JPS61294703A - Light transmitting conductive film and manufacture thereof - 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 light-transmitting conductive film formed on a light-transmitting substrate and a method for manufacturing the same.

<Conventional technology> Conventionally, methods for producing light-transparent conductive films formed on light-transparent substrates such as glass, plastic plates, and plastic films include: ■ physical vapor deposition on light-transparent substrates; A method of forming a thin film made of noble metals such as gold, platinum, palladium, etc. on a transparent substrate by physical vapor deposition method, chemical vapor deposition method,
Indium oxide (In2・O3) by spray method etc.
, stannic oxide (SnO2) indium tin oxide (
A method of forming a thin film made of an oxide semiconductor such as indium tin oxide (indium tin oxide) or cadmium tin oxide (cadmium tin oxide) has been adopted.

<Problems to be Solved by the Invention> The light-transmitting conductive film obtained by the above method (■) easily has a sheet resistance of 100 Ω/hole (Ω/hole is sheet resistance per unit square centimeter) or less. It is a light-transmissive conductive film that has excellent properties, has an excellent 1jffl property, and has an electromagnetic shielding effect.
There is a problem that the light transmittance is slightly inferior, and the light transmitting conductive film obtained by the method (2) above has a light transmittance of 85 to 90.
% and has excellent transmittance to visible light, but there is a problem that the sheet resistance is generally 100Ω/or more and the conductivity is slightly inferior.

Generally good light transmittance 3! It is said that a J electrical film must have a transmittance of 80% or more for JJ visible light and a conductivity of 100 Ω/hole or less in terms of sheet resistance per unit area. The transparent conductive film was also not fully satisfactory in terms of both transmittance and conductivity.

In addition, as described above, the light-transmitting II lightning film made of an oxide semiconductor thin film obtained by the method (2) above is
Generally, indium oxide and stannic oxide are used, but in order to reduce the sheet resistance, for example, indium oxide film is made of stannic oxide, and stannic oxide film is made of antimony oxide, cadmium oxide, etc. Methods of doping different types of oxide semiconductors, such as the above, are often used.

In contrast to such a method of doping a different type of oxide semiconductor, there is a method of doping fluorine into an oxide semiconductor film such as indium oxide or stannic oxide, and this method also has the same effect as the above method. It is also known to have the effect of reducing sheet resistance.

The above-mentioned method for doping fluorine into an oxide semiconductor thin film such as an indium oxide film generally includes a physical vapor deposition method, a chemical vapor deposition method, etc. To explain in more detail, In the ion blating method, which is a type of physical vapor deposition method, a fluorine-doped oxide semiconductor film is formed by vapor deposition in a mixed gas atmosphere of a fluorine-containing hydrocarbon gas such as carbon tetrafluoride (CF4). For example, a method of vapor deposition in a vapor deposition atmosphere in which CF4 gas is mixed in oxygen gas is employed.

In other physical vapor deposition methods and chemical vapor deposition methods, fluorine-containing hydrocarbon gas is used as the source of dopant fluff, and is mixed into the atmospheric gas during film formation or mixed into the source gas. It is almost the same in that the above-mentioned fluorine-doped oxide semiconductor film can be obtained by mixing with the fluorine-doped oxide semiconductor film.

In the above method of mixing fluorine-containing hydrocarbons into the atmospheric gas during film formation, the mixing ratio of the fluorine-containing gas in the mixed gas is adjusted to control the concentration and distribution of fluorine, which is a dopant, in the film. Alternatively, it is necessary to form a film while controlling the partial pressure one by one.

There is a disadvantage that the formation of a light-transmitting conductive film cannot be carried out very easily.

Furthermore, in the case of sputtering and ion blating methods, it is often necessary to mix argon gas into the deposition atmosphere gas in order to avoid stably generating plasma, making it even more difficult to control the atmosphere gas. There are problems, and the device becomes quite complex.

In addition, since it is necessary to use a fluorine-containing hydrocarbon gas, the light transmittance is 3! There is also the disadvantage that the manufacturing cost of the J-electromembrane increases.

This invention was made in view of the above problems,
To provide a light-transmitting conductive film having good transparency to visible light and excellent conductivity, and to provide a method for manufacturing a light-transmitting conductive film that is easy to manufacture and can reduce manufacturing cost. The purpose is to

Means for Solving the Problems> In order to achieve the above object, the light-transmitting conductive film of the present invention is made of indium oxide doped with aluminum fluoride, and the light-transmitting conductive film is manufactured by The method involves applying fluoride acetate onto a light-transmissive substrate.

An indium oxide layer doped with aluminum is formed by physical vapor deposition.

As the transparent substrate supporting the above-mentioned light-transmitting conductive film, glass, a plastic plate, or a plastic film τ can be used.

<Function> In the above method for producing a light-transmitting conductive film, a film of indium oxide doped with aluminum fluoride as a fluorine dopant is formed on a transparent substrate such as glass, a plastic plate, or a plastic film. Accordingly, a light-transmitting conductive film having excellent light transmittance and electrical conductivity can be obtained.

The above effect is achieved based on the effect obtained by doping indium oxide with amminium fluoride as a dopant, which the inventor discovered as a result of intensive research. By doping aluminum fluoride as a dopant to indium oxide, which has an excellent conductivity, it is possible to reduce the sheet resistance with almost no loss in light transmittance. This makes it possible to obtain a light-transmitting conductive film having specific characteristics.

Here, the doping ratio of aluminum fluoride to the indium oxide is not particularly limited, but is generally 1 to 30
It is thought that the weight percent is a preferable range; outside this range, the effect of reducing the surface resistance is not so great, and there is a possibility that the light transmittance may be reduced.

Furthermore, since aluminum fluoride is used as a dopant, there is no need to use fluorine hydrocarbon gas as a deposition atmosphere gas.

<Example> Hereinafter, it will be explained in detail using examples.

On a transparent substrate such as a transparent glass, plastic plate, or plastic film, indium oxide doped with 1 to 30% by weight of aluminum fluoride is deposited to an appropriate thickness by physical vapor deposition or chemical vapor deposition. By creating a transparent conductor with excellent light transmittance on a transparent substrate,
111 was able to be formed.

That is, when only indium oxide is deposited, the film thickness is 5.
In the case of 00A, the sheet resistance was 600 Ω/ro, whereas the film thickness was 5 Ω made of indium oxide doped with 1 to 30% by weight of aluminum fluoride.

When deposited to obtain A, the sheet resistance is 200 to 30
It can be reduced to 0 Ω/mouth, and the conductivity can be significantly improved.

In the above case, by using a plastic film with excellent flexibility as the transparent substrate, it is possible to obtain a flexible light-transmitting conductive film that is used in flexible liquid crystal panels and the like and requires flexibility. By using glass, plastic plates, etc. with poor flexibility,
We were able to obtain a light-transmitting conductive film that does not require flexibility and is used in solar cells and the like.

Further, in the above embodiments, the thickness of the deposited film is not particularly limited, but can be appropriately selected depending on the required characteristics of light transmittance and sheet resistance.

Furthermore, since no mixed gas containing fluorine-containing gas is used, the amount of fluorine in the film is reduced.

To easily form a light-transmitting TL conductive film without requiring complicated control to control distribution, and to lower manufacturing costs compared to the case of using fluorine-containing hydrocarbon gas. Can be done.

Experimental example 1 Thickness 0.5. sputtering method (target n203/At F
3 = 90/10 revision ratio, sintered at 900°C after molding) to deposit aluminum fluoride-doped indium oxide to a film thickness of 600°C, with a visible light transmittance of 85% and a nine-plane resistance of 220Ω/hole. A light-transmitting conductive film could be obtained.

Using only indium oxide not doped with aluminum fluoride as a sputtering target, the transmittance for visible light of a light-transmissive conductive film obtained by vapor-depositing to a film thickness of 600 mm in the same manner as above is 86
As is clear from the comparison with the %1 sheet resistance of 540Ω/hole, it was possible to obtain a light-transmitting conductive film which was considerably improved and had good light transmittance and conductivity.

Experimental Example 2 An acrylic plate with a thickness of 0.25 m (visible light transmittance of 92
%) on top of the ion brating method (vacuum degree 3x
1G'Torr, r f: 13.56 MII2
.
A light-transmissive conductive film with a resistance of 10Ω/mouth could be obtained.

The transmittance for visible light of a light-transmitting conductive film obtained by depositing only indium oxide not doped with aluminum fluoride to a film thickness of 500A by the ion blating method as described above is 81%
As is clear from the comparison with the 9-plane resistance of 620Ω/hole, it has been considerably improved, with good light transmittance and
A light-transmitting conductive film having both conductivity and conductivity could be obtained.

Experimental Example 3 Ion blating method (02 partial pressure 2X10'T
orr, rf: 13.56 MH2,20
Indium oxide doped with aluminum fluoride was evaporated to a film thickness of 600 mm using 0W). However, as the deposition raw material, indium oxide/aluminum fluoride-9
A light-transmitting conductive film having a visible light transmittance of 85% and a sheet resistance of 2710/hole was obtained.

The visible light transmittance of the light-transmissive conductive film obtained by evaporating indium oxide alone into a bullet-shaped evaporation material and depositing it to a film thickness of 600A using the ion blating method as described above is as follows. 86% single plane resistance is 4
As is clear from the comparison with 80Ω/mouth, it was possible to obtain a light-transmitting conductive film which was considerably improved and had good light transmittance and conductivity.

Experimental Example 4 RF magnetron sputtering method (argon/oxygen = 50150, 1x10' Tor
r, rf: 13.56 MH2,500W
) was used to deposit indium oxide doped with aluminum fluoride to a film thickness of 50 OA.However, as a sputtering target, a mixture of 85/15 (weight ratio) of indium oxide powder/aluminum fluoride powder was used as a sputtering target.
Molded into a cylindrical shape of 00Φ (900℃ after hot pressing).

A light-transmitting conductive NW with a visible light transmission rate of 83% and a nine-face resistance of 320Ω/hole.
I was able to get an A.

Using only indium oxide not doped with aluminum fluoride as a sputtering target, the light-transmissive conductive film obtained by vapor deposition to a film thickness of 500 A in the same manner as above has a transmittance of visible light of 85.
As is clear from comparison with the %1 sheet resistance of 550 Ω/hole, it was possible to obtain a light-transmissive conductive film that was considerably improved and had good light transmittance and conductivity.

Experimental Example 5 A cluster ion beam method (02 partial pressure 5X 10
Indium oxide doped with aluminum fluoride was evaporated to a film thickness of 650 mm using a method of 'T orr ). However, as the evaporation raw material, indium oxide/aluminum fluoride = 9515 (Iffi ratio) pellet was used), and the Transmittance is 85%.

A light-transmitting conductive film with a sheet resistance of 400Ω/hole was obtained.

65 in the same manner as above using only indium oxide not doped with aluminum fluoride as the evaporation raw material.
The light-transmissive conductive film obtained by vapor deposition to a film thickness of 0A has a visible light transmittance of 87% and a nine-plane resistance of 750.
As is clear from the comparison with Ω/mouth, it was possible to obtain a light-transmissive conductive film which was considerably improved and had good light transmittance and conductivity.

<Effects of the Invention> As described above, this invention simply forms a film of indium oxide doped with aluminum fluoride, which has excellent properties in terms of both light transmittance and conductivity. A light-transmitting conductive film can be obtained, and the vapor deposition atmosphere gas can be easily controlled, and the light-transmitting conductive film can be manufactured easily.

Claims (1)

[Claims] 1. The film formed on the light-transmissive substrate is Indium oxide doped with aluminum oxide Light transmission characterized by consisting of dium conductive film. 2. Aluminum fluoride on a light-transmissive substrate The indium oxide layer doped with Features: Formed by physical vapor deposition method A method for producing a light-transmitting conductive film.