Electrochromic device and method of manufacturing the same

Abstract

The present invention relates to electrochromic devices, methods for depositing organic electrochromic materials, and methods for manufacturing electrochromic devices. The devices are preferably electrochromic displays, preferably full-color electrochromic displays. The devices preferably comprise electrodeposited organic electrochromic materials and / or polymeric organic electrochromic materials. In one aspect, the present invention provides an electrochromic device comprising an active matrix comprising active components and electrodes connected to the active components, the device further comprising an organic electrochromic material deposited in electrical contact with the electrodes.

Description

[Technical Field]

[0001] The present invention relates to electrochromic devices, particularly electrochromic displays, methods for depositing organic electrochromic materials to provide pixels or subpixels of electrochromic devices, and methods for manufacturing electrochromic devices. [Background technology]

[0002] Electrochromic devices utilize the specific properties of electrochromic materials. These materials, also known as electrochromophores, can reversibly change their light absorption properties when they undergo a redox reaction. In electrochromic devices, a system of opposing electrodes and an electrolyte is typically used to reversibly control the repeated oxidation and reduction of the electrochromic material and adjust the desired color displayed by the device. Reduction or oxidation of the electrochromic material is achieved by applying a potential of appropriate magnitude and sign between the electrodes. Ion transport is mediated by the electrolyte to balance the charges on the electrodes.

[0003] Many different types of materials have been reported to exhibit electrochromism. Examples of inorganic materials include metal oxides such as tungsten oxide (WO). An example of an organic electrochromic compound is viologen. Patent document 1 discloses different derivatives of viologen with different colors, particularly derivatives with red, green, and blue colors.

[0004] Electrochromic displays have certain characteristics that distinguish them from other displays, such as liquid crystal displays (LCDs) and organic light-emitting diode (OLED) displays. Electrochromic displays do not emit light themselves, but reflect or transmit ambient light depending on the color properties of the electrochromic material. Therefore, electrochromic displays are sometimes called "passive displays." Compared to luminescent displays such as the aforementioned LCDs and OLEDs, electrochromic displays are believed to cause less eye fatigue with continued use. Viewing an electrochromic display is more like viewing printed material (reflecting ambient light) than using a display that utilizes brightness.

[0005] Compared to LCD and OLED displays, electrochromic displays exhibit a strong contrast ratio, especially when the ambient light intensity is high. Furthermore, electrochromic displays naturally have a wide viewing angle, low energy consumption, and excellent light utilization efficiency. Therefore, electrochromic displays may be considered particularly advantageous for outdoor displays (ambient light) and display-based reading (high contrast, less fatigue on the human eye).

[0006] The use of an active matrix in an electrochromic display was already disclosed in U.S. Patent No. 5,629,997, published in 1983. This active matrix comprises a grid of conductive lines and thin-film transistors (TFTs), arranged in rows and columns (an XY matrix) to selectively apply current to one of the TFTs, thereby establishing a voltage between a specific electrode in electrical contact with the transistor and a counter electrode. In this configuration, an electrochromic material is deposited on a specific electrode electrically connected to the drain pad of the TFT element. TFT panels or active matrices such as those disclosed in U.S. Patent No. 5,629,997 have been commercially available since the 1980s and have been used to drive electroluminescent displays (EL) and LCDs. An active matrix scheme is also shown in Figure 2A of U.S. Patent No. 5,629,997.

[0007] Full-color electrochromic displays can be fabricated by providing red, green, and blue electrochromic materials, for example, in adjacent pixels, with each pixel (or subpixel) having its own electrode and capable of being specifically addressed by an active matrix. In this way, a red-green-blue (RGB) additive color system can be provided, with three subpixels forming one pixel. Such devices may also include a grid barrier to separate pixels from adjacent pixels.

[0008] An example of an electrochromic display based on the RGB color mixing principle is disclosed in Patent Document 4, in which red, green, and blue electrochromic materials are provided to form subpixels separated by insulating separators, which allow specific reduction / oxidation of the appropriate electrochromic (green, red, or blue) electrochromic material and are presumably used to avoid crosstalk between subpixels. No electrolyte is disclosed in this device, making it difficult to understand how such a device can be fabricated and whether it is functional.

[0009] Another multicolor electrochromic display based on the cyan-magenta-yellow (CMY) subtractive color principle is disclosed in U.S. Patent No. 5,623,665, which discloses pixel elements consisting of stacked layers of yellow, magenta, or cyan electrochrome layers. Because different electrochrome layer materials require different voltages to induce a colored state, it is possible to induce a colored state in one, two, or all three of the three electrochrome layers by adjusting the appropriate voltage across a pixel consisting of three electrochrome layers.

[0010] Patent Document 6 discloses a method for fabricating an active matrix electrochromic device. This method includes immersing a substrate constituting the active matrix in a solution containing a metal oxide and forming an electrochromic metal oxide semiconductor layer by an electrophoretic process. Alternatively, an organic electrochromic material may be adsorbed onto the surface of the electrochromic semiconductor layer. Patent Document 6 requires the presence of a cell to separate the electrolyte of any pixel electrode from the electrolyte of other pixel electrodes. For this reason, a bank structure or wall structure is provided to separate the pixels. The bank structure is also used to coat active material-based transistors. Patent Document 6 does not discuss how to deposit the organic electrochromic material.

[0011] Patent Document 3 discloses depositing an organic electrochromic material (4,4'-bipyridinium derivative compound) as a self-assembled monolayer deposited from a solution. Patent Document 7 discloses depositing an organic electrochromic compound by spin coating.

[0012] More generally, in the case of CMY subtractive color mixing, three electrochromic layers and an insulating layer between them must be stacked, as shown in Patent Document 5. The manufacturing process is quite complicated, and the loss of light intensity due to the stacked layers reduces performance.

[0013] In RGB additive color mixing, each pixel is composed of three sub-pixels, each of whose electrochromic layers must reflect or transmit red, green, and blue light, respectively. To fabricate a full-color electrochromic device using this color mixing principle, a grid barrier is generally proposed to separate the pixels, and an additional patterning process is required, which usually involves photolithography for the three different electrochromic materials. This makes the manufacturing process complicated and expensive.

[0014] Patent Document 8 discloses an electrochromic display device including a transparent pixel electrode controlled by a TFT, a polymer layer made of an electrochromic material, and a solid electrolyte layer containing a colorant. As an example, Patent Document 8 discloses electrodeposition of black polypyrrole onto an ITO film.

[0015] Patent Document 9 discloses an electrochromic device comprising a pair of electrodes arranged side by side, facing upward, on a substrate. The two electrochromic materials deposited as a pair of electrodes are complementary. In the fabrication of these particular devices, bus bars and electrodes are deposited on the substrate, and an encapsulation layer is deposited in several steps to protect the bus bars from subsequent fabrication steps. Patent Document 9 generally uses a combination of various materials as electrochromic materials, including the electropolymerization of poly-3-methylthiophene combined with a WO3 electrode pair.

[0016] Patent Document 10 discloses a full-color EC display in which a nanoporous semiconductor layer is deposited on an electrode and an electrochromic (EC) dye is adsorbed into the nanoporous layer. While oxide semiconductors are primarily mentioned as nanoporous semiconductor materials, compound semiconductors such as CuGaS2 that can be formed by electrolytic deposition are also disclosed. The EC dye is adsorbed by one of several methods, including electropolymerization. [Prior art documents] [Patent documents]

[0017] [Patent Document 1] US Patent Application Publication No. 2017 / 0192334 [Patent Document 2] European Patent Application Publication No. 0084604 [Patent Document 3] US Patent Application Publication No. 2007 / 0171148 [Patent Document 4] International Publication No. 2019 / 071733 [Patent Document 5] US Patent Application Publication No. 2005 / 0270619 [Patent Document 6] U.S. Patent No. 8,654,431 [Patent Document 7] U.S. Patent No. 8,687,262 [Patent Document 8] European Patent Application Publication No. 1347330 [Patent Document 9] U.S. Patent No. 5,189,549 [Patent Document 10] Japanese Patent Application Laid-Open No. 2003-315840 Summary of the Invention [Problem to be solved by the invention]

[0018] The objective of the present invention is to provide a full-color EC device that can be obtained by a simple manufacturing method involving few steps, has a fast response time, ideally avoids crosstalk between adjacent electrodes or pixels, and avoids the disadvantages of solid electrolytes, and can be implemented using an active matrix.

[0019] The present invention addresses the problems and objectives set forth above. [Means for solving the problem]

[0020] In one aspect, the present invention provides an electrochromic device comprising an organic electrochromic material selected from polymeric organic electrochromic materials, and electrodeposited organic electrochromic materials, and both.

[0021] In one aspect, the present invention provides an electrochromic device comprising an active matrix comprising active components and electrodes connected to the active components, the device further comprising an organic electrochromic material deposited in electrical contact with the electrodes, the organic electrochromic material being selected from polymeric organic electrochromic materials, and electrodeposited organic electrochromic materials, and both.

[0022] In one aspect, the present invention provides an electrochromic device comprising pixels and / or sub-pixels, the pixels and / or sub-pixels comprising a polymeric organic electrochromic material.

[0023] In one aspect, the present invention provides an electrochromic device comprising pixels, wherein the pixels and / or sub-pixels comprise an organic electrochromic material deposited by electrodeposition and / or electropolymerization.

[0024] In one aspect, the present invention provides an electrochromic device comprising an array or pixel electrode and one or more counter electrodes, wherein an organic electrochromic material is provided in electrical contact with the array and / or pixel electrodes, wherein the organic electrochromic material is a polymeric organic electrochromic material, and / or the organic electrochromic material is an electrodeposited organic electrochromic material.

[0025] In one aspect, the present invention provides an electrochromic device comprising a first electrode, an organic electrochromic material in electrical contact with the first electrode, one or more counter electrodes, and a charge conducting material for transporting charge between the first electrode and the counter electrodes, wherein the electrochromic device is configured to establish an electric potential between the first electrode and the one or more counter electrodes, and the organic electrochromic material is an electrodeposited organic electrochromic material and / or an organic polymeric electrochromic material preferably obtained by electropolymerization.

[0026] In one aspect, the present invention provides a method for producing a pharmaceutical composition comprising: a plurality of pixels, each pixel comprising a pixel electrode and an organic electrochromic material, the organic electrochromic material being in electrical contact with the pixel electrode; a grid or matrix with conductive lines for supplying current to the pixel electrodes; one or more counter electrodes; an ion conducting material for transporting ions between the pixel and the one or more counter electrodes; An electrochromic device comprising: The electrochromic display is configured to establish an electric potential between any one particular pixel electrode and the one or more counter electrodes, and is characterized in that the organic electrochromic material is an electrodeposited organic electrochromic material and / or an organic polymer electrochromic material preferably obtained by electropolymerization.

[0027] In one aspect, the present invention provides a method for depositing an organic electrochromic material in electrical contact with an array electrode and / or a pixel electrode, the method comprising the steps of electrodepositing the organic electrochromic material in electrical contact with the array electrode and / or the pixel electrode, and / or electropolymerizing the organic electrochromic material.

[0028] In one aspect, the present invention provides a method for depositing an organic electrochromic material onto pixel electrodes of an electrochromic device, the method comprising the steps of: providing a grid or matrix comprising conductive lines and a plurality of pixel electrodes, with a specific line for each of the pixel electrodes; immersing the grid or matrix in a solution; adding a substance of the organic electrochromic material to the solution; providing a counter electrode in the solution; and applying a potential between some or all of the plurality of pixel electrodes and the counter electrode, thereby depositing the substance of the organic electrochromic material onto the pixel or sub-pixel electrodes.

[0029] In some embodiments, the present invention provides electrochromic devices, particularly methods of manufacturing electrochromic devices, comprising depositing an organic electrochromic material on an array electrode and / or a pixel electrode in accordance with the present invention.

[0030] In one aspect, the present invention provides a method for manufacturing an electrochromic device, the method comprising depositing an organic electrochromic material on a pixel electrode of an electrochromic device according to the present invention or a preferred embodiment disclosed herein, and assembling a counter electrode and a charge transport material to provide said electrochromic device.

[0031] Further aspects and preferred embodiments of the present invention are defined hereinafter and in the appended claims. Further features and advantages of the present invention will become apparent to those skilled in the art from the description of the preferred embodiments given below.

[0032] In the following, preferred embodiments of the device of the present invention are described for the purpose of illustrating the present invention, but are not intended to limit the scope of the present invention. [Brief explanation of the drawings]

[0033] [Figure 1] 1 shows a schematic diagram of one embodiment of an electrochromic display of the present invention. [Figure 2] 3A-3C illustrate schematically the deposition of an organic electrochromic material onto a pixel electrode according to one embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0034] Electrochromic device The present invention relates to an electrochromic device, preferably comprising and / or consisting essentially of an electrochromic display.

[0035] FIG. 1 shows a schematic representation of a portion of an electrochromic display 1. The display 1 is generally planar and comprises two first and second support structures or substrates 100, 110, defining first and second opposing outer surfaces 121, 122. One or both substrates 100, 110 may be at least partially transparent. The substrates may be constructed, for example, from glass and / or at least partially transparent plastic. Of course, at least one of the two substrates must be transparent in order for the device to function as a display.

[0036] For the purposes of this specification, the expression "comprising" is intended to mean "including, among other things." It is not intended to mean "consisting only of."

[0037] Conductive lines 108 (commonly referred to as "conductors") are provided on the interior surface of the first substrate 100. The conductive lines are generally electrically conductive. The conductors electrically connect external drivers (not shown in FIG. 1) with the active components 101-103 of the display.

[0038] The active components 101-103 and the conductors 108 are preferably electrically isolated and protected by an electrically insulating layer 114 deposited on the active components and the conductors 108. The conductors 108 preferably provide a plurality of conductive lines forming a grid or matrix.

[0039] In one embodiment, the electrochromic device comprises an insulating layer 114 disposed between the first substrate 100 and the sub-pixel electrodes 115-117, and the active matrix comprises conductive vias 104 extending across the insulating layer, the vias being provided to connect individual active components 101, 102, 103 with individual sub-pixel electrodes 115, 116, 117. Preferably, the pixel or sub-pixel electrodes are deposited on the insulating layer.

[0040] In one embodiment, the active components 101 are preferably transistors, e.g., thin film transistors (TFTs), or primarily TFT-based circuits. Together, all active components 101-103 may be an array of TFTs or TFT-based circuits electrically connected to pixel electrodes 115-117 of a display. The conductive lines 108 and active components 101-103 preferably provide a grid, array, or matrix, sometimes referred to as an "active matrix." Note that the conductive lines 108 are preferably provided in such a way that each active component 101-103 can be individually and / or independently addressed. Preferably, each active component 101-103 can be individually and / or independently supplied with current and / or exposed to an electric potential, as disclosed, for example, in U.S. Pat. No. 6,213,999 (FIG. 3) and U.S. Pat. No. 6,213,999 (FIG. 2A).

[0041] Typically, each active component 101-103 comprises a gate electrode, a source electrode, and a drain electrode. Typically, each array electrode 115-117 or each pixel cathode is connected to a drain electrode, preferably by a via 104. The via 104 is also conductive and can be thought of as a conductive connection between the active components provided on the first substrate and the pixel electrodes 115-117 provided on the insulating layer 114, such that the via provides a connection between different layers of the device, in particular between opposing surfaces of the insulating layer 114.

[0042] It should be noted that the term "active matrix" should not be confused with the notion that an electrochromic display is a "passive display." The latter term refers to the fact that electrochromic displays generally do not emit light, but are composed of electrochromic materials that can be controlled to have specific colors and thus reflect light of specific colors. The term "active matrix" refers to an electronic matrix comprising conductive lines 108 and active components 101-103 used to supply current to the array electrodes and / or pixels and / or expose the pixels to electrical potentials.

[0043] In one embodiment, the grid, array and / or matrix comprises an active matrix.

[0044] The active matrix preferably comprises active components 101-103, with the active components 101, 102, 103 provided for each array electrode 115-117 and / or each of the pixels 105-107, with each of the active components 101-103 electrically connected to one of the pixel electrodes 115-117, and a predetermined pixel potential being established via the active component 101.

[0045] In one embodiment, the grid, array and / or matrix comprises thin film transistors (TFTs), and every pixel or sub-pixel of the electrochromic device comprises at least one TFT for controlling the flow of current to or from a pixel or sub-pixel electrode.

[0046] For purposes of this specification, the term "pixel electrode" is interchangeable with the term "array electrode," and the two terms refer to the same structural features 115-117. Similarly, the term "array electrode" may also be interchangeable with the term "subpixel electrode," as disclosed elsewhere herein.

[0047] 1 preferably comprises a plurality of pixels 105 to 107. Preferably, each pixel comprises a pixel electrode 115 to 117 and an electrochromic material 125 to 127. Preferably, the electrochromic material comprises or consists of an organic electrochromic material 125 to 127.

[0048] Preferably, the organic electrochromic materials 125-127 are in electrical contact with the pixel electrodes 115-117.

[0049] For purposes of this specification, the terms "electrically connected" or "electrically in contact" mean that a steady flow of electrical current (electrons, holes) occurs between items that are electrically connected under a constant potential difference.

[0050] In one embodiment, the pixel electrodes 115-117 are preferably at least partially transparent to visible light. In one embodiment, the pixel electrodes 115-117 comprise and / or consist essentially of a transparent conductive material, preferably a transparent conductive oxide (TCO), which may be selected from the group consisting of, for example, indium tin oxide (ITO), fluorine-doped tin oxide (FTO), antimony-doped tin oxide (ATO), tin oxide (SnO), zinc oxide (ZnO), aluminum-doped zinc oxide (AZO), or indium zinc oxide (IZO).

[0051] In a preferred embodiment, the pixel electrodes 115-117 also comprise a nanostructured layer, preferably deposited on top of and / or above said conductive material, preferably a transparent conductive material as listed above (ITO, FTO, etc.). Preferably, an organic electrochromic material 125-127 is deposited on said nanostructured layer. The nanostructured layer comprises a metal oxide material. The nanostructured layer may comprise a semiconducting and / or conductive material. The nanostructured layer may be nanoporous. Preferably, the nanostructured layer may be selected from TCOs, for example those exemplified above (ATO, ITO, SnO, ZnO, etc.), and also from titanium dioxide (TiO2).

[0052] In one embodiment, the first pixel 105 comprises a first pixel electrode 115 and a first electrochromic material 125, the second pixel 106 comprises a second pixel electrode 116 and a second electrochromic material 126, the third pixel 107 comprises a third pixel electrode 117 and a third electrochromic material 127, etc., with the nth pixel comprising an nth pixel electrode and an nth electrochromic material. Preferably, the electrochromic material comprises or consists of an organic material, as described in more detail elsewhere herein.

[0053] When considering an entire electrochromic device comprising multiple pixels and / or subpixels, reference numerals 105, 106, 107 may also be used to refer to first, second, and third portions of pixels or subpixels, respectively. By analogy, reference numerals 115, 116, 117 may be understood as first, second, and third portions of a pixel (or subpixel or array) electrode.

[0054] The electrodes 115-117 of each pixel 105-107 are electrically connected to the active components 101-103 provided on the particular electrodes by vias 104. For example, the through vias 104 traverse the protective and / or insulating layers 114 to electrically connect the active components with their corresponding pixel electrodes.

[0055] Although three pixels 105-107 are shown in Figure 1, it will be understood that devices of the present invention preferably comprise many more pixels, and three pixels are shown for illustrative purposes.

[0056] In one embodiment, the electrochromic materials 125-127 are provided on top of the corresponding pixel electrodes 115-117, ie, the first electrochromic material 125 is on top of the first pixel electrode 115, and so on.

[0057] In one embodiment, the pixel electrodes 115-117 are provided in the form of a layer, for example deposited.

[0058] In one embodiment, the electrochromic materials 125-127 are provided, eg, deposited, as layers.

[0059] In one embodiment, the electrochromic materials 125-127 are provided, preferably deposited, to cover the pixel electrodes of the corresponding pixels 105-107. Preferably, the pixel electrodes are completely covered by said electrochromic material. Preferably, the pixel electrode materials 115-117 are: ion-conducting materials109. If the pixel electrode is completely surrounded or covered by the electrochromic material, the charge injection for coloring or bleaching may be more efficient. However, the device should function if the pixel electrode is not completely covered and / or has a surface in contact with the ion transport layer.

[0060] As can be appreciated, the electrochromic material associated with a corresponding pixel electrode is in electrical contact with that pixel electrode, and preferably only with the corresponding pixel electrode, e.g., first electrochromic material 105 is in electrical contact, and preferably physical contact, with first pixel electrode 115, etc.

[0061] As can be appreciated, the electrochromic material associated with a corresponding pixel electrode is preferably in direct physical contact with that pixel electrode, and preferably only with the corresponding pixel electrode, preferably as a result of depositing the electrochromic material directly onto the corresponding pixel electrode, as will be described in more detail elsewhere herein.

[0062] The device 1 of the present invention preferably comprises at least one counter electrode 120. The counter electrode 120 is preferably in contact with the second substrate 110. Preferably, at least a portion of the counter electrode is deposited directly on the inner surface of the second substrate 110.

[0063] In one embodiment, the at least one counter electrode 120 is preferably at least partially transparent to visible light. In one embodiment, the at least one counter electrode 120 comprises and / or consists essentially of a transparent conductive material, such as a transparent conductive oxide (TCO), which may be selected from the group consisting of indium tin oxide (ITO), fluorine-doped tin oxide (FTO), antimony-doped tin oxide (ATO), tin oxide (SnO), zinc oxide (ZnO), aluminum-doped zinc oxide (AZO), or indium zinc oxide (IZO). Preferably, the conductive material forms layer 111 of the device, preferably on the inner surface of the second substrate 110.

[0064] In a preferred embodiment, the counter electrode 120 comprises a conductive layer 111, as shown in FIG.

[0065] In a preferred embodiment, as shown in FIG. 1, the counter electrode 120 comprises an ion storage layer 112 .

[0066] In a preferred embodiment, the counter electrode 120 comprises a conductive layer 111 and an ion storage layer 112 .

[0067] The device 1 of the present invention preferably comprises at least one ion storage layer 112. In one embodiment, the ion storage layer 112 is deposited on the conductive layer 111. In one embodiment, the ion storage layer 112 comprises or consists essentially of a porous structure, preferably a nanoporous and / or nanocrystalline structure. Preferably, the porous structure is such that the electrolyte can penetrate into the body and ions can collect at the surface of the porous structure, and preferably also within the body of the ion storage layer. In other embodiments, the ion storage layer may be a compact and / or non-porous layer. A compact ion storage layer is expected to have a smaller overall surface available for ions to collect and therefore a smaller overall storage capacity. However, devices with compact ion storage layers will also function.

[0068] Preferably, the ion storage layer 112 is provided to have an appropriate ion storage capacity. The ion storage layer may be selected from the group consisting of conductive inorganic materials with a large surface area, such as mesoporous structures, nanowires, and nanotubes. The ion storage layer 112 may typically comprise or consist essentially of a doped metal oxide, such as antimony tin oxide (ATO). The ion storage layer 112 may also be selected from the group consisting of conductive polymers with a porous structure, or conductive hybrids of inorganic and organic materials.

[0069] In one embodiment, the device 1 of the present invention preferably comprises an ion-conducting material 109 for transporting ions between the pixels 105-107 and the one or more counter electrodes 120. The ion-conducting material 109 is preferably provided to allow and / or mediate the transport of ions, such as charged molecules or other (e.g., metal) ions. The ions may be cations or anions. The ions may be organic or inorganic.

[0070] Therefore, the ionically conductive material 109 is preferably an electrolytic layer and / or an electrolyte, for example, an electrolyte comprising dissolved ions and / or an ionic liquid. In a preferred embodiment, the ionically conductive material 109 may be selected from, for example, a liquid electrolyte, a gel electrolyte, an ionic liquid, and a eutectic melt.

[0071] In one embodiment, ion-conducting materials 109 includes one or more cations selected from lithium, sodium, potassium, alkylimidazolium, alkylpyridinium, alkylphosphonium, alkylammonium, and tetra-n-butylammonium. Preferably, the alkyl is a C1-C20 alkyl, more preferably a C1-C10 alkyl, and most preferably a C1-C4 alkyl, such as methyl.

[0072] In one embodiment, ion-conducting materials 109 includes a salt of any one of the above cations.

[0073] In one embodiment, ion-conducting materials 109 includes one or more anions selected from bistriflamide or TFSI ([(CF3SO2)2N]-), perchlorate (ClO4-), tetrafluoroborate (BF4-), or hexafluorophosphate (PF6-).

[0074] In one embodiment, ion-conducting materials 109 includes a salt of any one of the above anions.

[0075] In one embodiment, ion-conducting materials 109 includes one or more salts containing at least one of the above anions and at least one of the above cations.

[0076] In one particular embodiment, ion-conducting materials 109 includes one or more selected from LiTFSI, LiClO4, LiBF4, or LiPF6.

[0077] In one embodiment, ion-conducting materials 109 includes at least one solvent. The solvent may be selected from, for example, propylene carbonate, ethylene carbonate, tetrahydrofuran, dioxane, dimethyl sulfoxide, dimethylformamide, acetonitrile sulfolane, γ-butyrolactone, and solvent mixtures including one or more of the above-mentioned solvents. It should be noted that for certain electrolytes, such as ionic liquids (also known as ionic melts or liquid salts), a separate solvent may not be present, as the ionic liquid functions as the solvent and also provides ions for ionic transport.

[0078] In one embodiment, ion-conducting materials 109 includes at least one solvent, at least anions, and at least cations. ion-conducting materials109 comprises at least one or more selected from at least one salt of the aforementioned cations and at least one salt of the aforementioned cations, and optionally a solvent preferably selected from the aforementioned solvents.

[0079] In one embodiment, electrolysis The layer is , liquid, gel, or solid.

[0080] In a preferred embodiment, electrolysis The layer is Preferably, the liquid crystal and / or ionic liquid crystal comprises and / or consists essentially of a liquid crystal or an ionic liquid crystal, which is advantageous as it can contribute to reducing crosstalk effects between pixels.

[0081] In one embodiment, an ion-conducting material 109 is provided within a common space, and a plurality of pixels and / or sub-pixels 105-107 are preferably provided within said common space and / or are in contact with a continuous and / or homogenous ion-conducting material 109, preferably within said continuous space. This is shown in Figure 1, where reference numeral 109 refers to said common space, since this space is filled with an ion-conducting material 109, preferably the electrolyte as disclosed herein.

[0082] The ionically conductive material preferably has consistent and / or invariant electrical properties within said common continuous space.

[0083] In one embodiment, the device of the present invention comprises an insulating layer 114 to electrically isolate the ionically conductive material 109 from the grid or matrix comprising conductive lines 104, 108 and / or from the active components 101-103, if present.

[0084] Preferably, the device of the present invention does not have a separation wall or separation element for separating pixels and / or sub-pixels. Preferably, the device does not have a separation wall, element, boundary, and / or area element for separating pixels and / or sub-pixels. Such separation is provided in the prior art to electrically isolate adjacent pixels and / or adjacent sub-pixels, essentially to avoid crosstalk between electrodes. Such separation elements may also be used in the prior art to prevent continuous ion-conducting material from contacting different pixels, e.g., adjacent pixels.

[0085] This feature distinguishes the device of the present invention from prior art devices such as those disclosed in U.S. Patent Nos. 5,629,999; 5,629,999; and 5,629,999, among others, in which pixels (or sub-pixels) are separated by separation walls and each pixel (or sub-pixel) has its own confined electrolyte.

[0086] Preferably, continuous ion The conductive material 109 (e.g., electrolyte) is in physical contact with several different, e.g., adjacent pixels and / or adjacent array electrodes 115-117. In one embodiment, the ionically conductive material 109 (e.g., electrolyte) is in physical contact with electrochromic materials 125-127 deposited on different, preferably adjacent, array electrodes 115-117. Crosstalk during operation of the device is preferably minimized by: ion-conducting materials This can be prevented by using 109.

[0087] In a preferred embodiment, the ion-conducting material 109 comprises a liquid crystal. Patent Document 3 discloses the use of liquid crystal to avoid crosstalk between pixels. In one embodiment, ion-conducting materials 109 includes an electrolyte and a low molecular weight liquid crystal material, as disclosed in Patent Document 3.

[0088] Although the conductive materials 105-107 are designated as pixel electrodes, it is correct to consider the combination of the pixel (or subpixel or array) electrode 115 (and 116-117) and the electrochromic material 125 (126-127) deposited thereon together as a first electrode or pixel electrode. In other words, the term pixel as used herein with respect to the structure encompassed by reference numerals 105-107 can also be understood as a pixel electrode or first electrode, since the entire structure 105 may be considered an electrode.

[0089] Alternatively, all of the pixels 105-107 as a whole (including up to n pixels not shown) can be considered a first electrode, and the combination of layers 111 and 112 can be considered a counter electrode 120. Thus, the present invention encompasses different terminology or nomenclature that may be used in the literature to designate electrodes and counter electrodes.

[0090] The present invention also encompasses the possibility of providing an electrochromic material in electrical and / or physical contact with the counter electrode 120, more specifically, the ion storage layer 112. For example, the electrochromic material deposited on or as part of the counter electrode 120 may be selected from inorganic and / or organic materials, as disclosed, for example, in U.S. Patent No. 6,277,999. The electrochromic material may also be part of the counter electrode and thus configured within the counter electrode. Preferably, such electrochromic material is different from the electrochromic materials 125-127 generally disclosed herein as being associated with the pixel electrodes 115-117.

[0091] In a preferred embodiment, electrochromic materials 125-127 comprise or consist essentially of one or both selected from the group consisting of electrodeposited organic electrochromic materials and organic polymeric electrochromic materials.

[0092] In one embodiment, electrochromic materials 125-127 comprise organic or hybrid materials containing one or more materials selected from the electrodeposited organic electrochromic materials and / or organic polymer electrochromic materials. For purposes of this specification, a "hybrid material" is a material containing one or more inorganic materials and one or more organic materials. In the case of a hybrid material, an organic electrochromic material preferably provides at least one organic component of the hybrid material.

[0093] In one embodiment, the electrodeposited organic and / or organic polymer electrochromic materials are preferably selected from doped and / or undoped organic materials. If the organic material is doped, it may contain non-organic components or additives, such as metal ions, organometallic materials, and composite materials.

[0094] In a preferred embodiment, the electrodeposited organic electrochromic material and / or the organic polymer electrochromic material is obtained by electropolymerization.

[0095] In one embodiment, the electrodeposited organic material includes one or more selected from electrodeposited heterocycles. The heterocycle may or may not be aromatic. Examples of heterocycles include viologen, thiophene, pyridine, anthraquinone, imide, pyridine, and derivatives thereof, particularly compounds comprising these structures, optionally further comprising the substituents described in detail below. The electrochromic material may include an organic material obtained by electropolymerizing a heterocyclic compound and its derivative. The electrochromic material may include a polymerizable heterocycle.

[0096] In a preferred embodiment, the electrodeposited organic materials 125-127 comprise one or more selected from the group consisting of electrodeposited viologens, electrodeposited triphenylamines, electrodeposited thiophenes, electrodeposited 3,4-ethylenedioxythiophenes, electrodeposited pyridines, electrodeposited anilines, electrodeposited imides, electrodeposited aromatic ketones, electrodeposited anthraquinones, electrodeposited amides, electrodeposited norbornene-based compounds, electrodeposited carbazoles, electrodeposited thiocarbazoles, electrodeposited pyrroles, and electrodeposited derivatives of the indicated compounds. Derivatives of the indicated compounds include, in particular, the indicated compounds in which, for example, one or more hydrogen atoms may be optionally replaced with a substituent as defined below.

[0097] In one embodiment, electrochromic materials 125-127 can be formed by electropolymerizing, for example, viologen, triphenylamine, thiophene, 3,4-ethylenedioxythiophene, pyridine, pyrrole, aniline, imide, aromatic ketone, anthraquinone, amide, norbornene, carbazole, and thiocarbazole, including derivatives of any one or more of the foregoing. Derivatives of the depicted compounds specifically include, for example, the depicted compounds in which one or more hydrogens can be optionally replaced with a substituent, as defined below.

[0098] In one embodiment, the electrochromic materials 125 to 127 can be formed by electrolytic polymerization of, for example, a viologen-based compound, a triphenylamine-based compound, a thiophene-based compound, a 3,4-ethylenedioxythiophene-based compound, a pyridine-based compound, a pyrrole-based compound, an aniline-based compound, an imide-based compound, an aromatic ketone-based compound, an anthraquinone-based compound, an amide-based compound, a norbornene-based compound, a carbazole-based compound, and a thiocarbazole-based compound.

[0099] As used herein, the phrase "-based compounds" or "-based organic materials" is intended to encompass the indicated compound or material structure and derivatives thereof, which derivatives include the basic structure of the indicated compound or material. For example, such compounds may further include one or more optional substituents, as indicated herein below. For example, the phrase "viologen-based compounds" preferably encompasses compounds that include the basic viologen structure, but may further include one or more substituents that can affect the color and / or electrochromic properties or characteristics of the compound.

[0100] In a preferred embodiment, the polymerized organic materials 125 to 127 include one or more selected from the group consisting of polyviologen, polytriphenylamine, polythiophene, poly(3,4-ethylenedioxythiophene) (PEDOT), polypyridine, polypyrrole, polyaniline, polyimide, polymeric aromatic ketone, polyanthraquinone, polyamide, polynorbornene, polycarbazole, polythiocarbazole, and derivatives thereof.

[0101] In one embodiment, the polymerized organic materials 125 to 127 include one or more selected from the group consisting of polyviologen-based organic materials, polytriphenylamine-based organic materials, polythiophene-based organic materials, polypyridine-based organic materials, polypyrrole-based organic materials, polyaniline-based organic materials, polyimide-based organic materials, polymeric aromatic ketone-based organic materials, polyanthraquinone-based organic materials, polyamide-based organic materials, polynorbornene-based organic materials, polycarbazole-based organic materials, and polythiocarbazole-based organic materials.

[0102] An example of a polythiophene-based organic material is a poly(3,4-ethylenedioxythiophene) (PEDOT)-based organic material.

[0103] As indicated, derivatives of the aforementioned materials are also encompassed. For example, the term "electrodeposited viologen" encompasses electrodeposited derivatives of viologens that contain the basic viologen structure and one or more optional further substituents. The term "polyviologen" encompasses polymers of monomers that contain the basic viologen structure, which may be, for example, derivatized viologens to contain one or more optional additional substituents. For example, Patent Document 3 discloses derivatives of viologens, in which the substituents on the basic viologen structure can be selected to provide the viologen derivatives with specific color properties.

[0104] Any substituent of the organic material described above, particularly the exemplified electrodeposition material and polymerized organic material, may be selected from organic substituents having 1 to 50 carbon atoms and 0 to 20 heteroatoms, preferably 1 to 20 carbon atoms and 0 to 10 heteroatoms, and most preferably 1 to 10 carbon atoms and 0 to 5 heteroatoms.

[0105] In some embodiments, the substituents may be selected from aliphatic and aromatic substituents, esters and amines of aliphatic and aromatic moieties, where one or more hydrogens in said aliphatic or aromatic substituents or moieties are replaced by phosphonic acid (-PO(OH)), boronic acid (-B(OH)), -OH, -COOH, -NH, -NO, aminoxide (-N + (R)2-O-), halogen and -(CH2) n -Si(OR3)3, where R and R3 are independently selected from C1-C10 alkyl, preferably C1-C5 alkyl.

[0106] It should be noted that the substituted hydrogen may be, for example, a hydrogen bonded to a carbon or a hydrogen bonded to a heteroatom such as nitrogen of the basic organic material as described above, the latter being preferably applied when the substituent consists of a C atom which is bonded to the heteroatom.

[0107] In one embodiment, the substituents are selected from linear or branched alkyl, alkenyl, alkylaryl, and alkylarylalkyl (e.g., alkylphenylalkyl such as alkylbenzyl), where one or more hydrogens are replaced by -PO(OH), -B(OH), -OH, -COOH, -NH, -NO, aminoxide (-N + and optionally independently substituted with one or more selected from —(R)—O), halogen, and —(CH)—Si(OR), where R and R are independently as defined above.

[0108] In one embodiment, the optional substituents of the organic materials set forth above are independently selected from C1-10 alkyl, N-oxide, dimethylamino, acetonitrile, benzyl, phenyl, benzyl mono- or di-substituted with nitro; phenyl mono- or di-substituted with nitro, and substituents of formulas (1)-(9): [ka] may be selected from: n and m are independently integers from 1 to 10; R1-R3 are independently selected from C1-C10 alkyl; R4-R6 are independently selected from hydrogen, C1-C10 alkyl, C2-C10 alkylene, aryl, substituted aryl, halogen, nitro, and -OH, and the dotted line represents a single bond connecting the substituents, as the case may be, to the basic structure of the depicted organic material, compound, or monomer.

[0109] Substituent (8) is an example of a substituent that comprises an ester containing aliphatic and aromatic moieties.

[0110] The electrochromic material preferably has a specific color depending on the oxidation state of the material. In some embodiments, the electrochromic material has no color when in a first oxidation (or redox) state and a specific color (preferably red, green, or blue) when in a second oxidation state. In the devices of the present invention, the oxidation state of the electrochromic material is preferably controlled by the voltage to which the material is exposed via the pixel electrode and counter electrode arrangement. It can also be said that the current flow through the via 104 is preferably controlled or regulated by the active components 101-103. The current through the via 104 is preferably used to oxidize and / or reduce the electrochromic material to impart the color desired at a particular moment. The current flow is preferably the result of a voltage applied by the pixel electrode and counter electrode arrangement within the device. ion-conducting materials The ion flow in 109 preferably balances the charge accumulated on both electrodes.

[0111] These electrodeposited and / or polymeric organic electrochromic materials are preferably electrodeposited according to the methods of the present invention, as disclosed in some detail elsewhere herein.

[0112] In one embodiment, the device of the present invention is an electrochromic color device, preferably an electrochromic color display. Preferably, the device is a multicolor electrochromic device, most preferably a full-color electrochromic device. Preferably, the device is a display, especially a multicolor electrochromic display, most preferably a full-color electrochromic display.

[0113] In one embodiment, the color characteristics of the device are provided at least in part by the presence of organic electrochromic materials of different colors. In a preferred embodiment, adjacent pixels, preferably sub-pixels, are comprised of electrochromic materials of different colors, preferably red, green and blue (RGB colors).

[0114] Preferably, the device of the present invention is based on RBG color mixing.

[0115] 1 from the perspective of a color device, one of pixels 105-107 preferably contains a red electrochromic material, one preferably contains a green electrochromic material, and one preferably contains a blue electrochromic material. As noted above, the electrochromic material preferably comprises and / or consists essentially of a polymeric organic electrochromic material and / or an electrodeposited organic electrochromic material.

[0116] In a particular embodiment, the first pixel 105 includes a red organic electrochromic material 125 , the second pixel 106 includes a green electrochromic material 126 , and the third pixel 107 includes a blue organic electrochromic material 127 .

[0117] In a full-color device, the pixels 105-107 may be considered as sub-pixels that together provide one pixel and / or color, preferably through additive RGB color mixing. In this case, the sub-pixels 105-107 form one pixel of the electrochromic device. In this case, each sub-pixel includes a sub-pixel electrode 115-117, e.g., the first sub-pixel 105 includes the first sub-pixel electrode 115, the second sub-pixel 106 includes the second sub-pixel electrode 116, and the third sub-pixel 107 includes the third sub-pixel electrode 117.

[0118] Preferably, the sub-pixels 105-107 forming a pixel have a structure as described herein above and / or are made from materials as described herein above. For example, the sub-pixel electrodes 115-117 may comprise a nanostructured layer as detailed above. Preferably, the electrochromic material of the sub-pixels comprises an organic electrodeposited material and / or an organic polymer electrochromic material, preferably selected from the materials defined elsewhere herein.

[0119] In a preferred embodiment, the electrochromic device 1 is a full-color electrochromic device comprising a pixel, the pixel comprising a first sub-pixel 105, a second sub-pixel 106 and optionally a third sub-pixel 107, each of the sub-pixels comprising a sub-pixel electrode 115-117, and each of the first, second and optionally third sub-pixels comprising an organic electrochromic material 125-127 having a different color.

[0120] Those skilled in the art will appreciate that the subpixel electrodes 115-117 of the subpixels may be identical, and preferably are identical and / or made from the same material. In one embodiment, the electrochromic material 125-127 is the primary or only difference between the subpixels 105-107. It should be noted that the (array or pixel) electrodes 115-117 can be considered to be part of the active matrix. Thus, the (array or pixel) electrodes 115-117 are preferably part of both the pixels (or subpixels) 105, 106, 107 and the active matrix.

[0121] In a preferred embodiment of electrochromic device 1, the first subpixel 105 includes an organic electrochromic material 125 that has a red color when exposed to a specific voltage, the second subpixel 106 includes an organic electrochromic material 126 that has a green color when exposed to a specific voltage, and the optional third subpixel 107 includes an organic electrochromic material 127 that has a blue color when exposed to a specific voltage.

[0122] In a preferred embodiment, three sub-pixels 105, 106, 107 are provided adjacent to one another. Preferably, electrochromic materials of different colors are provided adjacent to one another on spaced-apart sub-pixels. Preferably, the sub-pixels are not in direct physical contact with one another. Preferably, the different electrochromic materials (which also have different color properties) are not in direct physical contact and are not overlapping. This embodiment preferably distinguishes the device of the present invention from devices consisting of overlapping electrochromic materials, as shown, for example, in US Pat. No. 6,279,999.

[0123] Preferably, the spaced-apart subpixels (or pixels) 105-107, and thus the corresponding electrochromic materials 125-127, are laterally and / or horizontally spaced apart, where the horizontal is defined by the plane of the generally flat electrochromic device. More specifically, one or both substrates 100 and 110 preferably extend in a plane parallel to the horizontal. Preferably, the pixels (or subpixels) 105-107 are in or on the same horizontal plane. Preferably, the electrochromic materials 125-127 of different, particularly adjacent, pixels or subpixels (i.e., subpixels in a color device) are optionally in the same horizontal plane. In one embodiment, most, preferably all, of the pixels and / or subpixels of the device are disposed in the same plane and / or are aligned in the same plane.

[0124] Preferably, adjacent sub-pixels of different RBG colours are provided side by side on an insulating layer. Preferably, the three sub-pixels that together provide a colour by RBG colour mixing are aligned in the same plane, which plane is substantially parallel with respect to at least one of the two opposing surfaces 121, 122 of the device. For example, the plane of the sub-pixels is defined by the surface of the insulating layer on which the pixel or sub-pixel electrodes are deposited.

[0125] In a preferred embodiment, the ion-conducting material 109 is provided within a common space, and at least three separate sub-pixels 105, 106, 107 are preferably provided within the common space and / or in contact with the continuous ion-conducting material 109.

[0126] In a preferred embodiment, the grid or matrix comprises an active matrix of active components 101-103, each of which is provided for one of the sub-pixels 105-107, and each of the active components 101-103 is electrically connected to one of the sub-pixel electrodes 115-117, establishing a predetermined sub-pixel potential via the active component 101.

[0127] The device of the present invention preferably includes external drive components and / or terminals (not shown in FIG. 1) configured to provide appropriate voltage potentials for each pixel or sub-pixel independently to generate the oxidation state of the electrochromic material, thereby enabling all pixels or sub-pixels together to collectively generate an image.

[0128] In one embodiment, the first substrate 100, the electrical insulating layer 114, the pixel electrodes 115 to 117, the electrolytic layer, The second substrate 110, counter electrode 111, and ion storage layer 112 may be transparent, providing a transparent electrochromic display, allowing a user to perceive images from both sides of the display and keeping objects behind the display visible.

[0129] In another embodiment, the first substrate 100, the electrical insulating layer 114, the pixel electrodes 115 to 117, and the electrolytic The layer is It may be transparent, and the ion storage layer 112 may be diffusely reflective, providing a reflective electrochromic display with a white background. The user can perceive the image from the pixel electrode side 121.

[0130] In yet another embodiment, a second substrate 110, a counter electrode 111, an ion storage layer 112, and an electrolytic The layer is It may be transparent, or the electrically insulating layer 114 may be diffusely reflective to provide a reflective electrochromic display with a white background. The user can perceive the image from the counter electrode side (side 122).

[0131] The present invention also relates to a method for depositing organic electrochromic materials 125-127 onto pixel electrodes 115-117 of an electrochromic device. The method of the present invention is illustrated in Figure 2. The organic electrochromic materials may be the same materials as those disclosed elsewhere herein. The array electrodes 115-117 may also be pixel or subpixel electrodes in a color electrochromic device, such as a color display, as disclosed elsewhere herein.

[0132] The method of the present invention preferably includes the step of providing a grid or matrix comprising conductive lines and / or vias 104, 108 and a plurality of pixel electrodes 115-117, with a specific via 104 for each of the pixel electrodes 115-117. Active matrices that can be used for the purposes of the method of the present invention are currently commercially available and are disclosed, for example, in U.S. Patent Nos. 5,999,949 and 5,999,952. In FIG. 2, the active matrix is ​​designated by reference numeral 220. The active matrix is ​​preferably an active matrix such as that included in the device of the present invention, for example, as shown in FIG. 1. Accordingly, reference numerals 100-108, 114-117 referring to elements or components of the active matrix 220 preferably have the same meaning as disclosed above with respect to FIG. 1. The array electrodes 115-117 may also be considered part of the active matrix.

[0133] The method of the present invention preferably includes the step of immersing said grid or matrix in a solution 200. In Figure 2, an active matrix 220 is immersed in a chemical bath 200.

[0134] The method of the present invention preferably includes the step of adding a substance of an organic electrochromic material to the solution. The substance is preferably an organic molecule that can be deposited by electrodeposition and / or polymerized by electropolymerization, preferably both. Preferably, the substance is a monomer of the organic electrochromic material 125-127.

[0135] In one embodiment, the substance of the organic electrochromic material is one or more monomers selected from the group consisting of polyviologen, polytriphenylamine, polythiophene, polypyridine, polypyrrole, polyaniline, polyimide, polymeric aromatic ketone, polyanthraquinone, polyamide, polynorbornene, polynorbornene-based compounds, polycarbazole, polythiocarbazole, and derivatives thereof.

[0136] In one embodiment, the monomers of these polymers may carry optional substituents, as disclosed elsewhere herein, which may be used to tailor the electrochromic properties of the resulting polymer. As indicated hereinabove, such substituents may be selected from organic substituents having 1 to 50 carbon atoms and 0 to 20 heteroatoms, preferably 1 to 20 carbon atoms and 0 to 10 heteroatoms, and most preferably 1 to 10 carbon atoms and 0 to 5 heteroatoms.

[0137] As set forth hereinabove, such substituents may be selected from aliphatic and aromatic substituents, esters and amines of aliphatic and aromatic moieties, in which one or more hydrogens may optionally be replaced by one or more selected from phosphonic acid (-PO(OH)2), boronic acid (-B(OH)2), -OH, -COOH, and -(CH2)n-Si(OR3)3. R3 is a C1-C10 alkyl, preferably a C1-C5 alkyl. Further embodiments as detailed hereinabove with respect to substituents apply to substituents included from the monomer moieties (e.g., C1-10 alkyl, N-oxide, dimethylamino, acetonitrile, benzyl, phenyl, benzyl mono- or di-substituted with nitro, phenyl mono- or di-substituted with nitro, and the substituents of formulas (1)-(9)).

[0138] It should be noted that the substances may be added to the solution 200 before, after, or simultaneously with the step of immersing the grid or matrix 220 in the solution. The solution may also be one that already contains the organic electrochromic material. Those skilled in the art will understand that the goal is to achieve the configuration shown schematically in Figure 2, whereby the order of addition of the components is generally irrelevant.

[0139] This also applies to the step of immersing the counter electrode 210 in the solution 200 according to the method of the present invention.

[0140] The above-described method feature may also be more generally referred to as providing a recipient 211 comprising an active matrix 220, a counter electrode 210, and a solution 200 containing substances (preferably monomers) of an organic electrochromic material, as illustrated in FIG. 2.

[0141] Preferably, the method of the present invention includes the step of applying a potential between some or all of the plurality of pixel electrodes 115 and the counter electrode 210, thereby providing deposition of the substance of the organic electrochromic material on the pixel or sub-pixel electrode 115. Preferably, the active matrix 220 is electrically connected to an external driver 209. Preferably, the counter electrode 210 is also electrically connected to the external driver 209, or possibly to another power source, or to an electrode terminal of the active matrix, as shown, for example, in US Pat.

[0142] The driver 209 is preferably configured to control the flow of current to and / or establish a desired potential between the pixel electrodes 115-117 and / or the counter electrode 210. Preferably, the driver 209 is capable of independently and individually addressing each active component 101, 102, 103 and thus each pixel or sub-pixel electrode 115, 116, 117. In another embodiment, the driver 209 is capable of independently and individually addressing one group 115 of a plurality of groups 115-117 of pixel or sub-pixel electrodes.

[0143] By applying a potential between all the pixel electrodes 115 to 117 and the counter electrode 210 in the solution, the organic material migrates to the pixel electrodes 115 to 117 and is electrodeposited and / or electropolymerized onto all the pixel electrodes.

[0144] In a preferred embodiment, the substance of the organic electrochromic material is a monomeric substance, and an organic electrochromic material is formed upon deposition of the monomeric portion onto the pixel electrode 115. Preferably, a polymeric organic electrochromic material is formed upon deposition of the monomeric portion.

[0145] In a preferred embodiment, the method of the present invention comprises electrodepositing and / or electropolymerizing the substance of the organic electrochromic material onto the pixel electrode 115 .

[0146] Preferably, the polymer is formed in situ, preferably on the respective pixel electrode or sub-pixel electrode as determined by the driving device.

[0147] In a preferred embodiment, the method includes providing an external driving device 209 configured to apply the potential between the plurality of pixel electrodes 115 and the counter electrode 210, thereby providing deposition of the substance of the organic electrochromic material on the plurality of pixel electrodes 115.

[0148] Preferably, the electrochromic properties of the electrodeposited organic electrochromic material and / or organic polymer electrochromic material 125-127 are those of materials obtained by electrodeposition and / or electropolymerization. The organic substances (e.g., monomers) added to the solution may or may not have electrochromic properties.

[0149] In one embodiment, the method of the present invention is for depositing different organic electrochromic materials on different pixel electrodes, e.g., on different subgroups of pixel electrodes. In this manner, it is possible to deposit electrochromic materials for color electrochromic devices, e.g., multicolor devices, and even full-color electrochromic devices, such as the RGB display disclosed in FIG. 1. For example, pixels may be grouped into subpixels, where a specific number of subpixels form a pixel, preferably three subpixels form a pixel, for example, according to the additive RGB principle discussed with respect to FIG. 1. In accordance with the present invention, electrochromic materials of a specific color may be deposited on only a portion of the pixel electrodes, preferably on the subpixel electrodes of a specific color (e.g., red, green, or blue).

[0150] In a preferred embodiment of the method, the grid, array or matrix comprises a plurality of subpixel electrodes 115-117, and the method includes providing an external driving device 209 configured to apply the potential between a first portion of the plurality of subpixel electrodes and the counter electrode 210, thereby providing deposition and / or electropolymerization of the organic electrochromic material only on the first portion of the plurality of subpixel electrodes 115.

[0151] In a preferred embodiment, a defined number of subpixels are designed to provide an individual pixel of the electrochromic device, and the first portion of the subpixel electrode encompasses only one or a portion of the subpixels of the individual pixel. For example, in a device using RGB additive color mixing, three subpixels may form one pixel.

[0152] For example, referring to FIG. 2, the driving device 209 may be controlled to apply a potential only between the pixel (or sub-pixel) electrode 115 and the counter electrode 210, but not between the pixels (or sub-pixels) 116 and 117 and the counter electrode, so that the organic electrochromic material is deposited only on the pixel electrode 115, and not on the other pixel electrodes 116 and 117.

[0153] An active matrix 220 is shown schematically in FIG. 2. There are a number of pixel (or subpixel) electrodes present in the active matrix, the number depending on the size and resolution of the display. In the embodiment detailed above, a pixel is formed by three subpixels, with reference numeral 115 indicating one subpixel electrode that will be present in one pixel in the final device, and reference numerals 116 and 117 indicating the other two subpixel electrodes. In this case, the active matrix preferably includes a number of subpixel electrodes 115 and an equal number of subpixel electrodes 116 and 117, with only one of the multiple subpixels shown in FIG. 2 for illustrative purposes. Therefore, in an embodiment of the method of the present invention, organic electrochromic material is deposited on all (sub)pixel electrodes 115, but not on the (sub)pixel electrodes 116 and 117 of the active matrix 220.

[0154] 2, reference numeral 115 may therefore represent a first portion of a pixel or subpixel electrode and therefore all pixels or subpixels in that portion. By analogy, reference numeral 116 may represent a second portion of a pixel or subpixel electrode, and reference numeral 117 may represent a third portion of a pixel or subpixel electrode.

[0155] For the avoidance of doubt, the present invention is not limited to a particular number of (sub)pixel electrode portions. Three pixel electrode portions are shown for illustrative purposes only. The present invention also encompasses electrochromic devices that consist of only one type of pixel electrode, where all pixels have the same organic electrochromic material and therefore the same color characteristics. The present invention also encompasses, for example, monochrome and / or black and white devices.

[0156] Every pixel electrode (or sub-pixel electrode) 115 may therefore represent a first portion or part of a pixel electrode onto which the substance of the organic electrochromic material is deposited.

[0157] Preferably, the deposition of the material is selected from the group consisting of electrodeposition, polymerization, electropolymerization, and a combination of two or more thereof. Preferably, the deposition of the material corresponds to deposition by electropolymerization. Preferably, the deposition of the organic material results in the deposition of the organic electrochromic material.

[0158] In embodiments in which the organic material is deposited on only a portion of a pixel electrode or subpixel electrode, the material is preferably a first material of first organic electrochromic material 125. The first organic electrochromic material preferably has a first color. Similarly, the solution containing the first material of the first organic electrochromic material is preferably a first solution.

[0159] It should be noted that the "first color" depends on the redox state of the first organic electrochromic material. The expression "first color" can be understood as a "first electrochromic color characteristic," and the same can be analogized to "second color" and "third color." Similarly, the expression "different color" is preferably understood as a "different electrochromic color characteristic." The "first color" can also be said to refer to a "first light-modulation characteristic," and the "second color" is understood to refer to a light-modulation characteristic that is different from the first light-modulation characteristic, particularly with respect to the color of light to be modulated.

[0160] In one embodiment, the method of the present invention comprises: Immersing the grid or matrix 220 in a second solution; adding a second substance of a second organic electrochromic material to the second solution, the second substance being different from the first substance and the second substance; applying an electric potential between second portions of the plurality of pixel or subpixel electrodes and the counter electrode 210, thereby providing a deposition of the second substance of the second organic electrochromic material 126 on the second portions of the plurality of pixel or subpixel electrodes; Including, The first and second organic electrochromic materials have different colors.

[0161] Regarding the deposition of the organic electrochromic material on the first portion of the pixel or subpixel electrode, the features of the step of immersing the grid or matrix in the second solution and the step of adding the second substance of the organic electrochromic material may be performed independently of each other. These features may be replaced by the step of "providing a solution containing the second substance, the grid or matrix 220, and the counter electrode 210." Preferably, at this stage, the first organic electrochromic material 125 has already been deposited on the first portion of the pixel or subpixel electrode.

[0162] Furthermore, applying a potential only across the second portion 116 of the pixel or sub-pixel electrode, and not on the first portion 115 and possibly on the third portion 117, is preferably achieved using an external driver 209.

[0163] The deposition of the second substance of the second organic electrochromic material 126 onto the second portions of the plurality of pixel or sub-pixel electrodes preferably results in electrodeposition and / or electropolymerization of the second organic electrochromic material, and thus the latter material is preferably formed by the electrodeposition and / or electropolymerization.

[0164] In one embodiment, the method includes rinsing the grid or matrix 220 prior to immersing the grid or matrix in the second solution, and preferably after removing the grid or matrix from the first solution.

[0165] In one embodiment, the method of the present invention comprises: immersing the grid or matrix 220 in a third solution; adding a third substance of a third organic electrochromic material 127 to the third solution; applying an electric potential between third portions 117 of the plurality of pixel or sub-pixel electrodes and the counter electrode 210, thereby providing a deposit of the third substance of the third organic electrochromic material 127 on the third portions 117 of the plurality of pixel or sub-pixel electrodes; Including, The first, second and third materials are all different from each other, and the first, second and third organic electrochromic materials 125-127 have different colors.

[0166] As detailed above with respect to the deposition of the second organic electrochromic material, the steps of immersing the grid or matrix in a third solution and adding the third organic electrochromic material may be performed independently of each other. These steps may be replaced by providing a solution containing the third material and the grid or matrix. Furthermore, applying a potential only between the pixel or subpixel electrodes 117 of the third portion, and not on the first portion 115 and the second portion 116, is preferably performed using an external driver 209.

[0167] In one embodiment, the method of the present invention includes the step of rinsing the grid or matrix prior to the step of immersing the grid or matrix in the third solution, and preferably after removing the grid or matrix from the second solution. The present invention also provides a method for fabricating an electrochromic device, preferably an electrochromic display, according to the present invention. To fabricate the device, an organic electrochromic material is deposited on an array (or pixel or subpixel) electrode according to the aspects and preferred embodiments disclosed herein. Further components of the device are then assembled. Such further components preferably include a counter electrode comprising an ion storage layer and an ion transport layer. Preferably, the device is provided with an active matrix, as disclosed with respect to the deposition of the organic electrochromic material. Other preferred components of the device are first and / or second substrates 100, 110. Such devices may be assembled conventionally.

[0168] For the avoidance of doubt, it should be noted that the terms pixel and subpixel are considered interchangeable, in that a reference to a pixel may encompass a reference to a subpixel. The term subpixel primarily pertains to multicolor or full-color devices in which three independently addressable elements are perceived by a human observer as a spot of a particular color when viewed from a certain distance from the device. In this manner, a particular color of a pixel may be produced by several distinct but spatially close subpixels. The distinction between pixel and subpixel does not necessarily imply any structural or other technical differences. In particular, in the figures, elements 105-107 are individually addressable elements having the structure described, regardless of whether the elements are considered "pixels," "subpixels," layered structures, arrangements, etc. Accordingly, the aforementioned terms may be used interchangeably to refer to structures 105-107. [Example]

[0169] (Manufacturing full-color electrochromic displays) A full-color electrochromic display based on the electropolymerization of red, green, and blue electrochromic materials on different subpixel electrodes is fabricated as described below.

[0170] (1. Preparation of the working electrode:) An active matrix thin film transistor (AM-TFT) backplane is used as the working electrode. Electrical connections are wired to provide different groups of subpixels that can be individually addressed. While a group of subpixels is being addressed, the channels of that group of subpixels are activated, allowing the desired voltage to be applied to the corresponding pixel electrode. For other groups of subpixels that are not addressed, the voltage of the pixel electrode is left floating and no current is supplied.

[0171] The AM-TFT backplane is inserted vertically into the tank facing an ITO glass substrate as the counter electrode (other examples include carbon felt or platinum mesh), which is filled with a solution containing monomers, electrolytes, and a solvent mixture suitable for forming an electrochromic organic polymer that is deposited on the pixel electrodes.

[0172] To achieve a full-color electrochromic display, red, green, and blue electrochromic polymers are sequentially electropolymerized onto one-third of the subpixel electrodes, so that each pixel contains three subpixels of red, green, and blue electrochromic polymer material.

[0173] To deposit the red electrochromic material, a 10 mM solution of 3,10-bis(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)-1-dodecyl-1H-phenanthro[1,10,9,8-c,d,e,f,g]carbazole (abbreviated as DEP) containing 0.1 M tetrabutylammonium hexafluorophosphite (TBAPF6) in acetonitrile was used. For electropolymerization, cyclic voltammetry was used. Using an Ag / AgCl standard reference electrode, the voltage between the red pixel electrode and the reference electrode was swept from -0.3 V to 1.1 V at a scan rate of 100 mV / s. The number of scan cycles was 10. During electropolymerization of the red electrochromic polymer, the desired voltage was applied only to the red subpixel electrode; the green and blue subpixel electrodes were left unaddressed. The AM-TFT backplane is removed from the tank, rinsed with deionized water, and then dried with compressed air or a nitrogen gun.

[0174] To deposit the green electrochromic polymer, a solution of 2 mM 5,8-bis(2,3-dihydro[3,4-b][1,4]dioxin-5-yl)-2,3-di(4-(hexadecyloxy)phenyl)quinoxaline (abbreviated as BOPEQ) containing 0.1 M TBAPF6 in acetonitrile / dichloromethane (volume ratio: 8 / 2) was used. Electropolymerization was performed using cyclic voltammetry with a sweep voltage of -0.6 V to 1.1 V, a scan rate of 100 mV / s, and 10 cycles. After the deposition process, the AM-TFT backplane was removed from the tank and washed and dried as described above.

[0175] For the deposition of the blue electrochromic polymer, use a solution of 1 mM 5,5'-(3,6-diphenylthieno[3,2-b]thiophene-2,5-diyl)bis(2,3-dihydrothieno[3,4-b][1,4]dioxin) containing 0.1 M TBAPF6 in acetonitrile / dichloromethane (volume ratio: 1 / 3). For the deposition by electropolymerization, use a sweep voltage of -0.8 V to 1.4 V, a scan rate of 100 mV / s, and 10 cycles.

[0176] 2. Preparation of antimony-doped tin oxide (ATO) paste: The ATO mesoporous membrane is used as the ion storage layer of the counter electrode. The ATO paste is prepared as follows.

[0177] 10.5 g of antimony-doped tin oxide (ATO) nanopowder (Alfa Aesar, particle size 13-22 nm) was suspended in ethanol (400 ml) and sonicated for 1 hour using a horn sonicator. The resulting colloidal solution was mixed with 33 g of ethyl cellulose solution (5% wt in 20:80 vol% ethanol:toluene) and 40 g of terpineol. The colloidal mixture was vigorously stirred for 30 minutes, after which the ethanol was removed under reduced pressure (max. 60 °C).

[0178] 3. Preparation of the counter electrode: An ITO substrate is used to prepare the counter electrode (an FTO substrate is used in another example). ATO paste is printed onto the ITO substrate by screen printing. After printing, the electrode is sintered at 450°C for 30 minutes at a slow heating rate of 10°C / min from room temperature to prevent cracking. The thickness of the sintered ATO mesoporous film is approximately 3 μm.

[0179] (4. Filling the electrolyte and assembling:) The electrolyte solution is prepared by mixing lithium bis(trifluoromethanesulfonyl)imide, 4-cyano-4'-pentylbiphenyl, and sulfolane in a weight ratio of 75:500:18. Assembly is performed using a standard single-drop filling device widely used in the liquid crystal display (LCD) industry. UV-curable adhesive is applied along the edge of the working electrode. A 10 μm-diameter spherical spacer is sprayed evenly onto the surface of the working electrode. A precise amount of electrolyte is precisely dispensed within the sealing adhesive frame. The amount of electrolyte is calculated to completely fill the gap volume between the working and counter electrodes. The counter electrode is then contacted with the sealing adhesive frame and secured with the spherical spacer. The adhesive is then cured by UV irradiation. This completes the full-color electrochromic display.

[0180] Although preferred embodiments of the present invention have been described and specifically exemplified above, it is not intended that the present invention be limited to such embodiments. Various modifications can be made thereto without departing from the scope and spirit of the present invention, as defined in the following claims. Examples of the present invention are disclosed herein below. These examples are for illustrative purposes only and are not intended to limit the scope of the present invention.

Claims

1. A full-color electrochromic device (1), comprising: a plurality of pixels, each pixel comprising first, second and third sub-pixels (105, 106, 107), each sub-pixel comprising a sub-pixel electrode (115-117) and an organic electrochromic material (125-127), the first sub-pixel (105) comprising a first electrochromic material (125), the second sub-pixel (106) comprising a second organic electrochromic material (126), and the third sub-pixel (107) comprising a third organic electrochromic material (127), the first, second and third organic electrochromic materials (125-127) having different colors; a first substrate (100) comprising an active matrix including conductive lines (104, 108) and active components (101, 102, 103) for providing current to the subpixel electrodes (115-117), wherein an active component (101, 102, 103) is provided for each of the subpixels (105-107), one active component (101) being electrically connected to one subpixel electrode (115), and a predetermined subpixel potential being established via the active component (101); a second substrate (110), said first and second substrates having opposing first and second outer surfaces (121, 122); one or more counter electrodes (111, 112) connected to said second substrate; an ion-conducting material (109) for transporting ions between the sub-pixels and the one or more counter electrodes (111, 112), the ion-conducting material (109) comprising one or more selected from the group consisting of at least one solvent, at least one anion and at least one cation; an ionic liquid; a liquid crystal; and an ionic liquid crystal, the ion-conducting material (109) being disposed within a common space, and at least three separate sub-pixels (105, 106, 107) being disposed within the common space and / or in contact with the continuous ion-conducting material (109); A full-color electrochromic device (1) comprising: The electrochromic device (1) is configured to establish an electric potential between any one particular subpixel (105-107) and the one or more counter electrodes (111, 112), and the first, second, and third organic electrochromic materials (125-127) are first, second, and third electrodeposited organic polymer electrochromic materials obtained by electropolymerization on the subpixel electrodes (115-117).

2. 2. The electrochromic device (1) of claim 1, further comprising an insulating layer (114) disposed between the first substrate (100) and the subpixel electrodes (115-117), the subpixel electrodes being deposited on the insulating layer, the active matrix comprising conductive vias (104) extending across the insulating layer, the conductive vias (104) being provided to connect individual active components (101, 102, 103) with individual subpixel electrodes (115, 116, 117).

3. 3. The electrochromic device (1) of claim 1 or 2, wherein the first sub-pixel (105) is made of an organic electrochromic material (125) that has a red color when exposed to a specific voltage, the second sub-pixel (106) is made of an organic electrochromic material (126) that has a green color when exposed to a specific voltage, and the optional third sub-pixel (107) is made of an organic electrochromic material (127) that has a blue color when exposed to a specific voltage.

4. 4. The electrochromic device (1) according to any one of claims 1 to 3, wherein the ion-conducting material (109) is provided within a common space, and a plurality of pixels are provided within the common space and / or are in contact with a continuous ion-conducting material (109).

5. The first, second and third electrodeposited organic polymer electrochromic materials (125 to 127) are selected from the group consisting of electrodeposited viologen, electrodeposited substituted viologen, electrodeposited triphenylamine, electrodeposited substituted triphenylamine, electrodeposited thiophene, electrodeposited substituted thiophene, electrodeposited 3,4-ethylenedioxythiophene, electrodeposited substituted 3,4-ethylenedioxythiophene, electrodeposited pyridine, electrodeposited substituted pyridine, electrodeposited aniline, electrodeposited substituted aniline, electrodeposited imide, electrodeposited substituted imide, electrodeposited aromatic ketone, electrodeposited substituted aromatic ketone, electrodeposited anthraquinone, electrodeposited substituted anthraquinone, electrodeposited amide, electrodeposited substituted amide, electrodeposited norbornene-based compound, electrodeposited substituted norbornene-based compound, electrodeposited carbazole, electrodeposited substituted carbazole, and electrodeposited thiocarbazole.

5. The electrochromic device (1) of claim 1, wherein the electrodeposited substituted viologen, electrodeposited substituted triphenylamine, electrodeposited substituted thiophene, electrodeposited substituted 3,4-ethylenedioxythiophene, electrodeposited substituted pyridine, electrodeposited substituted aniline, electrodeposited substituted imide, electrodeposited substituted aromatic ketone, electrodeposited substituted anthraquinone, electrodeposited substituted amide, electrodeposited substituted norbornene-based compound, electrodeposited substituted carbazole, electrodeposited substituted thiocarbazole, and electrodeposited substituted pyrrole comprise one or more substituents, the substituents being independently selected from organic substituents having 1 to 50 carbon atoms and 0 to 20 heteroatoms.

6. The first, second and third electrodeposited organic polymeric electrochromic materials (125-127) are selected from the group consisting of polyviologen, polymers of substituted viologen, polytriphenylamine, polymers of substituted triphenylamine, polythiophene, polymers of substituted thiophene, poly(3,4-ethylenedioxythiophene) (PEDOT), polymers of substituted (3,4-ethylenedioxythiophene) (PEDOT), polypyridine, polymers of substituted pyridine, polypyrrole, polymers of substituted pyrrole, polyaniline, polymers of substituted aniline, polyimide, polymers of substituted imide, polymeric aromatic ketone, polymers of substituted aromatic ketone, polyanthraquinone, polymers of substituted anthraquinone, polymeric heterocycle, polymers of substituted heterocycle, polyamide, 10. The electrochromic device (1) of claim 1, comprising one or more selected from the group consisting of polymers of substituted amides, polynorbornenes, polymers of substituted norbornenes, polycarbazoles, polymers of substituted carbazoles, polythiocarbazoles, and polymers of substituted thiocarbazoles, wherein the substituted viologens, substituted triphenylamines, substituted thiophenes, substituted 3,4-ethylenedioxythiophenes, substituted pyridines, substituted pyrroles, substituted anilines, substituted imides, substituted aromatic ketones, substituted anthraquinones, substituted heterocycles, substituted amides, substituted norbornenes, substituted carbazoles, and substituted thiocarbazoles comprise one or more substituents, the substituents being independently selected from organic substituents having 1 to 50 carbon atoms and 0 to 20 heteroatoms.

7. 7. The electrochromic device (1) of claim 5 or 6, wherein the substituents are independently selected from organic substituents having 1 to 20 carbon atoms and 0 to 10 heteroatoms.

8. The substituents are selected from aliphatic and aromatic substituents, esters and amines of aliphatic and aromatic moieties, and one or more hydrogens in the aliphatic or aromatic substituent or moiety are replaced by a phosphonic acid (-PO(OH) ２ ), boronic acid (-B(OH) ２ ), -OH, -COOH, -NH ２ , -NO ２ , aminoxide-N ＋ (R) ２ —O—), halogen and —(CH ２ ) ｎ -Si(OR ３ ) ３ and R and R ３ The electrochromic device (1) of claim 7, wherein is independently selected from C1 to C10 alkyl.

9. A method for depositing an organic electrochromic material (125-127) onto a pixel electrode (115) of an electrochromic device, comprising: providing an active matrix (220) comprising a first substrate (110), conductive lines (104, 108), active components (101, 102, 103) and a plurality of sub-pixel electrodes (115-117), said active matrix comprising a specific line (104) for each of said sub-pixel electrodes (115-117); - immersing said active matrix (220) in a first solution (200); adding a first monomeric material to the first solution; - immersing a counter electrode (210) in said first solution; - providing an external drive device (209); applying a potential between a first portion of the plurality of subpixel electrodes (115) and the counter electrode (210) to electropolymerize the first monomer material on the first portion of the plurality of subpixel electrodes (115), thereby depositing a first organic polymer electrochromic material having a first color on the first portion of the subpixel electrodes (115); - immersing the active matrix (220) in a second solution; adding a second monomeric material to the second solution; applying a potential between a second portion of the plurality of subpixel electrodes and the counter electrode (210) to electropolymerize the second monomer material on the second portion of the plurality of subpixel electrodes (116), thereby depositing a second organic polymer electrochromic material having a second color on the second portion of the subpixel electrodes (116); - immersing the active matrix (220) in a third solution; adding a third monomeric material to the third solution; applying a potential between a third portion of the plurality of subpixel electrodes and the counter electrode (210) to electropolymerize the third monomer material on the third portion of the plurality of subpixel electrodes (115), thereby depositing a third organic polymer electrochromic material having a third color on the third portion of the subpixel electrodes (117); Including, the first, second, and third monomeric materials are different from one another, the first, second, and third organic electrochromic materials have different colors, the first, second, and third portions of subpixel electrodes are different portions of an active matrix, and the pixel electrode is formed from three subpixel electrodes, each subpixel electrode being made of a different electrochromic material; The method further comprises assembling a counter electrode and an ionically conductive material (109) to provide the electrochromic device, the ionically conductive material (109) comprising one or more selected from the group consisting of at least one solvent, at least one anion, and at least one cation; an ionic liquid; a liquid crystal; and an ionic liquid crystal.

10. 10. The method of claim 9, further comprising rinsing the active matrix before immersing the active matrix in the second solution and after removing the active matrix from the first solution.

11. 11. The method of claim 9 or 10, comprising rinsing the active matrix before immersing the active matrix in the third solution and after removing the active matrix from the second solution.

12. 12. A method according to any one of claims 9 to 11, wherein the active matrix comprises thin film transistors (TFTs), and every sub-pixel of the electrochromic device comprises an individual TFT for controlling the flow of current to or from an individual sub-pixel electrode.

13. 13. The method of claim 9, wherein an insulating layer (114) is provided between the first substrate (100) and the sub-pixel electrodes (115-117), the sub-pixel electrodes being deposited on the insulating layer, and the active matrix comprises conductive vias (104) extending across the insulating layer, the conductive vias (104) being provided to connect individual active components (101, 102, 103) with their corresponding individual sub-pixel electrodes (115, 116, 117).

14. 9. An electrochromic device according to any one of claims 1 to 8, wherein there are no separating walls, components, boundaries and / or area components for electrically separating pixels and / or sub-pixels.

15. 10. The method of claim 9, wherein there are no separating walls, components, boundaries and / or area components for electrically isolating pixels and / or sub-pixels.

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