JPS59178434A - Fully solid state electrochromic element - Google Patents

Abstract

PURPOSE:To obtain a fully solid state electrochromic element which has a high response speed and coloring density by using a specific material in forming an electrochromic layer which is an anode side coloring layer. CONSTITUTION:The 1st electrode 2 consisting of an ITO film is formed on a glass substrate 1 having 0.8mm. thickness, and is installed in the prescribed position 18 in a reaction device 11. La or its oxide is used as an evaporating material, and gaseous O2 is introduced into said device from a cylinder 16. An electrochromic layer 3 which is an anode side coloring layer is formed on the electrode 2 by are active ion plating method. The layer 3 consists of La2O3. An insulating layer 4 consisting of Ta2O5 having 3,000Angstrom thickness is vacuum deposited thereon and a semitransparent conductive Au film of 300Angstrom is formed as the 2nd electrode 5 thereon. The fully solid state electrochromic element having a high response speed and coloring density is thus obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an electrochromink device that utilizes the trochromink phenomenon.

Electrochemically quenched dye elements, or electrochromic devices, utilize such electrochromic phenomena.
For example, it can be applied to numeric display elements, X-Y matrix display elements, 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 devices utilizing electrochromic phenomena are shown in FIGS. 1 and 2.

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 this is not limited to a glass plate, and may be any transparent plate such as a glass plate or an acrylic plate.
As for its position, it may be placed on the second electrode 5 instead of under the first electrode 2, or it may be placed on both sides depending on the purpose (for example, as a protective cover). good. However, depending on the case, it is necessary to use a transparent conductive film for the second electrode 5 or a transparent conductive film for both electrodes. If both electrodes are transparent electrodes, the element can be used as a transparent type. As such a transparent conductive film, IT
O film (tin oxide S nO2 in indium oxide In2o5
(containing around 5%), Nesa membrane, etc. are used.

In the above structure, the electrochromic layer 3, which is the coloring layer on the anode side, has conventionally been made of chromium trioxide (Cr 203
), iridium hydroxide (Ir(oH)2), nickel hydroxide (Ni(oH)2), etc.

The insulating layer 4 made of dielectric material is made of zircon dioxide (zrO2
), silicon oxide (SiO), silicon dioxide (S t
O2), oxides such as tantalum pentoxide (T a 20 s ), or lithium fluoride (LiF)
, magnesium fluoride (MgF2), and the like. Further, the electrochromic layer 6, which is a coloring layer on the cathode side, is made of tungsten dioxide (WO2
), tungsten trioxide (WO3), molybdenum dioxide (MOO2), molybdenum pentoxide' (MoO,s)
, vanadium pentoxide (vO), etc.

5 In the all-solid-state electrochromic element having such a structure, an electrochemical reaction occurs by applying a voltage 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 an electrochromic material, an oxidation-reduction reaction represented by the following formula (1) occurs, resulting in coloration.

WO3+ xH" + xe-: HxWO3(1)(
1) According to the formula, tungsten bronze HxWo s
However, if the applied voltage is reversed, the color will disappear. 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 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 (N
A material such as 1(OH)2) is formed by reactive sputtering or an 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 made of a completely new material different from conventional ones.
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 conventional devices that only develop and fade color on the cathode side.

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 sequentially laminated, or as shown in Fig. 2, a coloring layer on the cathode side is further provided between the insulating layer and the second electrode. 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 made of an oxidized material, which is a completely new material other than the above-mentioned materials in the conventional electrochromic device. It is composed of lanterns. This lanthanum oxide film is
It can be formed by reactive ion grating, and by using lanthanum (La) or its oxide as the evaporator and introducing 02f gas as the atmosphere, an electrochromic layer consisting of the desired lanthanum oxide (LIL203) can be formed. can be obtained.

FIG. 3 shows an example of a reactive ion grating 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 ion grating device, 12 is an electron gun (EB gun), and 13 is an umbrella (
(substrate holder), 14 is a DC that applies DC noise.
Bias source, 15 is a high frequency coil (RF coil), 16
02 gas pump for supplying 0□ gas, 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 is formed by adding an appropriate extraction electrode part and lead part on a substrate 1, and this is installed in the apparatus shown in Fig. 3 as shown at 18, and lanthanum (La) is used as an evaporation material.
Or, using the oxide, 02f Sunbe 16 to 0
2 gases are introduced, and an electrochromic layer 3, which is a coloring layer on the anode side, is formed on the former side of the first electrode 2 by a reactive ion grating method. Next, an insulating layer 4 is formed on this film by a vacuum evaporation method, and then the insulating layer 4
In the case of the electrochromic element shown in FIG. 1, a film of the second electrode 5 is formed on the insulating layer 4), or an electrochromic layer 6, which is a cathode side coloring layer, is formed by vacuum evaporation on the insulating layer 4Q). After forming the second electrode 5, 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, the response speed is faster compared to the conventional electrochromic element of the type that only develops and fades color on the cathode side.Examples of the present invention will be described below.

Example 1 Glass with a thickness of 0.8wn (Corning 7059
), a first electrode 2 made of an ITO film having an appropriate extraction electrode part and a lead part is formed, and the above-described process is performed using lanthanum (La) as a vapor deposition material by a reactive ion blating 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 and 3. OX was introduced to 10 Torr, and the deposition rate was set to 1. The film thickness is QX/See]
, 200X. This electrochromic layer 3 was made of lanthanum oxide (La2O3). On this film, 3,000 layers of Ta205 were formed as an insulator layer 4 by a vacuum evaporation method. The degree of vacuum at this time is 2. OX 10-” Torr, deposition rate 8X
/Sec. Furthermore, a semi-transparent conductive Au film 300 was attached as the second electrode 5 on top of these films.

The all-solid-state electrochromic device manufactured in this way is connected to a voltage of 2.2V between the first and second electrodes with a mark of 7JO'J.
When driven, it was 850 m5ec until the coloring density reached 0.3 in AOlo.

Example 2 Thickness OB-plus (Corning 7059)
A second electrode 2 made of a tTo film with a suitable extraction electrode part and lead part is formed on the substrate 1-L of the substrate 1-L, and the anode side is A first electrotalcomic layer 3, which is a coloring layer, was formed. The conditions are 0 gas and 3. OX was introduced up to 10-4 Torr, and the deposition rate was set to -f, (1,Q X/see.The film thickness was 1200 mm.

This electrochromic layer 3 has an oxidation rank '/(La
203). On this film 0), three layers of Ta205 are deposited as an insulator layer 4 by a vacuum evaporation method.
000″
10-5 Torr, and the deposition rate was 3X/3, respectively.
Sea.

and 10λ/SeC. Additionally, these membranes were attached.

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 0.03 at Δ0.0.
It was 50m5ec.

Example 3 0.8-thick glass (Corning 7059)
Appropriate extraction electrode parts and lead parts are placed on the substrate 1 (
A first electrode 2 made of a phosphorescent ITO film was formed, and an electrochromic layer 3, which was a coloring layer on the anode side, was formed by a reactive ion grating method using lanthanum oxide (L a20s ) as a vapor deposition material. The conditions are 02
f gas was introduced to 30X 10-' Torr, and the deposition rate was increased to 2. It was set as OX/sea. The film thickness was 1200X. This electrochromic layer 3 was made of ihilanthan acid. On this film Q), a layer of Ta205 of 3000X was deposited as an insulator layer 4 by a vacuum evaporation method. The degree of vacuum at this time is 2.0 x 10-”'ror
r, the deposition rate was 3i/sec.Furthermore, this film was applied at 300X.

When the all-solid-state electrochromic device manufactured in this way was driven with a rigid force of 2.2 V between the first and second electrodes, the coloring density reached 0.3 at Δ0.0. It was QQ m5ec.

[Brief explanation of drawings]

1 and 2 are cross sections showing two examples of an all-solid-state electrochromic device according to the present invention, and FIG. 3 is an ion grating device used to manufacture the device of the present invention. FIG. DESCRIPTION OF SYMBOLS 1...Substrate, 2...1st electrode, 3...electrochromic layer, 4...insulating layer, 5...2nd electrode, 6...
- Electrochromic layer, 11... Ionoblating device main body, 12...
Electron gun (EB gun), 13... Umbrella (substrate holder), 14... DC bias source, 15... High frequency coil (
RF coil), 16...o2tr'y,, gumpe, 1
7... Needle valve, 18... Substrate (deposited object)
.

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 are sequentially laminated, and the cutting is done by stacking the above insulating layer. Further, between the second electrode and the second electrode, there is a second coloring layer between the cathode and the second electrode.
An all-solid-state electrochromic device comprising laminated electrochromic layers, characterized in that the electrochromic layer, which is a coloring layer on the anode side, is made of lanthanum oxide.