JPS59123821A - All solid-state electrochromic element - Google Patents

Abstract

PURPOSE:To improve response speed, coloring density, color developing efficiency, life, etc. by forming an electrochromic layer made of iron hydroxide as a anode side color developing layer. CONSTITUTION:An all solid-state electrochromic (EC) layer is prepared by successively laminating the first electrode 2 of an electrically conductive film 2, an EC layer 3 of an anode side color developing layer, an insulating layer 4 of a dielectric film, and the second electrode film 5, or further, the second EC layer of a cathode side color developing layer 6 between the layer 4 and the film 5. The layer 3 is made of iron hydroxide. The film of iron hydroxide can be formed by reactive ion plating, iron or iron oxide is used as an evaporation source, and water vapor or gaseous O2 in addition to it are introduced as an atm. to obtain the desired EC layer.

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 many substances change color due to redox reactions when voltage is applied. Electrochemically quenched dye elements (i.e., electron) I=1 chromic elements that utilize such electrochromic phenomena can be applied to, for example, numeric display elements, X-Y matrix displays, optical shutters, aperture mechanisms, etc. According to their materials, they can be classified into liquid type and solid type, but 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 FIG. 1 and FIG.

The electrochromic element shown in FIG. 1 has a first electrode 2 (such as a transparent conductive film) on a transparent substrate 1', an electrochromic layer 3 (an anode side coloring layer), 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 1 is generally formed of a glass plate, but this is not limited to glass plates.
A transparent board such as a plastic board or an acrylic board is sufficient;
Regarding its position, it may be placed above the M2 electrode 5 instead of under the first electrode 2, or it may be provided on both sides depending on the purpose (for example, for the purpose of providing a protective shield). .

However, depending on these cases, it is necessary to make the second electrode &5 a transparent conductive film, or to make the electrodes on both sides transparent conductive films. If both electrodes are transparent electrodes, the element can be used as a transparent type. As such a transparent conductive film, i'ro
g (tin oxide 5n02 in indium oxide I n 20s
Contains around 5%] and Nesa dehydration are used. .

In the above structure, the chromium layer 3, which is the coloring layer on the one-pole side, has conventionally been made of chromium trioxide (Cr2O5),
It is formed from iridium hydroxide (IrC0H)2), nickel hydroxide (N5(oH)2), etc.

The insulating layer 4 made of dielectric material is made of zolcon dioxide (ZrO2
), silicon oxide (SiO), silicon dioxide (5in2)
, is-formed methanalum (Ta203), etc., or fluorides, such as lithium fluoride (LiF), magnesium fluoride (MgF2), etc., are used. The electrochromic layer 6, which is a coloring layer on the cathode side, includes tungsten dioxide (WO2), tungsten trioxide (WO3), diacid, and molybdenum (MoO2).
2), formed using molybdenum trioxide (Mo5s), vanadium pentoxide (V2O3), etc.

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

wo, + XH+ xe-;: mywo3(1)(
According to the 1-ton formula, Hxwos is formed and colored by the tungsten probe 2, but if the applied voltage is reversed at this point, the color becomes decolored. In an all-solid-state electrochromic device, such a reaction of formula (1) causes coloration due to the supply of protons H+ by an insulating layer inside the device.

In the above-mentioned electrochromic element, the electrochromic layer 3 which is the anode side coloring layer has conventionally been made of chromium trioxide (Cr2O3), iridium hydroxide (Ir(OH)2), nickel hydroxide (N1(OH)2), as described above.
) 2) etc., these materials are formed by a reactive snow ivy or anodic oxidation film method.

In the present invention, in such an Elm J trochromic element, the electrochromic layer, which is the coloring layer on the anode side, is composed of a completely new material different from conventional ones,
It is an object of the present invention to provide an all-unibody electrochromic device that can provide a color development f: response speed and color density that are superior to those of conventional devices.

The all-solid-state electrochromic device according to the present invention is characterized by consisting of a first electrode formed from 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. 2, a cathode-side coloring layer is added between the insulating layer and the second electrode. In an all-solid-state electrochromic device formed by laminating a second electrochromic layer, the electrochromic layer, which is a coloring layer on the anode side, is composed of iron hydroxide. This iron hydroxide film can be formed by reactive ion blating, using iron (Fe) or its oxide as the evaporating material, and introducing θ'H20 vapor or H20 vapor and 02 gas into the atmosphere. By doing so, a desired electrochromic layer film can be obtained.

An example of a reactive ion routing apparatus used to manufacture an all-solid-state electrochromic device according to the present invention is shown in FIGS. In the figure, 10 is the main body of the reactive ion blating device, 11 is the diffusion pump, and 12 is the electron gun (
EB gun), 13 is an umbrella (substrate holder), 14 is a DC 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, 17 is 02. Gas that supplies f-s? Nbe, 1
8 x and x 9 indicate needle pulp, and 20 indicates a substrate (object to be deposited).

The process of manufacturing an electrochromic device using the apparatus shown in Figure 3 will be explained in the following steps.

First, a first electrode 2 having an appropriate 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 iron (Fe 2 ) or Using the oxide, H20 vapor source 16
20 steam into the device, or H20 steam supply source 1
Introducing H20 steam from 6 and 02 gas cylinder 1
An electrochromic layer 3, which is a coloring layer on the anode side, is formed on the first electrode 2 by introducing 02 gas from 7 to 02 and using a reactive ion blating 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 to form the electrochromic device shown in FIG. 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 electrode 5 is formed (
In the case of the electrochromic device shown in FIG. 2).

According to the present invention, response speed, color development efficiency, and life span can be improved compared to conventional electrochromic elements.

Examples of the present invention will be described below.

Example 1 Glass (Corning 7
On the substrate 1 of 059), a first electrode 2 made of an ITO film with appropriate extraction electrode parts and lead parts was formed, and using Fa as the evaporation material, a reactive ion blating method was used to deposit the first electrode 2. An electrochromic layer 3, which is a coloring layer on the anode side, was formed on the first electrode 2 described above.

The conditions are as follows: 5. OX10 Tor
The vapor deposition rate was set to 1.2X/sec. The film thickness was 1000X. On top of this film, a layer of Ta205 of 3000X was deposited as an insulating layer 4 by a vacuum evaporation method. The degree of vacuum at this time is 2. OX 10 Torr,
The deposition rate was 8X/l+ec. Furthermore, on top of these films, a transparent conductive Au film with a thickness of 300 mm is applied as the second electrode 5.
I added an X.

When the all-solid-state electrochromic device manufactured in this manner was driven by applying a voltage of 2.2 V between the first and second electrodes, the coloring density was Δ0. It took 700 m5ec to reach 0.3 at D. 'Example 2 Glass with a thickness of 0.8 tna (Corning 705
9) A first electrode 2 consisting of an ITO film with suitable extraction electrode parts and lead parts is formed on the substrate 1 of 9). A side coloring layer (Ellen) 1=Diclock layer 3 was formed.

The conditions are as follows: 5. OX 10-'T
orr, and the deposition rate was set to 1.4 X/see. The film thickness was 1000X. On top of this film, a layer of Ta205 with a thickness of 300% is deposited as an insulating layer 4 by a vacuum evaporation method.
I added 0X. The degree of vacuum at this time is 2. OX 10-5T
orrs evaporation rate was 8 i/see. Further, on these films, WO was deposited as an electrochromic layer 6, which is a coloring layer on the cathode side, by a vacuum evaporation method.
000X, and furthermore, as the second electrode 5, transparent conductive A is attached.
A u film was attached at 300X.

When the all-solid-state electrochromic device manufactured in this way was driven by applying a voltage of 2.2 V between the first and second electrodes, the coloring density was Δ0. It took 500 m5ec to reach 0.4 at D.

Example 3 Glass with thickness o, s mx (Corning 7059
), a first electrode 2 made of an ITO film having appropriate extraction electrode parts and lead parts is formed on the substrate 1 of ), using the vapor deposition material KFeO and using the reactive ion grating method), as described above. An electrochromic layer 3, which is a coloring layer on the anode side, was formed on the first electrode 2.

The conditions are: 3. OX I O-'
Introduce up to Torr, 0□ gas 5. OX 10 To
rr, and the deposition rate was set to 1.5X/(6).

The film thickness was 1000X. On this film, a layer of Ta205 of 30,001 cm as an insulating layer 4 is deposited by vacuum evaporation.
I attached it. The degree of vacuum at this time is 2. OX 10-5 Tor
r, the deposition rate was 8X/w. Furthermore, on top of these films, a semi-transparent conductive Au film was placed as the second electrode 5 at 300X.
I attached it.

When the all-solid-state electrochromic device manufactured in this way was driven by applying a voltage of 2.2 V between the first and second electrodes, the coloring density was Δ0. It took 6'50 m5ec to reach 0.3 at D.

Example 4 Glass with a thickness of 0.8 mtt (Cornlng 7059
), a first electrode 2 made of an ITO film having an appropriate extraction electrode part and a lead part is formed, and an anode is formed by a reactive ion blating method using Fe 304 as the evaporation material. An electrochromic layer 3, which is a side coloring layer, was formed.

The conditions are H20 steam at 3.5 XI OTorr.
.

0□ Gas 5. The evaporation rate was 1.3 X/see. Film thickness is 1
It was 000X. On top of this film, a layer of TSL 20s was deposited as an insulating layer 4 by a vacuum evaporation method. The degree of vacuum at this time is 2. OX 10”-5Torr
, the deposition rate was 7X/sec.

Further, on these films, WO3 was deposited as an electrochromic layer 6, which is a coloring layer on the cathode side, by a vacuum evaporation method at a vacuum degree of 2. OX at 10-5 Torr, and furthermore, a semi-transparent conductive Au film was applied as the second electrode 5 at 300 Torr.
I added an X.

When the all-solid-state electrochromic device manufactured in this way was driven by applying a voltage of 2.2 V between the first and 211L electrodes, it took 700 m until the coloring density reached 0.5 in ΔQ and D. It was red.

[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 is a reactive ion silating apparatus used to manufacture the devices of the present invention. 1: Substrate, 2: First 'fIL pole, 3: Electrochromic layer, 4: Insulating layer, 5: Second electrode, 6: Electrochromic layer, 10 : Main body of reactive ion grating device, 11:
Diffusion pump, 12: Electron gun (EB gun), 13:
Umbrella (substrate holder), 14: DC bias source, 15: High frequency coil (RF coil), 16: H,0 vapor supply source, 17: 02 gas cylinder, 18.19: Needle pulp, 20: Substrate (deposited object) . Figure 1 Figure 2 Figure 3

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 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 further laminated between the electrode and the second electrode, the electrochromic layer formed on the coloring layer on the anode side is made of iron hydroxide. An all-solid-state shop electrochromi, Rielement.