JPH09152632A - Electrochromic device and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the resistance of an electrochromic(EC) device to repetitive use at the time of high-contrast driving and the environmental resistance at high temp. and humidity by forming a 1st transparent ionic conductive layer in an atmosphere of steam and a 2nd transparent ionic conductive layer in an atmosphere of oxygen. SOLUTION: A transparent electrode (transparent electrically conductive layer) 2a, an oxidation coloring EC layer 3, a layer 4 of a mixture of an oxidation coloring EC substance with a metal oxide, 1st and 2nd transparent ionic conductive layers 5, 6, a reduction coloring EC layer 7 and a transparent electrode (transparent electrically conductive layer) 2b are successively laminated on a transparent substrate 1 to obtain the objective EC device 10. Each of the 1st and 2nd transparent ionic conductive layer 5, 6 are made preferably of Ta2 O5 , ZrO2 , SiO2 or a mixture of such oxides, especially Ta2 O5 . The layer 5 is formed in an atmosphere contg. steam and the layer 6 is formed in an atmosphere contg. oxygen.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrochromic element used for a variable transmittance filter, a display element and the like and a method for manufacturing the same, and more particularly to an all-solid-state electrochromic element and a method for manufacturing the same.

[0002]

2. Description of the Related Art An electrochromic device (hereinafter referred to as an EC device) that is colored and erased by applying an electric field is
Compared with ordinary liquid crystal elements, etc., they have characteristics such as high light transmittance at the time of erasing, being unaffected by polarized light, and having memory characteristics, so application to display elements and variable transmittance filters has been studied. ing.

As an example of such an EC element, as shown in FIG. 5, a pair of transparent electrodes (transparent conductive layers) 102a, 1
02b, a reduction coloring electrochromic layer 105 made of tungsten oxide, molybdenum oxide or a mixture thereof, and an insulating thin film 10 made of tantalum pentoxide.
4 and a oxidative color forming electrochromic layer 103 consisting essentially of iridium hydroxide, nickel hydroxide or a mixture thereof, a five-layered complementary EC device is known (Japanese Patent Publication No. 60-31355). Bulletin, USP
4,350,414). The 5-layer structure is formed on the transparent substrate 101.

As the oxidative coloring electrochromic layer 103, a transparent dispersion layer formed of a dispersoid composed of iridium metal itself or its oxide or hydroxide thereof and a transparent solid dispersion medium is used. A complementary EC device having a five-layer structure is known (Japanese Patent Publication No. 5-333).
73, USP 4,652,090).

Further, a transparent conductive film for improving the coloring efficiency (response speed) and the decrease in the amount of change in optical density during aging (durability during repeated driving; hereinafter simply referred to as repeated durability), At least one of a tungsten trioxide-based electrochromic material layer (reduction coloring electrochromic layer) and a dielectric layer (transparent ion conductive layer) is formed by a physical vapor deposition method in an atmosphere containing water vapor. A method of manufacturing an EC element is disclosed in Japanese Patent Application Laid-Open No. 56-130723. In this manufacturing method, it is particularly effective to form the dielectric layer (transparent ion conductive layer) by the physical vapor deposition method in an atmosphere containing water vapor from the viewpoint of improving the coloring efficiency (response speed).

[0006]

However, in this manufacturing method, since the adhesion between the reduction coloring electrochromic layer and the dielectric layer (transparent ion conductive layer) is poor, the contrast ratio is set to 10 or more and repeated driving is performed. Go or
When left in an environment of high temperature and high humidity for a long time, there are problems that delamination occurs and the coloring speed becomes slow.

Therefore, an object of the present invention is to improve the repeated durability of the EC element during high contrast driving and the environmental resistance at high temperature and high humidity.

[0008]

In order to achieve the above object, the present invention provides a pair of opposing transparent conductive layers, a first transparent ion conductive layer sandwiched between the transparent conductive layers, and the first transparent ion conductive layer. An electrochromic device comprising at least a second transparent ion conductive layer adjacent to the transparent ion conductive layer, and a reduction color forming electrochromic layer adjacent to the second transparent ion conductive layer, wherein the first transparent The ion conductive layer is a layer formed in a water vapor atmosphere, and the second transparent ion conductive layer is a layer formed in an oxygen atmosphere, which is an electrochromic device.

The present invention also provides a pair of opposing transparent conductive layers, a first transparent ion conductive layer sandwiched between the transparent conductive layers, and a second transparent ion adjacent to the first transparent ion conductive layer. A method for producing an electrochromic device having at least a conductive layer and a reduction color forming electrochromic layer adjacent to the second transparent ion electric component layer, wherein the first transparent ion conductive layer is formed in a steam atmosphere. Then
The method for producing an electrochromic device is characterized in that the second transparent ion conductive layer is formed in an oxygen atmosphere.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Preferred embodiments of the present invention will be described below with reference to the drawings.

FIG. 1 is an EC according to an embodiment of the present invention.
3 is a schematic cross-sectional view showing the layer structure of the element 10. FIG.

The EC element 10 according to the present embodiment comprises a transparent electrode (transparent conductive layer) 2a, an oxidative coloring electrochromic layer 3, a mixture of an oxidative coloring electrochromic substance and a metal oxide on a transparent substrate 1. A layer (hereinafter, simply referred to as a mixed layer) 4, a first transparent ion conductive layer 5, a second transparent ion conductive layer 6, a reduction coloring electrochromic layer 7, and a transparent electrode (transparent conductive layer) 2b. It is an EC device having a laminated 7-layer structure. Of these layers, the oxidative coloring electrochromic layer 3 and the mixed layer 4
It is possible not to provide either one of them, but it is preferable to provide both of them because various characteristics can be improved.

A glass substrate is preferably used as the transparent substrate 1, but a substrate made of various transparent materials such as plastic can be used depending on the application of the EC device. Further, on the surface of the transparent substrate 1 opposite to the transparent electrode 2a, a single layer film made of a dielectric material such as Al ₂ O ₃ , TiO ₂ , MgF ₂ or a laminate of a plurality of single layer films is provided. Anti-reflection coating (AR
It is preferable to apply C).

In ₂ O is used as the transparent electrodes 2a and 2b.
₃ , SnO ₂ , ITO (indium tin oxide) and the like can be used, but ITO is preferable in terms of optical characteristics (light transmittance), resistance value, etc., and the ratio of In ₂ O ₃ to SnO ₂ is 95. : ITO of about 5 is more preferable. Incidentally, the resistivity of the transparent electrode formed later (2b in the present embodiment) is the transparent electrode formed earlier (2a in the present embodiment).
It may be higher than the resistivity of. Therefore, it is preferable that the thickness of the transparent electrode formed later is thicker than the thickness of the transparent electrode formed earlier.

The oxidative coloring electrochromic layer 3 comprises
Co, Ni, Fe, Ir, Cu, Ru, Rh, Pd, P
It is preferable to have at least one selected from t, Cr, Dy, and Er, and these are simple metals (M), oxides (MO _x ) thereof, or hydroxides (M _x ) thereof.
(OH) _x ) or its acid hydroxide (MO _x (OH)
It exists in the form of _y or a mixture thereof. The oxidative coloring electrochromic layer 3 is composed of iridium, iridium oxide, iridium hydroxide, iridium oxyhydroxide, cobalt, cobalt oxide, cobalt hydroxide, cobalt oxyhydroxide and nickel in terms of optical characteristics and repeated durability. More preferably, nickel oxide, nickel hydroxide, nickel oxyhydroxide, or a mixture of two or more substances selected from these.

The thickness of the oxidative coloring electrochromic layer 3 is preferably 1 nm to 50 nm. Layer thickness is 1 nm
If it becomes smaller than this, repeated durability deteriorates and the layer thickness becomes 5
When it is larger than 0 nm, the absorbance is large.

The oxidative coloring electrochromic material used for the mixed layer 4 is Co, Ni, Fe, Ir, Cu,
It is preferable to have at least one selected from Ru, Rh, Pd, Pt, Cr, Dy, and Er.
In the state of a metal simple substance (M), its oxide (MO _x ), its hydroxide (M (OH) _x ), its acid hydroxide (MO _x (OH) _y ), or a mixture thereof. Existing. Further, as the oxidative coloring electrochromic substance, in terms of optical characteristics and repeated durability, iridium, iridium oxide, iridium hydroxide, iridium oxide hydroxide, cobalt, cobalt oxide, cobalt hydroxide, cobalt oxyhydroxide, nickel. More preferably, nickel oxide, nickel hydroxide, nickel oxyhydroxide, or a mixture of two or more substances selected from these.

As the metal oxide used for the mixed layer 4, one having a high light transmittance is preferable. Further, the metal oxide has an electrochromism under a practical voltage application condition,
In particular, a substance that does not exhibit electrochromism by reducing coloring is preferable. Specific examples of the metal oxide include TiO ₂ , Ta ₂ O ₅ , ZrO ₂ , HfO ₂ , and Y _2.
One kind selected from O ₃ , Al ₂ O ₃ , SiO ₂ and SnO ₂ or a mixture of two or more kinds is preferable.

In the mixed layer 4, the weight ratio of the oxidative coloring electrochromic substance and the metal oxide is 0.02 ≦.
(Oxidative coloring electrochromic substance / metal oxide)
It is preferable that ≦ 1. When the weight ratio is greater than 1, the absorbance is high, and when the weight ratio is less than 0.02, the coloring speed (response speed) is slow and the durability is poor.

The layer thickness of the mixed layer 4 is from 10 nm to
5000 nm is desirable in terms of response speed and light transmittance.
When the layer thickness is greater than 5000 nm, the absorbance is high, and when the layer thickness is less than 10 nm, the coloring speed (response speed) is slow and the durability is poor.

The first transparent ion conductive layer 5 and the second transparent ion conductive layer 6 are made of Ta ₂ O ₅ , ZrO ₂ , SiO ₂ ,
It is preferably made of MgF ₂ or a mixture thereof, and Ta ₂ O ₅ is particularly preferable in terms of optical characteristics and repeated durability.

The first transparent ion conductive layer is a layer formed in an atmosphere containing water vapor, and the second transparent ion conductive layer is a layer formed in an atmosphere containing oxygen.

The reduction color forming electrochromic layer 7 comprises
WO ₃ , MoO ₃ , Nb ₂ O ₅ or a mixture thereof is preferable, and WO ₃ is particularly preferable in terms of coloring speed. Further, by forming the reduction color-forming electrochromic layer 7 using a mixture of WO ₃ and MoO ₃ , it is possible to obtain an EC element which becomes black when colored.

The layer thickness of each layer other than the oxidative coloring electrochromic layer 3 and the mixed layer 4 is 1 nm to 5000 nm.
Is preferable, and it is determined by required optical characteristics, repeated durability, and the like.

The EC device 10 according to the present embodiment comprises a transparent electrode 2a, an oxidative coloring electrochromic layer 3, a mixed layer 4, a first transparent ion conductive layer 5 on a transparent substrate 1.
The second transparent ion conductive layer 6, the reduction color-forming electrochromic layer 7, and the transparent electrode 2b are sequentially laminated,
On the contrary, on the transparent substrate, a transparent electrode, a reduction coloring electrochromic layer, a second transparent ion conductive layer, a first transparent ion conductive layer, a mixed layer, an oxidation coloring electrochromic layer, a transparent electrode are laminated in this order. It may have been done.

Next, the EC device 10 according to the present embodiment.
A method of manufacturing the device will be described.

First, the transparent electrode (transparent conductive layer) 2a is formed on the transparent substrate 1 by a known film forming method such as vacuum deposition, sputtering, ion plating, and CVD.

Next, the oxidative coloring electrochromic layer 3 is formed on the transparent electrode 2a by a known film forming method such as vacuum deposition, sputtering, ion plating or CVD.

Next, the mixed layer 4 is formed on the oxidative coloring electrochromic layer 3. The mixed layer 4 is preferably formed by a sputtering method in an atmosphere of steam, oxygen, a mixed gas of steam and oxygen, or a mixed gas of steam and argon. The sputtering is preferably performed in an atmosphere of water vapor, a mixed gas of water vapor and oxygen, or a mixed gas of water vapor and argon. In the above sputtering, water vapor or a mixed gas of water vapor and argon (gas pressure 1 Pa to 20 Pa, mixing ratio (flow rate ratio) of water vapor and argon: water vapor / Ar ≧ 0.
It is more preferable to carry out in the atmosphere of 5). here,
When sputtering is performed in a steam atmosphere or in a range where the mixing ratio (flow rate ratio) of steam and argon exceeds 20, the gas pressure is preferably 10 Pa or less. Further, when the sputtering is performed in a range where the mixing ratio (flow rate ratio) of water vapor and argon is 0.5 or more and 20 or less, the gas pressure is preferably 20 Pa or less. When the gas pressure is higher than these values, the film forming rate becomes slow, the productivity is deteriorated, and the vacuum pump (cryo pump, diffusion pump, etc.) of the exhaust system is adversely affected. When the gas pressure is less than 1 Pa, or when the mixing ratio (flow rate ratio) of water vapor and argon is less than 0.5, the absorbance of the mixed layer 4 increases. When the gas pressure is less than 1 Pa, the discharge stability becomes poor. More preferably, sputtering is performed under the conditions of 0.5 ≦ (water vapor / Ar) ≦ 20 and a gas pressure of 1 Pa or more and 10 Pa or less.

When these layers 3 and 4 are formed by the sputtering method, it is preferable to perform them at room temperature. At that time, the temperature may increase due to plasma, but the temperature after the increase is preferably 100 ° C. or lower.

Next, the first transparent ion conductive layer 5 and the second transparent ion conductive layer 6 are sequentially formed by the known film forming method as described above. At that time, the first transparent ion conductive layer is formed by forming a film in an atmosphere containing water vapor,
The second transparent ion conductive layer is formed by forming a film in an oxygen-containing atmosphere. It is preferable that these transparent ion conductive layers are formed by a vacuum vapor deposition method at a substrate temperature of 200 ° C. or higher in order to enhance the adhesiveness with a reduction color-forming electrochromic layer formed later. In consideration of the heat resistance of the glass substrate, the substrate temperature is preferably 400 ° C or lower. Further, these transparent ion conductive layers are preferably formed under an atmosphere of a gas pressure of 1 × 10 ⁻³ Pa to ¹ × 10 ⁻¹ Pa.

Subsequently, the electrochromic electrochromic layer 7 and the transparent electrode (transparent conductive layer) 2b are sequentially formed by the above-mentioned known film forming method to manufacture the EC device 10.
It should be noted that the reduction coloring electrochromic layer 7 is formed by a vacuum vapor deposition method under the conditions of a substrate temperature of 200 ° C. or higher in an oxygen-containing atmosphere in order to enhance the adhesion with the second transparent ion conductive layer 6. preferable. In consideration of the heat resistance of the glass substrate, the substrate temperature is preferably 400 ° C or lower.

Next, as a modification of the EC element according to the present embodiment, there is an EC element 20 as shown in FIG.

The EC element 20 will be described below with reference to FIG. The transparent electrode (transparent conductive layer) 2a is formed to the outside of one side surface (left side in FIG. 2) of the other layer. This outer portion is a portion for external connection (electrode extraction portion). The other transparent electrode (transparent conductive layer) 2b
Is formed to extend to the vicinity of the substrate 1 along the side surface of each layer 2a, 3, 4, 5, 6, 7 and has a portion for external connection (electrode extraction portion) on the substrate 1. There is. still,
In this EC element 20, the transparent electrode 2b and each layer 2
It is necessary to prevent the movement of electrons between a, 3, and 4. Therefore, for example, one or both of the transparent ion conductive layers 5 and 6 are formed to extend along the side surfaces of the layers 2a, 3 and 4 to the substrate 1. In FIG. 2, the reduction coloring electrochromic layer 7 is also formed to extend to the substrate 1, but it is not always necessary to do so.

The EC device 20 includes layers 2a, 3, 4,
In the step of forming 5, 6, 7, 2b, the shape as described above is obtained by, for example, changing the shape of the mask at the time of formation or shifting the position of the mask.

Hereinafter, preferred examples of the shape of the mask and the position of the mask when forming each layer will be described centering on the opening of the mask. The opening of the mask when forming the layer 2a is
It corresponds to the effective optical modulation area of the EC element and one external connection portion. The opening of the mask when forming the layers 3 and 4 corresponds to the effective optical modulation area of the EC element.
The opening of the mask when forming the layer 5 corresponds to the effective optical modulation area of the EC element and the portion for preventing electron transfer between the layer 2b and the layers 4, 3, 2a. Layer 6,
The openings of the mask when forming 7 and 2b correspond to the effective optical modulation area of the EC element and the other external connection portion. The shape of the mask when forming the layers 6, 7, 2b is
It may be the same as the mask for forming the layer 2a, and in that case, the mask for forming the layer 2a may be used in the reverse direction (rotated by about 180 °).

In this embodiment and its modification, each layer may contain impurities to the extent that its function is not deteriorated (specifically, 1% or less).

EC according to the present embodiment and its modification
The device is used after mounting. FIG. 3 is a schematic schematic cross-sectional view showing an example of a state after mounting the EC element 10 according to the present embodiment.

The transparent electrodes 2a, 2b of the EC element 10 are connected to a power source 32 by a conductor 31. A transparent substrate 8 is provided so as to face the transparent electrode 2b, and a transparent substrate 8 is provided between the transparent substrate 8 and the transparent electrode 2b and around each layer between the transparent electrode 2a and the transparent electrode 2b. A different resin 9 is provided. That is, the EC element 10 is resin-sealed. The resin 9 has a role of adhering the transparent electrode 2b and the transparent substrate 8 together with the oxidation coloring electrochromic layer 3, the mixed layer 4, the first transparent ion conductive layer 5,
It has a role of preventing the respective layers of the second transparent ion conductive layer 6 and the reduction coloring electrochromic layer 7 from coming into contact with the outside air. At this time, the external connection portions of the transparent electrodes 2a and 2b may be in contact with the outside air. The transparent substrate 8 is the same as the transparent substrate 1 described above, and it is preferable that the surface of the transparent substrate 8 opposite to the surface on the transparent electrode 2b side is subjected to ARC. In addition, before sealing with resin, E
It is preferable that each layer of the C element is made to contain water.

Next, FIG. 4 is a schematic cross-sectional view showing an example of a state after mounting the EC element 20 according to the modification of the present embodiment. In this figure, conductors and power supplies are not shown.

As shown in FIG. 4, each layer of the EC element 20 is resin-sealed except for the external connection portions of the transparent electrodes 2a and 2b. And in this part for external connection,
It is possible to make desired wiring.

Hereinafter, description will be made using examples and comparative examples.

Example 1 On the other surface of a glass substrate having an antireflection film on one surface, the substrate temperature = 300 ° C., O
The ITO was vacuum-deposited under the conditions of ₂ partial pressure = 5 × 10 ^-2 Pa,
As the first layer, a transparent electrode (transparent conductive layer) having a layer thickness of 150 nm was formed.

Next, on the transparent electrode, the substrate temperature = room temperature,
Under the condition of O ₂ partial pressure = 1 Pa, a film is formed by high frequency sputtering using metallic iridium as a target.
As a layer, an oxidative coloring electrochromic layer having a layer thickness of 5 nm was formed. At that time, the input power to the metal iridium target was 130 W. The oxidative coloring electrochromic layer contains iridium oxide as a main component.

Next, metal iridium and metal tin were formed on the oxidative color forming electrochromic layer under the conditions of substrate temperature = room temperature, mixed gas pressure of water vapor and argon = 5 Pa, and flow rate ratio of water vapor and argon = 3. A film was formed by binary high frequency sputtering using as a target, and as a third layer, a mixed layer of an oxidative coloring electrochromic substance and a metal oxide having a layer thickness of 400 nm was formed. At that time, the input power to the metal iridium target was 130 W, and the input power to the metal tin target was 700 W. The mixed layer is a mixed layer of iridium oxide and iridium hydroxide (oxidative coloring electrochromic substance) and tin oxide (metal oxide). The mixed layer is
In addition, it contains metallic iridium.

Next, on the mixed layer, a substrate temperature of 300 ° C.,
Tantalum pentoxide was vacuum-deposited under the condition of H ₂ O partial pressure = 3 × 10 ⁻² Pa to form a first transparent ion conductive layer having a layer thickness of 250 nm as a fourth layer.

Next, tantalum pentoxide was vacuum-deposited on the first transparent ion conductive layer under the conditions of a substrate temperature of 300 ° C. and an O ₂ partial pressure of 3 × 10 ⁻² Pa to form a layer as a fifth layer. Thickness 50n
m second transparent ion conductive layer was formed.

Next, tungsten trioxide was vacuum-deposited on the transparent ion conductive layer under the conditions of substrate temperature = 300 ° C. and O ₂ partial pressure = 5 × 10 ⁻² Pa to form a sixth layer having a layer thickness of 100.
A 0 nm reductive color forming electrochromic layer was formed.

Finally, on the reduction color-forming electrochromic layer, the substrate temperature = 300 ° C., the O ₂ partial pressure = 5 × 10 ⁻²
ITO was vapor-deposited by high-frequency ion plating under the conditions of Pa and high-frequency power of 150 W to form a transparent electrode (transparent conductive layer) having a layer thickness of 450 nm as the seventh layer.

As described above, an EC device having a 7-layer structure as shown in FIG. 1 was obtained.

After the EC element was sealed with resin as shown in FIG. 3, a voltage of ± 2 V was applied between the transparent electrodes to obtain a wavelength of 400
When a repeated durability test was conducted so that the contrast ratio (when erased / colored) of the average light transmittance of ˜700 nm was 10 or more, the repeated durability was 500,000 times or more. Further, at 70 ° C. and 85% R. H. Under the environment of 100
After leaving it for 0 hours, there was almost no change in its characteristics and appearance. In addition, repeated durability means that the light transmittance is 10
%, Or the number of times until the response speed becomes half or less, whichever is smaller. These evaluation methods are common to the following examples and comparative examples.

[Example 2] The sixth layer was formed in an argon atmosphere instead of an oxygen atmosphere, and not tungsten trioxide but a mixture of tungsten trioxide and molybdenum trioxide (weight ratio: WO ₃ / MoO ₃ = 9 /). An EC device having a 7-layer structure was obtained in the same manner as in Example 1 except that the EC device was formed from 1). Further, in this embodiment, an EC having a shape as shown in FIG.
The element. Example 1 was performed after resin-sealing this EC element.
When the durability was repeatedly measured by the same method, it was 500,000 times or more. Further, at 70 ° C. and 85% R. H. Even after being left for 1000 hours in the above environment, there was almost no change in the characteristics and appearance.

[Embodiment 3] An EC device having a 7-layer structure as shown in FIG. 1 was prepared in the same manner as in Embodiment 1 except that the substrate temperature was 150 ° C. when the fourth to seventh layers were formed. Got After the EC element was resin-sealed, the durability was measured repeatedly by the same method as in Example 1. When the durability was measured 120,000 times, the response speed was halved. Further, at 70 ° C. and 85% R. H. Under the environment
Some of the films left for 000 hours had delamination.

Comparative Example 1 An EC device having a 6-layer structure was obtained in the same manner as in Example 1 except that the fifth layer, that is, the second transparent ion conductive layer was not formed. After the EC element was sealed with resin, the durability was repeatedly measured by the same method as in Example 1, and the response speed was halved after 10,000 cycles. Also, 70
85% R.C. H. When left for 1000 hours in the above environment, delamination occurred in most of the devices.

[0055]

As described above, according to the present invention,
It is possible to provide an EC element which is excellent in repeated durability during high contrast driving and has improved high temperature and high humidity environment resistance, and a manufacturing method thereof.

[Brief description of the drawings]

FIG. 1 is a schematic schematic cross-sectional view showing a layer structure in an example of an EC device according to the present invention.

FIG. 2 is a schematic schematic cross-sectional view showing a layer structure in a modified example of the EC element according to the present invention.

FIG. 3 is a schematic schematic cross-sectional view showing an example of a state after mounting the EC element according to the present invention.

FIG. 4 is a schematic schematic cross-sectional view showing a modified example of a state after mounting the EC element according to the present invention.

FIG. 5 is a schematic schematic cross-sectional view showing a layer structure in an example of a conventional EC device.

[Explanation of symbols]

 1 Transparent Substrate 2a, 2b Transparent Electrode (Transparent Conductive Layer) 3 Oxidative Chromogenic Electrochromic Layer 4 Mixed Layer 5 First Transparent Ion Conductive Layer 6 Second Transparent Ion Conductive Layer 7 Reductive Chromogenic Electrochromic Layer 8 Transparent Substrate 9 Resin 10, 20 EC element 31 Conductive wire 32 Power source 101 Transparent substrate 102a, 102b Transparent electrode 103 Oxidative coloring electrochromic layer 104 Insulating thin film 105 Reduction coloring electrochromic layer

Claims (18)

[Claims] 1. A pair of opposing transparent conductive layers, a first transparent ion conductive layer sandwiched between the transparent conductive layers, and a second transparent ion conductive layer adjacent to the first transparent ion conductive layer. An electrochromic element having at least a reduction color forming electrochromic layer adjacent to the second transparent ion conductive layer, wherein the first transparent ion conductive layer is a layer formed in a water vapor-containing atmosphere. The electrochromic element, wherein the second transparent ion conductive layer is a layer formed in an oxygen-containing atmosphere. 2. The electrochromic device according to claim 1, wherein the reduction color-forming electrochromic layer is a layer formed in an oxygen-containing atmosphere. 3. The electrochromic device according to claim 1, further comprising a transparent substrate adjacent to at least one of opposite surfaces of the pair of opposed transparent conductive layers. 4. The electrochromic device according to claim 3, wherein an antireflection layer made of a dielectric material is provided on a surface of the transparent substrate opposite to the transparent conductive layer. 5. The electrochromic device according to claim 1, wherein the transparent conductive layer is made of indium tin oxide. 6. The first transparent ion conductive layer and the second transparent ion conductive layer are independently Ta ₂ O ₅ and Zr.
The electrochromic device according to claim 1, comprising at least one selected from O ₂ , SiO ₂ , and MgF ₂ . 7. The electrochromic device according to claim 6, wherein the first transparent ion conductive layer and the second transparent ion conductive layer are made of Ta ₂ O ₅ . 8. The electrochromic device according to claim 1, wherein the reduction color-forming electrochromic layer comprises at least one selected from WO ₃ , MoO ₃ , and Nb ₂ O ₅ . 9. The electrochromic device according to claim 8, wherein the reduction coloring electrochromic layer is made of WO ₃ . 10. The electrochromic device according to claim 8, wherein the reduction color-forming electrochromic layer is made of a mixture of WO ₃ and MoO ₃ . 11. The layer further comprising an oxidative coloring electrochromic material between the transparent electrodes.
10. The electrochromic device according to any one of 10 to 10. 12. The electrochromic device according to claim 1, further comprising a layer composed of an oxidative coloring electrochromic substance and a metal oxide between the transparent electrodes. 13. The electro according to claim 1, further comprising an oxidative coloring electrochromic layer and a layer formed of an oxidative coloring electrochromic substance and a metal oxide between the transparent electrodes. Chromic element. 14. A pair of opposed transparent substrates, a pair of opposed transparent conductive layers, a first transparent ion conductive layer sandwiched between the transparent conductive layers, and a first transparent ion conductive layer adjacent to the pair of opposed transparent substrates. A second transparent ion conductive layer, and an electrochromic element having at least a reduction color forming electrochromic layer adjacent to the second transparent ion conductive layer, wherein the first transparent ion conductive layer contains water vapor. A layer formed in an atmosphere, wherein the second transparent ion conductive layer is a layer formed in an oxygen-containing atmosphere, and at least the first transparent ion conductive layer and the first transparent ion conductive layer. A second transparent ion-conducting layer adjacent to the layer and a reduction color-forming electrochromic layer adjacent to the second transparent ion-conducting layer are coated with a resin. Ku element. 15. An electrochromic element comprising at least a pair of opposing transparent conductive layers and a reduction color-forming electrochromic layer sandwiched between the transparent conductive layers, the electrochromic element being formed first among the transparent conductive layers. An electrochromic device characterized in that the transparent conductive layer formed later is thicker than the transparent conductive layer. 16. A pair of opposing transparent conductive layers, a first transparent ion conductive layer sandwiched between the transparent conductive layers, and a second transparent ion conductive layer adjacent to the first transparent ion conductive layer. A reduction color forming electrochromic layer adjacent to the second transparent ion conductive layer, and a method for manufacturing an electrochromic device having at least the first transparent ion conductive layer in a water vapor-containing atmosphere, A method for manufacturing an electrochromic device, comprising forming the second transparent ion conductive layer in an oxygen-containing atmosphere. 17. The method for manufacturing an electrochromic device according to claim 16, wherein the reduction color forming electrochromic layer is formed in an oxygen-containing atmosphere. 18. The first transparent ion conductive layer, the second transparent ion conductive layer, and the reduction color-forming electrochromic layer are formed by vacuum deposition at a temperature of 200 to 400 ° C. The method for manufacturing an electrochromic device according to claim 16 or 17, characterized in that.