JP2003234028A - Transparent conductive film, forming method therefor, and article comprising the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a transparent conductive film, a method for forming the same, and an article comprising the same of high safety, excellent productivity, good optical and electric characteristics, and excellent threshold curvature radius on a plastic film base. <P>SOLUTION: An reactive gas is guided into a discharge space to form a plasma state under an atmospheric pressure or near it. By making the base to be exposed to the reactive gas in a plasma state, the transparent conductive film is formed on the base. The reactive gas contains reducing gas. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid crystal display device, an organic electroluminescence device (hereinafter referred to as an organic EL device), a plasma display panel (hereinafter referred to as PDP).
Abbreviated), a method for forming a transparent conductive film, which is preferably used for various electronic elements such as electronic papers, touch panels, and solar cells, and an article having the transparent conductive film.

[0002]

2. Description of the Related Art Conventionally, a transparent conductive film has been used for a liquid crystal display element,
Widely used in organic EL devices, solar cells, touch panels, electromagnetic wave shielding materials, infrared reflective films, and the like. As the transparent conductive film, a metal thin film of Pt, Au, Ag, Cu or the like, Sn
O ₂ , In ₂ O ₃ , CdO, ZnO ₂ , SnO ₂ : Sb, S
There are oxides such as nO ₂ : F, ZnO: AL, and In ₂ O ₃ : Sn, and complex oxide films made of dopants, chalcogenides, and non-oxides such as LaB ₆ , TiN, and TiC. Among them, the tin-doped indium oxide film (hereinafter referred to as ITO) is most widely used because of its excellent electric characteristics and ease of processing by etching. These are vacuum deposition method, sputtering method, ion plating method, vacuum plasma CVD method, spray pyrolysis method, and thermal CV.
It is formed by the D method, the sol-gel method, or the like.

In recent years, flat panel displays such as liquid crystal display elements and organic EL elements have been made larger in area and higher in definition, and a higher performance transparent conductive film is required. In a liquid crystal element, use of a transparent conductive film having high electron mobility is required in order to obtain an element or device having high electric field response. Further, in the organic EL element, a transparent conductive film having a lower resistance is required in order to adopt the current driving method.

Among the methods for forming the transparent conductive film, the vacuum deposition method and the sputtering method can obtain a transparent conductive film having a low resistance. Industrially, by using a DC magnetron sputtering device, an ITO film having an excellent conductivity of a specific resistance value of 10 ⁻⁴ Ω · cm can be obtained.

However, these physical manufacturing methods (P
In the VD method), a target substance is deposited on a substrate in a gas phase to grow a film, and a vacuum container is used. Therefore, the equipment is large and expensive, and the use efficiency of raw materials is poor, resulting in low productivity. In addition, it was difficult to form a large area film. Furthermore, in order to obtain a low resistance product, 200-300 ° C during film formation
Therefore, it is difficult to form a transparent conductive film having low resistance on a plastic film.

The sol-gel method (coating method) is dispersion preparation, coating,
Not only many processes such as drying are required, but also because the adhesiveness to the substrate to be treated is low, a binder resin is required and the transparency is deteriorated. Also, the electrical characteristics of the obtained transparent conductive film are inferior to those of the PVD method.

In the thermal CVD method, a film is formed by applying a precursor of a target substance to a base material by a spin coating method, a dip coating method, a printing method, etc. and firing (pyrolysis) this. It has the advantages that the device is simple, it has excellent productivity, and it is easy to form a large-area film.
There is a problem that the base material is limited because a high temperature treatment of 0 ° C. to 500 ° C. is required. In particular, it is difficult to form a film on a plastic film substrate.

As a method for overcoming the above-mentioned demerit of a highly functional thin film by the sol-gel method (coating method) and the demerit of low productivity by using a vacuum apparatus, the method is performed under atmospheric pressure or a pressure near atmospheric pressure. A method (hereinafter, referred to as atmospheric pressure plasma CVD method) of discharging and exciting plasma of a reactive gas to form a thin film on a substrate has been proposed. Japanese Unexamined Patent Application Publication No. 2000-303175 discloses a technique of forming a transparent conductive film by an atmospheric pressure plasma CVD method. However, the resistance of the obtained transparent conductive film is as high as a specific resistance value of -10 ^-2 Ω · cm, and the specific resistance value is 1 × 10 ^-3.
A liquid crystal element that requires excellent electrical characteristics of Ω · cm or less,
It is insufficient as a transparent conductive film for flat panel displays such as organic EL devices, PDPs, electronic papers and the like. Furthermore, triethylindium is used as a CVD raw material,
This compound also has a safety problem such as a risk of ignition and explosion in the atmosphere at room temperature.

[0009]

DISCLOSURE OF THE INVENTION As a result of various studies, the present inventors formed a transparent conductive film by an atmospheric pressure plasma CVD method using a reducing reactive gas, so that a transparent film having good optical and electrical characteristics can be obtained. It was found that a conductive film can be obtained with high productivity.

An object of the present invention is to provide a method for forming a transparent conductive film having high safety, excellent productivity, good optical and electrical characteristics, and an excellent limiting radius of curvature on a plastic film substrate. It is to provide a formed transparent conductive film and an article having the transparent conductive film.

[0011]

The above objects of the present invention have been achieved by the following constitutions.

1. At or near atmospheric pressure,
A transparent conductive film forming method of forming a transparent conductive film on the base material by exposing the base material to the plasma-state reactive gas by introducing a reactive gas into a discharge space to form a plasma state, A method for forming a transparent conductive film, wherein the gas contains a reducing gas.

2. The method for forming a transparent conductive film as described in the item 1, wherein the reducing gas is hydrogen.

3. 3. The transparent conductive film forming method as described in 1 or 2 above, wherein the reactive gas contains at least one material gas selected from organic metal compounds.

4. The mixed gas containing the reactive gas and an inert gas is introduced into the discharge space, and the inert gas contains argon or helium. The method for forming a transparent conductive film.

5. 5. The method for forming a transparent conductive film as described in the above item 4, wherein the amount of the reducing gas with respect to the mixed gas is in the range of 0.0001 to 5.0% by volume.

6. The mixed gas introduced into the discharge space,
6. The transparent conductive film forming method as described in 4 or 5 above, which contains substantially no oxygen.

7. The electric field applied to the discharge space has a frequency of 0.5 kHz or more and an output density of 100.
It is W / cm < ² > or less, The transparent conductive film formation method in any one of said 1-4 characterized by the above-mentioned.

8. The electric field applied to the discharge space exceeds a frequency of 100 kHz, and the power density is 1 W /
8. The method for forming a transparent conductive film as described in 7 above, wherein the method is cm ² or more.

9. 9. The method for forming a transparent conductive film according to any one of items 1 to 8, wherein the surface temperature of the base material on which the transparent conductive film is formed is 300 ° C. or lower.

10. A transparent conductive film formed by the method for forming a transparent conductive film according to any one of items 1 to 9 above.

11. The specific resistance value of the transparent conductive film is 1 × 1
11. The transparent conductive film as described in 10 above, which is 0 ⁻³ Ω · cm or less.

12. 12. The transparent conductive film as described in 10 or 11 above, wherein the carrier mobility of the transparent conductive film is 10 cm ² / V · sec or more.

13. The carrier density of the transparent conductive film is 1
× 10 ¹⁹ cm ⁻³ or more, the above 10
Item 13. The transparent conductive film according to any one of items 12.

14. The carrier density of the transparent conductive film is 1
× 10 ²⁰ cm ^-3 or more, the above 10
Item 13. The transparent conductive film according to any one of items 13.

15. The transparent conductive film is indium oxide,
Any one of tin oxide, zinc oxide, F-doped tin oxide, Al-doped zinc oxide, Sb-doped tin oxide, ITO, and In ₂ O ₃ —ZnO-based amorphous transparent conductive film is used as a main component. Item 15. The transparent conductive film according to any one of items 10 to 14.

16. The transparent conductive film is an ITO film, and the ITO film has an In / Sn atomic ratio of 100/0.
The above 1 characterized in that it is in the range of 1 to 100/15
Item 5. The transparent conductive film according to item 5.

17. The carbon content of the transparent conductive film is 0 to
The above 1 characterized by being in the range of 5.0 atomic number concentration
The transparent conductive film according to item 5 or 16.

18. In an article having a transparent conductive film on a substrate, the specific resistance value of the transparent conductive film is 1 × 10 ⁻³ Ω · c
An article characterized by being m or less.

19. Item 19. The article according to Item 18, wherein the carrier mobility of the transparent conductive film is 10 cm ² / V · sec or more.

20. The carrier density of the transparent conductive film is 1
An article according to the 18 or 19 wherein, characterized in that at × 10 ¹⁹ cm ^-3 or more.

21. The carrier density of the transparent conductive film is 1
× 10 ²⁰ cm ^-3 or more, the above 18 ~
Item 20. The article according to any one of item 20.

22. The transparent conductive film is indium oxide,
Any one of tin oxide, zinc oxide, F-doped tin oxide, Al-doped zinc oxide, Sb-doped tin oxide, ITO, and In ₂ O ₃ —ZnO-based amorphous transparent conductive film is used as a main component. The article according to any one of items 18 to 21.

23. Item 23. The article according to Item 22, wherein the ITO film has an In / Sn atomic ratio of 100 / 0.1 to 100/15.

24. The carbon content of the transparent conductive film is 0 to
The above 2 characterized by being in the range of 5.0 atomic number concentration
Item 2 or item 23.

25. 25. The article according to any one of items 22 to 24, wherein the base material is a transparent resin film.

26. Item 26. The article according to Item 25, wherein the transparent resin film is a film substrate for a touch panel, a liquid crystal element plastic substrate, an organic EL element plastic substrate, an electromagnetic shielding film for PDP, or a film substrate for electronic paper.

27. Item 27. The article according to any one of Items 18 to 26, wherein the limit radius of curvature of the transparent conductive film and the transparent conductive film formed on the substrate is 8 mm or less.

28. 28. The article according to any one of items 22 to 27, wherein the transparent conductive film is a patterned electrode.

29. In an article having a transparent conductive film on a substrate, a peak intensity ratio H / H of main metal element ions of hydrogen ions by dynamic SIMS measurement of the transparent conductive film is H /
An article having a transparent conductive film on a base material, wherein the variation of M in the depth direction is a coefficient of variation of 5% or less.

30. The transparent conductive film, under atmospheric pressure or near atmospheric pressure, introduces a reactive gas into the discharge space to form a plasma state, and exposes the base material to the plasma-state reactive gas to form the base material. Item 30. The article according to Item 29, wherein a transparent conductive film is formed on the article.

31. Item 31. The article according to Item 30, wherein the reactive gas contains a reducing gas.

32. The electric field applied to the discharge space exceeds a frequency of 100 kHz and the power density is 1 W.
/ Cm ² or more, the above 30 or 3 characterized in that
An article having a transparent conductive film on the substrate according to item 1.

The present invention will be described in detail below. In the present invention, the transparent conductive film is generally well known as an industrial material, and is visible light (400 to 700).
(nm) is a film that is transparent and has a good conductor. It is used as a transparent electrode or an antistatic film because the transmission characteristics of free charged bodies that carry electricity are high in the visible light range, transparent, and have high electric conductivity.

Although referred to as a "film", it may be formed on the object to be processed to the extent that it has the function depending on the application, and it is not necessarily a continuous film that covers all or part of the object. Absent. As the transparent conductive film, Pt, Au,
Metal thin film such as Ag, Cu, SnO ₂ , In ₂ O ₃ , Cd
_{O, ZnO 2, SnO 2:} Sb, SnO 2: F, ZnO:
AL, In ₂ O ₃ : Sn and other oxides and complex oxide films of dopants, chalcogenides, LaB ₆ , TiN,
There are non-oxides such as TiC.

Next, the atmospheric pressure plasma CVD method which is the method for forming the transparent conductive film of the present invention will be described.

According to the present invention, the reactive gas is introduced into the discharge space into a plasma state under atmospheric pressure or a pressure close to the atmospheric pressure, and the substrate is exposed to the plasma-state reactive gas. The method for forming a transparent conductive film according to claim 1, wherein the reactive gas contains a reducing gas.

In the atmospheric pressure plasma CVD of the present invention,
A high frequency voltage exceeding 0.5 kHz and a power (output density) of 100 W / cm ² or less are supplied between opposing electrodes to excite the reactive gas and generate plasma.

In the present invention, the upper limit of the frequency of the high frequency voltage applied between the electrodes is preferably 150 MHz or less. More preferably, it is 15 MHz or less.

The lower limit of the frequency of the high frequency voltage is preferably 0.5 kHz or more, more preferably 1
It is 0 kHz or more. More preferably, the frequency exceeds 100 KHz.

The lower limit of the power supplied between the electrodes is
It is preferably 0.1 W / cm ² or more, and more preferably 1 W / cm ² or more. The upper limit is preferably 100 W / cm ² or less, more preferably 60 W / c.
m ² or less. The discharge area (cm ² ) refers to the area of the area where discharge occurs in the electrode.

The high-frequency voltage applied between the electrodes may be an intermittent pulse wave or a continuous sine wave, but in order to obtain the effect of the present invention high, a continuous sine wave is required. Preferably it is a wave.

In the present invention, it is necessary to employ an electrode capable of maintaining a uniform glow discharge state by applying such a voltage to a plasma discharge treatment apparatus.

Such an electrode is preferably a metal base material coated with a dielectric. At least one side of the opposing application electrode and the ground electrode is coated with a dielectric material, and more preferably, both of the opposing application electrode and the ground electrode are coated with a dielectric material. The dielectric is preferably an inorganic material having a relative dielectric constant of 6 to 45. As such a dielectric, ceramics such as alumina and silicon nitride, or silicate glass, borate glass, etc. Glass lining materials.

When the substrate is placed between the electrodes or conveyed between the electrodes and exposed to the plasma, not only is the roll electrode specification in which the substrate can be conveyed in contact with one of the electrodes,
Furthermore, the surface of the dielectric is polished to a surface roughness Rma of the electrode.
By setting x (JIS B 0601) to 10 μm or less, the thickness of the dielectric and the gap between the electrodes can be kept constant, the discharge state can be stabilized, and further distortion and cracking due to the difference in thermal contraction and residual stress can be prevented. Durability can be greatly improved by eliminating and coating a highly accurate inorganic dielectric material that is not porous.

Further, in the production of an electrode by coating a metal base material with a dielectric at a high temperature, at least the dielectric on the side in contact with the base material is polished and the thermal expansion between the metal base material and the dielectric of the electrode is prevented. It is necessary to reduce the difference as much as possible, so in the manufacturing method, the amount of bubbles is controlled as a layer that can absorb stress on the surface of the base material to line the inorganic material, especially as the material is enamel etc. The glass obtained by the melting method is preferable, and the amount of bubbles mixed in the lowermost layer in contact with the conductive metal base material is 2
By setting 0 to 30 vol% and 5 vol% or less from the next layer onward, a good electrode that is dense and does not cause cracks or the like can be formed.

As another method for coating the base material of the electrode with the dielectric, thermal spraying of ceramics is performed at a porosity of 10 vol%.
It is to perform up to the following densely, and further to perform a pore-sealing treatment with an inorganic material that is cured by the sol-gel reaction. Here, for the purpose of promoting the sol-gel reaction, heat curing or UV curing is good, and the sealing liquid is further diluted. By repeating coating and curing several times in sequence, the mineralization is further improved and a dense electrode without deterioration can be obtained.

A plasma discharge treatment apparatus using such an electrode will be described with reference to FIGS. The plasma discharge treatment apparatus of FIGS. 1 to 6 discharges between a roll electrode, which is an earth electrode, and a fixed electrode, which is an application electrode arranged at an opposing position, and introduces a reactive gas between the electrodes. To form a thin film by exposing the long film-shaped base material wound around the roll electrode to the plasma-state reactive gas. The device to be used is not limited to this, and any device capable of stably maintaining glow discharge and exciting a reactive gas to form a thin film into a plasma state may be used. As another method, the base material is placed or transported near the electrodes instead of between the electrodes,
There is a jet method in which the generated plasma is blown onto the substrate to form a thin film.

FIG. 1 is a schematic view showing an example of a plasma discharge processing container of a plasma discharge processing apparatus used in the thin film forming method of the present invention.

In FIG. 1, a long film-shaped substrate F is a roll electrode 25 that rotates in the transport direction (clockwise in the figure).
It is transported while being wound around. The fixed electrode 26
Is composed of a plurality of cylinders and is installed so as to face the roll electrode 25. The base material F wound around the roll electrode 25 is
The guide roller 64 is pressed by the nip rollers 65 and 66.
Is conveyed to the discharge processing space regulated by the plasma discharge processing container 31 and secured by the plasma discharge processing container 31, and is subjected to discharge plasma processing
Then, it is conveyed to the next step via the guide roller 67. The partition plate 54 is disposed close to the nip rollers 65 and 66, and suppresses air entrained in the base material F from entering the plasma discharge processing container 31.

This entrained air is preferably suppressed to 1% by volume or less, and more preferably 0.1% by volume or less with respect to the total volume of the gas in the plasma discharge treatment container 31. By the nip rollers 65 and 66,
It is possible to achieve it.

The mixed gas (inert gas, reducing gas which is a reactive gas, and organometallic compound) used for the discharge plasma treatment is introduced into the plasma discharge treatment container 31 through the air supply port 52, and after the treatment. The gas is exhausted from the exhaust port 53.

Similar to FIG. 1, FIG. 2 is a schematic view showing an example of the plasma discharge treatment container installed in the plasma discharge treatment apparatus used in the manufacturing method of the present invention. In FIG. While the fixed electrode 26 facing 25 is a cylindrical electrode, a prismatic electrode 36 is used instead.

Compared with the cylindrical electrode 26 shown in FIG.
The prismatic electrode 36 shown in FIG. 2 has the effect of expanding the discharge range, and is therefore preferably used in the thin film forming method of the present invention.

FIGS. 3A and 3B are schematic views showing an example of the cylindrical roll electrode described above, and FIGS. 4A and 4B.
5A and 5B are schematic diagrams showing an example of electrodes fixed in a cylindrical shape, and FIGS. 5A and 5B are schematic diagrams showing examples of electrodes fixed in a prismatic shape, respectively.

In FIGS. 3 (a) and 3 (b), the roll electrode 25c, which is a ground electrode, is a ceramic in which a conductive base material 25a such as a metal is thermally sprayed with a ceramic and then sealed with an inorganic material. It is composed of a combination of coated dielectrics 25b. The ceramic-coated dielectric was coated with 1 mm of one-sided wall, and the roll diameter was coated so that it was 200φ and grounded. Alternatively, a roll electrode 25C may be formed by combining a conductive base material 25A such as a metal with a lining-processed dielectric 25B provided with an inorganic material by lining to cover the conductive base material 25A. As the lining material, silicate glass, borate glass, phosphate glass, germanate glass, tellurite glass, aluminate glass, vanadate glass, etc. are preferably used. Of these, borate-based glass is more preferably used because it is easy to process. As the conductive base materials 25a and 25A such as metal,
Examples thereof include metals such as silver, platinum, stainless steel, aluminum and iron, and stainless steel is preferable from the viewpoint of processing.
Alumina and silicon nitride are preferably used as the ceramic material used for thermal spraying. Among them, alumina is more preferably used because it is easy to process. still,
In the present embodiment, a stainless steel jacket roll base material having a cooling means by cooling water is used as the base material of the roll electrode (not shown).

FIGS. 4A and 4B and FIGS. 5A and 5B,
(B) is a fixed electrode 26c and electrode 26 which are application electrodes.
C, the electrode 36c, and the electrode 36C, which are configured in the same combination as the roll electrode 25c and the roll electrode 25C described above. That is, a hollow stainless steel pipe is coated with a dielectric material similar to the above, and cooling with cooling water can be performed during discharge. After being coated with the ceramic-coated dielectric, it is manufactured to have a diameter of 12 or 15 and the number of the electrodes is 14 along the circumference of the roll electrode.

As a power source for applying a voltage to the applying electrode,
High frequency power supply (200k
Hz), a high frequency power supply manufactured by Pearl Industry (800 kHz), a high frequency power supply manufactured by JEOL Ltd. (13.56 MHz), a high frequency power supply manufactured by Pearl Industry (150 MHz) and the like can be used.

FIG. 6 is a conceptual diagram showing an example of the plasma discharge processing apparatus used in the present invention. In FIG. 6, the plasma discharge processing container 31 is the same as that shown in FIG. 2, but a gas generator 51, a power supply 41, an electrode cooling unit 60 and the like are further arranged as a device configuration. As a cooling agent for the electrode cooling unit 60, an insulating material such as distilled water or oil is used.

The electrodes 25 and 36 shown in FIG.
This is similar to that shown in 4, 5, etc., and the gap between the opposing electrodes is set to about 1 mm, for example.

The distance between the electrodes is determined in consideration of the thickness of the solid dielectric material provided on the base material of the electrodes, the magnitude of the applied voltage, the purpose of utilizing plasma, and the like. The shortest distance between the solid dielectric and the electrode when the solid dielectric is installed on one of the electrodes, and the distance between the solid dielectrics when the solid dielectric is installed on both of the electrodes are uniform in all cases. From the viewpoint of discharging, it is preferably 0.5 mm to 20 mm, and particularly preferably 1 mm ± 0.5 mm.

The roll electrode 25 and the fixed electrode 36 are arranged at predetermined positions in the plasma discharge processing container 31, the flow rate of the mixed gas generated by the gas generator 51 is controlled, and the plasma is supplied from the air supply port 52. It is placed in the discharge processing container 31, the inside of the plasma discharge processing container 31 is filled with the mixed gas used for the plasma processing, and the gas is exhausted from the exhaust port 53. Next, a voltage is applied to the electrode 36 by the power source 41, and the roll electrode 2
The numeral 5 is grounded to the ground to generate discharge plasma. Here, the base material F is supplied from the roll-shaped original-winding base material 61, and the electrodes in the plasma discharge processing container 31 are in one-side contact (in contact with the roll electrode 25) via the guide roller 64. The surface of the base material F is conveyed, and the surface of the base material F is subjected to discharge treatment by discharge plasma during the conveyance. Here, the base material F is subjected to the discharge treatment only on the surface which is not in contact with the roll electrode 25.

The value of the voltage applied to the electrode 36 fixed by the power supply 41 is appropriately determined. For example, the voltage is about 0.5 to 10 kV and the power supply frequency is adjusted to 0.5 kHz to 150 MHz. It Regarding the method of applying a power source, either a continuous sine wave continuous oscillation mode called a continuous mode or an intermittent oscillation mode called ON / OFF which is intermittently called a pulse mode may be adopted, but the continuous mode is more preferable. A denser and better quality film can be obtained.

As the plasma discharge treatment container 31, a treatment container made of Pyrex (R) glass is preferably used.
It is also possible to use metal as long as it can be insulated from the electrodes. For example, a polyimide resin or the like may be attached to the inner surface of an aluminum or stainless steel frame, and the metal frame may be sprayed with ceramics to have an insulating property.

Further, in order to suppress the influence on the substrate during the discharge plasma treatment to a minimum, the temperature of the substrate surface during the discharge plasma treatment is set to a temperature from room temperature (15 ° C. to 25 ° C.) to 300 ° C. or lower. It is preferable to adjust, more preferably at room temperature to
The temperature is adjusted to 200 ° C. or lower, and more preferably to room temperature to 100 ° C. or lower. In order to adjust to the above temperature range, the electrode and the base material are subjected to discharge plasma treatment while being cooled by a cooling means, if necessary.

In the present invention, the above discharge plasma treatment is carried out at or near atmospheric pressure. Here, the term "atmospheric pressure" means a pressure of 20 kPa to 110 kPa, but the effects described in the present invention are preferred. 93 to get
It is preferably kPa to 104 kPa.

Further, in the discharge electrode according to the thin film forming method of the present invention, J on at least the side of the electrode that is in contact with the base material is
From the viewpoint of obtaining the effect described in the present invention, it is preferable that the maximum height (Rmax) of the surface roughness specified by IS B 0601 is adjusted to 10 μm or less.
The maximum value of the surface roughness is more preferably 8 μm or less, and particularly preferably adjusted to 7 μm or less.

The center line average surface roughness (Ra) defined by JIS B 0601 is preferably 0.5 μm or less, more preferably 0.1 μm or less.

The plasma discharge processing apparatus 10 shown in FIGS. 1 to 6 described above is an apparatus used when the base material F can be bent like a film, but it has a certain thickness. A substrate L or a rigid substrate L, for example
If it is difficult to wind the base material around the roll electrode such as glass or lens, the parallel plate type plasma discharge treatment apparatus 100 as shown in FIG. 7 can be used.

The plasma discharge processing apparatus 100 includes a power source 11
0, the electrode 120, etc., and the electrode 120 is
The upper flat plate electrode 121 and the lower flat plate electrode 122 are provided, and the upper flat plate electrode 121 and the lower flat plate electrode 122 are vertically opposed to each other.

The upper flat plate electrode 121 is formed by arranging a plurality of substantially rectangular flat plate electrodes 121a in a horizontal row, and the gaps between these plural electrodes 121a respectively form gas flow passage portions. And the gas supply port 123 has the base material L.
It is located to face. That is, the gas generator 124 is provided above the upper flat plate electrode 121, and the reactive gas and the inert gas are fed from the gas generator 124 to the respective gas supply ports 123, so that the lower flat plate It is ejected between the electrodes 122.

The lower flat plate electrode 122 is grounded to ground, the base material L is mounted on the surface thereof, and the base material L is placed in the left-right direction with respect to the gas supply port 123 as indicated by an arrow in the figure. Move back and forth. Therefore, when the lower flat plate electrode 122 moves, a plasma state is established between the upper flat plate electrode 121 and the lower flat plate electrode 122, and a film is formed on the substrate L. By moving the base material L in this way, not only the film formation can be performed on the base material L having a larger area than the discharge area, but also the uniform film formation without unevenness in film thickness becomes possible. .

The gas relating to the transparent conductive film forming method of the present invention will be described. In carrying out the transparent conductive film forming method of the present invention, the gas used varies depending on the type of the transparent conductive film desired to be provided on the substrate, but basically, it is an inert gas as a carrier gas for causing a discharge. , A mixed gas of a reactive gas that is in a plasma state to form a transparent conductive film.

The reactive gas used in the present invention contains a reducing gas. The reducing gas is a chemically reducing inorganic gas that does not contain oxygen in the molecule. Specific examples include hydrogen and hydrogen sulfide. Particularly preferred is hydrogen gas. The amount of the reducing gas can be used in the range of 0.0001 to 5.0% by volume based on the mixed gas. The preferred range is 0.001 to 3.0
% By volume.

It is considered that the reducing gas acts on the reactive gas forming the transparent conductive film and has an effect of forming the transparent conductive film having good electric characteristics.

The mixed gas introduced into the plasma discharge space in the present invention preferably contains substantially no oxygen gas. The term "substantially free of oxygen gas" means that the function of imparting good electric characteristics by the reducing gas as described above is not hindered. In the method for forming a transparent conductive film of the present invention, the presence of oxygen gas tends to deteriorate the electrical characteristics of the transparent conductive film, and a slight amount of oxygen gas is allowed unless it deteriorates. In order to form an atmosphere containing substantially no oxygen gas, it is preferable to use a high-purity gas as the inert gas used in the present invention.

The reactive gas was 0.01 with respect to the mixed gas.
It is preferable to contain 10 to 10 volume%. As the film thickness of the transparent conductive film, a transparent conductive film having a thickness in the range of 0.1 nm to 1000 nm can be obtained.

Examples of the above-mentioned inert gas include elements belonging to Group 18 of the periodic table, specifically, helium, neon, argon, krypton, xenon, radon, etc. In order to obtain the effects described in the present invention. Is particularly preferably argon or helium.

The reactive gas becomes a plasma state in the discharge space and contains a component forming a transparent conductive film, and an organic metal compound such as a β-diketone metal complex, a metal alkoxide or an alkyl metal is used. The reactive gas includes a reactive gas which is a main component of the transparent conductive film and a reactive gas which is used in a small amount for the purpose of doping. Further, there is a reactive gas used to adjust the resistance value of the transparent conductive film.

The transparent conductive film obtained by the transparent conductive film forming method of the present invention is characterized by having high carrier mobility. As is well known, the electric conductivity of a transparent conductive film is represented by the following formula (1).

Σ = neμ (1) where σ is the electrical conductivity, n is the carrier density, e is the amount of electricity of electrons, and μ is the mobility of carriers. In order to increase the electric conductivity, it is necessary to improve the carrier density or the carrier mobility, but as the carrier density is improved, the reflectivity increases from around 2 × 10 ²¹ cm ^{-3 and the} transparency is lost. . Therefore, in order to improve the electric conductivity, it is necessary to improve the carrier mobility. The carrier mobility of the transparent conductive film prepared by the commercially available DC magnetron sputtering method is 30c.
Although it is about m ² / sec · V, the transparent conductive film having carrier mobility higher than that of the transparent conductive film formed by the DC magnetron sputtering method by optimizing the conditions according to the method for forming a transparent conductive film of the present invention. It has been found possible to form a film.

Since the method for forming a transparent conductive film of the present invention has a high carrier mobility, it is possible to obtain a transparent conductive film having a low resistivity of 1 × 10 ⁻³ Ω · cm or less without doping. The resistance can be further reduced by doping to increase the carrier density. Moreover, a transparent conductive film having a high specific resistance of 1 × 10 ⁻² or more can be obtained by using a reactive gas that raises the resistance value if necessary.

The transparent conductive film obtained by the method for forming a transparent conductive film of the present invention has a carrier mobility of 10 cm ² /
V · sec or more.

The transparent conductive film obtained by the method for forming a transparent conductive film of the present invention has a carrier density of 1 × 10.
¹⁹ cm ⁻³ or more, 1 × 1 under more preferable conditions
It becomes 0 ²⁰ cm ^-3 or more.

Since the transparent conductive film of the present invention uses an organometallic compound as a reactive gas, it may contain a slight amount of carbon. In that case, the carbon content is 0 to 5.0.
The atomic number concentration is preferable. Particularly preferably 0.
It is preferably in the range of 0 to 1 to 3 atom number concentration.

In the transparent conductive film of the present invention, the variation of the peak intensity ratio H / M of hydrogen ions and main metal element ions in the depth direction by dynamic SIMS measurement of the transparent conductive film is 5% or less in the variation coefficient. It is characterized by
A method of manufacturing such a transparent conductive film can be obtained by using hydrogen gas as a reducing gas in the above-described thin film forming method by atmospheric pressure plasma discharge of the present invention.

In the transparent conductive film of the present invention, the variation in the depth direction of the peak intensity ratio H / M of hydrogen ions and main metal element ions in the depth direction by dynamic SIMS measurement of the transparent conductive film is 5% or less. When the dynamic secondary ion mass spectrometry measurement of the metal-containing film is performed, the peak intensity ratio H / M (H is a hydrogen ion peak) of hydrogen ions in the metal-containing film and metal element ions derived from the metal of the main metal oxide. Intensity, M is the peak intensity of the main metal element ion) and the variation in the depth direction is less than a certain value. The variation is preferably represented by a coefficient of variation, which is preferably within 5%, more preferably within 3%, and even more preferably within 1%. Dynamic secondary ion mass spectrometry (hereinafter referred to as dynamic SIMS including the apparatus) For this, refer to Practical Surface Analysis Secondary Ion Mass Spectrometry (2001, Maruzen) edited by The Surface Science Society.

Dynamic SI preferred in the present invention
The conditions for MS measurement are as follows.

Apparatus: Physical Electro
nics ADEPT1010 or 6300 type 2
Secondary ion mass spectrometer Primary ion: Cs Primary ion energy: 5.0 KeV Primary ion current: 200 nA Primary ion irradiation area: 600 μm square Secondary ion uptake ratio: 25% Secondary ion polarity: Negative detection Secondary ion species: H ⁻ And M ^{− Under the} above conditions, mass spectrometry is performed while performing sputtering in the depth direction of the metal-containing film. The peak intensity ratio H / M of the hydrogen ion and the metal element ion derived from the metal of the main metal oxide is determined from the obtained depth profile. The measuring points are 50 points or more per 100 nm, more preferably 75 points.
It is preferable to perform measurement at more than the points. After obtaining the H / M ratio in the depth direction, the average of the H / M ratio and the relative standard deviation are obtained for 15 to 85% in the depth direction, and the relative standard deviation is divided by the average and multiplied by 100. The coefficient of variation of the M ratio, that is, the variation is obtained.

In the present invention, the absolute value of H / M ratio is preferably between 0.001 and 50. More preferably, it is between 0.01 and 20. Also in this case, the H / M ratio is calculated based on the result measured under the above conditions in the depth direction using dynamic SIMS, and the
The average H / M ratio for 85% is defined as the H / M ratio.

Further, the hydrogen concentration in the transparent conductive film in the present invention is preferably 0.001 to 10 atomic%, more preferably 0.01 to 5 atomic%, and further preferably 0.5 to 1 atomic%. Is preferred. The evaluation of hydrogen concentration is also preferably performed by dynamic SIMS. The measurement conditions are as described above. Actually, first, the hydrogen concentration in the transparent conductive film as the reference was obtained by Rutherford backscattering spectroscopy, and the dynamic SIMS measurement of this reference product was performed.
The relative sensitivity coefficient is determined based on the intensity of the detected hydrogen ions, and then dynamic SIMS measurement is performed on the transparent conductive film that is actually used, and the signal strength obtained from the measurement and the relative sensitivity coefficient obtained previously are used. Then, the hydrogen concentration in the sample is calculated. The hydrogen concentration in the present invention is 15 to 8% of that of the transparent conductive film obtained by performing so-called depth profile to obtain the hydrogen concentration over the entire thickness direction of the transparent conductive film.
The average of the hydrogen concentrations at a depth of 5% is defined as the hydrogen concentration.

Peak intensity ratio H / of hydrogen ion and main metal element ion by dynamic SIMS measurement according to the present invention
The variation of M in the depth direction is 5% as a coefficient of variation.
The method for obtaining the following transparent conductive film is not particularly limited, but the film forming method by the atmospheric pressure plasma discharge treatment as described above can be employed. That is, by introducing a reactive gas into the discharge space into a plasma state under atmospheric pressure or a pressure near the atmospheric pressure, and exposing the base material to the reactive gas in the plasma state, a transparent conductive film is formed on the base material. Is a method of forming a transparent conductive film. Preferably, when the reactive gas contains a reducing gas, the variation coefficient is likely to be 5% or less. Further, more preferably, if the electric field applied to the discharge space exceeds a frequency of 100 kHz and the output density is 1 W / cm ² or more, the variation coefficient is likely to be 5% or less. Although the details are unknown, it is likely that such a reducing atmosphere and a high-power electric field condition are suitable for uniform film formation of the transparent conductive film. It is presumed that the variation of the peak intensity of the ions could be suppressed.

In the present invention, the reactive gas used as the main component of the transparent conductive film is preferably an organometallic compound having an oxygen atom in its molecule. For example, indium hexafluoropentanedionate, indium methyl (trimethyl) acetyl acetate, indium acetylacetonate, indium isoporopoxide, indium trifluoropentanedionate, tris (2,2,6,6-
Tetramethyl 3,5-heptanedionate) indium, di-n-butylbis (2,4-pentanedionate) tin, di-n-butyldiacetoxytin, di-t-
Butyl diacetoxy tin, tetraisopropoxy tin,
Tetrabutoxy tin, zinc acetylacetonate, etc. can be mentioned. Of these, indium acetylacetonate and tris (2,2,6,6) are particularly preferable.
-Tetramethyl 3,5-heptanedionate) indium, zinc acetylacetonate, di-n-butyldiacetoxytin.

Examples of the reactive gas used for doping include aluminum isopropoxide, nickel acetylacetonate, manganese acetylacetonate, boron isopropoxide, n-butoxy antimony, tri-n-butyl antimony, di-n. -Butyl bis (2,4-pentanedionate) tin, di-n-butyl diacetoxy tin, di-t-butyl diacetoxy tin,
Examples thereof include tetraisopropoxy tin, tetrabutoxy tin, tetrabutyl tin, zinc acetylacetonate, propylene hexafluoride, cyclobutane octafluoride, and methane tetrafluoride.

As the reactive gas used for adjusting the resistance value of the transparent conductive film, for example, titanium triisopropoxide, tetramethoxysilane, tetraethoxysilane,
Hexamethyldisiloxane etc. can be mentioned.

The ratio of the reactive gas used as the main component of the transparent conductive film to the reactive gas used in a small amount for the purpose of doping depends on the type of the transparent conductive film to be formed. For example, I obtained by doping indium oxide with soot
In the TO film, the amount of reactive gas is adjusted so that the resulting ITO film has an In / Sn atomic ratio of 100 / 0.1 to 100/15. Preferably, 100/0.
Adjust to a range of 5 to 100/10. In / S
The atomic ratio of n can be obtained by XPS measurement.

In the transparent conductive film (called FTO film) obtained by doping tin oxide with fluorine, the obtained F
The atomic ratio of Sn / F in the TO film is 100 / 0.01 to 10
The reactive gas amount ratio is adjusted so as to be in the range of 0/50. The atomic ratio of Sn / F can be obtained by XPS measurement.

In the In ₂ O ₃ —ZnO type amorphous transparent conductive film, the atomic ratio of In / Zn is 100/50 to 100/50.
The reactive gas amount ratio is adjusted so as to be in the range of 100/5. The atomic ratio of In / Zn can be obtained by XPS measurement.

The substrate that can be used in the present invention is not particularly limited as long as it can form a transparent conductive film on its surface, such as a film-shaped one, a sheet-shaped one, and a three-dimensional one such as a lens-shaped one. There is no. If the base material can be placed between the electrodes, it can be placed between the electrodes.If the base material cannot be placed between the electrodes, the generated plasma can be sprayed onto the base material to make the transparent conductive material. A film may be formed.

The material constituting the substrate is not particularly limited, either.
A resin film can be preferably used because it is under atmospheric pressure or a pressure close to atmospheric pressure and low-temperature glow discharge is performed. For example, cellulose ester such as film-like cellulose triacetate, polyester,
Polycarbonate, polystyrene, and those obtained by coating gelatin, polyvinyl alcohol (PVA), acrylic resin, polyester resin, cellulosic resin or the like on these may be used. In addition, these base materials are
An antiglare layer or a clear hard coat layer coated on the support, or a back coat layer or an antistatic layer coated on the support can be used.

The above support (also used as a base material)
Specifically, polyethylene terephthalate,
Polyester film such as polyethylene naphthalate,
Polyethylene film, polypropylene film, cellophane, cellulose diacetate film, cellulose acetate butyrate film, cellulose acetate propionate film, cellulose acetate phthalate film, cellulose triacetate, a film made of cellulose ester such as cellulose nitrate or a derivative thereof, Polyvinylidene chloride film, polyvinyl alcohol film, ethylene vinyl alcohol film, syndiotactic polystyrene film, polycarbonate film, norbornene resin film, polymethylpentene film, polyetherketone film, polyimide film, polyethersulfone film, polysulfone film , Polyetherketone imimi Films, polyamide films,
Examples thereof include a fluororesin film, a nylon film, a polymethylmethacrylate film, an acrylic film and a polyarylate film.

These materials may be used alone or in an appropriate mixture. Above all, Zeonex (manufactured by Nippon Zeon Co., Ltd.), ARTON (Nippon Synthetic Rubber Co., Ltd.)
Commercially available products such as manufactured products) can be preferably used. Furthermore, even for materials with a large intrinsic birefringence such as polycarbonate, polyarylate, polysulfone, and polyethersulfone, conditions such as solution casting and melt extrusion, as well as stretching conditions in the longitudinal and transverse directions, etc. are set appropriately. Can be obtained by doing. Further, the support according to the present invention is not limited to the above description. The film thickness is 10-1
A 000 μm film is preferably used.

In the present invention, the transparent conductive film is formed on a substrate such as glass or a plastic film. If necessary, an adhesive layer may be provided between the substrate and the transparent conductive film to improve the adhesiveness. It may be provided. Further, in order to improve the optical characteristics, it is possible to provide an antireflection film on the surface opposite to the surface provided with the transparent conductive film. Further, it is possible to provide an antifouling layer as the outermost layer of the film. In addition, a layer or the like for imparting gas barrier properties and solvent resistance may be provided if necessary.

The method for forming these layers is not particularly limited,
A coating method, a vacuum evaporation method, a sputtering method, an atmospheric pressure plasma CVD method, or the like can be used. Particularly preferable is the atmospheric pressure plasma CVD method.

As a method of forming these layers by atmospheric pressure plasma CVD, for example, a method disclosed in Japanese Patent Application No. 2000-21573 can be used as a method of forming an antireflection film.

In the present invention, when the transparent conductive film according to the present invention is provided on the surface of the substrate as described above, it is preferable that the film thickness deviation from the average film thickness is ± 10%. It is more preferably within ± 5%, particularly preferably within ± 1%.

[0117]

Example 1 A glass substrate (50 mm × 50 mm × 1 mm) on which a silica film having a thickness of about 50 nm was formed as an alkali barrier coat was prepared as a base material.

A parallel plate type electrode shown in FIG. 7 was used as a plasma discharge device, the glass substrate was placed between the electrodes, and a mixed gas was introduced to form a thin film.

The electrodes used were as follows. 200m
A m × 200 mm × 2 mm stainless steel plate was coated with a high-density, highly-adhesive alumina sprayed film, and then a solution prepared by diluting tetramethoxysilane with ethyl acetate was applied, dried, and then cured by ultraviolet irradiation for sealing treatment. It was The dielectric surface coated in this way is polished and smoothed to obtain Rma
It was processed to have a size of 5 μm. The electrode was prepared in this manner and grounded.

On the other hand, as the applying electrodes, a plurality of hollow rectangular pure titanium pipes coated with the same dielectric as the above under the same conditions were prepared to form opposing electrode groups.

As a power source used for plasma generation, a high frequency power source JRF-10000 manufactured by JEOL Ltd. was used to supply a voltage of 13.56 MHz and a power of 5 W / cm ² .

A gas having the following composition was passed between the electrodes. Inert gas: Helium 98.5% by volume Reactive gas 1: Hydrogen 0.25% by volume Reactive gas 2: Tris (2,4-pentanedionato) indium 1.2% by volume Reactive gas 3: Dibutyltindi Acetate 0.05 volume% A glass substrate was subjected to atmospheric pressure plasma treatment under the above reaction gas and reaction conditions to form a tin-doped indium oxide film. The prepared film was evaluated by the following method.

<Transmittance> According to JIS-R-1635,
The measurement was performed using a spectrophotometer 1U-4000 manufactured by Hitachi Ltd. The wavelength of the test light was 550 nm.

<Film Thickness and Film Forming Speed> The film thickness was measured by a FE-3000 reflection spectroscopic film thickness meter manufactured by Photoal Co., and the obtained film thickness was divided by the plasma treatment time to obtain the film forming speed.

<Resistivity> According to JIS-R-1637,
It was determined by the four-terminal method. For the measurement, Loresta GP and MCP-T600 manufactured by Mitsubishi Chemical were used.

<Hall Effect> Sanwa Radio Instruments Research Laboratory M1
The carrier density and carrier mobility were determined by the van der Pauw method using a -675 system.

<Film Composition> The film on the glass substrate was dissolved in hydrochloric acid, and the amounts of indium and tin in the film were determined using an inductively coupled plasma emission spectroscope (SPS-4000 manufactured by Seiko Denshi).

<Measurement of Carbon Content> The film composition and carbon content are measured with an XPS surface analyzer. X
The PS surface analyzer is not particularly limited, and any model can be used, but in this embodiment, the VG is used.
ESCALAB-200R made by Scientific Fix Co.
Was used. Mg is used for the X-ray anode and the output is 600W
(Acceleration voltage 15 kV, emission current 40 mA). The energy resolution was set to be 1.5 to 1.7 eV when defined by the full width at half maximum of a clean Ag3d5 / 2 peak. Before the measurement, the surface layer corresponding to 10 to 20% of the thickness of the thin film needs to be removed by etching in order to remove the influence of contamination. For removing the surface layer, it is preferable to use an ion gun capable of utilizing rare gas ions, and as the ion species, He, Ne, A
r, Xe, Kr, etc. can be used. In this measurement, A
The surface layer was removed using r-ion etching.

First, the binding energy from 0 eV to 1100
The range of eV was measured at a data acquisition interval of 1.0 eV to determine what element was detected.

Next, with respect to all the detected elements except the etching ion species, the data acquisition interval is set to 0.
A narrow scan was performed on the photoelectron peak giving the maximum intensity at 2 eV, and the spectrum of each element was measured. The obtained spectrum is VAMAS-SCA-J in order to prevent the difference in the content calculation result due to the difference of the measuring device or the computer.
APAN-made COMMON DATA PROCESS
After transferring to ING SYSTEM (preferably Ver. 2.3 or later), the same software is used to calculate the carbon content value by atomic concentration (atomic concent).
(Tration: at%). The ratio of tin and indium was also the ratio of the atomic number concentrations obtained from the above results.

Before performing the quantitative processing, the Count Scale was calibrated for each element, and the 5-point smoothing processing was performed. In the quantitative treatment, the peak area intensity (cps * eV) from which the background was removed was used. The method by Shirley was used for the background treatment.

For the Shirley method, see D.W. A. S
hirley, Phys. Rev. , B5,4709
(1972) can be referred to.

Example 2 A tin-doped indium oxide film was prepared in the same manner as in Example 1 except that the reactive gas concentration was changed to the following.

Inert gas: Helium 98.65% by volume Reactive gas 1: Hydrogen 0.10% by volume Reactive gas 2: Tris (2,4-pentanedionato) indium 1.2% by volume Reactive gas 3: Dibutyltin diacetate 0.05% by volume (Example 3) A tin-doped indium oxide film was prepared and evaluated in the same manner as in Example 1 except that the concentration of the reactive gas was changed to the following in Example 1. .

Inert gas: Helium 98.25% by volume Reactive gas 1: Hydrogen 0.5% by volume Reactive gas 2: Tris (2,4-pentanedionato) indium 1.2% by volume Reactive gas 3: Dibutyltin diacetate 0.05% by volume (Example 4) A tin-doped indium oxide film was prepared and evaluated in the same manner as in Example 1 except that the concentration of the reactive gas was changed to the following. .

Inert gas: Helium 98.75% by volume Reactive gas 1: Hydrogen 1.00% by volume Reactive gas 2: Tris (2,4-pentanedionato) indium 1.2% by volume Reactive gas 3: Dibutyltin diacetate 0.05% by volume (Example 5) A tin-doped indium oxide film was prepared and evaluated in the same manner as in Example 1 except that the concentration of the reactive gas was changed to the following in Example 1. .

Inert gas: Helium 98.5% by volume Reactive gas 1: Hydrogen sulfide 0.25% by volume Reactive gas 2: Tris (2,4-pentanedionato) indium 1.2% by volume Reactive gas 3 : Dibutyltin diacetate 0.05% by volume (Example 6) A tin-doped indium oxide film was prepared and evaluated in the same manner as in Example 1 except that the concentration of the reactive gas in Example 1 was changed to the following. It was

Inert gas: Argon 98.5% by volume Reactive gas 1: Hydrogen 0.25% by volume Reactive gas 2: Tris (2,4-pentanedionato) indium 1.2% by volume Reactive gas 3: Dibutyltin diacetate 0.05% by volume (Example 7) A tin-doped indium oxide film was prepared and evaluated in the same manner as in Example 1 except that the concentration of the reactive gas was changed to the following in Example 1. .

Inert gas: Argon 98.65% by volume Reactive gas 1: Hydrogen 0.10% by volume Reactive gas 2: Tris (2,4-pentanedionato) indium 1.2% by volume Reactive gas 3: Dibutyltin diacetate 0.05% by volume (Example 8) A tin-doped indium oxide film was prepared and evaluated in the same manner as in Example 1 except that the concentration of the reactive gas was changed to the following in Example 1. .

Inert gas: mixed gas of helium and argon (helium / argon volume ratio 70/30) 98.5
Volume% Reactive gas 1: Hydrogen 0.25 volume% Reactive gas 2: Tris (2,4-pentanedionato) indium 1.2 volume% Reactive gas 3: Dibutyltin diacetate 0.05 volume% Example 9) A tin-doped indium oxide film was prepared and evaluated in the same manner as in Example 1 except that the concentration of the reactive gas in Example 1 was changed to the following.

Inert gas: mixed gas of helium and argon (helium / argon volume ratio 70/30) 98.6
5 volume% Reactive gas 1: Hydrogen 0.10 volume% Reactive gas 2: Tris (2,4-pentanedionato) indium 1.2 volume% Reactive gas 3: Dibutyltin diacetate 0.05 volume% ( Example 10) A tin-doped indium oxide film was prepared and evaluated in the same manner as in Example 1 except that the reactive gas concentration in Example 1 was changed to the following.

Inert gas: Nitrogen 98.5% by volume Reactive gas 1: Hydrogen 0.25% by volume Reactive gas 2: Tris (2,4-pentanedionato) indium 1.2% by volume Reactive gas 3: Dibutyltin diacetate 0.05% by volume (Comparative Example 1) The glass substrate used in Example 1 was mounted on a DC magnetron sputtering apparatus, and the inside of the vacuum chamber was 1 × 10 ⁻³ P.
The pressure was reduced to a or less. The sputtering target used had a composition of indium oxide: tin oxide 95: 5. Then, a mixed gas of argon gas and oxygen gas (Ar: O ₂ = 1000: 3) was introduced until the pressure became 1 × 10 ⁻³ Pa, the sputtering output was 100 W, and the substrate temperature was 100 ° C.
The film was formed in and evaluated.

Comparative Example 2 A tin-doped indium oxide film was prepared and evaluated in the same manner as in Example 1 except that the concentration of the reactive gas was changed to the following.

Inert gas: Helium 98.5% by volume Reactive gas 1: Oxygen 0.25% by volume Reactive gas 2: Tris (2,4-pentanedionato) indium 1.2% by volume Reactive gas 3: Dibutyltin diacetate 0.05% by volume (Comparative Example 3) A tin-doped indium oxide film was prepared and evaluated in the same manner as in Example 1 except that the concentration of the reactive gas in Example 1 was changed to the following. .

Inert gas: Helium 98.70% by volume Reactive gas 1: Oxygen 0.05% by volume Reactive gas 2: Tris (2,4-pentanedionato) indium 1.2% by volume Reactive gas 3: Dibutyltin diacetate 0.05% by volume (Comparative Example 4) A tin-doped indium oxide film was prepared and evaluated in the same manner as in Example 1 except that the concentration of the reactive gas in Example 1 was changed to the following. .

Inert gas: Argon 98.5% by volume Reactive gas 1: Oxygen 0.25% by volume Reactive gas 2: Tris (2,4-pentanedionato) indium 1.2% by volume Reactive gas 3: Dibutyltin diacetate 0.05% by volume (Comparative Example 5) A tin-doped indium oxide film was prepared and evaluated in the same manner as in Example 1 except that the reactive gas concentration in Example 1 was changed to the following. .

Inert gas: mixed gas of helium and argon (helium / argon volume ratio 70/30) 98.5
Volume% Reactive gas 1: Oxygen 0.25 volume% Reactive gas 2: Tris (2,4-pentanedionato) indium 1.2 volume% Reactive gas 3: Dibutyltin diacetate 0.05 volume% (Comparison Example 6) To 22.2 g of 2-methoxymethanol, 0.4 g of monoethanolamine and 3.8 g of indium acetate,
0.16 g of Sn (OC ₄ H ₉ ) was added and mixed with stirring for 10 minutes. This solution was dip-coated with the same glass substrate as used in Example 1 at a rate of 1.2 cm / min. After coating, it was heated in an electric furnace at 500 ° C. for 1 hour.

The evaluation results of Examples 1 to 10 and Comparative Examples 1 to 6 are summarized in Table 1.

[0149]

[Table 1]

(Example 11) A film was formed on a glass substrate in the same manner as in Example 1 except that the reactive gas was changed as follows.

Inert gas: Helium 98.65% by volume Reactive gas 1: Hydrogen 0.15% by volume Reactive gas 2: Bis (2,4-pentanedionato) zinc 1.2% by volume (Example 12) A film was formed on a glass substrate in the same manner as in Example 1 except that the reactive gas was changed as follows in Example 1.

Inert gas: Helium 98.65% by volume Reactive gas 1: Hydrogen 0.15% by volume Reactive gas 2: Dibutyltin diacetate 1.2% by volume (Example 13) The reactive gas in Example 1 A film was formed on the glass substrate in the same manner as in Example 1 except that the above was performed.

Inert gas: Argon 98.65% by volume Reactive gas 1: Hydrogen 0.15% by volume Reactive gas 2: Bis (2,4-pentanedionato) tin
1.2% by volume (Example 14) A film was formed on a glass substrate in the same manner as in Example 1 except that the reactive gas in Example 1 was changed as follows.

Inert gas: Helium 98.65% by volume Reactive gas 1: Hydrogen 0.14% by volume Reactive gas 2: Bis (2,4-pentanedionato) tin
1.2% by volume Reactive gas 3: 4 Fluorinated methane 0.01% by volume (Example 15) On a glass substrate in the same manner as in Example 1 except that the reactive gas was changed as follows in Example 1. Was formed into a film.

Inert gas: Helium 98.65% by volume Reactive gas 1: Hydrogen 0.10% by volume Reactive gas 2: Tris (2,4-pentanedionato) indium 1.2% by volume Reactive gas 3: Bis (2,4-pentanedionato) zinc 0.5% by volume (Example 16) A film was formed on a glass substrate in the same manner as in Example 1 except that the reactive gas in Example 1 was changed as follows. I went.

Inert gas: Helium 98.65% by volume Reactive gas 1: Hydrogen 0.10% by volume Reactive gas 2: Tris (2,4-pentanedionato) indium 1.2% by volume Reactive gas 3: Bis (2,4-pentanedionato) tin
0.5% by volume (Example 17) A film was formed on a glass substrate in the same manner as in Example 1 except that the reactive gas in Example 1 was changed as follows.

Inert gas: Helium 98.65% by volume Reactive gas 1: Hydrogen 0.10% by volume Reactive gas 2: Tris (2,2,6,6-tetramethyl-3,5-heptanedionato) indium 1 .2% by volume reactive gas 3: bis (2,4-pentanedionato) tin
0.5% by volume (Example 18) A film was formed on a glass substrate in the same manner as in Example 1 except that the reactive gas in Example 1 was changed as follows.

Inert gas: Helium 98.65% by volume Reactive gas 1: Hydrogen 0.10% by volume Reactive gas 2: Tris (2,4-pentanedionato) indium 1.2% by volume Reactive gas 3: Tetrabutyltin 0.5% by volume (Example 19) A film was formed on a glass substrate in the same manner as in Example 1 except that the reactive gas in Example 1 was changed as follows.

Inert gas: Helium 98.65% by volume Reactive gas 1: Hydrogen 0.10% by volume Reactive gas 2: Triethylindium 1.2% by volume Reactive gas 3: Dibutyltin diacetate 0.5% by volume (Comparative Example 7) A film was formed on a glass substrate in the same manner as in Example 1 except that zinc oxide was used as the sputtering target in Comparative Example 1.

(Comparative Example 8) A film was formed on a glass substrate in the same manner as in Example 1 except that tin oxide was used as the sputtering target in Comparative Example 1.

Comparative Example 9 Indium oxide: zinc oxide = 95: 5 was used as the sputtering target in Comparative Example 1.
A film was formed on the glass substrate in the same manner as in Example 1 except that the above was adopted.

(Comparative Example 10) A film was formed on a glass substrate in the same manner as in Example 11 except that hydrogen gas was changed to oxygen gas in Example 11.

(Comparative Example 11) A film was formed on a glass substrate in the same manner as in Example 12 except that hydrogen gas was changed to oxygen gas in Example 12.

(Comparative Example 12) A film was formed on a glass substrate in the same manner as in Example 13 except that hydrogen gas was used as oxygen gas in Example 13.

(Comparative Example 13) A film was formed on a glass substrate in the same manner as in Example 14 except that hydrogen gas was changed to oxygen gas in Example 14.

(Comparative Example 14) A film was formed on a glass substrate in the same manner as in Example 15 except that hydrogen gas was changed to oxygen gas.

(Comparative Example 15) A film was formed on a glass substrate in the same manner as in Example 16 except that hydrogen gas was changed to oxygen gas.

(Comparative Example 16) A film was formed on a glass substrate in the same manner as in Example 17 except that hydrogen gas was changed to oxygen gas in Example 17.

Examples 11 to 19 and Comparative Examples 7-1
With respect to the film of No. 6, the film forming speed, the transmittance and the specific resistance were measured in the same manner as in Example 1. The evaluation results are shown in Table 2.

The details of the abbreviations of the reaction gases shown in Table 2 are as follows. In (AcAc) ₃ : tris (2,4-pentanedionato) indium Zn (AcAc) ₂ : bis (2,4-pentanedionato) zinc DBDTA: dibutylditin diacetate Sn (AcAc) ₂ : bis (2,2) 4-pentanedionato) tin _{In (C 2 H 5) 3} : triethyl indium TBT: tetrabutyl tin an In (TMHD) _3: tris (2,2,6,6-tetramethyl-3,5-heptanedionato) indium

[0171]

[Table 2]

(Example 20) The plasma discharge device shown in FIG. 6 was used in Example 1, except that the substrate was an amorphous cyclopolyolefin resin film (ARTON film manufactured by JSR: thickness 100 μm). Example 1
A tin-doped indium oxide film was prepared in the same manner as in. The film formation rate, transmittance, and specific resistance of the film obtained in the same manner as in Example 1 were measured.

The critical radius of curvature was measured by the following procedure. <Measurement of Limiting Radius of Curvature> The film with tin-doped indium oxide obtained in Example 20 was cut into a length of 10 cm. About this film, room temperature 25 ℃, humidity 60
% Surface resistance as Mitsubishi Chemical Loresta-GP, MC
It measured using P-T600. This surface resistance value is R0
And This film was wrapped around a stainless steel rod having a radius of 10 mm so that no gap was formed. After holding in that state for 3 minutes, the film was taken from the round bar and the surface resistance was measured again. Let this value be R. The radius of the round bar was reduced from 10 mm by 1 mm, and the same measurement was repeated. R / R
The radius of the round bar having a value of 0 exceeding 1 was defined as the limit radius of curvature.

(Example 21) A tin-doped indium oxide film was prepared in the same manner as in Example 20 except that the substrate used in Example 20 was ZEONOR ZF16 (100 μm in thickness) manufactured by Nippon Zeon Co., Ltd. Similar evaluation was performed.

(Example 22) In Example 20, the base material used in Example 20 was the polycarbonate film formed by the casting method (Pure Ace manufactured by Teijin Ltd .: thickness 100 µm).
A tin-doped indium oxide film was prepared in the same manner as in Example 0 and evaluated in the same manner as in Example 20.

(Example 23) A tin-doped indium oxide film was prepared in the same manner as in Example 20 except that the substrate was removed and an acetyl cellulose film (thickness: 100 µm) was prepared in Example 20. Was evaluated.

(Comparative Example 17) A tin-doped indium oxide film was formed on polyethylene terephthalate using a winding type magnetron sputtering apparatus having a vacuum chamber, a sputtering target and a gas introduction system. The film was introduced into the apparatus, and the inside pressure was reduced to 4 × 10 ⁻⁴ Pa. The sputtering target was indium oxide:
A composition of tin oxide 95: 5 was used. After this, the film was rewound and degassed. Then, a mixed gas of argon gas and oxygen gas (Ar: O ₂ = 9)
8.8: 1.2) until it reaches 1 × 10 ⁻³ Pa,
Film formation was carried out with the temperature of the main roll at room temperature, the film feed rate was 0.1 m / min, and the input power density was 1 W / cm ² , and the same evaluation as in Example 14 was performed.

Table 3 shows the evaluation results of Examples 20 to 23 and Comparative Example 17.

[0179]

[Table 3]

Next, Examples 24, 25 and 2 shown below
The transparent conductive film of No. 6 was produced. (Example 24) Using the parallel plate type atmospheric pressure plasma processing apparatus of FIG. 7, a transparent conductive film was produced in the same manner as in Example 1 except for the following conditions.

Electric field condition Frequency: 13.56 MHz, Output: 5 W / cm ² Gas condition Inert gas: Helium 98.74% by volume Reactive gas 1: Water 0.01% by volume Reactive gas 2: Indium acetylacetonate 1 0.2 vol% Reactive gas 3: dibutyltin diacetate 0.05 vol% (Example 25) Except for the following conditions, atmospheric pressure plasma treatment was performed in the same manner as in Example 24 to deposit ITO on the substrate. It was made.

Gas conditions Inert gas: Helium 98.60% by volume Reactive gas 1: Hydrogen 0.15% by volume Reactive gas 2: Indium acetylacetonate 1.2% by volume Reactive gas 3: Dibutyltin diacetate 0 0.05% by volume (Example 26) A transparent conductive film was produced using the film formation method by atmospheric pressure plasma discharge treatment described in Example 3 of JP 2000-303175 A. However, with respect to the base material, electrodes and the like, the same processes as those described in Examples 24 and 25 were performed. The following conditions were used for the electric field condition and the gas condition.

Electric field conditions Frequency: 10 kHz, Output: 0.8 W / cm ² (PHF-4K manufactured by HEIDEN R & D Co.) Gas conditions Inert gas: Helium 98.75% by volume Reactive gas 1: Hydrogen 0.5% by volume Reactive gas 2: Indium acetylacetonate 1.2% by volume Reactive gas 3: Dibutyltin diacetate 0.05% by volume Then, with respect to the transparent conductive films prepared in Examples 24, 25 and 26 of the present invention. Then, the variation coefficient and the hydrogen concentration of the peak intensity ratio H / M of the hydrogen ions and the main metal element ions in the depth direction were obtained by the above-mentioned dynamic SIMS measurement, and the results are shown in Table 4. Table 4 also shows the evaluation of the resistivity and the light transmittance.

[0184]

[Table 4]

From the results in Table 4, it was confirmed that the performance of the transparent conductive film was further improved by setting the variation coefficient of the peak intensity ratio H / M of the transparent conductive film according to the present invention within 5%.

[0186]

According to the present invention, there is provided a method for forming a transparent conductive film having high safety, excellent productivity, good optical and electrical characteristics, and an excellent limiting radius of curvature on a plastic film substrate. It was possible to provide the formed transparent conductive film and the article having the transparent conductive film.

[Brief description of drawings]

FIG. 1 is a schematic view showing an example of a plasma discharge treatment container installed in a plasma discharge treatment apparatus used in a manufacturing method of the present invention.

FIG. 2 is a schematic view showing an example of a plasma discharge treatment container installed in a plasma discharge treatment apparatus used in the manufacturing method of the present invention.

3 (a) and 3 (b) are each a schematic view showing an example of a cylindrical roll electrode used in the plasma discharge treatment according to the present invention.

4A and 4B are schematic views each showing an example of a fixed cylindrical electrode used in the plasma discharge treatment according to the present invention.

5 (a) and 5 (b) are schematic views each showing an example of a fixed prismatic electrode used in the plasma discharge treatment according to the present invention.

FIG. 6 is a conceptual diagram showing an example of a plasma discharge treatment apparatus used in the transparent conductive film forming method of the present invention.

FIG. 7 is a conceptual diagram showing an example of a parallel plate type plasma discharge processing apparatus used in the transparent conductive film forming method of the present invention.

[Explanation of symbols]

25, 25c, 25C Roll electrode 26, 26c, 26C, 36, 36c, 36C Electrode 25a, 25A, 26a, 26A, 36a, 36A Conductive base material 25b, 26b, 36b such as metal Ceramic coated dielectric 25B, 26B , 36B Lining treatment Dielectric 31 Plasma discharge treatment vessel 41, 110 Power supply 51, 124 Gas generator 52 Air supply port 53 Exhaust port 60 Electrode cooling unit 61 Original winding base material 65, 66 Nip rollers 64, 67 Guide roller 100 Plasma discharge treatment Device L Base material 120 Electrode 121 Upper flat plate electrode 122 Lower flat plate electrode 123 Gas supply port

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) G02F 1/1343 G02F 1/1343 5G323 H01B 5/14 H01B 5/14 A 5H032 // H01M 14/00 H01M 14 / 00 PF term (reference) 2H090 JA06 JB03 JC04 JD01 LA01 2H092 HA04 MA08 NA01 NA28 PA01 4G075 AA24 AA30 BC01 BC04 BD14 CA14 CA25 CA47 CA62 CA63 EC21 FC11 4K030 AA17 BA35 BA42 BA45 CA07 CA12 EA03 FA01 JA11 JA16 JA16 JA16 JA16 JA16 JA16 JA01 JA01 JA16 JA16 JA01 JA01 JA16 JA01 JA01 FA02 FB01 FC03 FC09 5G323 BA02 BB03 BC02 5H032 AA06 AS16 BB05 BB07 EE02 EE04 EE07 HH00 HH01 HH06 HH08

Claims (32)

[Claims] 1. A reactive gas is introduced into the discharge space into a plasma state under atmospheric pressure or a pressure close to the atmospheric pressure, and the substrate is exposed to the reactive gas in the plasma state.
A method for forming a transparent conductive film, comprising forming a transparent conductive film on the substrate, wherein the reactive gas contains a reducing gas. 2. The method for forming a transparent conductive film according to claim 1, wherein the reducing gas is hydrogen. 3. The method for forming a transparent conductive film according to claim 1, wherein the reactive gas contains at least one material gas selected from organometallic compounds. 4. The mixed gas containing the reactive gas and an inert gas is introduced into the discharge space, and the inert gas contains argon or helium. 2. The method for forming a transparent conductive film as described in 1 above. 5. The method for forming a transparent conductive film according to claim 4, wherein the amount of the reducing gas with respect to the mixed gas is in the range of 0.0001 to 5.0% by volume. 6. The method of forming a transparent conductive film according to claim 4, wherein the mixed gas introduced into the discharge space does not substantially contain oxygen. 7. The electric field applied to the discharge space has a frequency of 0.5 kHz or more and an output density of 100 W.
/ Cm < ² > or less, The transparent conductive film formation method of any one of Claims 1-4 characterized by the above-mentioned. 8. The electric field applied to the discharge space has a frequency exceeding 100 kHz and an output density of 1 W / c.
The method for forming a transparent conductive film according to claim 7, wherein the transparent conductive film is m ² or more. 9. The method for forming a transparent conductive film according to claim 1, wherein a surface temperature of the base material on which the transparent conductive film is formed is 300 ° C. or lower. 10. A transparent conductive film formed by the method for forming a transparent conductive film according to claim 1. 11. The specific resistance value of the transparent conductive film is 1 × 10.
The transparent conductive film according to claim 10, wherein the transparent conductive film has a resistance of ⁻³ Ω · cm or less. 12. The carrier mobility of the transparent conductive film is 1.
The transparent conductive film according to claim 10 or 11, wherein the transparent conductive film has a thickness of 0 cm ² / V · sec or more. 13. The carrier density of the transparent conductive film is 1 ×.
It is 10 ¹⁹ cm ⁻³ or more, and
13. The transparent conductive film according to any one of 12. 14. The carrier density of the transparent conductive film is 1 ×.
It is 10 ²⁰ cm ⁻³ or more, and
13. The transparent conductive film according to any one of 13 above. 15. The indium oxide, tin oxide, zinc oxide, F-doped tin oxide, Al-doped zinc oxide, Sb-doped tin oxide, ITO, In ₂ O ₃ —ZnO-based amorphous transparent conductive film, The transparent conductive film according to any one of claims 10 to 14, wherein any one of them is a main component. 16. The transparent conductive film is an ITO film,
The ITO film has an In / Sn atomic ratio of 100 / 0.1 to 0.1.
16. A range of 100/15, wherein the range is 100/15.
The transparent conductive film according to. 17. The carbon content of the transparent conductive film is 0 to
The transparent conductive film according to claim 15, which has a concentration range of 5.0 atomic number. 18. An article having a transparent conductive film on a substrate, wherein the specific resistance value of the transparent conductive film is 1 × 10 ⁻³ Ω · cm.
An article characterized by the following: 19. The carrier mobility of the transparent conductive film is 1.
19. The article according to claim 18, which is 0 cm ² / V · sec or more. 20. The carrier density of the transparent conductive film is 1 ×.
20. The article according to claim 18 or 19, which is 10 ¹⁹ cm ^-3 or more. 21. The carrier density of the transparent conductive film is 1 ×.
It is 10 ²⁰ cm ⁻³ or more, and
20. The article according to any one of 20. 22. The indium oxide, tin oxide, zinc oxide, F-doped tin oxide, Al-doped zinc oxide, Sb-doped tin oxide, ITO, In ₂ O ₃ —ZnO-based amorphous transparent conductive film, 22. The article according to claim 18, wherein any one of them is a main component. 23. The article according to claim 22, wherein the ITO film has an In / Sn atomic ratio of 100 / 0.1 to 100/15. 24. The carbon content of the transparent conductive film is 0-5.
23. The atomic number concentration range is 0.
Or the article according to 23. 25. The article according to any one of claims 22 to 24, wherein the base material is a transparent resin film. 26. The transparent resin film is a film base material for a touch panel, a liquid crystal element plastic substrate, an organic E
26. The article according to claim 25, which is an L-element plastic substrate, an electromagnetic shielding film for PDP, or a film substrate for electronic paper. 27. The article according to claim 18, wherein the transparent conductive film and the transparent conductive film formed on the substrate have a critical radius of curvature of 8 mm or less. 28. The article according to any one of claims 22 to 27, wherein the transparent conductive film is a patterned electrode. 29. In an article having a transparent conductive film on a substrate, the peak intensity ratio H / M of hydrogen ions and main metal element ions measured by dynamic SIMS of the transparent conductive film.
In the depth direction has a coefficient of variation of 5% or less, an article having a transparent conductive film on a substrate. 30. The transparent conductive film is exposed to the reactive gas in the plasma state by introducing the reactive gas into the discharge space into a plasma state under atmospheric pressure or a pressure near the atmospheric pressure. 30. The article according to claim 29, wherein a transparent conductive film is formed on the substrate by. 31. The article of claim 30, wherein the reactive gas comprises a reducing gas. 32. The electric field applied to the discharge space exceeds a frequency of 100 kHz, and the power density is 1 W /
31 or 3 which is at least cm ^2.
An article having a transparent conductive film on the substrate according to 1.