JPH0971857A - Transparent conductive film and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a transparent conductive film having low resistance, high transparency and excellent patterning characteristics formed on such a base body that has low heat resistance and low durability against plasma and that easily causes degeneration, deterioration, thermal decomposition or release of gases due to influences of heating or plasma, and to obtain a method for easily producing the object transparent conductive film. SOLUTION: This transparent conductive film has grains which show >=5 of intensities I1 /I2 , wherein I1 is the peak intensity of the (222) plane and I2 is the peak intensity of (400) plane in a X-ray diffraction method, and has 0.8×10<-4> to 3.5×10<-4> Ω.cm specific resistance. This transparent conductive film is formed on a base body 12 by using a hollow cathode ion plating method to form plasma between the vapor source 11 and the base body 12 under such conditions that the base body is not badly influenced by the plasma.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transparent conductive film, particularly a low resistance transparent conductive film formed on a substrate having low heat resistance and plasma resistance, and a method for producing such a transparent conductive film.

[0002]

2. Description of the Related Art Conventionally, a transparent conductive film has been used for various electronic components, image display devices, and the like. The transparent conductive film is made of indium tin oxide (ITO), zinc oxide (ZnO),
It is formed by using tin oxide (SnO) or the like and its alloy or the like by a film forming method such as a sputtering method, a vacuum deposition method, a CVD method or the like.

Among the above film forming methods, the sputtering method is, for example, a method in which an ITO oxide target material is sputtered with Ar ions to form an ITO film on a base material. Such an ITO film has a low resistance by being crystallized by setting the base material temperature during film formation and the annealing temperature after film formation at 200 to 300 ° C., and has been given patterning characteristics.

However, some of the substrates on which the transparent conductive film is formed have a degassing phenomenon in which gases such as water and organic components are generated due to the influence of heating during formation of film and plasma, or , Some may cause alteration, deterioration, and thermal decomposition. When there is degassing from the base material, the generated gas causes crystal grain agglomerates in the transparent conductive film to form a coarse and dense film,
The resistance reduction of the transparent conductive film is hindered. Further, for example, in the case where the transparent conductive film is formed on a substrate having a color filter for a liquid crystal display, the alignment of the liquid crystal in contact with the surface of the transparent conductive film is caused by the above-mentioned crystal grain agglomerates generated in the transparent conductive film. There is a problem that the condition is adversely affected. For this reason, a thin film having a gas barrier property is previously formed on a substrate that causes degassing as described above, and a transparent conductive film is formed on this thin film.

[0005]

However, the above gas barrier thin film is an electrically insulating thin film such as an inorganic thin film such as silicon oxide or an organic thin film such as synthetic resin.
By forming such a gas barrier thin film,
The manufacturing process of the transparent conductive film is complicated, resulting in an increase in manufacturing cost. Further, even when a gas barrier thin film is provided, it is possible to avoid deterioration or deterioration of the substrate having low heat resistance (for example, change in color difference of color filter) by forming the transparent conductive film at high temperature. Absent.

In order to deal with this, a method has been proposed in which a transparent conductive film is formed by a sputtering method at a substrate temperature of 150 ° C. or lower, and then heat treatment (160 to 250 ° C.) is performed to crystallize. (Japanese Patent Application Laid-Open No. 1-259
320). However, such a transparent conductive film has a complicated process, and is degassed from the base material due to the influence of plasma or the like, that is, gas generation with a mass number of 68 or more occurs when measured with a mass spectrometer, and is formed. The film has a grain structure, and there is a problem that a transparent conductive film having a low specific resistance cannot be obtained.

The present invention has been made in view of the above circumstances, and is a substrate having low heat resistance and plasma resistance that causes deterioration, deterioration, thermal decomposition or degassing due to heating or plasma. It is an object of the present invention to provide a transparent conductive film having a low resistance, a high transparency and an excellent patterning property, and a manufacturing method capable of easily forming such a transparent conductive film.

[0008]

In order to achieve such an object, the transparent conductive film of the present invention has crystal grains, and the peak intensity I ₁ and (40) of the (222) plane in the X-ray diffraction method.
The ratio I ₁ / I ₂ to the peak intensity I ₂ of the 0) plane is 5 or more, and the specific resistance is 0.8 × 10 ^{−4 to} 3.5 × 10 ^−4.
The configuration is such that the range is Ω · cm.

Further, the transparent conductive film of the present invention has a mobility of 3
The structure having a range of 0 to 50 cm ² / Vsec, the structure having a transmittance of 80 to 100% with respect to light having a wavelength of 550 nm, and the area occupancy of a groove having a size of 100 Å or more on the surface of the transparent conductive film. The composition is set to 15% or less.

The method for producing a transparent conductive film of the present invention uses a reactive vapor deposition method to form plasma between a vapor deposition source and a substrate, and the substrate exposed to the plasma is adversely affected. The transparent conductive film was formed on the base material under such conditions.

The method for producing a transparent conductive film of the present invention is
When the above-mentioned conditions were exposed to the plasma atmosphere or the heating atmosphere, the mass number 68 was measured by a mass spectrometer.
The configuration is such that the partial pressure ratio of the output corresponding to the above is such that it is less than 1 × 10 ⁻¹¹ Torr.

In the present invention as described above, since the transparent conductive film is formed by the reactive vapor deposition method without the substrate being exposed to plasma and being adversely affected, the substrate is deteriorated by heating,
Even if it is a substrate with low heat resistance and plasma resistance that causes deterioration, thermal decomposition, or degassing, the formed transparent conductive film has fine grains and excellent surface flatness. There is no vacancy in the film structure, so that the specific resistance is 0.8 × 10 ^{−4 to} 3.5 × 10 ⁻⁴ Ω · cm.
And it will be extremely low.

[0013]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below with reference to the drawings.

The transparent conductive film of the present invention has crystal grains, and the transparent conductive film (22) in the X-ray diffraction method is used.
2) Peak intensity I _{1 of the} plane and peak intensity I of the (400) plane
₂ ratio I ₁ / I ₂ of 5 or more, preferably a 6-100, forming a well-defined crystalline structure rather than amorphous. The above crystal grains have an average particle size of 300 to 1000Å
Although the particles are crystalline to some extent, no crystal grain agglomerates are present and the surface of the transparent conductive film is flat. When the peak intensity ratio I ₁ / I ₂ is less than 5, the crystallinity of the transparent conductive film is insufficient and the following favorable specific resistance and mobility cannot be obtained. Here, in the present invention, the peak intensity ratio I ₁ / I ₂ of the X-ray diffraction is calculated from the ratio of the peak height of the (222) plane to the peak height of the (400) plane of the X-ray diffraction curve with the background removed. It is to be calculated.

In the transparent conductive film of the present invention, there are no domains that are different depending on the grain boundaries associated with the crystal grains and the orientation direction of the crystal grains. Since the crystal grains are densely packed without any gaps, no voids are formed in the film structure, which results in a resistivity of 0.8 × 10 5.
^{-4 to} 3.5 × 10 ^-4 Ω · cm, which is extremely low. In addition, the transparent conductive film of the present invention has a mobility of 30.
˜50 cm ² / Vsec and a wavelength of 55
The transmittance for 0 nm light is 80 to 100%. Therefore, the transparent conductive film of the present invention is a transparent conductive film having low resistance and high transparency.

Further, on the surface of the transparent conductive film of the present invention, the area occupancy of the grooves having a size of 100 Å or more is 15% or less, and the surface is extremely flat. The area occupancy of the groove of 100 Å or more on the surface of the transparent conductive film is the area occupied by the groove of 1 mm or more in the area of 7 cm × 7 cm in the surface observation with a scanning electron microscope (SEM) (magnification: 100,000 times). Is calculated by calculating the total sum of.

Such a transparent conductive film of the present invention includes indium tin oxide (ITO), zinc oxide (ZnO), its alloy (AZO (Al-doped ZnO film)), N.
It is a thin film formed of an ESA film (SnO ₂ ) or the like and has a thickness of 50 to 10000Å, preferably 500 to 3000Å
It can be a degree.

Next, a method of manufacturing the transparent conductive film of the present invention will be described.

The method for producing a transparent conductive film of the present invention has a heat resistance such that the transparent conductive film of the present invention as described above is deteriorated, deteriorated, thermally decomposed or degassed by the influence of heating or plasma. It is a film that can be easily formed on a substrate with low plasma resistance. A reactive vapor deposition method is used to form plasma between the vapor deposition source and the substrate, and the substrate exposed to this plasma is used. The transparent conductive film is formed on the base material under the condition that no adverse effect occurs.

Here, the base material having low heat resistance and low plasma resistance in the present invention corresponds to a mass number of 68 or more in a mass spectrometer when the base material is heated in vacuum at 200 ° C. or exposed to an Ar plasma atmosphere. The output voltage division ratio is 1 ×
It means a substrate exhibiting 10 ^-11 Torr or more. Further, the condition that the base material is not exposed to plasma and adversely affected is that when the base material is exposed to the plasma atmosphere, the partial pressure ratio of the output corresponding to the mass number 68 or more in the mass spectrometer is 1 × 10. ^It means that the condition is less than ^-11 Torr.

Examples of the reactive vapor deposition method used in the method for producing the transparent conductive film of the present invention include a forocathode type ion plating method, a DC type ion plating method, an RF type ion plating method and the like.

Here, the follow cathode type ion plating method will be described with reference to FIG. FIG. 1 is a block diagram showing an example of a horizontal foro-cathode type ion plating apparatus. In FIG. 1, a follow cathode type ion plating apparatus 1 includes a vacuum chamber 2 provided with an exhaust port 2a and a reaction gas supply port 2b, an anode (hearth) 3 disposed under the vacuum chamber 2 and a vacuum chamber 2. A substrate holder 4 arranged in the upper part of the chamber 2, a plasma gun 5, a cathode 6, an intermediate electrode 7 and an auxiliary coil 8 arranged at a predetermined position of the vacuum chamber 2 (the left wall of the vacuum chamber in the illustrated example). I have it. Further, a permanent magnet 9 is arranged below the anode 3.

The formation of the transparent conductive film by the ion plating method using the above-described cathode type ion plating apparatus 1 is performed as follows. First, the evaporation source 11 is arranged on the anode 3, the base material 12 which is a transparent conductive film forming object is held on the base material holder 4, and the inside of the vacuum chamber 2 is evacuated to about 10 ⁻⁶ to 10 ⁻⁵ Torr. Every time. In this state, a plasma gas such as argon (Ar) is introduced into the plasma gun 5. Then, the plasma beam 15 generated by the plasma gun 5 is drawn into the vacuum chamber 2 by the magnetic field formed by the auxiliary coil 8, and is converged on the evaporation source 11 by the magnetic field created by the permanent magnet 9 below the anode 3, and this evaporation is performed. Heat the source 11. As a result, the evaporation source 11 in the heated portion evaporates, partially ionizes when passing through the region of the plasma beam 15, reaches the base material 12 held by the base material holder 4, and forms a film on the surface. Form.

The method of manufacturing the transparent conductive film of the present invention as described above is characterized in that the base material 12 is arranged at a position where it is not exposed to the plasma beam 15. This is because when a base material with low heat resistance and plasma resistance, such as a color filter for liquid crystal displays, which causes thermal decomposition or degassing when heated is exposed to plasma, degassing from the base material occurs. Then, it was due to the fact that crystal grains were generated in the formed ITO film to form a coarse and dense film, which hinders resistance reduction. That is, in the method for producing a transparent conductive film of the present invention, the temperature of the base material, which is an object on which the transparent conductive film is formed, is set to the ITO by the conventional sputtering method.
The temperature can be set significantly lower than when the film is formed, and because the transparent conductive film is formed by the ion plating method without exposing the substrate to plasma, alteration, deterioration, or thermal decomposition due to heating may occur. It is possible to form a transparent conductive film even on a base material having low heat resistance that causes outgassing, within the heat resistance temperature of the base material. In the present invention, since the transparent conductive film is formed while effectively preventing the degassing of the base material, a complicated process such as a two-layer film formation in which the transparent conductive film is formed on a conventional gas barrier thin film. Is unnecessary, and productivity is greatly improved. Moreover, a transparent conductive film having excellent patterning characteristics can be obtained as compared with the conventional transparent conductive film formed by two-layer film formation.

The ion plating apparatus used in the reactive vapor deposition method in the method for producing a transparent conductive film of the present invention is
The ion plating apparatus may be configured so that the above conditions are satisfied even when the substrate is exposed to the plasma formed between the evaporation source and the substrate, and is limited to that shown in FIG. Not a thing.

[0026]

Next, the present invention will be described in more detail with reference to examples. Example 1 A glass substrate having a thickness of 1.1 mm (7059 manufactured by Corning Incorporated) and a color filter substrate having a color filter for a liquid crystal display formed on one surface of the glass substrate by a pigment dispersion method were prepared.

Next, the above color filter substrate or glass substrate was held on the base material holder of the foro cathode type ion plating apparatus as shown in FIG.
In addition, a vapor deposition material (In ₂
O ₃ -SnO ₂ sintered body (SnO ₂ 5 wt%)) was placed. After that, a film was formed under the following film forming conditions to form a transparent conductive film (Sample 1, Comparative Sample 1) having a thickness of 1500Å on the substrate.

(Deposition conditions) Deposition degree of vacuum: 2.4 × 10 ⁻⁴ Torr Introduced gas: Ar = 30 sccm, O ₂ = 7 sc
cm ・ Plasma gun: voltage = 60 V, current = 150 A, beam diameter = several 10 mm ・ Base material temperature: 190 ° C. ・ Film forming rate: 1500 Å / min For comparison, the base material temperature was 60 ° C. Transparent conductive films (Comparative Samples 2 and 3) having a thickness of 1500 Å were prepared on the base material in the same manner as in Sample 1.

Further, for comparison, a glass plate and a color filter substrate similar to those described above were used, and a film was formed by a sputtering method under the following film forming conditions to give a thickness of 15 on the substrate.
00Å transparent conductive films (Comparative Samples 4 to 7) were prepared.

(Film forming conditions) Atmosphere gas: Ar = 100 sccm, O ₂ = 2 s
ccm ・ Atmospheric pressure: 6 × 10 ^-3 Torr ・ Introduction power: DC 2.5 W / cm ²・ Film formation rate: 720 Å / min ・ Substrate temperature: 60 ° C, 190 ° C ・ Target material: In ₂ O ₃ -SnO ₂ sintering Body (Sn
O ₂ 10% by weight) Further, as a comparison, the thickness on the substrate was the same as for Samples 1 and 2 above (substrate temperature 190 ° C.) except that the substrate holder was positioned in the plasma discharge. A transparent conductive film of 1500 Å (Comparative Samples 8 and 9) was prepared. In this case,
The substrate is a mass spectrometer (quadrupole mass spectrometer (SKK Vacuum Engineering Co., Ltd. DAQ200 / DX
M)) with mass numbers 61, 91 (resist), 12
The outputs (corresponding to a partial pressure ratio of 1 × 10 ⁻¹¹ to 10 × 10 ⁻¹¹ Torr) corresponding to 9,172 (pigment) and 190 (initiator) were exhibited. The material used in this example has an output from such a mass spectrometer, but if the material used changes, the mass number naturally changes. However, as the base material in which the resin or pigment is used, a material having a mass number of 68 or higher is detected.

The transparent conductive film prepared as described above (Sample 1)
And the comparative samples 1 to 9), the crystal structure, the specific resistance,
The mobility, transmittance and suitability for the alignment film were measured and evaluated, and the results are shown in Table 1 below.

[0032] The (crystal Evaluation of structures) X-ray diffraction method, the diffraction peak intensity I ₂ of the diffraction peak intensity I ₁ and the 2 [Theta] = 35.12 ° of 2θ = 30.08 ° (222) showing a crystalline (400) The ratio I ₁ / I _{2 of} was calculated.

X-ray Diffraction Measuring Conditions / Measuring Equipment: Powder X-ray diffractometer (Rigaku Denki Co., Ltd.)
(Made by wide angle goniometer, CuKα ray, 2θ / θ scan) ・ Tube voltage: 40Kv ・ Tube current: 200mA ・ Sampling width: 0.020 ° ・ Scanning speed: 4 ° / min ・ Diffusion slit: 1 ° ・ Scattering slit : 1 ° ・ Light-receiving slit: 0.30 nm (Measurement of specific resistance) Surface resistance meter LOR manufactured by Mitsubishi Petrochemical Co., Ltd.
The sheet resistance R _s (Ω / □) was measured using ESTA-FP, and the thickness d (Å) of the transparent conductive film was calculated as shown in formula (1).
The specific resistance ρ (Ω · cm) was calculated by multiplying by.

Ρ = d × R _s (1) (Measurement of mobility) It was calculated by the Van der Pauw method.

(Measurement of Transmittance) The transparent conductive film formed on the glass substrate was measured for transmittance at a wavelength of 550 nm.

(Evaluation of Alignment Film Suitability) It was evaluated whether or not the coloring material of the color filter would flow out by dropping n-methylproteide (NMP), which is a solvent for polyimide coating.

Evaluation Criteria ◯: No outflow of color material occurs Δ: Some outflow of color material appears ×: Outflow of color material is noticeable

[0038]

[Table 1] As shown in Table 1, the transparent conductive film (Sample 1) formed on the color filter substrate had the same X-ray diffraction peak intensity ratio I as the transparent conductive film (Comparative Sample 1) formed on the glass plate.
₁ / I ₂ was 5 or more, and the transparent conductive film had good crystallinity. The transparent conductive film of the present invention has a specific resistance of 3.5 × 10 ⁻⁴ Ω · cm or less and a mobility of 30 cm ² / V.
It was confirmed to be a transparent conductive film having excellent electrical characteristics and transparency, which is not less than sec and the transmittance at a wavelength of 550 nm is not less than 80% (in Comparative Sample 1). Furthermore, the alignment film characteristics were good, and it could be put to practical use as a transparent conductive film for liquid crystal displays.

On the other hand, the transparent conductive film (Comparative Samples 2, 3, 4, 6) formed at a comparatively low base material temperature by the ion plating method or the conventional sputtering method has X
The line diffraction peak intensities I ₁ and I ₂ were extremely small and were close to amorphous, and the specific resistance and mobility were insufficient. Further, among the transparent conductive films (comparative samples 5 and 7) formed at a relatively high base material temperature, the transparent conductive film (comparative sample 8) formed on the color filter substrate has an X-ray diffraction peak intensity ratio I. _{When 1} / I ₂ is less than 5, the crystal orientation is different and the structure is different. Therefore, the specific resistance is 3.5 × 10 ⁻⁴ Ω.
cm, mobility of less than 30 cm ² / Vsec,
The electrical properties were poor and the alignment film properties were also poor, so that it could not be put to practical use as a transparent conductive film for liquid crystal displays. (Example 2) In the same manner as in Example 1, a thickness of 1500 was formed on a substrate under the following conditions by the method for producing a transparent conductive film of the present invention.
Å transparent conductive film (Sample I, Comparative Sample I) was prepared.
The transparent conductive film (Sample I, Comparative Sample I) corresponds to the transparent conductive film of Example 1 (Sample 1, Comparative Sample 1).

(Deposition conditions) ・ Achieved vacuum degree: 1.0 × 10 ^-5 Torr or less ・ Deposition vacuum degree: 2.4 × 10 ^-4 Torr ・ Introduced gas: Ar = 30 sccm, O ₂ = 7 sc
cm ・ Plasma gun: voltage = 60 V, current = 150 A, beam diameter = several 10 mm ・ Base material temperature: 190 ° C. ・ Film formation rate: 1500 Å / min For comparison, the same glass plate and color filter substrate as in Example 1 were used. A transparent conductive film (Comparative Samples II and III) having a thickness of 1500 Å was formed on the base material by the sputtering method under the following film forming conditions.

(Film forming conditions) Atmosphere gas: Ar = 100 sccm, O ₂ = 2 s
ccm ・ Atmospheric pressure: 6 × 10 ^-3 Torr ・ Introduction power: DC 2.5 W / cm ²・ Film formation rate: 720 Å / min ・ Substrate temperature: 165 ° C. ・ Target material: In ₂ O ₃ -SnO ₂ sintered body (Sn)
O ₂ 10% by weight) Further, as a comparison, using a similar color filter substrate as in Example 1, performed by a sputtering method at a film formation under the following conditions, then subjected to heat treatment (200 ° C., 30 minutes) A transparent conductive film with a thickness of 2400Å on the substrate (comparative sample
IV) was prepared.

(Film forming conditions) Atmosphere gas: Ar = 100 sccm, O ₂ = 2 s
ccm ・ Atmospheric pressure: 6 × 10 ^-3 Torr ・ Introduction power: DC 2.5 W / cm ²・ Film formation rate: 720 Å / min ・ Substrate temperature: 60 ° C ・ Target material: In ₂ O ₃ -SnO ₂ sintered body (Sn)
O ₂ 10% by weight) The surfaces of the transparent conductive films (Sample I and Comparative Samples I to IV) produced as described above were observed with a scanning electron microscope (SE).
M) was used to photograph the surface state (magnification: 100,000 times), and the results are shown in FIGS. 2 to 6. Further, the specific resistance, the transmittance and the suitability for the alignment film were measured and evaluated in the same manner as in Example 1, and the results are shown in Table 2 below.

[0043]

[Table 2] The transparent conductive film (Sample I) formed on the color filter substrate shown in FIG. 2 has dense crystal grains like the transparent conductive film (Comparative Sample I) formed on the glass plate shown in FIG. The surface is flat, there are no domains that are different in each region where the crystal grain orientation method is present, and as shown in Table 2, the X-ray diffraction peak intensity ratio I ₁ / I ₂ is 5 or more. It was a transparent conductive film having good crystallinity. The transparent conductive film of the present invention has a specific resistance of 4.0 ×.
It was confirmed that the transparent conductive film had excellent electrical characteristics and transparency, having a transmittance of 10 ⁻⁴ Ω · cm or less and a wavelength of 550 nm of 80% or more. Furthermore, the alignment film characteristics were good, and it could be put to practical use as a transparent conductive film for liquid crystal displays.

On the other hand, the transparent conductive film (Comparative Sample III) formed on the color filter substrate by the conventional sputtering method has the effect of the gas generated from the color filter during film formation as shown in FIG. Grain lumps are formed and a dense film is formed. Therefore, the X-ray diffraction peak intensity ratio I
₁ / I ₂ was extremely small and the specific resistance was insufficient.

On the other hand, the transparent conductive film (Comparative Sample IV) which was heat-treated after being formed on the color filter substrate at a relatively low base material temperature did not generate degassing during film formation, and therefore, FIG.
As shown in (3), although it is a dense film due to crystal grain agglomeration, the specific resistance and the transmittance are greatly improved by the heat treatment. However, this transparent conductive film (Comparative Sample IV) had poor alignment film characteristics and could not be put to practical use as a transparent conductive film for liquid crystal displays.

[0046]

As described above in detail, according to the present invention, the base material has a low heat resistance such that the base material is deteriorated, deteriorated, pyrolyzed or degassed by the influence of heating or plasma. However, since the transparent conductive film is formed by the foro-cathode ion plating method without exposing the base material to plasma, alteration, deterioration, thermal decomposition, etc. of the base material and degassing from the base material are prevented. is prevented, the formed transparent conductive film, the ratio I of the X-ray diffraction method has a crystal grain (222) plane peak intensity I ₁ and (400) peak of the plane intensity I _2
1 / I ₂ is 5 or more, which is dense and has excellent surface flatness, and is a transparent conductive film having few pores in the film structure, and therefore has a specific resistance of 0.8 × 10 ^{−4 to} 3.5 × 10 ^−4. Ω · cm, which is extremely low. Further, the transparent conductive film of the present invention has a single-layer structure and can be patterned by one kind of etching agent, and a transparent conductive film having excellent patterning characteristics can be obtained.
Furthermore, since the transparent conductive film of the present invention has excellent surface flatness, it is suitable for an alignment film in a liquid crystal display or the like.

[Brief description of drawings]

FIG. 1 is a configuration diagram showing an example of a horizontal forocathode type ion plating apparatus that can be used in the method for producing a transparent conductive film of the present invention.

FIG. 2 is a drawing-substitute photograph in which the transparent conductive film of the present invention is observed with a scanning electron microscope.

FIG. 3 is a drawing-substitute photograph in which a transparent conductive film formed on a glass substrate is observed with a scanning electron microscope.

FIG. 4 is a drawing-substitute photograph observing a conventional transparent conductive film with a scanning electron microscope.

FIG. 5 is a drawing-substitute photograph obtained by observing a conventional transparent conductive film with a scanning electron microscope.

FIG. 6 is a drawing-substitute photograph of a conventional transparent conductive film observed with a scanning electron microscope.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Foro cathode type ion plating apparatus 2 ... Vacuum chamber 3 ... Anode (haas) 4 ... Base material holder 5 ... Plasma gun 6 ... Cathode 7 ... Intermediate electrode 8 ... Auxiliary coil 11 ... Evaporation source 12 ... Substrate 15 ... Plasma beam

Claims (6)

[Claims] 1. A transparent conductive film provided on a substrate having low heat resistance and plasma resistance, which has crystal grains and has a peak intensity I ₁ of (222) plane and an intensity of (400) plane of X-ray diffraction method. Ratio of peak intensity I ₂ to I ₁
/ I ₂ is 5 or more and the specific resistance is 0.8 × 10.
^{-4 to} 3.5 × 10 ^-4 Ω · cm in range, a transparent conductive film. 2. The transparent conductive film according to claim 1, having a mobility of 30 to 50 cm ² / Vsec. 3. The transmittance for light having a wavelength of 550 nm is 8
It is 0 to 100%, The transparent conductive film of Claim 1 or Claim 2 characterized by the above-mentioned. 4. The transparent conductive film according to claim 1, wherein an area occupancy rate of a groove having a size of 100 Å or more on the surface of the transparent conductive film is 15% or less. . 5. A reactive vapor deposition method is used to form plasma between a vapor deposition source and a base material, and the base material exposed to the plasma is not adversely affected on the base material. A method for producing a transparent conductive film, which comprises forming a transparent conductive film on the substrate. 6. The condition is that when the substrate is exposed to a plasma atmosphere or a heating atmosphere, the partial pressure ratio of the output corresponding to a mass number of 68 or higher in the mass spectrometer is 1 × 10.
^The method for producing a transparent conductive film according to claim 5, wherein the condition is such that it is less than ^-11 Torr.