JPS6042739A - Preparation of electrochromic element - Google Patents

Abstract

PURPOSE:To improve appearance of a pattern by laminating an electrochromic (EC) layer on the first electrode, and bringing an Ar atm. excited by glow discharge into contact with the parts of said EC layer not to be used as said EC layer to erase the EC function. CONSTITUTION:An EC layer 3 is laminated on the first electrode 2 formed on a base plate 1, and then, an atm. of Ar excited by glow discharge, such as ion plating, is brought into contact with the parts of the EC layer 3 not to be used as said EC layer to erase the EC function and form a pattern. An insulating layer 4 is formed on the layer 3, and further, the second electrode layer 5 is formed on this layer 4. Ar ions are produced in the Ar atm. excited by such a glow discharge and attack the parts of the layer 3 to form an intended pattern. Since the EC layer itself is divided into the parts having the EC function and the parts having no EC function by this treatment, the layer 3 has no or very little level difference, and hence, an EC element good in appearance can be obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for manufacturing an element that applies the electrochemical coloring/decoloring phenomenon, that is, the Elek I Lochromic phenomenon, and includes an electrochromic process in such an electrochromic element. It concerns layer patterning.

Two conventional examples of all-solid-state electrochromic devices that utilize the electrochromic phenomenon are shown in Figures 1 and 2.
As shown in the figure.

The electrochromic element shown in FIG. 1 has a first electrode 2 made of a transparent conductor film on a transparent substrate 1, an electrochromic layer 3 which is a coloring layer on the cathode side, an insulating layer 4. The second electrode 5 made of a conductor is successively laminated. Furthermore, the electrochromic element shown in FIG.
A second electrochromic layer 6, which is a coloring layer on the anode side, is further laminated between the insulating layer 4 and the second electrode 5 in the structure shown in FIG.

In the above structure, the substrate l is generally formed of a glass plate, but this is not limited to a glass plate, and it can also be made of plastic.
Any plate that is colorless and transparent, such as a black plate or an acrylic plate, may be used.Also, regarding the first shift, it may be provided above the second electrode 5 instead of under the first electrode 822, or it may be provided on the second electrode 5 depending on the purpose. one on each side (for example, as a protective cover).
It's okay to die. Regarding the electrodes 2 and 5, it is sufficient if either one of the electrodes is transparent, and if both sides are transparent, a transmissive type element can be obtained.

Representative examples of film materials commonly used in all-solid-state electrochromic devices described in J.2 are listed below. 1st T1
．． As the transparent conductive film constituting the pole 2, a TTO film (indium oxide In2O3 doped with %5N02 oxide), a NESA film, or the like is used.

The electrochromic layer 3, which is a coloring layer on the cathode side, is made of tungsten trioxide (WO2), tungsten trioxide (W
Ch), molybdenum dioxide (MOO2), molybdenum trioxide (nio03), vanadium pentoxide (v, is
) etc.

The insulating layer 4 is made of zirconium dioxide (Zr02), I
Silicon e-oxide (Sin), silicon dioxide (Sigh)
, oxides such as tantalum pentoxide (Ta207.), or fluorides such as lithium fluoride (LiF) and magnesium fluoride (MgF2) are used; Instead, a solid electrolyte or the like may be used.

For the $2 electrode 5, for example, a semi-transparent conductive material made of Au is used. In addition, in the one shown in FIG. 2, the second electrochromic layer 6, which is the coloring layer on the anode side, is composed of chromium pentoxide (Cr203), iridium hydroxide (Ir(OHh)
), nickel hydroxide (Ni(OHb)), etc.

In the all-solid-state electro-C7 lithium-ion element having such a structure, when a voltage is applied between the first electrode 2 and the second electrode 5, an electrochemical reaction occurs to cause coloring and decoloring. This coloring mechanism is, for example, the first electrochromic layer 3
It is generally said that bronze formation is due to the double injection of cations and electrons into the metal. For example, when l1103 is used as the electrochromic substance, an oxidation-reduction reaction represented by the following formula (+) occurs, resulting in coloration.

WO3+ xH" + xe-'; HxWO3(+)
(+) According to the formula, tungsten bronze HxwO3
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 by an insulating layer inside the device, resulting in coloration.

Conventionally, in order to pattern the electrochromic layer in the electrochromic element as described in 1-,
Patterning has been carried out by mask vapor deposition and resist etching. However, with such conventional patterning, a step is created between the base and the area where the electrochromic layer is formed, and in the case of an all-solid-state electrochromic device, the step may be visible or the liquid electrolyte If the electrochromic layer is of the electrochromic type (electrochromic) or rochromic element r type, a process such as adding a new insulating layer S to the part where there is no electrochromic layer is required.

An object of the present invention is to provide a method for manufacturing an electrochromic device that eliminates the drawbacks of conventional patterning as described above.

The method for manufacturing an electrochromic device according to the present invention includes:
In manufacturing an electrochromic element including a first electrode made of a conductive film, an electrochromic layer, an insulating layer, and a second electrode made of a conductive film, an electrochromic layer is laminated on the first electrode. Later, when patterning this layer, the part not used as the electrochromic layer is exposed to an Ar atmosphere excited by glow discharge to cause this part to lose its electrochromic function, and then patterned. It is something.

According to the method of the present invention, the electrochromic layer itself is divided into areas where an electrochromic phenomenon occurs and areas where it does not occur, resulting in a layer with no or only a few steps, which makes it difficult to see. points etc. will be improved.

Although there are various electrochromic materials that can be used in the present invention, tungsten oxide is preferably used, and the glow discharge is also preferably treated in an ion blating device.

When glow discharge is performed in an Ar atmosphere in this way, Ar ions excited by the claw discharge attack the electrochromic layer, causing a change in the structure of the material 1 that makes up the electrochromic layer, and the electrochromic The desired patterning is achieved by eliminating the chromic function.

An example of an ion blating apparatus used to manufacture an electrochromic device according to the present invention is shown in FIG. In the figure, 11 is the main body of the ion brating device,
12 is an electron gun (EB can), 13 is an umbrella ()^ plate holder), 14 is a DC bias source that applies an OC bias,
15 is an elevated coil (RF coil), 16 is an Arf and S combination source, 17 is a needle valve, and 18 is a plate (plate).
NM body) is shown.

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. An electrochromic layer of WO3 is formed by a vacuum deposition method using an electron gun 12. After forming the electrochromic layer, the substrate is masked and glow discharge is caused in an Ar atmosphere introduced from the Ar supply source 16.

This glow discharge achieves the desired patterning effect.

Next, an insulating layer 4 is formed on this film by a vacuum evaporation method, and then a film of a second electrode 5 is formed on the insulating layer 4 (in the case of the electrochromic device shown in FIG. 1), or On the second side of the insulating layer 4, an anode-side coloring layer 6 is formed using a vacuum evaporation method, and then a second electrode 5 is formed.
(In the case of the electrochromic device shown in FIG. 2) 6 Next, an example of a method for manufacturing an electrochromic device according to the present invention will be described.

Example 1 Glass with a thickness of 0.8 mm (Corning 7059)
A first electrode 2 of an ITO film with appropriate extraction electrode parts and lead parts Mfi is formed on a substrate l made of a plate of 1.
Using tungsten oxide (WO:+) as a material, a 103 film was formed as the electrochromic layer 3 on the first electrode 2'' by a vacuum deposition method using an electron gun 12. The basic conditions at this time were that the degree of vacuum was 2. Q
lN5 Torr.

1-Note 1! After forming the electrochromic layer 3 (
WO, layer), glow tribe? I put K on it. The conditions at this time were: degree of vacuum after introducing Ar, 5 X IN' Torr,
The glow discharge spacing was 3 m1n. (RF power 2
000w) Next, a layer of tantalum oxide (Ta206) was applied as the insulating layer 4, and furthermore, Au1li was applied as the second electrode 5 on these films. Film thickness is 30
It was 0X. When driven at 1.5 V, a good-looking electrochromic element with no visible patterning traces was produced.Example 2 Glass with a thickness of 0.8 mm (Corning 70!!9)
), a first electrode 2 of a TTO film with suitable extraction electrode parts and lead parts is formed, and tungsten oxide (WCL+) is used as the evaporation material, and an electron gun 1 is formed on the substrate l.
A WO3 film was formed as an electrochromic layer 3 on the first electrode 2 by a vacuum evaporation method using 2. The evaporation conditions at this time were a degree of vacuum of 2. Q X lN5T
orr, ta.

After the film is formed, the substrate is masked and the Ar supply source 16
A glow discharge was applied to the electrochromic layer 3 (WO2 layer) by the high frequency ion blating method in an Ar atmosphere introduced by the electrochromic layer 3 (WO2 layer). The conditions at this time were that the degree of vacuum after introducing Ar was 5 x 10-' Torr, and the glow discharge time was 3 min. (RF power 200w)
Next, a layer of tantalum diluted (Ta2's) was added as the insulating layer 4, and the thickness of the 611 layer was 3oooA.
There was a time.

After this treatment, a Ni(OH)2 layer of 80 OA was applied as the second electrochromic layer 6 and an Au film of 300 Å was applied as the second electrode 5 to 11!2 +2. 2. When driven with OV, the electrochromic element shows no traces of patterning and has a good appearance.

[Brief explanation of the drawing]

1 and 2 are cross-sectional views showing two examples of electrochromic devices manufactured by the method according to the present invention, and FIG. 3 is an ion blating device used to manufacture the device according to the present invention. FIG. 1... Substrate 2... 281 electrode 3... Electrochromic layer 4... Insulating layer 5... Second electrode 6... Electrochromic layer 11... Ion blating device main body 12 ...Electron gun ("EB gun") 13...Umbrella (substrate holder) 14...[]C/Haias source 15...High frequency coil (RF coil) 16...A
r supply SA source 1 7...Needle/Hell
B18...no1 (plate (deposited object)

Claims (1)

[Claims] In manufacturing an electrochromic device including a first electrode made of a conductor 11, an electrochromic layer, an insulating layer, and a second electrode made of a conductor film, the first
After laminating the electrochromic layer on the electrode, when patterning this layer, by applying an atmosphere excited by glow discharge to the part not used as the electrochromic layer, the electrochromic function is applied to this part. A method for manufacturing an electrochromic element characterized by patterning.