JPS61248742A - Manufacture of conductive transparent member - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for manufacturing a conductive transparent member in which a transparent conductive thin film, an insulating protective film and an antireflection film are laminated in this order on a transparent substrate.

The conductive transparent member obtained by the present invention is suitable for transparent electrodes for liquid crystal displays, heating elements for antifogging glass, selective transmission films that block infrared rays, and the like.

[Conventional technology]

ITO film [Indium oxide (IntOz) and tin dioxide (
A transparent conductive thin film made of a solid solution of Snow) is formed on a substrate such as glass by a vacuum deposition method such as vacuum evaporation, sputtering, or ion blasting, or a spray method, and is used for various purposes. It is provided.

By the way, in the past, transparent conductive thin films were often used in relatively static environments, such as in displays and optical systems, and therefore there was little demand for the durability of transparent conductive thin films. . However, in recent years, the excellent properties of transparent and conductive thin films have attracted attention, and they have begun to be used dynamically in vehicles, aircraft, architecture, etc., and are exposed to harsh physical and chemical environments. . For this reason, it has become necessary to increase the durability of transparent conductive thin films, and various protection methods have been taken.

Conventional methods for protecting such a transparent conductive thin film include sandwiching the transparent conductive thin film within a laminated glass together with a polyvinyl butyral interlayer, covering it with a plastic cover, coating it with a resin such as acrylic or urethane, or Methods such as vapor deposition of silicon dioxide (Sing) have been adopted.

However, the laminated glass in which a transparent conductive thin film is formed has performance problems such as thermal efficiency, and the glass covered with a plastic cover does not look good and has problems in terms of design. In this respect, it is desirable to form a protective film directly on the transparent conductive thin film. However, conventional transparent conductive thin films coated with resin or silicon dioxide have problems in that they do not have sufficient abrasion resistance, scratch resistance, or adhesion.

Therefore, the present applicant proposed a transparent conductive thin film with a protective film, in which an aluminum oxide film or a zirconium oxide film with good adhesion is formed as an insulating protective film on a transparent conductive thin film. Although this improved durability, the reflectance of visible light increased slightly, so we proposed a low-reflection transparent conductive thin film with a protective film on which an antireflection film was formed.

[Problem that the invention seeks to solve]

By the way, by forming an insulating protective film and an antireflection film on a transparent conductive thin film, a conductive transparent member with excellent durability and low reflectance of visible light can be obtained.
If these are simply laminated by a vacuum film forming method such as a sputtering method, their adhesion may not necessarily be sufficient. In particular, this tendency becomes more pronounced when attempting to apply the method to relatively large objects such as automobile windshields.

For this reason, it has been desired to develop a method for increasing the adhesion between the transparent conductive thin film, the insulating protective film, and the antireflection film, and further improving the durability.

[Means for solving problems]

The above technical problem is solved by the method for manufacturing a conductive transparent member of the present invention, which will be described below.

That is, the method for manufacturing a conductive transparent member of the present invention is a method for manufacturing a conductive transparent member in which a transparent conductive thin film, an insulating protective film, and an antireflection film are laminated in this order on a transparent substrate, the method comprising: The method is characterized in that a transparent conductive thin film, an insulating protective film, and an antireflection film are formed thereon by a vacuum film-forming method, and then a vacuum heat treatment is performed. ----------・First Invention Furthermore, the method for manufacturing a conductive transparent member of the present invention comprises laminating a transparent conductive thin film, an insulating protective film, and an antireflection film in this order on a transparent substrate. A method for manufacturing a conductive transparent member, which involves forming a transparent conductive thin film, an insulating protective film, and an anti-reflection film on a transparent substrate by a vacuum film-forming method while heating the substrate; It is characterized by heat treatment. -------1--Second Invention In the present invention, it is desirable to use aluminum oxide (AAzO*) or zirconium oxide (ZrOz) as the insulating protective film.

In addition, as an anti-reflection film, silicon dioxide (SiO2),
Magnesium fluoride (MgFt), aluminum oxide (A
j! zOs) etc. can be used.

The thickness of this antireflection film is set to 1/4 or 3/4 of the wavelength λ of visible light whose reflection is to be prevented.

In addition, the film thickness and sheet resistance of the transparent conductive thin film can be adjusted as appropriate depending on the site and purpose of use, and the film thickness is usually 20.
00 to 15,000 people, sheet resistance 1.2 to 50Ω/
Use the mouth part.

The vacuum heat treatment is usually performed by heating at a temperature of 300° C. to 450° C. for 1 to several hours in a vacuum of 10 −′ Pa or less. The optimum conditions for this vacuum heat treatment vary depending on the material, thickness, etc. of the film, and can be determined as appropriate depending on the film quality, etc.

Further, when substrate heating and vacuum heat treatment are used together (second invention), the processing time of vacuum heat treatment can be significantly shortened compared to the case of only vacuum heat treatment.

[Effect]

According to the method for manufacturing a conductive transparent member of the present invention, by performing vacuum heat treatment or substrate heating and vacuum heat treatment, diffusion occurs at each interface of the transparent conductive thin film, the insulating protective film, and the antireflection film, and the material Depending on the situation, a reaction may occur. As a result, a diffusion layer and, in some cases, a reaction layer are formed at the interfaces of each film, which firmly connects each film and improves adhesion.

〔Example〕

Next, the present invention will be explained in detail.

(First example) As a first example, an example of the first invention will be shown.

Here, FIG. 1 is a schematic configuration diagram of a conductive transparent member obtained by the method for manufacturing a conductive transparent member according to the first embodiment of the present invention, and FIG. 2 is a schematic diagram of the conductive transparent member according to the first embodiment of the present invention. FIG. 2 is a schematic configuration diagram showing a state of a conductive transparent member before vacuum heat treatment.

Approximately 1 inch of ITO film 2 as a transparent conductive thin film is applied to a transparent glass 1 in the shape of an automobile window glass measuring 800 mm long, 1300 wM wide, and 5 fl thick by RF sputtering.
0000 people formed. The sheet resistance at this time is 3.8Ω
/It was a mouth. Next, a zirconium oxide film 3 was formed as an insulating protective film to a thickness of 3000 nm by RF sputtering.

Further, on this zirconium oxide film 3, a silicon dioxide film 4 with a thickness of about 90% is applied as an antireflection film by RF sputtering.
0 people formed. The film thickness d of this silicon dioxide film 4 is set to 55Qnm, which is the center wavelength of visible light that is not desired to be reflected.
nd=λ/4, n-1,45 (refractive index of silicon dioxide)
, was slightly thinner than the value of 950 people, which was obtained by substituting λ=550 nm. The reason for reducing the thickness of the silicon dioxide film 4 is to take into consideration that zirconium oxide particles will enter the silicon dioxide film 4 due to the vacuum heat treatment performed after film formation, and the refractive index of the silicon dioxide film 4 will increase slightly. It is.

As a result, the conductive transparent member shown in Fig. 2 was obtained *T
Then, vacuum heat treatment was performed in the same sputtering apparatus. At this time, the degree of vacuum was set to about 5 x 10-''pa, the substrate temperature was heated to 400°C, and the treatment was carried out for 2 hours. As a result, a conductive transparent member as shown in Fig. 1 was obtained. A diffusion layer 5 is formed at the interface between 2 and the zirconium oxide film 3.
is formed, and zircon (ZrOz.5) as a reaction layer is formed at the interface between the zirconium oxide film 3 and the silicon dioxide film 4.
iOX) layer 6 is formed between the zircon layer 6 and the zirconium oxide film 3 and between the zircon layer 6 and the silicon dioxide film 4.
Diffusion layers 7 and 8 were formed between them.

Next, in order to examine durability, the conductive transparent member obtained in this example was subjected to a Taber type abrasion tester to examine the degree of haze (haze value). Here, the Taber type abrasion tester rotates a rubber wheel containing abrasive powder on the sample surface and wears it down, thereby measuring the weight of the sample after the test. This is a machine that examines the degree of decrease or cloudiness. The test was performed using a worn wheel (C5-10F
) was rotated 1000 times under a load of 500 g, and the increase in cloudiness was measured using a haze meter.

As a result, in the conductive transparent member of this example, the haze value increased by 4.5% before the vacuum heat treatment, but decreased to 1.8% after the vacuum heat treatment.

In this way, by performing vacuum heat treatment, ITO film,
A diffusion layer and a reaction layer are formed between the zirconium oxide film and the silicon dioxide film, which increases the adhesion strength of each film.
As in this example, even a large-area object such as an automobile window glass was able to have sufficient durability.

(Second example) The second invention will be shown as a second embodiment.

The second example differs from the first example in that an ion blating method was used instead of the RF sputtering method as the vacuum film forming method, and the substrate was heated at 400°C during film formation. As a result, the vacuum heat treatment could be shortened to 30 minutes. The rest is substantially the same as the first embodiment.

The conductive transparent member obtained as a result had durability similar to that of the first example. Further, in this example, since substrate heating and vacuum heat treatment were used in combination, the vacuum heat treatment time could be significantly shortened compared to the first example, and the working time could be shortened.

Although specific embodiments of the present invention have been described above, the present invention is not limited to these embodiments, and includes various embodiments within the scope of the claims. .

〔Effect of the invention〕

As described above, the method for manufacturing a conductive transparent member of the present invention provides the following effects.

(a) Vacuum heat treatment forms a diffusion layer or a reaction layer between each film, increasing the adhesion between each film, thereby greatly improving durability. Therefore, it can be used for large automobile windshields, etc., and can also be used in harsh environments, greatly expanding the range of applications.

(b) Manufacturing time can be shortened by using substrate heating and vacuum heat treatment together.

[Brief explanation of the drawing]

FIG. 1 is a schematic configuration diagram of a conductive transparent member obtained by the method for manufacturing a conductive transparent member according to the first example of the present invention, and FIG. 2 is a schematic diagram of the conductive transparent member according to the first example of the present invention. FIG. 2 is a schematic configuration diagram showing a state before vacuum heat treatment. 1-・-・-・Transparent glass (transparent substrate) 2・-・-・I
TO film (transparent conductive thin film) 3 --- Zirconium oxide film (insulating image m film) 4 --- Silicon dioxide film (anti-reflection film) 5.7.8 --- Diffusion layer

Claims (2)

[Claims] (1) A method for producing a conductive transparent member in which a transparent conductive thin film, an insulating protective film, and an antireflection film are laminated in this order on a transparent substrate, the method comprising: forming a transparent conductive member on the transparent substrate by a vacuum film forming method; A method for producing a conductive transparent member, which comprises performing vacuum heat treatment after forming a thin film, an insulating protective film, and an antireflection film. (2) A method for producing a conductive transparent member in which a transparent conductive thin film, an insulating protective film, and an anti-reflection film are laminated in this order on a transparent substrate, the method comprising: heating the substrate while vacuum forming the transparent conductive film on the transparent substrate; A method for producing a conductive transparent member, which comprises forming a transparent conductive thin film, an insulating protective film, and an antireflection film by a film method, and subsequently performing vacuum heat treatment after the film formation.