JP2000056339A - Electrochromic element and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for stably producing the electrochromic(EC) element, which satisfies the request specifications on the element characteristics, without large variations among lots in the element characteristics (decoloring transmissivity, response rate in the coloring and decoloring, or the like) of the produced EC element, and to provide the EC element excellent in the element characteristics. SOLUTION: The EC element is produced by laminating at least a lower electrode layer 11, an electrolytic oxidation color developable thin film layer 15, an ionic electroconductive layer 14, an electrolytic reduction color developable thin layer 13 and an upper electrode layer 12 on a substrate 10. In this case, the ionic electroconductive layer 14 contains an electrolytic oxidation color developable material in an amount of <=1,000 ppm.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrochromic device having excellent responsiveness and appearance and a method for manufacturing the same.

[0002]

2. Description of the Related Art When a voltage is applied, a phenomenon in which an electrolytic oxidation reaction or an electrolytic reduction reaction occurs reversibly and a color is reversibly turned on and off is called electrochromism. An electrochromic device (EC device) that uses an electrochromic (EC) material exhibiting such a phenomenon to color-decolor by operating a voltage
For more than 20 years, attempts have been made to use this EC element as a light quantity control element (for example, a light control glass, an anti-glare mirror, etc.) or a numerical display element using 7 segments.

[0003] EC elements are roughly classified into a solution type, a gel type, an all solid type and the like according to the material form of each layer constituting the element. Among them, the all solid type EC element is formed by laminating all the layers in a thin film form. I have. For this reason, the all-solid-state EC device does not require a process of forming each layer on a separate substrate and bonding the two substrates or a process of sealing a liquid material, such as when manufacturing a solution-type or gel-type EC device. (Excellent in productivity) and easy to increase in size.

[0004] For example, an EC element in which a transparent electrode layer (cathode), a tungsten trioxide thin film layer (EC layer), an insulating layer such as silicon dioxide, and an electrode layer (anode) are sequentially laminated on a glass substrate ( Japanese Patent Publication No. 52-46098) is known as an all-solid-state EC device. When a voltage (coloring voltage) is applied to such an EC element, tungsten trioxide (WO)
₃ ) The thin film layer is colored blue. Thereafter, when a voltage of a reverse polarity (decoloring voltage) is applied to the EC element, the blue color of the WO ₃ thin film layer disappears and the color returns to colorless.

[0005] This wear decolored mechanism not been elucidated in detail, when a small amount of water contained in the WO ₃ thin layer and the insulating layer (ion conductive layer) dominates wearing decoloring WO ₃ Is understood. The coloring reaction equation is estimated as follows. H ₂ O → H ⁺ + OH ⁻ Cathode side (WO ₃ layer): WO ₃ + nH ⁺ + ne ⁻ → HnWO ₃ Colorless and transparent blue coloring Anode side (insulating layer): OH ⁻ → (1/2) H ₂ O + (1/4) ) O ₂ ↑ + e ^{− As} can be seen from the above reaction formula, this type of EC device (Japanese Patent Publication No. 52-46098) has the following disadvantages. (1) During the coloring reaction, the contained water is consumed by an undesired side reaction of generating oxygen gas. (2) Since water is not generated by the reverse decoloring reaction, replenishment of water from the atmosphere is necessary for repetition of coloring.

In particular, for the reason described in the latter (2). This type of device has the disadvantage that the reproducibility of the coloring is influenced by atmospheric moisture. Therefore, the same amount of water as the water consumed by the coloring reaction is generated by the decoloring reaction, so that it is possible to repeat the coloration and decoloring without replenishing water from the outside, and the coloring concentration repeatedly affects the influence of the outside. An all-solid-state EC device that does not receive the light was proposed (Japanese Patent Laid-Open No. 52-7 / 1982).
No. 3749).

This device is basically composed of a transparent electrode film, an electrolytic
Reduction chromogenic thin film (EC layer, for example WO _ThreeLayer), electrolytic oxidation
Thin film (EC layer, for example Cr_TwoO_ThreeLayer) and counter electrode sequentially
It consists of layers. According to the above publication, the voltage
When the voltage is released after the coloring by application, the coloring becomes spontaneous discharge.
After the voltage is released,
Gives the EC element the property that the coloring is preserved (memory property)
In order to obtain the desired position,
Insulating film (for example, silicon dioxide, magnesium fluoride
Which thin film) is required.

According to Japanese Patent Publication No. Sho 62-52845, it is inferred that the insulating film is not a good conductor of electrons, but is a substance capable of freely moving protons and hydroxy ions (ie, an ion conductive substance). ing. Further, according to the above publication, it is most desirable that the insulating film (ion conductive layer) is disposed between the electrolytic reduction color-forming thin film and the electrolytic oxidation thin film. It is alleged that they have found that it is sufficient to change the color (it is only necessary to have a color developing property) so that any one of them can identify the change from the outside.

At least one of the pair of electrode layers sandwiching the EC layer, directly or indirectly, must be transparent in order to make the coloration and discoloration of the EC layer appear to the outside. In particular, in the case of a transmissive EC element, both electrode layers must be transparent. At present, SnO ₂ ,
In ₂ O ₃ , ITO (a mixture of In ₂ O ₃ and SnO ₂ ), ZnO, and the like are known. However, since these materials have relatively poor transparency, it is necessary to make them thin, so that the EC element is used as a substrate (for example, , A glass plate or a plastic plate).

A pair of electrode layers is provided with an extraction electrode which is a connection portion with an external wiring in order to apply a voltage from an external power supply. When a transparent electrode layer is used as the electrode layer,
Since the transparent electrode layer has a high resistance to external wiring, a low-resistance extraction electrode is often provided so as to overlap (ie, contact) the transparent electrode layer.

Usually, a low-resistance electrode portion is provided in a strip shape around a transparent electrode layer located at an end portion of the substrate surface (for example, a metal clip is attached or a low-resistance metal material is plated) to provide a low-resistance electrode portion. Electrode. In addition, depending on the application, an EC element is provided with a sealing substrate for protecting the element facing the substrate on which the EC element is formed, and for example, using an epoxy resin or the like to hermetically seal the element surface. Can be

[0012]

As described above, the all-solid-state EC device has characteristics such as excellent color erasing and erasing characteristics and the possibility of increasing the size. However, when an all-solid-state EC device is actually manufactured, the device characteristics of the manufactured EC device greatly vary from manufacturing lot to manufacturing lot, and the decoloring transmittance and the response speed of color erasing / decoloring do not satisfy required specifications (decoloring). The transmittance is too low, the response speed is too slow)
Had become a problem.

The present invention has been made in view of such a problem, and the device characteristics (such as the decoloration transmittance and the response speed of color erasing and erasing) of the manufactured EC device may vary greatly from one production lot to another. Therefore, a method of manufacturing an EC element capable of stably manufacturing an EC element satisfying the required specifications relating to the element characteristics, and an E element having an excellent element characteristic
It is intended to provide a C element.

[0014]

For this purpose, the present invention firstly provides a laminate comprising at least a lower electrode layer, an electrolytic oxidation color-forming thin film layer, an ion conductive layer, an electrolytic reduction color-forming thin film layer and an upper electrode layer. An electrochromic device provided as described above, wherein the amount of the electro-oxidative coloring material contained in the ion conductive layer is 1000 ppm or less.

The present invention also provides a second aspect of the present invention wherein "the area of the electrolytic oxidation color-forming thin film layer (first area) is smaller than the area of the electrolytic reduction color-forming thin film layer (second area). 2. The electrochromic device according to claim 1, wherein the overlapping region of the second region corresponds to a display unit, and the non-overlapping region corresponds to a non-display unit.

The present invention also provides a third aspect of the present invention which provides an electro-optical device comprising at least a laminate of a lower electrode layer, an electrolytic oxidation coloring thin film layer, an ion conductive layer, an electrolytic reduction coloring thin film layer and an upper electrode layer. In the method for producing a chromic element, the amount of the electrolytically oxidized coloring substance contained in the ion-conductive layer after film formation is 1 by a vacuum film-forming method.
A method for producing an electrochromic device, wherein the device is formed in a vacuum chamber whose atmosphere is controlled to be 000 ppm or less (Claim 3).

Further, the present invention is a fourth aspect of the present invention wherein "the electrolytic oxidation color-forming thin film layer is formed in a vacuum chamber by a vacuum film forming method, and then the ion conductive layer is formed by a vacuum film forming method. When the amount of the electrolytic oxidation color-forming substance contained in the conductive layer is 10
The manufacturing method according to claim 3 (claim 4), which is formed in another vacuum chamber that has been cleaned so as to have a concentration of 00 ppm or less.

Further, the present invention is a fifth aspect of the present invention wherein the substrate is taken out of the vacuum chamber after the electrolytic oxidation color-forming thin film layer is formed by a vacuum film forming method, and the inside of the vacuum chamber is cleaned. The method according to claim 3, wherein the amount of the electrolytic oxidative coloring substance contained in the ion conductive layer to be formed is 1000 ppm or less.

A sixth aspect of the present invention is the manufacturing method according to the fourth or fifth aspect, wherein the cleaning is performed by mechanically removing the electrolytic oxidation coloring thin film layer adhered in the vacuum chamber. (Claim 6) "is provided. A seventh aspect of the present invention is the method according to the fourth or fifth aspect, wherein the cleaning is performed by removing the electrolytic oxidation color-forming thin film layer adhered in the vacuum chamber by ion bombardment. Claim 7) is provided.

Further, the present invention is an eighth aspect of the present invention wherein the electrolytic oxidation color-forming thin film layer is formed in a vacuum chamber by a vacuum film forming method, the substrate is taken out, and the electrolytic oxidation color-forming thin film layer attached to the vacuum chamber is removed. 4. The method according to claim 3, wherein the amount of the electrolytic oxidative coloring substance contained in the ion conductive layer formed thereafter is 1000 ppm or less by coating with a substance having no electrolytic oxidative coloring property. Manufacturing method (Claim 8) "is provided.

The ninth aspect of the present invention is that the substance having no electrolytic oxidation coloring property is at least one of an ion conductive substance, an electrolytic reduction coloring substance, and an electrode layer forming substance. The manufacturing method according to claim 8 (claim 9) "is provided.

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION The present inventors have found that among the EC devices manufactured by the conventional manufacturing method in which the device characteristics (decoloration transmittance and response speed of color erasing and erasing) vary greatly among manufacturing lots,
As a result of analyzing an EC device that does not satisfy the required specifications for the decoloring transmittance and the response speed of color erasing and discoloring (the decoloring transmittance is too low and the response speed is too slow), EC that satisfies the required specifications is obtained.
It has been found that the amount of the electrolytic oxidation coloring substance contained in the ion conductive layer is larger than that of the device.

Furthermore, the present inventors have found that the amount of the electrolytic oxidation coloring substance contained in the ion conductive layer of the EC element is less than 10%.
It has been found that, when the content is not more than 00 ppm, the required specifications (practicality) are satisfied with respect to the decoloring transmittance and the response speed of color erasing. Therefore, the EC device according to the present invention, which is formed by laminating at least a lower electrode layer, an electrolytic oxidation color-forming thin film layer, an ion conductive layer, an electrolytic reduction color-forming thin film layer and an upper electrode layer on a substrate, comprises an ion conductive layer. The amount of the electro-oxidative color-forming substance contained in the material is 1000 ppm or less (claim 1).

Also, at least a lower electrode layer on the substrate,
In the method according to the present invention for producing an electrochromic device comprising a laminate of an electrolytic oxidation color-forming thin film layer, an ion conductive layer, an electrolytic reduction color-forming thin film layer and an upper electrode layer, the ion conductive layer is formed by a vacuum film forming method. The amount of the electrolytic oxidative coloring substance contained in the ion conductive layer after film formation is 1000 ppm
It is formed in a vacuum chamber whose atmosphere is controlled as follows (claim 3).

The EC element according to the present invention (claims 1 to 9) has a sufficiently small amount (1000 ppm or less) of the electrolytic oxidative coloring substance contained in the ion conductive layer. And the response speed of color-discoloration). When particularly excellent element characteristics are required, it is desirable that the mixing amount is 500 ppm or less.

The effect is that the region of the electrolytic oxidation color-forming thin film layer (first region) is smaller than the region of the electrolytic reduction color-forming thin film layer (second region), and the first region and the second region
This is particularly noticeable in a display-type EC device in which the overlapping area corresponds to the display section and the non-overlapping area corresponds to the non-display section. In such a display-type EC element, if the amount of the electrolytic oxidation coloring substance contained in the ionic conductive layer is too large, the decoloring transmittance of the non-display part is greatly reduced with an increase in the number of times the element is driven, and the display is not performed. The difference from the decoloring transmittance of the portion becomes large.

If the difference between the erasing transmittances of the display section and the non-display section is large, the erasing state (non-display state) of the EC element is obtained.
In this case, the display part is visually recognized, the display contrast in the colored state (display state) of the EC element is poor, and the response speed of the color erasing / decoloring is slow. However, the display type EC element according to the present invention ( In claim 2), this problem is solved.

Here, the electrolytic oxidation color-forming thin film layer is patterned, and the area of the electrolytic oxidation color-forming thin film layer 25 (first area) is smaller than the area of the electrolytic reduction color-forming thin film layer 23 (second area). FIG. 2 shows an example of a display-type EC device in which an overlapping area A of the first area and the second area corresponds to a display section, and a non-overlapping area B corresponds to a non-display section. The display-type EC element having inferior element characteristics has a region B (non-display portion) where the electrolytic oxidation color-forming thin film layer is not formed when the color erasing drive is repeated.
Gradually discolors and the decolorizing transmittance decreases.

Further, according to the present invention, which has good device characteristics,
In the C element, the non-display portion does not change color even if the color erasing drive is repeated, and the color erasing transmittance does not decrease. In the method for manufacturing an EC device according to the present invention (claim 3), the amount of the electrolytically oxidized coloring substance contained in the ion conductive layer after film formation is reduced to 1000 ppm or less by a vacuum film forming method. In order to form the film in a vacuum chamber controlled in atmosphere, for example, after forming an electrolytic oxidation color-forming thin film layer in a vacuum chamber by a vacuum film forming method, and then forming an ion conductive layer by a vacuum film forming method, The amount of the electrolytic oxidation color-forming substance contained in the ion conductive layer is 1
What is necessary is just to form in another vacuum chamber which was cleaned so that it might become 000 ppm or less (claim 4).

Alternatively, after forming the electrolytic oxidation color-forming thin film layer by a vacuum film forming method, the substrate is taken out of the vacuum chamber and the inside of the vacuum chamber is cleaned, so that the substrate is contained in the ion conductive layer formed thereafter. The amount of the electrolytic oxidative coloring substance may be 1000 ppm or less (claim 5). The cleaning can be performed, for example, by mechanically removing the electrolytic oxidation color-forming thin film layer adhered in the vacuum chamber (claim 6) or by ion bombardment (claim 7). The inside of the vacuum chamber may be heated during ion bombardment.

In the method for manufacturing an EC device according to the present invention (claim 3), the amount of the electrolytically oxidized coloring substance contained in the ion conductive layer after film formation is reduced by vacuum film formation. In order to form the thin film layer of electrolytic oxidation coloring in a vacuum chamber by a vacuum film forming method, the substrate is taken out, and the substrate is taken out of the vacuum chamber controlled to 1000 ppm or less. By coating the color-forming thin film layer with a substance having no electrolytic oxidation color-forming property, the amount of the electrolytic oxidation color-forming substance contained in the ion conductive layer to be formed thereafter may be 1000 ppm or less. 8).

Examples of the substance having no electrolytic oxidation coloring property include at least one of an ion conductive substance, an electrolytic reduction coloring substance and an electrode layer forming substance. In consideration of the case where these coating substances (ionic conductive substance, electrolytic reduction coloring substance or electrode layer forming substance) adhere to the element substrate by dropping in a later process, the coating substance layer is transparent. Desirably.

In the method of manufacturing an EC device according to the present invention (claims 3 to 14), the amount of the electrolytic oxidation coloring substance contained in the ion conductive layer after film formation is reduced by vacuum film formation. Since it is formed to be 1000 ppm or less, E
The element characteristics of the C element (such as the decolorizing transmittance and the response speed of color erasing and erasing) do not vary greatly from one production lot to another, and therefore, EC satisfying the required specifications for the element characteristics described above.
The element can be manufactured stably.

The thickness of the electrolytic reduction color-forming thin film layer according to the present invention is desirably 0.1 μm or more and 3 μm or less. If the film thickness is smaller than this, a sufficient coloring density cannot be obtained, and if the film thickness is larger than this, transparency at the time of decoloring deteriorates. The thickness of the ion conductive layer according to the present invention is desirably 0.1 μm or more and 5 μm or less. If the film thickness is smaller than this, the leak current increases, and it is not possible to obtain a sufficiently colored element. On the other hand, if the film thickness is larger than this, the response speed becomes slow.

The thickness of the electrolytic oxidation color-forming thin film layer according to the present invention is desirably 0.01 μm or more and 2 μm or less. If the film thickness is smaller than this, a sufficient coloring density cannot be obtained, and if the film thickness is larger than this, the response speed becomes slow. In the film formation of each layer constituting the EC element according to the present invention, the management of the film thickness is one of the important factors which determines the EC characteristics.

Accordingly, these films can be formed by a wet method such as a sol-gel method, but it is more effective to form a film by a vacuum thin film forming method for precise film thickness control. Examples of the method for forming a vacuum thin film include techniques such as vacuum deposition, ion plating, and sputtering.

Hereinafter, the material of each layer used in the EC device according to the present invention will be described. As a material for the transparent electrode layer, for example, SnO ₂ , In ₂ O ₃ , ITO, ZnO, or the like is used. If the electrode layer does not need to be transparent, the electrode layer is formed of a metal material or carbon. As the metal material, for example, gold, silver, aluminum, chromium, tin, zinc, nickel, ruthenium, rhodium, stainless steel and the like are used. The metal electrode layer has a much lower resistance even if the transparent electrode layer has the lowest possible resistance.

In general, WO ₃ , M
oO ₃ or a mixture thereof is used. For the ion conductive layer, for example, silicon oxide, tantalum oxide, titanium oxide, aluminum oxide, niobium oxide, zirconium oxide, hafnium oxide, lanthanum oxide, magnesium fluoride, and the like are used.

The ionic conductive layer is an insulator for electrons, but is a good conductor for protons (H ⁺ ) and hydroxy ions (OH ⁻ ). A cation is required for the color-decoloring reaction of the EC layer, and it is necessary to include H ⁺ and Li ⁺ in the EC layer and the like. H ⁺ does not need to be an ion from the beginning, and H ⁺ only needs to be generated when a voltage is applied, and therefore water may be contained instead of H ⁺ . This water is very small and sufficient, and often discolors even water that naturally enters from the atmosphere.

Examples of the electrolytic oxidation color-forming thin film layer include oxide or iridium hydroxide, nickel, chromium, vanadium, ruthenium, rhodium and the like. Other EC coloring substances include, for example, metal oxides and metal sulfides such as titanium oxide, cobalt oxide, iron oxide, silicon oxide, lead oxide, copper oxide, iron sulfide, bismuth oxide, niobium sulfide, and hydroquinone derivatives , Iron berlin derivatives, metal phthalocyanine derivatives (phthalocyanine derivatives of Co, Fe, Zn, Ni, and Cu), Prussian blue, Prussian blue-like compounds, indium nitride, tin nitride, zirconium nitride chloride, viologen-based organic electrochromic materials, A styryl-based organic electrochromic material, polyaniline, or the like can be used for the electrochromic layer.

As other examples of the ion conductive layer, a layer having ion conductivity and adhesiveness can be used. For example, (A) poly (2-acrylamido-2-methylpropanesulfonic acid), poly (styrene) -Sulfonic acid), poly (ethylene-sulfonic acid), polyvinyl sulfonic acid,
A polymer comprising a fluorinated copolymer or the like, (B) a first monomer (for example, vinylsulfonic acid, sodium vinylsulfonate, vinylsulfonyl fluoride) and a second monomer (for example, vinylpyrrolidinone, Butyl vinyl ether, ethyl vinyl ether, isopropyl vinyl ether, cyclohexyl vinyl ether, isobutylene); (C) a copolymer of the first monomer and the second monomer with sodium styrene sulfonate; ) A hydrophilic acrylate monomer (for example, poly (ethylene oxide) dimethacrylate, ethoxytriethylene, glycol methacrylate, ethylene oxide-dimethylcyclohexane acrylate, hydroxypropyl acrylate, ethyl acrylate) and a sulfonic acid monomer (for example, 2-acrylamide) 2-methylpropane sulfonic acid, styrene - sulfonic acid, ethylene - sulfonic acid, and copolymers composed of such layers of vinyl sulfonic acid).

As the sealing agent, for example, epoxy resin, urethane resin, acrylic resin, vinyl acetate resin,
Transparent materials such as en-thiol-based resins, silicone-based resins, and modified polymer-based materials are preferred, but not limited thereto. Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

[0043]

DESCRIPTION OF THE PREFERRED EMBODIMENTS At least lower electrode layers 11 and 2 on substrates 10 and 20
1, electrolytic oxidation coloring thin film layer 15, 25, ion conductive layer 14, 24,
The EC device of this embodiment (Examples 1 to 14), which is formed by laminating the electrolytic reduction chromogenic thin film layers 13 and 23 and the upper electrode layers 12 and 22, is composed of the electrolytic oxidation contained in the ion conductive layers 14 and 24. The amount of the coloring substance is 1000 ppm or less.

FIG. 1 shows a schematic configuration of the EC elements of Examples 1 to 7.
Shown in In the EC devices of Examples 8 to 14, the electrolytic oxidation chromogenic thin film layer 25 was patterned and the region (first region) was formed.
Area) is the area of the electrolytic reduction chromogenic thin film layer 23 (second area)
The overlapping area A of the first area and the second area is a display-type EC element which corresponds to a display section, and the non-overlapping area B corresponds to a non-display section (FIG. 2).

The process of manufacturing the EC device of each embodiment and the device characteristics of the EC device will be described below. <Example 1> Step 1: A 4-inch square, 1 mm thick glass plate on which a transparent electrode layer (ITO) having a thickness of about 0.2 μm was formed was used as a substrate 10.
The transparent electrode layer was patterned by photolithography (formation of an electrode extraction portion of the upper electrode layer and a lower electrode layer).

Step 2: Patterned lower transparent electrode layer
A mixed thin film layer of iridium oxide and tin oxide (film thickness: 0.1 μm) was formed as an electrolytic oxidation color-forming thin film layer 15 on the substrate 11 by an ion plating method. The film formation conditions were an oxygen gas pressure of 4 × 10 ⁻⁴ Torr, an RF power of 100 W, and a deposition time of 20 minutes.

Step 3: A tantalum pentoxide as an ion conductive layer 14 is formed on the electrolytic oxidation color-forming thin film layer by using a vacuum chamber different from the vacuum chamber in which the electrolytic oxidation color-forming thin film layer is formed in step 2. Was formed by an ion plating method. The film formation conditions were an oxygen gas pressure of 2 × 10 ⁻⁴ Torr, an RF power of 400 W, and a deposition time of 45 minutes.

Here, the another vacuum chamber is provided with an amount of the electro-oxidative coloring substance contained in the ion-conductive layer after film formation of 500.
This is a vacuum chamber that has been previously cleaned so as to be less than ppm. Step 4: Using a vacuum chamber in which the ion conductive layer was formed in Step 3, a tungsten trioxide thin film layer (thickness: 0.7) was formed on the ion conductive layer as the electrolytic reduction color-forming thin film layer 13.
μm) was formed by a vacuum evaporation method.

The film formation conditions were as follows: oxygen gas pressure 4 × 10 ^-4
Torr and a deposition time of 12 minutes. Step 5: An ITO thin film layer (2 μm thick) was formed as an upper transparent electrode layer 12 on the electrolytic reduction color-forming thin film layer by an ion plating method. The film formation conditions were an oxygen gas pressure of 2 × 10 ⁻⁴ Torr, an RF power of 180 W, and a deposition time of 8 minutes.

Through the above steps, an EC device having the structure shown in FIG. 1 is obtained. Step 6: The element surface of the EC element having the configuration shown in FIG. 1 was sealed with an epoxy resin and a glass sealing substrate having a thickness of 0.3 mm to complete the EC element of this example. In addition, FIG.
FIG. 2 is a schematic configuration diagram showing a state where an element surface of an EC element formed by forming a lower electrode layer 31, an EC layer 33, and an upper electrode layer 32 on a substrate 30 is sealed with a sealing resin 34 and a sealing substrate 35;

Of the two electrode layers constituting the EC element of this embodiment, the upper electrode layer 12 on the upper side is connected to the cathode of an external power supply, and the other lower electrode layer 11 is connected to the anode of the external power supply. When a voltage of +1.35 V was applied, the device developed a blue color within 1 second. Thereafter, even when the voltage application was stopped, the device maintained a blue color developing state. Also, with the polarity reversed,
When a voltage of 1.35 V was applied, the color was erased within 1 second and returned to the original transparent state.

The transmittance at a wavelength of 633 nm is 20 when colored.
%, And 85% at the time of decoloration. The amount of the electro-oxidative coloring substance contained in the ion conductive layer of the EC element was 200 ppm. <Example 2> Step 1: The transparent electrode layer on the substrate was patterned in the same manner as in Step 1 of Example 1.

Step 2: In the same manner as in Step 2 of Example 1,
An electrolytic oxidation color-forming thin film layer was formed on the lower transparent electrode layer. Step 3-1: The substrate on which the transparent electrode layer and the electrolytic oxidation color-forming thin film layer are formed is taken out of the vacuum chamber and the inside of the vacuum chamber is cleaned (cleaned), so that the substrate is contained in the ion conductive layer formed thereafter. The amount of the electrolytic oxidation coloring substance is 50
It was set to 0 ppm or less.

Here, the cleaning is carried out by removing the electrolytic oxidation coloring substance adhered to the inner wall of the vacuum chamber on which the electrolytic oxidation coloring thin film layer is formed and the internal components by sandblasting or a wire brush. The amount of the electrolytic oxidative coloring substance contained in the ion conductive layer to be formed is 1000 pp
m or less. Step 3-2: Using a cleaned vacuum chamber, apply a tantalum pentoxide thin film layer (thickness 0.8 μm) as an ion conductive layer on the electrolytic oxidation color-forming thin film layer formed in step 2 by ion plating. The film was formed by the method.

The film formation conditions were as follows: oxygen gas pressure 2 × 10 ⁻⁴
Torr, RF power 400 W, and deposition time 45 minutes. Step 4: An electrolytic reduction color-forming thin film layer was formed on the ionic conductive layer in the same manner as in Step 4 of Example 1. Step 5: An upper transparent electrode layer was formed on the electrolytic reduction color-forming thin film layer in the same manner as in Step 5 of Example 1.

Through the above steps, an EC device having the structure shown in FIG. 1 is obtained. Step 6: Similar to step 6 of Example 1, the element surface was sealed with an epoxy resin and a glass sealing substrate having a thickness of 0.3 mm to complete the EC element of this example. EC of this embodiment
When the upper electrode layer 12 is connected to the cathode of the external power supply and the other lower electrode layer 11 is connected to the anode of the external power supply, and a voltage of +1.35 V is applied. The device developed a blue color within 1 second.

Thereafter, even when the application of the voltage was stopped, the device maintained a blue color developing state. In addition, the polarity is reversed to -1.35V
When the voltage was applied, the color was erased within 1 second and returned to the original transparent state. The transmittance at a wavelength of 633 nm is 20 when colored.
%, And 85% at the time of decoloration. Further, the amount of the electro-oxidative coloring substance contained in the ion conductive layer of the EC element was 600 ppm. <Example 3> Instead of sandblasting, ion bombarding (RF power 400 W, time 45 minutes, vacuum chamber temperature 30) was performed as cleaning shown in step 3-1 of Example 2.
EC device of this example was manufactured in the same manner as in Example 2 except that the temperature was 0 ° C.).

Of the two electrode layers constituting the EC device of this embodiment, the upper electrode layer 12 on the upper side is connected to the cathode of an external power supply, and the other lower electrode layer 11 is connected to the anode of the external power supply. When a voltage of +1.35 V was applied, the device developed a blue color within 1 second. Thereafter, even when the voltage application was stopped, the device maintained a blue color developing state. Also, with the polarity reversed,
When a voltage of 1.35 V was applied, the color was erased within 1 second and returned to the original transparent state.

The transmittance at a wavelength of 633 nm is 20 when colored.
%, And 85% at the time of decoloration. Further, the amount of the electro-oxidative coloring substance contained in the ion conductive layer of the EC element was 600 ppm. <Example 4> Step 1: Patterning of the transparent electrode layer on the substrate was performed in the same manner as in Step 1 of Example 1.

Step 2: In the same manner as in Step 2 of Example 1,
An electrolytic oxidation color-forming thin film layer was formed on the lower transparent electrode layer. Step 3-1: The substrate on which the transparent electrode layer and the electrolytic oxidation color-forming thin film layer are formed is taken out of the vacuum chamber, and the electrolytic oxidation color-forming thin film layer adhered in the vacuum chamber is formed of a silicon dioxide thin film having no electrolytic oxidation color development property. By coating, the amount of the electrolytic oxidative coloring substance contained in the ion conductive layer formed thereafter was adjusted to 500 ppm or less.

Here, the silicon dioxide thin film was formed by vapor deposition at an oxygen gas pressure of 2 × 10 ⁻⁴ Torr and a film formation rate of 5 ° /
s for 20 minutes. Step 3-2: Using the vacuum tank in which the electrolytic oxidation color-forming thin film layer attached to the inside of the vacuum chamber is covered with a silicon dioxide thin film, as an ion conductive layer on the electrolytic oxidation color-forming thin film layer formed in step 2 Tantalum pentoxide thin film layer (0.8 μm thickness)
Was formed by ion plating.

The film forming conditions were as follows: oxygen gas pressure 2 × 10 ⁻⁴
Torr, RF power 400 W, and deposition time 45 minutes. Step 4: An electrolytic reduction color-forming thin film layer was formed on the ionic conductive layer in the same manner as in Step 4 of Example 1. Step 5: An upper transparent electrode layer was formed on the electrolytic reduction color-forming thin film layer in the same manner as in Step 5 of Example 1.

Through the above steps, an EC device having the structure shown in FIG. 1 is obtained. Step 6: Similar to step 6 of Example 1, the element surface was sealed with an epoxy resin and a glass sealing substrate having a thickness of 0.3 mm to complete the EC element of this example. EC of this embodiment
When the upper electrode layer 12 is connected to the cathode of the external power supply and the other lower electrode layer 11 is connected to the anode of the external power supply, and a voltage of +1.35 V is applied. The device developed a blue color within 1 second.

After that, even when the application of the voltage was stopped, the device maintained a blue color developing state. In addition, the polarity is reversed to -1.35V
When the voltage was applied, the color was erased within 1 second and returned to the original transparent state. The transmittance at a wavelength of 633 nm is 20 when colored.
%, And 85% at the time of decoloration. The amount of the electro-oxidative coloring substance contained in the ion conductive layer of the EC element was 300 ppm. <Example 5> Step 1: Patterning of the transparent electrode layer on the substrate was performed in the same manner as in Step 1 of Example 1.

Step 2: In the same manner as in Step 2 of Example 1,
An electrolytic oxidation color-forming thin film layer was formed on the lower transparent electrode layer. Step 3-1: The substrate on which the transparent electrode layer and the electrolytic oxidation color-forming thin film layer are formed is taken out of the vacuum chamber, and the electrolytic oxidation color-forming thin film layer adhered in the vacuum chamber is removed from the tantalum pentoxide thin film having no electrolytic oxidation color development property. , So that the amount of the electrolytic oxidation color-forming substance contained in the ion conductive layer to be formed later was 500 ppm or less.

Here, the tantalum pentoxide thin film was formed by an ion plating method at an oxygen gas pressure of 2 × 10 ^-4 Torr,
The film was formed at an RF power of 400 W and a film formation rate of 3 ° / s for 40 minutes. Step 3-2: Using the vacuum chamber in which the electrolytic oxidation color-forming thin film layer attached in the vacuum chamber is coated with a tantalum pentoxide thin film,
On the electrolytic oxidation color-forming thin film layer formed in step 2, a tantalum pentoxide thin film layer (0.8 μm thick) was formed as an ion conductive layer.
m) was formed into a film by the ion plating method.

The film formation conditions were an oxygen gas pressure of 2 × 10 ^-4.
Torr, RF power 400 W, and deposition time 45 minutes. Step 4: An electrolytic reduction color-forming thin film layer was formed on the ionic conductive layer in the same manner as in Step 4 of Example 1. Step 5: An upper transparent electrode layer was formed on the electrolytic reduction color-forming thin film layer in the same manner as in Step 5 of Example 1.

Through the above steps, an EC device having the structure shown in FIG. 1 is obtained. Step 6: Similar to step 6 of Example 1, the element surface was sealed with an epoxy resin and a glass sealing substrate having a thickness of 0.3 mm to complete the EC element of this example. EC of this embodiment
When the upper electrode layer 12 is connected to the cathode of the external power supply and the other lower electrode layer 11 is connected to the anode of the external power supply, and a voltage of +1.35 V is applied. The device developed a blue color within 1 second.

Thereafter, even when the application of the voltage was stopped, the device maintained a blue color developing state. In addition, the polarity is reversed to -1.35V
When the voltage was applied, the color was erased within 1 second and returned to the original transparent state. The transmittance at a wavelength of 633 nm is 20 when colored.
%, And 85% at the time of decoloration. The amount of the electro-oxidative coloring substance contained in the ion conductive layer of the EC element was 300 ppm. Example 6 Step 1: The transparent electrode layer on the substrate was patterned in the same manner as in Step 1 of Example 1.

Step 2: In the same manner as in Step 2 of Example 1,
An electrolytic oxidation color-forming thin film layer was formed on the lower transparent electrode layer. Step 3-1: The substrate on which the transparent electrode layer and the electrolytic oxidation color-forming thin film layer are formed is taken out of the vacuum chamber, and the electrolytic oxidation color-forming thin film layer adhered in the vacuum chamber is replaced with a tungsten trioxide thin film having no electrolytic oxidation color development property. , So that the amount of the electrolytic oxidation color-forming substance contained in the ion conductive layer to be formed later was 500 ppm or less.

Here, the tungsten trioxide thin film was formed by vapor deposition at an oxygen gas pressure of 4 × 10 ⁻⁴ Torr and a film formation rate of 6
The film was formed at Å / s for 12 minutes. Step 3-2: An ionic conductive layer is formed on the electrolytic oxidation color-forming thin film layer formed in step 2 by using the vacuum chamber in which the electrolytic oxidation color-forming thin film layer adhered in the vacuum chamber is coated with a tungsten trioxide thin film. As a thin layer of tantalum pentoxide (thickness 0.8
μm) was formed by an ion plating method.

The film forming conditions were as follows: oxygen gas pressure 2 × 10 ⁻⁴
Torr, RF power 400 W, and deposition time 45 minutes. Step 4: An electrolytic reduction color-forming thin film layer was formed on the ionic conductive layer in the same manner as in Step 4 of Example 1. Step 5: An upper transparent electrode layer was formed on the electrolytic reduction color-forming thin film layer in the same manner as in Step 5 of Example 1.

Through the above steps, an EC device having the structure shown in FIG. 1 is obtained. Step 6: Similar to step 6 of Example 1, the element surface was sealed with an epoxy resin and a glass sealing substrate having a thickness of 0.3 mm to complete the EC element of this example. EC of this embodiment
When the upper electrode layer 12 is connected to the cathode of the external power supply and the other lower electrode layer 11 is connected to the anode of the external power supply, and a voltage of +1.35 V is applied. The device developed a blue color within 1 second.

Thereafter, even when the voltage application was stopped, the device maintained a blue color developing state. In addition, the polarity is reversed to -1.35V
When the voltage was applied, the color was erased within 1 second and returned to the original transparent state. The transmittance at a wavelength of 633 nm is 20 when colored.
%, And 85% at the time of decoloration. The amount of the electro-oxidative coloring substance contained in the ion conductive layer of the EC element was 300 ppm. <Example 7> Step 1: The transparent electrode layer on the substrate was patterned in the same manner as in Step 1 of Example 1.

Step 2: In the same manner as in Step 2 of Example 1,
An electrolytic oxidation color-forming thin film layer was formed on the lower transparent electrode layer. Step 3-1: The substrate on which the transparent electrode layer and the electrolytic oxidation color-forming thin film layer are formed is taken out of the vacuum chamber, and the electrolytic oxidation color-forming thin film layer adhering to the inside of the vacuum chamber is not subjected to electrolytic oxidation color development.
By coating with a TO thin film, the amount of the electrolytically oxidized coloring substance contained in the ion conductive layer formed thereafter is 500
ppm or less.

Here, the ITO thin film was formed by an ion plating method at an oxygen gas pressure of 2 × 10 ⁻⁴ Torr, an RF power of 180 W, and a film formation rate of ⁴ ° / s for 8 minutes. Step 3-2: Using the above-described vacuum chamber in which the electrolytic oxidation color-forming thin film layer adhered in the vacuum chamber is covered with the ITO thin film, a five-layered ion conductive layer is formed on the electrolytic oxidation color-forming thin layer formed in step 2. A thin film layer (0.8 μm thick) of tantalum oxide was formed by an ion plating method.

The film forming conditions are as follows: oxygen gas pressure 2 × 10 ⁻⁴
Torr, RF power 400 W, and deposition time 45 minutes. Step 4: An electrolytic reduction color-forming thin film layer was formed on the ionic conductive layer in the same manner as in Step 4 of Example 1. Step 5: An upper transparent electrode layer was formed on the electrolytic reduction color-forming thin film layer in the same manner as in Step 5 of Example 1.

Through the above steps, an EC device having the structure shown in FIG. 1 is obtained. Step 6: Similar to step 6 of Example 1, the element surface was sealed with an epoxy resin and a glass sealing substrate having a thickness of 0.3 mm to complete the EC element of this example. EC of this embodiment
When the upper electrode layer 12 is connected to the cathode of the external power supply and the other lower electrode layer 11 is connected to the anode of the external power supply, and a voltage of +1.35 V is applied. The device developed a blue color within 1 second.

Thereafter, even when the voltage application was stopped, the device maintained a blue color developing state. In addition, the polarity is reversed to -1.35V
When the voltage was applied, the color was erased within 1 second and returned to the original transparent state. The transmittance at a wavelength of 633 nm is 20 when colored.
%, And 85% at the time of decoloration. The amount of the electro-oxidative coloring substance contained in the ion conductive layer of the EC element was 300 ppm. <Example 8> The EC of this example was formed in the same manner as in Example 1 except that the electrolytic oxidation color-forming thin film layer was formed by a lift-off method in forming the electrolytic oxidation color-forming thin film layer shown in Step 2 of Example 1. The device was manufactured.

Of the two electrode layers constituting the EC device of this embodiment, the upper electrode layer 22 on the upper side is connected to the cathode of an external power supply, and the other lower electrode layer 21 is connected to the anode of the external power supply. When a voltage of +1.35 V was applied, the region A (display portion) on which the electrolytic oxidation color-forming thin film layer was formed was colored blue within 0.5 seconds. After that, even when the voltage application was stopped, the device maintained a blue color developing state. Also, the polarity is reversed to -1.3.
When a voltage of 5 V was applied, the color was erased within 0.5 seconds and returned to the original transparent state.

The transmittance of the region A (display portion) at a wavelength of 633 nm was 20% when colored and 85% when decolored. Further, a region B where the electrolytic oxidation color-forming thin film layer is not formed
The transmittance of the (non-display portion) was 86% immediately after the film formation, and there was no change in the transmittance even after repeating the color erasing drive for 24 hours. The amount of the electro-oxidative coloring substance contained in the ion conductive layer of the EC element was 200 ppm. <Embodiment 9> The EC of this embodiment was formed in the same manner as in Embodiment 2 except that the electrolytic oxidation chromogenic thin film layer was formed by the lift-off method in the formation of the electrolytic oxidation chromogenic thin film layer shown in Step 2 of Embodiment 2. The device was manufactured.

Of the two electrode layers constituting the EC device of this embodiment, the upper electrode layer 22 on the upper side is connected to the cathode of an external power supply, and the other lower electrode layer 21 is connected to the anode of the external power supply. When a voltage of +1.35 V was applied, the region A (display portion) on which the electrolytic oxidation color-forming thin film layer was formed was colored blue within 0.5 seconds. After that, even when the voltage application was stopped, the device maintained a blue color developing state. Also, the polarity is reversed to -1.3.
When a voltage of 5 V was applied, the color was erased within 0.5 seconds and returned to the original transparent state.

The transmittance of the region A (display portion) at a wavelength of 633 nm was 20% when colored and 85% when decolored. Further, a region B where the electrolytic oxidation color-forming thin film layer is not formed
The transmittance of the (non-display portion) was 86% immediately after the film formation, and there was no change in the transmittance even after repeating the color erasing drive for 24 hours. The amount of the electro-oxidative coloring substance contained in the ion conductive layer of the EC element was 300 ppm. Example 10 The EC of this example was formed in the same manner as in Example 3 except that the electrolytic oxidation color-forming thin film layer was formed by the lift-off method in forming the electrolytic oxidation color-forming thin film layer shown in Step 2 of Example 3. The device was manufactured.

Of the two electrode layers constituting the EC device of this embodiment, the upper electrode layer 22 on the upper side is connected to the cathode of an external power supply, and the other lower electrode layer 21 is connected to the anode of the external power supply. When a voltage of +1.35 V was applied, the region A (display portion) on which the electrolytic oxidation color-forming thin film layer was formed was colored blue within 0.5 seconds. After that, even when the voltage application was stopped, the device maintained a blue color developing state. Also, the polarity is reversed to -1.3.
When a voltage of 5 V was applied, the color was erased within 0.5 seconds and returned to the original transparent state.

The transmittance of the region A (display portion) at a wavelength of 633 nm was 20% when colored and 85% when decolored. Further, a region B where the electrolytic oxidation color-forming thin film layer is not formed
The transmittance of the (non-display portion) was 86% immediately after the film formation, and there was no change in the transmittance even after repeating the color erasing drive for 24 hours. The amount of the electro-oxidative coloring substance contained in the ion conductive layer of the EC element was 300 ppm. <Embodiment 11> The EC of this embodiment was formed in the same manner as in Embodiment 4 except that the electrolytic oxidation chromogenic thin film layer was formed by the lift-off method in the formation of the electrolytic oxidation chromogenic thin film layer shown in Step 2 of Embodiment 4. The device was manufactured.

Of the two electrode layers constituting the EC element of this embodiment, the upper electrode layer 22 on the upper side is connected to the cathode of an external power supply, and the other lower electrode layer 21 is connected to the anode of the external power supply. When a voltage of +1.35 V was applied, the region A (display portion) on which the electrolytic oxidation color-forming thin film layer was formed was colored blue within 0.5 seconds. After that, even when the voltage application was stopped, the device maintained a blue color developing state. Also, the polarity is reversed to -1.3.
When a voltage of 5 V was applied, the color was erased within 0.5 seconds and returned to the original transparent state.

The transmittance of the region A (display portion) at a wavelength of 633 nm was 20% when colored and 85% when decolored. Further, a region B where the electrolytic oxidation color-forming thin film layer is not formed
The transmittance of the (non-display portion) was 86% immediately after the film formation, and there was no change in the transmittance even after repeating the color erasing drive for 24 hours. The amount of the electro-oxidative coloring substance contained in the ion conductive layer of the EC element was 200 ppm. <Example 12> The EC of this example was formed in the same manner as in Example 5 except that the electrolytic oxidation color-forming thin film layer was formed by the lift-off method in forming the electrolytic oxidation color-forming thin film layer shown in Step 2 of Example 5. The device was manufactured.

Of the two electrode layers constituting the EC device of this embodiment, the upper electrode layer 22 on the upper side is connected to the cathode of the external power supply, and the other lower electrode layer 21 is connected to the anode of the external power supply. When a voltage of +1.35 V was applied, the region A (display portion) on which the electrolytic oxidation color-forming thin film layer was formed was colored blue within 0.5 seconds. After that, even when the voltage application was stopped, the device maintained a blue color developing state. Also, the polarity is reversed to -1.3.
When a voltage of 5 V was applied, the color was erased within 0.5 seconds and returned to the original transparent state.

The transmittance of the region A (display portion) at a wavelength of 633 nm was 20% when colored and 85% when decolored. Further, a region B where the electrolytic oxidation color-forming thin film layer is not formed
The transmittance of the (non-display portion) was 86% immediately after the film formation, and there was no change in the transmittance even after repeating the color erasing drive for 24 hours. The amount of the electro-oxidative coloring substance contained in the ion conductive layer of the EC element was 200 ppm. Example 13 The EC of this example was formed in the same manner as in Example 6 except that the electrolytic oxidation color-forming thin film layer was formed by the lift-off method in the formation of the electrolytic oxidation color-forming thin film layer shown in Step 2 of Example 6. The device was manufactured.

Of the two electrode layers constituting the EC device of this embodiment, the upper electrode layer 22 on the upper side is connected to the cathode of an external power supply, and the other lower electrode layer 21 is connected to the anode of the external power supply. When a voltage of +1.35 V was applied, the region A (display portion) on which the electrolytic oxidation color-forming thin film layer was formed was colored blue within 0.5 seconds. After that, even when the voltage application was stopped, the device maintained a blue color developing state. Also, the polarity is reversed to -1.3.
When a voltage of 5 V was applied, the color was erased within 0.5 seconds and returned to the original transparent state.

The transmittance of the region A (display portion) at a wavelength of 633 nm was 20% when colored and 85% when decolored. Further, a region B where the electrolytic oxidation color-forming thin film layer is not formed
The transmittance of the (non-display portion) was 86% immediately after the film formation, and there was no change in the transmittance even after repeating the color erasing drive for 24 hours. The amount of the electro-oxidative coloring substance contained in the ion conductive layer of the EC element was 200 ppm. <Example 14> The EC of this example was formed in the same manner as in Example 7 except that the electrolytic oxidation color-forming thin film layer was formed by the lift-off method in forming the electrolytic oxidation color-forming thin film layer shown in Step 2 of Example 7. The device was manufactured.

Of the two electrode layers constituting the EC device of this embodiment, the upper electrode layer 22 on the upper side is connected to the cathode of an external power supply, and the other lower electrode layer 21 is connected to the anode of the external power supply. When a voltage of +1.35 V was applied, the region A (display portion) on which the electrolytic oxidation color-forming thin film layer was formed was colored blue within 0.5 seconds. After that, even when the voltage application was stopped, the device maintained a blue color developing state. Also, the polarity is reversed to -1.3.
When a voltage of 5 V was applied, the color was erased within 0.5 seconds and returned to the original transparent state.

The transmittance of the region A (display portion) at a wavelength of 633 nm was 20% when colored and 85% when decolored. Further, a region B where the electrolytic oxidation color-forming thin film layer is not formed
The transmittance of the (non-display portion) was 86% immediately after the film formation, and there was no change in the transmittance even after repeating the color erasing drive for 24 hours. The amount of the electro-oxidative coloring substance contained in the ion conductive layer of the EC element was 200 ppm.

The EC elements according to Examples 1 to 14 described above have a sufficiently small amount (1000 ppm or less) of the electrolytic oxidative coloring substance contained in the ion conductive layer, and therefore have the element characteristics (decoloration transmittance and adhesion). (Response speed of decoloring, etc.). This effect is particularly remarkable in the display type EC device (Examples 8 to 14). In the method for manufacturing an EC element according to Examples 1 to 14, the ion conductive layer is formed by a vacuum film forming method such that the amount of the electrolytic oxidation coloring substance contained in the ion conductive layer after film formation is 1000 ppm or less. Therefore, the device characteristics of the EC device (such as the color erasing transmittance and the response speed of color erasing and erasing) do not vary greatly from one production lot to another, and therefore satisfy the required specifications (practicality) relating to the device characteristics. An EC device can be manufactured stably. <Comparative Example 1> Step 1: The transparent electrode layer on the substrate was patterned in the same manner as in Step 1 of Example 1.

Step 2: In the same manner as in Step 2 of Example 1,
An electrolytic oxidation color-forming thin film layer was formed on the lower transparent electrode layer. Step 3: Using the same vacuum chamber, a thin film layer of tantalum pentoxide (thickness 0.8 μm) was formed as an ion conductive layer on the electrolytic oxidation coloring thin film layer by ion plating.

The film forming conditions were as follows: oxygen gas pressure 2 × 10 ⁻⁴
Torr, RF power 400 W, and deposition time 45 minutes. Step 4: An electrolytic reduction color-forming thin film layer was formed on the ionic conductive layer in the same manner as in Step 4 of Example 1. Step 5: An upper transparent electrode layer was formed on the electrolytic reduction color-forming thin film layer in the same manner as in Step 5 of Example 1.

Step 6: In the same manner as in Step 6 of Example 1, the element surface was sealed with an epoxy resin and a glass sealing substrate having a thickness of 0.3 mm to complete the EC element of this comparative example. Of the two electrode layers constituting the EC device of this comparative example, the upper electrode layer on the upper side was connected to the cathode of the external power supply, and the other lower electrode layer was connected to the anode of the external power supply, and a voltage of +1.35 V was applied. Applied, the element was colored blue, but it took more than 2 seconds.

After that, even when the voltage application was stopped, the device maintained a blue color developing state. When a voltage of -1.35 V was applied with the polarity reversed, the device was decolored, but it took more than 3 seconds. The transmittance at a wavelength of 633 nm is 18% when colored,
It was 65% when the color was erased. The amount of the electro-oxidative coloring substance in the ion conductive layer of the EC element was 2000 ppm or more.

In the EC element of this comparative example, the amount of the electrolytic oxidation coloring substance contained in the ion conductive layer was too large.
The required specifications could not be satisfied with respect to the erasing transmittance and the response speed of the erasing / erasing. <Comparative Example 2> The EC of this comparative example was formed in the same manner as in Comparative Example 1 except that the electrolytic oxidation color-forming thin film layer was formed by the lift-off method in forming the electrolytic oxidation color-forming thin film layer shown in Step 2 of Comparative Example 1. The device was manufactured.

Of the two electrode layers constituting the EC device of this comparative example, the upper electrode layer on the upper side was connected to the cathode of the external power supply, and the other lower electrode layer was connected to the anode of the external power supply, and +1. When a voltage of 35 V was applied, the region A (display portion) where the electrolytic oxidation color-forming thin film layer was formed was colored blue,
It took more than a second. After that, even when the voltage application was stopped, the device maintained a blue color developing state. Also, with the polarity reversed,
When a voltage of 1.35 V is applied, the area A (display section)
Although the color was erased, it took more than 3 seconds.

The transmittance of the region A (display portion) at a wavelength of 633 nm was 20% when colored and 65% when decolored.
Further, a region B where the electrolytic oxidation color-forming thin film layer is not formed
The decoloring transmittance of the (non-display part) is 80% immediately after film formation,
The color erasing transmittance after repeating the color erasing drive for 24 hours is 70.
%Met. The mixing amount of the electrolytic oxidation color-forming substance in the ion conductive layer of the EC element was 2000 ppm or more.

In the display-type EC element of this comparative example, the amount of the electro-oxidative coloring substance contained in the ion conductive layer was too large, so that the decoloring transmittance of the non-display part was increased as the number of driving of the element was increased. The difference greatly decreased, and the difference from the decoloring transmittance of the display section increased. Then, the difference in the decoloring transmittance between the display unit and the non-display unit increases, and the display unit is visually recognized even in the decolored state (non-display state) of the EC element. Display contrast is poor,
There is a problem that the response speed of the color erasing and discoloring is slow.

[0103]

As described above, the present invention (Claim 1)
In the EC devices according to (14) to (14), the amount of the electro-oxidative coloring substance contained in the ion conductive layer is sufficiently small (100).
(0 ppm or less), so that it has an effect of being excellent in element characteristics (color erasing transmittance and response speed of color erasing and erasing).

This effect is particularly remarkable in the display type EC device (claims 8 to 14). In the method for manufacturing an EC device according to the present invention (claims 3 to 14), the amount of the electrolytic oxidation coloring substance contained in the ion conductive layer after film formation is 1000 ppm by a vacuum film forming method.
Since it is formed as described below, the device characteristics of the EC device (such as the decoloration transmittance and the response speed of color erasing and erasing) do not vary greatly from one production lot to another, and therefore satisfy the required specifications for the device characteristics. An EC device can be manufactured stably.

The EC device according to the present invention (claims 1 to 14) can be used as a dimming device such as sunglasses or windows of buildings that change color reversibly, or can be used as a camera, a clock, a calculator, various measuring instruments, and the like. Can be widely used over a long period of time.

[Brief description of the drawings]

FIG. 1 is a schematic configuration diagram showing EC elements of Examples 1 to 7.

FIG. 2 is a schematic configuration diagram showing EC devices of Examples 8 to 14.

FIG. 3 is a schematic configuration diagram showing an EC element in which an element surface is sealed by a sealing resin and a sealing substrate.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 10 ... Substrate 11 ... Lower electrode layer 12 ... Upper electrode layer 13 ... Electrolytic reduction chromogenic thin film layer 14 ... Ion conductive layer 15 ... Electrolytic oxidation chromogenic thin film layer 20 ... Substrate 21 ... Lower electrode layer 22 ... Upper electrode layer 23 ... Electrolytic reduction coloring layer 24 ... Ion conductive layer 25 ... Electrooxidation coloring layer 30 ... Substrate 31 ... · Lower electrode layer 32 · · · Upper electrode layer 33 · · · EC layer in a broad sense (electrolytic oxidation coloring thin film layer, ionic conductive layer, electrolytic reduction coloring thin film layer) 34 ... sealing resin 35 ... sealing Substrate A: Area where electrolytic oxidative coloring thin film layer is formed (display part) B ... Area where electrolytic oxidative coloring thin film layer is not formed (non-display part)

Claims (9)

[Claims] 1. An electrochromic device comprising a substrate and at least a lower electrode layer, an electrolytic oxidation color-forming thin film layer, an ion conductive layer, an electrolytic reduction color-forming thin film layer, and an upper electrode layer provided in layers. An electrochromic device, wherein the amount of the electro-oxidative coloring substance contained in the layer is 1000 ppm or less. 2. A region (first region) of the electrolytic oxidation color-forming thin film layer.
Region) is a region (second region) of the electrolytic oxidation color-forming thin film layer.
2. The electrochromic device according to claim 1, wherein the overlapping region of the first region and the second region is smaller than the first region and the second region corresponds to a display unit, and the non-overlapping region corresponds to a non-display unit. 3. A method for producing an electrochromic device comprising a substrate and at least a lower electrode layer, an electrolytic oxidation color-forming thin film layer, an ionic conductive layer, an electrolytic reduction color-forming thin film layer, and an upper electrode layer laminated and provided. The amount of the electrolytically oxidized coloring substance contained in the ion-conductive layer after film formation by the vacuum film-forming method is 1000.
A method for manufacturing an electrochromic device, wherein the device is formed in a vacuum chamber whose atmosphere is controlled to be less than or equal to ppm. 4. The method according to claim 1, wherein the electrolytic oxidation color-forming thin film layer is formed in a vacuum chamber by a vacuum film forming method, and then the ionic conductive layer is formed by a vacuum film forming method. 4. The production method according to claim 3, wherein the oxidized color-forming substance is formed in another vacuum chamber which has been cleaned so as to have an amount of 1000 ppm or less. 5. After forming the electrolytic oxidation color-forming thin film layer by a vacuum film forming method, the substrate is taken out of the vacuum chamber and the inside of the vacuum chamber is cleaned to contain the substrate in an ion conductive layer formed thereafter. 4. The method according to claim 3, wherein the amount of the electro-oxidative coloring material to be used is 1000 ppm or less. 6. The manufacturing method according to claim 4, wherein the cleaning is performed by mechanically removing the electrolytic oxidation color-forming thin film layer adhered in the vacuum chamber. 7. The method according to claim 4, wherein the cleaning is performed by removing the electrolytic oxidation color-forming thin film layer adhered in the vacuum chamber by ion bombardment. 8. After forming the electrolytic oxidation color-forming thin film layer in a vacuum chamber by a vacuum film forming method, the substrate is taken out, and the electrolytic oxidation color-forming thin film layer attached in the vacuum chamber does not have the electrolytic oxidation color development property. 4. The method according to claim 3, wherein the amount of the electro-oxidative coloring material contained in the ion conductive layer formed thereafter is 1000 ppm or less by coating with a substance. 9. The substance having no electrolytic oxidative coloring property,
The method according to claim 8, wherein the material is at least one of an ion conductive material, an electrolytic reduction coloring material, and an electrode layer forming material.