JPS59228630A - Entirely solid electrochromic element - Google Patents

Abstract

PURPOSE:To develop color of high density at a high response speed by using a film of a mixture of two kinds of materials as an electrochromic layer which is a color developing layer on the anode side. CONSTITUTION:The 1st electrode 2 provided with a proper leading-out electrode part and a lead part is formed on a substrate 1, and it is set in an apparatus as shown by a symbol 20. Steam is introduced into the apparatus from a steam feeding source 16, or gaseous O2 is introduced from a gaseous O2 cylinder 17 together with steam, and a film of a mixture of cobalt hydroxide with nickel hydroxide is formed on the electrode 2 as an electrochromic layer 3 which is a color developing layer on the anode side by a reactive ion plating method using metallic cobalt and metallic nickel or compounds thereof such as oxides as materials to be vapor-deposited. An insulating layer 4 is then formed by a vacuum deposition method, and the 2nd electrode 5 made of a film is formed on the layer 4. The resulting element has an increased response speed, improved color developing efficiency and a prolonged life.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an electrochromic device that utilizes an electrochemical coloring/decoloring phenomenon, that is, an electrochromic phenomenon.

Electrochemically quenching dye elements, or electrochromink devices, utilize such electrochromic phenomena.
For example, it can be applied to numeric display elements, X-Y matrix displays, optical shutters, aperture mechanisms, etc. Classified by material, it can be divided into liquid type and solid type, but the present invention is particularly applicable to all-solid type electrochromic devices. It is related to the element.

Two structural examples of all-solid-state electrochromic elements utilizing electrochromic phenomena are shown in FIGS. 1 and 2. These figures show the general structure of an all-solid-state electrochromic device.

The electrochromic element shown in FIG. 1 has a first electrode 2 made of a transparent conductive film on a transparent substrate 1, an electrochromic layer 3 which is a coloring layer on the anode side, an insulating layer 4 made of a dielectric film, The second electrode 5 made of a conductive film is sequentially laminated.

Furthermore, the electrochromic element shown in FIG.
Between the insulating layer 4 and the second electrode 5 in the structure shown in the figure,
Further, a second electrochromic layer 6, which is a coloring layer on the cathode side, is laminated.

In the above structure, the substrate 1 is generally formed of a glass plate, but it is not limited to a glass plate, and may be any colorless and transparent plate such as a plastic plate or an acrylic plate. It may be provided not under the first electrode 2 but above the second electrode 5, or may be provided on both sides depending on the purpose (for example, for the purpose of serving as a protective cover). However, depending on these cases, it is necessary that the second electrode 5 is made of a transparent conductive film, and that both electrodes on both sides are made of a transparent conductive film. If both electrodes are transparent electrodes, a transparent element can be created. The insulating layer 4 may be made of not only a dielectric but also a solid electrolyte or the like.

As a transparent conductive film, ■TO film (indium oxide In2
(O, doped with tin oxide (SnO2)), Nesa film, etc. are used. The electrochromic layer 3, which is the coloring layer on the anode side, has conventionally been made of chromium trioxide (cr2o3), iridium hydroxide (Ir(OH)2), nickel hydroxide (
It is formed from Nl(OH)2) and the like. The insulating layer 4 made of dielectric material is made of zircon dioxide (Z ro 2 )
, tannium pentoxide fi A/ (Ta205), silicon oxide (Sin, 5in2), etc., lithium heptatide (LiF), magnesium fluoride (
It is formed using a fluoride such as MgF2).

Further, the electrochromic layer 6, which is a coloring layer on the cathode side, is formed using tungsten oxide (WO2+W05), molybdenum oxide (Mo02rMoOs), vanadium pentoxide (205), or the like.

In an all-solid-state electrochromic device having such a structure, a vapor chemical reaction occurs when a voltage is applied between the first electrode 2 and the second electrode 5, and the stain is colored or decolored. It is generally said that this coloring mechanism is based on the formation of bronze by double injection of cations and electrons into the electrochromic layer 6, for example. For example, when WO3 is used as an electrochromic substance, an oxidation-reduction reaction represented by the following formula (1) occurs, resulting in coloration.

WO, + xH++ xe 'nee HxWO, (1)
According to formula (1), tungsten bronze HxWO5Z
>" is formed and colored, but if the applied voltage is reversed at this point, the color disappears. In an all-solid-state electrochromic device, this reaction in equation (1) Proton H+ is supplied and colored.

In the above-mentioned electrochromic device, the electrochromic layer 3, which is the coloring layer on the anode side, has conventionally been made of iridium hydroxide (Ir(OH)2), nickel hydroxide (Nl
A material such as (OH)2) is formed by a reactive ivy or anodic oxidation film method.

In such an electrochromic element, the present invention consists of an electrochromic layer, which is a coloring layer on the anode side, made of a mixed film of 92 materials different from conventional ones, so that the electrochromic layer, which is the coloring layer on the anode side, is composed of a mixed film of 92 kinds of materials. The object of the present invention is to provide an all-solid-state electrochromic device that can produce a response speed and color density superior to those of the conventional type.

The all-solid-state electrochromic device according to the present invention is characterized by a first electrode made of a conductive film, an electrochromic layer which is a coloring layer on the anode side, and an insulating film made of a dielectric film, as shown in FIG. An all-solid-state electrochromic device in which a layer and a second electrode made of a conductive film are successively laminated, or as shown in FIG. In an all-solid-state electrochromic device formed by laminating a certain second electrochromic layer, the electrochromic layer, which is the coloring layer on the anode side, is a mixed film in which nickel hydroxide is added to cobalt hydroxide.

The electrochromic layer composed of the above-mentioned mixed film of cobalt hydroxide and nickel hydroxide is formed using a reactive high frequency ion blating method. At this time, compounds such as metal cobal, (Co) metal nickel, or their oxides are used as the vapor deposition material, and a mixed film is produced by methods such as mixed pellets or simultaneous vapor deposition. In this case, the mixing ratio of cobalt hydroxide and nickel hydroxide in the mixed film is preferably less than 1 part cobalt hydroxide to 1 part nickel hydroxide.

FIG. 3 shows an example of a reactive high frequency ion blating apparatus used to manufacture the all-solid-state electrochromic device according to the present invention. In the figure, 11 is the main body of the reactive ion blating device, 12 is the electron gun (EB j!n), 13 is the umbrella (substrate holder), 14 is the DC bias source that applies DC bias, and 15 is the high frequency coil (RF coil). ), 16 is an H20 vapor supply source that supplies H20 vapor, 17 is a gas source that supplies 02I gas, 18 and 1
Reference numeral 9 indicates needle pulp, and 20 indicates a substrate (object to be deposited).

The steps for manufacturing an electrochromic device using the apparatus shown in FIG. 3 are as follows.

First, a first electrode 2 having a suitable extraction electrode part and a lead part is formed on a substrate 1, and this is installed in the apparatus shown in FIG. Alternatively, using compounds such as these oxides, H20 vapor is introduced into the device from the H20 vapor supply source 16, or H20 vapor is introduced from the H20 vapor supply source 16 and 0□ gas is introduced from the tank 17. Then, an electrochromic layer 3, which is a coloring layer on the anode side, is formed on the first electrode 2 by a reactive ion silating method. Next, an insulating layer 4 is formed on this film by a vacuum evaporation method, and then a second electrode 5 is formed on the insulating layer 4.
(in the case of the electrochromic element shown in FIG. A film is formed (in the case of the electrochromic device shown in FIG. 2).

According to the present invention, it is possible to improve the response speed, coloring efficiency, and lifespan compared to the conventional electrochromic element that only develops and fades color on the cathode side.

Examples of the present invention will be described below.

Example 1 Galley with a thickness of 0.8 m, (Cornlng 7059
), a first electrode 2 made of an ITO film 9 having an appropriately wide extraction electrode part and a lead part is formed, metal cobalt and metal nickel are used as vapor deposition materials, and the above first electrode 2 is formed. A first electrochromic layer 3, which is a coloring layer on the anode side, was formed thereon by simultaneous vapor deposition using a reactive high frequency ion grating method.

The conditions were 4. H20 steam. OX 10-' Tor
r i and the deposition rate is set to k 1. OX/'see
Oyo (1,0,7X/see I: did. Film thickness is 15
It was 00X. As a result, a first electrochromic layer 3 consisting of a mixed film of cobalt hydroxide and nickel hydroxide was formed on the first electrode 2.

On this film, a layer of Ta205 was applied as an insulator layer 4 to 3000 nm by vacuum evaporation. The degree of vacuum at this time is 2. OX I F5 Torr, deposition rate is 8X/s
It was ec. Further, on these films, WO2 is applied as a second electrochromic layer 6, which is a cathode coloring layer.
The layer was applied using a vacuum evaporation method, 4000X, then a second layer.
A translucent Au film 3001 was attached as the electrode 5.

When the all-solid-state electrochromic device manufactured in this manner was driven by applying 2.2V between the first and second electrodes, the coloring density reached 0.3 at ΔOD.
It was 0 m5ec.

Example 2 Glass 0.8 m thick (Corning 7059
), a first electrode 2 made of an ITO film 9 having appropriate extraction electrode portions and lead portions was formed, and a mixed pellet of metallic cobalt and metallic nickel (mixing ratio 1:0.6) was formed as the evaporation material. ), an electrochromic layer 3, which is a coloring layer on the anode side, was formed on the first electrode 2 by a reactive high frequency ion blating method.

The conditions were 3. H20 vapor. OX 10-' Tor
4. Introduce up to r and 0□ gas. OX 10"-'
Torr was introduced, and the deposition rate was set to 0.8 i/see. The film thickness was 100OX. This allows the first
An electrochromic layer consisting of a mixed film of cobalt hydroxide and nickel hydroxide was formed on the electrode 2.

On top of this film, a layer of Ta205 of 3000X was deposited as an insulator layer 4 using a vacuum evaporation method. The degree of vacuum at this time is 2. OX 10-5 Torr, deposition rate 8X/se
It was c. Furthermore, a 300× translucent Au film was attached as the second electrode 5 on top of these films.

When the all-solid-state electrochromic device manufactured in this way was driven by applying 2.2V between the first and second electrodes, the coloring density reached 35
It was 0m5ec.

Example 3 Glass with a thickness of 0.8 mm (Corning 7059)
A first electrode 2 consisting of an ITO film 9 having appropriate extraction electrode parts and lead parts is formed on the substrate 1 of A first electrochromic layer 3, which is a coloring layer on the anode side, was formed by a reactive high frequency ion silating method.

As a condition, H20 vapor was heated at 5 X 10-' Torr.
t, and the deposition rates were 1.01/5T1c and 0.7X/sec, respectively. The film thickness was 1600X. As a result, a first electrochromic layer consisting of a mixed film of cobalt hydroxide and nickel hydroxide was formed on the first electrode 2.

On top of this film, a layer of Ta205 was deposited at 3000X as an insulator layer 4 by vacuum evaporation. The degree of vacuum at this time is 2. OX 10-5 Torr s Deposition rate is 81/s
It was ec. Further, on these films, a second electrochromic layer 6, which is a cathode coloring layer, is formed of WO,
A layer of Q4000X is applied by vacuum evaporation method, then a second
As the electrode 5, a translucent Au film with 300×ζ 7 sand was used.

When the all-solid-state electrochromic device manufactured in this way was driven by applying 2.2 V between the first and second electrodes, the coloring density reached 40
It was 0 m5ec.

Example 4 Glass with a thickness of 0.8 m (Cornlng 7059)
A first electrode 2 consisting of an ITO film 9 having appropriate extraction electrode portions and lead portions was formed on the substrate 1 of the present invention.

The vapor deposition materials include metal copal (Co) and metal nickel (
Ni) was simultaneously vapor-deposited on the first electrode 2 by a reactive high frequency ion silating method to form a first electrochromic layer 3, which is a coloring layer on the anode side.

As a condition, H20 vapor was heated to 5.5 x 10-'Tor.
r, and the deposition rate was set at each k O,6X/see,
It was set to 0.8X/see.

The film thickness at this time was 1200X.

In this way, the first electrochromic layer 3 made of cobalt hydroxide and nickel hydroxide was formed on the first electrode 2.

On top of this film, an insulating layer 4 of T
A layer of a205 was applied at 3000X. Further, on these films, a WO2 layer was deposited as the first electrochromic layer 6, which is a coloring layer on the cathode side, using a vacuum evaporation method.
After attaching OX, a semi-transparent Au film with a thickness of 300 mm was applied as the second electrode 5.
I added an X.

When the electrochromic element manufactured in this way was driven by applying 2.2V between the first and second electrodes, the coloring density reached 380 m5e by the time the ΔOD reached 0.4.
It was c.

[Brief explanation of the drawing]

FIGS. 1 and 2 are cross-sectional views showing two examples of all-solid-state electrochromic devices according to the present invention, and FIG. 3 shows a reactive ion blating device used to manufacture the devices of the present invention. It is a schematic diagram. 1... Substrate, 2... First electrode, 3...
Electrochromic layer, 4... Insulating layer, 5... Second electrode, 6...
Electrochromic layer, 11... Main body of reactive ion blating device, 1
2... Electron gun (EB gun), 13... Umbrella (substrate holder), 14... DC bias source, 15... High frequency: +il (RF coil), 16...
H20 vapor source, 17...02 gas dempé, 18.
19... Needle valve, 20... Substrate (deposited object).

Claims (1)

[Claims] A first electrode made of a conductive film, an electrochromic layer as an anode side coloring layer, an insulating layer made of a dielectric film, and a second electrode made of a dielectric film are laminated in sequence, or the above insulating layer is laminated in sequence. In an all-solid-state electrochromic device in which a second electrochromic layer, which is a coloring layer on the cathode side, is laminated between the electrode and the second electrode, the electrochromic layer, which is the coloring layer on the anode side, is made of cobalt hydroxide and nickel hydroxide. An all-solid-state electrochromic device characterized by having a mixed film of.