Electrochromic element for light control device, method for manufacturing electrochromic element for light control device, transparent electrode layer, and method for manufacturing transparent electrode layer

Abstract

This electrochromic element for a light control device has a multilayer structure including a first electrochromic layer, an electrolyte layer, and a second electrochromic layer in this order between a first transparent electrode layer and a second transparent electrode layer on a transparent substrate. The first transparent electrode layer and the second transparent electrode layer each contain indium (In) oxide alone and / or indium (In) oxide containing one or more types selected from the group consisting of Ce, W, Ti, Zr, and Mo, have a carrier mobility of 70 cm2 / V•s or more and have a transmittance of 75% or more in a near-infrared band (800-2500 nm).

Description

Electrochromic element for light-modulating device, method for manufacturing electrochromic element for light-modulating device, transparent electrode layer, and method for manufacturing transparent electrode layer

[0001] The present invention relates to an electrochromic element for a light-adjusting device that changes color through an electrochemical reaction and a method for manufacturing the same, and more particularly to an electrochromic element for a light-adjusting device that provides a high-contrast color change in the near-infrared band (wavelengths of 800 to 2500 nm) and a method for manufacturing the same.The present invention also relates to a transparent electrode layer used in such an electrochromic element for a light-adjusting device and a method for manufacturing the transparent electrode layer.

[0002] In a light-control window using an electrochromic element, it is desirable to control the transmission and blocking of heat rays (infrared rays) contained in sunlight, for example, by adjusting the amount of heat taken into a room and reducing the air-conditioning load. However, transparent electrodes made of indium tin oxide (ITO), which are commonly used in electrochromic elements, have low transmittance in the near-infrared to mid-infrared band (wavelengths of 800 to 4000 nm), and are therefore considered unsuitable for controlling the transmission and blocking of heat rays.

[0003] When light is incident on a material, some of the light is reflected or absorbed inside the material, and the rest is transmitted. Since ITO is an n-type degenerate semiconductor, electrons, which act as carriers, contribute to electrical conduction. These carrier electrons reflect and absorb light above a certain wavelength. The light wavelength is expressed as N: carrier density, e: elementary charge, m ＊ : effective mass of electron, ε: dielectric constant, plasma frequency: w ｐ =√(Ne ２ / (m ＊ ε)), which depends on the carrier density and is generally located in the near-infrared region. In other words, in a typical ITO thin film, when the carrier density is 1×10 ２１ cm －３ The resistivity is about 2×10 －４ Its resistivity is extremely low at Ω·cm, so infrared rays of 1000 nm or more are absorbed or reflected, with almost no transmission.

[0004] On the other hand, for example, Patent Document 1 discloses an electrochromic element that can significantly change the transmittance not only in the visible light region but also in the infrared light region by controlling the carrier electron density of a transparent electrode (conductive film). The carrier electron density of at least one of the two opposing transparent electrodes is set to 1 to 4 × 10 in consideration of the balance with the response speed of the transmittance control. ２０ cm －３ By controlling the transmittance to a low level, it is possible to significantly change not only the transmittance in the visible light region but also the transmittance in the infrared light region.

[0005] JP 2008-107587 A

[0006] To achieve high-speed dimming response as an electrochromic element for a dimming device, the film thickness should be increased to increase the conductivity of the transparent electrode. However, transparent electrodes such as ITO result in lower transmittance in the near-infrared band. Here, the resistivity of a material is defined as 1 / (Neμ), where μ is mobility, and is inversely proportional to the product of the carrier electron density N and the mobility μ. Therefore, as described in Patent Document 1, if the carrier electron density is reduced to increase the transmittance in the infrared light region, the resistivity increases, making it difficult to respond to high-speed dimming.

[0007] The present invention has been made in view of the above-described circumstances, and an object of the present invention is to provide an electrochromic element for a light-adjusting device that imparts a color change in the near-infrared to mid-infrared band (wavelength 800 to 4000 nm), and that imparts a high-contrast color change in the near-infrared band (wavelength 800 to 2500 nm), in particular, a method for manufacturing the same, a transparent electrode layer, and a method for manufacturing the transparent electrode layer.

[0008] The present inventors have investigated the use of known zinc oxide-based transparent electrode layers, such as aluminum-doped zinc oxide and gallium-doped zinc oxide, instead of ITO, but found that these materials had poor adhesion to the electrochromic layer and failed to exhibit sufficient functionality. After extensive research, they discovered that a transparent electrode film with high carrier mobility and high solar transmittance can be obtained by forming a precursor film made of indium oxide containing an amorphous phase or a higher amorphous phase component than a polycrystalline component, followed by crystallization by light irradiation at a temperature of 100°C or less or by heat treatment at a temperature exceeding 150°C in air or vacuum. This transparent electrode film is chemically stable when combined with an electrochromic layer made of a transition metal oxide and an electrochromic layer containing a metal cyano complex, and provides an electrochromic device that exhibits stable color changes in the mid-infrared range (wavelengths of 800 to 4000 nm) and stable color changes with high contrast in the near-infrared range (wavelengths of 800 to 2500 nm).

[0009] Furthermore, since the transparent electrode layer can be polycrystallized by light irradiation, it is possible to use a low heat-resistant substrate that has flexibility, such as a resin sheet, but is subject to heating restrictions, enabling versatile development with various electrochromic elements according to needs.

[0010] [1] The present invention provides an electrochromic element for a light-modulating device, which has a multilayer structure including a first electrochromic layer, an electrolyte layer, and a second electrochromic layer in this order between a first transparent electrode layer on a first transparent substrate and a second transparent electrode layer on a second transparent substrate, wherein the first transparent electrode layer and the second transparent electrode layer contain at least one of an oxide of indium (In) alone and an oxide of indium (In) containing one or more kinds selected from the group consisting of Ce, W, Ti, Zr, and Mo, and the first transparent electrode layer and the second transparent electrode layer contain at least one of an oxide of indium (In) alone and an oxide of indium (In) containing one or more kinds selected from the group consisting of Ce, W, Ti, Zr, and Mo, and the first transparent electrode layer and the second transparent electrode layer contain at least one of an oxide of indium (In) alone and an oxide of indium (In) containing one or more kinds selected from the group consisting of Ce, W, Ti, Zr, and Mo, and the first transparent electrode layer and the second transparent electrode layer contain at least one of an oxide of indium (In) alone and an oxide of indium (In) containing at least one kind ... second transparent electrode layer and the second transparent electrode layer contain at least one of an oxide of indium (In) alone and an oxide of indium (In) containing at least one kind selected from the group consisting of Ce, W, Ti, Zr, and Mo, and the first transparent electrode layer and the second transparent electrode layer contain at least one of an oxide of ２ The material is characterized by a carrier mobility of 1000 .mu.m / V.s or more and a transmittance of 75% or more in the near-infrared region (800 to 2500 nm).

[0011] According to this feature, it is possible to provide an electrochromic element for a light-controlling device that provides a color change in the mid-infrared band and a color change with high contrast in the near-infrared band.

[0012] [2] In the invention of [1], the first transparent electrode layer and the second transparent electrode layer may be made of a crystalline phase obtained by crystallizing an amorphous phase. According to this feature, it is possible to provide an electrochromic element for a light-controlling device that provides a color change in the mid-infrared band and a stable color change with high contrast in the near-infrared band.

[0013] [3] In the invention of [1] or [2], the first transparent substrate and the second transparent substrate may be resin sheets. According to this feature, a flexible electrochromic element for a light-adjusting device can be provided.

[0014] [4] In any of the inventions [1] to [3], the electrolyte layer may contain one or more organic solvents selected from the group consisting of propylene carbonate, ethylene carbonate, and diethyl carbonate, along with one or more of bis(trifluoromethanesulfonyl)imide, lithium bis(trifluoromethanesulfonyl)imide, potassium bis(trifluoromethanesulfonyl)imide, and sodium bis(trifluoromethanesulfonyl)imide, and may be solidified with one or more of acrylic resin and epoxy resin, the first electrochromic layer may contain a transition metal oxide, and the second electrochromic layer may contain a metal cyano complex, and may be characterized in that a color change is possible by applying a voltage to the first transparent electrode layer and the second transparent electrode layer.

[0015] [5] In the invention of [4], the transition metal oxide may contain at least one of tungsten oxide, molybdenum oxide, niobium oxide, vanadium oxide, and titanium oxide.

[0016] [6] In the invention of [4] or [5], the metal cyano complex may be such that A is a cation selected from the group consisting of hydrogen, lithium, sodium, potassium, rubidium, cesium, and ammonium; M is a metal atom selected from the group consisting of vanadium, chromium, manganese, iron, ruthenium, cobalt, rhodium, nickel, palladium, platinum, copper, silver, zinc, lanthanum, europium, gadolinium, lutetium, barium, strontium, and calcium; M' is a metal atom selected from the group consisting of vanadium, chromium, molybdenum, tungsten, manganese, iron, ruthenium, cobalt, nickel, platinum, and copper; x is a rational number from 0 to 3; y is a rational number from 0.3 to 1.5; and z is a rational number from 0 to 30; and A ｘ M [M' (CN) ６ ] ｙ ・zH ２ The present invention may be characterized in that the Prussian blue-type metal complex is one or more Prussian blue-type metal complexes selected from the group consisting of Prussian blue-type metal complexes represented by the general formula: O. According to this feature, it is possible to provide an electrochromic element for a light-modulating device that provides a color change in the mid-infrared band and a stable color change with high contrast in the near-infrared band.

[0017] [7] The present invention provides a transparent electrode layer used in an electrochromic element for a light-adjusting device, which is formed on a transparent substrate and contains at least one of an oxide of indium (In) alone and an oxide of indium (In) containing one or more selected from the group consisting of Ce, W, Ti, Zr, and Mo, and has a thickness of 70 cm ２ The electrochromic element for a light-controlling device is characterized by a carrier mobility of 1 / 2 V·s or more and a transmittance of 75% or more in the near-infrared band (800 to 2500 nm). Such characteristics make it possible to provide an electrochromic element for a light-controlling device that provides a color change in the mid-infrared band and a color change with high contrast in the near-infrared band.

[0018] [8] The present invention provides a method for manufacturing an electrochromic element for a light-modulating device having a multilayer structure including a first electrochromic layer, an electrolyte layer, and a second electrochromic layer in this order between a first transparent electrode layer on a first transparent substrate and a second transparent electrode layer on a second transparent substrate, the method comprising: forming the first transparent electrode layer on the first transparent substrate and / or forming the second transparent electrode layer on the second transparent substrate; and forming a precursor film on the first transparent substrate and / or the second transparent substrate, the precursor film including an amorphous phase containing at least one of an oxide of indium (In) and an oxide of indium (In) containing one or more kinds selected from the group consisting of Ce, W, Ti, Zr, and Mo; and crystallizing the precursor film to form an amorphous phase of 70 cm. ２ and a second step of forming the first transparent electrode layer and / or the second transparent electrode layer, each of which has a carrier mobility of 1000 nm to 1500 nm / V·s or more and a transmittance of 75% or more in the near-infrared band (800 to 2500 nm).

[0019] According to this feature, it is possible to provide an electrochromic element for a light-controlling device that provides a color change in the mid-infrared band and a color change with high contrast in the near-infrared band.

[0020] [9] In the invention of [8], the second step includes a step of irradiating light.

[0021] In the invention of

[10] , [9] or [8], the crystallization step may be a step of treating at a temperature of 100° C. or less.

[0022] In the invention of

[11] , [9] or

[10] , the first transparent substrate and the second transparent substrate may be resin sheets. According to this feature, a flexible electrochromic element for a light-controlling device can be obtained through a simple process.

[0023]

[12] In any one of the inventions [8] to

[11] , the electrolyte layer may contain one or more organic solvents selected from the group consisting of propylene carbonate, ethylene carbonate, and diethyl carbonate, together with one or more of bis(trifluoromethanesulfonyl)imide, lithium bis(trifluoromethanesulfonyl)imide, potassium bis(trifluoromethanesulfonyl)imide, and sodium bis(trifluoromethanesulfonyl)imide, and may be solidified with one or more of acrylic resin and epoxy resin; the first electrochromic layer may contain a transition metal oxide; the second electrochromic layer may contain a metal cyano complex; and the electrochromic element for the light-modulating device may be capable of changing color by applying a voltage to the first transparent electrode layer and the second transparent electrode layer.

[0024]

[13] In any one of the inventions [8] to

[12] , the invention may further include a photo-aging treatment step of irradiating the multilayer structure with light after formation of the multilayer structure. According to this feature, it is possible to stably and reliably provide an electrochromic element for a light-controlling device that imparts a color change in the mid-infrared band and a color change with high contrast in the near-infrared band.

[0025]

[14] A method for producing a transparent electrode layer used in an electrochromic element for a light-adjusting device, comprising: an electrode forming step of forming a transparent electrode layer on a transparent substrate; the electrode forming step includes a first step of forming, on the transparent substrate, a precursor film having an amorphous phase containing at least one of an oxide of indium (In) alone and an oxide of indium (In) containing one or more kinds selected from the group consisting of Ce, W, Ti, Zr, and Mo; and a second step of crystallizing the precursor film to form a transparent electrode layer having an amorphous phase of 70 cm. ２ and a second step of forming the transparent electrode layer having a carrier mobility of 1000 nm / V·s or more and a transmittance of 75% or more in the near-infrared band (800 to 2500 nm).

[0026] According to this feature, it is possible to provide an electrochromic element for a light-controlling device that provides a color change in the mid-infrared band and a color change with high contrast in the near-infrared band.

[0027] FIG. 1 is a cross-sectional view showing an electrochromic element according to the present invention; FIG. 2 is a diagram showing (a) a transmission spectrum and (b) a reflection spectrum of each transparent electrode layer; FIG. 3 is a diagram showing the surface roughness of each transparent electrode layer; FIG. 4 is a diagram showing the water contact angle of each transparent electrode layer after each treatment; ３ 1 shows the spectroscopic spectra when a thin film (multilayer film A) or a PB thin film (multilayer film B) is applied, and when no thin film is applied (substrate only). It is a table summarizing various spectroscopic characteristics. It is a diagram showing (a) a cyclic voltammogram of an ECD, and (b) the time change in transmittance related to the color change reaction. It is a diagram showing (a) the electrochemical characteristics of an ECD by chronocoulometry, and (b) the change in transmittance. It is a diagram showing the optical spectral changes in transmittance and reflectance for the bleaching reaction and coloring reaction of an ECD. It is a table summarizing various spectroscopic characteristics of an ECD. It is a diagram showing the time characteristics of the optical spectral change (transmittance when bleached) of an ECD. It is a diagram showing the optical characteristics (transmittance when bleached) of an ECD in the mid-infrared band, measured using Fourier transform infrared spectroscopy.

[0028] An electrochromic device (ECD) according to one embodiment of the present invention will be described in detail below.

[0029] 1, the electrochromic device (ECD) 1 has a multilayer structure using a transition metal oxide and a metal cyano complex as electrochromic materials (EC materials). That is, the electrochromic device (ECD) 1 has a first electrochromic (EC) layer 12a containing a transition metal oxide, a second electrochromic (EC) layer 12b containing a metal cyano complex, an electrolyte layer 10 sandwiched between these layers, and indium oxide (In) layers connected to the first EC layer 12a and the second EC layer 12b from the outside, respectively. ２ O ３The electrolytic capacitor includes a first transparent electrode layer 14a and a second transparent electrode layer 14b mainly composed of a crystalline polymer. The first transparent electrode layer 14a and the second transparent electrode layer 14b are further provided with a first transparent substrate 16a and a second transparent substrate 16b, each made of a transparent material such as resin or glass, on the outer side of the first transparent electrode layer 14a and the second transparent electrode layer 14b. That is, the first transparent substrate 16a, the first transparent electrode layer 14a, the first EC layer 12a, the electrolyte layer 10, the second EC layer 12b, the second transparent electrode layer 14b, and the second transparent substrate 16b are stacked in this order. In the following description, when it is not necessary to distinguish between the first transparent electrode layer 14a and the second transparent electrode layer 14b, they will be referred to as transparent electrode layers, and when it is not necessary to distinguish between the first transparent substrate 16a and the second transparent substrate 16b, they will be referred to as transparent substrates. As can be understood from the above explanation, the electrochromic element for a light-adjusting device according to this embodiment has a multilayer structure including a first electrochromic layer, an electrolyte layer, and a second electrochromic layer, in this order, between a first transparent electrode layer on a first transparent substrate and a second transparent electrode layer on a second transparent substrate.

[0030] In addition, indium oxide (In ２ O ３ The electrolyte layer 10, the first EC layer 12a, and the second EC layer 12b to be combined with the first transparent electrode layer 14a and the second transparent electrode layer 14b each having a main component of ethylenediaminetetraacetic acid (EPO) as a main component are preferably of a known structure disclosed in, for example, JP-A-2018-185424.

[0031] In other words, the transition metal oxide of the first EC layer 12a is a material that can change color depending on the electrolyte layer 10 described below, and in particular, is a material that reverses the coloring or decoloring reaction between the oxidized state and the reduced state compared to the second EC layer 12b. Specifically, the transition metal oxide of the first EC layer 12a can be, for example, tungsten oxide, molybdenum oxide, niobium oxide, vanadium oxide, titanium oxide, etc., and it is preferable to include at least one of these. It is preferable that the transition metal oxide be contained in the first EC layer 12a in an amount of 50 mass% or more.

[0032] The metal cyano complex of the second EC layer 12b may be a Prussian blue-type metal complex, but may be any other material that undergoes reversible electrochemical oxidation-reduction, and is a material that reverses the coloring and decoloring reactions under oxidized and reduced conditions compared to the first EC layer 12a. The metal cyano complex is preferably contained in the second EC layer 12b in an amount of 50% by mass or more.

[0033] When a metal cyano complex is used as the EC material, a typical manufacturing method involves forming a thin film of the EC material on the second transparent electrode layer 14b, and using this thin film as the EC layer. However, the manufacturing method of the EC layer is not limited as long as the desired color change can be achieved electrochemically. For example, the EC layer may be formed by dispersing a metal cyano complex in an electrolyte in contact with the second transparent electrode layer 14b.

[0034] Prussian blue-type metal complexes are those whose composition is A ｘ M [M' (CN) ６ ] ｙ ・zH ２ O. When M and M' are identified, the complex is called an M-M' cyano complex. For example, when M = zinc and M' = iron, the complex is called a zinc-iron cyano complex.

[0035] The composition of the metal cyano complex can be selected according to the required color change behavior. As the metal atom M, a metal atom selected from the group consisting of vanadium, chromium, manganese, iron, ruthenium, cobalt, rhodium, nickel, palladium, platinum, copper, silver, zinc, lanthanum, europium, gadolinium, lutetium, barium, strontium, and calcium is preferred, and a metal atom selected from the group consisting of vanadium, chromium, manganese, iron, ruthenium, cobalt, nickel, copper, and zinc is more preferred. Furthermore, as the metal atom M, a metal atom selected from the group consisting of manganese, iron, cobalt, nickel, copper, and zinc is particularly preferred.

[0036] The metal atom M' is preferably a metal atom selected from the group consisting of vanadium, chromium, molybdenum, tungsten, manganese, iron, ruthenium, cobalt, nickel, platinum, and copper, more preferably a metal atom selected from the group consisting of manganese, iron, ruthenium, cobalt, and platinum, and particularly preferably a metal atom selected from the group consisting of iron and cobalt.

[0037] A is an atom selected from the group consisting of hydrogen, lithium, sodium, potassium, rubidium, cesium, and ammonium, which is ionized from the metal cyano complex used to form a cation.

[0038] The Prussian blue-type metal cyano complex may be a mixture of one or more compositions selected from the above-described general formulas based on the combination of A, M, and M'. The Prussian blue-type metal cyano complex may also contain impurities such as other atoms that are not present in the composition.

[0039] Generally speaking, a small particle size is desirable for a metal cyano complex. That is, from the viewpoint of electrochemical response speed, it is preferable to increase the specific surface area by reducing the particle size. Furthermore, from the viewpoint of forming a smooth thin film, it is preferable to reduce the particle size of the metal cyano complex. Therefore, nanoparticles are preferable. For example, the primary particle size of the metal cyano complex is preferably 500 nm or less, more preferably 300 nm or less, and particularly preferably 100 nm or less. On the other hand, there is no lower limit for the primary particle size of the metal cyano complex, but practically, it is 4 nm or more. Here, the primary particle size refers to the diameter of the primary particle, and can be, for example, the circle-equivalent diameter of the primary particle derived from the half-width of the peak in powder X-ray structural analysis. Furthermore, when a ligand or the like is adsorbed on the particle surface, the primary particle size is derived as the primary particle excluding the ligand.

[0040] The first transparent electrode layer 14a and the second transparent electrode layer 14b of the present invention have a thickness of 70 cm ２ / V·s or more, and the transmittance in the near-infrared band (800 to 2500 nm) is 75% or more. From the viewpoint of even lower resistivity, the carrier mobility is 80 cm ２ / V·s or more, and ２ / V·s or more, and more preferably 100 cm ２ / V·s or more, and more preferably 110 cm ２ / V·s or more is particularly preferred. Furthermore, the transmittance in the near-infrared band (800 to 2500 nm) is more preferably 77% or more, and even more preferably 80% or more. The carrier mobility can be determined by measuring the Hall effect. The transmittance in the near-infrared band (800 to 2500 nm) can be determined from a transmission spectrum measured with a spectrophotometer. The upper limit of the carrier mobility and the upper limit of the transmittance in the near-infrared band (800 to 2500 nm) are not particularly limited.

[0041] The material constituting the transparent electrode layers (14a, 14b) is not limited as long as it is a conductive material and does not cause deterioration such as corrosion to the extent that it causes practical problems when used as an electrochemical element. In particular, a transparent electrode layer containing indium oxide exhibits high transmittance in the near-infrared band (wavelength 800 to 2500 nm), and its use in an element makes it possible to improve the ability to control the amount of sunlight absorbed in the near-infrared band.

[0042] The step of forming a transparent electrode layer (hereinafter referred to as the "electrode formation step") will be described in detail below. In the electrode formation step, a transparent electrode layer is formed on a transparent substrate. Specifically, the electrode formation step includes a first step and a second step.

[0043] The transparent substrate is preferably formed of a transparent material having a transmittance of 90% or more in the near-infrared band (800 to 2500 nm). Examples of such materials include polymeric materials such as acrylic resin, polyester (polyethylene terephthalate (PET), polyethylene naphthalate (PEN)), polyacrylonitrile, polystyrene, liquid crystal polymer (LCP), polyetherimide (PEI), and polycarbonate. The transparent substrate is preferably a resin sheet.

[0044] The first step is, for example, a step of forming a precursor film having an amorphous phase on a transparent substrate by physical vapor deposition using a target containing indium (In) oxide. Note that a precursor film having an amorphous phase only needs to contain a larger amount of amorphous phase components than polycrystalline components, and does not necessarily need to be entirely composed of amorphous phase. Specifically, the ratio of amorphous phase components to polycrystalline components (amorphous phase component / polycrystalline component) needs to be greater than 1. The amorphous phase component / polycrystalline component ratio can be determined within the range of an electron microscope observation image, for example, by combining crystal orientation analysis using electron backscatter diffraction (EBSD).

[0045] For example, when physical vapor deposition such as sputtering is used, the target is indium oxide (In ２ O ３ It is preferable that the material is made of a material containing indium oxide (In ２ O ３ The term "mainly composed of indium oxide" means that 97 mass % or more of the target is made up of indium oxide. ２ O ３ ) may contain other elements as dopant components. For example, indium oxide may contain at least one or more species selected from the group consisting of Ce, W, Ti, Zr, and Mo as dopant components. Specific examples include indium-cerium (ICeO) oxide, indium-tungsten (IWO) oxide, indium-titanium (ITiO) oxide, indium-zirconium (IZrO) oxide, and indium-molybdenum (IMoO) oxide. The target used in the first step contains at least one of an oxide of indium (In) alone and an oxide of indium (In) containing one or more species selected from the group consisting of Ce, W, Ti, Zr, and Mo. In the present embodiment, the term "indium oxide" includes both an oxide of indium (In) alone and an oxide of indium (In) containing one or more species selected from the group consisting of Ce, W, Ti, Zr, and Mo.

[0046] However, the method for forming (forming) the precursor in the first step is not particularly limited, and examples thereof include physical vapor deposition (PVD) methods such as vacuum deposition, DC magnetron sputtering, radio frequency magnetron sputtering, radio frequency superimposed DC magnetron sputtering, and ion plating, chemical vapor deposition (CVD) methods in which raw materials are reacted and deposited, and coating methods such as spraying, spin coating, dip coating, and screen printing. In the first step, regardless of the method for forming the precursor film, it is sufficient to form a precursor film containing an amorphous phase containing at least one of an oxide of indium (In) alone and an oxide of indium (In) containing one or more elements selected from the group consisting of Ce, W, Ti, Zr, and Mo on a transparent substrate.

[0047] In the second step, the precursor film formed in the first step is crystallized and ２ This is a process for forming a transparent electrode layer having a carrier mobility of 1 / V·s or more and a transmittance of 75% or more in the near-infrared band (800 to 2500 nm). The transparent electrode layer is mainly composed of a crystalline phase, but it is also expected that a small amount (for example, 10 mass % or less) of a phase other than the crystalline phase may be contained.

[0048] In the second step of this embodiment, the precursor film of the transparent electrode layer having an amorphous phase formed on the transparent substrate is heated and / or irradiated with light to cause crystal growth.

[0049] The heating temperature for heating the precursor film of the transparent electrode layer is preferably 150° C. or higher, more preferably 170° C. or higher. The atmosphere during heating is not particularly limited, and may be any of air, vacuum, oxygen gas, nitrogen gas, rare gas, hydrogen, or a mixed atmosphere of these. The atmospheric gas may be an air stream using a tubular furnace or the like, or may be a still chamber.

[0050] Even when irradiating the precursor film of the transparent electrode layer with light, the transparent substrate may be heated to a temperature not deteriorating the transparent substrate, preferably at room temperature or above and 100°C or below. This allows the use of a transparent substrate with low heat resistance, such as a resin sheet, which is flexible but whose heating is limited, and a flexible optical component can be obtained. The direction of light irradiation is not particularly limited, but it is preferable to irradiate the laminate consisting of a transparent substrate and a precursor film of the transparent electrode layer with light from the precursor film side.

[0051] The light irradiated onto the precursor film is not particularly limited, and examples thereof include an ArF excimer laser with a wavelength of 193 nm, a KrF excimer laser with a wavelength of 248 nm, a XeCl excimer laser with a wavelength of 308 nm, ultraviolet light, visible light, and infrared light. Among these, ultraviolet light including excimer laser is preferred because it has high photon energy and can promote crystallization by the precursor film absorbing the light energy. The light source for irradiating the light is not particularly limited, and examples thereof include an excimer lamp, an excimer laser, a YAG laser, a dye laser, a femtosecond laser, a high-pressure mercury lamp, a low-pressure mercury lamp, a microwave-excited metal halide lamp, a microwave-excited mercury lamp, and a flash lamp.

[0052] The intensity of the light irradiated onto the precursor film was 20 mJ / cm ２ It is preferable that the concentration is 30 mJ / cm or more. ２ It is more preferable that the intensity of the irradiated light is 20 mJ / cm or more. ２ If the temperature is above this level, crystallization of the transparent electrode layer is sufficiently promoted.

[0053] The atmosphere in which the precursor film is irradiated with light is not particularly limited, and may be any of air, vacuum, oxygen gas, nitrogen gas, rare gas, hydrogen, or a mixture thereof. The atmospheric gas may be an air flow using a tubular furnace or the like, or may be a static chamber.

[0054] The transparent electrode layer obtained in the second step is made of indium oxide (In ２ O ３ ) as the main component. ２O ３ The expression "containing indium oxide as a main component" means that 97 mass % or more of the entire transparent electrode layer is made of indium oxide. ２ O ３ ) contains at least one of an oxide of indium (In) and an oxide of indium (In) containing one or more elements selected from the group consisting of Ce, W, Ti, Zr, and Mo, as described above for the target material. The transparent electrode layer may further contain hydrogen in addition to a metal oxide such as indium oxide. This is because hydrogen may be present in the chamber during film formation and may be incorporated into the transparent electrode layer. Impurities contained in the raw material pellets or the target may be contained in the transparent electrode layer as inevitable impurities.

[0055] Although the transparent electrode layers 14a and 14b are typically smooth, plate-like bodies, they are not limited to being plate-like. In particular, increasing the contact area with the EC layers 12a and 12b improves response speed, so the smoothness of the transparent electrode layers 14a and 14b may be intentionally reduced. For example, a conductive material may be attached to the smooth surfaces of the transparent electrode layers 14a and 14b to create irregularities. Furthermore, other materials may be added to the transparent electrode layers 14a and 14b to improve adhesion with the EC layers 12a and 12b or to prevent corrosion. Furthermore, as long as electrical continuity is achieved between the EC layer 12a and the transparent electrode layer 14a, other materials, such as insulating materials, may be provided on the surface of the transparent electrode layer 14a opposite the EC layer 12a. Similarly, as long as electrical continuity is achieved between the EC layer 12b and the transparent electrode layer 14b, other materials, such as insulating materials, may be provided on the surface of the transparent electrode layer 14b opposite the EC layer 12b.

[0056] The characteristics of the transparent electrode layers (14a, 14b) formed by the above electrode formation process will be described in detail below.

[0057] The contact angle of the surface of the transparent electrode layer (14a, 14b) when made hydrophilic is, for example, 40° or less, preferably 30° or less, and more preferably 20° or less. The lower limit of the contact angle is not particularly limited, but is, for example, 10° or more.

[0058] The treatment for making the surface of the transparent electrode layer hydrophilic is plasma irradiation (plasma treatment) or ultraviolet irradiation (UV treatment). In the case of UV treatment, for example, a short wavelength 365 nm UV-LED, a low-pressure mercury lamp, or a high-pressure mercury lamp is suitable. In the case of plasma treatment, treatment by introducing argon or oxygen gas is considered, but there are no particular restrictions on the type of introduced gas as long as it can make the surface hydrophilic.

[0059] The electrolyte layer 10 contains at least bis(trifluoromethanesulfonyl)imide or a (trifluoromethanesulfonyl)imide salt. The (trifluoromethanesulfonyl)imide salt may be one or more of lithium bis(trifluoromethanesulfonyl)imide, potassium bis(trifluoromethanesulfonyl)imide, and sodium bis(trifluoromethanesulfonyl)imide. The electrolyte layer 10 may contain one or more organic solvents, such as propylene carbonate, ethylene carbonate, and diethyl carbonate, and may further contain one or more acrylic resins and epoxy resins, so that the electrolyte layer 10 can be solidified by heat and / or ultraviolet irradiation. The electrolyte layer 10 may be either transparent or non-transparent.

[0060] The ECD is driven by applying a voltage between the electrodes consisting of two transparent electrode layers 14a and 14b. That is, the color change between State 1, in which the first EC layer 12a is in an oxidized state and the second EC layer 12b is in a reduced state, and State 2, in which the first EC layer 12a is in a reduced state and the second EC layer 12b is in an oxidized state, can be controlled by applying a voltage. For example, State 1 is achieved by applying a voltage of −0.7 to −3.0 V, and State 2 is achieved by applying a voltage of 1.0 to 3.0 V.

[0061] For example, if tungsten oxide is used for the first EC layer 12a, an iron-iron cyano complex is used for the second EC layer 12b, and a transparent material is used for the electrolyte layer 10, the ECD exhibits a color change from dark blue to colorless and transparent. Tungsten oxide is almost colorless and transparent in its oxidized state, and the iron-iron cyano complex is almost colorless and transparent in its reduced state. Therefore, the ECD is colorless and transparent in State 1. Furthermore, tungsten oxide is colored blue in its reduced state, and the iron-iron cyano complex is colored blue in its oxidized state. Therefore, the ECD exhibits a dark blue color in State 2.

[0062] In one example of a method for manufacturing the entire electrochromic element according to this embodiment, the first transparent electrode layer 14a is formed on the first transparent substrate 16a and the second transparent electrode layer 14b is formed on the second transparent substrate 16b by the electrode formation process described above. The first EC layer 12a is then formed on the first transparent electrode layer 14a, and the second EC layer 12b is formed on the second transparent electrode layer 14b. Next, the electrolyte layer 10 is formed on the first EC layer 12a or the second EC layer 12b using, for example, a dispenser. The laminate on the first transparent substrate 16a side and the laminate on the second transparent substrate 16b side are then pressed together to form the electrochromic element. Note that the various steps of the manufacturing method of the present invention, other than the electrode formation step, can be performed using any known technique.

[0063] The method for manufacturing an electrochromic element according to this embodiment preferably includes a photo-aging treatment step of forming a multilayer structure including a first electrochromic layer, an electrolyte layer, and a second electrochromic layer in this order between a first transparent electrode layer on a first transparent substrate and a second transparent electrode layer on a second transparent substrate, and then irradiating the multilayer structure with light.

[0064] The photo-aging treatment step is a step of irradiating the formed multilayer structure with light in a predetermined wavelength range. For example, a photo-irradiation device that irradiates light in a wavelength range of 180 nm to 750 nm, preferably 180 nm to 380 nm, is used in the photo-aging treatment step.

[0065] Here, if the storage time is long after the formation of the multilayer structure, the transmittance in the bleached state in a specific wavelength range (about 700 to 1000 nm) may gradually decrease. By performing a photo-aging treatment step, the decreased transmittance in the bleached state can be increased.

[0066] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0067] [Transparent Electrode Layer (First Transparent Electrode Layer, Second Transparent Electrode Layer)] Here, a transparent electrode film of indium oxide having an amorphous phase was formed on a 30 × 30 mm glass substrate in an atmosphere containing water vapor, oxygen, and argon by high-frequency magnetron sputtering using a sintered body of indium oxide (single indium oxide) as a target. The substrate was not heated, and the film was formed at room temperature. The amount of water vapor introduced was 1 × 10 －４ The obtained film thickness was about 120 nm.

[0068] The film was then heat-treated in a vacuum at 200°C for 30 minutes to crystallize it, forming a crystalline indium oxide transparent electrode film. Hereinafter, the indium oxide transparent electrode film will be referred to as an IOH film, and when distinguishing between an amorphous transparent electrode film and a crystalline transparent electrode film, they will be referred to as an a-IOH film and a c-IOH film, respectively. A conventional ITO film was also prepared, and hereafter, the indium oxide transparent electrode film will be referred to as an ITO film in contrast to the IOH film. The c-IOH film corresponds to an example, and the a-IOH film and ITO film correspond to comparative examples.

[0069] Figure 2 shows the optical spectra of the IOH film and the ITO film. Compared to the ITO film, the IOH film has a high transmittance of 50% or more in the near-infrared band (wavelengths of 800 to 2500 nm) and also has reduced reflectance. In particular, the c-IOH film has a solar transmittance of 79 to 85%, approximately 80% or more, across the entire near-infrared band, achieving a transmittance variation range of 60% or more.

[0070] The carrier mobility of the ITO film is 38 cm ２ / V·s, while the carrier mobility of IOH was 30 cm２ / V·s, 124 cm for c-IOH film ２ / V·s. Generally, the carrier mobility is 70 cm ２ / V·s or more, sufficient infrared transmittance can be expected for various applications in electrochromic devices. The transmittance was measured using an ultraviolet-visible-near-infrared spectrophotometer. The carrier mobility was measured by Hall effect measurement using a resistivity / Hall measurement system (ResiTest 8300, manufactured by Toyo Corporation).

[0071] The results of measuring the surface shapes of the IOH film and the ITO film are shown in Figure 3. The IOH film was smoother than the ITO film, and the c-IOH film was smoother than the a-IOH film.

[0072] Figure 4 shows the water contact angles of IOH and ITO films whose surfaces were hydrophilized by plasma irradiation (plasma treatment) or ultraviolet irradiation (UV treatment), along with the measured values ​​before and after treatment in an untreated state. Because an EC layer is formed on the transparent electrode layer using a wet process, surface wettability is a very important parameter in the manufacturing process. Plasma treatment was performed for 3 minutes using a Harrick Plasma plasma cleaner. UV treatment was performed for 1 minute using a UV-LED light source with a wavelength of 365 nm. The arithmetic mean height (Sa) and maximum height (Sz) were calculated using a laser displacement meter using white light interferometry. As can be seen from Figure 4, c-IOH had the smallest contact angle, particularly when surface-modified by UV treatment (ultraviolet irradiation). Note that the water contact angle for surface modification by plasma treatment was 0° because it exceeded the measurement limit of the dynamic contact angle measured by a contact angle meter.

[0073] [EC Layer on Transparent Electrode Layer] Various characteristics will be described when the first EC layer is provided on the first transparent electrode layer and the second EC layer is provided on the second transparent electrode layer.

[0074] <First EC Layer> A thin film made of tungsten oxide was formed as the first EC layer on the coated glass substrate (corresponding to the first transparent base material and the first transparent electrode layer) provided with an IOH film (multilayer film A).

[0075] Here, 75 μL of the tungsten oxide nanoparticle dispersion was measured with a micropipette and dropped onto a 30 × 30 mm IOH-coated glass substrate placed on a spin coater, and the substrate was rotated at 200 rpm for 600 seconds, and then at 1600 rpm for 10 seconds to form a thin film. The resulting film thickness was approximately 600 nm (multilayer film A). Note that hereinafter, the tungsten oxide thin film will be referred to as WO ３ It is referred to as a thin film.

[0076] From the viewpoint of increasing the efficiency of film formation, the method of producing a tungsten oxide thin film using a tungsten oxide nanoparticle dispersion liquid as described above is superior, but there are no limitations as long as it is possible to cause an oxidation-reduction reaction suitable for ECD, and a sol-gel method using tungsten chloride, metallic tungsten, or the like, or a vacuum process such as a vapor deposition method or a sputtering method, which are simple physical processes, can also be used.

[0077] <Second EC Layer> A thin film of a metal cyano complex was formed as an EC layer on the coated glass substrate (corresponding to the second transparent substrate and second transparent electrode layer) provided with an IOH film (multilayer film B).

[0078] Here, 30 mL of an aqueous solution of 16.2 g of iron nitrate nonahydrate dissolved in water was mixed with 14.5 g of sodium ferrocyanide decahydrate dissolved in 60 mL of water, and the mixture was stirred for 5 minutes. The resulting precipitate of Prussian blue, a blue iron-iron cyano complex, was centrifuged, washed three times with water, then once with methanol, and dried under reduced pressure to obtain sample AFe1. The yield was 11.0 g, and the yield was Fe[Fe(CN) ６ ] ０．７５ ・3.75H ２ The precipitate of the prepared iron-iron cyano complex was analyzed by a powder X-ray diffractometer, and found to be identical to Fe, which is Prussian blue, found in a standard sample database. ４ [Fe(CN) ６ ] ３ Measurement by transmission electron microscope revealed that sample AFe1 was an aggregate of nanoparticles with diameters of 5 to 20 nm.

[0079] Next, 0.40 g of the sample AFe1 obtained above was suspended in 8 mL of water. 80 mg of sodium ferrocyanide decahydrate was added to this suspension, and upon stirring, the solution turned into a transparent blue solution. In this way, a dispersion of an iron-iron cyano complex was obtained. A thin film of the iron-iron cyano complex was formed on a 30 x 30 mm IOH-coated glass substrate by spin coating. More specifically, 75 μL of the dispersion adjusted to 9 wt % was dropped, and the substrate was rotated at 800 rpm for 10 seconds, followed by rotation at 1600 rpm for 10 seconds to form a thin film of the iron-iron cyano complex on the IOH-coated glass substrate. The resulting film thickness was approximately 1000 nm (multilayer film B). Here, the iron-iron cyano complex thin film is referred to as a PB thin film. Multilayer films A and B of the ITO films were also obtained using the same method as for the IOH film.

[0080] <Various characteristics of the first EC layer and the second EC layer> Figure 5 shows the optical spectra of the multilayer films A and B described above, which are composed of an ITO film, a c-IOH film, and an a-IOH film, and a coated glass substrate coated with only a transparent electrode layer for comparison. ３ In both the multilayer film B (including the PB thin film) and the multilayer film C (including the PB thin film), the transmittance in the near-infrared region was affected by the transmittance of the coated glass substrate on which the transparent electrode layer was coated. Therefore, the multilayer film A (WO ３ Multilayer film B (including PB thin film) showed a high transmittance of 70% or more in the wavelength range of 1300 to 2500 nm, and multilayer film B (including PB thin film) showed a high transmittance of approximately 80% or more in the same wavelength range.

[0081] FIG. 6 shows the results of measurements of the transmission spectrum of the ECD in which the first EC layer and the second EC layer are combined.

[0082] As mentioned above, ECD is ３An electrolyte layer was sandwiched between a glass substrate coated with a transparent electrode layer on which a thin film had been formed and a glass substrate coated with a transparent electrode layer on which a PB thin film had been formed, with each glass substrate facing outward. The electrolyte for the electrolyte layer was a 0.5 mol / L solution of potassium bis(trifluoromethanesulfonyl)imide (KTFSI) in propylene carbonate, to which acrylic resin had been added to make a total volume of 0.06 ml. The electrolyte was solidified by irradiating it with ultraviolet light, to form an all-solid-state device.

[0083] Figure 7(a) shows the cyclic voltammogram (CV) of the ECD measured at a scan rate of 5 mV / s when each transparent electrode layer was used, and Figure 7(b) shows the time change in transmittance associated with the color change reaction. The CV curve of the element using c-IOH (crystalline) almost overlapped with the curve when using the existing ITO substrate, but the timing of the applied voltage generating the peak current associated with the color change reaction was delayed in the element using a-IOH (amorphous). In other words, c-IOH is considered to be more suitable as a transparent electrode layer for use in the element.

[0084] Figure 8(a) shows the electrochemical characteristics of the ECD measured by chronocoulometry (CC). The measurement conditions were CC1 (+1.0 V → -1.2 V x 60 seconds) and CC2 (-1.2 V → +1.0 V x 60 seconds). Figure 8(b) shows the results of measuring the transmittance at 60 seconds in (a). It can be seen that the charging rate is clearly slower in the element using a-IOH.

[0085] Figure 9 shows the optical spectra of the ECDs using each transparent electrode layer, showing (a) the transmittance when bleached, (b) the reflectance when bleached, (c) the transmittance when colored, and (d) the reflectance when colored. All ECDs were bleached with an applied voltage of +1 V and colored with an applied voltage of -1.2 V. The optical characteristics change. Measurements were taken on the day the devices were assembled. The bleached transmittance of the devices using c-IOH and a-IOH was approximately 30% in the wavelength range of approximately 1300 nm, which was not significantly higher than that of the devices using ITO films. In contrast, the colored transmittance was almost the same in the wavelength range of 250 to 1500 nm, but the devices using IOH films tended to have higher transmittance at wavelengths of 1500 nm or higher. Overall, it can be seen that from the visible light to near-infrared range, c-IOH, a-IOH, and ITO are superior in this order.

[0086] FIG. 10 summarizes the relevant optical properties calculated from FIG.

[0087] Figure 11 shows the results of the change over time in the optical spectrum of ECDs fabricated with transparent electrode layers of (a) ITO, (b) c-IOH, and (c) a-IOH. The voltage application conditions are the same as those in Figure 9. For all elements, the bleached transmittance in the approximately 700-1000 nm band gradually decreases over time when stored indoors. This decrease can be largely restored by photoaging (irradiation with simulated sunlight or UV light for several minutes). In the examples, photoaging was performed by irradiating light using a xenon weather meter that emits light approximating full-spectrum natural sunlight. Furthermore, for (b) c-IOH and (c) a-IOH, the bleached transmittance was initially low at approximately 20-30% in the wavelength range of 1000 nm or more, but increased to over 60% over time. Similarly, the bleached transmittance can also be increased by second photoaging. In other words, stable operation can be expected by performing light aging treatment during the manufacturing process.

[0088] Figure 12 shows the optical characteristics (transmittance when bleached) of an ECD in the mid-infrared band measured using Fourier transform infrared spectroscopy. An element using an ITO film transmits almost no light in the mid-infrared band, but an element using an IOH film maintains transmittance. Thus, by using an IOH film, it is possible to switch the optical characteristics up to the mid-infrared band and produce color changes.

[0089] As described above, the present invention makes it possible to realize an electrochromic element that can tune optical properties in the near-infrared to mid-infrared band (800 to 4000 nm), and that performs high-contrast coloring and bleaching with a large range of transmittance change, particularly in the near-infrared band (800 to 2500 nm). Such an element is expected to be used in light-controlling devices such as light-controlling glass, displays, and indicator elements, and because it has improved controllability, particularly of long-wavelength components, compared to existing technologies, it is expected to be used as a component of an energy-saving light-controlling device that optimizes the inflow of infrared rays, which are the heat component of solar energy, into window glass for automobiles, building materials, etc.

[0090] Although the embodiments of the present invention have been described above, the present invention is not necessarily limited to these, and a person skilled in the art will be able to find various alternative embodiments and modifications without departing from the spirit of the present invention or the scope of the appended claims.

[0091] REFERENCE SIGNS LIST 1 Electrochromic device (ECD) 10 Electrolyte layer 12a First electrochromic (EC) layer 12b Second electrochromic (EC) layer 14a First transparent electrode layer 14b Second transparent electrode layer 16a First transparent substrate 16b Second transparent substrate

Claims

1. An electrochromic element for a dimming device having a multilayer structure comprising a first transparent electrode layer on a first transparent substrate and a second transparent electrode layer on a second transparent substrate, with a first electrochromic layer, an electrolyte layer, and a second electrochromic layer in that order between them, The first transparent electrode layer and the second transparent electrode layer each contain at least one of indium (In) oxide alone and indium (In) oxide containing one or more elements selected from the group consisting of Ce, W, Zr, and Mo, and are 70 cm². ２ An electrochromic element for dimming devices, characterized by having a carrier mobility of 1 / V·s or higher and a transmittance of 75% or higher in the near-infrared band (800-2500 nm).

2. The electrochromic element for a dimming device according to claim 1, characterized in that the first transparent electrode layer and the second transparent electrode layer are made of a crystalline phase obtained by crystallizing an amorphous phase.

3. The electrochromic element for a dimming device according to claim 2, characterized in that the first transparent substrate and the second transparent substrate are resin sheets.

4. The electrolyte layer contains one or more of the following: bis(trifluoromethanesulfonyl)imide, lithium bis(trifluoromethanesulfonyl)imide, potassium bis(trifluoromethanesulfonyl)imide, and sodium bis(trifluoromethanesulfonyl)imide, along with one or more of the following organic solvents: propylene carbonate, ethylene carbonate, and diethyl carbonate, and is solidified with one or more of the following: acrylic resin or epoxy resin. The first electrochromic layer contains a transition metal oxide, and the second electrochromic layer contains a metal cyano complex. An electrochromic element for a dimming device according to one of claims 1 to 3, characterized in that it enables color change by applying a voltage to the first transparent electrode layer and the second transparent electrode layer.

5. The electrochromic element for a dimming device according to claim 4, characterized in that the transition metal oxide includes at least one of tungsten oxide, molybdenum oxide, niobium oxide, vanadium oxide, and titanium oxide.

6. The aforementioned metal cyano complex is A is a cation composed of atoms selected from the group consisting of hydrogen, lithium, sodium, potassium, rubidium, cesium, and ammonium. M is a metal atom selected from the group consisting of vanadium, chromium, manganese, iron, ruthenium, cobalt, rhodium, nickel, palladium, platinum, copper, silver, zinc, lanthanum, europium, gadolinium, lutetium, barium, strontium, and calcium. M' is a metal atom selected from the group consisting of vanadium, chromium, molybdenum, tungsten, manganese, iron, ruthenium, cobalt, nickel, platinum, and copper. Let x be a rational number between 0 and 3, y be a rational number between 0.3 and 1.5, and z be a rational number between 0 and 30. A ｘ M[M'(CN) ６ ] ｙ ・zH ２ O The electrochromic element for a dimming device according to claim 4, characterized in that it is a Prussian blue type metal complex consisting of one or more types selected from the group represented by the general formula.

7. A transparent electrode layer used in an electrochromic element for a dimming device, Formed on a transparent substrate, The solution comprises at least one element of indium (In) oxide, and at least one of indium (In) oxides containing one or more elements selected from the group consisting of Ce, W, Zr, and Mo, and is 70 cm². ２ A transparent electrode layer characterized by having a carrier mobility of 1 / V·s or higher, and a transmittance of 75% or higher in the near-infrared band (800-2500 nm).

8. A method for manufacturing an electrochromic element for a dimming device having a multilayer structure comprising a first electrochromic layer, an electrolyte layer, and a second electrochromic layer in that order between a first transparent electrode layer on a first transparent substrate and a second transparent electrode layer on a second transparent substrate, The process includes the steps of forming a first transparent electrode layer on the first transparent substrate and / or forming a second transparent electrode layer on the second transparent substrate, The electrode formation step is, A first step of forming a precursor film on the first transparent substrate and / or the second transparent substrate, the precursor film comprising an amorphous phase containing at least one of indium (In) oxide and one or more indium (In) oxides selected from the group consisting of Ce, W, Zr, and Mo, The precursor film is crystallized, and 70 cm ２ A method for manufacturing an electrochromic element for a dimming device, comprising: a second step of forming the first transparent electrode layer and / or the second transparent electrode layer having a carrier mobility of 1 / V·s or higher and a transmittance of 75% or higher in the near-infrared band (800 to 2500 nm).

9. The method for manufacturing an electrochromic element for a dimming device according to claim 8, characterized in that the second step includes a step of irradiating with light.

10. The method for manufacturing an electrochromic element for a dimming device according to claim 9, characterized in that the second step is a step of processing at a temperature of 100°C or less.

11. A method for manufacturing an electrochromic element for a dimming device according to claim 9 or 10, characterized in that the first transparent substrate and the second transparent substrate are resin sheets.

12. The electrolyte layer contains one or more of the following: bis(trifluoromethanesulfonyl)imide, lithium bis(trifluoromethanesulfonyl)imide, potassium bis(trifluoromethanesulfonyl)imide, and sodium bis(trifluoromethanesulfonyl)imide, along with one or more of the following organic solvents: propylene carbonate, ethylene carbonate, and diethyl carbonate, and is solidified with one or more of the following: acrylic resin or epoxy resin. The first electrochromic layer contains a transition metal oxide, and the second electrochromic layer contains a metal cyano complex. The method for manufacturing an electrochromic element for a dimming device according to claim 8, characterized in that the electrochromic element for the dimming device is capable of changing color by applying a voltage to the first transparent electrode layer and the second transparent electrode layer.

13. A method for manufacturing an electrochromic element for a dimming device according to claim 8, characterized in that it includes a photoaging process of irradiating with light after forming the multilayer structure.

14. A method for manufacturing a transparent electrode layer used in an electrochromic element for a dimming device, The process includes an electrode formation step of forming a transparent electrode layer on a transparent substrate, The electrode formation step is, A first step is to form a precursor film having an amorphous phase on the transparent substrate, which includes at least one of indium (In) oxide element and indium (In) oxide containing one or more elements selected from the group consisting of Ce, W, Zr, and Mo. The precursor film is crystallized, and 70 cm ２ A method for manufacturing a transparent electrode layer, comprising a second step of forming the transparent electrode layer having a carrier mobility of 1 / V·s or higher and a transmittance of 75% or higher in the near-infrared band (800 to 2500 nm).