JPS604925A - Electrochromic element - Google Patents

Abstract

PURPOSE:To obtain a fully solid-state electrochromic element by using a mixture of three kinds of hydroxides of specified elements for the first electrochromic layer. CONSTITUTION:A base plate 1 is made of a colorless transparent glass or the like and the first electrochromic layer 3 of a color developing layer on the anode side is made of CrO3, iridium hydroxide, and nickel hydroxide. An insulating layer 4 is made of a dielectric of SiO2 or other oxides, or MgF2 or other fluorides. The second electrochromic layer 6 of a color developing layer on a cathode side is made of WO3 or the like. When voltage is impressed between the electrodes 2, 5, electrochemical reaction is caused to erase a color. The layer 3 is formed by the reactive high frequency ion plating method, Co, Ir, or Ni pellets or powder is used for the vapor deposition material, and a film is formed by using an electron gun alone or together with a resistance heater.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a first electrochromic layer in the production of an element that applies an electrochemical coloring/discoloring phenomenon, that is, an electrochromic phenomenon, using cobalt, iridium, and nickel hydroxides. This invention relates to an electrochromic device having a mixed film of three types.

A conventional example of an all-solid-state electrochromic element to which electrochromic phenomenon is applied will be explained with reference to FIGS. 1 and 2. 1 and 2 are cross-sectional views showing the general structure of an all-solid-state electrochromic device.

In the figure, 1 is a glass substrate, 2 is a transparent conductive film, 6 is a first electrochromic layer which is a coloring layer on the anode side, 4 is an insulating layer made of a dielectric, and 6 is a second electrochromic layer which is a coloring layer on the cathode side. , 5 are electrodes.

Here, the glass substrate 1 is not only made of glass, but may be made of plastic, acrylic, etc., as long as it is colorless and transparent, and its position may be on either side of the electrode, or it may be on both sides. good. Regarding electrodes 2 and 5, it is sufficient if either one is transparent, and if both sides are transparent, a transmissive type element can be obtained. 4 may also be made of not only a dielectric material but also a solid electrolyte or the like.

The transparent conductive film is an I'rO film (indium oxide).

InsQg (in which tin oxide, 8 nm) is doped), Nesa film, etc. are used.

The first electric F color layer, which is the coloring layer on the anode side of B, is made of chromium trioxide (OrtomiOs) and iridium hydroxide (I).
r(O)1)*), nickel pyrolyl acetate (N4(O)), etc.

The insulating layer made of the derivative No. 4 is made of zircon dioxide (ZrO
s), pentoxide tank/l/ (Ta5ks), silicon oxide (Sl, 81oz), etc., or lithium fluoride (LlF), magnesium fluoride (MgF*), etc. Fluoride is used.

The second electrochromic layer, which is the coloring layer on the cathode side of No. 6, is made of tungsten oxide (W), molybdenum oxide (Moss, Moon), vanadium pentoxide (Vm).
Formed using materials such as Oa).

In an all-solid-state electrochromic element having such a structure, by applying a voltage between the first electrode 2 and the second electrode 5, an electrochemical reaction occurs to cause coloring and decoloring.

This coloring mechanism is generally said to be, for example, formation of bronze by double injection of cations and electrons into the second electromic material layer 6. If vyos is used as the electrochromic substance in situ, a fermentation-reduction reaction represented by the following formula (1) occurs, resulting in coloration.

WOs +xH” + s:e-;HxWOs (1)
According to formula (1), tungsten bronze 1-hWOs
However, if the applied voltage is reversed, the color disappears.

In an all-solid-state electrochromic device, such a reaction expressed by formula (1) is said to be caused by the supply of protons H+ by an insulating layer inside the device, causing coloration.

The first electro-tetrachromic layer consists of iridium hydroxide (I
Hydroxide such as r (OH) oxide can also be formed by reactive sputtering or an anodic oxidation film method, but in the present invention, it was formed using a reactive high frequency ion blating method. Cobalt (Co) and iridium (Ir) are used as vapor deposition materials.
A film was formed using a pellet or powder of nickel (Ni) using an electron gun or a combination of resistance heating.

An example of an ion blating apparatus used to carry out the method according to the invention is shown in FIG.

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), 16 is an umbrella, 1
4 is a DC bias source that applies a DCA bias, 15 is a high frequency coil (concentration coil), 16 is an 02 gas cylinder that supplies zero leakage gas, and 17 is a needle pulp.

Next, an example of the method of the present invention for manufacturing an all-solid-state electrochromic device will be described.

Example 1 On a Corning 7059 glass substrate with a thickness of 0.8 mm, an I.
On the TO film, the metal coating (Co) is added to the vapor deposition material.
, by a reactive high-frequency ion blating method using metallic iridium (Ir) and metallic nickel (N1),
A first electrochromic layer, which is a coloring layer on the anode side, was formed.

The conditions were as follows: HsO vapor 5. OX up to 10-' Torr, and the deposition rate was set at 1. Q A / sso total 3. OJ/sea
And so. The film thickness was 1500A.

On top of this film, an insulating layer T
A layer of ames of 300 OA was applied. The degree of vacuum at this time is 2
．． OX 10-' Torr, deposition rate 8A/
ss.

Met. Furthermore, on top of these films, a WOs layer, which is a second electrochromic layer, which is a cathode coloring layer, is deposited at 4000 A by a vacuum evaporation method. A translucent AU film of 30 OA was attached as the pole.

When the all-solid-state electrochromic device manufactured in this way was driven by applying 2.2 V between the 1.2 mm poles, the coloring density reached 3
00 m5eo.

Example 2 On a Corning 7059 glass substrate with a thickness of 0.8 mm, an appropriate square electrode portion and lead portion were provided.
■On the TO film, using metallic Subaru (Co) and metallic nickel (N1) alloy pellets (1:1λ) and iridium (Ir) pellets for gold as evaporation materials, color is developed on the anode side by reactive high frequency ion blating method. The first layer is
An electrochromic layer was formed.

The conditions are 5.0 steam. OX was introduced up to 10''-'Torr, and the deposition rate was A in each case.

On top of this film, an insulating layer T
A layer of aaOa was applied for 3000 i. The degree of vacuum at this time is 2. OX 10-'Torr, deposition rate 8A/
see te was there. Furthermore, on top of these films, a second electrochromic layer (VK) which is a cathode coloring layer is formed.
The s layer was attached at 4000 A by a vacuum evaporation method, and the second
A translucent Atr film of 60 OA was attached as an electrode.

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 ΔOD of 0.4! 1
It was 50 maeo.

Example 6 Appropriate extraction electrode portions and lead portions were provided on an Earning 7059 glass substrate with a thickness of 0.8 mm.
On the ITO film, a coloring layer is formed on the anode side by using a reactive high-frequency ion blating method using Hellet (1:1), an alloy of metal cobal (Co) and metal iridium (Ir), and powdered nickel as vapor deposition materials. A first electrochromic layer was formed.

As a condition, the needle valve 17' is opened and the water reservoir 19
5. H dew O vapor from The deposition rate was 120 OA, and the film thickness was 120 OA.

On top of this film, an insulating layer T
A layer of 300 OA of a-Os was applied. The degree of vacuum at this time is 2
．． OX 10''-'Torr, deposition rate 8A/
Furthermore, on top of these films, there was a second electrochromic layer, W, which was a cathode coloring layer.
The AS layer was attached at 4000 A by a vacuum evaporation method, and the second
A translucent Atr film serving as an electrode was attached at 600A.

When the all-solid-state electrochromic device manufactured in this way was driven by applying a voltage of 2.2μ between the first and second electrodes, the coloring density reached ΔOD of 0.4.
It was 0m5θC.

Example 4 On a Corning 7059 glass substrate with a thickness of O-8 mm, appropriate extraction electrode parts and lead parts were provided.
A first electrochromic layer, which is a coloring layer on the anode side, is formed on the TO film by a reactive high-frequency ion blasting method using pellets containing a mixture of cobalt, iridium, and nickel oxides (1:1:1) as a vapor deposition material. was formed.

The conditions were 4. H20 steam. OX was introduced to 10-'Torr, and the deposition rate was 1.5. On top of this film, an insulating layer of TaaOa was deposited at 300 OA by vacuum deposition. The degree of vacuum at this time is 2. OX 10-'Torr, deposition rate 8
It was A/sea. Furthermore, on top of these membranes,
A W)s layer, which is a second electrochromic layer, which is a cathode coloring layer, was attached at 4000 A by vacuum evaporation, and a translucent Atr film, which was a second electrode, was attached at 60 OA.

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 300% by the time it reached ΔOD of 0.4.
It was m5eo.

[Brief explanation of the drawing]

FIGS. 1 and 2 are cross-sectional views showing two examples of all-solid-state electrochromic devices manufactured by the method of the present invention, and FIG. 6 is an ion plating device used in the method of the present invention. FIG. 1: Substrate, 2: First electrode, 6: Electrochromic layer, 4: Insulating layer, 5: Second electrode, 6: Electrochromic layer, 10: Ion plating device main body, 11: Diffusion pump, 12: Electron gun (EB gun), 13: Umbrella, 14:
DC bias source, 15: High frequency coil ('R, F coil) 16: O snow gas cylinder, 17: Needle valve, 1'
9: Water puddle. Patent applicant: Canon Co., Ltd.

Claims (1)

[Claims] When the transparent conductor as the first electrode is the first layer, the first electrochromic layer is the second layer, the insulating layer is the third ff, the second electrochromic layer is the fourth layer, and the second electrode is the fifth layer. , the first to fifth layers or 1.2, 3.5
1. An all-solid-state electrochromic device constructed by sequentially laminating layers, characterized in that the first electrochromic layer is a mixed film of six types of hydrated products of cobalt-1-iridium and nickel.