JPS59228629A - 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 or more kinds of materials as an electrochromic layer which is a color developing layer on the anode side. CONSTITUTION:The 1st electrode 2 provided with an electrode part and a lead part is formed on a substrate 1, and it is set as shown by a symbol 20. Steam is introduced 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 nickel hydroxide with at least one among iron hydroxide, manganese hydroxide and lanthanum 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 nickel and at least one among iron, manganese and lanthanum or oxides thereof 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.

Electrochemical quenching dye elements, or electrochromic devices, which utilize this electrochromic phenomenon,
For example, it can be applied to numeric display elements, x-y matrix display devices, 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. This invention relates to electrochromic devices.

Two structural examples of all-solid-state electrochromic devices 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 is made of a transparent substrate 1, on which a ml electrode 2 made of a transparent conductive film, an electrochromic layer 3 which is a coloring layer on the anode side, and an insulating layer 4 made of a dielectric film. , a 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 l is generally formed of a glass plate, but this is not limited to glass plates, and can be
Any colorless and transparent plate such as a mirror plate or an acrylic plate may be used, and its position may be above the second electrode 5 instead of under the first electrode 2, depending on the purpose (e.g. , for the purpose of serving as a protective cover, etc.) may be provided on both sides. However, depending on these cases, it is necessary to make the second electrode 5 a transparent conductive film or to make both the electrodes on both sides transparent conductive films. 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.

The transparent conductive film is an ITO film (indium oxide In2
O5 (K in O5, doped tin oxide 5nQ2), Nesa film, etc. are used. The electrochromic layer 3, which is the coloring layer on the anode side, has conventionally been formed of chromium trioxide (Cr205), iridium hydroxide (Ir(OH)2), nickel hydroxide (Ni(OH)2), or the like. The insulating layer 4 made of dielectric material is made of zircon dioxide (ZrO2).
- Tantalum pentoxide (Ta205) Quasi oxide (si)
oxides such as o, sto□), or 7
Lithium tsulfide (LIF), i-gnesium heptadide (Mg
It is formed using a fluoride such as F2). In addition, the electrochromic layer 6, which is the coloring layer on the cathode side, is
Tungsten oxide (wo, wo,), molybdenum oxide (
MOO2y Mo5s ), vanadium pentoxide (v20
5) etc.

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 WO5 is used as an electrochromic substance, an oxidation-reduction reaction represented by the following formula (1) occurs, resulting in coloration.

wo, + xH+ x* oHxW05
(1) According to the formula (1), Mengesten bronze Hx
Wo3 is formed and colored, but if the applied voltage is reversed at this point, the color disappears. In the reaction of formula (1), in an all-solid-state electrochromic device, Groton H is supplied by the insulating layer inside the device and the device is colored.

In the above-mentioned electrochromic element, the electrochromic layer 3, which is the coloring layer on the anode side of the anode 1, is formed by forming a hydroxide such as iridium hydroxide (Ir(on)2) using a reactive film or an anodic oxidation film method. are doing.

In the present invention, in such an electrochromic cable, the electrochromic layer, which is the coloring layer on the anode side, is composed of a mixed film of two or more materials, which is different from the conventional one, and the electrochromic layer is different from the conventional one on the cathode side. It is an object of the present invention to provide an all-solid-state electrochromic device that can obtain color development with superior response speed and color density compared to a type that only develops and fades color.

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 a dielectric film, as shown in FIG. An all-solid-state electrochromic device in which an insulating 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 in which a second electrochromic layer, which is a coloring layer on the cathode side, is laminated between the electrodes, the electrochromic layer, which is the coloring layer on the anode side, is made of nickel hydroxide, iron hydroxide, and water. The film is a mixture of at least one of manganese oxide and lanthanum hydroxide.

The electrochromic layer, which is a coloring layer on the anode side, is composed of a film containing nickel hydroxide and at least one of iron hydroxide, manganese hydroxide, and lanthanum hydroxide, and is formed using a reactive high-frequency ion grating method. I can do something. In this case, the above-mentioned electrochromic layer can be formed by using nickel or its oxide, and iron, manganese, lanthanum, or their oxides individually or as a mixed pellet as vapor deposition materials.

FIG. 3 shows an example of a reactive high frequency ion grating device used to manufacture the all-solid-state electrochromic device according to the present invention. In the figure, 11 is the reactive ion grating device main body, 12 is an electron gun (FB gun),
13 is an umbrella (substrate holder); 14 is a DCd bias source that applies DC bias; 15 is a high frequency coil (RF coil); 16 is an H20 vapor supply source that supplies H20 vapor;
7 is a gas cylinder for supplying 02 gas, 18 and 19 are needle pulp, and 20 is a substrate (object to be evaporated) O. The process of manufacturing an electrochromic device using the apparatus shown in FIG. 3 is 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. 3 as shown at 20, and the above-mentioned material is used as a vapor deposition material. , H20 vapor is introduced into the apparatus 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 pump 17 to perform a reactive ion plating method. An electrochromic layer 3, which is a coloring layer on the anode side, is formed on the first electrode 2. Next, on this film, an insulating layer 4 is formed by the cylindrical method, and then a film of the second electrode 5 is formed on the insulating layer 4. (in the case of an electrochromic element), or an electrochromic layer 6, which is a coloring layer on the first cathode side, is formed on the insulating layer 4 by vacuum evaporation, and then a film of the second electrode 5 is formed (an electrochromic layer 6 as shown in FIG. (for chromic elements).

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 Glass 0.8 m thick (Cornlng 7059
), a first electrode 2 made of an ITO film 9 with appropriate extraction electrode parts and lead parts is formed, and using metal nickel (N1) and metal iron (Fe) as vapor deposition materials, the above-mentioned 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 grating method.

The conditions were 5. OX 10 Torr
The nickel deposition rate was increased to 0.3 X/sec.
% iron (D) was simultaneously deposited at a deposition rate of 0.6X/sec.The film thickness was 1300X.As a result,
An electrochromic layer 3 consisting of a mixed film of nickel hydroxide and iron hydroxide was formed.

On this film, a layer of Ta 20 s of 3000× was applied as an insulator layer 4 using a vacuum evaporation method. The true degree at this time is 20 x 10-5 Torr, and the deposition rate is 8ηe.
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 electrodes at the 1st 211t, it took 880m5ec until the coloring density reached ΔOD of 0.3.・Example 2 Glass with a thickness of 0.8 sheets (Corning 7059)
A first electrode 2 consisting of an ITO film 9 having appropriate extraction electrode portions and lead portions is formed on a substrate 1 of the substrate 1, and mixed pellets (mixed A first electrochromic layer 3, which is a coloring layer on the anode side, was formed on the first electrode 2 using a reactive high frequency ion grating method (using a ratio of 1:1) and metallic nickel).

The conditions were 4. H20 steam. OX 10' Tor
9) Js.
The deposition rate of the ecX metal nickle was set to 0.5X/sec. The film thickness was 1500X. An electrochromic layer 3 consisting of a mixed film of nickel hydroxide, iron hydroxide, and manganese hydroxide is formed on top of this film.
A layer of Ta205 was deposited at 3000X as the insulator layer 4 using a vacuum evaporation method. The degree of vacuum at this time is 2. OXI
OTorr and deposition rate were 8)/1 sec. Further, on these films, a WO layer of jl+, 400 Oi was applied as a second electrochromic layer 6, which is a cathode coloring layer, by a vacuum evaporation method, and then a semitransparent 8AAu film was applied as a second electrode 5. I attached 300X.

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 35V by the time ΔOD reached 0.4.
It was 0 m5ec.

Example 3 Glass with a thickness of 0.8 mm+ (Corning 7059
) A first electrode 2 made of an ITO film having an appropriate extraction electrode part and a lead part is formed on a substrate 1 (1), and mixed pellets of metallic iron, manganese, and lanthanum (mixing ratio 1:1) are used as the evaporation material. : Using 3) and nickel oxide, a first 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 grating method.

The conditions were 3. H20 vapor. OX 10 Torr
and the deposition rate of the mixing pellet was set to 1.0 X/s.
ec, the deposition rate of nickel oxide is 0.8X/'see
And so. The film thickness was 1500X.

As a result, an electrochromic layer 3 consisting of a mixed film of nickel hydroxide, iron hydroxide, manganese hydroxide, and lanthanum hydroxide was formed.

On top of this film, a layer of Ta 205 with a thickness of 3000% is applied as an insulating layer 4 by a vacuum evaporation method. I attached it. At this time, the degree of vacuum was 2, OX 10'-5 Torr, and the deposition rate was 8.
X/1! It was @0. Furthermore, on top of these films, a WOS layer as a second electrochromic layer 6 which is a cathode coloring layer is deposited at 4000X using a vacuum evaporation method, and then a translucent Au film is deposited at 300X as a second electrode 5. I attached it.

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 0.4K at ΔOD.
40 m5ec.Example 4 Glass with a thickness of 0.8 wr (Corning 7059
) A first electrode 2 consisting of an ITO film 9 provided with appropriate extraction electrode portions and lead portions was formed on the substrate 1 of (1).

Metal nickel (Ni) and manganese oxide (M
A first electrochromic layer 3, which is a coloring layer on the anode side, was formed on the first electrode 2 using reactive high frequency ion blating method and simultaneous vapor deposition using nO2).

The conditions were 3. H20 vapor. OX 10-' To
After introducing 02 gas to rr, 4. Q X 10
−' Torr i, and the deposition rate was set to 0.4, respectively.
) v'II % 0.6 X/see. The film thickness at this time was 1200XT.

In this manner, the first electrochromic layer 3 consisting of a mixed film of nickel hydroxide and manganese hydroxide was formed on the first electrode 2.

On top of this film, a vacuum evaporation method is applied.
30001 layers of a205 were attached. Further, on top of these films, a WO5 layer is deposited as a first and second electrochromic layer 6, which is a coloring layer on the cathode side, by a total deposition method.
ozH, and then a semi-transparent Au film of 300 oz as the second electrode 5.
I added an X.

When the electrochromic element manufactured in this manner was driven by applying 2.2V between the first and second electrodes, the coloring density reached 400 m@e by the time the coloring density reached 0.4 in ΔOD.
It was c.

Example 5 Thickness 0.8 cod glass (Cornlng 7059)
A first 'tL pole 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.

Metallic nickel (N1) and lanthanum (La) are used as vapor deposition materials.
A first electrochromic layer, which is a coloring layer on the anode side, is simultaneously deposited on the first electrode 2 using a reactive high frequency ion blating method.

A layer 3 was formed.

The conditions were 3. H20 vapor. OX 10-' To
After introducing O2 gas to rr, 5X10 Tor
It was introduced at rt and the deposition rate was 0.6/81114 for each kO, 51/s.

The film thickness at this time was 1300X 〇 In this way,
A first electrochromic layer 3 consisting of a mixed film of nickel hydroxide and lanthanum hydroxide was formed on the first electrode 2 .

On top of this film, a T
A layer of JL205 was attached at 3000X. Furthermore, a w03 layer as a second electrochromic layer 6, which is a coloring layer on the cathode side, is deposited on the film of this film using a vacuum evaporation method.
000X, and then a semi-transparent Au film 3 as the second electrode 5.
I added 00X.

When the electrochromic element manufactured in this way was driven by applying 2.2V between the first and second electrodes, the coloring density reached 400 m5e by ΔOD of 0.3.
It was c.

Example 6 Glass with a thickness of 0.8 was (Cornlng 705
On the substrate 1 of 9), a first electrode 2 made of an ITO film having a suitable extraction electrode part and a lead part was formed.

Mixed pellets of nickel oxide and iron oxide (mixing ratio 1:1) and lanthanum oxide (Laz03) were used as vapor deposition materials, and they were simultaneously vapor-deposited on the first electrode 2 using a reactive high frequency ion grating method, and then the anode was formed. The first coloring layer is the side coloring layer.
An electrochromic layer 3 was formed.

The conditions were 4. H20 steam. OX 10-' To
rr, and the deposition rate was set to hO, 8: lv/s, 0
．． 4 X/II@1! And so. The film thickness at this time is 150
It was 0X.

In this manner, a first electrochromic layer 3 consisting of a mixed film of nickel hydroxide, iron hydroxide, and lanthanum hydroxide was formed on the first electrode 2.

On top of this film, an insulating layer 4 of T
3000 layers of A205! I attached it. Furthermore, on top of these films, a second electrochromic layer, which is a coloring layer on the cathode side, is formed.
WO3 layer as layer 6 was deposited by vacuum deposition method at 9.40%
00X, and then a semi-transparent Au film with a thickness of 30 mm as the second electrode 5.
When the electrochromic element manufactured in this way was driven by applying 2.2V between the 1st and 2nd electrodes, it took 320 m+s for the coloring density to reach 0.3 in ΔOD.
It was hard with ec ◎ Example 7 0.8-thick glass (Cornlng 7059)
A first electrode 2 made of an ITO film having appropriate extraction electrode portions and lead portions was formed on the substrate 1 .

Mixed pellets of lanthanum oxide and manganese oxide (mixing ratio 1:1) and metallic nickel are used as vapor deposition materials, and they are simultaneously vapor-deposited on the first electrode 2 by the reactive high-frequency ion grating method, and color is developed on the anode side. A first electrochromic layer 3 was formed.

As a condition, H20 vapor was heated at 5 X 10-' Torr.
and the deposition rate was set to 0.6X/11XO, respectively.
4) It was set as Jsec. The film thickness at this time was 1200X.

In this way, the first electrochromic layer 3 consisting of lanthanum hydroxide, manganese hydroxide, and nickel hydroxide was formed on the first electrode 2.

On top of this film, four insulating layers are deposited using a vacuum evaporation method.
&2050 layer was attached to 3000X. Furthermore, on the film of et al., a WO3 layer was formed as a second electrochromic layer 6, which is a coloring layer on the cathode side, by a vacuum evaporation method! D, 40
00X, and then a semi-transparent Au film with 300X as the second electrode.
I added an X.

When the electrochromic element manufactured in this way was driven by applying 2.2V between the first and second electrodes, it took 380 ms@ for the coloring density to reach ΔOD of 0.4.
It was c.

[Brief explanation of drawings]

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 grating 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 1 11 ... Main body of reactive ion blating device, 1
2...Electron gun (EB gun) 1 13...Umbrella (substrate boulder)\14...DC bias source, 15...High frequency coil (RF coil), 16...H
20g air supply source, 17...O2 gas cylinder, 18.1
9... 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 conductive film are sequentially laminated, or the above insulating layer 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 nickel hydroxide and hydroxide. An all-solid-state electrochromic device characterized by having a film mixed with at least one of iron, manganese hydroxide, and lanthanum hydroxide.