JP2000038654A - Production of substrate with transparent electrically conductive film, substrate with transparent electrically conductive film and liquid crystal displaying element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To coat the surface of an organic substance such as a color filter or the like for liq. crystal display with an ITO transparent electrically conductive film good in adhesion and small in specific resistance. SOLUTION: In the method for producing a substrate 20 with an ITO transparent electrically conductive film in which an indium oxide vapor depositing material contg. tin oxide is irradiated with arc discharge plasma, and the vapor depositing material is evaporated to coat the surface of a transparent substrate 21 with an ITO film, the gas atmosphere is composed of the one contg. gaseous xenon, gaseous krypton or the gaseous mixture thereof. The total content of xenon and krypton occupied in the gas atmosphere is preferably controlled to >=30 vol.%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of manufacturing a substrate coated with a tin-containing indium oxide polycrystalline transparent conductive film and a substrate using the method, and is particularly preferably used for a transparent electrode such as a liquid crystal display device. The present invention relates to a method for manufacturing a substrate with an ITO transparent conductive film having good adhesion to a substrate and low specific resistance, and a substrate using the method.

[0002]

2. Description of the Related Art Hitherto, several methods have been proposed as methods for lowering the specific resistance of an ITO film. For example, Japanese Patent Application Laid-Open No. 3-29216 discloses a film forming method using arc discharge plasma using argon gas as a gas atmosphere. This method is characterized in that an ITO polycrystalline film can be densely deposited at a low temperature, and the electron carrier density in the film can be significantly increased. As a result, the electric resistance of the transparent conductive film can be significantly reduced. It is.

By using this method, an ITO having a lower specific resistance can be obtained as compared with an ITO polycrystalline film formed by a magnetron sputtering method which is widely used in the industry at present.
It is known that a polycrystalline film can be obtained.

[0004]

In the above-described film forming method using arc discharge plasma, the gas atmosphere is adjusted from the viewpoint that the cost of the discharge gas is the least and that the plasma excitation efficiency is high. Argon is used as the gas. However, although the cause has not been fully elucidated, the IT
The O film (ITO polycrystalline film) has a problem that the compressive stress is remarkably large.

[0005] In particular, when the thickness of the film is increased to reduce the sheet resistance, the value of the compressive stress increases, and when this film having a large compressive stress is used as a transparent electrode of a liquid crystal display device, it is difficult to manufacture the film during the manufacturing process of the display device. There is a problem that a crack occurs in the transparent conductive film due to release of the compressive stress. This problem is practically important especially for an ITO film coated on a color filter containing an organic resin component used for color display or the like.

According to the present invention, when forming an ITO film,
A method for manufacturing a substrate with an ITO transparent conductive film that combines low compressive stress and low specific resistance, and was obtained as a result of intensive research to solve the problem of how to reduce the compressive stress of the film. An object of the present invention is to provide a substrate with an ITO transparent conductive film obtained by the method.

[0007]

According to the first aspect of the present invention, there is provided a film forming chamber capable of adjusting a gas atmosphere reduced in pressure by exhaustion by a vacuum exhaust pump, introduction of a total pressure adjusting gas, and introduction of a discharge gas.
The vapor deposition material of indium oxide containing tin oxide is irradiated with arc discharge plasma generated by an arc discharge plasma generation gun to evaporate the vapor deposition material, and ITO is deposited on a transparent substrate.
A method for manufacturing a substrate with an ITO transparent conductive film, which covers the film, wherein the gas atmosphere is a gas atmosphere containing xenon and / or krypton.

According to the present invention, in forming an arc discharge plasma in a film forming chamber, one or both of a discharge gas for generating plasma and a total pressure adjusting gas directly introduced into the film forming chamber for the purpose of adjusting the atmospheric pressure. Xenon (Xe)
Alternatively, it has been found that the use of krypton (Kr) gas can significantly reduce the compressive stress of the ITO film without deteriorating the electric resistance characteristics.

Although it is not clear why the compressive stress of the film can be reduced, the argon (A) used in the prior art is not clear.
r) of 15.759 eV according to Iwanami Shoten's “Iwanami Physical and Chemical Dictionary 4th Edition” and 12.1 according to the ionization voltage of Xenon (Iwanami Shoten and “Iwanami Physical and Chemical Dictionary 4th Edition”).
30 eV) and the low ionization voltage of krypton (13.999 eV according to Iwanami Shoten's “Iwanami Physical and Chemical Dictionary 4th Edition”).

As the gas atmosphere, a mixed gas of argon and xenon, a mixed gas of argon and krypton, a gas of single component xenon and a gas of single component krypton,
A mixed gas of xenon and krypton, a mixed gas of argon, xenon, and krypton, and the like can be used.
In particular, an ITO film containing xenon, krypton, or both to such an extent that it can be detected in an ITO film can be obtained by an arc discharge plasma method (hereinafter referred to as an AP method).
While maintaining the low resistivity property of the TO film, the film can have a significantly reduced compressive stress.

A second aspect of the present invention is characterized in that, in the first aspect of the present invention, the ratio of the total amount of xenon and krypton in the gas atmosphere in the film forming chamber is 30% by volume or more.

In order to minimize the compressive stress, it is preferable to use a gas atmosphere of 100% xenon or 100% krypton. Xenon or krypton is preferably used by diluting it with argon from the viewpoint of reducing the amount of expensive gas which becomes a part of the coating cost at the same time as reducing the compressive stress. For this purpose, it is preferable that the ratio of the total amount of xenon and krypton to the total amount of the atmosphere gas be 30% by volume or more. Assuming that the total amount is 30% or more, xenon or krypton incorporated in the obtained ITO film can be converted into a secondary ion mass spectrometer (hereinafter, SIM).
S) is the amount of the level detected.

A third aspect of the present invention is characterized in that, in the first or second aspect of the invention, xenon and / or krypton in a gas atmosphere are introduced into a film forming chamber as a discharge gas. Adjustment of gas atmosphere pressure and gas components
The evacuation speed of the vacuum exhaust pump that exhausts the atmosphere in the film formation chamber, the amount of discharge gas introduced into the film formation chamber through the arc discharge plasma generation gun to generate discharge plasma in the film formation chamber, and the This is performed by controlling the amount of the total pressure adjusting gas directly introduced.

In order to efficiently incorporate xenon gas or krypton gas into the obtained ITO film, it is preferable to introduce these gases as a discharge gas into the film formation chamber. As a preferred method of introducing a gas, a discharge gas is a mixed gas of argon and xenon, a mixed gas of argon and krypton, a mixed gas of xenon and krypton, a mixed gas of argon, xenon, and krypton, or a single component of xenon or krypton. However, a method in which the total pressure adjusting gas is argon is exemplified.

According to a fourth aspect of the present invention, an ITO film (hereinafter referred to as a strain reducing layer) is formed by coating a part or all of the film in the thickness direction by the manufacturing method according to any one of the first to third aspects. It is characterized by.

[0016] A part of the ITO film in the thickness direction is constituted by a strain reducing layer covered with a gas atmosphere containing xenon or krypton, and the other part of the ITO film is constituted by an ITO coating obtained by using argon as a gas atmosphere. Is preferable because the amount of xenon or krypton gas, which is more expensive than argon, is suppressed and the compressive stress of the entire film is reduced.

According to a fifth aspect of the present invention, in the fourth aspect of the present invention, the thickness of the strain reducing layer is 10% of the total thickness of the ITO film.
-100%.

The thickness of the strain reducing layer is preferably at least 10% of the total thickness of the ITO film, more preferably at least 20%. When the thickness of the strain reducing layer is less than 10% of the total thickness of the ITO film, the effect of strain reduction is reduced. The thickness of the strain reducing layer is set to 70% or less of the total thickness from the viewpoint of reducing the amount of expensive gas used and from the viewpoint that the compressive stress is not effectively reduced even if the thickness ratio is further increased. Is preferred. The strain reducing layer may be provided at any of the initial stage of the coating of the ITO film, the final stage of the coating (surface layer), and the intermediate stage of the coating (intermediate layer).

The gas atmosphere of the strain reducing layer is preferably adjusted so that the total amount of xenon and krypton is 30% by volume or more.

According to a sixth aspect of the present invention, in the fourth or fifth aspect, the transparent substrate is a substrate in which a liquid crystal color filter containing an organic resin and a colorant is formed on a glass plate. Features.

In the present invention, the transparent substrate is not particularly limited. However, in the case of a substrate on which a color filter containing an organic resin and a colorant is formed on a glass plate, the transparent conductive film and the resin material are formed by reducing the compressive stress. The practical value is particularly great in that the adhesion to the surface is increased, and as a result, peeling and cracking of the film can be prevented.

According to a seventh aspect of the present invention, there is provided a liquid crystal display device in which the substrate with a transparent conductive film according to any one of the fourth to sixth aspects is at least one opposing substrate. Using the substrate with a transparent conductive film of the present invention, a liquid crystal display device such as a TN type, an STN type, and a TFT type can be manufactured.

[0023]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below with reference to embodiments and the accompanying drawings. FIG. 1 is a schematic sectional view of one embodiment of an ion plating film forming apparatus used for coating an ITO film on a substrate according to the present invention. FIG. 2 is a cross-sectional view of the substrate with an ITO transparent conductive film of the present invention. First, FIG. 1 will be described. Arc discharge plasma 13
Is an arc discharge plasma generating gun 2 and a permanent magnet 8 on the bottom.
And a hearth 7 acting as an anode, and a voltage is applied by a plasma generating DC power supply 5 to generate the voltage. As the arc discharge plasma generating gun 2, a composite cathode type plasma generating device, a pressure gradient type plasma generating device, or a plasma generating device combining the both is preferably used. For such a plasma generator,
Known ones described in Vacuum Vol. 25, No. 10, (1982) can be used.

As shown in FIG. 1, an arc discharge plasma generating gun 2 as a discharge cathode and a first
Intermediate electrode 11, second intermediate electrode 1 incorporating magnetic coil 4
2 and a large-diameter magnetic coil 14 are arranged in this order on the side wall of the film forming chamber 6, and a hearth 7 provided with a permanent magnet 8 below the bottom of the film forming chamber 6 is used as a vapor deposition means.

The hearth 7 functions as an anode of the arc discharge plasma 13 and the arc discharge plasma generating gun 2 functions as its cathode. Arc discharge plasma 1 drawn into film formation chamber 6 by a horizontal magnetic field formed by magnetic coil 4
In order to guide the bundle 3 to the hearth 7 filled with the vapor deposition material,
A permanent magnet 8 is provided at the bottom of the hearth 7. The arc discharge plasma 13 is bent downward by about 90 ° in the film forming chamber 6 by the vertical magnetic field of the magnet, and is irradiated on the deposition material. A heater 16 is provided on the back surface of the substrate 15.
The discharge gas 1 whose gas composition is controlled is introduced into the film forming chamber 6 through the arc discharge plasma generation gun 2. Further, in order to control the total pressure and composition of the gas atmosphere in the film forming chamber 6, the total pressure adjusting gas 10 is introduced from a gas introducing pipe provided on the side wall of the film forming chamber 6 separately from the discharge gas 1. . The atmospheric gas in the film forming chamber 6 is a vacuum exhaust port 9.
And is evacuated by a vacuum exhaust pump (not shown).

Next, FIG. 2 will be described. FIG. 2A shows an embodiment of the substrate with an ITO transparent conductive film according to the present invention. In the substrate 20 with a transparent conductive film, a transparent substrate 21 is covered with an ITO polycrystalline film 22. FIG. 2 (b) shows the IT of the present invention.
In another embodiment of the substrate 20 with the O transparent conductive film, the transparent substrate 21
Is covered with a laminated type ITO polycrystalline film 22. The ITO polycrystalline film 22 is a laminate of a film 22a coated with a gas atmosphere of argon and a film 22b coated with a gas atmosphere of xenon. I have.

Items common to the following examples and comparative examples are shown below. 1) Transparent substrate: A color filter for RGB color liquid crystal display (heat-resistant temperature of about 220 ° C.) formed on a glass plate 2) Substrate temperature during film formation: 200 ° C. 3) Evaporation material: indium oxide 96 4% by weight tin oxide 4% by weight 4) The composition of the discharge gas and the gas for adjusting the total pressure was the same in all the examples except for Example 10 and Example 11.
Shown in 5) Total thickness of ITO: 300 nm

The method of analyzing the atmosphere gas in the film forming chamber and the method of testing the obtained ITO film are as follows. 1) Composition of gas atmosphere: measured by a quadrupole mass spectrometer (not shown) installed on the side wall of the film forming chamber, and the volume% of each gas component with respect to the total amount of xenon, krypton and argon is shown in Table 1. . 2) Sheet resistance of ITO film: Measured by a four-terminal method, and the specific resistance was calculated from the relationship with the film thickness. 3) Compressive stress: measured by an X-ray diffraction method. The diffraction angle defined by the crystal lattice spacing observed by X-ray diffraction,
Compared to the diffraction angle observed when measuring ITO powder without stress, the deviation is used as the crystal distortion to obtain the amount of crystal structure distortion, and the relationship between the amount of distortion and the compressive stress is calculated using various physical property values of ITO. did. Rigaku RAD-rC X-ray diffractometer (tube: Cr (40 KV, 200 mA): λ = 2.2897)
Using A), the calculation was performed by a stress measurement program attached to the apparatus. As the above-mentioned various physical property values of ITO, a Young's modulus = 116,000 MPa, a Poisson's ratio = 0.350, and a stress constant value = −659.89 MPa were used. The diffraction angle compared is 97.30200 ° when there is no distortion.
Calculated as 4) Analysis of atmospheric gas components in the film: SIMS analysis was used. 5) Heat resistance test: Maintained at 200 ° C for 1 hour. ：: No problem in appearance inspection, Δ: Minor crack in appearance inspection, ×: Crack in appearance inspection.

Description of Table 1) The layers in Table 1 are on the side closer to the substrate.

Example 1 A substrate was placed in a film forming chamber, and 0.00 0.00
The substrate was once evacuated to a pressure of 27 Pa or less to heat the substrate. Thereafter, xenon gas was introduced as a discharge gas and a gas for adjusting the total pressure, and a current of 150 A was supplied to an arc discharge plasma generating gun to generate arc discharge plasma. The deposition material was irradiated with the generated arc discharge plasma to form an ITO film on the substrate. Table 2 shows the evaluation results of the obtained ITO films. While maintaining a low specific resistance of 1.4 × 10 ⁻⁴ Ωcm, it had a small compressive stress of 360 MPa. The value of this stress was about 33 of the value of Comparative Example 1 described later.
%Met.

In Comparative Example 1 to be described later, X in the ITO film obtained by using only argon as the discharge gas and the total pressure adjusting gas was used.
Compared with the background of m (mass) / z (atomic number) = 131 due to e ⁺ (Xe is not included in this ITO film), a peak of m / z = 131 is detected,
It was confirmed that xenon was contained in the film. When this ITO film was subjected to a heat resistance test, it was confirmed that both the color filter and the ITO film had no change in appearance and no change in electrical characteristics.

Examples 2 to 4 An ITO film was coated in the same manner as in Example 1 except that the discharge gas and the total pressure adjusting gas were adjusted to the composition ratios shown in Table 1.
Table 2 shows the evaluation results of the obtained ITO films. These samples range from 1.4 × 10 ⁻⁴ Ωcm to 1.5 × 10 ⁻⁴ Ωc.
490 MPa-6 while maintaining a low specific resistance of
It had a small compressive stress of 00 MPa. In Example 2 and Example 4, m attributable to Kr ^{+ of} Comparative Example 1 was used.
/ Z = 84 background (this ITO film has Kr
(Not included), a peak at m / z = 84 was detected. Therefore, it was confirmed that this film contained krypton.

Further, in Example 3, compared with the background of m / z = 131 caused by Xe ^{+ of} Comparative Example 1,
A peak at m / z = 131 was detected, confirming that xenon was contained in the film. In addition, these ITO
When the film was subjected to a heat test, the color filter and I
It was confirmed that the appearance of the TO film did not change at all and the electrical characteristics did not change.

Example 5 A substrate was placed in a film forming chamber, and was evacuated to 0.000 by a vacuum pump.
It was evacuated to a pressure of 27 Pa or less and heated. Thereafter, xenon gas was introduced as a discharge gas and a gas for adjusting the total pressure, and a current of 150 A was supplied to the arc discharge plasma generation gun.
An arc discharge plasma was generated. First, a 60-nm ITO film was formed using the generated arc discharge plasma. After that, 0.0027 again by the vacuum pump.
The gas was evacuated to a pressure of Pa or less, and then argon gas was introduced as a discharge gas and a gas for adjusting the total pressure, and a current of 150 A was again supplied to the arc discharge plasma generation gun to generate arc discharge plasma. The film was formed into a two-layer laminated type ITO film having a total thickness of 300 nm.

Table 2 shows the evaluation results of the obtained ITO films. While maintaining a low specific resistance of 1.4 × 10 ⁻⁴ Ωcm, it had a small compressive stress of 580 MPa. M / z due to Xe ⁺ in the ITO film of Comparative Example 1
Compared with the background of 131, a peak of m / z = 131 was detected in the ITO film on the side closer to the substrate, and it was confirmed that xenon was present in the film. Further, when the ITO film was subjected to a heat resistance test, it was confirmed that both the color filter and the ITO film had no change in appearance and no change in electrical characteristics.

Examples 6 to 8 In the same manner as in Example 5, an ITO film having a total film thickness of 300 nm formed under different gas atmosphere conditions was coated on the substrate. Table 2 shows the evaluation results of the obtained ITO films. 1.5
While maintaining a low specific resistance of × 10 ^-4 Ωcm, 48
It had a small compressive stress of 0 MPa to 600 MPa. Similarly, m / z due to Xe ⁺ in the ITO film
= 131 background and m due to Kr ⁺
Compared with the background of / z = 84, peaks specific to each element were detected from the layer formed under the condition that the discharge gas and the total pressure adjusting gas contained xenon or krypton. In addition, when these ITO films were subjected to a heat resistance test, it was confirmed that both the color filter and the ITO film had no change in appearance and no change in electrical characteristics.

Example 9 An ITO film was formed in the same manner as in Example 1 except that the discharge gas and the total pressure adjusting gas were adjusted to the composition ratios shown in Table 1. Table 2 shows the evaluation results of the obtained ITO films. 1.4 × 10 ^-4 Ω
cm, while having a low compressive stress of 400 MPa. In comparison with the background of m / z = 84 caused by Kr ⁺ and the background of m / z = 131 caused by Xe ⁺ in the ITO film prepared in Comparative Example 1, peaks were detected at those positions. It was confirmed that xenon and krypton were contained in the film. Further, when the ITO film was subjected to a heat resistance test, it was confirmed that both the color filter and the ITO film had no change in appearance and no change in electrical characteristics.

Example 10 Xenon gas was used as the discharge gas, and a mixed gas of xenon gas and argon gas was used as the total pressure adjusting gas. The composition ratio of the adjusting gas was determined. Other than this, I was the same as in the first embodiment.
A TO film was formed. Table 2 shows the electrical characteristics of the obtained ITO film and the values of the compressive stress measured by the X-ray diffraction method. 1.
While maintaining a low specific resistance of 5 × 10 ⁻⁴ Ωcm, 4
It had a small compressive stress of 20 MPa. M / z = 1 due to Xe ⁺ in the ITO film manufactured in Comparative Example 1.
A peak at m / z = 131 was detected as compared with the background of No. 31, confirming that xenon was contained in the film. Further, when the ITO film was subjected to a heat resistance test, it was confirmed that both the color filter and the ITO film had no change in appearance and no change in electrical characteristics.

Example 11 Argon gas was used as a discharge gas, a mixed gas of xenon gas and argon gas was used as a gas for adjusting the total pressure, and the gas composition for adjusting the total pressure was adjusted so that the gas composition of the atmosphere became the value shown in Table 1. The composition ratio was determined. Except for this, ITO was used in the same manner as in Example 1.
A film was formed. Table 2 shows the evaluation results of the obtained ITO films. While maintaining a low specific resistance of 1.5 × 10 ⁻⁴ Ωcm, it had a small compressive stress of 580 MPa. In Comparative Example 1, m / z = caused by Xe ⁺ in the ITO film
A peak at m / z = 131 was detected in comparison with the background of 131, confirming that xenon was contained in the film. In addition, when this ITO film was subjected to a heat resistance test, it was confirmed that both the color filter and the ITO film had no change in appearance and no change in electrical characteristics.

The composition of the gas atmosphere in the film formation chamber is xenon 3
Example 10 (discharge gas: 100% by volume of xenon) and Example 3 even if the volume is the same as 70% by volume of 0% by volume argon.
(Discharge gas: xenon 30% by volume), and the films obtained in Example 11 (discharge gas: argon 100% by volume) were 420 MPa, 550 MPa, and 580 MPa, respectively. It has been found that the use of a gas having a high xenon concentration as the discharge gas effectively reduces the compressive stress of the ITO film. Even when krypton gas is used to reduce compressive stress, it has the same effect as xenon.

Example 12 The procedure of Example 1 was repeated except that the discharge gas and the gas for adjusting the total pressure were adjusted to 10% by volume of xenon and 90% by volume of argon.
A TO film was formed. Table 2 shows the evaluation results of the obtained ITO films.
Shown in While maintaining a low specific resistance of 1.4 × 10 ⁻⁴ Ωcm, it had a compressive stress of 700 MPa.
The value of this stress was about 64% of Comparative Example 1. Comparative Example 1
M / z = 13 due to Xe ⁺ in the ITO film prepared in
As compared with the background of No. 1, the peak at m / z = 131 was buried in the background level and was not clearly recognized. However, when this ITO film was subjected to a heat resistance test, minute cracks were being formed on the film surface, but the size and depth of the cracks were extremely small as compared with Comparative Example 1 described later.

Example 13 A laminated type ITO film was formed in the same manner as in Example 5 except that the composition ratio of the discharge gas and the total pressure adjusting gas was controlled as shown in Table 1. Table 2 shows the evaluation results of the obtained ITO films. It had a compressive stress of 750 MPa while maintaining a low specific resistance of 1.4 × 10 ⁻⁴ Ωcm. The value of this stress was about 68% of Comparative Example 1. Compared with the background of m / z = 131 caused by Xe ⁺ in the ITO film manufactured in Comparative Example 1, the layer closer to the substrate
m / z = 131 peaks were detected. When this ITO film was subjected to a heat resistance test, fine cracks were formed on the surface of the ITO film, but the size was smaller than that of Comparative Example 1 described later.

Comparative Example 1 An ITO film was formed in the same manner as in Example 1 except that a gas consisting of only argon was used as the discharge gas and the gas for adjusting the total pressure. Table 2 shows the evaluation results of the obtained ITO films.
Although it had a low specific resistance of 1.4 × 10 ⁻⁴ Ωcm, the compressive stress was 1100 MPa. When this ITO film was subjected to a heat resistance test, several large cracks were formed in the ITO film. This crack was presumed to have been caused by the release of the large compressive stress inherent in the ITO film.

From the above Examples and Comparative Examples, it can be seen that when coating a substrate with an ITO film, the gas atmosphere containing xenon or krypton reduces the value of the compressive stress of the film. This reduction in the compressive stress increases the adhesion to the substrate and prevents cracks that cause insulation failure as display electrodes.

[0045]

[Table 1] ================================= Example 1 layer 2 layers 3 layers Gas atmosphere Thickness Gas atmosphere Thickness Gas atmosphere Thickness (% by volume) (nm) (% by volume) (nm) (% by volume) (nm) −−−−−−−−−−−−−−−−−−−−−−−−−− −−−−−−−−−− Example 1 Xe100 300 Example 2 Kr100 300 Example 3 Xe 30 300 Ar 70 Example 4 Kr 70 300 Ar 30 Example 5 Xe100 60 Ar 100 240 Example 6 Kr100 100 Ar 100 200 Example 7 Ar100 100 Xe 100 200 Example 8 Ar100 100 Xe 100 100 Ar100 100 Example 9 Xe40 300 Kr30 Ar30 Example 10 Xe30 300 Ar70 Example 11 Xe30 300 Ar70 Example 12 Xe10 300 Ar90 Example 13 Xe100 30 Ar 100 270 Comparative Example 1 Ar100 300 ==================================

[0046]

[Table 2] ============================= Example Sheet resistance Specific resistance Compressive stress Heat resistance test (Ω / □) (× 10 ^-4 (MPa) (Appearance) Ωcm) −−−−−−−−−−−−−−−−−−−−−−−−−−−−−− Example 1 4.78 1.4 360 360 ◎ Example 2 4.701 0.4490 Example 3 4.99 1.5 550 Example 4 4.82 1.5 600 △ to △ Example 5 4.80 1.4 580 Example 6 4.87 1.5 580 ◎ Example 7 4.90 1.5 480 Example 8 5.10 1.5 600 実 施 Example 9 4.75 1.4 400 実 施 Example 10 5.02 1.5 420 実 施 Example 11 4.92 1.5 580 ◎ Example 12 4.80 1.4 700 △ Example 13 4.75 1.4 750 △ Comparative Example 1 4.70 1.4 1100 × ============ ==================

[0047]

According to the present invention, I using the arc discharge plasma of the present invention can be used.
According to the method for manufacturing a substrate with a TO transparent conductive film, the gas atmosphere is an atmosphere containing xenon or krypton, so that the compressive stress of the ITO film is reduced. This allows
It is possible to obtain a substrate with an ITO transparent conductive film, in which the adhesion to the substrate is increased and cracks are not generated due to release of stress.

By setting the ratio of the total amount of xenon and krypton in the gas atmosphere to 30% by volume or more, an ITO film having a small compressive stress value can be obtained.

Further, when the atmosphere containing xenon or krypton is introduced into the film forming chamber through the arc discharge plasma generating gun, the compressive stress of the film can be effectively reduced.

Further, no crack is generated on the surface of a thermally unstable organic substance such as a color filter for a liquid crystal containing an organic resin and a colorant in the ITO film.

When the gas atmosphere is covered with a gas atmosphere containing xenon or krypton in a part of the ITO film in the thickness direction, the use amount of these expensive gases can be reduced, which leads to a reduction in manufacturing cost.

Further, in the color liquid crystal display device using the substrate of the present invention in which the ITO transparent conductive film is coated on a color filter as a counter substrate, no cracks are generated in the transparent electrode, and therefore, the pixel is turned on by the disconnection of the transparent electrode. Failure can be prevented. In addition, since the compressive stress of the transparent electrode is small, the display element has high adhesion to the substrate and high reliability.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view of an embodiment of a film forming apparatus used for carrying out the present invention.

FIG. 2 is a cross-sectional view of one embodiment of a substrate with an ITO transparent conductive film of the present invention.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Discharge gas, 2 ... Arc discharge plasma generation gun, 3, 8 ... Permanent magnet, 4 ... Magnetic coil, 5
DC power source 6 for plasma generation Film forming chamber 7 Hearth 9 Vacuum exhaust port 10 Total pressure adjusting gas 11 First intermediate electrode 12 2nd intermediate electrode, 13 ... arc discharge plasma, 14 ... large-diameter magnetic coil, 15 ... substrate, 16 ... heater, 2
0 ... substrate with ITO transparent conductive film, 21 ... transparent substrate, 22 ... ITO polycrystalline film, 22a ... film coated with argon in gas atmosphere, 22b ... xenon coated in gas atmosphere Membrane

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H01B 5/14 H01B 5/14 A 5G307 13/00 503 13/00 503B 5G323 F-term (Reference) 2H091 FA02Y FC01 FC02 FC29 GA03 LA02 LA12 2H092 HA04 MA08 MA35 NA18 NA28 PA08 4G059 AA08 AB19 AC12 EA03 EB03 GA01 GA12 4K029 AA09 BA50 BB02 BB08 BC09 DD05 EA05 5G301 CA02 CA15 CA23 CD03 CE01 5G307 FA01 FA02 FB01 FC05 FC10 FC05 FC10 FC05 FC10

Claims (7)

[Claims] 1. An arc discharge plasma generation gun for depositing indium oxide containing indium oxide in a film forming chamber in which a gas atmosphere reduced in pressure can be adjusted by exhaustion by a vacuum exhaust pump, introduction of a total pressure adjusting gas and introduction of a discharge gas. The evaporation material is evaporated by irradiating the arc discharge plasma generated in the
A method for manufacturing a substrate with an ITO transparent conductive film, wherein the gas atmosphere is a gas atmosphere containing xenon and / or krypton, wherein the ITO film is coated on the transparent substrate. 2. The method for manufacturing a substrate with an ITO transparent conductive film according to claim 1, wherein the ratio of the total amount of xenon and krypton in the gas atmosphere in the film formation chamber is 30% by volume or more. . 3. A method for manufacturing a substrate with an ITO transparent conductive film, wherein xenon and / or krypton in the gas atmosphere is introduced at least as a discharge gas into a film forming chamber via an arc discharge plasma generation gun. . 4. A method according to claim 1, wherein a part or the whole in the thickness direction is provided.
3. A substrate with an ITO transparent conductive film, comprising a ITO film coated by the production method according to any one of 3. 5. The thickness of the ITO film according to claim 4,
The substrate with an ITO transparent conductive film according to claim 4, wherein the total thickness of the O film is 10% to 100%. 6. The method according to claim 4, wherein the transparent substrate is a substrate in which a liquid crystal color filter containing an organic resin and a colorant is formed on a glass plate.
Substrate with TO transparent conductive film. 7. The ITO according to any one of claims 4 to 6, wherein
A liquid crystal display element using a substrate with a transparent conductive film as at least one counter substrate.