JPS59154426A - Entirely solid electrochromic element - Google Patents

Abstract

PURPOSE:To develop color of high density at a high response speed by using manganese oxide as the material of an electrochromic layer as a color developing layer at the anode side. CONSTITUTION:The 1st electrode 2 made of a transparent electric conductor film, an electrochromic layer 3 as a color developing layer at the anode side, an insulating layer 4 made of a dielectric film, and the 2nd electrode 5 made of an electric conductor film are successively laminated on a transparent substrate 1 to obtain an entirely solid electrochromic element. The 2nd electrochromic layer 6 as a color developing layer at the cathode side may be further laminated. At this time, the electrochromic layer 3 is made of manganese oxide. The manganese oxide film is formed by reactive ion plating in an atmosphere of gaseous O2 using manganese or manganese oxide as an evaporating material.

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.

Electrochromic phenomenon refers to the phenomenon in which substances change color due to redox reactions when voltage is applied. Electrochemical quenching dye elements, that is, electrochromic elements that utilize such electrochromic phenomena, can be applied to, for example, numeric display elements, X-Y matrix displays, optical shutters, aperture mechanisms, etc. Although they are classified into liquid type and solid type, the present invention particularly relates to an all-solid type electrochromic element.

Two structural examples of all-solid-state electrochromic devices utilizing electrochromic phenomena are shown in FIGS. 1 and 2.

The electrochromic element shown in FIG. 1 consists of a transparent substrate 1, a first electrode 2 made of a transparent conductive film, an electrochromic layer 3 which is a coloring layer on the anode side, an insulating layer 4 made of a dielectric film, and a conductive layer 4. 2'i6, which consists of body membranes. It is formed by sequentially stacking poles 5.

In addition, the electrochromic cord (r:i
, the insulating layer 4 and the second electrode (pigeon Y5) in the structure shown in FIG.
In addition, a second electrochromic layer 6, which is a coloring layer on the cathode side, is placed between t? This is what I did.

In the above structure, the substrate 1 is generally formed of a glass plate, but this is not limited to a glass plate, and may be any transparent plate such as a plastic plate or an acrylic plate. , not under the first electrode 2, but under the second electrode.
Depending on the purpose (for example,
They may be provided on both sides (for purposes such as serving as a protective cover).

However, depending on the case, the second electrode 5 may be a transparent conductor.
If a thin film is used, both electrodes on both sides must be made of transparent conductive film. If both electrodes are transparent electrodes, the element can be used as a transparent type. As such a transparent conductive film, ITO
IP (tin oxide S nO in insium oxide n2o5
2), Nesa membrane, etc. are used.

In the above structure, the electrochromic layer 3, which is the coloring layer on the anode side, is conventionally made of chromium trioxide (Cr20g).
, irisium hydroxide (Ir(OH)2), nickel hydroxide (N1(oH)2), etc.

The insulating layer 4 made of dielectric material is made of norcon dioxide (Z r
O2), silicon oxide (SiO), dioxide'y (
-A (5102), oxides such as tantalum pentoxide (Ta2o5), or lithium fluoride (LiF')
), magnesium fluoride (MgF2), etc. In addition, the electrochromic layer 6, which is the coloring layer on the thoracic pole side, is made of tungsten dioxide (W).
O2), tungsten trioxide (WO6), molybdenum dioxide (MoC2), molybdenum trioxide (MoOs)
, vanazium pentoxide (v205), 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. This coloring process is generally thought to involve bronze formation by double injection of cations and I into the layer 6, such as electrochromic. For example, when WO5 is used as an electrochromic substance, an oxidation-reduction reaction represented by the following formula (1) occurs, resulting in coloration.

WO3+XH"1xe; HxV7v705
(1) (1) 2K Therefore, tungsten bronze) Lx*03 is formed and colored, but if the applied voltage is reversed at this point, the color becomes decolored. In an all-one-type electrochromic element, such a reaction of formula (1) is caused by the supply of protons (-4-) by the insulating layer inside the element, resulting in coloring.

In the above-mentioned electrochromic device, the electrochromic layer 3, which is a color-developing layer, is conventionally made of irinium hydroxide (Ir(OH)2), nickel hydroxide (
Hamura such as N1 (on) 2) is formed by a reactive film, film or anodic oxidation film method.

The present invention provides such an electrochromic device in which the electrochromic layer, which is the coloring layer on the anode side, is composed of a completely new coating material different from conventional ones.
It is an object of the present invention to provide an all-solid-state electrochromic element that can obtain color development with superior response speed and coloring density compared to the conventional type that only develops and fades on the cathode side.

The features of the all-solid-state mold 1/chrochromic device according to the present invention are as shown in FIG. An all-solid-state electrothermic device in which an insulating layer made of a body film and a second electrode made of a conductive film are sequentially laminated, or as shown in FIG. In an all-solid-state electrochromic element in which a second electrochromic layer, which is a coloring layer on the cathode side, is laminated in between, the electrochromic layer, which is the coloring layer on the anode side, is made of manganese oxide.

This oxidized cancer film can be formed by reactive ion blating, using manganese (,'An) or its oxide (Mn011VIn0) as the evaporator.
2. Mn2O3, Mn304)' was used, and the atmosphere was 0
A desired electrochromic layer can be obtained by adding two gases.

Manufacture all-solid-state electrochromic device according to the present invention↓
An example of a reactive ion brating device f~ used to make a 1. In the figure, 10 is the main body of the ion blating device, 11 is a diffusion pump, 12 is an electron gun (EB gun), 13 is an umbrella (substrate holder), 14 is a DC bias source that applies DC bias, and 15 is a high frequency coil. (RF coil), A6 supplies 02 gas
A gas cylinder, 17 a needle valve, and 18 a substrate (object to be evaporated).

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. 3 as shown at 18, and -y7 electrodes ( M
n) or its oxide (Mn-0, MnO2.

Using Mn2031Mn203l, 0□ gas cylinder 16
0□ gas is introduced from the electrochromic layer 3, which is a coloring layer on the anode side, by a reactive ion silating method.
is formed on the first electrode 2 described above. 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. (case), or on the insulating layer 4, an electrochromic layer 6, which is a coloring layer on the cathode side, is formed by vacuum evaporation, and then a film of the second flash 5 is formed (
In the case of the electrochromic device shown in FIG. 2).

According to the present invention, response speed, coloring efficiency and lifespan can be improved compared to conventional electrochromic elements having only a coloring layer on the cathode side.

Examples of the present invention will be described below.

Example 1 Glass 0.8 am thick (Corning 7059
) A first electrode 2 made of an ITO film having a suitable extraction electrode part and lead part is formed on the substrate 1 of An electrochromic layer 3, which is a coloring layer on the anode side, was formed on the first electrode 2.

The conditions are (0□ gas) as 3-OX 10'To
rr '1, and the deposition rate was 2.5 X/aec.
,! : did. The film thickness was i 000×. This electrochromic layer 3 is made of manganese oxide (Mn0z)
It consisted of:

On this film, a layer of Ta2O5 of 3000X was deposited as an insulator layer 4 by vacuum evaporation. The degree of vacuum at this time is 2. OX 10'Torr, deposition rate 8/
It was 8ee. Further, on top of these films, a 300X semi-transparent conductive Au film was attached as the second electrode 5.

When the all-solid-state electrochromic device fabricated in steps 1 to 1 was driven by applying a voltage of 22V between the first and second electrodes, the coloring density reached 0.3 at Δ0.0, and 6 pulses were generated in 9607 nsec.・Example 2 Glass with a thickness of 0.8 mm (Corning 7059)
A first electrode 2 made of an ITO film having appropriate extraction/extraction electrode parts and lead parts is formed on a substrate 1, and the above-described process is performed using MnOZ as a vapor deposition material by a reactive ion silating method. An electrochromic layer 3, which is a coloring layer on the anode side, was formed on the first electrode 2.

The conditions are 02 gas at 2.0 x 10 Torr.
r, and the deposition rate was increased to 13. OX//'sec. The film thickness was 2000X. This electrochromic layer consisted of manganese oxide (MnO2). An insulator layer 4 is deposited on this film by a vacuum evaporation method.
As a result, the Ta205 layer is 3000 years old. The degree of vacuum at this time is 2. OX 10-5 Torr, deposition rate 8
It was X/sec. Further, on these films, WO is formed as an electrochromic layer 6 which is a coloring layer on the cathode side.
A film of p4oooi is attached by a vacuum evaporation method, and further,
A semi-transparent conductive Au film of 300X was attached as the second electrode 5.

When the thus manufactured all-solid-state electrochromic device was driven by applying a voltage of 22 μ between the first and second electrodes, it took 700 m5 ec until the coloring density reached 04 in ΔQ,D.

Example 3 Glass with a thickness of 0.8 mm (Corning 7059
), a first electrode 2 made of an ITO film with appropriate extraction electrode parts and lead parts is formed, and using MuO2f as the evaporation material, a color forming layer on the anode side is formed by a reactive ion blating method. be. An electrochromic layer of 3 gold was formed.

The conditions are 02 gas and 3. OX ], OTor
The deposition rate was set to 2. oku/Fle C. The film thickness was 2000X. This electrochromic double layer was composed of manganese oxide (Mn0z).

On top of this film, a 3000X layer of Ta 205 was applied as an insulator layer 4 by a vacuum evaporation method. The degree of vacuum at this time was 2.0 x 10.5 Torr, and the deposition rate was 8X/s.
It was ee. Furthermore, a second electrode 5 is placed on top of these films.
A translucent conductive Au film of 300X was attached as a layer.

When the all-solid-state electrochromic device manufactured in this manner was driven by applying a voltage LL of 2.2 V between the first and second electrodes, the coloring density was Δ0. 98. by the time D reaches 0.3. It was Otn see.

[Brief explanation of drawings]

FIGS. 1 and 2 are cross-sectional views showing two examples of all-solid-state electrochromic eggs according to the present invention, and FIG.
FIG. 1 is a schematic diagram showing an ion silating apparatus used to manufacture the device of the present invention. l-... Substrate 2... First electrode; 3... Electrochromic layer 4... Insulating layer 5... Second electrode 6... Electrochromic layer 10... Ion silating device main body 11.・・Diffusion pump 12・・Electron gun (EB power gun) 13・・・
Umbrella (board holder)

Claims (1)

[Claims] A first electrode made of a conductive film, an electrochromic layer which is a coloring layer on the anode side, an insulating layer made of a dielectric film, and a second electrode made of a conductive film, in this order? ', or a second electrochromic layer, which is a coloring layer on the cathode side, is further laminated between the above insulating layer and the second electrode. An all-solid-state electrochromic element characterized in that the electrochromic layer, which is a coloring layer on the anode side, is made of manganese oxide.