JPH09175837A - Electrically conductive transparent film and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrically conductive transparent film composed of an amorphous oxide containing In, Zn, O and a specific element as essential constituent elements and exhibiting excellent electrical conductivity and light- transmittance even in the case of forming a film at a low substrate temperature. SOLUTION: This film is composed of an amorphous oxide containing In, Zn, O and one or more kinds of halogens (preferably F) as essential constituent elements at an atomic ratio In/(In+Zn) of preferably 0.55-0.9. The constituent elements may further contain as necessary one or more kind of a 3rd metal element having a valence of >=3 (e.g. Sn) at an atomic ratio (total 3rd element)/(In+Zn+total 3rd element) of <=0.2. The atomic ratio of the total halogen (total halogen)/(In+Zn+total 3rd element) is preferably adjusted to <=0.3.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a transparent conductive film, a method for producing the same, and a transparent conductive laminate.

[0002]

2. Description of the Related Art In recent years, the development of the semiconductor industry has been remarkable,
In particular, since liquid crystal display devices can be made lighter and thinner, they can be used in personal computers, word processors, etc.
It is being actively introduced into A-device. In a display panel (liquid crystal display panel) of this liquid crystal display device, two base materials each having a transparent electrode having a predetermined pattern on one surface are arranged at predetermined intervals such that the transparent electrodes face each other. A liquid crystal is sealed between the two base materials.

The transparent electrode is usually formed on a transparent substrate directly or through a color filter, and a glass substrate has been conventionally used as the transparent substrate, but recently, a liquid crystal display device. In order to further reduce the weight, a transparent resin substrate (including a film-shaped material and a sheet-shaped material) has been used in place of the transparent glass substrate. As the transparent electrode, a transparent electrode made of a tin-containing indium oxide film (hereinafter abbreviated as “ITO film”) is often used.

The ITO film generally exhibits high conductivity (low electrical resistivity) and high light transmittance in the visible light region when formed at a substrate temperature of 200 ° C. or higher. Therefore, it is difficult to form an ITO film having both high conductivity and high light transmittance on a transparent resin substrate having a lower heat resistance than a glass substrate. Further, when the ITO film is formed on the transparent resin substrate, especially on the transparent resin film by increasing the substrate temperature, the transparent resin film is likely to warp after the film formation, so that the yield of the products is reduced. By increasing the thickness of the ITO film formed on the transparent resin substrate,
It is possible to form an ITO film having a low surface resistance even at a low substrate temperature, but in this case, the light transmittance of the ITO film is reduced, and as in the case of forming a film at a high substrate temperature, When the transparent resin substrate is a transparent resin film, the transparent resin film after film formation tends to warp.

By the way, in recent years, liquid crystal display devices having the above-mentioned advantages have been made larger in area and higher in definition.
There is an increasing demand for low driving power and high contrast. As one of the methods to meet such a demand, there is a lower electric resistance and a higher transparency of a transparent electrode, which is one of the indispensable constituent members of a liquid crystal display panel, which further reduces the weight of the liquid crystal display device. Along with the use of a transparent resin substrate for the purpose, it is desired to develop a transparent conductive film that exhibits excellent conductivity and excellent light transmittance even when formed under a low substrate temperature.

As a transparent conductive film exhibiting high conductivity and high light transmission even when formed at a low substrate temperature, a transparent conductive film formed by doping a metal oxide with fluorine or a fluorine compound is used. The constituent elements of Zn, In, and C are
A transparent conductive film which is d or an alloy containing these metals is known (see Japanese Patent Laid-Open No. 63-241805).
In addition, as disclosed in Japanese Patent Laid-Open No. 6-318406, In ₂ O ₃ —Zn is used as a sputtering target.
By performing sputtering film formation using an O-based material, it is possible to obtain a transparent conductive film that is amorphous but has low electric resistance even at a low substrate temperature.

[0007]

However, the conductivity of the fluorine-doped zinc oxide film, which is the only transparent conductive film specifically shown as an example in JP-A-63-241805, is 1050 Scm ^{− at the} maximum. ^{Is 1} ,
The current demand for transparent electrodes for liquid crystal display panels cannot always be satisfied. In addition, the light transmission characteristic of the transparent conductive film is 85 to 87 for light having a wavelength of 550 nm.
%, Which does not always satisfy the current demand for transparent electrodes for liquid crystal display panels. The light transmission characteristics of the amorphous transparent conductive film disclosed in Japanese Patent Application Laid-Open No. 6-318406 do not always meet the current demand for transparent electrodes for liquid crystal display panels.

A first object of the present invention is to provide a transparent conductive film which exhibits excellent conductivity and excellent light transmittance even when formed into a film at a low substrate temperature, and a method for producing the same.

A second object of the present invention is to provide a transparent conductive laminate having a transparent conductive film which exhibits excellent conductivity and light transmittance even when formed under a low substrate temperature. It is in.

[0010]

The transparent conductive film of the present invention which achieves the first object has indium (In), zinc (Zn), oxygen (O) and at least one halogen as essential constituent elements. It is characterized in that it is made of an amorphous oxide.

Further, the method for producing a transparent conductive film of the present invention which achieves the first object uses a sputtering target containing at least one kind of halogen or a film forming gas containing at least one kind of halogen. Indium (In), zinc (Z
n), oxygen (O) and at least one kind of halogen as an essential constituent element, a transparent conductive film comprising an amorphous oxide film is formed (hereinafter, this method will be referred to as “method I”). ".).

Another method for producing a transparent conductive film of the present invention that achieves the first object is to use a vapor deposition material containing at least one halogen or a film forming gas containing at least one halogen. Indium (In), zinc (Zn), oxygen (O) by the conventional ion plating method.
And a transparent conductive film made of an amorphous oxide containing at least one kind of halogen as an essential constituent element (hereinafter, this method is referred to as "method II").

The transparent conductive laminate of the present invention which achieves the second object has an electrically insulating transparent substrate and a transparent conductive film formed on the transparent substrate. Is composed of the above-mentioned transparent conductive film of the present invention.

[0014]

Embodiments of the present invention will be described below in detail. First, the transparent conductive film of the present invention will be explained. It consists of things.

The "amorphous oxide" referred to in the present invention is "ceramics characterization technique".
(Published by The Ceramic Society of Japan, 1987, 44th to 45th
Page), the crystallinity of the oxide is measured according to the internal standard method, and when the remaining amount is amorphous, an oxide having an amorphous content of 50% by weight or more is selected. means. The internal standard method is a method of quantitative analysis by the X-ray diffraction method, and "to measure the crystallinity in the oxide according to the internal standard method" here is specifically performed as follows. .

First, an In ₂ O ₃ thin film having the same thickness as the thin film sample whose amorphous content is to be measured is formed on a quartz glass substrate, and this In ₂ O ₃ thin film is fired at 1000 ° C. to crystallize. The degree of conversion is close to 100%, and I in this state
The X-ray diffraction intensity (hereinafter referred to as “diffraction intensity I”) of the n ₂ O ₃ thin film is measured. Next, the X-ray diffraction intensity (hereinafter referred to as “diffraction intensity II”) of the thin film sample whose amorphous content is to be measured is measured, and this diffraction intensity II corresponds to the peak position of In ₂ O _3. By comparing the diffraction intensity of the portion with the diffraction intensity I described above, the ratio of the crystalline substance in the thin film sample is calculated.

The amorphous content (amorphous content based on the above definition) is preferably 70% by weight or more,
It is more preferably 80% by weight or more. Note that oxygen in the above amorphous oxide may be partially deficient. Further, the oxide includes all forms of oxides such as a mixture, a composition, and a solid solution.

If the atomic ratio In / (In + Zn) of indium (In) in the transparent conductive film of the present invention is less than 0.55, it becomes difficult to obtain a transparent conductive film having high conductivity, and the atomic ratio When the ratio exceeds 0.9, it becomes difficult to obtain a transparent conductive film having high etching property or heat resistance, so 0.55 to 0.9 is preferable. The atomic ratio In / (In + Zn) of indium is 0.6.
It is more preferable that the ratio is ˜0.9, and it is particularly preferable that the ratio is 0.7 to 0.9.

In addition to the indium (In), zinc (Zn), oxygen (O) and at least one kind of halogen, the transparent conductive film of the present invention includes at least one kind having a valence of at least positive trivalence. The third metal element may be a constituent element.
Specific examples of the third metal element include tin (Sn), aluminum (Al), antimony (Sb), gallium (Ga), titanium (Ti), silicon (Si), zirconium (Zr), germanium (Ge). , Vanadium (V), tungsten (W), lanthanum (La) and ruthenium (Ru). Among these third metal elements, tin (S
n) is particularly preferred.

The atomic ratio of the total amount of the third metal element (total third
(Metal element) / (In + Zn + all third metal elements) is 0.2
If it exceeds 1.0, the conductivity is lowered, so that the atomic ratio of the total amount of the third metal element is preferably 0.2 or less,
It is particularly preferable to set it to 1 or less.

On the other hand, the atomic ratio (total halogen) / total amount of halogen which is an essential constituent element in the transparent conductive film of the present invention /
(In + Zn + all third metal elements) is 0.01 to 0.3
It is preferred that The atomic ratio of the total amount of halogen (total halogen) / (In + Zn + total third metal element) is 0.01
When the amount is less than the above, improvement in conductivity and light transmittance due to addition of halogen is not substantially observed, and when this atomic ratio exceeds 0.3, the conductivity decreases. The atomic ratio (total halogen) / (In + Zn + total third metal element) of the total amount of halogen is more preferably 0.2 or less. The atomic ratio of the total amount of halogen (total halogen) / (In + Zn +
When the transparent conductive film does not have the above-mentioned third metal element as a constituent element in obtaining all the third metal elements), the value of all the third metal elements is set to 0 in the above equation.
Is calculated as

Specific examples of the above halogen include fluorine (F), chlorine (Cl), bromine (Br) and iodine (I). Fluorine is particularly preferable from the viewpoint that a low transparent conductive film can be obtained.

The transparent conductive film of the present invention exhibits high conductivity of about 3 × 10 ⁻⁴ Ωcm or less when the film thickness is 150 nm even when the film is formed at a substrate temperature of, for example, room temperature. Further, the transparent conductive film of the present invention shows a high light transmittance of about 95% or more at a thickness of 150 nm with respect to light having a wavelength of 550 nm even when the film is formed at a substrate temperature of, for example, room temperature. The film thickness of the transparent conductive film can be appropriately selected within a range of approximately 20 to 300 nm depending on its application and the like.

The transparent conductive film of the present invention having such characteristics is a transparent electrode for a liquid crystal display panel, a transparent electrode for a color filter used in a liquid crystal display panel or the like, an electroluminescence panel (display panel or surface light source. It is suitable as a transparent electrode for various uses such as a transparent electrode for the same), a transparent wiring, or a material thereof.
When the transparent conductive film of the present invention formed on a transparent resin substrate is used as a transparent electrode for a liquid crystal display panel or a material thereof, the weight of the liquid crystal display device is reduced and its area and size are increased. It is possible to achieve higher definition, lower driving power, higher contrast and the like.

The transparent conductive film of the present invention can be formed by various methods such as a coating thermal decomposition method, a sputtering method, an ion plating method, a vacuum deposition method and a CVD method. From the viewpoint of film performance, productivity, etc., it is particularly preferable to form a film by the method I or method II of the present invention described in detail below.

In the method I of the present invention, as described above, the sputtering target containing at least one kind of halogen or the film forming gas containing at least one kind of halogen (in the method I, the atmosphere during sputtering is The transparent conductive film of the present invention described above is formed by a sputtering method (including a reactive sputtering method) using a gas introduced into the apparatus for forming the same.

A method of forming a target transparent conductive film using a sputtering target containing at least one kind of halogen and a film forming gas containing no halogen is hereinafter referred to as "method IA", and it contains halogen. A method of forming a target transparent conductive film by using a sputtering target which is not formed and a film forming gas containing at least one halogen is hereinafter referred to as “method IB”, and contains at least one halogen. A method for forming a target transparent conductive film using a sputtering target and a film forming gas containing at least one kind of halogen will be described below in “Method I”.
C ”will be described in detail for each of these methods.

First, the method IA will be described. In the method IA, as described above, the sputtering target containing at least one kind of halogen and the film forming gas containing no halogen are used. The sputtering target has an atomic ratio of In / In /
It is sufficient that a transparent conductive film made of an amorphous oxide having desired atomic ratio (total halogen) / (In + Zn + total third metal element) of (In + Zn) and total amount of halogen can be formed. . The sputtering may be single-source or multi-source, but single-source sputtering is preferable because the composition of the film-forming gas can be easily optimized and a uniform and large-area film can be easily obtained. In the case of multi-source sputtering, it is sufficient that at least one of all sputtering targets contains at least one kind of halogen.

The "third metal element" in the above formula, which represents the atomic ratio of the total amount of halogen, is an optional component as described later, and when the third metal element is not contained, the above-mentioned The atomic ratio of the total amount of halogen is calculated by setting the value of "total third metal element" in the formula to 0.

When the desired transparent conductive film is formed by mono-sputtering in the method IA, as the sputtering target, for example, indium metal, zinc metal,
Indium-zinc alloy, indium oxide, zinc oxide, indium halide, zinc halide, In ₂ O ₃ (Zn
O) _m (m = 2 to 20), indium oxide with a solid solution of halogen, zinc oxide with a solid solution of halogen, and In ₂ O ₃ (ZnO) _m (m = 2 to 20) with a solid solution of halogen. It is possible to use a single substance or a mixture of these substances, which contains indium, zinc and halogen. Specific examples of the above sputtering target are not particularly limited,
The following (1) to (13) are listed.

(1) Sintered body made of a mixture of indium oxide and / or indium halide (indium fluoride, indium chloride, etc.) and zinc oxide and / or zinc halide (zinc fluoride, zinc chloride, etc.) A target containing at least one of indium halide and zinc halide. (2) In a sintered compact target made of a mixture of indium oxide in which indium oxide and / or halogen are solid-dissolved and zinc oxide in which zinc oxide and / or halogen is solid-dissolved, indium oxide and halogen in which halogen is solid-dissolved are Those containing at least one of solid-solved zinc oxide.

(3) In ₂ O ₃ (ZnO) _m (m = 2 to 2)
0) A sintered body target comprising at least one hexagonal layered compound in which halogen is solid-solved in 0). In addition, the reason why the value of m is limited to 2 to 20 in the above formula representing the hexagonal layered compound is that if the value of m is out of the above range, the compound does not become a hexagonal layered compound (hereinafter the same). (4) A target in which tablets of zinc halide and / or zinc halide powder are arranged in a required amount on a sintered disk made of indium oxide.

(5) A tablet made of indium halide or zinc halide and / or a required amount of indium halide powder or zinc halide powder is placed on a sintered body disk made of a mixture of indium oxide and zinc oxide. The target that will be done. (6) A tablet made of indium halide or zinc halide on a sintered body disk made of at least one kind of hexagonal layered compound represented by In ₂ O ₃ (ZnO) _m (m = 2 to 20). And / or a target in which a required amount of indium halide powder or zinc halide powder is arranged.

(7) In ₂ O ₃ (ZnO) _m (m = 2 to 2)
0) a hexagonal layered compound represented by a mixture of at least one of indium oxide and / or zinc oxide, and a tablet and / or halogenated indium halide or zinc halide on a sintered disk. A target in which a required amount of indium powder or zinc halide powder is arranged. (8) A tablet made of zinc oxide and / or a zinc oxide powder and a tablet made of indium halide or zinc halide and / or an indium halide powder or a zinc halide powder are required on a sintered disk made of indium oxide. Targets arranged in quantity.

(9) In ₂ O ₃ (ZnO) _m (m = 2 to 2)
0) A sintered compact target composed of a mixture of at least one kind of hexagonal layered compound represented by 0) and indium oxide and / or zinc oxide, wherein at least one of the substances contained in the mixture is used. A solid solution of halogen. (10) At least one kind of hexagonal layered compound represented by In ₂ O ₃ (ZnO) _m (m = 2 to 20), indium oxide and / or zinc oxide, indium halide and / or zinc halide A sintered body target made of a mixture with. (11) A sintered body target made of a mixture of at least one hexagonal layered compound represented by In ₂ O ₃ (ZnO) _m (m = 2 to 20) and indium halide and / or zinc halide.

(12) A target in which tablets of indium halide and / or indium halide powder are placed on a sintered disk of zinc oxide in a required amount. (13) In ₂ O ₃ (ZnO) _m (m = 2 to 20), indium oxide, indium halide, zinc halide, indium oxide with a solid solution of halogen, zinc oxide with a solid solution of halogen, and halogen. In ₂ O ₃ (ZnO) _m
A target made of a mixture of substances selected from (m = 2 to 20) and containing indium, zinc and halogen.

In the case of forming the target transparent conductive film by multi-source sputtering in the method IA, for example, indium metal, zinc metal, indium-zinc alloy, indium oxide, zinc oxide, indium halide, halogenated. Zinc, In ₂ O ₃ (ZnO) _m (m = 2 to 20), halogen-solved indium oxide, halogen-solved zinc oxide, and halogen-solved In ₂ O ₃ (ZnO) _m
A single substance selected from (m = 2 to 20) or a mixture of these substances can be used as one target, and a total of two or more targets can be used as the sputtering target. At this time, at least one of all the targets containing indium and / or zinc and halogen is used, and the one containing indium, zinc and halogen is used when the whole sputtering target is seen. Specific examples of the sputtering target include, but are not limited to, the following (20) to (24).

(20) A sintered body target made of indium oxide and a sintered body target made of zinc halide. (21) A sintered body target made of a mixture of indium oxide and zinc oxide, and a sintered body target made of indium halide and / or zinc halide. (22) Sintered body target made of at least one kind of hexagonal layered compound represented by In ₂ O ₃ (ZnO) _m (m = 2 to 20) and indium halide and / or zinc halide Union target. (23) A sintered body target comprising a mixture of at least one hexagonal layered compound represented by In ₂ O ₃ (ZnO) _m (m = 2 to 20) and indium oxide and / or zinc oxide, and a halogen. A sintered body target made of indium halide and / or zinc halide. (24) A sintered body target made of zinc oxide and a sintered body target made of indium halide.

Specific examples of the halogen contained in the sputtering target include fluorine (F), chlorine (Cl), bromine (Br) and iodine (I). In both the single-source sputtering and the multi-source sputtering, the halogen contained in the sputtering target may be only one kind or two or more kinds. As described in the description of the transparent conductive film of the present invention, since fluorine is particularly preferable as the halogen which is a constituent element of the transparent conductive film, fluorine is particularly preferable as the halogen contained in the sputtering target.

When the transparent conductive film is formed by the method IA, it is between the atomic ratio In / (In + Zn) of indium in the entire sputtering target and the atomic ratio In / (In + Zn) of indium in the formed transparent conductive film. May be slightly deviated. Therefore, the atomic ratio In / (In + Zn) of indium in the entire sputtering target is appropriately adjusted so as to obtain the target transparent conductive film. For example, as described in the description of the transparent conductive film of the present invention, the atomic ratio In / (In + Zn) of indium in the transparent conductive film is 0.55.
It is preferable that the ratio is to 0.9, but the above (1)
~ (3), (9) to (11) and (13), the atomic ratio In / (In + Zn) of indium was 0 by unitary sputtering using a sputtering target composed of one sintered body. When a transparent conductive film having a thickness of 55 to 0.9 is to be formed, the atomic ratio of indium In / (I
It is preferable that (n + Zn) is approximately 0.45 to 0.9.

Similarly, when the transparent conductive film is formed by the method IA, the atomic ratio of the total amount of halogen in the entire sputtering target (total halogen) / (In + Zn +).
A slight deviation may occur between the atomic ratio (total halogen) / (In + Zn + total third metal element) of the total amount of halogen in the formed transparent conductive film). Therefore, the atomic ratio of the total amount of halogen (total halogen) / (In + Z
(n + all third metal element) is appropriately adjusted so that the target transparent conductive film is obtained. For example, above (1) ~ (3), (9)
The atomic ratio (total halogen) / (In + Zn + total third metal element) of the total amount of halogen is determined by one-way sputtering using a sputtering target composed of one sintered body like the sputtering targets of (11) and (13). When a transparent conductive film having a thickness of 0.3 or less is to be formed, the atomic ratio (total halogen) / (In + Zn + total third metal element) of the total amount of halogen in the sputtering target is set to approximately 0.35 or less. Preferably.

In addition to indium (In), zinc (Zn), oxygen (O), and at least one halogen, a transparent conductive material containing at least one third metal element having a positive trivalence or more as a constituent element. When the film is formed by the method IA, a sputtering target containing a desired third metal element in addition to indium (In), zinc (Zn) and at least one halogen is used.

The term "sputtering target containing a third metal element" used in the method IA means that when the sputtering target is a single plate-like object, the sputtering target is the third element as its constituent element. When the sputtering target is composed of one disk and a tablet and / or powder arranged on the disk, it means that it contains at least one metal element. Means that at least one of these contains at least one third metal element as its constituent element. Further, in the case of multi-source sputtering, it means that at least one of all sputtering targets is the above-mentioned “sputtering target containing the third metal element”.

Specific examples of the third metal element include tin (Sn), aluminum (Al), antimony (S) as described in the description of the transparent conductive film of the present invention.
b), gallium (Ga), titanium (Ti), silicon (S
i), zirconium (Zr), germanium (Ge),
Vanadium (V), tungsten (W), lanthanum (L
a) and ruthenium (Ru). These third
Among the metal elements, tin (Sn) is particularly preferable as described above, so that the third target included in the sputtering target is
Tin (Sn) is particularly preferable as the metal element. .

The above-mentioned third metal element is contained in a single sputtering target in the state of simple substance, oxide, halide (fluoride, chloride, bromide, iodide, etc .; the same applies hereinafter). Alternatively, it may be contained in a single sputtering target in a solid solution with another substance. When the sputtering target is composed of a disk and tablets and / or powders placed on the disk, the above-mentioned third metal element simple substance, oxide, halide, etc., or the third metal element is used. Indium oxide or indium halide in solid solution, zinc oxide or zinc halide in solid solution with the third metal element, alloy of indium and / or zinc with the third metal element, etc. It can be used as a powder. Further, in the case of multi-source sputtering, as one of all sputtering targets, a simple substance of the above-mentioned third metal element, an oxide, a halide (fluoride, chloride, bromide, iodide, etc.) is applied. )
Etc., indium oxide or indium halide in which the third metal element forms a solid solution, zinc oxide or zinc halide in which the third metal element forms a solid solution, the third metal element and indium and / or zinc It is also possible to use an alloy or the like.

The atomic ratio of the total amount of the third metal element in the entire sputtering target (total third metal element) / (In
+ Zn + all third metal elements) are appropriately adjusted so that the target transparent conductive film is obtained. Atomic ratio of total amount of third metal element in transparent conductive film (total third metal element) / (In + Z
As described above, the n + total third metal element) is preferably 0.2 or less, and more preferably 0.1 or less.

In the method IA, when the sputtering target contains oxygen (O), a film forming gas containing an inert gas such as argon gas or a film containing a mixed gas of an inert gas and oxygen gas is formed. Use gas. Further, when the sputtering target does not contain oxygen (O), a film forming gas including a mixed gas of an inert gas and an oxygen gas is used. The necessity of using the film forming gas containing oxygen gas and the amount of oxygen gas used (introduced amount) when using the film forming gas containing oxygen gas are determined by the composition of the sputtering target and the target transparent conductivity. It is appropriately determined in consideration of the composition of the film, film forming conditions, and the like depending on whether or not composition compensation for oxygen (O) is necessary.

The "sputtering target containing oxygen (O)" in the method IA means that when the sputtering target is a single plate-shaped object, the sputtering target is oxygen (O) as a constituent element. )
When the sputtering target is composed of one disk and a tablet and / or powder arranged on the disk, at least one of the disk, the tablet and the powder is a constituent element of the disk. Means that it contains oxygen (O). In the case of multi-source sputtering, at least one of all sputtering targets is the above-mentioned "sputtering target containing oxygen (O)".
Means that A specific example of film forming conditions in Method IA will be described later.

Next, the method IB will be described. Method I
As described above, B is formed by a sputtering method using a halogen-free sputtering target and a film-forming gas containing at least one halogen.
This is a method of forming a target transparent conductive film. The sputtering target used at this time may be one that can form a transparent conductive film made of an amorphous oxide having an indium atomic ratio In / (In + Zn) of a desired value. Further, the sputtering may be multi-source sputtering of two or more elements, but single-source sputtering is preferable because the composition of the film-forming gas can be optimized easily and a uniform and large-area film can be easily obtained.

When the desired transparent conductive film is formed by mono-sputtering in the method IB, the sputtering target may be, for example, indium metal, zinc metal,
It is composed of a single substance selected from indium-zinc alloy, indium oxide, zinc oxide and In ₂ O ₃ (ZnO) _m (m = 2 to 20) or a mixture of these substances, and contains indium and zinc. Any thing can be used. Specific examples of the above sputtering target include, but are not limited to, the following (30) to (36).

(30) A sintered body target made of a mixture of indium oxide and zinc oxide. (31) A sintered body target comprising at least one hexagonal layered compound represented by In ₂ O ₃ (ZnO) _m (m = 2 to 20). (32) A sintered body target comprising a mixture of at least one hexagonal layered compound represented by In ₂ O ₃ (ZnO) _m (m = 2 to 20) and indium oxide and / or zinc oxide.

(33) A target in which a required amount of tablets made of zinc oxide and / or zinc oxide powder is placed on a disk made of a sintered body of indium oxide. (34) On the disk made of the sintered body of (30) to (32) above,
A target comprising at least one selected from a tablet made of indium oxide, an indium oxide powder, a tablet made of zinc oxide and a powder of zinc oxide. (35) A target made of an alloy of indium and zinc. (36) A target comprising a tablet made of indium oxide and / or an indium oxide powder arranged in a required amount on a disk made of a sintered body of zinc oxide.

Also in the method IB, as in the case of forming the transparent conductive film by the above-mentioned method IA, the atomic ratio In / In of the entire sputtering target In /
A slight deviation may occur between (In + Zn) and the atomic ratio In / (In + Zn) of indium in the formed transparent conductive film. Therefore, the atomic ratio of indium In / (In
+ Zn) is appropriately adjusted in the same manner as in the above-mentioned method IA so that a desired transparent conductive film can be obtained. For example, the atomic ratio In / In / is obtained by unitary sputtering using a sputtering target composed of one sintered body like the above-mentioned sputtering targets (30) to (32).
When a transparent conductive film having (In + Zn) of 0.55 to 0.9 is to be formed, the atomic ratio of indium in the sputtering target is In / (In + Z).
It is preferable that n) is approximately 0.45 to 0.9.

Further, indium (In), zinc (Z
n), oxygen (O), and at least one kind of halogen, a transparent conductive film having at least one kind of third metal element having a positive trivalence or more as a constituent element is formed by the method IB. Is indium (In) and zinc (Z
In addition to n), a sputtering target containing a desired third metal element is used. Here, the “sputtering target containing the third metal element” in the method IB is the “containing the third metal element” in the above-mentioned method IA, except that the sputtering target does not contain halogen. It is the same as the "sputtering target". Atomic ratio of total amount of third metal element in total sputtering target (total third metal element) / (In + Z
(n + all third metal element) is appropriately adjusted in the same manner as in the above-mentioned method IA so as to obtain a target transparent conductive film.

In Method IB, when the sputtering target contains oxygen (O),
In addition to an inert gas such as argon gas, a gas that becomes a halogen source (hereinafter, a gas that becomes a halogen source is simply referred to as a “halogen source”).
That. ) Is used together, or a mixed gas of an inert gas and an oxygen gas is used together with a halogen source. When the sputtering target does not contain oxygen (O), a film forming gas using a halogen source together with a mixed gas of an inert gas and an oxygen gas is used.

Specific examples of the halogen source are not particularly limited, but halogen gas (F ₂ , Cl
₂ , Br ₂ , I _2, etc.), hydrogen halides (HF, HC
1, HBr, HI, etc., halogenated carbon (CF ₄ , CC)
l ₄ etc.), nitrogen halides (NF ₃ , NCl ₃ etc.), silicon halides (SiF ₄ , SiCl ₄ etc.) and the like. Since the halogen contained in the film forming gas may be only one kind or two or more kinds, the halogen source used may be only one kind or two or more kinds. May be

As the halogen which is a constituent element of the transparent conductive film, fluorine is particularly preferable as described in the description of the transparent conductive film of the present invention. Therefore, the halogen source is fluorine gas (F ₂ ) or fluorine. It is preferable to use fluorides such as hydrogen fluoride (HF), carbon fluoride (CF ₄ ), nitrogen fluoride (NF ₃ ), and silicon fluoride (SiF ₄ ).

The amount of halogen source used (introduced amount) is the characteristics of each sputtering apparatus, the film forming conditions, the composition of the entire sputtering target, the type of halogen source used, and the total number of halogen atoms in the target transparent conductive film. It is appropriately adjusted according to the ratio (total halogen) / (In + Zn + total third metal element) and the like. This adjustment is obtained by converting the volumes of all types of halogens contained in the halogen source used into halogen molecules (hereinafter, this volume is referred to as “halogen molecule equivalent volume”), and the volume of the film forming gas It can be carried out by appropriately selecting the ratio of the volume equivalent to the halogen molecule (the volume equivalent to the halogen molecule) / (volume of the film forming gas). The atomic ratio (total halogen) / (In + Zn + total third metal element) of the total amount of halogen in the transparent conductive film is preferably 0.3 or less, and more preferably 0.2 or less as described above. preferable.

Also in the method IB, as in the case of the above-mentioned method IA, the necessity of using the film-forming gas containing oxygen gas and the oxygen gas when the film-forming gas containing oxygen gas is used. The amount used (introduced amount) is appropriately determined in consideration of the composition of the sputtering target, the composition of the target transparent conductive film, the film forming conditions, etc., depending on whether or not composition compensation for oxygen (O) is necessary. It is determined. Method I
Specific examples of the film forming conditions in B will be described later.

Next, the method IC of the present invention will be described. As described above, the method IC is a sputtering method using a sputtering target containing at least one kind of halogen and a film forming gas containing at least one kind of halogen to form a target transparent conductive film. Is the way to do it.

Atomic ratio of total halogen in sputtering target used in method IC (total halogen) /
Since (In + Zn + all third metal elements) contains halogen in the film forming gas, it may be lower than the value in Method IA. Similarly, the amount of halogen source used (introduced amount) in the film-forming gas used in Method IC is equal to that of Method IB because the sputtering target contains halogen.
May be lower than the value at. Except for these points, the sputtering target used in Method IC can be similar to the sputtering target used in Method IA,
Since the film-forming gas used in the method IC can be similar to the film-forming gas used in the method IB, the description thereof will be omitted here. Specific examples of film forming conditions in the method IC will be described later.

Method IA, Method IB and Method I described above
Regardless of which method C is used to form the transparent conductive film, the purity of the sputtering target is preferably 98% or more. If it is less than 98%, the moisture and heat resistance of the obtained film may decrease, the conductivity may decrease, or the light transmittance may decrease due to the presence of impurities. A more preferred purity is 99% or more, and an even more preferred purity is 9%.
9.9% or more. When using a sintered compact target, the relative density of the sintered compact target is preferably 60% or more. When the relative density is less than 60%, the film formation rate and the film quality are likely to decrease. A more preferable relative density is 85% or more, and further preferably 90% or more.

In any of the method IA, the method IB and the method IC, the film forming conditions such as the degree of vacuum, the applied power and the substrate temperature are variously changed depending on the sputtering method and the characteristics of the apparatus used. Although it is difficult to unconditionally specify, for example, in the case of the DC magnetron sputtering method, it can be set as follows.

(I) Degree of vacuum and applied power: Degree of vacuum during sputtering is 1 × 10 ^{-2 to} 5 × 10 ⁰ P
a, more preferably 5 × 10 ^{−2 to} 5 × 10 ⁰ Pa, and further preferably 1 × 10 ⁻¹ to 1 × 10 ⁰ Pa. The applied power per unit target area is 0.1 to
5 W / cm ² is preferred. Even if the degree of vacuum during sputtering is lower than 1 × 10 ^-2 Pa, 5 × 10 ⁰ P
Even if the pressure is higher than a, the stability of plasma deteriorates.
In addition, the applied power to the sputtering target is 0.1
If it is less than W / cm ² , the film formation rate is low, and if it is more than 5 W / cm ² , the sputtering target is greatly damaged and the sputtering target may be damaged.

(Ii) Substrate Temperature The substrate temperature is not particularly limited and may be a general substrate temperature, that is, -50 ° C. to the heat resistant temperature of the substrate, but a transparent resin substrate, particularly a transparent resin film is used as the substrate. In this case, the temperature is preferably −50 to 50 ° C. in order to prevent the transparent resin film after film formation from being warped.

The substrate on which the transparent conductive film is formed by the method IA, the method IB or the method IC as described above is a glass substrate, a ceramic substrate, a metal substrate, a thermoplastic resin substrate, a thermosetting resin substrate, an amorphous substrate. , A color filter, a thin-film solar cell, etc., depending on the intended use of the transparent conductive film. When a lightweight liquid crystal display panel is to be obtained by using the transparent conductive film as a transparent electrode, the substrate may be a polycarbonate resin, a polyarylate resin, a polyester resin, a polyether sulfone resin, an amorphous polyolefin resin, or polystyrene. It is preferable to use a film or sheet made of a transparent resin such as a resin or an acrylic resin, and among them, it is preferable to use a film made of a polycarbonate resin or a polyarylate resin from the viewpoint of transparency and thermal stability.

When the transparent conductive film is formed on the transparent resin substrate, a crosslinkable resin layer may be previously provided on the surface of the transparent resin substrate on the side where the transparent conductive film is provided. This crosslinkable resin layer is useful for improving the adhesion between the transparent resin substrate and the transparent conductive film. The crosslinkable resin layer is preferably made of epoxy resin, phenoxy ether resin, acrylic resin, or the like. The crosslinkable resin layer can be formed by a conventional method such as applying a predetermined material by a spin coating method, a dip coating method or the like, and then crosslinking it by a UV curing method or a heat curing method.
Further, an adhesive layer or a gas barrier layer may be interposed between the transparent resin substrate and the crosslinkable resin layer. Examples of the material of the adhesive layer include epoxy-based, acrylic urethane-based, and phenoxyether-based adhesives. The gas barrier layer is useful for preventing diffusion of water vapor, oxygen and the like into the liquid crystal when the transparent conductive film is finally used as a transparent electrode of a liquid crystal display panel, for example. Examples of the material for the gas barrier layer include organic polymers such as ethylene-vinyl alcohol copolymer, polyvinyl alcohol, polyacrylonitrile, polyvinylidene chloride, and polyvinylidene fluoride, and Al ₂ O ₃ and SiO _x (0 <x ≦ 2). , ZnO, T
iO ₂ , AlN, Si ₃ N ₄ , TiN, SiC, BaC
And other ceramics. The adhesive layer and the gas barrier layer can be formed by methods such as spin coating, dip coating, and RF sputtering.

The method I of the present invention described above (method IA,
According to the method IB and the method IC), the above-mentioned characteristics, that is, even when the film is formed at a substrate temperature of, for example, room temperature, the specific resistance at a film thickness of 150 nm is about 3 × 10 ^−4.
High conductivity of Ω · cm or less and a wavelength of 55
It is possible to obtain the transparent conductive film of the present invention having a high light transmittance of about 95% or more for a thickness of 150 nm with respect to 0 nm light.

Next, the method II of the present invention will be described.
Method II is, as described above, a vapor deposition material containing at least one kind of halogen (meaning a material to be vapor deposited; hereinafter the same) or a film forming gas containing at least one kind of halogen (Method II. Is a gas that is introduced into the apparatus to form an atmosphere during ion plating. The same applies to the following.) Indium (In), zinc (Zn), oxygen (O) ) And at least one kind of halogen as an essential constituent element, a transparent conductive film made of an amorphous oxide is formed.

A method of forming a target transparent conductive film using a vapor deposition material containing at least one kind of halogen and a film forming gas containing no halogen is referred to as "Method IIA".
That is, a method for forming a target transparent conductive film using a vapor deposition material containing no halogen and a film forming gas containing at least one kind of halogen is referred to as "method IIB", and at least one kind The method for forming a target transparent conductive film by using the halogen-containing vapor deposition material and the film-forming gas containing at least one kind of halogen is described below as “method”.
IIC ”will be described in detail for each of these methods.

First, the method IIA will be described. In the method IIA, as described above, the vapor deposition material containing at least one kind of halogen and the film forming gas containing no halogen are used. The vapor deposition material is a transparent conductive film made of an amorphous oxide having an indium atomic ratio In / (In + Zn) and a total halogen atomic ratio (total halogen) / (In + Zn + total third metal element) of desired values. What is necessary is just to be able to form a film. Further, the ion plating may be one that uses only one evaporation source (hereinafter referred to as "one-dimensional ion plating"), or one that uses two or more evaporation sources (hereinafter referred to as "multi-source ion"). “Plating”). In the case of multi-source ion plating, it is sufficient that at least one of all vapor deposition materials contains at least one halogen.

The "third metal element" in the above formula, which represents the atomic ratio of the total amount of halogen, is an optional component as will be described later, and when the third metal element is not contained, the above The atomic ratio of the total amount of halogen is calculated by setting the value of "total third metal element" in the formula to 0.

In the method IIA, when the desired transparent conductive film is formed by unitary ion plating, a sintered body, granules, a pressure molded product or the like can be used as the vapor deposition material. Examples of the vapor deposition material include indium metal, zinc metal, indium-zinc alloy, indium oxide, zinc oxide, indium halide, zinc halide, In ₂ O ₃ (ZnO) _m (m = 2 to 20), halogen. Oxide in which is dissolved, zinc oxide in which halogen is dissolved, and In ₂ O ₃ (ZnO) _m (m
= 2 to 20), a single substance selected from the above, a mixture of these substances, or the like, and a substance containing indium, zinc, and halogen can be used. Specific examples of the above vapor deposition material include, but are not limited to, the following (40) to (45).

(40) A mixture of indium oxide and / or indium halide and zinc oxide and / or zinc halide, containing at least one of indium halide and zinc halide. (41) A mixture of indium oxide in which indium oxide and / or halogen forms a solid solution and zinc oxide in which zinc oxide and / or halogen forms a solid solution, and indium oxide in which a halogen forms a solid solution and zinc oxide in which a halogen forms a solid solution Containing at least one of the above. (42) A mixture of at least one hexagonal layered compound represented by In ₂ O ₃ (ZnO) _m (m = 2 to 20) and indium halide and / or indium oxide in which halogen is solid-dissolved. .

(43) In ₂ O ₃ (ZnO) _m (m = 2 to 2)
A solid solution of halogen in at least one kind of the hexagonal layered compound represented by 0). (44) A mixture of at least one hexagonal layered compound represented by In ₂ O ₃ (ZnO) _m (m = 2 to 20) and indium oxide and / or zinc oxide, which is included in this mixture. A solid solution of halogen in at least one of the substances. (45) In ₂ O ₃ (ZnO) _m (m = 2 to 20), at least one selected from indium oxide, indium halide, and indium oxide in which halogen is solid-dissolved, zinc oxide, zinc halide, and Consisting of a mixed phase with at least one selected from zinc oxide in which halogen is dissolved,
A material containing at least one of indium halide, indium oxide having a solid solution of halogen, zinc halide, and zinc oxide having a solid solution of halogen.

Also, in the method IIA, when the target transparent conductive film is formed by multi-dimensional ion plating, it is preferable to use sintered bodies, granules, pressure molded products, etc. as the vapor deposition materials. it can. In this case, for example, indium metal, zinc metal, indium-zinc alloy, indium oxide, zinc oxide, indium halide, zinc halide, In ₂ O ₃ (ZnO) _m (m = 2 to 20), and halogen are solid solutions. Indium oxide, zinc oxide with a solid solution of halogen, and In ₂ O ₃ (ZnO) _m (m
= 2 to 20), a single substance selected from the group consisting of a single substance or a mixture of these substances can be used as one vapor deposition material, and a total of two or more vapor deposition materials can be used. At this time,
A material containing indium and / or zinc and a halogen is used as at least one of all vapor deposition materials, and a material containing indium, zinc and halogen is used when the entire vapor deposition material is viewed. Specific examples of the above vapor deposition material are not particularly limited,
The following (50) to (53) are mentioned.

(50) A vapor deposition material made of indium oxide and a vapor deposition material made of zinc halide. (51) A vapor deposition material composed of a mixture of indium oxide and zinc oxide, and a vapor deposition material composed of indium halide and / or zinc halide. (52) A vapor deposition material composed of one or more hexagonal layered compounds represented by In ₂ O ₃ (ZnO) _m (m = 2 to 20) and a vapor deposition material composed of indium halide and / or zinc halide. (53) In ₂ O ₃ (ZnO) _m (m = 2 to 20) and at least one hexagonal layered compound and indium oxide and /
Alternatively, a vapor deposition material including a mixture with zinc oxide and an vapor deposition material including indium halide and / or zinc halide.

Specific examples of the halogen contained in the vapor deposition material include fluorine (F), chlorine (Cl), bromine (Br) and iodine (I). In both the single-source ion plating and the multi-source ion plating, the halogen contained in the vapor deposition material may be only one type, or may be two or more types. As described in the description of the transparent conductive film of the present invention, since fluorine is particularly preferable as the halogen which is a constituent element of the transparent conductive film,
Fluorine is particularly preferable as the halogen contained in the vapor deposition material.

When the transparent conductive film is formed by the method IIA, the atomic ratio of indium in the entire evaporation material In /
A slight deviation may occur between (In + Zn) and the atomic ratio In / (In + Zn) of indium in the formed transparent conductive film. Therefore, the atomic ratio In / (In + Zn) of indium in the entire vapor deposition material is appropriately adjusted so that a target transparent conductive film can be obtained. For example, as described in the description of the transparent conductive film of the present invention, the atomic ratio of indium In / (I
It is preferable that (n + Zn) is 0.55 to 0.9.
When a transparent conductive film having a ratio of / (In + Zn) of 0.55 to 0.9 is to be formed, the atomic ratio In / (In + Zn) of indium in the entire vapor deposition material is approximately 0.45.
It is preferable to set to 0.9.

Similarly, when the transparent conductive film is formed by the method IIA, the atomic ratio of the total amount of halogen in the entire vapor deposition material (total halogen) / (In + Zn + total third metal element)
There may be a slight deviation between the atomic ratio (total halogen) / (In + Zn + total third metal element) of the total amount of halogen in the formed transparent conductive film. Therefore,
The atomic ratio (total halogen) / (In + Zn + total third metal element) of the total amount of halogen in the entire vapor deposition material is appropriately adjusted so that a target transparent conductive film can be obtained. Atomic ratio of total halogen (total halogen) / (In
+ Zn + total third metal element) is 0.3 or less, the vapor deposition material is a vapor deposition material. 3 metal elements) is approximately 0.35
It is preferable to use the following.

In addition to indium (In), zinc (Zn), oxygen (O), and at least one halogen, a transparent conductive material containing at least one third metal element having a positive trivalence or more as a constituent element. When the film is formed by Method IIA, an evaporation material containing a desired third metal element in addition to indium (In), zinc (Zn) and at least one halogen is used.

Here, the term "vapor deposition material containing a third metal element" as used in Method IIA means that in the case of unitary ion plating, the vapor deposition material contains at least one third metal element as a constituent element. In the case of multi-dimensional ion plating, at least one of all vapor deposition materials is used. , At least one third metal element as a constituent element, or at least one third metal
It is meant to include a substance whose constituent element is a metal element.

Specific examples of the third metal element include tin (Sn), aluminum (Al), antimony (S) as described in the description of the transparent conductive film of the present invention.
b), gallium (Ga), titanium (Ti), silicon (S
i), zirconium (Zr), germanium (Ge),
Vanadium (V), tungsten (W), lanthanum (L
a) and ruthenium (Ru). These third
Among the metal elements, tin (Sn) is particularly preferable as described above, and thus tin (Sn) is particularly preferable as the third metal element contained in the vapor deposition material.

The above-mentioned third metal element may be contained in one vapor deposition material in the state of a simple substance, an oxide, a halide (fluoride, chloride, bromide, iodide, etc .; the same applies hereinafter). Alternatively, it may be contained in one vapor deposition material in a solid solution with another substance. In the case of multi-source ion plating, one of all vapor deposition materials,
A simple substance, oxide, halide or the like of the above-mentioned third metal element, indium oxide or indium halide in which the third metal element is in solid solution, zinc oxide or halogen in which the third metal element is in solid solution. Zinc oxide, an alloy of the third metal element and indium and / or zinc, or the like can be used.

The atomic ratio (total third metal element) / (In + Zn + total third metal element) of the total amount of the third metal element in the entire vapor deposition material is appropriately adjusted so as to obtain a target transparent conductive film. The atomic ratio (total third metal element) / (In + Zn + total third metal element) of the total amount of the third metal element in the transparent conductive film is preferably 0.2 or less, and 0.1 or less, as described above. More preferably.

In the method IIA, when the vapor deposition material contains oxygen (O), a film forming gas composed of an inert gas such as argon gas or a film composed of a mixed gas of an inert gas and an oxygen gas. Use gas. When the vapor deposition material does not contain oxygen (O), a film forming gas containing oxygen gas or a film forming gas containing a mixed gas of an inert gas and oxygen gas is used. Whether or not the film forming gas containing oxygen gas is used and the amount of oxygen gas used (introduced amount) when the film forming gas containing oxygen gas is used are determined by the composition of the vapor deposition material and the target transparent conductivity. It is appropriately determined in consideration of the composition of the film, film forming conditions, and the like depending on whether or not composition compensation for oxygen (O) is necessary.

The "deposition material containing oxygen (O)" referred to in Method IIA means, in the case of unitary ion plating, does the deposition material consist of a substance containing oxygen (O) as a constituent element? , Or a substance containing oxygen (O) as a constituent element, and in the case of multi-source ion plating, at least one of all vapor deposition materials contains oxygen (O) as a constituent element. Or a substance containing oxygen (O) as a constituent element. Specific examples of film forming conditions in Method IIA will be described later.

Next, the method IIB will be described. Method II
As described above, B is a method for forming a target transparent conductive film by an ion plating method using a vapor deposition material containing no halogen and a film forming gas containing at least one kind of halogen. is there. The vapor deposition material used at this time may be one capable of forming a transparent conductive film made of an amorphous oxide having an indium atomic ratio In / (In + Zn) of a desired value. Further, although the ion plating may be multi-elements of two or more elements, the single-element ion plating is preferable because it is easy to optimize the composition of the film forming gas, and it is easy to obtain a uniform and large-area film. .

Also in the method IIB, when the target transparent conductive film is formed by unitary ion plating, a sintered body, granules, a press-molded product or the like can be used as the vapor deposition material. Examples of the vapor deposition material include indium metal, zinc metal, indium-zinc alloy, indium oxide, zinc oxide and In ₂ O ₃ (ZnO) _m (m
= 2 to 20), a single substance selected from the above, a mixture of these substances, or the like, and a substance containing indium and zinc can be used. Specific examples of the above vapor deposition material are not particularly limited, but the following (60)
~ (63).

(60) A mixture of indium oxide and zinc oxide. (61) A compound comprising at least one kind of hexagonal layered compound represented by In ₂ O ₃ (ZnO) _m (m = 2 to 20). (62) One or more hexagonal layered compounds represented by In ₂ O ₃ (ZnO) _m (m = 2 to 20) and indium oxide and /
Or consisting of a mixture with zinc oxide. (63) Made of an alloy of indium and zinc.

Also in Method IIB, the atomic ratio In / (In + Zn) of indium in the entire vapor deposition material and indium atom in the formed transparent conductive film are the same as in the case of forming the transparent conductive film by Method IIA described above. Ratio In
A slight deviation may occur between / (In + Zn). Therefore, the atomic ratio In / (In + Zn) of indium in the entire vapor deposition material is appropriately adjusted so as to obtain the target transparent conductive film, as in the method IIA described above. For example, when a transparent conductive film having an indium atomic ratio In / (In + Zn) of 0.55 to 0.9 is to be formed by the method IIB, the indium atomic ratio In / (In + Zn) in the entire evaporation material is Is preferably 0.45 to 0.9.

Further, indium (In), zinc (Z
n), oxygen (O), and at least one kind of halogen, in addition to the method IIB, a transparent conductive film having at least one kind of third metal element having a positive trivalence or more as a constituent element is formed. Is indium (In) and zinc (Z
In addition to n), a vapor deposition material containing a desired third metal element is used. Here, “the vapor deposition material containing a third metal element” in the method IIB means “the third vapor element containing the third metal element” in the above-mentioned method IIA, except that the vapor deposition material does not contain halogen.
It is the same as the “deposition material containing a metal element”. The atomic ratio (third metal element) / (In + Zn + total third metal element) of the total amount of the third metal element in the entire vapor deposition material is appropriately set in the same manner as in the above-mentioned Method IIA so that the target transparent conductive film can be obtained. adjust.

In Method IIB, when the vapor deposition material contains oxygen (O), a deposition gas in which at least one halogen source is used in combination with an inert gas such as argon gas, or In addition to a mixed gas of an inert gas and an oxygen gas, a film forming gas in which at least one halogen source is used in combination is used. In addition, when the vapor deposition material does not contain oxygen (O), in addition to oxygen gas, a deposition gas in which at least a halogen source of at least one species is used together or a mixed gas of an inert gas and oxygen gas is used. A film forming gas containing at least one halogen source is used.

Specific examples of the above-mentioned halogen source include the same ones as exemplified in the explanation of the method IB. As the halogen which is a constituent element of the transparent conductive film, fluorine is particularly preferable as described in the description of the transparent conductive film of the present invention.
It is preferable to use fluorine gas (F ₂ ) or fluorides such as hydrogen fluoride (HF), carbon fluoride (CF ₄ ), nitrogen fluoride (NF ₃ ), and silicon fluoride (SiF ₄ ).

The amount (introduction amount) of the halogen source used is the characteristics of each ion plating apparatus, the film forming conditions, the composition of the entire vapor deposition material, the kind of gas serving as the halogen source, and the halogen content in the target transparent conductive film. It is appropriately adjusted according to the atomic ratio (total halogen) / (In + Zn + total third metal element) of the total amount. For this adjustment, as described in the explanation of the method IB, the ratio of the volume of the halogen gas equivalent to the volume of the film forming gas (volume of the halogen molecule equivalent) / (volume of the film forming gas) is appropriately selected. It can be done by
The atomic ratio (total halogen) / (In + Zn + total third metal element) of the total amount of halogen in the transparent conductive film is preferably 0.3 or less, and more preferably 0.2 or less as described above. preferable.

Also in Method IIB, as in the case of Method IIA described above, the necessity of using the film forming gas containing oxygen gas and the use of oxygen gas when the film forming gas containing oxygen gas is used. The amount (introduced amount) is appropriately determined in consideration of the composition of the sputtering target, the composition of the target transparent conductive film, the film forming conditions, and the like depending on whether or not composition compensation for oxygen (O) is necessary. It Specific examples of film forming conditions in Method IIB will be described later.

Next, the method IIC of the present invention will be described. Method IIC is, as described above, a target transparent conductive film by an ion plating method using a vapor deposition material containing at least one halogen and a film forming gas containing at least one halogen. This is a method of forming a film.

The atomic ratio (total halogen) / (In + Zn + total third metal element) of the total amount of halogen in the vapor deposition material used in Method IIC is lower than the value in Method IIA because the film-forming gas contains halogen. May be. Similarly, the amount of halogen source used (introduced amount) in the film-forming gas used in Method IIC may be lower than that in Method IIB because the vapor deposition material contains halogen. Except for these points, the vapor deposition material used in Method IIC is Method IIA.
The vapor deposition material used in Step IIC can be applied, and the film-forming gas used in Method IIC can be applied to the film-forming gas used in Method IIB. Therefore, the description thereof is omitted here. Specific examples of film forming conditions in Method IIC will be described later.

Method IIA, Method IIB and Method II described above
Whatever method C is used to form the transparent conductive film, the purity of the vapor deposition material is preferably 98% or more. If it is less than 98%, the moisture and heat resistance of the obtained film may decrease, the conductivity may decrease, or the light transmittance may decrease due to the presence of impurities. More preferable purity is 9
It is 9% or more, and more preferably 99.9% or more.

Further, Method IIA, Method IIB and Method IIC
In any of the above methods, the film forming conditions such as the degree of vacuum, the applied power, the substrate temperature, etc. are variously changed depending on the method of ion plating and the characteristics of the apparatus used, etc. However, for example, in the case of the RF ion plating method, it can be set as follows.

(I) Vacuum Degree, Applied Power The vacuum degree at the time of ion plating is not particularly limited as long as it is a vacuum degree capable of forming a film, and is generally 1 × 10.
^{It is −2} to 1 × 10 ¹ Pa. Further, the applied voltage is not particularly limited as long as it is an applied voltage capable of forming a film, and is generally several tens to several thousands V.

(Ii) Substrate Temperature The substrate temperature is not particularly limited, and may be a general substrate temperature, that is, between −50 ° C. and the heat resistant temperature of the substrate, but a transparent resin substrate, particularly a transparent resin film is used as the substrate. In this case, the temperature is preferably -50 to 50 ° C in order to prevent the transparent resin film after film formation from being warped.

The substrate on which the transparent conductive film is formed by the method IIA, the method IIB, or the method IIC as described above can be appropriately selected according to the intended use of the transparent conductive film. The same ones as exemplified in the description of the above-mentioned method I (method IA, method IB and method IC) can be mentioned.

When the transparent conductive film is formed on the transparent resin substrate, the transparent resin is formed on the transparent resin substrate by the method I described above. A crosslinkable resin layer may be previously provided on the surface of the substrate on which the transparent conductive film is provided, and an adhesive layer or a gas barrier layer may be interposed between the transparent resin substrate and the crosslinkable resin layer. Good.

The method II of the present invention described above (method IIA,
According to the method IIB and the method IIC), the above-mentioned characteristics,
That is, even when a film is formed at a substrate temperature of, for example, room temperature, the specific resistance when the film thickness is 150 nm is about 3 × 10 ^−4.
High conductivity of Ω · cm or less and a wavelength of 55
It is possible to obtain the transparent conductive film of the present invention having a high light transmittance of about 95% or more for a thickness of 150 nm with respect to 0 nm light.

Next, the transparent conductive laminate of the present invention will be described. The transparent conductive laminate of the present invention, as described above,
It is characterized in that it has an electrically insulating transparent substrate and a transparent conductive film formed on this transparent substrate, and that the transparent conductive film is the transparent conductive film of the present invention described above.

Specific examples of the electrically insulating transparent substrate that constitutes this transparent conductive laminate are a glass substrate, a ceramic substrate, a thermoplastic resin substrate, a thermosetting resin substrate, an amorphous substrate, a color filter, and a thin film solar cell. A battery etc. are mentioned. What kind of transparent substrate is used is appropriately selected according to the intended use of the transparent conductive laminate and the method for forming a transparent conductive film which is another component of the transparent conductive laminate.

When a light-weight liquid crystal display panel is to be obtained by using the transparent conductive film forming the transparent conductive laminate of the present invention as a transparent electrode, the transparent substrate may be polycarbonate resin, polyarylate resin, It is preferable to use a film or sheet made of a transparent resin such as a polyester resin, a polyether sulfone resin, an amorphous polyolefin resin, a polystyrene resin, or an acrylic resin. Above all, from the viewpoint of transparency and thermal stability, polycarbonate resin or poly It is preferable to use a resin made of an arylate resin.

The transparent conductive laminate of the present invention can be obtained by forming the above-mentioned transparent conductive film of the present invention on the above-mentioned transparent substrate. The method for forming the transparent conductive film is not particularly limited, but it is preferable to form the transparent conductive film by the above-mentioned method I or method II of the present invention. When the above-mentioned transparent conductive film is formed on the transparent resin substrate, as described in the description of each of the method I and the method II of the present invention,
A crosslinkable resin layer may be preliminarily provided on the surface of the transparent resin substrate on which the transparent conductive film is provided, and an adhesive layer or a gas barrier layer may be interposed between the transparent resin substrate and the crosslinkable resin layer. May be.

The film thickness of the transparent conductive film can be appropriately selected within the range of about 20 to 300 nm depending on the intended use of the transparent conductive laminate. In addition, the transparent conductive film is formed into a desired shape such as a flat film shape or a parallel stripe pattern according to the intended use of the transparent conductive laminate. The transparent conductive film may be formed by using a mask having a predetermined shape at the time of film formation, or may be formed by a photolithography method after once forming a flat film.

The transparent conductive layered product of the present invention which can be obtained as described above has high conductivity and high light since the transparent conductive film forming the same is the transparent conductive film of the present invention described above. Has transparency. The transparent conductive laminate of the present invention having such characteristics is suitable as a constituent member of a liquid crystal display panel or a material thereof, a constituent member of an electroluminescence panel or a material thereof, and the like. And
When the transparent conductive laminate of the present invention is used as a constituent member of a liquid crystal display panel or a material thereof, the liquid crystal display device can be reduced in weight and its area can be increased, its definition can be improved, its driving power can be reduced, and its contrast can be increased. And so on.

When the transparent conductive film is formed by the above-mentioned method I or method II of the present invention for obtaining the transparent conductive laminate of the present invention, the substrate temperature during film formation is low (for example, room temperature). Even so, it is possible to obtain a transparent conductive laminate having desired conductivity and light transmittance. As a result, even when a transparent resin film is used as the transparent substrate, it is possible to suppress warpage of the transparent resin film after film formation, and obtain the target transparent conductive laminate with a high yield. It will be possible.

[0113]

Embodiments of the present invention will be described below. Example 1 A 100 μm thick polycarbonate film (hereinafter abbreviated as “PC film”) was used as a transparent resin substrate, and as shown in Table 1, two zinc fluorides (ZnF ₂ ) were used.
Tablet (10 mm diameter) and 4 zinc oxide (Zn
O) A tablet (diameter 10 mm) and a indium oxide (In ₂ O ₃ ) sintered body (purity 99.9% or more, relative density 90%) arranged on a disk having a diameter of 4 inches are used as a sputtering target. A transparent conductive laminate was prepared using the following procedure.

First, the PC film was attached to the RF magnetron sputtering apparatus, and the inside of the vacuum chamber was set to 2 × 1.
The pressure was reduced to 0 ^-4 Pa. Then, argon gas (purity 99.99%) as a film forming gas was introduced into the vacuum chamber so that the vacuum pressure was 0.2 Pa, and sputtering was performed under the conditions of a target applied voltage of 50 W and a substrate temperature of room temperature. A transparent conductive film was formed on the PC film. As a result, a transparent conductive laminate was obtained.

When the crystallinity of the above transparent conductive film was determined by X-ray diffraction measurement, it was amorphous. The measurement result at this time is shown in FIG. Further, the atomic ratio In / (In + Zn) of indium and the atomic ratio (total halogen) / (In + Zn + all third metal element) of the total amount of halogen in this transparent conductive film (however, in the present embodiment, all third metal element = 0). And the film thickness of the transparent conductive film, the specific resistance, and the transmittance of light having a wavelength of 550 nm. Table 2 shows the results.

As for the atomic ratio of indium and the atomic ratio of the total amount of halogen (only fluorine in this embodiment), the composition of the transparent conductive film was determined by XPS (X-ray photoelectron spectroscopy analysis).
Was calculated by using the above formula.
The film thickness of the transparent conductive film was measured by the stylus method, and the specific resistance was determined by multiplying the surface resistance measured by the four-point probe method by the film thickness. Then, the light transmittance was obtained by spectroscopic measurement (using model: UV-3100S manufactured by Shimadzu Corporation) using a PC film as a reference.

Further, a sample having a size of 6 × 6 cm in plan view was cut out from the above transparent conductive laminate, and the sample was aged for 24 hours in an environment of temperature 25 ° C. and humidity 35%, and then the degree of warpage Was calculated as follows. In other words, place the cured sample on a horizontal table, measure the height of the gap between the center of the sample in plan view and the table surface using a caliper, and measure this value as the degree of warpage. did. At this time, the cured sample was placed on the above-mentioned table so that the central portion in plan view was convex upward. The results are also shown in Table 2.

Example 2 As shown in Table 1, two zinc chloride (ZnCl ₂ ) tablets (diameter 10 mm) and four zinc oxide (ZnO)
Tablet (diameter 10 mm) and indium oxide (In
₂ O ₃ ) sintered body (purity 99.9% or more, relative density 90
%), Which was placed on a disc having a diameter of 4 inches, was used as a sputtering target to form a transparent conductive film on a PC film in the same manner as in Example 1.
This obtained the transparent conductive laminated body. Regarding the above transparent conductive film, the same items as those obtained in Example 1 were obtained in the same manner as in Example 1. Further, in the same manner as in Example 1, the degree of warpage of the above transparent conductive laminate was determined. Table 2 shows the results.

Example 3 Indium oxide (In ₂ O ₃ ), zinc oxide (ZnO) and zinc fluoride (ZnF ₂ ) were used as raw materials, and a sintered body target (diameter 4 inches) having the composition shown in Table 1 was used. Got Then, a 100 μm thick PC film was used as the transparent resin substrate, and the above-mentioned sintered body target was used as the sputtering target to prepare a transparent conductive laminate in the following manner. First, the PC film was attached to the DC magnetron sputtering device, and the inside of the vacuum chamber was set to 2 × 10.
^The pressure was reduced to ^-4 Pa. After this, argon gas (purity 9
9.99%) and oxygen gas (purity 99.99%) mixed gas (Ar: O ₂ = 97: 3 (volume ratio)) is used as a film forming gas, and the film forming gas has a vacuum pressure of 0. It was introduced into the vacuum chamber so that the pressure was 2 Pa, and the target applied voltage was 7
Sputtering is performed under the conditions of 5 W and substrate temperature of room temperature,
A transparent conductive film was formed on the PC film. This allows
A transparent conductive laminate was obtained. Regarding the above transparent conductive film, the same items as those obtained in Example 1 were obtained in the same manner as in Example 1. Further, in the same manner as in Example 1, the degree of warpage of the above transparent conductive laminate was determined. Table 2 shows the results.

Example 4 Using indium, zinc and tin as the third metal element, an alloy target (diameter 4 inches) having the composition shown in Table 1 was prepared. Then, using this alloy target as a sputtering target, argon gas (purity 99.9
9%), oxygen gas (purity 99.99%), and fluorine gas (purity 99.99%) as a halogen source (purity 99.99%) mixed gas (Ar: O ₂ : F ₂ = 70: 28.5: 1.5 ( (Volume ratio)) was used as the film forming gas, and a transparent conductive film was formed on the PC film in the same manner as in Example 3 except that the target applied voltage was 50 W, whereby a transparent conductive laminate was obtained. . Regarding the above transparent conductive film, the same items as those obtained in Example 1 were obtained in the same manner as in Example 1. Further, in the same manner as in Example 1, the degree of warpage of the above transparent conductive laminate was determined. Table 2 shows the results.

Comparative Example 1 As shown in Table 1, a total of 6 zinc oxide (ZnO) tablets (diameter 10 mm) were used without using zinc fluoride tablets.
Is a sintered body of indium oxide (In ₂ O ₃ ) (purity 99.9).
% Or more, relative density of 90%) and a transparent conductive film was formed on a PC film in the same manner as in Example 1 except that a disk having a diameter of 4 inches was used as a sputtering target. A conductive laminate was obtained. The transparent conductive film is a transparent conductive film outside the scope of the present invention in that halogen is not a constituent element. Regarding the above transparent conductive film, the same items as those obtained in Example 1 were obtained in the same manner as in Example 1. In addition, Example 1
Similarly to the above, the degree of warpage of the above transparent conductive laminate was determined. Table 2 shows the results.

Comparative Example 2 As shown in Table 1, a sputtering target having the same composition as that used in Example 4 was used, and argon gas (purity 99.99%) and oxygen gas (purity 9) were used as film forming gases.
Mixed gas (Ar: O ₂ = 70: 30)
PC in the same manner as in Example 4 except that (volume ratio) was used.
A transparent conductive film was formed on the film to obtain a transparent conductive laminate. The transparent conductive film is a transparent conductive film outside the scope of the present invention in that halogen is not a constituent element. Regarding the above transparent conductive film, the same items as those obtained in Example 1 were obtained in the same manner as in Example 1. Also,
In the same manner as in Example 1, the degree of warpage of the above transparent conductive laminate was determined. Table 2 shows the results.

Comparative Example 3 P was prepared in the same manner as in Comparative Example 2 except that the substrate temperature was 80 ° C.
A transparent conductive film was formed on the C film to obtain a transparent conductive laminate. The transparent conductive film is a transparent conductive film outside the scope of the present invention in that halogen is not a constituent element. Regarding the above transparent conductive film, the same items as those obtained in Example 1 were obtained in the same manner as in Example 1. Further, in the same manner as in Example 1, the degree of warpage of the above transparent conductive laminate was determined. Table 2 shows the results.

Comparative Example 4 As shown in Table 1, indium (In) and zinc (Zn)
Using a sintered body target (sintered body target composed of a hexagonal layered compound represented by In ₂ O ₃ (ZnO) ₄ and indium oxide) containing as a constituent element oxygen and oxygen (O) as a sputtering target And a mixed gas (Ar: O ₂ = 100) of argon gas (purity 99.99%) and oxygen gas (purity 99.99%) as a film forming gas.
0: 2.8 (volume ratio)) was used. Then, after depressurizing the inside of the vacuum chamber to 5 × 10 ⁻⁴ Pa, the film forming gas is introduced into the vacuum chamber so that the vacuum pressure becomes 0.3 Pa, the target applied power is 100 W, and the substrate temperature is 20.
Perform RF magnetron sputtering under the condition of ℃,
A transparent conductive film was formed on the PC film. This allows
A transparent conductive laminate was obtained. The transparent conductive film is a transparent conductive film outside the scope of the present invention in that halogen is not a constituent element. Regarding the above transparent conductive film,
The same items as those obtained in Example 1 were obtained in the same manner as in Example 1. Further, in the same manner as in Example 1, the degree of warpage of the above transparent conductive laminate was determined. Table 2 shows the results.

[0125]

[Table 1]

[0126]

[Table 2]

As shown in Table 2, Examples 1 to 4
Each of the transparent conductive films formed in 1. had a specific resistance of 2.9 × 10 ^{−4 to} 3.1 × 10 ⁻ when the film thickness was around 150 nm, even though the transparent conductive film was formed at a substrate temperature of room temperature. ^It is as low as ⁴ Ωcm and has excellent conductivity. And Example 1-Example 4
The transmittance of light having a wavelength of 550 nm in each of the transparent conductive films formed in 1. is 94.3 to 95.7%, and these transparent conductive films have excellent light transmittance. Furthermore, Example 1
-Temperature of each transparent conductive laminate produced in Example 4 was 25 ° C,
The degree of warpage that occurs when cured for 24 hours in an environment with a humidity of 35% is 4.4 to 4.6 mm, and in these transparent conductive laminates, the substrate temperature is 120 ° C. to form a transparent conductive film. Warpage is less likely to occur than in the transparent conductive laminate of Comparative Example 3.

On the other hand, Comparative Examples 1, 2 and 4 each made of an amorphous oxide containing no halogen as a constituent element.
Each of the transparent conductive films of No. 1 has a specific resistance of 3.6 × 10 ^{−4 to} 4.2 × 10 ⁻⁴ Ωcm when the film thickness is around 150 nm, and is formed in each of Examples 1 to 4. It is inferior in conductivity to the transparent conductive film. In addition, the transmittance of light having a wavelength of 550 nm in each of the transparent conductive films of Comparative Examples 1, 2 and 4 is 90.1 to 90.8%, and these transparent conductive films are used in Examples 1 to 1 The light transmittance is inferior to that of each transparent conductive film formed in 4. Although the transparent conductive film formed in Comparative Example 3 is superior in conductivity to each transparent conductive film formed in Examples 1 to 4, its light transmittance is shown in Examples 1 to 4 It is inferior to each transparent conductive film formed in. In addition, as described above, the transparent conductive laminate manufactured in Comparative Example 3 is more likely to be warped than the transparent conductive laminates manufactured in Examples 1 to 4.

Example 5 A PC film having a thickness of 100 μm was used as a transparent resin substrate, and zinc oxide (ZnO) powder and indium fluoride (In) were used.
A transparent conductive laminate was prepared in the following manner using 100 pressure-molded products (diameter 10 mm) of mixed powder of F ₃ ) powder and indium oxide (In ₂ O ₃ ) powder as vapor deposition materials. First, the PC film was attached to an RF ion plating apparatus, and the pressure inside the vacuum chamber was reduced to 2 × 10 ⁻⁴ Pa. Then, argon gas (purity 99.99%) as a film forming gas is introduced into the vacuum chamber so that the vacuum pressure is 1 × 10 ^-2, and the ion plating is performed under the conditions of an applied voltage of 1 kV and a substrate temperature of room temperature. Then, a transparent conductive film was formed on the PC film. As a result, a transparent conductive laminate was obtained. Regarding the above transparent conductive film, the same items as those obtained in Example 1 were obtained in the same manner as in Example 1. Further, in the same manner as in Example 1, the degree of warpage of the above transparent conductive laminate was determined. Table 3 shows the results.

Example 6 100 alloys (diameter 10 mm) having the same composition as the alloy target used in Example 4 were used as vapor deposition materials, and oxygen gas (purity 99.99%) and fluorine gas (purity 99.
99%) mixed gas (O ₂ : F ₂ = 98.5: 1.5)
PC in the same manner as in Example 5 except that (volume ratio) was used.
A transparent conductive film was formed on the film to obtain a transparent conductive laminate. Regarding the above transparent conductive film, the same items as those obtained in Example 1 were obtained in the same manner as in Example 1. Further, in the same manner as in Example 1, the degree of warpage of the above transparent conductive laminate was determined. Table 3 shows the results.

[0131]

[Table 3]

As shown in Table 3, each of the transparent conductive films formed in Example 5 and Example 6 had a film thickness of 150 nm even though the film was formed at the substrate temperature of room temperature. Specific resistance is 3.1 × 10 ^-4 Ωcm or 3.0 × 10 ^-4
It has a low Ωcm and excellent conductivity. And Example 5
And a wavelength of 5 in each transparent conductive film formed in Example 6.
The transmittance of 50 nm light is 94.8% or 95.0%, and these transparent conductive films have excellent light transmittance. Furthermore, the degree of warpage that occurs when the transparent conductive laminates produced in Examples 5 and 6 are aged for 24 hours in an environment of a temperature of 25 ° C. and a humidity of 35% is 4.6 mm or 4.4 mm, These transparent conductive laminates are unlikely to cause warpage, like the transparent conductive laminates produced in Examples 1 to 4.

[0133]

As described above, the transparent conductive film of the present invention exhibits excellent conductivity and light transmittance even when formed at a low substrate temperature. Therefore, according to the present invention, for example, a demand for a large area, high definition, low driving power, high contrast, etc., which has been recently demanded for a liquid crystal display device, is met by using a transparent resin substrate as a substrate for transparent electrodes By using it, it becomes possible to realize the liquid crystal display device while reducing its weight.

[Brief description of the drawings]

FIG. 1 is a graph showing the results of X-ray diffraction measurement on a transparent conductive film formed in Example 1.

Claims (16)

[Claims] 1. A transparent conductive film comprising an amorphous oxide containing indium (In), zinc (Zn), oxygen (O) and at least one halogen as essential constituent elements. 2. Indium atomic ratio In / (In + Z
The transparent conductive film according to claim 1, wherein n) is 0.55 to 0.9. 3. Indium (In), zinc (Zn), oxygen (O), and at least one halogen, in addition to at least one third metal element having a positive trivalence or more, as a constituent element, The transparent conductive film according to claim 1 or 2, wherein the atomic ratio (total third metal element) / (In + Zn + total third metal element) of the total amount of the third metal element is 0.2 or less. 4. Atomic ratio of total amount of halogen (total halogen)
The transparent conductive film according to any one of claims 1 to 3, wherein / (In + Zn + all third metal elements) is 0.3 or less. 5. The transparent conductive film according to claim 1, wherein the halogen is fluorine. 6. Indium (In), zinc (Zn), oxygen (O) by a sputtering method using a sputtering target containing at least one kind of halogen or a film forming gas containing at least one kind of halogen. And a method for producing a transparent conductive film, which comprises forming a transparent conductive film made of an amorphous oxide containing at least one kind of halogen as an essential constituent element. 7. Indium atomic ratio In / (In + Z
The method according to claim 6, wherein a transparent conductive film made of an amorphous oxide having n of 0.55 to 0.9 is formed. 8. An indium (In), zinc (Zn), oxygen (O), at least one kind using a sputtering target containing at least one kind of third metal element having a valence of positive trivalence or more. Of the halogen and the third metal element as constituent elements, and the atomic ratio of the total amount of the third metal element (total third metal element) / (In + Zn + total third metal element)
The method according to claim 6 or 7, wherein a transparent conductive film made of an amorphous oxide having a value of 0.2 or less is formed. 9. Atomic ratio of total amount of halogen (total halogen)
9. The method according to claim 6, wherein a transparent conductive film made of an amorphous oxide having a ratio of / (In + Zn + all third metal elements) of 0.3 or less is formed. 10. The method according to claim 6, wherein the halogen is fluorine.
The method according to claim 9. 11. An ion plating method using a vapor deposition material containing at least one halogen or a film-forming gas containing at least one halogen,
Manufacture of a transparent conductive film characterized by forming a transparent conductive film made of an amorphous oxide containing indium (In), zinc (Zn), oxygen (O) and at least one kind of halogen as essential constituent elements. Method. 12. Indium atomic ratio In / (In + Z
The method according to claim 11, wherein a transparent conductive film made of an amorphous oxide having n of 0.55 to 0.9 is formed. 13. A valence of at least 1 having a positive valence of 3 or more.
Using a vapor deposition material containing a third metal element of a species, indium (In), zinc (Zn), oxygen (O), at least one halogen and the third metal element as constituent elements, Atomic ratio of total amount of metallic elements (all third metallic elements)
13. The method according to claim 11 or 12, wherein a transparent conductive film made of an amorphous oxide in which / (In + Zn + all third metal elements) is 0.2 or less is formed. 14. A transparent conductive film made of an amorphous oxide having an atomic ratio (total halogen) / (In + Zn + total third metal element) of the total amount of halogen of 0.3 or less is formed.
The method according to any one of claims 1 to 13. 15. The halogen according to claim 11, wherein the halogen is fluorine.
~ The method according to any one of claims 14 to 15. 16. The transparent conductive film according to claim 1, comprising an electrically insulating transparent substrate and a transparent conductive film formed on the transparent substrate. A transparent electroconductive laminate comprising a film.