate layers due to variations in other components in the layers, with one layer comprising the disclosed n-doped organic conductive polymer serving as the TC layer and the other layer comprising the disclosed n-doped organic conductive polymer serving as the ion storage layer. The TC layer 810 may also include or consist of the disclosed n-doped organic conductive polymer, or may be a TC layer without the disclosed n-doped organic conductive polymer, such as ITO. In some embodiments, layer 804 comprising the disclosed n-doped organic conductive polymer may be separated into two separate layers, with one layer comprising or consisting of the disclosed n-doped organic conductive polymer as an ion storage layer and the other TC layer without the disclosed n-doped organic conductive polymer, such as ITO, and TC layer 810 may also comprise or consist of the disclosed n-doped organic conductive polymer. In some embodiments, the disclosed electrochromic device has a layer composed of the disclosed n-doped organic conductive polymer that serves as both a TC layer and an ion storage layer.

In one embodiment, the example n-doped organic conductive polymer n-PBDF was assembled into an electrochromic device using ECP-B as electrochromic layer 808 (working electrode), 0.2M TBATFSI in an in-situ crosslinked 1:1pegda:pc as electrolyte layer 806, an n-PBDF thin film as transparent conductive layer 810 for working electrode 808, and n-PBDF layer 804. The n-PBDF layer 804 serves as both a transparent conductor and an ion storage layer for the counter electrode. The optical performance of the electrochromic device is illustrated in fig. 9 (a) and 9 (B). Fig. 9 (a) is a diagram describing the transmission spectrum of the electrochromic device. The transmission spectrum shows a large change during the coloring process, indicating that the electrochromic device successfully switches between the colored state and the faded state. The switching kinetics from the step potential fast SPFC are shown in fig. 9 (B), which shows that the electrochromic device achieves a fast switching from 18% to 70% at 612 nm. These results demonstrate that the disclosed n-doped organic conductive polymers perform well as transparent conductors and ion storage materials for counter electrodes.

The above structural configuration can also be applied to other types of ECPs. For example, ECP-B of electrochromic layer 808 may be replaced with ECP-M or ECP-BK. The optical performance of the electrochromic device with the electrochromic layer 808 of ECP-M is illustrated in fig. 10 (a) and 10 (B). Fig. 10 (a) is a graph depicting the transmission spectrum of an electrochromic device. The transmission spectrum showed a large change during the coloring process, indicating that the electrochromic device successfully switched between the colored state and the fade state. The switching kinetics from the step potential fast SPFC are shown in fig. 10 (B), which shows that the electrochromic device achieves a fast switching from 22% to 78% at 550 nm. These results demonstrate that the disclosed n-doped organic conductive polymers work well as transparent conductors and ion storage materials paired with ECP-M electrochromic layer 808.

The optical performance of the electrochromic device with the ECP-BK electrochromic layer 808 is illustrated in fig. 11 (a) and 11 (B). Fig. 11 (a) is a diagram describing the transmission spectrum of an electrochromic device. The transmission spectrum showed a large change during the coloring process, indicating that the electrochromic device successfully switched between the colored state and the fade state. The switching kinetics from the step potential fast SPFC are shown in fig. 11 (B), which shows that the electrochromic device achieves a fast switching from 7% to 40% at 550 nm. These results demonstrate that the disclosed n-doped organic conductive polymers work well as transparent conductors and/or ion storage materials paired with the ECP-BK electrochromic layer 808.

Both inorganic and organic electrochromic materials may be used in the electrochromic layers in the electrochromic devices disclosed herein. In some embodiments, the electrochromic layer in the electrochromic devices disclosed herein comprises one or more of WO ₃、NiO、IrO₂、V₂O₅, isoindigo, polydecyl viologen and derivatives thereof, polyaniline and derivatives thereof, electrochromic conjugated polymers including polypyrrole and derivatives thereof, polythiophene and derivatives thereof, poly (3, 4-ethylenedioxythiophene) and derivatives thereof, poly (propylenedioxythiophene) and derivatives thereof, polyfluorene and derivatives thereof, polycarbazole and derivatives thereof, copolymers thereof, or copolymers comprising an acceptor unit including benzothiadiazole, benzotriazole, or pyrrolopyrroldione. Different types of electrolyte materials (e.g., liquid electrolytes, gel electrolytes, or solid electrolytes) may be used in the electrolyte layers in the electrochromic devices disclosed herein. In some embodiments, the electrolyte layer in the electrochromic devices disclosed herein comprises a solid electrolyte or a gel electrolyte.

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

In another aspect, the invention also relates to the use of the disclosed n-doped organic conductive polymers as electrochromic layers. The exemplary organic conductive polymer PBDF and the exemplary n-doped organic conductive polymer n-PBDF are redox couples. Thus, they can potentially be used as electrochromic materials. The exemplary n-doped organic conductive polymer n-PBDF in 0.2M TBA-TFSI in PC was spectroelectrochemically characterized. As shown in fig. 12, n-PBDF may perform a redox reaction and exhibit a color having a maximum absorbance around 850nm, and the absorbance increases with an increase in applied voltage. Fig. 13 depicts a configuration of an electrochromic device 1300 employing the disclosed n-doped organic conductive polymer as an electrochromic material for a counter electrode according to one example embodiment. The electrochromic device 1300 includes: a first insulating substrate 1302; a first conductive layer 1304 disposed over the first insulating substrate 1302; a first electrochromic layer 1306 comprising the disclosed n-doped organic conductive polymer, disposed over the first conductive layer 1304; an electrolyte layer 1308 disposed over the first electrochromic layer 1306 comprising the disclosed n-doped organic conductive polymer; a second electrochromic layer 1310 comprising a p-doped electrochromic material disposed over the electrolyte layer 1308; a second conductive layer 1312 disposed over the second electrochromic layer 1310 including the p-doped electrochromic material; and a second insulating substrate 1314 disposed over the second conductive layer 1312. In some embodiments, one of the first conductive layer 1304 and the second conductive layer 1312 may include 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, to form 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 the disclosed n-doped organic conductive polymer, as the disclosed n-doped organic conductive polymer may be colored under the applied voltage window of such a dual polymer ECD as exemplified herein. The disclosed n-doped organic conductive polymer in the first electrochromic layer 1306 is used as an n-doped ECP. Electrochromic device 1300 also includes circuitry 1316 to manipulate electrochromic device 1300. In some embodiments, the first electrochromic layer 1306 is comprised of the disclosed n-doped organic conductive polymers.

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 NiO, irO ₂、V₂O₅, isoindigo, polydecyl viologen and derivatives thereof, polyaniline and derivatives thereof, electrochromic conjugated polymers including polypyrrole and derivatives thereof, polythiophene and derivatives thereof, poly (3, 4-ethylenedioxythiophene) and derivatives thereof, poly (propylenedioxythiophene) and derivatives thereof, polyfluorene and derivatives thereof, polycarbazole and derivatives thereof, copolymers thereof, or copolymers comprising acceptor units including benzothiadiazole, benzotriazole, or pyrrolopyrroldione. In some embodiments, the p-doped electrochromic material is a p-doped electrochromic polymer. Different types of electrolyte materials (e.g., liquid electrolyte, gel electrolyte, or solid electrolyte) may be used in 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.

To demonstrate the performance of the disclosed n-doped organic conductive polymer as an EC layer, an example n-PBDF was paired with one example p-doped polymer PEDOT: PSS to fabricate a dual polymer electrochromic device. In one embodiment, the n-PBDF is assembled into an electrochromic device using PEDOT: PSS as the p-doped ECP, 0.2M TBATFSI in an in-situ cross-linked 1:1PEGDA: PC as the electrolyte, and n-PBDF as the n-doped ECP. A schematic is drawn in fig. 13. As shown in fig. 14 (a) (only a few voltages are shown as examples), spectroelectrochemical measurements were recorded between-0.5V and 1.5V in 0.2V increments. On one electrode, the n-PBDF loses electrons upon oxidation and returns to a neutral state with an increase in absorption peak around 850 nm. On the other electrode, PEDOT: PSS was reduced and returned to the neutral state with an increase in absorption peak around 700 nm. Electrochromic devices show fast switching kinetics and high optical contrast of 50%. As shown in fig. 14 (B), the electrochromic device reached a discolored state within 0.2s at an applied voltage of-0.5V and became colored within 3s at an applied voltage of 1.5V. The device shows a high coloring efficiency of 1900cm ²/C, which is the highest value recorded in the known electrochromic device.

N-doped capacitor conductor

The disclosed n-doped organic conductive polymer is an n-doped transparent capacitive conductor that can be successfully substituted for conventional ITO in ECD with its air/water stability, high conductivity. More interestingly, the disclosed n-doped organic conductive polymers can directly balance the charge consumed at electrochromic polymers (ECPs) through high mixed ionic and electronic conductivity, and have efficient capacitor behavior as ion storage layers. In some embodiments, typical Cyclic Voltammetry (CV) of an example n-doped organic conductive polymer n-PBDF film is recorded at different scan rates. They show similar CV shapes independent of thickness with quasi-rectangular behavior and clear faraday peaks. It is the result of the combination of pure capacitance created via charge accumulation at the volumetric polymer/electrolyte interface and capacitance created by a reversible redox reaction, resulting in a pseudocapacitance that creates a high specific capacitance. Furthermore, they retain their shape beyond 100mV s ^-1, which suggests that ions can be easily and quickly inserted/extracted into the capacitive polymer film. With the high capacitance nature, the n-PBDF film at the counter electrode can directly act like a complementary charge balance layer, without the need for an additional ion storage layer, which can fade and color with the cathodically colored ECP. In addition to capacitive conductors, the disclosed n-doped organic conductive polymers may also be used as electrodes and/or electrical interconnects.

FIG. 15 shows CV results for two polymer conductors (n-PBDF and PEDOT: PSS) and a typical p-type electrochromic polymer for electroactive voltage window comparison. Both polymer conductors exhibit purely capacitive properties, charge accumulating at the bulk polymer/electrolyte interface, which has greater charge storage than the inorganic control-ITO. Which results in a large amount of potential independent current even at high oxidation (for PEDOT: PSS) or reduction (for n-PBDF) potentials. The non-faraday electric double layer formed in the polymer domain contributes mainly to the capacitance at high doping levels. Interestingly, n-PBDF exhibited a greater volumetric capacitance in CV curves of the same unreacted film thickness (about 3 times, n-PBDF about 206F cm ^-3 versus PEDOT: PSS about 72F cm ^-3) because ions and charge carriers more readily access the conjugated network beyond the polymer/electrolyte interface. Due to the high mixed ionic and electronic conductivity in the polymer film, the formation of the bilayer is not limited to polymer/electrolyte interface layers, but extends within the conjugated network of ionic and charge carriers. The linear current dependence of differential anode/cathode charge density and scan rate confirmed excellent and stable electrolyte ion diffusion. In linear slope, the high volume specific capacitance at the current plateau through an Electric Double Layer (EDL) n-PBDF film is estimated to be 200-250F cm ^-3 (area specific capacitance is about 500 μf cm ^-2), which is higher than conventional carbon materials and comparable to oxide hybrid materials. They show a well-retained, rather high capacitive behaviour by faraday redox reactions at high positive voltages (+0.7v, 170f cm ^-3), indicating excellent capacitive properties in a large electroactive potential window. Faraday behavior was tested in fully-tuned n-PBDF films, as we found a significant decrease in faraday capacitance in the electrochemical cycle. However, the n-PBDF film shows stable box-shaped CV properties during capacitance from EDL, which are not affected by electrochemical cycling.

Minimum color-changing transparency

In addition to having high conductivity and high ionic capacity, the disclosed n-doped organic conductive polymers exhibit minimal color change transparency during a full range of electroactive potential windows when used as conductors and/or ion storage materials. In some embodiments, the disclosed n-doped organic conductive polymers exhibit minimal color-shifting transparency over a wavelength range of 380nm to 800nm, wherein the color shift Δc between the oxidized and reduced states of the n-doped organic conductive polymer is less than 5. In some embodiments, the disclosed n-doped organic conductive polymers exhibit minimal color-shifting transparency over a wavelength range of 380nm to 800nm, wherein the color shift Δc between the oxidized and reduced states of the n-doped organic conductive polymer is less than 4, or 3, or 2, or 1.5, or 1. The disclosed n-doped organic conductive polymer film at the working electrode is partially undoped by oxidation of the ECP under positive bias applied, resulting in the ECPs having color residues in the discolored state. The electrochemical coloring effect of the example n-PBDF film was confirmed by measurement of light absorption as a function of applied voltage in a three electrode system. As shown in fig. 16 (a), when a higher forward bias is applied, the n-PBDF film becomes more undoped and significantly colored. When the bias voltage is higher than 0.8V, the n-PBDF is completely undoped and the neutral PBDF film shows an absorption peak at 877nm and a small shoulder around 493nm, resulting in a still higher optical transmittance in the visible region. The n-PBDF electrode exhibits minimal color change properties both at the operation and at the location of ECDs due to low coloring efficiency and small absorption change in the visible region. More detailed color presentation in the human eye was calculated and studied by CIE L x a x b x color coordinates in 1976. Interestingly, the n-PBDF film showed little colorimetric change throughout the redox state. As shown in fig. 16 (B), both the color coordinates a and B of the n-PBDF film with 20nm in the working electrode showed minimal change (a increased by about 0.4, B increased by about 0.09), and the chromaticity C (c= (a ²+b*²)^1/2) also showed small change (Δc about 0.43 in the wavelength range of 380nm to 800 nm.) the n-PBDF film with 30nm in the counter electrode also observed a similar trend (a increased by about 0.8, B decreased by about 0.2, Δc about 0.78 in the wavelength range of 380nm to 800 nm) this indicates no color residue in the fade state or no addition of color in the color state in ECDs in transmissive electrochromic display applications, the absence of chromaticity in the overall electrochemical process was very heavy for neutral color display (i.e., color of the electrochromic active material itself) and high optical contrast, as well as the high as the p-PBDF material required to have a full color change between 3 and 800nm, which may lead to a full charge-to a change in the color of about 3nm or more than is required at a full charge of 3 nm.

This property makes our PBDF an excellent candidate as a transparent conductor in various electrochemical device applications beyond traditional transparent polymer conductors, which lead to severe color changes in electronic devices due to unavoidable electrochemical reactions or charge transfer. In fact, the n-PBDF conductor exhibits minimal discoloration during the full range of electrochemical reactions compared to the outstanding p-type conductor PEDOT: PSS. As shown in FIG. 17, the color coordinate values of two polymer conductors (n-PBDF and PEDOT: PSS) are compared. For comparison, the PEDOT: PSS film was fabricated without additional post-treatments that would render the PEDOT: PSS more functional. In polymer films of the same thickness (about 30 nm), both polymer conductors exhibited similar brightness variations from 98 to 92. However, PEDOT: PSS shows a significant color change, and chromaticity change Δc is about 7.1, and exhibits a significant blue shift and a modest green shift at-1.0V bias. These variations are detrimental to their use as transparent conductors, particularly when used as counter electrodes and using existing high performance p-type electrochromic polymers on the corresponding working electrodes. When the p-type electrochromic polymer on the working electrode is discolored at positive voltage, it results in strong oxidation of the electrode material. Furthermore, coloring effects may occur at the working electrode due to the undoped PEDOT: PSS portion due to unexpected charge transfer or voltage applied for p-type ECP coloring. In contrast, regardless of the film thickness, n-PBDF showed minimal color change from the oxidized state (-0.4V) to the reduced state (+1.0V), indicating that it is suitable for both working and counter electrodes.

Low lowest unoccupied molecular orbital (Lowest Unoccupied Molecular Orbital, LUMO) and low operating voltage

The disclosed n-doped organic conductive polymers have a low lowest unoccupied molecular orbital (Lowest Unoccupied Molecular Orbital, LUMO) energy 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-4.9 eV, or-5.1 eV. The low LUMO allows the n-doped conductor to be used at ambient conditions by avoiding the reduction reaction of water and oxygen. In addition, due to small doping variations, low LUMOs can create stable and strong capacitive behavior from the Electrical Double Layer (EDL) without unnecessary charge transfer to or from oxygen or poor charge injection and transport in the strongly undoped state. Furthermore, a low LUMO level results in a readily doped or low reduction potential, such that ECDs has a more extensive discolored state in the electroactive region. For the exemplary n-PBDFs, as shown in fig. 16 (a), they tend to remain doped and the resultant transparent properties, up to around +0.7V bias. Since the dedoping ability is very weak, they show a significant increase in visible light absorption at applied voltages higher than +0.8v. The low initial reduction potential (about +0.7v) brings about a larger potential window by capacitance EDL and effective electroactive match with existing p-type electrochromic polymers, as shown in fig. 15. When a conventional n-type transition metal oxide or a non-conductive n-type polymer (e.g., PEDOT: PSS shown in fig. 15) is used as the ion storage material in an unbalanced configuration, the charge balance voltage applied to the counter electrode is spread to one end of the more negative electrode. However, the extremely low reduction potential in n-PBDF allows it to form a close matched electroactive potential window with the p-type polymer, with significantly more negative voltages applied to the electrodes. The low reduction potential and narrow operating voltage prevents electrochemical degradation due to peroxidation in p-type electrochromic polymers and n-PBDF, allowing ECDs to achieve better cycling stability. In some embodiments, the disclosed ECD operates at less than 3 volts. In some embodiments, the disclosed ECD operates at less than 2 volts, or 1.5 volts, or1 volt.

Use in all polymer devices

The disclosed n-doped organic conductive polymers are applicable to inorganic-based electronic devices and all-polymer electronic devices. Conventionally, inorganic-based transparent conductive materials are used. However, they suffer from various problems such as poor mechanical flexibility and processing incompatibility. The emerging all-polymer electronics can make significant progress in the development of complex wearable and portable electronics due to the inexpensive, flexible, foldable, lightweight, low energy consumption, and tunable optoelectronic properties. PEDOT: PSS clearly provides many advantages over several decades, such as high processability, aqueous solution coating, stability in air and water, and high electrical conductivity and optical transparency, making it a unique polymer conductor in all polymer electronic devices. In addition, the high pseudocapacitance nature allows for a variety of electrochemical device applications, such as supercapacitors and energy converters. However, PEDOT: PSS presents some challenging problems as transparent and minimally discolored electroactive conductors and ion storage materials for all polymer electrochromic devices: i) Transparent in the doped state but clearly color-changing to blue when undoped, ii) relatively low conductivity without post-treatment, iii) difficult matching of the electroactive voltage to other standard anodically coloured p-type electrochromic polymers. On the other hand, the disclosed n-doped organic conductive polymers have air/water stability, good compatibility with various substrate/electrolyte/EC materials, good patterning ability, high conductivity (> 1000S cm ^-1), minimal color change transparency, and high capacitance, and thus, in all polymer electronic devices, the disclosed n-doped organic conductive polymers have proven to be transparent polymer conductors and capacitors. As described above, the disclosed n-doped organic conductive polymers may be used as a conductive layer or ion storage layer alone or as both a conductive layer and ion storage layer and/or electrical interconnect in a circuit.

In some embodiments, the disclosed n-PBDFs are used for transparent conductors and conductive ion storage layers in electrochromic devices. During polymerization and ink preparation, the PBDF immediately undergoes reductive doping by water oxidation to form an n-doped PBDF, resulting in a very stable enhancement of conductivity and a low absorption coefficient in the visible region. In some embodiments, n-PBDF is combined with photopatternable ECP-B and a solid electrolyte to make an all-polymer ECDs. Transparent capacitive n-PBDF polymer conductors can be successfully substituted for existing oxide-based ion storage layers and ITO at the counter and working electrodes. When n-PBDF is introduced, a redox reaction occurs between the p-type electrochromic polymer and the ion-storing n-PBDF layer over a small operating voltage range, and the full polymer ECD shows a significant change in optical absorption (as shown in fig. 18 (a)). While complementary charge balance is achieved during electrochromic polymer reduction by dedoping the n-PBDF at the counter electrode, ECD shows a pure blue color of ECP-B due to the small absorption of PBDF in the visible region. In the ECD fade state, the doped n-PBDF helps achieve high transparency properties, and thus high optical contrast. In the device fade state, the full polymer ECD observed partial dedoping of the n-PBDF at the working electrode, with a slight increase in absorbance at 500nm and a relatively large absorbance in the near infrared range (700-800 nm) compared to those of PBDF alone replacing the counter electrode or those based on the existing VO _x ion storage layer and ITO conductor. However, the shoulder at 500nm of the partially undoped n-PBDF is a secondary absorption, while the remaining primary absorption is mainly concentrated in the near infrared region, which does not affect the optical contrast and color display in the visible region. Stable reversible transmittance changes during DPSC show high optical contrast and promote ionic liquid insertion and extraction into the polymer capacitive conductor at the working and counter electrodes (as shown in fig. 18 (B)).

From an energy efficiency perspective, the coloring and fading efficiencies are calculated at 95% change in optical contrast of the total polymer ECDs. The electrochromic efficiencies of the total polymer ECDs at 610nm for fade and color were 760cm ² C^-1 and 560cm ² C^-1, respectively. Efficient electrochromic behavior is superior to most metal oxide-based electrochromic materials and electrochromic polymers. While the low reduction potential of n-PBDF gives it many advantages as a counter electrode material, such as the transparent nature of the full electrochemical range and low operating voltage, it instead creates a detrimental self-fade phenomenon under open circuit conditions to maintain overall electroneutrality. Due to the energy level of the closed match between the p-type electrochromic polymer and the conductive n-PBDF, electrons spontaneously transfer from the electrochromic polymer to the n-PBDF, resulting in unintended oxidation of the electrochromic polymer at the polymer/electrolyte interface, thereby forming additional charge. Thus, when using low LUMO n-type polymers, compact EDL between the polymer and the electrolyte is more important for suppressing self-fading behavior. The photocrosslinked solid electrolyte based on fluid ionic liquid can form compact EDL and has strong interaction with electrochromic polymer film.

Electrochromic devices show excellent bistability when the disclosed n-doped organic conductive polymers are used as working or counter or both working and counter electrodes in the device. In some embodiments, the disclosed device operates at an open circuit potential for 1000 seconds at each reduction or oxidation potential bias, with a transmittance decay Δt <5%. In some embodiments, the disclosed devices operate at an open circuit potential for 1000 seconds at each reduction or oxidation potential bias, with a transmittance decay of Δt <4%, or Δt <3%, or Δt <2%, or Δt <1%. In some embodiments, when n-PBDF is used as both the working electrode and the counter electrode, the full polymer ECDs shows good bistability by residual charge, with Δt decay <0.7% when the reduction potential is changed from +1v to-0.6V (fig. 18 (C)). However, at a high electrochemical reduction potential of-1.2V, the transmittance change in open circuit potential is relatively large (delta T decays by about 3% after 1000 seconds). It may result from slow but not negligible penetration of fluid ions into the thick electrochromic polymer layer and from the stronger self-fading effect produced by the n-PBDF at the working electrode. In fact, no unstable bistable (Δt decays <0.3%,) was observed in ECDs where n-PBDF was used as the only counter electrode and ITO was used as the working electrode, similar to ECDs based on the conventional VO _x ion storage layer.

The effect of slow redox behaviour at the interface between the electrochromic polymer and the n-PBDF conductor at the working electrode was also observed in the electrochemical kinetics during the colouring and bleaching process. In the DPSC characterization, the coloring and fading conversion of the all-polymer ECD is estimated as a function of time to reach 95% full optical contrast t _95％. The introduction of n-PBDF at the working electrode reduces the transmittance conversion, especially during tinting. For example, ECDs with n-PBDF counter and ITO working electrodes, t _B is about 2.8s, and t _C is about 4.2s, while ECDs using n-PBDF as the working and counter electrodes, for example, t _B is about 3.2s, and t _C is about 8.7s. During the coloring process, the doped liquid ions migrate out of the electrochromic polymer layer to adjust charge neutrality. The redox reaction and charge transfer between the n-PBDF and electrochromic polymer impedes fast ion movement, resulting in slow transmittance differences. Quantitative comparisons of electrochromic properties of see-through displays are shown in fig. 19 (a) - (B). ECD using only n-PBDF as counter electrode shows comparable optical contrast and electrochromic switching time compared to conventional ITO/VO _x -based ECDs, indicating that transparent polymer conductors can successfully replace oxide-based electrodes and ion storage layers. However, the full polymer ECDs using n-PBDF as the working and counter electrodes shows relatively low electrochromic efficiency, particularly during tinting. Similar to the longer switching time in the coloration process, this is due to the charge transfer at the working electrode and the additional redox reaction that requires more charge. Despite the redox behavior present at the working electrode, the all-polymer ECDs using n-PBDF as the working and counter electrodes showed excellent color display with minimal discoloration properties at both the working and counter electrodes (fig. 19 (C)). They show a non-coloured state in which the colour coordinates a and b are closer to zero in the fade state. Furthermore, a small color change from the fade state to the tint state was observed on the a-axis, indicating that ECP-B showed a solid color in the all-polymer platform.

In some embodiments, to make ECDs, e.g., non-patterned ECDs, electrochromic polymer (20-40 mg) is dissolved in 1mL chloroform and stirred continuously overnight. PBDF inks were prepared in DMSO solution. The PBDF ink was spin coated on UV ozone treated glass or PET substrates. The prepared electrochromic polymer solution was spin coated on ITO or PBDF deposited substrates. An ion storage layer based on VO _x was fabricated on another pre-washed ITO substrate. For conventional ECD fabrication without patternable solid electrolyte, PEGDA, PC containing 0.2M LiTFSI, and HMPP were mixed in a 5:5:1 volume ratio. After stirring for 10 minutes, the solution was drop coated onto the substrate on which the ion storage layer was deposited. The electrochromic polymer deposited substrate is transferred to the top after flipping. After waiting a few seconds for the electrolyte precursor solution to become homogeneous, the electrolyte was crosslinked under UV light irradiation (about 2000mJ cm ^-2; 405 nm). For electrical contact, copper tape is applied to both sides of the conductive layer. For ECD fabrication using a patternable solid electrolyte, PEGDA, TT, EMIT-TFSI and HMPP are mixed in a weight ratio of 1:1:2:0.1. After stirring for 10 minutes, the precursor solution was applied dropwise to the ion storage layer or electrochromic layer. The electrolyte was crosslinked under UV light irradiation (about 300mJ cm ^-2; 405 nm). In some embodiments, n-doped organic conductive polymer films having the same thickness are disclosed for the two conductive layers (counter electrode and working electrode), respectively. In some embodiments, a slightly thicker conductive film (e.g., about 30 nm) is used for the counter electrode compared to the working electrode (e.g., about 20 nm) to achieve charge balance in the electrochemical reaction with the electrochromic polymer film.

Use in displays and patterned displays

Displays play a key role in the modern digital world, serving as the primary interface for communication, entertainment, and information dissemination. Emissive displays such as LEDs and LCDs are popular because of their vivid color, high brightness, and clear resolution. However, they also have disadvantages including high energy consumption and prolonged exposure to bright artificial light can lead to potential eyestrain. In this case, development of electrochromic displays (which are transmissive non-emissive displays) is of paramount importance. These displays, such as see-through electrochromic displays, offer a promising alternative. They are characterized by low power consumption, strong outdoor readability, and can alleviate eye strain because they can modulate natural light rather than self-emitted light. The technology not only lays a road for more sustainable and comfortable visual experience, but also opens up a new way for innovative application in intelligent equipment and architectural design, and integrates functions and aesthetic appeal. However, developing see-through transmissive electrochromic displays presents significant challenges, mainly due to the complexity of manufacturing multiple layers and incompatible processing requirements. The transparent conductor, ion storage material, solid state electrolyte and electrochromic layer each require different fabrication conditions and materials, complicating patterning, scaling and integration of these components. This complexity often leads to technical hurdles that make it challenging to produce a large electrochromic display of consistent performance suitable for commercial applications. How to reduce crosstalk and response time also presents challenges for electrochromic displays. By taking advantage of the unique properties of solution processability that allow n-PBDF to be handled in solution, the disclosed n-doped organic conductive polymer films have good compatibility with a variety of substrates, electrolytes, and EC materials, good patterning capability that enables segmented and pixellated EC devices/displays to be produced, good conductivity, ability to store large amounts of charge, low molecular weight, flexibility, ease of tuning, and in combination with patternable solid state electrolytes and unique fabrication methods, the disclosed technology produces a first perspective all polymer flexible electrochromic display with greatly reduced cross talk, low power consumption, and good bistability. The chemical structure of the disclosed n-doped organic conductive polymers is theoretically predicted to have poor solubility and difficult to solution process, however, the disclosed techniques have successfully made them solution processable, which makes compatible processing possible and well suited for production. The inventors found that the disclosed n-doped organic conductive polymers have good compatibility with a variety of substrates, electrolytes and EC materials. This discovery allows for easy deposition and patterning of not only the disclosed n-doped organic conductive polymers on a variety of substrates, but also of electrolytes and electrochromic materials on the disclosed conductive layers. Patterning of electrolytes has traditionally presented a significant challenge, particularly for electrochromic displays, because it is difficult to form smooth surfaces of uniform thickness over the micrometer scale. Thus, additional patterning templates are conventionally required to separate the electrolyte solution, which not only increases process complexity, but also is not cost-friendly. In addition, the electrolyte is easily swelled by various solvents, and thus it is difficult for the electrolyte to use a solution-based method. However, the inventors were able to successfully pattern the electrolyte over the n-doped organic conductive polymer. The method of the present invention is solution processable, simple, transferable to manufacture and cost effective, which are highly desirable for successful commercialization. In the disclosed technology, the inventors demonstrate compatible patterning of all polymer layers (i.e., conductive layers, ion storage layers, electrolyte layers, electrochromic layers). The method not only enables low cost fabrication of high performance EC devices/displays, but also greatly reduces the crosstalk problems common in passive matrix electrochromic displays. The inventors have successfully fabricated the disclosed electrochromic devices/displays with low operating voltages using the high conductivity and capacity of the disclosed n-doped conjugated polymers, along with passive matrix structures and optical memory effects (i.e., bistable) in the circuit. The disclosed EC device/display shows application prospects in energy-saving displays with low frequency information refresh and even information storage. Furthermore, due to the fast ion movement and high conductivity in both the electrochromic polymer and the disclosed n-doped organic conductive polymer as electrodes, the disclosed electrochromic display exhibits a fast response time and completes the color conversion in seconds. Based on these findings, the inventors were the first to succeed in producing high performance all-polymer EC devices/displays with or without pixels/segments. Furthermore, the inventors were the first to succeed in producing high performance see-through all-polymer EC devices/displays with pixels/segments. To achieve high flexibility and humanization in see-through display displays, transparent polymer components such as electrochromic active materials, electrolytes, ion storage layers, and electrodes including n-PBDF are employed.

In some embodiments, the disclosed n-doped organic conductive polymers can be fabricated into patterned devices, such as full polymer based patterned electrochromic displays. The patterned electrochromic display may be a segmented display or a pixellated display, and both have been successfully produced by the disclosed techniques. In some embodiments, the patterning of electrochromic polymers, solid electrolytes, and the disclosed n-doped organic conductive polymer films in the disclosed patterned devices is fabricated using in situ photolithography. In some embodiments, electrochromic polymer (20-40 mg) and a photocrosslinker (5 wt%, e.g., bis (fluorophenylazide) (bisFA) crosslinker, which induces large solvent resistance via photocrosslinking) are dissolved in 1mL chloroform and stirred continuously overnight. The spin-coated film was crosslinked by UV light irradiation (about 2000mJ cm ^-2; 405 nm) through a photomask. Toluene was used to remove the unexposed areas. In some embodiments, five color EC polymers based on poly (3, 4-propyldioxythiophene) (PProDOT) were studied to demonstrate multiple color expression in display applications. Electrochromic polymers (ECPs) are denoted as ECP-C, ECP-M, ECP-Y, ECP-BK and ECP-B for cyan, magenta, yellow, black and blue, respectively. For see-through display applications, the optical properties of all electrochromic assemblies were investigated. All ECP films exhibit reversible absorption changes in electrochemical reactions. Although azide molecules have strong photocrosslinking, they show little change in absorbance in the reduced state and have clear five chromatographic representations corresponding to photographic images. They show a significant decrease in visible absorbance to a highly transparent state with the application of a positive bias.

In some embodiments, the same method is used to prepare the electrolyte precursor solution in order to manufacture the solid electrolyte layer. Photopolymerization of acrylate groups is carried out in the presence of ionic liquids and thiol monomers. The thiol monomer can realize the chain growth and step-growth free radical photopolymerization of polyethylene glycol diacrylate (PEGDA), thereby shortening the polymerization time and improving the energy efficiency in the photoetching process. Furthermore, the use of ionic liquids without the need for additional polar solvents and the addition of thiol molecules enhances the wettability of the precursor solution on various surfaces in display applications (e.g., metal oxide, glass, ITO, and polymer layers), which allows the fabrication of patterned solid electrolyte layers of tunable dimensions, up to tens of nanometers in thickness, using simple spin-on processes. The prepared precursor solution is spin-coated or drop-coated onto a substrate on which ITO or doped organic conductive polymer is deposited, and then subjected to selective UV photocrosslinking (about 300mJ cm ^-2; 405 nm) through a photomask. The unexposed areas are rinsed with deionized water. For see-through display applications, the transmission spectrum of the patternable solid electrolyte layer was studied as a function of different mixing ratios of thiol molecules, PEGDA and ionic liquid. The mixed thiol and ionic liquid does not disturb the optical transmittance of the whole polymer matrix system, which makes it highly transmissive (> 98%) throughout the visible region. ECDs is fabricated by ECP-B, conventional metal oxide based charge balance materials, VO _x, and ITO deposition glasses using the ion conductivity of the photopatternable solid electrolyte. When their static absorbance in colored and discolored states is considered, there is no significant change in peak shape, intensity and spectral optical contrast under solid electrolyte conditions of different mixing ratios. Dynamic optical properties of the ECP-B film were recorded by transmittance changes in a dual potential step-and-time absorption (DPSC) characterization. With increasing addition of ionic liquid, electrochromic kinetics based on ECP-B devices can be directly enhanced, and at 75wt% ionic liquid addition, the fade and color time is reduced to 3.5 seconds and 3.9 seconds, respectively. This indicates that the presence of the polymer network does not adversely affect the movement of liquid ions and the resulting ionic conductivity. Ionic conductivity is also improved by the addition of thiol monomers in the polymer gel-based solid electrolyte layer, which may result from reduced cross-linking of acrylate photopolymerization via a chain growth mechanism in the presence of thiol monomers and reduced UV light power of cross-linking.

The disclosed n-doped organic conductive polymers are useful for conductors, conductive ion storage layers, and electrical interconnects in electrochromic devices. During polymerization and ink preparation, the exemplary organic conductive polymer PBDF is immediately reductively doped by water oxidation to produce an n-doped PBDF (n-PBDF), resulting in a very stable conductivity enhancement and low absorption coefficient in the visible region. In some embodiments, the disclosed patterning of n-doped organic conductive polymer films is fabricated using existing photolithography in combination with Reactive Ion Etching (RIE) dry processes and etch-stop layers. In some embodiments, AZ1518 (Microchemicals) was spin-coated on a pre-deposited n-PBDF film as an etch stop layer (5000 rpm,45 s) and baked at 110℃for 2 minutes to remove residual solvent. The photoresist film was then exposed to near UV light (405 nm,100mJ cm ^-2) using a maskless aligner (Heidelberg MLA 150). The film was developed in a developer solution (Microposit, MF-26A) for 45 seconds. After rinsing with DI water, the patterned film was exposed to an etching plasma for 30 minutes to remove the unprotected polymer layer. After plasma etching, all remaining photoresist film was removed with acetone. The conductive polymer film has chemical and mechanical stability after heat treatment and orthogonal solution treatment in the photolithography process, thereby forming a clear micro-scale pattern with sharp edges.

To fabricate a patterned electrochromic device or display, a first conductive layer is coated over a first substrate, and the first conductive layer comprises 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 over the second substrate and the second conductive layer is patterned to form second regions and second electrical interconnects between adjacent second regions. Electrical interconnects provide a way to precisely activate and control these regions. Then one of the following steps is performed: a) Forming a first electrolyte layer over each first region, wherein the first electrolyte layers are separated from each other; forming an electrochromic layer over each second area, wherein the electrochromic layers are separated from each other; forming a second electrolyte layer over each electrochromic layer, wherein the second electrolyte layers are separated from each other; and laminating the first substrate and the second substrate such that the first electrolyte layer is aligned with and in contact with the second electrolyte layer; or b) forming an electrolyte layer over each first region, wherein the electrolyte layers are separated from each other; forming an electrochromic layer over each electrolyte layer, wherein the electrochromic layers are separated from each other; and laminating the first substrate and the second substrate such that the electrochromic layer is aligned with and in contact with the second region; or c) forming an electrochromic layer over each of the second areas, wherein the electrochromic layers are separated from each other; forming an electrolyte layer over each electrochromic layer, wherein the electrolyte layers are separated from each other; and laminating the first substrate and the second substrate such that the electrolyte layer is aligned with and in contact with the first region. In some embodiments, patterning is performed by a photolithographic or printing method (e.g., ink printing). A similar but unpatterned fabrication method is used to fabricate the non-patterned electrochromic device. A similar fabrication method, but without patterning the electrolyte layer and the second conductive layer, is used to make segmented electrochromic devices.

In some embodiments, to fabricate a patterned electrochromic device/display, such as an all-polymer pixellated electrochromic display, as shown in fig. 20, the disclosed n-doped organic conductive polymer is included in the first and second conductive layers and step a described above is used. The disclosed n-doped organic conductive polymer conductor lines are fabricated by patterning an n-doped organic conductive polymer film as described above and are used as working electrodes, ion storage conductive layers (counter electrodes) and electrical interconnects. On top of the working electrode, an electrochromic polymer film is spin coated and patterned using in situ photolithography. To make a two (or four) color display, the same process is repeated twice (or four times) on a conductively patterned substrate. The precursor solution is drop coated onto the ion-storing conductive layer (counter electrode) and electrochromic polymer surface, and then UV photocrosslinking is performed on the drop coated precursor solution with a photomask. The unexposed areas were removed using acetone. The two substrates were carefully assembled and evacuated using a rotary pump for 1 hour. In some embodiments, similar fabrication methods described above and in fig. 20 may be used without patterning to make non-patterned electrochromic devices.

For capacitive electrode applications in all-polymer ECDs, in some embodiments, a polymer dispersion solution in simple spin-on dimethyl sulfoxide (DMSO) is used to fabricate a transparent n-PBDF film. An n-PBDF film (about 30 nm) thicker than the working electrode (about 20 nm) was used as the counter electrode in order to maintain charge balance when it electrochemically reacted with the electrochromic polymer film. Both n-PBDF films exhibited highly transparent properties, with a transmittance of greater than 80% throughout the visible region (fig. 21). The optical transparency of the n-PBDF film is comparable to ITO and superior to that of capacitive metal oxide deposited ITO films.

In some embodiments, the disclosed pixelated electrochromic display employs a passive matrix structure. The passive matrix structure is selected to take advantage of low energy operation by virtue of the excellent optical memory effect in the disclosed all-polymer ECDs. However, in passive matrix driving, severe image crosstalk may be caused due to unintentional charge transfer between pixels through the electrolyte layer. Thus, in order to achieve a certain separation in the individual pixels, the solid electrolyte is patterned on each pixel by in-situ photolithography to manufacture a passive matrix-based display having 8×8 matrix pixels (see fig. 22 (a) - (B)). A solid electrolyte membrane was successfully deposited over the photopatterned electrochromic polymer and n-PBDF films for the working and counter electrodes, respectively. The first substrate and the second substrate are then laminated such that the first electrolyte layer is aligned with and in contact with the second electrolyte layer to make a device.

Photolithographic patterning allows for clear localization and sharp edges of all solid electrolytes, the disclosed conductors, and electrochromic polymer layers to facilitate fabrication of electrochromic passive matrix display pixels. The techniques of the present invention facilitate the fabrication of EC displays/devices and are cost effective, and greatly reduce cross-talk by using the disclosed techniques (e.g., solution processability and compatible patterning of layers in electrochromic displays). Because the disclosed n-doped organic conductive polymer can serve as both a conductive layer, an ion storage layer, and an electrical interconnect in a display circuit, a single step of patterning the disclosed n-doped organic conductive polymer produces a three-function integrated layer, further reducing process complexity and cost.

Referring to fig. 22 (a) and 22 (B), an example method for forming an electrochromic device/display is provided. In fig. 22 (a), a conductive film (e.g., an 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, translucent or reflective. A patterning process is then performed on the conductive film. During this patterning, a photoresist film is deposited on the conductive film and a photolithography step is performed, which includes exposing the photoresist film to UV light through a photomask having a desired pattern including areas or pixels and interconnects between the areas or pixels. The exposed photoresist film is then developed to form a photoresist pattern over 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 may separate conductive layers and/or different electrical interconnects over different areas (e.g., pixels or segments). In some embodiments, the above described process may be used not only to form pixelated devices, but also to form segmented devices. In some embodiments, the patterning process described above for the conductive film may be omitted when forming the non-patterned electrochromic device.

After patterning the conductive film on the substrate, an electrochromic polymer (EC polymer) layer is coated over the substrate. A photolithographic process is then performed on the EC polymer layer (including UV exposure through a photomask on the EC polymer layer and removal of the uncured EC polymer layer by wet etching after UV exposure) to pattern the EC polymer layer. The patterning process may separate the EC polymer layer on each pixel or segment. To make a two (or more) color display, the same process is repeated two (or more) times on the conductively patterned substrate. Note that the EC polymer is removed from the area or the interconnect between pixels, as shown in fig. 22 (a). To form a non-patterned electrochromic device, only the coating of the EC polymer layer is performed without performing the patterning process.

Next, an electrolyte solution is coated on the substrate to form an electrolyte membrane. A photolithography process is then performed on the electrolyte membrane (including performing UV exposure on the electrolyte membrane through a photomask, and removing the uncured electrolyte membrane by wet etching after UV exposure) to pattern the electrolyte membrane. The patterning process may separate the electrolyte membrane on each pixel or segment. Note that the electrolyte membrane is removed from the region or the interconnect between the pixels, as shown in fig. 22 (a). To form a segmented or unpatterned electrochromic device, only the application of the electrolyte solution is performed without a patterning process. This step ultimately forms a working electrode for an EC device or display (e.g., the passive matrix-based EC device or display in fig. 22 (a)).

Referring now 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., an n-PBDF film or other suitable conductive film) is deposited on the substrate. The substrate may be rigid (e.g., glass, metal, etc.) or flexible (e.g., plastic). The substrate may be transparent, translucent or reflective. A patterning process is then performed on the conductive film. During this patterning, a photoresist film is deposited on the conductive film and a photolithography step is performed, including exposing the photoresist film to UV light through a photomask having a desired pattern including regions or pixels and interconnects between the regions or pixels. The exposed photoresist film is then developed to form a photoresist pattern over 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 may separate conductive layers and/or different electrical interconnects over different areas (e.g., pixels or segments). In some embodiments, the patterning of the conductive film described above may be omitted when forming segmented or non-patterned electrochromic devices.

Next, an electrolyte solution is coated on the substrate to form an electrolyte membrane. A photolithography process is then performed on the electrolyte membrane (including UV exposure of the electrolyte membrane through a photomask, and removal of the uncured electrolyte membrane by wet etching after UV exposure) to pattern the electrolyte membrane. The patterning process may separate the electrolyte membrane on each pixel. Note that as shown in fig. 22 (B), the electrolyte membrane is removed from the region or the interconnect between the pixels. To form a segmented or non-patterned electrochromic device, only the application of the electrolyte solution is performed without a patterning process. This step ultimately forms a counter electrode for an EC device or display (e.g., the passive matrix-based EC device or display in fig. 22 (B)).

After preparing the working electrode substrate and the counter electrode substrate, the two substrates may be laminated such that the electrolyte layer on the working electrode substrate is aligned with and in contact with the electrolyte layer on the counter electrode substrate, as shown in fig. 20. The lamination method forms an electrochromic device by contacting two electrolyte layers to improve the yield and performance of the EC device because the contact interface is formed of the same electrolyte. It eliminates potential contamination at many critical interfaces, such as the interface between a conductive layer and an electrolyte or ion storage layer, the interface between a conductive layer and an electrochromic layer, or the interface between an electrolyte layer and an electrochromic layer. In some embodiments, the two patterned electrolyte layers are gel-like and can be easily assembled with only a vacuum. The lamination method also allows for the formation of a uniform electrolyte layer.

In some embodiments, the electrolyte membrane/layer and electrochromic layer may be formed over the same substrate. For example, when both the electrolyte membrane/layer and the electrochromic layer are formed over the first substrate, the two substrates are stacked such that the electrochromic layer over the first substrate is aligned with and in contact with the conductive layer over the second substrate. In some embodiments, when both the electrolyte membrane/layer and the electrochromic layer are formed over the second substrate, the two substrates are stacked such that the electrolyte layer over the second substrate is aligned with and in contact with the conductive layer over the first substrate.

To demonstrate cross-talk minimization for passive matrix based full polymer electrochromic displays using in-situ patterned solid electrolyte localization, after all pixels are set to a fully faded state with a positive voltage (+1.0V) for a few seconds, a negative voltage (-0.8V) is applied to turn on (color) the target pixel at the intersection of a particular row and column electrode line. When a negative voltage is applied for 10 seconds, only the target pixel shows a significant coloration, while the adjacent eight pixels have no significant color change, indicating that signal crosstalk in our electrolyte localized passive matrix electrochromic display is greatly reduced (fig. 23 (a)). On the other hand, very severe crosstalk was observed in electrochromic displays where the electrolyte was not localized. Although the off-voltage (+1.0v) is applied to only two crossing electrodes to achieve target pixel color fading, it affects surrounding pixels and causes them to completely color fade on the working electrode line and the counter electrode line within one second. Significant and rapid crosstalk was also observed at electrochromic polymer patterned electrochromic displays, indicating that crosstalk resulted from unwanted charge transfer via the delocalized electrolyte layer in pixels sharing the same row or column electrode. As shown in fig. 23 (B), the multi-pixel coloring process and the fading process also confirm the suppression of crosstalk in the electrolyte localized electrochromic display. When two target pixels separated by a pixel distance are biased by-0.8V for 10 seconds, they show a clear blue color without significant crosstalk.

Also exhibiting good bi-stability. When a fade voltage (+1.0v) is applied to four target pixels at intervals of 30 seconds, they show a clear color fade at the target pixels and maintain the transmittance of the fade at the open circuit potential due to their high optical memory. Notably, our electrochromic display maintains signals without active matrix driving using thin film transistors, which require high manufacturing costs, complex device structures, and large space. In some embodiments, a passive matrix based display shows a similar color display when a voltage of-0.8V is applied for 10 seconds and held at an open circuit potential for 1000 seconds, which means that the display has a large bi-stability. By virtue of the large bistable, passive matrix driving can significantly reduce power consumption in pixelated display applications. Excellent bistability can achieve excellent energy-saving display applications. The energy consumption of each coloring or bleaching process is recorded in terms of a current distribution in the timed amperometric response of the individual pixels in the passive matrix display. Notably, the energy required for one color conversion is only 0.71±0.05mJ cm ^-2. In a scenario involving static content, if the content is not updated, the power consumption remains at about 0.7 μW cm ^-2 for 1000 seconds. Compared to the 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 energy consumed only during the conversion and update process.

The optical absorption spectra of nine pixels, including one target pixel, two pixels sharing a working line, two pixels sharing a pair of lines, and four diagonal pixels, were quantitatively recorded. For static absorption measurements, the spectrum is measured 30 seconds after the voltage is applied to the target pixel. As the applied negative voltage increases from-0.6V to-1.0V, coloration at the target pixel becomes more pronounced. However, we observe a slight increase in absorption at pixels sharing the working and alignment lines, unlike the diagonal positions. Small color changes are also confirmed at the photographic image. To elucidate the root cause of small cross-talk, we measured the dynamic absorbance change during target coloring in non-patterned, electrochromic polymer-only patterned and electrolyte localized electrochromic displays. When a voltage is applied to a target pixel in a non-patterned electrochromic display, the change in absorption intensity in the pixels of the shared operating and alignment reaches about 100% (Δabs) as compared to the absorption change of the target pixel in 1-4 seconds. Patterning of the polymer slightly delayed the switching speed of adjacent pixels, but they showed full colored and faded states within 5 seconds. On the other hand, the dynamic absorption change saturation at the pixels sharing the work and alignment is about 20% compared to the change at the target pixel in the electrolyte localized electrochromic display, indicating that the remaining crosstalk is derived from other mechanisms, not from charge transfer through the electrolyte layer. We have found that the voltages recorded at adjacent pixels in an electrolyte patterned display are another source of crosstalk. In the case of a bias applied to a target pixel, the pixels of the shared working or alignment show small but significant voltage variations due to interactions between pixels through electrodes associated with the matrix. Voltage communication effects in circuit designs can be addressed by incorporating semiconductor diodes in integrated circuits or printed circuit boards for further electrical applications.

The problems in the circuit are relatively small (about 20%) compared to the unwanted charge transfer in the delocalized electrolyte, so that the use of passive matrix electrochromic displays demonstrates real-time pixellated image display by sequentially applying voltages to the target pixels along the counter electrode lines. Although the interval between applied voltages is about 10 seconds due to the lack of advanced processing chips, all-polymer electrochromic displays exhibit well-resolved "P" and "U" pixelated letter patterns with their excellent optical memory. Electrochromic displays successfully exhibit the desired graphics with reduced cross-talk and reversible image changes. Because of its large optical memory, no additional power is required to maintain the displayed content. Our research results open up new possibilities for implementing compact see-through pixelized displays in energy-efficient on-chip platforms by efficient energy consumption and pixelized image projection in all-polymer non-emissive displays.

In some embodiments, the transmissive display for forming the segmented pattern is achieved by photolithographic patterning of the all-polymer electrochromic assembly. First, the two electrochromic polymers of blue and magenta are directly patterned by selective UV light exposure to achieve the desired graphic display. After spin coating the ECP-B solution with the photocrosslinker, the film is exposed to selective UV light and treated in a solvent to remove the uncrosslinked polymer layer. Another ECP-M pattern is also formed by the same process. Due to the large solvent resistance via photocrosslinking in the polymer chain, complex patterns can be formed without cross-talk even on the microscale. Patterned electrochromic displays show excellent see-through properties through optical modulation (depending on the epitaxial potential) between transmissive "train" patterns and transparent blanks.

In some embodiments, the fabrication of the flexible all-polymer ECD begins by depositing a polymer conductor on a plastic substrate. The n-PBDF film was easily formed by spin coating DMSO solution onto a flexible polyethylene terephthalate (PET) substrate, without additional heat treatment, indicating its high compatibility with flexible plastic substrates. The deposition of the other electrochromic assemblies is similar to stiffness ECDs. The flexibility characterization was performed at different bending radii to investigate the mechanical flexibility and operational stability of the total polymer ECDs. The bending test was performed at five bending radii (i.e., 4.0, 2.5, 2.0, 1.4, and 0.5 cm). Based on the optical absorption spectra of the total polymer ECDs in colored and faded states of various radii (including initial state), the total polymer ECDs shows highly stable color conversion at various bend radii (as low as 1.4 cm). Electrochemical stability at different bending radii was tested by recording ECDs transient currents in the redox reaction. As the bend radius increases, they exhibit a highly stable and relatively enhanced transient current. It may result from thinner devices, particularly from variations in electrolyte thickness due to increased tensile strain. Since it is difficult to set a curved sample in a linear path between the beam and the detector in our spectrometer, the optical density at smaller bending radii cannot be recorded. In contrast, the color conversion in the highly curved state is demonstrated as shown in the photographic image of an all-polymer device with a radius of curvature of 5 mm. They show stable and reversible color conversion by a small electrical bias (coloring process-1.2V, and fading process +1.2v). In addition, a bending cycle test was performed to investigate the mechanical stability of the device at a bending radius of 5 mm. Absorbance and transient current of the whole polymer ECDs were monitored before and after 100, 1000, and 10000 bending cycles. Although a slight decrease in transient current in electrochromic polymer oxidation was indicated, the reduction transient current, switching time, and static absorbance changes in the coloration and discoloration of ECDs were negligible. This result clearly demonstrates the effectiveness of the full polymer ECDs in terms of flexibility and operational electrochemical stability, even under repeated and severe bending conditions.

The all-polymer system developed herein is used to carefully fabricate a paper-like see-through electrochromic display while taking into account advantages such as high optical contrast, neutral color expression, reliable flexibility, and photopatternable properties in the all-polymer ECDs. For practical pattern generation, we have more complex patterning designs of polymer conductors and electrochromic polymers for flexible all-polymer electrochromic displays. One example of an all-polymer display attached to human skin exhibits a designed transmissive electrochromic polymer pattern on a transparent n-PBDF conductor layer. In addition, two 7-segment displays were operated for all numerical representations and other "heart", letter and "1" graphic displays, as shown in fig. 24, fifteen PBDF conductors and contact lines were first deposited on a plastic substrate and patterned using existing photolithography. ECPs of two colors are deposited on the patterned n-PBDF conductor lines and patterned directly with selective UV light. As a co-cathode, n-PBDF was deposited on another PET substrate and overlaid on an anode substrate onto which an electrolyte precursor solution was drop coated, followed by electrolyte crosslinking by UV light irradiation. The electrochromic patterns were digitally driven using a custom multiplexed multi-channel controller, with power supplied through the n-PBDF contact line and common cathode. Full polymer electrochromic displays successfully exhibit different "numbers" and graphics through staged selective driving and can be refreshed within a few seconds through redox reactions. Using this feature of the all-polymer platform, flexible see-through displays were applied to watchbands and human skin with a ring-like structure to demonstrate their practical application potential (fig. 25 (a) - (B)). With reliable flexibility and strong electrochemical stability, the all-polymer display can exhibit a real-time transmissive graphic display with good resolution even on a human finger using a ring-shaped structure with a bending radius of 1.5cm under bending conditions. With further development of conjugated systems, flexible all-polymer electronic devices using transparent/capacitive n-type conductors are expected to function in next-generation optoelectronic devices.

The use of the disclosed n-doped organic conductive polymers as capacitive transparent organic conductors represents a novel strategy for manufacturing flexible electrochromic displays and is expected to promote the development of other electrochemical devices. The disclosed n-doped organic conductive polymers exhibit high conductivity and capacitance properties while maintaining high transmittance and minimal color change transparency over the electrochemical potential window, and can be used as both transparent conductors and ion storage materials, as counter electrodes in electrochromic devices, and as transparent working electrodes and electrical interconnects in devices. Furthermore, low reduction potentials can achieve operational stability at ambient conditions, and the potential window is well matched to the p-type electrochromic polymer. In situ photolithographic patterning in ECPs and solid electrolytes allows the development of patterned devices (e.g., all-polymer displays) for segmentation and pixelation applications without significant crosstalk. These photopatternable electrochromic assemblies are highly transparent, enabling see-through display applications, have excellent outdoor readability and non-emissive eye-protection modes, and excellent energy-saving capabilities. Furthermore, electrochromic devices exhibit excellent bistable properties (e.g., optical memory) due to the strong and dense EDLs formed from ionic liquids. Our results demonstrate a successful approach for transparent capacitive polymer conductors and photopatternable electrochromic assemblies, which can be a commercially viable practical solution for biocompatible, flexible photovoltaic devices through an all-polymer platform.

Referring now to fig. 26, fig. 26 is a flowchart of a method 260 for forming an electrochromic device/display according to an example embodiment. At 2602, a first conductive layer is formed over a first substrate. The first conductive layer may be the n-doped organic conductive polymer described above, 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, translucent or reflective. At 2604, a first electrolyte layer is formed over the first conductive layer. The first electrolyte layer may be a solid electrolyte, a gel-like solid electrolyte, or a gel electrolyte. At 2606, a second conductive layer is formed over the 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 over the second conductive layer. At 2610, a second electrolyte layer is formed over the electrochromic layer. In some embodiments, the second electrolyte layer may comprise the same or different material as the first electrolyte layer. In some embodiments, the thickness of the second electrolyte layer may be the same as or different from the thickness of the first electrolyte layer. At 2612, the first substrate and the second substrate are stacked such that the first electrolyte layer is in contact with the second electrolyte layer to form an electrochromic device/display. In some embodiments, laminating the first substrate and the second substrate includes applying at least one sealant to the outer perimeter of one or both substrates. The disclosed technology can form electrochromic devices by contacting two electrolyte layers to improve the yield and performance of EC devices because the contact interface is formed from the same electrolyte. This eliminates potential contamination at many critical interfaces, such as the interface between a conductive layer and an electrolyte or ion storage layer, the interface between a conductive layer and an electrochromic layer, or the interface between an electrolyte layer and an electrochromic layer. In some embodiments, the two electrolyte layers after patterning are gelatinous, which allows for easy assembly.

Fig. 27 is a flowchart of a method 270 for forming an electrochromic device/display, according to an example embodiment. Operations 2602, 2604, 2606, and 2612 are the same as explained in connection with fig. 26 and will not be described further for brevity. After 2606, at 2614, the second conductive layer is patterned to form a second region. In some embodiments, patterning the second conductive layer also forms second electrical interconnects between adjacent second regions. The second regions may be separated from each other except at the location of the second electrical interconnect. Forming an electrochromic layer over the second conductive layer may then include, as shown in operation 2608 of fig. 26: at 2608a, an electrochromic layer is patterned to form an electrochromic film over each second region. The electrochromic films are separated from each other. After operation 2608a, forming a second electrolyte layer over the electrochromic layer, as shown in operation 2610 of fig. 26, may include: at 2610a, a second electrolyte layer is formed over each electrochromic film and/or second electrical interconnect and/or in the gaps between adjacent second regions.

Fig. 28 is a flowchart of a method 280 for forming an electrochromic device/display, according to an example embodiment. Operations 2602, 2606, 2614, and 2608a are the same as explained in connection with fig. 27 and will not be described further for brevity. After operation 2602, at 2616, the first conductive layer is patterned to form a first region. In some embodiments, the first conductive layer is patterned to form first electrical interconnects between adjacent first regions. The first regions may be separated from each other except at the location of the first electrical interconnect. Then forming a first electrolyte layer over the first conductive layer, as shown in operation 2604 of fig. 27, may include: at 2604a, the first electrolyte layer is patterned to form a first electrolyte membrane over each first region. The first electrolyte membranes are separated from each other. After operation 2608a, forming a second electrolyte layer over the electrochromic layer, as shown in operation 2610 of fig. 26, may include: at 2610b, the second electrolyte layer is patterned to form a second electrolyte membrane over each electrochromic film. The second electrolyte membranes are separated from each other. As shown in operation 2612 of fig. 26, stacking the first substrate and the second substrate such that the first electrolyte layer is in contact with the second electrolyte layer may include: at 2612a, the first substrate and the second substrate are laminated such that the first electrolyte membrane is in contact with the second electrolyte membrane. In some embodiments, the first electrolyte membrane is aligned with the second electrolyte membrane. The first electrolyte membrane may be aligned one-to-one with the second electrolyte membrane such that the first electrolyte membrane is in contact with only the corresponding second electrolyte membrane, and does not contact an adjacent second electrolyte membrane of the second electrolyte membrane.

Fig. 29 is a flowchart of a method 290 for forming an electrochromic device/display, according to an example embodiment. Operations 2602, 2604, 2606, 2608, 2610, and 2612 are the same as explained in connection with fig. 26 and will not be further described for brevity. Between operations 2602 and 2604, the method 290 further includes forming an ion storage layer over the first conductive layer at operation 2618. Thus, forming the first electrolyte layer over the first conductive layer in operation 2604 actually becomes forming the first electrolyte layer over the ion storage layer. That is, operation 2618 allows an ion storage layer to be formed between the first conductive layer and the first electrolyte layer.

Fig. 30 is a flowchart of a method 300 for forming an electrochromic device/display, according to an example embodiment. Operations 2602, 2604, 2606, 2612, and 2618 are the same as explained in connection with fig. 30 and will not be described further for brevity. After 2606, at 2614, the second conductive layer is patterned to form a second region. In some embodiments, patterning the second conductive layer also forms second electrical interconnects between adjacent second regions. The second regions may be separated from each other except at the location of the second electrical interconnect. Forming an electrochromic layer over the second conductive layer may then include, as shown in operation 2608 of fig. 26: at 2608a, an electrochromic layer is patterned to form an electrochromic film over each second region. The electrochromic films are separated from each other. After operation 2608a, forming a second electrolyte layer over the electrochromic layer, as shown in operation 2610 of fig. 26, may include: at 2610a, a second electrolyte layer is formed over each electrochromic film and/or second electrical interconnect and/or in the gaps between adjacent second regions.

Fig. 31 is a flowchart of a method 310 for forming an electrochromic device/display, according to an example embodiment. Operations 2602, 2606, 2614, and 2608a are the same as explained in connection with fig. 30 and will not be described further for brevity. After operation 2602, at 2616, the first conductive layer is patterned to form a first region. In some embodiments, patterning the first conductive layer also forms a first electrical interconnect between adjacent first regions. The first regions may be separated from each other except at the location of the first electrical interconnect. Then forming an ion storage layer over the first conductive layer, as shown in operation 2618 of fig. 30, may include: at 2618a, the ion storage layer is patterned to form an ion storage film over each first region. The ion storage membranes are separated from each other. Then forming a first electrolyte layer over the first conductive layer, as shown in operation 2604 of fig. 30, may include: at 2604a, the first electrolyte layer is patterned to form a first electrolyte membrane over each first region. The first electrolyte membranes are separated from each other. After operation 2608a, forming a second electrolyte layer over the electrochromic layer, as shown in operation 2610 of fig. 26, may include: at 2610b, the second electrolyte layer is patterned to form a second electrolyte membrane over each electrochromic film. The second electrolyte membranes are separated from each other. As shown in operation 2612 of fig. 26, stacking the first substrate and the second substrate such that the first electrolyte layer is in contact with the second electrolyte layer may include: at 2612a, the first substrate and the second substrate are laminated such that the first electrolyte membrane is in contact with the second electrolyte membrane. In some embodiments, the first electrolyte membrane is aligned with the second electrolyte membrane. The first electrolyte membrane may be aligned one-to-one with the second electrolyte membrane such that the first electrolyte membrane is in contact with only the corresponding second electrolyte membrane, and does not contact an adjacent second electrolyte membrane of the second electrolyte membrane.

Fig. 32 is a flowchart of a method 320 for forming an electrochromic device/display, according to an example embodiment. At 3202, a first conductive layer is coated over a first substrate. The first conductive layer may be the n-doped organic conductive polymer described above, 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, translucent or reflective. At 3204, the first conductive layer is patterned to form a first region. In some embodiments, patterning the first conductive layer also forms a first electrical interconnect between adjacent first regions. At 3206, a second conductive layer is coated over the 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 3208, the second conductive layer is patterned to form a second region. In some embodiments, patterning the second conductive layer also forms second electrical interconnects between adjacent second regions. Method 320 then branches to operations 3210 or 3212. At 3210, the method includes the operations of: forming an electrolyte layer over each first region, wherein the electrolyte layers are separated from each other; and forming an electrochromic layer over each electrolyte layer, wherein the electrochromic layers are separated from each other; and laminating the first substrate and the second substrate such that the electrochromic layer is in contact with the second region. At 3212, the method includes the operations of: forming an electrochromic layer over each second area, wherein the electrochromic layers are separated from each other; forming an electrolyte layer over each electrochromic layer, wherein the electrolyte layers are separated from each other; and laminating the first substrate and the second substrate such that the electrolyte layer is in contact with the first region.

Fig. 33 is a flowchart of a method 330 for forming an electrochromic device/display according to another example embodiment. At 3302, a first conductive layer is coated over a first substrate. The first conductive layer may be the n-doped organic conductive polymer described above, 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, translucent or reflective. At 3304, the first conductive layer is patterned to form a first region. In some embodiments, patterning the first conductive layer also forms a first electrical interconnect between adjacent first regions. At 3306, a second conductive layer is coated over the 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. Method 330 then branches to either operations 3308 or 3310. At 3308, the method includes the operations of: forming an electrochromic layer over each first region, wherein the electrochromic layers are separated from each other; and forming an electrolyte layer over 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. At 3310, the method includes the operations of: forming an electrolyte layer over the second conductive layer; forming an electrochromic layer over the electrolyte layer; patterning the electrochromic layer to form a plurality of electrochromic layer regions over the electrolyte layer; and laminating the first substrate and the second substrate such that the electrochromic layer area is in contact with the first area.

In some embodiments, one or more of the above-described patterning operations are performed by a lithographic or printing method (e.g., ink printing).

The disclosed electrochemical devices comprise the disclosed n-doped organic conductive polymers for use as transparent conductors, and/or ion storage materials, and/or electrical interconnects in electronic circuits. The electrochromic device disclosed is selected from the group consisting of an energy storage device, a bioelectronic device, a biosensor, and an optoelectronic device.

The foregoing description of the invention has been presented for purposes of illustration and description. It is not intended to be exhaustive or to limit the invention to the precise form disclosed. The breadth and scope of the present invention should not be limited by any of the above-described exemplary embodiments. Many modifications and variations will be apparent to practitioners skilled in the art. Modifications and variations include any relevant combination of the disclosed features. The embodiments were chosen and described in order to best explain the principles of the invention and its practical application, to thereby enable others skilled in the art to understand the invention for various embodiments and with various modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the following claims and their equivalents.

Claims

1. A method for forming an electrochromic device, comprising:

forming a first conductive layer over a first substrate;

Forming a first electrolyte layer over the first conductive layer;

Forming a second conductive layer over the second substrate;

Forming an electrochromic layer over the second conductive layer;

Forming a second electrolyte layer over the electrochromic layer; and

The first substrate and the second substrate are laminated such that the first electrolyte layer is in contact with the second electrolyte layer.

2. The method of claim 1, further comprising:

The second conductive layer is patterned to form second regions and second electrical interconnects between adjacent second regions.

3. The method according to claim 2, wherein:

Forming the electrochromic layer over the second conductive layer includes: patterning the electrochromic layer to form an electrochromic film over each of the second areas, wherein the electrochromic films are separated from each other; and

Forming the second electrolyte layer over the electrochromic layer includes: the second electrolyte layer is formed in a gap over each of the electrochromic films and the second electrical interconnect and between the adjacent second regions.

4. The method of claim 3, wherein the first conductive layer comprises a compound of formulaWherein X is O, S or Se; each of m and n is an integer greater than zero; each of R ₁ and R ₂ is independently selected from one of hydrogen or C ₁-C₁₀ alkyl; and M ⁺ is an organic or metal cation.

5. The method according to claim 2, wherein:

Forming the second electrolyte layer over the electrochromic layer includes: patterning the second electrolyte layer to form a second electrolyte membrane over each of the electrochromic films, wherein the second electrolyte membranes are separated from each other.

6. The method of claim 5, further comprising:

Patterning the first conductive layer to form first regions and first electrical interconnects between adjacent first regions,

Wherein the first conductive layer comprises a compound having a chemical formulaWherein X is O, S or Se; each of m and n is an integer greater than zero; each of R ₁ and R ₂ is independently selected from one of hydrogen or C ₁-C₁₀ alkyl; and M ⁺ is an organic or metal cation.

7. The method of claim 6, wherein forming the first electrolyte layer over the first conductive layer comprises:

patterning the first electrolyte layer to form a first electrolyte membrane over each of the first regions, wherein the first electrolyte membranes are separated from each other; and

Wherein stacking the first substrate and the second substrate such that the first electrolyte layer contacts the second electrolyte layer includes:

The first substrate and the second substrate are laminated such that the first electrolyte membrane is in contact with the second electrolyte membrane.

8. The method of claim 7, wherein at least one of the patterning operations is performed by a photolithographic or printing method.

9. The method of claim 1, wherein the second conductive layer comprises a compound of formulaWherein X is O, S or Se; each of m and n is an integer greater than zero; each of R ₁ and R ₂ is independently selected from one of hydrogen or C ₁-C₁₀ alkyl; and M ⁺ is an organic or metal cation.

10. The method of claim 1, further comprising:

an ion storage layer is formed between the first conductive layer and the first electrolyte layer.

11. The method of claim 10, further comprising:

12. The method according to claim 11, wherein:

13. The method according to claim 11, wherein:

14. The method of claim 13, further comprising:

the first conductive layer is patterned to form first regions and first electrical interconnects between adjacent first regions.

15. The method according to claim 14,

Wherein forming the ion storage layer between the first conductive layer and the first electrolyte layer comprises: patterning the ion storage layer to form ion storage membranes over each of the first regions, wherein the ion storage membranes are separated from each other;

Wherein forming the first electrolyte layer over the first conductive layer comprises: patterning the first electrolyte layer to form a first electrolyte membrane over each of the ion storage membranes, wherein the first electrolyte membranes are separated from each other; and

Wherein stacking the first substrate and the second substrate such that the first electrolyte layer contacts the second electrolyte layer includes: the first substrate and the second substrate are laminated such that the first electrolyte membrane is in contact with the second electrolyte membrane.

16. The method of claim 15, wherein at least one of the patterning operations is performed by a photolithographic or printing method.

17. The method of claim 10, wherein the second conductive layer comprises a compound of formulaWherein X is O, S or Se; each of m and n is an integer greater than zero; each of R ₁ and R ₂ is independently selected from one of hydrogen or C ₁-C₁₀ alkyl; and M ⁺ is an organic or metal cation.

18. A method for forming an electrochromic device, comprising:

coating a first conductive layer over a first substrate, wherein the first conductive layer comprises a compound of formula Wherein X is O, S or Se; each of m and n is an integer greater than zero; each of R ₁ and R ₂ is independently selected from one of hydrogen or C ₁-C₁₀ alkyl; and 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 a second conductive layer over the second substrate;

Patterning the second conductive layer to form second regions and second electrical interconnects between adjacent second regions; and

One of the following operations is performed:

a) Forming an electrolyte layer over each of the first regions, wherein the electrolyte layers are separated from each other; forming an electrochromic layer over each of the electrolyte layers, wherein the electrochromic layers are separated from each other; and laminating the first substrate and the second substrate such that the electrochromic layer is in contact with the second region; or alternatively

B) Forming an electrochromic layer over each of the second areas, wherein the electrochromic layers are separated from each other; forming an electrolyte layer over each of the electrochromic layers, wherein the electrolyte layers are separated from each other; and laminating the first substrate and the second substrate such that the electrolyte layer is in contact with the first region.

19. The method of claim 18, wherein at least one of the patterning operations is performed by a photolithographic or printing method.

20. A method for forming an electrochromic device, comprising:

coating a second conductive layer over the second substrate; and

One of the following operations is performed:

a) Forming an electrochromic layer over each of the first regions, wherein the electrochromic layers are separated from each other; forming an electrolyte layer over 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 alternatively

B) Forming an electrolyte layer over the second conductive layer; forming an electrochromic layer over the electrolyte layer; patterning the electrochromic layer to form a plurality of electrochromic layer regions over the electrolyte layer; and laminating the first substrate and the second substrate such that the electrochromic layer area is in contact with the first area.