JPH10237630A - Oxide coating, laminated body and heir production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain oxide coating low in internal stress by executing sputtering using a target consisting essentially of metals in an atmosphere contg. a gas contg. carbon atoms. SOLUTION: As a carbon-contg. gas, CO2 , a gaseous mixture of CO2 and Ar or the like is preferable, and CO2 is particularly suitable since it is free from explosibility, combustibility and toxicity, is easily treatable and is low-cost. As the target to be used, the one essentially consisting of one or more kinds of metals selected from the groups of Zn, Sn and In is particularly suitable. Thus, the obtd. oxide coating is consisting essentially of the oxides the above metals, and furthermore, by the cracking of the carbon-contg. gas or the like, carbon is taken in the coating in the process of growing. The content of carbon is preferably regulated to 0.03 to 15% by atom to the total content of the above metals contained in the oxide coating from the viewpoint of reducing the internal stress.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an oxide film suitable for a heat-shielding film for buildings or automobiles and a transparent conductive film for a transparent electrode, and a laminate using the oxide film. And their manufacturing methods.

[0002]

2. Description of the Related Art An oxide film mainly containing an oxide of a metal such as In, Zn, and Sn is widely used in various fields such as a transparent conductive film material. As a method for forming the oxide film on a glass or transparent plastic substrate, a vacuum evaporation method, an ion plating method, and a sputtering method are used. Among them, the sputtering method is a method that can uniformly coat a large area with high productivity.
It is suitable for forming a film on a large area such as a liquid crystal display element for a flat panel display and a touch panel.

[0003] As one example, the sputtering method is used for IT.
When forming an O (composite oxide of indium and tin) film,
1) a method of sputtering using a mixed sintered body of indium (In) oxide and tin (Sn) oxide as a target, and 2) a target made of an alloy of In and Sn using a mixed gas of Ar and O _2. A method in which a film is formed while sputtering in an oxidizing atmosphere to oxidize metal atoms beaten from a target, that is, a reactive sputtering method.

It is widely known that the conductivity of ITO is greatly influenced by oxygen deficiency in addition to whether or not Sn oxide doped as a main component functions effectively as a dopant. It is important to control the degree of oxidation of the film.

In the method 1) using a mixed sintered body of In oxide and Sn oxide as a target, when pure Ar is used as a sputtering gas, usually only a film exhibiting brown absorption due to oxygen deficiency is obtained. . Therefore, in order to compensate for oxygen deficiency, sputtering is usually performed by slightly adding O ₂ as an oxidizing gas to the sputtering gas.
However, when O ₂ is low, a brownish absorbing film is obtained,
If the O2 _content is too large, the specific resistance film will rise rapidly. That is, in order to obtain a film having uniform characteristics with good reproducibility, O
_{(2) It} is essential to control the amount of addition.

[0006] For this reason, due to the change over time of the evacuation rate of the vacuum pump or the change over time in the minute amount of O ₂ concentration caused by the change over time in the gas supply system, the film is excessively oxidized to form a high resistivity film, or insufficiently oxidized. Thus, it was difficult to obtain a film having the same characteristics with good reproducibility.

In addition, when a film is formed on a large area substrate, if the O ₂ concentration is distributed in the chamber, the characteristics are uneven in the plane, and it is difficult to obtain a uniform film. For this reason,
Applications of transparent conductive films have been limited to small area substrates.

In the conventional method, when the O ₂ content is increased to obtain a high specific resistance film, the specific resistance rapidly increases. Therefore, it is almost impossible to control the specific resistance of the film by adjusting the O ₂ content. It was impossible.

In the reactive sputtering method 2), the alloy target is considerably cheaper than the sintered target and has a great advantage in cost. On the other hand, the degree of oxidation of the film that greatly contributes to conductivity is controlled by the flow ratio of the O ₂ gas in the mixed gas sputtering of Ar and O ₂ . In this control, the change from an underoxidized state (a state where an optical absorption film is formed) to a peroxidation state (a state where a high specific resistance film is formed) is sharp, and an intermediate region (a transparent and low specific resistance film is formed). The obtained area) had a very narrow condition width. In addition, because it is affected by the partial pressure of water, which is a residual gas component,
It has been difficult to obtain optimal conditions with good reproducibility or stably. In addition, due to distribution and fluctuation of conditions in the apparatus, an in-plane distribution of optical properties such as a resistance value, a film thickness, a transmittance, and a haze tends to occur, and the tendency is particularly strong when a film is formed on a large-area substrate. There was a problem.

As described above, in the prior art, the controllability of the degree of oxidation relating to conductivity is not always sufficient, and it is not always easy to stably obtain conditions for developing good conductivity. In particular, when applied to a large-area substrate, it has been desired to improve the uniformity of in-plane electrical characteristics and optical characteristics.

Furthermore, when a conductive thin film having a high specific resistance is to be obtained while controlling the resistance value, the specific resistance changes excessively in an oxidized state.
Moreover, it has been difficult to obtain an in-plane distribution uniformly.

On the other hand, an oxide film containing ZnO or SnO ₂ as a main component is preferably used as, for example, a heat ray blocking film. As a film configuration of the heat ray blocking film used for building or automobile, 1) a film in which three layers of an oxide film, an Ag film, and an oxide film are sequentially stacked on a transparent substrate, or 2) an oxide film , An Ag film, an oxide film, and a film in which five layers of an Ag film and an oxide film are stacked. These heat ray blocking films are called Low-E (Low-Emissivity) films, and the glass on which they are formed is called Low-E glass.

The main Low-E glass has a film configuration of ZnO, Ag, and ZnO in order from the glass, and is usually used as a double glazing or a laminated glass. However, this film configuration has a problem in moisture resistance,
During storage of a single plate from a film formation to a multi-layer vitrification or laminated vitrification process, white spots are generated due to moisture in the environment, and there is a problem in storage and handling.

As described in JP-A-4-357,025,
It has been found that reducing the internal stress of the uppermost oxide is effective for improving the moisture resistance of the Low-E glass. As an oxide film having a low internal stress, for example, 1) a tin oxide film,
2) ZnO films to which other elements (for example, Al, Si, B, Sn, Mg, Cr, etc.) having an ionic radius smaller than that of Zn ^{2+ in an} oxidized state are added.

[0015] In particular, when it is intended to form a laminate using the above-mentioned SnO ₂ film, ZnO film, or the like by a large film forming apparatus used for manufacturing architectural glass or automotive glass, the film remains in the sputtering apparatus. Due to the large amount of water, even if the above-described oxide film is selected, the internal stress of the oxide film does not sufficiently decrease. As a result, the obtained laminate often has insufficient moisture resistance, and improvement has been desired.

[0016]

SUMMARY OF THE INVENTION The present invention provides (1) an oxide film having a lower internal stress than the prior art, and a method for manufacturing the same.
By using this oxide film, a laminate having further improved moisture resistance and further facilitated storage and handling as a single plate and a method for producing the same, and (3) stable electrical and optical properties can be obtained. It is another object of the present invention to provide a method for manufacturing an oxide film which can be obtained with good in-plane distribution.

[0017]

According to the present invention, there is provided a method comprising the steps of:
In a method for manufacturing an oxide film on a substrate, there is provided a method for manufacturing an oxide film, wherein sputtering is performed in an atmosphere containing a gas containing carbon atoms.

The sputtering method in the present invention is not particularly limited, and examples thereof include an RF (high frequency) magnetron sputtering method and a DC (direct current) magnetron sputtering method. The DC magnetron sputtering method is suitable for forming a laminated body uniformly at low cost with good productivity on a substrate for a large area, such as glass used for construction, automobiles, and vehicles.

As a target mainly composed of a metal,
It is preferable to use a target mainly composed of one or more metals selected from the group consisting of Zn, Sn, In, Al and Ti.

As will be described later, the effect of the carbon content is as follows with respect to an oxide film mainly containing an oxide of at least one metal selected from the group consisting of Zn, Sn and In.
Especially, Zn, Sn and In
It is preferable to use a target mainly composed of at least one metal selected from the group consisting of:

According to the present invention, there is provided an oxide film containing, as a main component, an oxide of at least one metal selected from the group consisting of Zn, Sn, In, Al and Ti, wherein the oxide film contains carbon. (Hereinafter referred to as a low stress oxide film).

From the viewpoint of reducing the internal stress, the content ratio of carbon is determined based on the atomic ratio with respect to the total amount of at least one metal selected from the group consisting of Zn, Sn, In, Al and Ti contained in the oxide film. Is preferably 0.03 to 15 atomic%. In particular, the content is preferably 0.03 to 5 atomic%.

In the present invention, since the effect is remarkable, the oxide film is an oxide film containing, as a main component, an oxide of at least one metal selected from the group consisting of Zn, Sn and In. Is preferred. The oxide film is made of Al, Ga, S
It is also preferable to contain one or more metals (subcomponent metals) selected from the group consisting of i and Ti. From the viewpoint of reducing the internal stress, the content ratio of the sub-component metal is such that the total amount of the sub-component metal is such that Zn, Sn, and In contained in the oxide film.
Is preferably 0.1 to 10 atomic% with respect to the total amount of one or more metals selected from the group consisting of The present invention
It is preferable to apply to a transparent conductive film as described above.

Generally, an oxide film has a compressive stress. Low
In the -E film, if the internal stress of the oxide film, particularly the uppermost oxide film, is large, cracks occur in the oxide film, and the moisture that has penetrated therethrough erodes the metal (especially Ag) layer. It is known. The use of the low stress oxide film of the present invention makes it difficult for moisture from the outside to permeate and diffuse through the upper oxide film, so that the metal layer is less likely to be affected by moisture in the external atmosphere. The moisture resistance of the E film is improved.

According to the present invention, there is provided a laminate comprising (2n + 1) layers (n is an integer of 1 or more) alternately laminated with an oxide film, a metal film, and an oxide film on a substrate. One of
A laminate and a method for manufacturing the same, wherein at least the layers are the low-stress oxide films described above.

As the number of layers of the laminate, an oxide film, a metal film, an oxide film, a metal film, and an oxide film are sequentially laminated to form a (2n + 1) layer (n is an integer of 1 or more). ), And any number of layers can be used. Actually, when seven or more layers are laminated, visible light transmittance is insufficiently low enough to be used as a window for buildings, automobiles, and railway vehicles. Material film, metal film,
A three-layer system composed of an oxide film or a two-layer system composed of 2) an oxide film, a metal film, an oxide film, a metal film, and an oxide film is preferable.

The low-stress oxide film of the present invention can be used as a part or all of the oxide film of the laminate as appropriate in accordance with productivity, material cost, durability, restrictions on the configuration of manufacturing equipment, and the like. By using a low-stress oxide film for at least one of the oxide films in the laminate, when such a laminate is used as a heat ray blocking film, the moisture resistance is improved, and storage and handling in a single plate can be improved. Can be easier. In particular, it is preferable to use it as the (2n + 1) th layer oxide film.

As a specific example of the low stress oxide film, oxides of Zn and Sn are the main components and contain carbon, and Sn is contained in an amount of 0.1 to 90 atomic% with respect to the total amount of Zn and Sn. An oxide film may be used. The oxide film is particularly (2n +
1) It is preferable to use it as the oxide film of the layer.

As a specific example of another preferred low-stress oxide film of the (2n + 1) th layer, an oxide film of Si and Sn and containing carbon (Si-Sn-based low-stress oxide film) Is mentioned. In this case, it is preferable to contain 0.1 to 90 atomic% of Si with respect to the total amount of Sn and Si.

For the purpose of improving physical durability and chemical durability, an oxide of Sn as a main component and Si as Sn and S
It is preferable to form an overcoat film containing 5 to 95 atomic% based on the total amount of i. The overcoat film is particularly effective when the (2n + 1) th layer oxide film is different from the Si—Sn-based low stress oxide film. The overcoat film contains carbon in an amount of 0.0
The content may be 3 to 15 atomic%.

As the metal film in the laminate, a metal film containing Ag as a main component is preferably used from the viewpoint of heat ray reflection performance and the like. Further, in order to improve the durability, in addition to Ag, 1 is selected from the group consisting of Pd, Au, and Cu.
It is more preferable to include at least one kind of metal. Especially P
d is preferred. The content ratio of Ag to Ag is 0.
1-10 atomic% is preferred.

In the laminate of the present invention, if necessary, 1) another layer such as an oxidation barrier layer (a layer for preventing oxidation of the metal layer) or an adhesion improving layer may be provided between the metal film and the oxide film. A layer may be interposed, or 2) another layer such as an alkali barrier layer (a layer for preventing diffusion of an alkali component in the substrate) or an adhesion improving layer may be interposed between the substrate and the oxide film.

The substrate used in the present invention is not particularly limited, and includes a glass plate, a plastic sheet, a plastic film and the like.

By forming the low stress oxide film of the present invention on a substrate, a transparent electrode can be obtained. The transparent electrode is suitable for a transparent electrode for a touch panel and a transparent electrode for a liquid crystal display element. When used as a transparent electrode for a touch panel, the sheet resistance is preferably from 200 Ω / □ to 2 kΩ / □.

According to the method of the present invention, it is possible to prevent the absorption of the previously formed metal film (particularly, the Ag film) due to oxidation and to stably produce an oxide film having no absorption.
Therefore, it is suitable for application to an electromagnetic shield plate or the like that requires a very low resistance of, for example, 4 Ω / □ or less, with a small decrease in transmittance. In addition, since the oxidation of the metal film is suppressed, when the metal film is used for an electrothermal glass using the heat generation film, the reliability thereof is improved.

The flow rate of the sputtering gas used in the present invention varies depending on the sputtering conditions. For example, when the target size is 4 inches, the sputtering gas flow rate is 10 to 100 sccm (c in standard condition conversion).
c / min).

The sputtering conditions depend on apparatus conditions such as the volume of the sputtering film forming chamber, the area of the target, the pumping speed of the vacuum pump, the flow rate of the introduced gas, and the arrangement of the target and the substrate.

A specific example will be described. Prior to the film formation, the inside of the chamber is evacuated to a degree of vacuum of 2 × 10 ⁻⁵ Torr. When a 6-inch target is used, a flow rate of CO ₂ introduced into the chamber as a sputtering gas is 35 sccm, a DC pressure of 500 W is applied to the metal Zn target at a sputtering pressure of 2 × 10 ⁻³ Torr, and a deposition rate of 35 nm / min is obtained. A transparent carbon-containing ZnO film (hereinafter, referred to as C: ZnO film) is obtained. When the same film forming apparatus uses the same flow rate of O ₂ gas instead of CO ₂ gas as the sputtering gas, a transparent ZnO film can be obtained at a film formation rate of 34 nm / min.

The internal stress of the obtained film is 1.6 × 10 ¹⁰ dyn / cm ² (compression) for the C: ZnO film and 2.0 × 10 ¹⁰ dyn / cm ₂ for the ZnO film using O ₂ gas. ^The value was sufficiently low for ² (compression).

Another example will be described. Ar introduced into the chamber as a sputtering gas using a 4-inch target
A flow rate ratio of CO ₂ is eight ninety-two (total flow rate 30scc
m), a sputtering pressure of 3 × 10 ⁻³ Torr and In−
Sn alloy target (10% by weight of S
n), a DC power of 100 W
A transparent conductive film made of ITO having a specific resistance of 2.7 × 10 ⁻⁴ Ωcm is obtained at a deposition rate of 35 nm / min on a glass substrate heated to 0 ° C.

In the same film forming apparatus, the sputtering gas
When a gas mixture of r and O ₂ is used, a transparent ITO having a specific resistance of 3.5 × 10 ⁻⁴ Ωcm and a film formation rate of 33 nm / min when the flow ratio of Ar and O ₂ is 54:46 is used. A film is obtained.

[0042] Figure 9, CO ₂ flow rate ratio (the ratio of CO ₂ flow rate to the total flow rate of Ar and CO _2, is also the same or less)
FIG. 10 shows the relationship between the O ₂ flow rate ratio and the specific resistance (the specific resistance when the transparent film is formed). As is clear from the comparison between FIG. 9 and FIG. 10, when a mixed gas of Ar and CO ₂ is used,
As compared with the case where a mixed gas of Ar and O ₂ is used, a film having the same low specific resistance can be obtained in a wider range.

The content ratio of carbon in the case of the ITO film is In
It is preferable to form a film so that the total amount of Sn and Sn is 0.03 to 5 atomic%. If it is less than 0.03 atomic%, the effect of containing carbon is small, and if it exceeds 5 atomic%, the brownish optical absorption due to the released carbon atoms cannot be ignored, which hinders the application as a transparent conductive film. It is particularly preferred that the content be 0.1 to 3 atomic%.

The Sn content ratio is expressed as I oxide in terms of Sn oxide.
4 to 16% by weight based on the total amount of n oxide and Sn oxide
It is preferred that If it is less than 4% by weight, it is difficult to obtain a low-resistance film. If it exceeds 16% by weight, an etching residue of Sn oxide is likely to be generated when etching is performed in a subsequent step. Particularly preferred is 7 to 13% by weight.

In the present invention, a gas containing a carbon atom (hereinafter, simply referred to as a C-containing gas) is used for a part or all of the gas as a sputtering gas. Examples of the C-containing gas include CO ₂ , CO, CH ₄ , C ₂ H ₆ , C ₂ H ₄ ,
C ₂ H ₂ , CH ₃ OH, C ₂ H ₅ OH, C ₃ H ₇ OH and the like can be mentioned. _{(1) CO 2, (2} ) a mixed gas of CO ₂ and Ar, (3) a gas mixture of CO ₂ and Ar and O _2, are preferred. CO ₂ is particularly suitable for industrial use because CO ₂ is easy to handle and inexpensive because it has no explosiveness, flammability or toxicity.

In the above-mentioned C-containing gas, CO ₂
When using a gas with weak or no oxidizing property other than
₂ , an oxidizing gas such as N ₂ O, that is, a reactive gas is appropriately used in combination.

In the case of sputtering with a mixed gas of CO ₂ and Ar, the ratio of CO _{2 to} the total gas flow is preferably 50% or more. At a CO ₂ ratio of less than 50%, the metal atoms sputtered out of the target tend to be incorporated into the film in a metal state that is not sufficiently oxidized, resulting in a colored film.

O ₂ , N ₂ O and the like can be used as a reactive gas in combination with CO ₂ . Also in that case, the ratio of the total reactive gas to the total gas flow is preferably 50% or more for the same reason as described above.

[0049]

In the sputtering method, ions in a glow discharge generated by applying a high electric field to a target are used in a film forming process. In such a glow discharge atmosphere, various active species are generated by ionization of a gas.

The decomposition of the C-containing gas or the reaction between the C-containing gas and the oxidizing gas produces various reducing gas components such as CO gas, and carbon atoms or compounds containing carbon atoms grow. It is taken up by the film inside. Thus, the oxide film does not become in an oxygen-excess state during the growth, so that the crystal growth direction of the film is uniform and dense, and the internal stress is reduced.

In a mixed gas of Ar and CO ₂ or CO ₂
By performing the sputtering in the inside, a region (a so-called transition region) where the transparent film can be obtained at the maximum film forming rate can be stably obtained. The presence of CO, which is a reducing gas, was confirmed in the sputtering film formation atmosphere, and it is considered that a reduction reaction by the CO gas occurred simultaneously with the oxidation reaction. This is considered to be due to the fact that the progress of the overall reaction is slowed by these balances.

That is, the crystal growth of the film proceeds in a weakly oxidizing atmosphere that is not in a peroxidized state. In addition, the incorporation of H, which inhibits crystal growth, into the film is suppressed. for that reason,
Defects due to excess oxygen in the film are reduced, and the internal stress of the film is reduced. The effect is particularly remarkable in the case of a SnO ₂ film, a ZnO film, or the like.

On the other hand, the degree of oxidation of the oxide film, which is a factor determining the conductivity, is controlled by the flow ratio and the pressure of the oxidizing gas. For example, in the case of mixed gas sputtering of Ar / CO ₂ , it can be controlled by changing the CO ₂ flow ratio. In the case of CO ₂ 100% sputtering it can be controlled by adjusting the sputtering pressure increases and decreases in conductance valve or the like CO ₂ flow rate or amount of exhaust.

[0054] More specifically, 1) the case of mixing of O ₂ increases the O ₂ flow ratio, 2) CO ₂ increases the flow rate, or 3) reducing the increase or pumping speed of the CO ₂ flow rate Accordingly, the oxidizing property of the atmosphere is increased, and as a result, the degree of oxidation of the oxide film can be increased. When the substrate is heated during the film formation, the oxidation reaction can proceed more effectively and more stably.

When the C-containing gas and the generated CO in the sputtering gas are activated by glow discharge, they themselves are oxidized to CO ₂ . In addition, carbon atoms or bonds containing carbon atoms generated on the film surface are oxidized to form gas (oxidized gas) and are separated from the film.
That is, it is considered that the CO or the oxidized gas acts as a reducing agent, for example, to cause a reaction in the reduction direction from an In oxide to a lower-grade In oxide or metal In.

As a result of the reaction in the reduction direction coexisting with the reaction in the oxidation direction, the change in the film characteristics with respect to the film forming conditions is moderated, and the controllability is improved. Therefore, it is considered that 1) the optimum conditions are easily obtained, and 2) the reproducibility, stability, and in-plane uniformity of the characteristics are greatly improved even with respect to fluctuations in the conditions and in-plane fluctuations. The degree of oxidation (that is, specific resistance) of the obtained oxide film is finally determined by the balance between oxidation and reduction described above. According to the present invention, the degree of oxidation can be easily adjusted.

According to the present invention, 1) a film having a low specific resistance equivalent to that of the conventional Ar / O ₂ mixed gas sputtering method can be obtained, and 2) a film having a higher specific resistance can be formed with good controllability. . Therefore, introducing CO as a reducing gas is theoretically effective. However, CO is a toxic gas, and has a difficulty in industrial use.

On the other hand, in the conventional Ar / O ₂ mixed gas sputtering method, nodules are generated on targets such as Zn, Sn, and In, and as a result, fluctuations in resistance, lack of in-plane uniformity, and occurrence of arcing occur. Had been a problem.

In arcing, an electric charge is charged to an oxide film formed on a target surface or a film material powder generated in a film forming chamber, and the electric charge is released at a time when the accumulated electric charge exceeds a certain threshold value. This is a phenomenon that occurs, and the overcurrent generated at this time activates the protection circuit of the sputtering power supply and shuts off the discharge, or the target material melts locally and scatters and spitting, pinholes, films that adhere to the substrate This was the cause of defects such as uneven thickness.

Since CO ₂ has a lower oxidizing power than O _{2, the} oxide film formed on the target surface and the powder formed in the film forming chamber become oxygen-deficient and become conductive, so that electric charge is hardly accumulated. And arcing can be effectively prevented. That is, by using the method of the present invention, the generation of nodules is reduced, and the above problem can be solved.

For example, reducing CO, CH ₄ , C ₂ H ₆ , C ₂ H ₄ , C ₂ H _{2 and the} like are mixed in an atmosphere containing O ₂ . However, 1) lack of toxicity and explosive, 2) can be simplified conditions by reducing the type of raw material gas, 3) the raw material is inexpensive and easily available, and the like, CO ₂ or,, A
It is preferable to use a mixed gas of r and CO ₂ .

On the other hand, as a method for effectively suppressing arcing caused by accumulation of electric charge in an oxide film formed on the surface of a target or the like, there is known a sputtering method (intermittent application of sputtering power) (pulse sputtering method). Have been. By using a pulse sputtering method as a sputtering method, film formation stability and product yield can be further improved.

When an oxide film is formed by a conventional method (a reactive sputtering method in a mixed gas of Ar and O ₂ or in an O ₂ gas atmosphere), the Ag film immediately below is oxidized during the formation of the oxide film. Barrier layer (thin Zn,
A metal film such as Ti) is inserted. Since the barrier layer is very thin, it is difficult to set the conditions.Furthermore, in the case of manufacturing with a production machine, even once the conditions are set, the thickness fluctuates due to subtle fluctuations in the film forming conditions, and frequent adjustments of the conditions are required. Was. Further, a very thin metal film is likely to become an island-shaped discontinuous film, so that the oxidation of the Ag layer cannot be completely prevented.

If the conductive oxide target is formed by sputtering in an Ar gas atmosphere (or an Ar gas atmosphere to which O ₂ is slightly added), oxidation of the Ag layer can be prevented. However, compared to metal targets, oxide targets are very expensive and are industrially disadvantageous.

According to the present invention, when an oxide film is formed directly on the Ag film, the use of CO ₂ gas having a mild oxidizing power allows the formation of an oxide film.
The oxidation of the g layer is suppressed, and a higher visible light transmittance than the conventional method can be obtained. Furthermore, if the conditions of CO ₂ sputtering are selected, an oxide film can be laminated on the Ag film without using a barrier layer.

[0066]

EXAMPLES Examples and comparative examples of the present invention will be specifically described below. However, the present invention is not limited by these.

Example 1 and Comparative Example 1 Soda lime silica glass (10 cm × 10 cm × 2
mm thick) substrate with a pressure of 2 × 10 ⁻³ Torr using a 5 inch × 17 inch rectangular metal target.
And in a mixed atmosphere of CO _2, C: ZnO _x layer (100n
m), C: A ZnAl _x O _y film (100 nm) was formed by DC sputtering. C: ZnO _x film, C: Zn
The Al _x O _y film means a carbon-containing ZnO _x film and a carbon-containing ZnAl _x O _y film, respectively, and the same applies hereinafter. The C: ZnAl _x O _y film was formed using a target containing Zn at 3 atomic% (Example 1).

FIG. 1 shows the relationship between the discharge voltage and the flow rate ratio of the reactive gas (CO ₂ ) and the film forming speed (film forming speed at the time of forming the transparent film) vs. the reactive gas (CO) for the C: ZnO _x film.
₂ ) It is a graph showing a flow rate ratio, and FIG.
l _x O _y film of the discharge voltage vs the reactive gas (CO
₂ ) A graph showing a flow rate ratio and a film forming rate (film forming rate at the time of forming a transparent film) vs. a reactive gas (CO ₂ ) flow rate ratio. The gas flow rate was 100 sccm.

As a comparative sample, the prior art A
A ZnO _x film (100 nm) and a ZnAl _x O _y film (100 nm) were formed in a mixed atmosphere of r and O ₂ under the same conditions as in Example 1 (Comparative Example 1).

FIG. 3 shows the discharge voltage vs. the flow ratio of the reactive gas (O ₂ ) and the film forming speed (film forming speed in forming a transparent film) vs. the reactive gas (O ₂ ) for the ZnO _x film of Comparative Example 1. ₂ ) is a graph showing the flow rate ratio, and FIG. 4 shows the discharge voltage vs. the flow rate ratio of the reactive gas (O ₂ ) and the film forming rate (at the time of forming the transparent film) for the ZnAl _x O _y film of Comparative Example 1. 6 is a graph showing a film formation rate) vs. a flow rate ratio of a reactive gas (O ₂ ).

When FIGS. 1 and 3 and FIGS. 2 and 4 are compared with each other, it is clear that the use of CO ₂ gas for both ZnO _x and ZnAl _x O _y provides a stable condition (reaction In a region where the change in the discharge voltage with respect to the concentration of the reactive gas is small, for example, in FIG. 1, the film forming speed is high in a region where the CO ₂ concentration is 80% or more.

In the conventional method, the film formation near the transition region where the film formation speed of the transparent film is high (the region where the transparent film starts to be obtained by turning from the absorption film) is based on the change width of the discharge voltage with respect to the change of the reaction gas amount. Is large, that is, it is difficult to stably obtain a desired film forming speed. However, in the method of the present invention, since CO ₂ has a lower oxidizing power than O _{2 and} suppresses oxidation of the target, it is easy to perform stable film formation near the transition region where the film formation rate of the transparent film is high. Met.

Although ZnO does not substantially form carbides, since CO ₂ is used as a sputtering gas,
C is taken into the nO film or the ZnAl _x O _y film.
FIG. 5 shows the same procedure as in Example 1 except that only CO ₂ was used as the sputtering gas.
₂ is a graph showing the amount of C incorporated into the ZnO film (the ratio of carbon to Zn (atomic%)) when the flow rate is changed.

Next, FIG. 6 shows the internal stress (transparent region) vs. the reactive gas flow ratio (CO 2) for the (C:) ZnO film.
₂ or O ₂ ). FIG. 7 shows (C:) ZnA
The internal stress (transparent region) vs. reactive gas flow ratio (CO ₂ or O ₂ ) for the l _x O _y film is shown. C: ZnO
_{Both the x} film and the C: ZnAl _x O _y film have reduced internal stress over the entire transparent region.

[Examples 2 to 7 and Comparative Examples 2 to 5] Using the same apparatus as in Example 1, a DC sputtering method was performed on a sufficiently washed soda lime silica glass (10 cm × 10 cm × 2 mm thick) substrate. Thus, various layered products were obtained with the film configurations shown in Table 1. Table 2 shows the film forming conditions of each film. However, C: CO during ZnAl _x O _y film formation
_{2. The} flow rates were 67 sccm in Examples 2, 4 and 6, and 103 sccm in Examples 3 and 5. Also, Ar
A mixed gas of O ₂ and Ar: 20sccm, O _2: 80s
ccm.

In Table 1, “G” means soda lime silica glass (10 cm × 10 cm × 2 mm thick).
In the "gas" means the gas of the sputtering atmosphere,
"Pressure" indicates the pressure during sputtering. Also, "Z
“n-3 at% Al” means a target containing 3 atomic% of Al in Zn, and “Ag-1 at% Pd” means A
This means a target containing 1 atomic% of Pd in g.
"Sn-50at% Si" means that 50% of Si is contained in Sn.
It means a target containing atomic% (that is, Sn: Si = 1: 1). The carbon content of the C: SnSi _x O _y film (carbon content relative to the total amount of Sn and Si) was about 3.5 atomic%.

<Examples 2 to 3 and Comparative Example 2>
And 3 had a visible light transmittance (T _v ) of 84% and Comparative Example 2 had a T _v of 78%. For each sample of Examples 2-3 and Comparative Example 2, a constant temperature and humidity test (temperature 40
(In a constant temperature bath at 90 ° C. and a humidity of 90% for 3 weeks). As shown in FIG. 8, the samples of Examples 2 and 3 exhibited more white spots than the sample of Comparative Example 2 (number / cm □). And showed excellent moisture resistance.

<Examples 4 and 5 and Comparative Example 3> Example 4
Table 3 shows the results of the same constant temperature and humidity test as described above for each of the samples Nos. 5 to 5 and Comparative Example 3. The numbers in Table 3 are the number of white spots (pieces / cm □).

<Example 6 and Comparative Example 4> As a durability test of Example 6 and Comparative Example 4, a scratch test was conducted using a scratch tester “HEIDON-18” manufactured by Haydon Corporation.
This was performed using A sapphire needle with a diameter of 0.2 mmφ,
The film was scanned over the film surface while increasing the load from 0 to 200 g, and the critical load causing the film to peel was measured five times. As a result, in Example 6, 174 ± 1
1 g and 120 ± 8 g for Comparative Example 4. In Example 6, the critical load causing peeling of the film was larger than that in Comparative Example 4, and sufficient scratch resistance was exhibited.

<Example 7 and Comparative Example 5> A scratch test was performed on Example 7 and Comparative Example 5 in the same manner as in Example 6. As a result, in Comparative Example 5, the critical load was 180 ± 5 g. In Example 7, the film did not peel even at a load of 200 g.

[0081]

[Table 1]

[0082]

[Table 2]

[0083]

[Table 3]

Examples 8 to 9 and Comparative Example 6 2500
The C: ZnAl _x O _y film (14) was formed using an in-line sputtering apparatus having a target size of mm × 300 mm.
nm), an Ag film (10 nm), and a C: ZnAl _x O _y film (38 nm) were transported on a conveyor 240
1 mm on a glass substrate of 0 mm x 1600 mm x 3 mm
The layers were sequentially stacked by one-way conveyance. The first layer and the third layer
Layer C: The ZnAl _x O _y film contains 3 atomic% of Al in Zn.
It was formed by reactive sputtering in a CO ₂ atmosphere using the added target.

Further, C: ZnAl _x O of the Ag layer and the third layer
_{Between the y} film and a target in which 3 atomic% of Al is added to Zn, the target is sputtered in an Ar atmosphere to have a thickness of 2 n.
m Al-containing Zn barrier layer was inserted.

For the formation of the ZnAl _x O _y film, two targets were used for each layer. The discharge power at that time is 15
~ 20 kW / target, sputtering gas is CO ₂
Using only gas, 600 scc per target
m, and the sputtering pressure at that time is 2 × 1
0 ^-3 Torr. For the Ag layer and the Zn barrier layer, Ar gas was introduced at 600 sccm into each target, and sputtering was performed at a discharge power of 6 kW and 2 kW, respectively. The transfer speed of the substrate was 1.0 m / min (Example 8).

Using the same apparatus as in Example 8, ZnAl
_x O _y film (31 nm), Ag film (10 nm), ZnAl
_x O _y film (62 nm), Ag film (10 nm), ZnAl
5-layer film of _x O _y film (24 nm), was laminated to the same substrate as in Example 8. The manufacturing conditions for each film were the same as in Example 8. The same as in Example 8 was provided between the Ag film of the second layer and the ZnAl _x O _y film of the third layer, and between the Ag film of the fourth layer and the ZnAl _x O _y film of the fifth layer. An Al-containing Zn barrier layer was inserted (Example 9 above).

As a comparative example, ZnAl of the first layer and the third layer
For the formation of the _x O _y layer, with the Ar gas 150sccm and an O ₂ gas 450sccm mixed gas instead of CO ₂ gas, the comparative examples 8 and a three-layer film was formed under the same conditions (or example after 6).

In Examples 8 and 9, for one week after the start of sputtering, no powder was observed on the target surface, no arcing occurred, and a stable film could be continuously formed. Regarding Comparative Example 6, powder began to be generated on the target surface two days after the start of sputtering, and arcing began to occur frequently, and after three days, film formation could not be performed continuously.

Table 3 shows the results of the same temperature and humidity test as in Examples 8 to 9 and Comparative Example 6.

Using the above in-line sputtering apparatus, a 1 μm thick film was formed on a Ni film instead of a glass substrate.
For a sample in which a m: C: ZnAl _x O _y film was formed under the same conditions as in Example 8, the sample was incorporated into the film using a CS (simultaneous carbon and sulfur) analyzer (EMIA-820, manufactured by Horiba, Ltd.). When the amount of carbon was measured, it was about 3.2 atomic%.
(Content of carbon with respect to Zn).

Example 10 and Comparative Example 7 Using the same apparatus as in Example 1, on a sufficiently washed soda lime silica glass (10 cm × 10 cm × 2 mm thick) substrate,
Using a target obtained by adding 5 atomic% of Al to Zn, 1
C: Zn with a thickness of 100 nm in an atmosphere of 00% CO ₂
An Al _x O _y film was formed by DC sputtering. The amount of CO ₂ introduced was 82 sccm, 92 sccm, 10 sccm.
As three conditions of 3 sccm, the sputtering pressure at that time is 3.2 × 10 ⁻³ Torr and 3.8 × 10 ⁻³ Torr, respectively.
⁻³ Torr and 4.4 × 10 ⁻³ Torr. FIG. 15 shows a change in the discharge voltage when the CO ₂ flow rate is changed.

As a comparative sample, the conventional technique O
₂ Films were formed under the same conditions under 100% atmosphere. The film was formed at an O ₂ introduction amount of 100 sccm, and the pressure during sputtering was 3.8 × 10 ⁻³ Torr.

X-ray diffraction peak profiles of the prepared samples are shown in FIGS. When O ₂ gas was used as the sputtering gas, (100), (00)
2) While peaks corresponding to three plane orientations of (101) were detected, when CO ₂ was used, (002)
It had a single orientation in which only peaks from the plane were detected. Further, the peak intensity was strong, the half width was small, and the crystallinity was good.

Table 4 shows the refractive index and specific resistance. CO
_{(2) As the} flow rate is increased, the refractive index tends to decrease, and the specific resistance increases. Further, the C: ZnAl _x O _y film is made of O ₂
The refractive index is the same or slightly smaller than that of a ZnAl _x O _y film formed by gas sputtering, and the specific resistance tends to be small. It is considered that the difference between the refractive index and the specific resistance depending on the type of the sputtering gas is caused by the amount of C contained in the film and the above-described crystallinity.

Example 11 and Comparative Example 8 Example 10
C: ZnAl _x O _y film (38 nm), A
g film (10 nm), Zn-Al film (barrier layer), C: Z
nAl _x O _y films (38 nm) were sequentially formed by DC sputtering. C: ZnAl _x O of the first and third layers
_{The y} film is formed using a target in which 5 atomic% of Al is added to Zn, and 100% CO ₂ with a CO ₂ introduction amount of 92 sccm.
Formed in an atmosphere of The Zn-Al film is formed by adding 5 Al to Zn.
It was formed in an Ar atmosphere using a target to which atomic% was added.

As a comparative example, a 100% O ₂ gas with an O ₂ gas introduction amount of 100 sccm was used instead of CO ₂ ,
A laminate having the same configuration as in Example 11 was formed except that an nAl _x O _y film was formed.

FIG. 18 shows the peak profile of the X-ray diffraction. As can be seen from the figure, C: ZnA with good crystallinity
The crystal growth of the Ag film stacked on the l _x O _y film is promoted, and the Ag film has a stronger peak intensity than the Ag film stacked on the ZnAl _x O _y film by O ₂ sputtering.

Table 5 shows the results of a moisture resistance test performed on these. C: Since the Ag film laminated on the ZnAl _x O _y film has good crystallinity, the Ag film is stabilized, and the Ag film laminated on the ZnAl _x O _y film obtained by O ₂ sputtering. Superior moisture resistance compared to membranes.

Example 12 and Comparative Example 9 Example 10
In the same manner as described above, a C: ZnAl _x O _y film (16 nm), an Ag film (10 nm), a Zn—Al film (barrier layer), and a C: ZnAl _x O _y film (38 nm) were formed in this order from the substrate side. . However, assuming that the pumping speed is constant and the CO ₂ introduction amount is 6
It was changed to 7 sccm, 82 sccm, and 103 sccm. The sputtering pressure at this time was 3.2 ×
10 ⁻³ Torr, 3.8 × 10 ⁻³ Torr, 4.4 × 1
0 ^-3 Torr. Further, the thickness of the barrier layer is 0 to 5
In order to change in the range of nm, the input power at the time of sputtering is 0 kW, 0.02 kW,
Four conditions of 0.04 kW and 0.06 kW were changed. Here, the input power of 0 kW means that there is no barrier layer.

For the series of samples obtained, C: Z
nAl _x O _y film formation time of the CO ₂ flow rate and T _v of the laminated film of the barrier layer 3 layers obtained with respect to the input power at the time of film formation are shown in Figure 19. C: CO ₂ flow rate during film formation of ZnAl _x O _y is 82 s
In the case of ccm or 103 sccm, if there is no barrier layer, the Ag film is oxidized during the lamination of the C: ZnAl _x O _y film of the third layer, and only a three-layer film having a low T _{v and a} high sheet resistance is obtained. Absent. As the thickness of the barrier layer increases, T _v increases, and at the same time, the sheet resistance decreases. 0.02k each
W, and maximum T _v in the case of 0.04KW, the lowest sheet resistance. When the barrier layer is further thickened, a part of the barrier layer remains unoxidized and T _v decreases.

When the flow rate is 67 sccm, the highest T _v and the lowest sheet resistance are obtained when there is no barrier layer. The condition of the flow rate of 67 sccm is that the obtained C: ZnA
Since the l _x O _y film is in a condition (so-called transition region sputtering condition) immediately after the change from the fine absorption film (slightly colored film) to a transparent film, and the oxidizing power of the atmosphere is not excessive, Ag is used.
It is believed that the film does not undergo oxidation. If it is less than 62 sccm, the resulting C: ZnAl
_{The xOy} film was a slightly absorbing film.

As described above, C: ZnAl _x O _{y is formed} on the Ag film.
If a transition region sputtering condition is selected by adjusting the flow rate of CO ₂ when forming a film, the Ag film can be laminated without oxidizing even without a barrier layer.

Example 13 and Comparative Example 10 Example 1
1, in the order from the substrate, C: ZnAl _x O _y
Film (16 nm), Ag film (10 nm), C: ZnAl _x
O _y films (38 nm) were sequentially formed. However, C: Zn
At the time of forming the Al _x O _y film, a target in which Zn was added to 3 atomic% of Zn was used. As the sputtering gas, from the first layer to the third layer, Ar: 20%,
A mixed gas of CO ₂ : 80% was used.

As a comparative sample, a sample having the same film thickness configuration as that of the above-described embodiment, except that the sputtering atmosphere of the second Ag layer was changed to the Ar atmosphere, which is a conventional technique, was prepared. Table 6 shows T _v and emissivity ε of these samples.

From Table 6, it can be seen that T _v and ε are the same within an error range even when the sputtering atmosphere at the time of forming the second Ag layer is different. That is, if an appropriate gas ratio of Ar gas and CO ₂ is selected, a buffer chamber with an orifice for gas separation or a gate valve is not provided,
A Low-E film can be formed continuously in the same gas atmosphere in one continuous chamber.

[0107]

[Table 4]

[0108]

[Table 5]

[0109]

[Table 6]

Example 14 and Comparative Example 11 A soda lime silica glass (10 cm × 10 3) sufficiently washed using a sputtering apparatus having a target size of 4 inches.
A C: ITO film was formed on a substrate (cm × 2 mm thick) in a mixed gas atmosphere of Ar and CO ₂ (Example 14).

The target is an In—Sn alloy target (containing 10% by weight of Sn in terms of Sn oxide;
n-10Sn target), the input power is 100 W, the total flow rate of the introduced gas is 30 sccm, the sputtering pressure is 3 × 10 ⁻³ Torr, and the substrate heating temperature is 250.
C. and the film formation time was 5 minutes.

[0112] relation to Figure 11 and CO ₂ flow rate ratio and the discharge voltage, the relationship between the CO ₂ flow rate ratio in FIG. 12 and the film forming rate (deposition rate at the transparent film), and CO ₂ flow rate ratio in FIG. 9 6 shows a relationship with specific resistance (specific resistance at the time of forming a transparent film).
C: The carbon concentration in the ITO film was analyzed by the ESCA method after excavating about 10 nm from the surface by Ar ion etching in order to eliminate the influence of carbon adsorbed on the film surface. As a result, the carbon concentration was 1.9 to 2.2 atomic%.

In Example 14, the atmosphere was Ar and O _2.
An ITO film was formed in the same manner as in Example 14 except that the mixed gas atmosphere was changed (Comparative Example 11). FIG. 13 shows the relationship between the O ₂ flow ratio and the discharge voltage, FIG. 14 shows the relationship between the O ₂ flow ratio and the film forming speed (film forming speed when forming a transparent film), and FIG.
And O ₂ flow ratio and specific resistance (specific resistance when forming a transparent film)
The relationship is shown below.

A comparison between FIG. 11 and FIG. 13 shows that the discharge voltage characteristics are different, and that the ratio of oxidizing gas required to obtain a transparent film is larger when CO ₂ is used. this is,
It is considered that CO ₂ has a lower oxidizing power than O ₂ , and the reaction is caused to occur more slowly with respect to the oxidizing gas ratio. Further, by comparing FIGS. 12 and 14 and FIGS. 9 and 10, changes in the film formation rate and the specific resistance with respect to the oxidizing gas ratio are smaller when CO ₂ is used, and the CO ₂ is transparent in a wider gas ratio region. It can be seen that a conductive film is obtained.

Further, as a result of examining the in-plane distribution and reproducibility of the C: ITO film of Example 14, good results were obtained. Furthermore, it was also confirmed that higher conductive films can be separately formed with good control. It is considered that these effects also result from the fact that the reaction occurs slowly with respect to the oxidizing gas ratio.

Example 15 A soda lime glass substrate (100 cm × 100 cm) was formed by DC sputtering.
× 2 mm thick) and C: in a mixed atmosphere of Ar and CO ₂
An ITO film was formed. The target used was an In-10Sn target, the input power was 2.2 kW, the total flow rate of the introduced gas was 300 sccm, and the sputtering pressure was 3 × 10 ⁻³ To.
rr, a substrate heating temperature was 250 ° C., a film was formed while the substrate was being transferred under the target, and the substrate transfer speed was determined so that the film formation time was 5 minutes.

The obtained C: ITO film has in-plane uniformity of specific resistance of ± 3%, and resistance fluctuation between batches (film formation 5 times).
Was good at ± 5%. Further, the optical characteristics were uniform and good in the plane. In addition, generation of nodules during film formation was reduced, and no generation of pinholes due to arcing and no stopping of a sputtering power supply by a protection circuit were observed.

Example 16 Soda lime silica glass (10 cm × 10 cm × 1.1 mm thick) having a SiO ₂ film formed by CVD as an alkali barrier coat using a sputtering apparatus having a target size of 4 inches
Was sufficiently washed, and a C: ITO film was formed on the substrate in a mixed gas atmosphere of Ar and CO ₂ . Thereafter, patterning was performed to form a transparent electrode for a touch panel.

The target was an In-10Sn target, the input power was 100 W, and the total flow rate of the introduced gas was 30 s.
ccm, the sputtering pressure was 3 × 10 ⁻³ Torr, the substrate heating temperature was 400 ° C., and the film thickness was 10 nm. The patterning was performed by applying a resist on the C: ITO film and immersing it in an iron chloride-based etchant using the resist as a mask. The obtained transparent electrode for touch panel is 200Ω / □
Good sheet resistance.

Example 17 A transparent electrode for a liquid crystal display element was prepared in the same manner as in Example 16 except that the film thickness was changed to 100 nm. The obtained transparent electrode for a liquid crystal display element has a resistance of 20Ω.
/ □ showed a good sheet resistance.

[0121]

When the oxide film of the present invention is used as an upper layer film of a laminate, it is difficult for moisture to permeate and diffuse, so that the metal layer constituting the laminate is not affected by moisture in an external atmosphere. It is difficult to receive, and the moisture resistance is improved. In particular, Low-E
Suitable for membranes.

According to the present invention, the following effects 1) to 7) can be obtained. 1) An oxide film in which the crystal growth direction of the film is uniform and dense, and the internal stress is further reduced is obtained. 2) A transparent oxide film can be stably obtained at the maximum film forming rate.

3) Oxidation of a metal layer such as an Ag layer is suppressed.
A higher visible light transmittance than the conventional method can be obtained.
An oxide film can be laminated on a metal layer without using a barrier layer (a layer for preventing oxidation of the metal layer) which has been conventionally required.
The production process of the ow-E film can be simplified.

4) The barrier layer is usually made of a metal film (Zn or Sn).
Etc.). The adhesion between the metal film such as the Ag film and the barrier layer is determined by the metal film such as the Ag film and the oxide film (ZnO or SnO).
₂ ) is weaker than the adhesive strength. Therefore, if the barrier layer remains without being oxidized, the scratch resistance is reduced. As a result of eliminating the need for the barrier layer, it is easy to obtain a Low-E film having good scratch resistance.

5) When a film is continuously formed, the conventional method (Ar
The occurrence frequency of arcing is reduced as compared with the case where sputtering is performed in a mixed gas of gas and O ₂ gas or in an atmosphere containing only O ₂ gas). The time that can be produced continuously becomes longer,
Product defects including pinholes are reduced.

6) Oxidation by sputtering on a substrate which is easily deteriorated when exposed to oxidizing plasma, such as a plastic substrate represented by an acrylic resin plate or a polycarbonate resin plate, or various substrates having a resin-coated surface. An object film can be formed. For example, an underlayer (SiO ₂ or Al) effective for suppressing gas diffusion through a plastic
₂ O ₃ ) can be formed while suppressing damage to the substrate.

7) A transparent conductive film having a uniform in-plane distribution of electric characteristics and optical characteristics can be stably manufactured with high productivity.
Further, generation of nodules during film formation is reduced.

[Brief description of the drawings]

FIG. 1 is a graph showing a relationship between a discharge voltage and a flow ratio of a reactive gas (CO ₂ ) and a film forming speed (film forming speed in forming a transparent film) vs. a reactive gas (C) for a carbon-containing ZnO _x film of Example 1.
A graph showing O ₂ ) flow rate ratio.

FIG. 2 shows a relationship between a discharge voltage and a flow ratio of a reactive gas (CO ₂ ) and a film formation rate (a film formation rate at the time of forming a transparent film) vs. a reactive gas (a carbon film-containing ZnAl _x O _y film of Example 1). 4 is a graph showing CO ₂ ) flow rate ratio.

FIG. 3 shows a discharge voltage v for the ZnO _x film of Comparative Example 1.
4 is a graph showing a flow rate ratio between a reactive gas (O ₂ ) and a deposition rate (a deposition rate when a transparent film is formed) versus a flow rate of a reactive gas (O ₂ ).

[Figure 4] for ZnAl _x O _y film of Comparative Example 1, the discharge voltage vs the reactive (O ₂₎ gas and flow rate, deposition rate (film-forming speed at the time of a transparent film) vs the reactive gas (O ₂ 3) a graph showing the flow ratio.

FIG. 5 is a graph showing the relationship between the sputtering gas CO ₂
(100%), the amount of C in the ZnO film was changed.
The graph which shows the intake amount of.

FIG. 6 shows the internal stress (transparent region) v of a ZnO film.
5 is a graph showing a reactive gas flow ratio (CO ₂ or O ₂ ).

FIG. 7 is a graph showing an internal stress (transparent region) vs. a reactive gas flow ratio (CO ₂ or O ₂ ) for a ZnAl _x O _y film.

FIG. 8 is a graph showing the results of a constant-temperature and constant-humidity test for each laminated film sample of Example 2, Example 3, and Comparative Example 2.

FIG. 9 is a graph showing the relationship between the CO ₂ flow ratio and the specific resistance.

FIG. 10 is a graph showing the relationship between the O ₂ flow ratio and the specific resistance.

FIG. 11 is a graph showing a relationship between a CO ₂ flow ratio and a discharge voltage.

FIG. 12 is a graph showing a relationship between a CO ₂ flow ratio and a deposition rate.

FIG. 13 is a graph showing a relationship between an O ₂ flow ratio and a discharge voltage.

FIG. 14 is a graph showing the relationship between the O ₂ flow rate ratio and the film formation rate.

FIG. 15 is a graph showing a relationship between a CO ₂ flow rate and a discharge voltage in Example 10.

FIG. 16 is a X-ray diffraction peak profile of the oxide film of Example 10.

17 shows an X-ray diffraction peak profile of the oxide film of Comparative Example 7. FIG.

FIG. 18 shows X-ray diffraction peak profiles of Ag films of Example 11 and Comparative Example 8.

FIG. 19 is a graph showing a relationship between a CO ₂ flow rate and visible light transmittance.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Satoru Satoru Takagi 1150 Hazawa-cho, Kanagawa-ku, Yokohama-shi, Kanagawa-ken Asahi Glass Co., Ltd.

Claims (16)

[Claims] 1. Using a target mainly composed of a metal,
A method for manufacturing an oxide film on a substrate by a sputtering method, wherein sputtering is performed in an atmosphere containing a gas containing carbon atoms. 2. The method according to claim 1, wherein CO ₂ gas is used as the gas containing carbon atoms. 3. A target containing a metal as a main component, Z
3. The method for forming an oxide film according to claim 1, wherein a target mainly containing at least one metal selected from the group consisting of n, Sn, and In is used. 4. An oxide film containing, as a main component, an oxide of one or more metals selected from the group consisting of Zn, Sn, In, Al, and Ti, wherein the oxide film contains carbon. Material film. 5. An atomic ratio of carbon of at least 0.03 to the total amount of one or more metals selected from the group consisting of Zn, Sn, In, Al and Ti contained in the oxide film.
5. The oxide film according to claim 4, wherein the content is 15 atomic%. 6. The oxide film according to claim 4, wherein the oxide film is mainly composed of an oxide of at least one metal selected from the group consisting of Zn, Sn and In. 7. An oxide film comprising Al, Ga, Si and Ti
The oxide film according to claim 6, further comprising one or more metals selected from the group consisting of: 8. A (2n + 1) layer (n is an integer of 1 or more) alternately laminated on a substrate with an oxide film, a metal film, and an oxide film
A laminate comprising at least one of the oxide films,
A laminate, which is the oxide film according to claim 4, 5, 6, or 7. 9. The (2n + 1) -th oxide film according to claim 4.
The laminate according to claim 8, which is the oxide film according to (1). 10. The laminate according to claim 8, wherein the metal film is a metal film containing Ag as a main component. 11. The metal film also contains at least one metal selected from the group consisting of Pd, Au and Cu.
0. The laminate according to 0. 12. A laminate comprising three layers of oxide film / metal film / oxide film, or oxide film / metal film / oxide film / metal film /
8. The semiconductor device according to claim 8, wherein the oxide film comprises five layers.
2. The laminate according to 1. 13. An overcoat film containing Sn oxide as a main component and containing Si in an amount of 5 to 95 atomic% based on the total amount of Sn and Si, on the (2n + 1) th layer oxide film of the laminate. Is formed.
The laminate according to the above. 14. The laminate according to claim 13, wherein the overcoat film contains 0.03 to 15 atomic% of carbon based on Sn. 15. An oxide film, a metal film, an oxide film,
4. A method for producing a laminate comprising (2n + 1) layers (n is an integer of 1 or more) alternately laminated, wherein at least one of the oxide films is produced by the production method according to claim 1, 2 or 3. A method for producing a laminate. 16. A transparent electrode comprising the oxide film according to claim 4, formed on a substrate.