Electrochromic device and method of manufacturing the same

Abstract

The present invention relates to an electrochromic device, a method for depositing an organic electrochromic material and a method of producing an electrochromic device. The device is preferably an electrochromic display, preferably a full color electrochromic display. The device preferably comprises an electrodeposited organic electrochromic material and / or a polymerized organic electrochromic material.

Description

Technical Field

[0001] This invention relates to an electrochromic device, particularly an electrochromic display, a method for depositing organic electrochromic materials to provide pixels or subpixels of an electrochromic device, and a method for manufacturing an electrochromic device. Background Technology

[0002] Electrochromic devices utilize the unique properties of electrochromic materials. These materials (also known as electrochromophores) can reversibly alter their light absorption characteristics upon undergoing a redox reaction. Electrochromic devices typically employ a system of opposing electrodes and an electrolyte to control the reversible and repeatable oxidation and reduction of the electrochromic material and to adjust the desired color displayed by the device. The reduction or oxidation of the electrochromic material is achieved by applying a potential of appropriate amount and sign between the electrodes. Ion transport is mediated by the electrolyte to balance the charge at the electrodes.

[0003] It has been reported that many different types of materials exhibit electrochromic properties. Examples of inorganic materials include certain metal oxides, such as tungsten oxide (WO3). An example of an organic electrochromic compound is viologen. US2017 / 0192334 discloses various derivatives of viologen with different colors, particularly derivatives with red, green, and blue hues.

[0004] Electrochromic displays possess certain characteristics that distinguish them from other displays, such as liquid crystal displays (LCDs) or organic light-emitting diode (OLEDs). Electrochromic displays do not emit light themselves; instead, they reflect or transmit ambient light based on the color properties of the electrochromic materials. Therefore, electrochromic displays are sometimes referred to as "passive displays." Continuous use of electrochromic displays results in less eye strain compared to light-emitting, illuminated displays, such as the aforementioned LCDs and OLEDs. Compared to gaze-based luminance displays, gaze-based electrochromic displays correspond more closely to gazing at a printed medium (which reflects light from the environment).

[0005] Compared to LCD and OLED displays, electrochromic displays offer stronger contrast, especially under high ambient light. Furthermore, electrochromic displays naturally offer wider viewing angles, lower power consumption, and better light utilization efficiency. Therefore, electrochromic displays can be considered particularly advantageous for outdoor displays (under ambient light) and monitor-based reading (high contrast, less eye strain).

[0006] EP0084604, published in 1983, disclosed the use of an active matrix in electrochromic displays. The active matrix includes a grid of wires and thin-film transistors (TFTs), wherein the grid of wires is arranged in multiple rows and columns (XY matrix) to selectively supply current to any one of the TFTs, and is thus configured to establish a voltage between a specific electrode and a counter electrode that are electrically in contact with the transistor. In this configuration, electrochromic material is deposited on a specific electrode electrically connected to the drain disk of the TFT element. Since the 1980s, TFT panels or active matrices, such as those disclosed in this reference, have been commercialized and used to drive electroluminescent displays (EL) and LCDs. US2007 / 0171148 Figure 2 A also shows a scheme with an active matrix.

[0007] A full-color electrochromic display can be manufactured, for example, by providing red, green, and blue electrochromic materials on adjacent pixels, where each pixel (or sub-pixel) has its own electrode and can be specifically addressed by an active matrix. In this way, a red-green-blue (RGB) additive color mixing system can be provided, where three sub-pixels form one pixel. Such a device may include grid barriers to separate pixels from adjacent pixels.

[0008] WO2019 / 071733 discloses an example of an electrochromic display based on the RGB color mixing principle, providing red, green, and blue electrochromic materials to form sub-pixels separated by insulating separators, thereby achieving specific reduction / oxidation in the appropriate electrochromic (green, red, or blue) material and potentially avoiding crosstalk between sub-pixels. The electrolyte is not disclosed in this device, and it is difficult to understand how such a device is manufactured and whether it functions.

[0009] US2005 / 0270619 discloses another multicolor electrochromic display based on the cyan-magenta-yellow (CMY) subtractive color mixing principle, which discloses that the pixel elements include a stack of yellow, magenta, or cyan electrochromic layers. The materials in different electrochromic layers require different voltages to induce a color state, such that by adjusting the appropriate voltage through a pixel comprising three electrochromic layers, a color state can be induced in one, two, or all three electrochromic layers.

[0010] US 8,654,431 discloses a method for fabricating an active matrix electrochromic device. The method includes immersing a substrate containing an active matrix in a solution containing a metal oxide and forming an electrochromic metal oxide semiconductor layer by an electrophoretic process. Organic electrochromic materials can also be adsorbed onto the surface of the electrochromic semiconductor layer. This reference requires the presence of a unit for separating the electrolyte of any pixel electrode from the electrolyte of any other pixel electrode. For this purpose, bank or wall structures for separating pixels are provided. The bank structures are also used to cover active material-based transistors. The document does not mention how the organic electrochromic material is deposited.

[0011] US 2007 / 0171148 discloses the deposition of an organic electrochromic material (4,4'-bipyridinium derivative) as a self-assembled monolayer from solution deposition. US 8,687,262 discloses the deposition of an organic electrochromic compound by spin coating.

[0012] More typically, as shown in US2005 / 0270619, CMY subtractive color mixing requires stacking three electrochromic layers and a separator layer between them. The manufacturing process is quite complex. Furthermore, the performance is reduced by the loss of light intensity due to the stacked layers.

[0013] Regarding RGB additive color mixing, each pixel consists of three sub-pixels, and its electrochromic layer should reflect or transmit red, green, and blue light respectively. To fabricate full-color electrochromic devices using this color mixing principle, it is generally recommended to use grid barriers to separate pixels and additional patterning processes (typically including photolithography) for the three different electrochromic materials. This also makes the manufacturing process complex and expensive.

[0014] EP1347330A1 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. In one example, the document discloses the electrodeposition of black polypyrrole on an ITO thin film.

[0015] US 5,189,549 discloses an electrochromic device comprising a pair of electrodes arranged side-by-side, facing upwards on a substrate. The two electrochromic materials deposited as a pair of electrodes are complementary. In the fabrication of these specific devices, a busbar and electrodes are deposited on the substrate, and an encapsulation layer is deposited in several steps to protect the busbar from subsequent fabrication steps. Regarding the electrochromic materials, the document generally uses a variety of material combinations, including WO3 electrode pairs combined with the deposition of poly(3-methylthiophene).

[0016] JP2003315840 A discloses a full-color EC display in which a nanoporous semiconductor layer is deposited on electrodes, and an electrochromic (EC) dye is adsorbed onto the nanoporous layer. Regarding the nanoporous semiconductor material, oxide semiconductors are primarily mentioned, but compound semiconductors, such as CuGaS2, are also disclosed, which can be formed by electrolytic deposition. The EC dye is said to be adsorbed via any of several methods, including electric field polymerization.

[0017] The object of this invention is to provide a full-color electrochromic device that can be obtained through a simple manufacturing method involving very few steps. It also aims to provide an electrochromic device with a fast response time and ideally avoids crosstalk between adjacent electrodes or pixels, as well as the inconveniences of solid electrolytes. Furthermore, it aims to provide an electrochromic device that can be implemented using an active matrix.

[0018] The present invention solves the above-mentioned problems and objectives. Summary of the Invention

[0019] On one hand, the present invention provides an electrochromic device comprising an organic electrochromic material, wherein the organic electrochromic material is selected from polymeric organic electrochromic materials, electrodeposited organic electrochromic materials, and both.

[0020] On one hand, the present invention provides an electrochromic device comprising an active matrix containing active components and electrodes connected to the active components, wherein the device further comprises an organic electrochromic material deposited to make electrical contact with the electrodes, wherein the organic electrochromic material is selected from polymeric organic electrochromic materials, electrodeposited organic electrochromic materials, and both.

[0021] On one hand, the present invention provides an electrochromic device comprising pixels and / or subpixels, wherein the pixels and / or subpixels comprise polymeric organic electrochromic materials.

[0022] On one hand, the present invention provides an electrochromic device including pixels, wherein the pixels and / or subpixels include organic electrochromic materials deposited by electrodeposition and / or electropolymerization.

[0023] On one hand, 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 electrode, and wherein the organic electrochromic material is a polymeric organic electrochromic material and / or wherein the organic electrochromic material is an electrodeposited organic electrochromic material.

[0024] On one hand, 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 transferring charge between the first electrode and the counter electrodes; wherein the electrochromic device is configured to establish a potential between the first electrode and the one or more counter electrodes, wherein the organic electrochromic material is an electrodeposited organic electrochromic material and / or preferably an organic polymer electrochromic material obtained by electropolymerization.

[0025] On one hand, the present invention provides an electrochromic device, comprising:

[0026] - Multiple pixels, wherein each pixel includes a pixel electrode and an organic electrochromic material, the organic electrochromic material being in electrical contact with the pixel electrode;

[0027] - Includes a grid or matrix of wires for supplying current to the pixel electrodes;

[0028] - One or more counter electrodes; and

[0029] - An ion-conducting material for transporting ions between the pixel and the one or more counter electrodes;

[0030] The electrochromic display is configured to establish a potential between any specific pixel electrode and the one or more counter electrodes, wherein the organic electrochromic material is an electrodeposited organic electrochromic material and / or preferably an organic polymer electrochromic material obtained by electropolymerization.

[0031] On one hand, the present invention provides a method for depositing an organic electrochromic material to make electrical contact with an array electrode and / or a pixel electrode, comprising the steps of electrodepositing the organic electrochromic material and / or electropolymerizing the organic electrochromic material to make electrical contact with the array electrode and / or the pixel electrode.

[0032] On one hand, the present invention provides a method for depositing an organic electrochromic material on a pixel electrode of an electrochromic device, the method comprising: providing a grid or matrix including wires and a plurality of pixel electrodes, wherein each of the pixel electrodes has a specific wire; immersing the grid or matrix in a solution; adding an entity 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 providing deposition of the entity of the organic electrochromic material on the pixel or sub-pixel electrode.

[0033] In some aspects, the present invention provides a method for producing electrochromic devices, particularly electrochromic devices, the method comprising depositing an organic electrochromic material on an array and / or pixel electrode according to the present invention.

[0034] On one hand, the present invention provides a method for producing 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 the electrochromic device.

[0035] Other aspects and preferred embodiments of the invention are defined below and in the appended claims. Other features and advantages of the invention will be apparent to those skilled in the art from the description of the preferred embodiments given below.

[0036] Preferred embodiments of the device of the present invention will now be described to illustrate the invention, but are not intended to limit the scope of the invention. Attached Figure Description

[0037] Figure 1 An embodiment of the electrochromic display of the present invention is illustrated schematically;

[0038] Figure 2 The illustration shows the deposition of an organic electrochromic material on a pixel electrode according to an embodiment of the present invention. Detailed Implementation

[0039] This invention relates to electrochromic devices. Preferably, the electrochromic device comprises and / or is substantially composed of an electrochromic display.

[0040] Figure 1 A portion of an electrochromic display 1 is schematically shown. The display 1 is generally flat and includes two first and second support structures or substrates 100, 110, defining opposing first and second outer surfaces 121, 122. One or both substrates 100, 110 may be at least partially transparent. For example, the substrates may comprise glass and / or at least partially transparent plastic. Of course, at least one of the two substrates needs to be transparent so that the device can be used as a display.

[0041] In this specification, the word "comprising" is intended to mean "among others, including," and does not mean "consisting only of."

[0042] A wire 108 (commonly referred to as a "conductor") is disposed on the inner surface of the first substrate 100. The wire is conductive. The conductor will connect the external actuator ( Figure 1 (Not shown) is electrically connected to the active components 101-103 of the display.

[0043] Active components 101-103 and conductor 108 are preferably electrically insulated and protected by an electrical insulating layer 114 deposited on the active components and conductor 108. Conductor 108 is preferably provided with multiple wires forming a grid or matrix.

[0044] In one embodiment, the electrochromic device includes an insulating layer 114 disposed between the first substrate 100 and the sub-pixel electrodes 115-117, wherein the active matrix includes conductive vias 104 extending through the insulating layer, wherein the vias are provided to connect individual active components 101, 102, 103 to individual sub-pixel electrodes 115, 116, 117. Preferably, the pixel or sub-pixel electrode is deposited on the insulating layer.

[0045] In one embodiment, the active component 101 is preferably a transistor, such as a thin-film transistor (TFT), or a TFT-based circuit. In summary, all active components 101-103 can be a TFT array or TFT-based circuit electrically connected to the pixel electrodes 115-117 of the display. The conductors 108 and active components 101-103 are preferably provided as a grid, array, or matrix, which may be referred to as an "active matrix." It is noteworthy that the conductors 108 are preferably arranged in such a way that each active component 101-103 can be addressed individually and / or independently. Preferably, each active component 101-103 can be provided with current and / or exposed to a voltage potential individually and / or independently, for example as in EP0084604 (FIG. 3) and US 2007 / 0171148 (FIG. 3). Figure 2 As disclosed in A).

[0046] Typically, each active component 101-103 includes a gate electrode, a source electrode, and a drain electrode. Typically, the cathode of each array electrode 115-117 or each pixel is preferably connected to the drain electrode via a via 104. The via 104 is also conductive and can be considered as a conductive connection between the active components disposed on the first substrate and the pixel electrodes 115-117 disposed on the insulating layer 114, such that the via provides connection between different layers of the device, particularly between opposing surfaces of the insulating layer 114.

[0047] It is important to note that the term "active matrix" should not be confused with the concept of an electrochromic display, which is a "passive display." A passive display refers to an electrochromic display that typically does not produce light but includes electrochromic materials that can be controlled to have a specific color and thus reflect light of that specific color. The term "active matrix" refers to an electronic matrix comprising wires 108 for supplying current to array electrodes and / or pixels and / or exposing pixels to a voltage potential, and active components 101-103.

[0048] In one embodiment, the grid, array, and / or matrix includes an active matrix.

[0049] The active matrix preferably includes active components 101-103, wherein an active component 101, 102, 103 is provided for each array electrode 115-117 and / or for each pixel 105-107, wherein one active component 101-103 is electrically connected to a pixel electrode 115-117, and wherein a predetermined pixel potential is established through the active component 101.

[0050] In one embodiment, the grid, array, and / or matrix includes thin-film transistors (TFTs), wherein each pixel or sub-pixel of the electrochromic device includes at least one TFT for controlling the flow of current to or out of the pixel or sub-pixel electrode.

[0051] In this specification, the terms "pixel electrode" and "array electrode" are used interchangeably, referring to the same structural features 115-117. Similarly, the term "array electrode" may also replace the term "sub-pixel electrode" disclosed elsewhere in this specification.

[0052] Figure 1 The display shown preferably includes a plurality of pixels 105-107. Preferably, each pixel includes a pixel electrode 115-117 and an electrochromic material 125-127. The electrochromic material preferably includes or is composed of an organic electrochromic material 125-127.

[0053] Preferably, the organic electrochromic material 125-127 is in electrical contact with the pixel electrode 115-117.

[0054] In this specification, the term "electrical connection" or "electrical contact" refers to the stable flow of current (electrons, holes) between electrically connected objects under a fixed potential difference.

[0055] In one embodiment, pixel electrodes 115-117 are preferably at least partially transparent to visible light. In one embodiment, pixel electrodes 115-117 comprise a transparent conductive material, preferably a transparent conductive oxide (TCO), and / or are substantially composed of the same, which may be selected from, for example, 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).

[0056] In a preferred embodiment, pixel electrodes 115-117 also include a nanostructure layer, preferably deposited on the conductive material, preferably a transparent conductive material as listed above (ITO, FTO, etc.), and / or on top of it. Preferably, organic electrochromic material 125-127 is deposited on the nanostructure layer. The nanostructure layer may comprise a metal oxide material. The nanostructure layer may comprise a semiconductor and / or conductive material. The nanostructure layer may be nanoporous. Preferably, the nanostructure layer may be selected from, for example, TCO (ATO, ITO, SnO, ZnO, etc.) as exemplified above, or may be selected from titanium dioxide (TiO2).

[0057] In one embodiment, the first pixel 105 includes a first pixel electrode 115 and a first electrochromic material 125; the second pixel 106 includes a second pixel electrode 116 and a second electrochromic material 126; the third pixel 107 includes a third pixel electrode 117 and a third electrochromic material 127; similarly, the nth pixel includes an nth pixel electrode and an nth electrochromic material. Preferably, the electrochromic material comprises or is composed of organic materials, as further detailed elsewhere in this specification.

[0058] When considering an overall electrochromic device comprising numerous pixels and / or subpixels, reference numerals 105, 106, and 107 can also be used to refer to the first, second, and third portions of a pixel or subpixel, respectively. Similarly, reference numerals 115, 116, and 117 can be understood as the first, second, and third portions of a pixel (or subpixel or array) electrode.

[0059] Electrodes 115-117 of each pixel 105-107 are electrically connected to active components 101-103 provided for a specific electrode via via 104. For example, via 104 passes through a protective layer and / or an insulating layer 114 to electrically connect an active component to its corresponding pixel electrode.

[0060] Although Figure 1 Three pixels 105-107 are shown, but it will be understood that the device of the present invention preferably includes more pixels. Three pixels are shown for illustrative purposes.

[0061] In one embodiment, electrochromic materials 125-127 are disposed on top of the corresponding pixel electrodes 115-117, that is, the first electrochromic material 125 is disposed on top of the first pixel electrode 115, and so on.

[0062] In one embodiment, pixel electrodes 115-117 are disposed in layers, for example, deposited.

[0063] In one embodiment, electrochromic materials 125-127 are disposed, for example, deposited as layers.

[0064] In one embodiment, an electrochromic material 125-127 is disposed, preferably deposited, to cover the pixel electrodes corresponding to pixels 105-107. Preferably, the pixel electrodes are completely covered by the electrochromic material. Preferably, the pixel electrode material 115-117 does not contact the ion transport material 109. If the pixel electrodes are completely surrounded or covered by the electrochromic material, the charge injection efficiency for coloring or fading may be higher. However, the device should also function if the pixel electrodes are not completely covered and / or include surfaces in contact with the ion transport layer.

[0065] As can be understood, the electrochromic material associated with the corresponding pixel electrode is in electrical contact with that pixel electrode, and preferably only in electrical contact with the corresponding pixel electrode. For example, the first electrochromic material 105 is in electrical contact with the first pixel electrode 115, and preferably in physical contact, and so on.

[0066] As can be understood, the electrochromic material associated with the corresponding pixel electrode is preferably in direct physical contact with the pixel electrode, and preferably only in contact with the corresponding pixel electrode. This is preferably the result of the electrochromic material being directly deposited on the corresponding pixel electrode, as will be described in more detail elsewhere in this specification.

[0067] The device 1 of the present invention preferably includes 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.

[0068] In one embodiment, at least one counter electrode 120 is preferably at least partially transparent to visible light. In one embodiment, at least one counter electrode 120 comprises a transparent conductive material, such as a transparent conductive oxide (TCO), and / or is substantially composed of such a material, which may be selected from, for example, 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 of the present invention, preferably on the inner surface of the second substrate 110.

[0069] In a preferred embodiment and as Figure 1 As shown, the counter electrode 120 includes a conductive layer 111.

[0070] In a preferred embodiment and as Figure 1 As shown, the counter electrode 120 includes an ion storage layer 112.

[0071] In a preferred embodiment, the counter electrode 120 includes a conductive layer 111 and an ion storage layer 112.

[0072] The device 1 of the present invention preferably includes at least one ion storage layer 112. In one embodiment, the ion storage layer 112 is deposited on a conductive layer 111. In one embodiment, the ion storage layer 112 includes a porous structure, preferably a nanoporous and / or nanocrystalline structure, or is substantially composed of the latter. Preferably, the porous structure allows electrolyte to permeate into the bulk, and ions can accumulate at the surface of the porous structure, preferably also within the bulk of the ion storage layer. In other embodiments, the ion storage layer may be a dense and / or non-porous layer. It is contemplated that a dense ion storage layer has less total surface area for ion accumulation, and therefore a lower total storage capacity. However, devices including a dense ion storage layer can also function.

[0073] Preferably, the ion storage layer 112 is provided to have an appropriate ion storage capacity. The ion storage layer can be selected from the group consisting of conductive inorganic materials with high surface area, such as mesoporous structures, nanowires, and nanotubes. The ion storage layer 112 typically includes or is substantially composed of a doped metal oxide, such as antimony tin oxide (ATO). The ion storage layer 112 can also be selected from the group consisting of conductive polymers with porous structures, or from the group consisting of conductive mixtures of inorganic and organic materials.

[0074] In one embodiment, the device 1 of the present invention preferably includes 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 configured to realize and / or mediate the transport of ions, such as charged molecules or other (e.g., metal) ions. The ions can be cations or anions. The ions can be organic or inorganic.

[0075] Therefore, the ion-conducting material 109 is preferably an electrolyte layer and / or an electrolyte, such as an electrolyte containing dissolved ions and / or an ionic liquid. In a preferred embodiment, the ion-conducting material 109 may be selected from, for example, liquid electrolytes, gel electrolytes, ionic liquids, and eutectic melts.

[0076] In one embodiment, the ion transport material 109 comprises one or more cations selected from lithium, sodium, potassium, alkylimidazolium, alkylpyridinium, alkylphosphonium, alkylammonium, and tetrabutylammonium. Preferably, the alkyl group is a C1-C20 alkyl group, more preferably a C1-C10 alkyl group, most preferably a C1-C4 alkyl group, such as methyl.

[0077] In one embodiment, the ion transport material 109 comprises a salt of any of the aforementioned cations.

[0078] In one embodiment, the ion transport material 109 comprises one or more components selected from bis(trifluoromethanesulfonyl)imide or TFSI ([(CF3SO2)2N]). - ), perchlorate (ClO4)- ), tetrafluoroborate (BF4) - It is an anion of phosphophosphate (PF6-) or hexafluorophosphate (PF6-).

[0079] In one embodiment, the ion transport material 109 comprises a salt of any of the anions described above.

[0080] In one embodiment, the ion transport material 109 comprises one or more salts including at least one of the above-described anions and at least one of the above-described cations.

[0081] In a particular embodiment, the ion transport material 109 includes one or more selected from LiTFSI, LiClO4, LiBF4 or LiPF6.

[0082] In one embodiment, the ion transport material 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 solvents. It is noteworthy that in some electrolytes, such as ionic liquids (also called ionic melts or liquid salts), a separate solvent may not be present, as the ionic liquid acts as both a solvent and provides ions for ion transport.

[0083] In one embodiment, the ion transport material 109 comprises at least one solvent, at least one anion, and at least one cation. In another embodiment, the ion transport material 109 comprises at least one or more salts selected from at least one of the aforementioned cations and at least one of the aforementioned cations, and optionally, preferably, a solvent selected from the aforementioned solvent.

[0084] In one embodiment, the electrolytic layer 109 may be a liquid, a gel, or a solid.

[0085] In a preferred embodiment, the electrolytic layer 109 preferably comprises liquid crystal or ionomer liquid crystal and / or is substantially composed of it. Such liquid crystal and / or ionomer liquid crystal is advantageous because it can help reduce crosstalk effects between pixels.

[0086] In one embodiment, ion-conducting material 109 is disposed within a common space, wherein a plurality of pixels and / or sub-pixels 105-107 are preferably disposed within said common space and / or in contact with continuous and / or homogeneous ion-conducting material 109 preferably disposed within said continuous space. This in Figure 1 As shown in the figure, reference numeral 109 also refers to the common space, as the space is filled with ion-conducting material 109, preferably the electrolyte as disclosed herein.

[0087] The ion-conducting material preferably has consistent and / or unchanging electrical properties within the common continuous space.

[0088] In one embodiment, the device of the present invention includes an insulating layer 114 for electrically isolating the ion-conducting material 109 from the grid or matrix including conductive lines 104, 108 and / or from the active components 101-103 (if present).

[0089] Preferably, the device of the present invention does not include separator walls or separator components for separating pixels and / or subpixels. Preferably, the device lacks separator walls, components, boundary and / or region components for separating pixels and / or subpixels. Such separation is provided in the prior art to electrically isolate adjacent pixels and / or adjacent subpixels, primarily to avoid crosstalk between electrodes. The aforementioned separator elements can be used in the prior art to prevent continuous ion-conducting material from contacting different, for example, adjacent pixels.

[0090] Among other things, this feature distinguishes the device of the present invention from prior art devices, such as those disclosed in WO2019 / 071733, US 8,654,431, US2017 / 0192334, etc., in which pixels (or sub-pixels) are separated by partition walls and each pixel (or sub-pixel) contains its own confined electrolyte.

[0091] Preferably, the continuous conductive material 109 (e.g., an electrolyte) is in physical contact with several different, for example, adjacent pixels and / or adjacent array electrodes 115-117. In one embodiment, the ion-conducting material 109 (e.g., an electrolyte) is in physical contact with electrochromic materials 125-127 deposited on different, preferably adjacent, array electrodes 115-117. The use of the ion-conducting material 109 preferably prevents crosstalk during device operation.

[0092] In a preferred embodiment, the ion-conducting material 109 comprises liquid crystal. US 8,687,262 discloses the use of liquid crystal to avoid crosstalk between pixels. In one embodiment, the ion-conducting material 109 comprises an electrolyte and a low-molecular-weight liquid crystal material as disclosed in US 8,687,262.

[0093] Although conductive materials 105-107 are designated as pixel electrodes, it is correct to consider the pixel (or sub-pixel or array) electrodes 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" used herein with respect to the structure enclosed by reference numerals 105-107 can also be understood as a pixel electrode or a first electrode, since the entire structure 105 can be considered as an electrode.

[0094] Alternatively, all pixels 105-107 can be considered as a whole (including up to n pixels not shown) as the first electrode, and the combination of layers 111 and 112 can be considered as the counter electrode 120. Therefore, the present invention includes different terms or names used in the literature to indicate electrodes and counter electrodes.

[0095] The invention also includes the possibility of providing an electrochromic material on or in the counter electrode 120, or in electrical and / or physical contact with the counter electrode 120, more specifically with the ion storage layer 112. For example, the electrochromic material deposited on or as part of the counter electrode 120 may be selected from, for example, inorganic and / or organic materials disclosed in US 2007 / 0192334. The electrochromic material may also be a component and therefore included in the counter electrode. This electrochromic material is preferably different from the electrochromic materials 125-127 typically disclosed herein and associated with the pixel electrodes 115-117.

[0096] In a preferred embodiment, the electrochromic materials 125-127 comprise one or two, or substantially comprise, selected from the group consisting of: electrodeposited organic electrochromic materials and organic polymer electrochromic materials.

[0097] In one embodiment, the electrochromic materials 125-127 comprise organic or mixed materials, including one or more selected from the electrodeposited organic electrochromic materials and / or organic polymer electrochromic materials. In this specification, "mixed material" encompasses a material containing one or more inorganic materials and one or more organic materials. In the case of mixed materials, the organic electrochromic material preferably provides at least one organic component of the mixed material.

[0098] In one embodiment, the electrodeposited organic electrochromic material and / or organic polymer electrochromic material is preferably selected from doped and / or undoped organic materials. If the organic material is doped, it may include non-organic components or additives, such as metal ions, organometallic materials, and composite materials.

[0099] In a preferred embodiment, the electrodeposited organic electrochromic material and / or organic polymer electrochromic material is obtained by electropolymerization.

[0100] In one embodiment, the electrodeposited organic material comprises one or more selected from electrodeposited heterocycles. The heterocycle may or may not be aromatic. Examples of heterocycles are viologen, thiophene, pyridine, anthraquinone, imide, pyridine, and derivatives thereof, particularly compounds comprising these structures and optionally further comprising substituents detailed below. Electrochromic materials may comprise organic materials obtained by electropolymerization of heterocyclic compounds and their derivatives. Electrochromic materials may comprise polymerized heterocycles.

[0101] In a preferred embodiment, the electrodeposited organic materials 125-127 comprise one or more selected from the group consisting of: electrodeposited viologen, electrodeposited triphenylamine, electrodeposited thiophene, electrodeposited 3,4-ethylenedioxythiophene, electrodeposited pyridine, electrodeposited aniline, electrodeposited imide, electrodeposited aromatic ketone, electrodeposited anthraquinone, electrodeposited amide, electrodeposited norbornene-based compounds, electrodeposited carbazole, electrodeposited thiocarbazole, electrodeposited pyrrole, and derivatives of the electrodeposited compounds. Derivatives of the compounds particularly include those compounds in which one or more hydrogen atoms may optionally be substituted with substituents, such as those described below.

[0102] In one embodiment, the electrochromic materials 125-127 can be formed by electropolymerization of, for example, viologen, triphenylamine, thiophene, 3,4-ethylenedioxythiophene, pyridine, pyrrole, aniline, imide, aromatic ketone, anthraquinone, amide, norbornene, carbazole, and thiocarbazole, including any one or more of the above derivatives. Derivatives of the compounds shown particularly include those compounds in which one or more hydrogen atoms are optionally substituted by substituents as described below.

[0103] In one embodiment, the electrochromic materials 125-127 can be formed by electropolymerization of, for example, viologenyl compounds, triphenylamineyl compounds, thiopheneyl compounds, 3,4-ethylenedioxythiopheneyl compounds, pyridyl compounds, pyrroleyl compounds, anilineyl compounds, imideyl compounds, aromatic ketoneyl compounds, anthraquinoneyl compounds, amideyl compounds, norborneneyl compounds, carbazoleyl compounds, and thiocarbazoleyl compounds.

[0104] As used in this specification, the terms "-based compound" or "-based organic material" refer to structures including the compounds or materials shown and their derivatives, wherein the derivatives include the basic structure of the compounds or materials shown. For example, such compounds may further include one or more optional substituents as shown below. For example, "violin-based compound" preferably includes compounds having the basic structure of viologen, but may also include one or more substituents that may affect the color and / or electrochromic properties or characteristics of the compound.

[0105] In a preferred embodiment, the polymeric organic materials 125-127 comprise one or more selected from the group consisting of polyvioletin, polytriphenylamine, polythiophene, poly(3,4-ethylenedioxythiophene) (PEDOT), polypyridine, polypyrrole, polyaniline, polyimide, polyaromatic ketone, polyanthraquinone, polyamide, polynorbornene, polycarbazole, polythiocarbazole and their derivatives.

[0106] In one embodiment, the polymeric organic materials 125-127 include one or more selected from the group consisting of polyviolet-based organic materials, polytriphenylamine-based organic materials, polythiophene-based organic materials, polypyridyl-based organic materials, polypyrrole-based organic materials, polyaniline-based organic materials, polyimide-based organic materials, polyaromatic 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.

[0107] An example of polythiophene-based organic materials is poly(3,4-ethylenedioxythiophene) (PEDOT)-based organic materials.

[0108] As noted, derivatives of the aforementioned materials are also included. For example, the expression "electrodeposited viologen" includes electrodeposited viologen derivatives, which include the basic structure of viologen and one or more optional substituents. "Polyvioletin" includes polymers of monomers that include the basic structure of viologen and may be derived viologens, thereby containing, for example, one or more optional additional substituents. For example, US20070171148 discloses viologen derivatives in which substituents of the basic viologen structure can be selected to provide viologen derivatives with specific color properties.

[0109] The optional substituents of the above-mentioned organic materials, particularly the exemplary electrodeposition materials, and the polymeric organic materials may be selected from organic substituents comprising 1-50 carbon atoms and 0-20 heteroatoms, preferably 1-20 carbon atoms and 0-10 heteroatoms, and most preferably 1-10 carbon atoms and 0-5 heteroatoms.

[0110] In some embodiments, the substituents may be selected from aliphatic and aromatic substituents, aliphatic and aromatic moieties of esters and amines, wherein in said aliphatic or aromatic substituents or moieties, one or more hydrogens are optionally independently selected from phosphonates (-PO(OH)2), boric acid (-B(OH)2), -OH, -COOH, -NH2, -NO2, amine oxides (-N + (R)2-O - ), halogens and –(CH2) n One or more substitutions of -Si(OR3)3. R and R3 are independently selected from C1-C10 alkyl groups, preferably C1-C5 alkyl groups.

[0111] It is worth noting that the substituted hydrogen may be hydrogen attached to carbon or a heteroatom, such as nitrogen in a basic organic material as described above. If the substituent includes a C- atom attached to the heteroatom, the latter is preferred.

[0112] In one embodiment, the substituent is selected from straight-chain or branched alkyl, alkenyl, alkylaryl, and alkylarylalkyl (e.g., alkylphenylalkyl, e.g., alkylbenzyl), wherein one or more hydrogens are optionally independently selected from -PO(OH)2, -B(OH)2, -OH, -COOH, -NH2, -NO2, amine oxide (-N) + (R)2-O - ), halogens and –(CH2) n One or more substitutions of -Si(OR3)3. R and R3 are independently as defined above.

[0113] In one embodiment, the optional substituents of the above-mentioned organic material can be independently selected from:

[0114] C 1-10 Alkyl, N-oxide, dimethylamino, acetonitrile, benzyl, phenyl, benzyl mono- or di-substituted with nitro, phenyl mono- or di-substituted with nitro, and substituents selected from formulas (1)-(9):

[0115]

[0116] Where n and m are independent integers from 1 to 10.

[0117] R1-R3 are independently selected from C1-C10 alkyl groups.

[0118] R4-R6 are independently selected from hydrogen, C1-C10 alkyl, C2-C10 alkylene, aryl, substituted aryl, halogen, nitro and -OH, and wherein the dashed line represents a single bond connected to the basic structure of the organic material, compound or monomer shown by its substituent, if applicable.

[0119] Substituent (8) is an example of a substituent that includes an ester, which includes both aliphatic and aromatic moieties.

[0120] The electrochromic material preferably has a specific color depending on the oxidation state of the material. In some embodiments, the electrochromic material is colorless in a first oxidation (or redox) state and has a specific color (preferably red, green, or blue) in a second oxidation state. In the device of the present invention, the oxidation state of the electrochromic material is preferably controlled by the voltage exposed to the arrangement of the pixel electrode and the counter electrode. Alternatively, the current flowing 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, thereby imparting it with the desired color at a particular moment. The current is preferably a result of the voltage applied to the pixel electrode and the counter electrode arrangement within the device. The ion flow within the ion transport material 109 preferably balances the accumulated charge at the two electrodes.

[0121] These electrodeposited and / or polymerized organic electrochromic materials are preferably deposited according to the methods of the present invention, as disclosed in more detail elsewhere in this specification.

[0122] 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, particularly a multicolor electrochromic display, most preferably a full-color electrochromic display.

[0123] In one embodiment, the color characteristics of the device are provided at least in part by organic electrochromic materials of different colors present. In a preferred embodiment, adjacent pixels, preferably sub-pixels, comprise electrochromic materials of different colors, preferably red, green, and blue (RGB colors).

[0124] Preferably, the device of the present invention is based on RGB color mixing.

[0125] refer to Figure 1 Considering a color device, one of pixels 105-107 preferably includes a red electrochromic material, one preferably includes a green electrochromic material, and one preferably includes a blue electrochromic material. As described above, the electrochromic material preferably includes a polymeric organic electrochromic material and / or an electrodeposited organic electrochromic material and / or is substantially composed of therein.

[0126] 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.

[0127] In a full-color device, pixels 105-107 can be considered subpixels, which preferably provide a pixel and / or color together through superimposed RGB color mixing. In this case, subpixels 105-107 form a pixel of the electrochromic device. In this case, each subpixel includes subpixel electrodes 115-117, for example, the first subpixel 105 includes a first subpixel electrode 115, the second subpixel 106 includes a second subpixel electrode 116, and the third subpixel 107 includes a third subpixel electrode 117.

[0128] Preferably, the sub-pixels 105-107 forming the pixels have the structure described above and / or are made of the materials described above. For example, the sub-pixel electrodes 115-117 may include the nanostructure layers detailed above. Preferably, the electrochromic material of the sub-pixels includes organic electrodeposited and / or organic polymeric electrochromic materials, preferably selected from materials listed elsewhere in this specification.

[0129] In a preferred embodiment, the electrochromic device 1 is a full-color electrochromic device, including pixels having first, second, and optionally third sub-pixels 105, 106, and 107, each sub-pixel including sub-pixel electrodes 115-117, and each first, second, and optionally third sub-pixel including organic electrochromic materials 125-127 of different colors.

[0130] Those skilled in the art will understand that the sub-pixel electrodes 115-117 of the sub-pixels can be, and preferably are, the same and / or made of the same material. In one embodiment, the electrochromic material 125-127 is the primary or sole distinguishing feature between sub-pixels 105-107. It is noteworthy that the (array or pixel) electrodes 115-117 can be considered as part of the active matrix. Therefore, the (array or pixel) electrodes 115-117 are preferably part of both pixels (or sub-pixels) 105, 106, 107 and the active matrix.

[0131] In a preferred embodiment of the electrochromic device 1, the first sub-pixel 105 includes an organic electrochromic material 125 that is red when exposed to a specific voltage, the second sub-pixel 106 includes an organic electrochromic material 126 that is green when exposed to a specific voltage, and the optional third sub-pixel 107 includes an organic electrochromic material 127 that is blue when exposed to a specific voltage.

[0132] In a preferred embodiment, three sub-pixels 105, 106, and 107 are arranged adjacent to each other. Preferably, electrochromic materials of different colors are arranged adjacent to each other on spaced-apart sub-pixels. Preferably, the sub-pixels are not in direct physical contact with each other. Preferably, the different electrochromic materials (which also have different color properties) are not in direct physical contact and are not superimposed. Preferably, this embodiment distinguishes the device of the present invention from devices including superimposed electrochromic materials, such as those shown in US2005 / 0270619.

[0133] Preferably, the spaced-apart sub-pixels (or pixels) 105-107 and thus the corresponding electrochromic materials 125-127 are spaced laterally and / or horizontally, wherein the horizontal is defined by the plane of the generally flat electrochromic device. More specifically, one or both of the substrates 100 and 110 preferably extend in a plane parallel to the horizontal direction. Preferably, the pixels (or sub-pixels) 105-107 are located in or on the same horizontal plane. Preferably, the electrochromic materials 125-127 of different, particularly adjacent pixels or sub-pixels (i.e., sub-pixels in a color device) are located in the same horizontal plane, depending on the situation. In one embodiment, most, preferably all, of the pixels and / or sub-pixels of the device are disposed in the same plane and / or aligned in the same plane.

[0134] Preferably, adjacent subpixels of different RGB colors are arranged side-by-side on the insulating layer. Preferably, three subpixels that provide color together through RGB mixing are arranged aligned in a plane substantially parallel to at least one of the two opposing surfaces 121, 122 of the device. For example, the plane of the subpixel is defined by the surface of an insulating layer on which pixel or subpixel electrodes are deposited.

[0135] In a preferred embodiment, the ion-conducting material 109 is disposed within a common space, wherein at least three separate sub-pixels 105, 106, 107 are preferably disposed within the common space and / or in contact with the continuous ion-conducting material 109.

[0136] In a preferred embodiment, the grid or matrix includes an active matrix including active components 101-103, wherein active components 101, 102, and 103 are disposed for each of the sub-pixels 105-107, wherein one of the active components 101-103 is electrically connected to a sub-pixel electrode 115-117, wherein a predetermined sub-pixel potential is established through the active component 101.

[0137] The device of the present invention preferably includes an external driving component and / or terminals. Figure 1 (Not shown in the image). The driving component is configured to independently provide an appropriate voltage potential relative to each pixel or subpixel to generate the oxidation state of the electrochromic material, which allows an image to be generated holistically from all pixels or subpixels together.

[0138] In one embodiment, the first substrate 100, the electrically insulating layer 114, the pixel electrodes 115-117, the electrolytic layer 109, the second substrate 110, the counter electrode 111, and the ion storage layer 112 may be transparent, providing a transparent electrochromic display that allows users to perceive images from both sides of the display while keeping objects behind the display visible.

[0139] In another embodiment, the first substrate 100, the electrically insulating layer 114, the pixel electrodes 115-117, and the electrolytic layer 109 may be transparent, while the ion storage layer 112 may be diffusely reflective, thereby providing a reflective electrochromic display with a white background. The user can perceive the image from the pixel electrode side 121.

[0140] In another embodiment, the second substrate 110, counter electrode 111, ion storage layer 112, and electrolytic layer 109 may be transparent, while the electrically insulating layer 114 may be diffusely reflective, thereby providing a reflective electrochromic display with a white background. The user can perceive the image from the counter electrode side (side 122).

[0141] The present invention also relates to a method for depositing organic electrochromic materials 125-127 on pixel electrodes 115-117 of an electrochromic device. The method of the present invention is as follows: Figure 2 As shown. The organic electrochromic material can be the same material disclosed elsewhere in this specification. The array electrodes 115-117 can also be pixel or subpixel electrodes, for example in color electrochromic devices, such as color displays, as disclosed elsewhere in this specification.

[0142] The method of the present invention preferably includes providing a grid or matrix comprising conductive lines and / or vias 104, 108 and a plurality of pixel electrodes 115-117, each of said pixel electrodes 115-117 having a specific via 104. Active matrices that can be used in the method of the present invention are now commercially available and have been disclosed, for example, in EP0084604 and US20070171148. Figure 2 In the figure, the active matrix is ​​denoted by reference numeral 220. The active matrix is ​​preferably an active matrix included in the device of the present invention, such as... Figure 1 As shown. Therefore, reference numerals 100-108, 114-117 (which refer to components or parts of the active matrix 220) preferably have the same characteristics as described above regarding... Figure 1 The same meaning is publicly available. Array electrodes 115-117 can also be considered as part of an active matrix.

[0143] The method of the present invention preferably includes immersing the grid or matrix in solution 200. Figure 2 In the middle, the active matrix 220 has been immersed in the chemical bath 200.

[0144] The method of the present invention preferably includes adding an organic electrochromic material entity to the solution. The entity is preferably an organic molecule that can be deposited by electrodeposition and / or polymerized by electropolymerization, preferably both. Preferably, the entity is a monomer of the organic electrochromic material 125-127.

[0145] In one embodiment, the organic electrochromic material is one or more monomers selected from the group consisting of polyvioletin, polytriphenylamine, polythiophene, polypyridine, polypyrrole, polyaniline, polyimide, polyaromatic ketone, polyanthraquinone, polyamide, polynorbornene, polynorbornene-based compounds, polycarbazole, polythiocarbazole and their derivatives.

[0146] In one embodiment, the monomers of these polymers may carry optional substituents disclosed elsewhere in this specification, which can be used to adjust the electrochromic properties of the resulting polymers. As described above, such substituents may be selected from organic substituents comprising 1-50 carbon atoms and 0-20 heteroatoms, preferably 1-20 carbon atoms and 0-10 heteroatoms, and most preferably 1-10 carbon atoms and 0-5 heteroatoms.

[0147] As described above, such substituents can be selected from aliphatic and aromatic substituents, aliphatic and aromatic moieties of esters and amines, wherein in said aliphatic or aromatic substituents or moieties, one or more hydrogens are optionally selected from phosphonates (-PO(OH)2), boric acid (-B(OH)2), -OH, -COOH and –(CH2). n One or more substitutions of -Si(OR3)3. R3 is a C1-C10 alkyl, preferably a C1-C5 alkyl. Other examples detailed above regarding substituents apply to substituents contained on the monomer moiety (e.g., C...). 1-10 Alkyl, N-oxide, dimethylamino, acetonitrile, benzyl, phenyl, benzyl mono- or di-substituted with nitro, phenyl mono- or di-substituted with nitro, and substituents from formulas (1)-(9), etc.).

[0148] It is worth noting that the entity can be added to the solution before, after, or simultaneously with immersing the grid or matrix 220 into the solution 200. The solution can be a solution that already contains the organic electrochromic material entity. Those skilled in the art will understand that the objective is to achieve Figure 2 The configuration shown in the diagram is schematic, and the order in which the components are added is generally irrelevant.

[0149] This also applies to immersing the counter electrode 210 in the solution 200 according to the method of the present invention.

[0150] The prior method can also be more generally described as providing a receiver 211 comprising an active matrix 220, a counter electrode 210, and a solution 200, wherein the solution 200 comprises a solid (preferably a monomer) of an organic electrochromic material, such as... Figure 2 As shown.

[0151] The method of the present invention preferably includes applying a potential between some or all of the plurality of pixel electrodes 115 and the counter electrode 210, thereby providing deposition of the bulk 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 electrically connected to another power source or electrode terminal of the active matrix, for example as shown in US 8,654,431 (FIG. 5).

[0152] The driver 209 is preferably configured to control the current flowing to the pixel electrodes 115-117 and / or the counter electrode 210, and / or to establish a desired voltage potential between the pixel electrodes 115-117 and / or the counter electrode 210. Preferably, the driver 209 can independently and individually address each active component 101, 102, 103, and thus address each pixel or sub-pixel electrode 115, 116, 117. In another embodiment, the driver 209 can independently and individually address one group of pixel or sub-pixel electrodes 115 from a plurality of groups of pixel or sub-pixel electrodes 115-117.

[0153] By applying a voltage potential between all pixel electrodes 115-117 and counter electrode 210 in the solution, organic entities migrate to pixel electrodes 115-117 and are electrodeposited and / or electropolymerized on all pixel electrodes.

[0154] In a preferred embodiment, the organic electrochromic material is a monomeric entity, and the organic electrochromic material is formed when the monomeric portion is deposited on the pixel electrode 115. Preferably, a polymeric organic electrochromic material is formed when the monomeric portion is deposited.

[0155] In a preferred embodiment, the method of the present invention includes electrodepositing and / or electropolymerizing the organic electrochromic material on the pixel electrode 115.

[0156] Preferably, the polymer is formed in situ on the corresponding pixel or sub-pixel electrode, as is preferably determined by the driving device.

[0157] 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 the deposition of the solid organic electrochromic material on the plurality of pixel electrodes 115.

[0158] Preferably, the electrochromic properties of the electrodeposited organic electrochromic material and / or organic polymer electrochromic material 125-127 are characteristics of the materials obtained by electrodeposition and / or electropolymerization. The organic entity (e.g., monomer) added to the solution may or may not have electrochromic properties.

[0159] In one embodiment, the method of the present invention aims to deposit different organic electrochromic materials on different pixel electrodes, such as different pixel electrode subgroups. In this way, electrochromic materials can be deposited for use in color electrochromic devices, such as multicolor devices and even full-color electrochromic devices, for example... Figure 1The RGB display disclosed herein. For example, pixels can be divided into subpixels, where a certain number of subpixels form a pixel, preferably three subpixels form a pixel, for example regarding... Figure 1 The discussion is based on the superposition of RGB principles. According to the present invention, electrochromic materials of a specific color can be deposited only on a portion of the pixel electrodes, preferably on sub-pixel electrodes of a specific color (e.g., red, green, or blue).

[0160] In a preferred embodiment of the method, the grid, array, or matrix includes a plurality of sub-pixel electrodes 115-117, wherein the method includes providing an external driving device 209 configured to apply the potential between a first portion of the plurality of sub-pixel electrodes and the counter electrode 210, thereby providing deposition and / or electropolymerization of the organic electrochromic material only on the first portion 115 of the plurality of sub-pixel electrodes.

[0161] In a preferred embodiment, a predetermined number of subpixels are designed to provide a single pixel for the electrochromic device, and a first portion of the subpixel electrode comprises only one or only a portion of the subpixels of the single pixel. For example, in a device using RGB additive color, three subpixels can form one pixel.

[0162] For example, refer to Figure 2 The driving device 209 can be electronically controlled to apply a voltage potential only between the pixel (or sub-pixel) electrode 115 and the counter electrode 210, and not between the pixel (or sub-pixel) 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.

[0163] The active matrix 220 shown is in Figure 2 The diagram illustrates this schematically. An active matrix contains a large number of pixel (or sub-pixel) electrodes, the number depending on the size and resolution of the display. In the embodiment detailed above, a pixel is formed by three sub-pixels, and reference numeral 115 can indicate one sub-pixel electrode that will be present in a pixel of the final device, while reference numerals 116 and 117 indicate two other sub-pixel electrodes. In this case, the active matrix preferably includes a plurality of sub-pixel electrodes 115 and an equal number of sub-pixel electrodes 116 and 117, for illustration. Figure 2 Only one of the multiple sub-pixels is shown. Therefore, in an embodiment of the method of the present invention, the organic electrochromic material is solidly deposited on all (sub)pixel electrodes 115 of the active matrix 220, but not on (sub)pixel electrodes 116 and 117.

[0164] exist Figure 2Therefore, reference numeral 115 can represent the first portion of a pixel or subpixel electrode, and thus all pixels or subpixels of that portion. Similarly, reference numeral 116 can represent the second portion of a pixel or subpixel electrode, and reference numeral 117 can represent the third portion of a pixel or subpixel electrode.

[0165] To avoid ambiguity, this invention is not limited to a specific number of (sub)pixel electrode portions. The three portions of the pixel electrode shown are for illustrative purposes only. This invention also includes electrochromic devices comprising only one type of pixel electrode, where all pixels have the same organic electrochromic material and therefore have the same color properties. For example, this invention also includes monochrome and / or black-and-white devices.

[0166] Therefore, all pixel electrodes (or sub-pixel electrodes) 115 may represent a first portion or part of a pixel electrode on which the organic electrochromic material is deposited.

[0167] Preferably, the deposition of the entity is selected from the group consisting of electrodeposition, polymerization, electropolymerization, and combinations of two or more of the above. Preferably, the deposition of the entity corresponds to deposition via electropolymerization. Preferably, the deposition of the organic entity results in the deposition of the organic electrochromic material.

[0168] In embodiments where the organic entity is deposited only on a portion of a pixel electrode or sub-pixel electrode, the entity is preferably a first entity of a first organic electrochromic material 125. The first organic electrochromic material preferably has a first color. Similarly, the solution containing the first entity of the first organic electrochromic material is preferably a first solution.

[0169] It is worth noting that the "first color" depends on the redox state of the first organic electrochromic material. The term "first color" can be understood as "first electrochromic color characteristic," and similarly, this applies to "second color" and "third color." Likewise, the term "different colors" is preferably understood as "different electrochromic color characteristics." Alternatively, "first color" can be said to refer to "first light modulation characteristic," and it should be understood that "second color" refers to light modulation characteristics different from the first light modulation characteristic, particularly regarding the color of the modulated light.

[0170] In one embodiment, the method of the present invention includes:

[0171] - Immerse the grid or matrix 220 in the second solution.

[0172] - A second entity of a second organic electrochromic material is added to the second solution, wherein the first and second entities are different.

[0173] - An electric potential is applied between the second portion of the plurality of pixel or sub-pixel electrodes and the counter electrode 210, thereby providing deposition of the second entity of the second organic electrochromic material 126 on the second portion of the plurality of pixel or sub-pixel electrodes.

[0174] The first and second organic electrochromic materials have different colors.

[0175] Regarding the deposition of the organic electrochromic material on the first portion of the pixel or sub-pixel electrode, the features of immersing the grid or matrix in the second solution and adding the organic electrochromic material to the second entity can be performed independently of each other as appropriate. These features can be replaced by "providing a solution comprising the second entity, 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 sub-pixel electrode.

[0176] Furthermore, the external driver 209 preferably applies a voltage potential only between the second portions 116 of the pixel or sub-pixel electrodes, and not on the first portion 115 and possibly on the third portion 117.

[0177] The deposition of the second entity of the second organic electrochromic material 126 on the second portion of the plurality of pixel or sub-pixel electrodes preferably results in electrodeposition and / or electropolymerization of the second organic electrochromic material. Therefore, the second organic electrochromic material is preferably formed by said electrodeposition and / or electropolymerization.

[0178] In one embodiment, the method includes rinsing the grid or matrix 220 before immersing it in the second solution and preferably after removing it from the first solution.

[0179] In one embodiment, the method of the present invention includes:

[0180] - Immerse the grid or matrix 220 in the third solution.

[0181] - Add the third entity of the third organic electrochromic material 127 to the third solution.

[0182] - An electric potential is applied between the third portion 117 of the plurality of pixel or sub-pixel electrodes and the counter electrode 210, thereby providing deposition of the third entity of the third organic electrochromic material 127 on the third portion 117 of the plurality of pixel or sub-pixel electrodes.

[0183] The first, second, and third entities are different from each other, and the first, second, and third organic electrochromic materials 125-127 have different colors.

[0184] As detailed above regarding the deposition of the second organic electrochromic material, the immersion of the grid or matrix in the third solution and the addition of the third organic electrochromic material entity can be performed independently of each other as appropriate. These features can be replaced by "providing a solution comprising the third entity and the grid or matrix". Furthermore, the external driver 209 preferably applies a voltage potential only between the third portions 117 of the pixel or sub-pixel electrodes, without applying it to the first portion 115 and the second portion 116.

[0185] In one embodiment, the method of the present invention includes rinsing the grid or matrix before immersing it in the third solution and preferably after removing it from the second solution.

[0186] The present invention also provides a method for producing an electrochromic device, preferably an electrochromic display, according to the invention. To produce the device, an organic electrochromic material is deposited on an array (or pixel or subpixel) electrode, according to aspects and preferred embodiments disclosed herein. Other components of the device are then assembled. These other components include counter electrodes, preferably comprising an ion storage layer and an ion transport layer. As disclosed with respect to the deposition of the organic electrochromic material, an active matrix is ​​preferably provided in the device. Other preferred components of the device are first and / or second substrates 100, 110. This device can be conventionally assembled.

[0187] To avoid ambiguity, it is worth noting that the terms pixel and subpixel are considered interchangeable; that is, referring to a pixel may include referring to a subpixel. The term subpixel is essentially associated with multicolor or full-color devices, where, when viewed from a distance from the device, three independently addressable elements are perceived by a human observer as points of a specific color. Therefore, the specific color of a pixel can be produced by several separate but spatially close subpixels. The distinction between pixel and subpixel does not necessarily imply structural or other technical differences. Specifically, in the figures, elements 105-107 are separate and independently addressable elements having the aforementioned structure, independent of elements considered, for example, as “pixels,” “subpixels,” layer structures, arrangements, or other elements. Therefore, the foregoing terms are used interchangeably to refer to structures 105-107.

[0188] Example: Production of full-color electrochromic displays

[0189] A full-color electrochromic display based on the electropolymerization of red, green, and blue electrochromic materials on different sub-pixel electrodes is manufactured as described below.

[0190] 1. Working electrode preparation:

[0191] The backplane of the active matrix thin-film transistor (AM-TFT) serves as the working electrode. Sufficient electrical connections are routed to provide independently addressable groups of sub-pixels. When a group of sub-pixels is addressed, the channels of that group are activated, allowing a desired voltage to be applied to the corresponding pixel electrode. For other unaddressed groups of sub-pixels, the voltage at the pixel electrode remains floating, and no current is supplied.

[0192] The AM-TFT backplane is perpendicularly inserted into a trench, with the ITO glass substrate (in other examples, carbon felt or platinum mesh as the counter electrode) facing inwards. The trench is filled with a solution of monomers, electrolyte, and solvent suitable for forming the electrochromic organic polymer to be deposited on the pixel electrode.

[0193] To achieve a full-color electrochromic display, red, green, and blue electrochromic polymers are sequentially electropolymerized on one-third of the sub-pixel electrodes, so that each pixel includes three sub-pixels of red, green, and blue electrochromic polymer materials.

[0194] For the deposition of the red electrochromic material, an acetonitrile solution of 10 mM 3,10-bis(2,3-dihydrothiophene[3,4-b][1,4]dioxin-5-yl)-1-dodecyl-1H-phenanthrene[1,10,9,8-c,d,e,f,g]carbazole (DEP) and 0.1 M tetrabutylammonium hexafluorophosphate (TBAPF6) was used. Electropolymerization was performed using cyclic voltammetry. An Ag / AgCl standard reference electrode was used, and the voltage between the red pixel electrode and the reference electrode was scanned between -0.3 V and 1.1 V at a scan rate of 100 mV / s. The number of scan cycles was 10. During the electropolymerization of the red electrochromic polymer, only the red sub-pixel electrode was addressed with the required voltage; the green and blue sub-pixel electrodes were not addressed. The AM-TFT backplane was removed from the tank, rinsed with deionized water, and dried with compressed air or a nitrogen gun.

[0195] For the deposition of the green electrochromic polymer, a 2 mM solution of 5,8-bis(2,3-dihydro)[3,4-B][1,4]dioxin-5-yl)-2,3-bis(4-(hexadecyloxy)phenyl)quinoxaline (BOPEQ) and 0.1 M TBAPF6 in acetonitrile / dichloromethane (volume ratio: 8 / 2) was used. Electropolymerization was performed using cyclic voltammetry with a scan voltage between -0.6 V and 1.1 V, a scan rate of 100 mV / s, and 10 cycles. After the deposition process was completed, the AM-TFT backplate was removed from the tank and cleaned and dried as described above.

[0196] For the deposition of the blue electrochromic polymer, an acetonitrile / dichloromethane (volume ratio: 1 / 3) solution of 1 mM 5,5'-(3,6-diphenylthiophene[3,2-b]thiophene-2,5-diyl)bis(2,3-dihydrothiophene[3,4-b][1,4]dioxin) and 0.1 M TBAPF6 was used. The scan voltage was between -0.8 V and 1.4 V, the scan rate was 100 mV / s, and the number of cycles was 10, with deposition performed via electropolymerization.

[0197] 2. Preparation of antimony-doped tin oxide (ATO) paste:

[0198] An ATO mesoporous membrane was used as the ion storage layer on the counter electrode. The ATO slurry was prepared as follows:

[0199] 10.5 g of antimony-doped tin oxide (ATO) nanoparticles (Alfa Aesar, particle size: 13–22 nm) were suspended in ethanol (400 ml) and sonicated for 1 hour using a horn sonicator. The resulting colloidal solution was then mixed with 33 g of ethyl cellulose solution (5% wt ethanol:toluene (20:80 vol%)) and 40 g of terpineol. The colloidal mixture was vigorously stirred for 30 minutes, and then the ethanol was removed under reduced pressure (maximum 60 °C).

[0200] 3. Electrode preparation:

[0201] The counter electrode was fabricated using an ITO substrate (in another example, an FTO substrate was used). ATO paste was screen-printed onto the ITO substrate. After printing, the electrode was sintered at 450°C for 30 minutes, with the temperature gradually increased from ambient temperature to 450°C at a slow rate of 10°C / min to avoid crack formation. The thickness of the sintered ATO mesoporous film was approximately 3 μm.

[0202] 4. Electrolyte filling and assembly:

[0203] The electrolyte was prepared by mixing lithium bis(trifluoromethanesulfonyl)imide, 4-cyano-4'-pentylbiphenyl, and sulfolane (weight ratio = 75:500:18). Assembly was performed using a standard drop-feed injector widely used in the liquid crystal display (LCD) industry. UV-curable adhesive was dispensed along the edge of the working electrode. Spherical spacers with a diameter of 10 μm were uniformly sprayed above the surface of the working electrode. A precise amount of electrolyte was dispensed within the sealant frame. The amount of electrolyte was calculated to perfectly fill the gap volume between the working and counter electrodes. The counter electrode was then brought into contact with the sealant frame and further blocked by the spherical spacers. The adhesive was then cured with UV light. Thus, a full-color electrochromic display was completed.

[0204] Although certain preferred embodiments of the invention have been described and specifically illustrated above, the invention is not limited to these embodiments. Various modifications can be made thereto without departing from the scope and spirit of the invention as set forth in the following claims. Examples of the invention are disclosed below. These examples are for illustrative purposes only and are not intended to limit the scope of the invention.

Claims

1. A full-color electrochromic device (1), comprising: - Multiple pixels, wherein each pixel includes a first sub-pixel (105), a second sub-pixel (106), and a third sub-pixel (107), wherein the first sub-pixel (105) includes a first sub-pixel electrode (115) and a first organic electrochromic material (125), wherein the second sub-pixel (106) includes a second sub-pixel electrode (116) and a second organic electrochromic material (126), and wherein the third sub-pixel (107) includes a third sub-pixel electrode (117) and a third organic electrochromic material (127). Among them, the first organic electrochromic material (125), the second organic electrochromic material (126) and the third organic electrochromic material (127) are different organic electrochromic materials having different colors depending on the oxidation state of the corresponding first organic electrochromic material, the oxidation state of the second organic electrochromic material and the oxidation state of the third organic electrochromic material; - A first substrate (100) includes an active matrix comprising conductive lines and active components for providing current to a first sub-pixel electrode (115), a second sub-pixel electrode (116), and a third sub-pixel electrode (117), wherein an active component is provided for each of the first sub-pixel (105), the second sub-pixel (106), and the third sub-pixel (107), wherein an active component is electrically connected to one of the first sub-pixel electrodes (115), the second sub-pixel electrode (116), and the third sub-pixel electrode (117), and wherein a predetermined sub-pixel potential is established through the active component; - A second substrate (110), wherein the first substrate has a first outer surface (121), the second substrate has a second outer surface (122), and the first outer surface (121) and the second outer surface (122) are opposite to each other; - One or more counter electrodes (111, 112) connected to the second substrate; and - An ion-conducting material (109) for transporting ions between the pixel and the one or more counter electrodes (111, 112). The ion-conducting material includes one or more of the following: 1) at least one solvent, at least one anion, and at least one cation; 2) an ionic liquid in which no solvent exists; and 3) a liquid crystal; The ion-conducting material (109) is disposed within a common space, wherein at least the first sub-pixel (105), the second sub-pixel (106), and the third sub-pixel (107) are disposed within the common space and / or in contact with the continuous ion-conducting material (109). The electrochromic device (1) is configured to establish a potential between any one of the first sub-pixel (105), the second sub-pixel (106), and the third sub-pixel (107) and the one or more counter electrodes (111, 112) to control the oxidation state of the first organic electrochromic material, the second organic electrochromic material, and the third organic electrochromic material, respectively. The first organic electrochromic material (125), the second organic electrochromic material (126), and the third organic electrochromic material (127) are electrodeposited organic polymer electrochromic materials obtained by electropolymerization on the first sub-pixel electrode (115), the second sub-pixel electrode (116), and the third sub-pixel electrode (117).

2. The electrochromic device (1) according to claim 1, comprising an insulating layer (114) disposed between the first substrate (100) and the first sub-pixel electrode (115), the second sub-pixel electrode (116), and the third sub-pixel electrode (117), wherein the first sub-pixel electrode (115), the second sub-pixel electrode (116), and the third sub-pixel electrode (117) are deposited on the insulating layer, wherein the active matrix includes conductive vias extending through the insulating layer, and wherein the vias are provided to connect a single active component to a single sub-pixel electrode among the first sub-pixel electrode (115), the second sub-pixel electrode (116), and the third sub-pixel electrode (117).

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

4. The electrochromic device (1) according to claim 1 or 2, wherein the liquid crystal is an ion liquid crystal.

5. The electrochromic device (1) according to claim 1 or 2, wherein a plurality of pixels are disposed within the common space and / or in contact with the continuous ion-conducting material.

6. The electrochromic device (1) according to claim 1 or 2, wherein the electrodeposited organic polymer electrochromic material comprises one or more selected from the group consisting of: electrodeposited viologen, electrodeposited triphenylamine, electrodeposited thiophene, electrodeposited 3,4-ethylenedioxythiophene, electrodeposited pyridine, electrodeposited aniline, electrodeposited imide, electrodeposited aromatic ketone, electrodeposited anthraquinone, electrodeposited amide, electrodeposited norbornene-based compound, electrodeposited carbazole, electrodeposited thiocarbazole, electrodeposited pyrrole, and the above-mentioned electrodeposited derivatives.

7. The electrochromic device (1) according to claim 1 or 2, wherein the electrodeposited organic polymer electrochromic material comprises one or more selected from the group consisting of polyvioletin, polytriphenylamine, polythiophene, poly(3,4-ethylenedioxythiophene) (PEDOT), polypyridine, polypyrrole, polyaniline, polyimide, polyaromatic ketone, polyanthraquinone, polyhexane, polyamide, polynorbornene, polycarbazole, polythiocarbazole and its derivatives.

8. The electrochromic device (1) according to claim 7, wherein the derivative is a material comprising an organic material basic structure and further comprising one or more substituents, the substituents being independently selected from organic substituents comprising 1-50 carbons and 0-20 heteroatoms.

9. The electrochromic device (1) according to claim 7, wherein the derivative is a material comprising an organic material basic structure and further comprising one or more substituents, the substituents being independently selected from organic substituents comprising 1-20 carbons and 0-10 heteroatoms.

10. The electrochromic device (1) according to claim 7, wherein the derivative is a material comprising an organic material basic structure and further comprising one or more substituents, the substituents being independently selected from organic substituents comprising 1-10 carbons and 0-5 heteroatoms.

11. The electrochromic device (1) according to any one of claims 8 to 10, wherein the one or more substituents are selected from aliphatic and aromatic substituents, aliphatic and aromatic esters and amines.

12. The electrochromic device (1) according to any one of claims 8 to 10, wherein the one or more substituents are selected from aliphatic and aromatic substituents, aliphatic and aromatic moieties of esters and amines, wherein in the aliphatic or aromatic substituents or moieties, one or more hydrogens are independently substituted by one or more selected from phosphonates (-PO(OH)2), boric acid (-B(OH)2), -OH, -COOH, -NH2, -NO2, amine oxides (-N+(R)2-O-), halogens and -(CH2)n-Si(OR3)3, and R and R3 are independently selected from C1-C10 alkyl groups.

13. The electrochromic device (1) according to claim 1 or 2, wherein the electrochromic device (1) does not have components for electrically separating pixels.

14. The electrochromic device (1) according to claim 1 or 2, wherein the electrochromic device (1) does not have components for electrically separating sub-pixels.

15. A method for depositing an organic electrochromic material on a pixel electrode of an electrochromic device according to any one of claims 1 to 14, the method comprising: - An active matrix (220) is provided, comprising a first substrate (100), conductive lines, active components, a plurality of first sub-pixel electrodes, a plurality of second sub-pixel electrodes, and a plurality of third sub-pixel electrodes, wherein the active matrix includes specific conductive lines for each of the plurality of first sub-pixel electrodes, the plurality of second sub-pixel electrodes, and the plurality of third sub-pixel electrodes. - Immerse the active matrix (220) in the first solution (200), - Add the first monomer entity to the first solution. - Immerse the counter electrode in the first solution. - Provide external drive device (209). - An electric potential is applied between the plurality of first sub-pixel electrodes and the counter electrode to electropolymerize the first monomer entity on the plurality of first sub-pixel electrodes, thereby depositing a first organic polymer electrochromic material having a first color on the plurality of first sub-pixel electrodes. - Immerse the active matrix (220) in the second solution. - Add the second monomer entity to the second solution. - An electric potential is applied between the plurality of second sub-pixel electrodes and the counter electrode to electropolymerize the second monomer entity on the plurality of second sub-pixel electrodes, thereby depositing a second organic polymer electrochromic material having a second color on the plurality of second sub-pixel electrodes. - Immerse the active matrix (220) in the third solution. - Add the third monomer entity to the third solution. - An electric potential is applied between the plurality of third sub-pixel electrodes and the counter electrode to electropolymerize the third monomer entity on the plurality of third sub-pixel electrodes, thereby depositing a third organic polymer electrochromic material having a third color on the plurality of third sub-pixel electrodes (117). The first, second, and third individual entities are different from each other. The first organic polymer electrochromic material, the second organic polymer electrochromic material, and the third organic polymer electrochromic material have different colors. The individual pixel electrode of the electrochromic device includes a first sub-pixel electrode (115) of the plurality of first sub-pixel electrodes, a second sub-pixel electrode (116) of the plurality of second sub-pixel electrodes, and a third sub-pixel electrode (117) of the plurality of third sub-pixel electrodes, wherein each of the first sub-pixel electrode (115), the second sub-pixel electrode (116), and the third sub-pixel electrode (117) includes a different electrochromic material.

16. The method of claim 15, wherein the method comprises rinsing the active matrix prior to immersing the active matrix in the second solution.

17. The method of claim 15, wherein the method comprises rinsing the active matrix after removing the active matrix from the first solution.

18. The method according to any one of claims 15 to 17, the method comprising rinsing the active matrix prior to immersing the active matrix in the third solution.

19. The method according to any one of claims 15 to 17, the method comprising rinsing the active matrix after removing it from the second solution.

20. The method of any one of claims 15 to 17, wherein the active matrix comprises thin-film transistors, and each sub-pixel of the electrochromic device comprises a separate thin-film transistor for controlling the flow of current to or out of a single sub-pixel electrode.

21. The method according to any one of claims 15 to 17, wherein an insulating layer (114) is provided between the first substrate (100) and the plurality of first sub-pixel electrodes, the plurality of second sub-pixel electrodes and the plurality of third sub-pixel electrodes, wherein the plurality of first sub-pixel electrodes, the plurality of second sub-pixel electrodes and the plurality of third sub-pixel electrodes are deposited on the insulating layer, wherein the active matrix includes conductive vias extending through the insulating layer, and wherein vias are provided to connect a single active component to a single corresponding sub-pixel electrode.

22. The method according to any one of claims 15 to 17, comprising: - Assemble the counter electrode and ion-conducting material (109) to provide the electrochromic device.

23. The method according to claim 22, wherein, The ion-conducting material includes liquid crystal.

24. The method according to claim 23, wherein, The liquid crystal is an ion-based liquid crystal.

25. The method according to any one of claims 15 to 17, wherein the electrochromic device has no components for electrically separating sub-pixels.

26. The method according to any one of claims 15 to 17, wherein the electrochromic device has no component for electrically separating pixels.

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