JP5722473B2 - Transparent conductive film - Google Patents

Description

The present invention relates to a method for producing a transparent conductive thin film. The transparent conductive thin film is used not only for a new display system such as a liquid crystal display or an electroluminescence display, or for a transparent electrode such as a touch panel, but also for preventing charging of a transparent article or blocking electromagnetic waves.

Conventionally, as a transparent conductive thin film, it has excellent transparency, so indium oxide
Tin oxide (ITO) thin films are used. The transparent conductive thin film is used for the above-mentioned applications. For example, when applied to a touch panel or the like, a high resistance value may be desired from the viewpoint of position detection accuracy. Moreover, since the transparent conductive thin film is used for the above-mentioned use,
It is required to satisfy the reliability in a high temperature and high humidity environment (the smaller the rate of change in resistance value, the higher the reliability). Further, in order to improve the reliability of the transparent conductive thin film, the film can be crystallized after the film is formed.

However, a transparent conductive thin film using an indium oxide / tin oxide thin film has a low resistance value and the reliability is not sufficient. The reliability can be improved by increasing the film thickness of the transparent conductive thin film. However, increasing the film thickness is not preferable because the transparency and the resistance value decrease. The reliability of the transparent conductive thin film can be improved by increasing the ratio of tin oxide in the indium oxide / tin oxide thin film. However, if the ratio of tin oxide is excessively increased, the time required for crystallization is increased. Is not preferable in that it becomes very long.

In order to solve the above problem, doping of indium oxide / tin oxide thin film with nitrogen has been proposed (for example, see Patent Document 1). In Patent Document 1, the transparent conductive thin film containing nitrogen contains at least 0.25% by weight or more in nitrogen content with respect to indium oxide / tin oxide. It describes that it has the effect of improving the reliability. However, the transparent conductive thin film described in Patent Document 1 is amorphous, and it takes a very long time for crystallization to crystallize the transparent conductive thin film to improve the reliability.

Thus, conventionally, a crystalline transparent conductive film doped with nitrogen gas at a ratio of 0.45 atomic% or less has been proposed (for example, see Patent Document 2). In the crystalline transparent conductive film of Patent Document 2, by setting the content ratio of nitrogen to indium oxide / tin oxide to be 0.45 atomic% or more, it has high resistance and is in a high temperature / high humidity environment. Reliability is good.

JP-A-4-308612 JP 2007-200823 A

The crystalline transparent conductive film described in Patent Document 2 is a mixture of indium oxide and tin oxide in an argon atmosphere containing nitrogen gas in a range of 3000 ppm to 13000 ppm with respect to the total of argon gas and nitrogen gas. Using the sintered body as a transparent conductive thin film forming material, a film of indium oxide / tin oxide containing 9% by weight or less of tin oxide with respect to the total of indium oxide and tin oxide is formed by a vapor phase method. Forming. However, when the nitrogen gas is contained in the argon atmosphere as in the method for producing a crystalline transparent conductive film described in Patent Document 2, there may be variations in the resistance value of the obtained crystalline transparent conductive film. There was a new problem, and there was room for improvement in terms of stable production.

The present invention has been made in view of the above-described problems, and an object of the present invention is to provide a method for producing a transparent conductive film that reduces variation in the resistance value of the obtained crystalline transparent conductive film and enables stable production. Is to provide.

In order to achieve the above object, the present inventors have conducted intensive research on a method for producing a transparent conductive thin film. As a result, when nitrogen is contained in the argon atmosphere, variation in resistance value of the produced crystalline transparent conductive thin film is improved by keeping the content of the water vapor gas in the argon atmosphere within a specific range. As a result, the present invention has been completed.

That is, the method for producing a transparent conductive thin film according to the present invention comprises forming a transparent conductive thin film on a transparent film substrate by a vapor phase method using a target mainly composed of indium oxide / tin oxide. A production method comprising argon gas, nitrogen gas and water vapor gas,
The nitrogen gas content is within a range of 2500 ppm to 8500 ppm with respect to the argon gas, and the water vapor gas content is within a range of 1450 ppm to 135 with respect to the argon gas.
The film formation is performed in an argon atmosphere within a range of 00 ppm.

According to the said structure, in forming the said transparent conductive thin film by a gaseous-phase method, it carries out in argon atmosphere which contains nitrogen gas in 2500ppm-8500ppm in the range with respect to argon gas. Since the ratio of nitrogen gas in the argon atmosphere is 2500 ppm or more,
The amount of nitrogen contained in the transparent conductive thin film to be formed can be sufficient, and the resistance value can be improved. In addition, the reliability in a high temperature and high humidity environment can be made sufficient. On the other hand, since the ratio of nitrogen gas in the argon atmosphere is 8500 ppm or less, when crystallizing the transparent conductive thin film, the process can be shortened and the production efficiency can be improved. .

Moreover, when forming the said transparent conductive thin film by a gaseous-phase method, it carries out in argon atmosphere which contains water vapor | steam gas within the range of 1450 ppm-13500 ppm with respect to argon gas.
As described above, when nitrogen gas is added to the argon atmosphere at the time of film formation in order to obtain a high-resistance transparent conductive film, the amount of water (amount of water vapor gas) in the argon atmosphere in the film formation chamber is small. Even when the amount of moisture slightly changes, the resistance value of the crystalline transparent conductive film obtained by crystallizing the transparent conductive thin film changes greatly. On the other hand, when the amount of moisture in the argon atmosphere in the film formation chamber is increased, variation in the resistance value of the crystalline transparent conductive film is suppressed, but crystallization due to heat treatment hardly occurs. In the present invention, since the ratio of the water vapor gas in the argon atmosphere is 1450 ppm or more, variation in the resistance value of the crystalline transparent conductive film obtained by crystallizing the transparent conductive thin film is reduced, and stable production is achieved. Is possible. On the other hand, the ratio of water vapor gas in the argon atmosphere is 13500 pp.
Since it is m or less, when crystallizing a transparent conductive thin film, the process can be made into a short time and manufacturing efficiency can be made favorable.

The said structure WHEREIN: It is preferable that the said target contains a tin oxide within the range of 1-9 weight% with respect to the sum total of an indium oxide and a tin oxide. Forming a film of indium oxide and tin oxide containing tin oxide in the range of 1 to 9% by weight with respect to the sum of indium oxide and tin oxide, so that the decrease in resistance value due to the inclusion of tin oxide is reduced. Since it is controlled, the resistance value of the transparent conductive thin film to be formed can be increased.

Moreover, the manufacturing method of the crystalline transparent conductive thin film of this invention has a crystallization process which heat-processes and crystallizes the transparent conductive thin film obtained by the manufacturing method of the transparent conductive thin film described above. Features. Since the ratio of nitrogen gas and water vapor gas contained in the transparent conductive thin film is not more than a certain amount, the crystallization process performed thereafter can be shortened and the production efficiency can be improved.

In the said structure, the heat processing conditions in the said crystallization process are 120-155 degreeC,
It is preferable that it is 2.5 hours or less. The heat treatment conditions in the crystallization step are, for example, when using a plastic substrate as a transparent film substrate for forming a transparent conductive thin film,
When the temperature is high, the performance of the film substrate may be impaired. On the other hand, if the heating temperature is not a certain level, the crystallization speed is reduced and the production efficiency is lowered. 155 ° C is preferred. In the present invention, although the transparent conductive thin film subjected to the crystallization step contains nitrogen, its content is very small and does not impair the crystallization speed. Therefore, if it is the range of the said heating temperature, a crystallization process can be performed preferably in 2.5 hours or less, and a crystallization process can be performed efficiently.

In the method for producing a transparent conductive thin film according to the present embodiment, first, a target mainly composed of indium oxide / tin oxide is used, and contains argon gas, nitrogen gas, and water vapor gas, and the nitrogen gas content is argon. The film is formed by a vapor phase method in an argon atmosphere having a range of 2500 ppm to 8500 ppm with respect to the gas and a content of the water vapor gas within a range of 1450 ppm to 13500 ppm with respect to the argon gas. A thin film is formed. Thereby, nitrogen is contained in the transparent conductive thin film.

Moreover, in the manufacturing method of the transparent conductive thin film which concerns on this embodiment, since the target which has an indium oxide and tin oxide as a main component is used, the reliability in a high temperature and high humidity environment can be made favorable. It is preferable to use a target that is mixed and sintered so that the ratio of tin oxide is in the range of 1 to 9% by weight with respect to the total of indium oxide and tin oxide.
The ratio of the tin oxide is preferably 2 to 9% by weight, and more preferably 3 to 8% by weight. By making the said ratio of a tin oxide 9 weight% or less, the fall of the resistance value by containing a tin oxide is suppressed. Moreover, the fall of the crystallization rate can be suppressed. In general, the ratio of indium oxide to tin oxide in the target is
This is substantially the same as the composition ratio in the formed transparent conductive thin film. As an auxiliary component other than indium oxide and tin oxide contained in the target, for example, titanium, zinc, copper, antimony,
Thulium, lithium, magnesium and the like can be mentioned. The content of the subcomponent is preferably 1 to 10% by weight with respect to indium oxide / tin oxide.

As the vapor phase method, various means can be adopted. For example, an electron beam evaporation method, a sputtering method,
Examples thereof include an ion plating method. Among these, the sputtering method is preferable because a uniform thin film can be obtained. When the sputtering method is employed, the DC magnetron sputtering method can be employed.

As described above, the nitrogen gas content in the argon atmosphere is in the range of 2500 ppm to 8500 ppm in terms of the volume ratio with respect to the argon gas, and 2500 ppm to 8000 p.
It is preferably pm, more preferably 3000 ppm to 6500 ppm. Since the ratio of nitrogen gas in the argon atmosphere is 2500 ppm or more, the amount of nitrogen contained in the transparent conductive thin film to be formed can be sufficient, and the resistance value can be improved. In addition, the reliability in a high temperature and high humidity environment can be made sufficient.
On the other hand, since the ratio of nitrogen gas in the argon atmosphere is 8500 ppm or less, when crystallizing the transparent conductive thin film, the process can be shortened and the production efficiency can be improved. .

Further, as described above, the content of the water vapor gas in the argon atmosphere is in the range of 1450 ppm to 13500 ppm in terms of the volume ratio with respect to the argon gas.
It is preferably 12000 ppm, and more preferably 2000 ppm to 10000 ppm. Since the ratio of the water vapor gas in the argon atmosphere is 1450 ppm or more, variation in the resistance value of the transparent conductive thin film to be formed is reduced, and stable production becomes possible. In particular, when the transparent conductive thin film is continuously manufactured while being wound on a roll, variation in resistance value in the entire long transparent conductive thin film is reduced, and stable production becomes possible. On the other hand, since the ratio of water vapor gas in the argon atmosphere is 13500 ppm or less, when crystallizing the transparent conductive thin film, the process can be shortened and the production efficiency can be improved. .

The content of water vapor gas in an argon atmosphere is 1450 ppm to 13500 ppm
As a method of controlling within the range, for example, a means for controlling the content of water vapor gas in the argon atmosphere is adopted in a conventionally known film forming apparatus (for example, an electron beam vapor deposition apparatus, a sputtering apparatus, an ion plating apparatus). Can be controlled. In particular,
Water supply means for supplying water vapor gas into the film formation chamber of the film formation apparatus, and exhaust means for exhausting the water vapor gas in the film formation chamber, and water vapor gas concentration for measuring the concentration of water vapor gas in the film formation chamber A measuring device is provided. Then, based on the concentration of the water vapor gas obtained by the water vapor gas concentration measuring device, there is a method of supplying the water vapor gas by the water supply means or exhausting the water vapor gas by the exhaust means. Such control can be performed using a control device including a CPU, a RAM, and the like.

The argon atmosphere can contain oxygen gas in addition to nitrogen gas and water vapor gas. Although content in particular of oxygen gas is not restrict | limited, It is 20000 ppm or less by volume ratio with respect to argon gas, Furthermore, it is 3000 ppm-20000 ppm. By setting the content of oxygen gas to 20000 ppm or less so that the proportion of oxygen gas does not increase, crystallization by heat treatment described later can be improved.

As a film thickness of the transparent conductive thin film to form, it can be normally 10 nm or more, Preferably it is 10-300 nm, More preferably, it is 15-100 nm, More preferably, it is 20-70.
nm. By setting the film thickness to 10 nm or more, it is easy to obtain a continuous film having good conductivity with a surface electric resistance of a certain value or less (for example, 1 × 10 ³ Ω / □ or less). on the other hand,
By setting the film thickness to 300 nm or less, transparency can be maintained high.

In the method for producing a transparent conductive thin film according to the present embodiment, the transparent conductive thin film is then crystallized by heat treatment. The heat treatment conditions in the crystallization step are 120 to 155 ° C. and 2
. It is preferably 5 hours or less. When a plastic substrate is used as the film substrate for forming the transparent conductive thin film, the performance of the film substrate may be impaired at a high temperature. On the other hand, if the heating temperature is not a certain level, the crystallization rate is slowed and the production efficiency is lowered. Therefore, the heating temperature in the crystallization step is preferably 120 to 155 ° C, more preferably 135 to 155 ° C, and still more preferably 140 to 155 ° C. Moreover, although the transparent conductive thin film to which a crystallization process is performed contains nitrogen, the content is trace amount and does not impair the crystallization speed. Therefore, within the range of the heating temperature, the crystallization process can be performed preferably in 2.5 hours or less, more preferably 2 hours or less, and even more preferably 1.5 hours or less. Can be done well.

In the said manufacturing method, the ratio of the crystal | crystallization in a transparent conductive thin film can be 50 area% or more. By setting the ratio of the crystal to 50 area% or more, high reliability in a high temperature and high humidity environment can be maintained. The ratio of the crystal is preferably 70 area% or more, and more preferably 80 area% or more. Moreover, all can also be made into a crystal | crystallization. As a method for confirming crystallization, a laminate having an ITO film formed on a substrate is heated in a heating oven at 140 ° C. for 90 minutes, and the taken-out laminate is crystallized by resistance after being immersed in hydrochloric acid. Completion can be determined.

Moreover, in the said manufacturing method, the maximum particle diameter of the crystal | crystallization which forms a transparent conductive thin film can be 350 nm or less. The maximum particle size is preferably 250 nm or less, more preferably 150 nm or less. In addition, the maximum grain size of the crystal is extremely large from the viewpoint of suppressing a decrease in reliability in a high-temperature / high-humidity environment due to an increase in a portion similar to an amorphous state in the thin film. In order not to become too small, it is preferably 10 nm or more,
More preferably, it is 30 nm or more.

The maximum grain size and distribution of the crystal are determined by observing the surface of the conductive thin film with a field emission transmission electron microscope (FE-TEM). The maximum crystal grain size is the largest diagonal or diameter in each observed polygonal or oval region. In addition, the content of the crystal having the maximum grain size is specifically the unit area (1 in the electron microscope image).
. 5 μm × 1.5 μm) is the area occupied by crystals of each grain size.

By the above production method, a transparent conductive thin film mainly composed of indium oxide and tin oxide can be formed on various base materials. For example, a transparent conductive thin film can be formed on one side of a transparent film substrate, whereby a transparent conductive film is obtained.

The material for the transparent film substrate is not particularly limited, and an appropriate material can be used. Specifically, polyester resin, acetate resin, polyether sulfone resin, polycarbonate resin, polyamide resin, polyimide resin, polyolefin resin, cycloolefin resin, acrylic resin, polyvinyl chloride resin, Examples include polystyrene resins, polyvinyl alcohol resins, polyarylate resins, polyphenylene sulfide resins, polyvinylidene chloride resins, (meth) acrylic resins, and the like. Among these, polyester resins, polycarbonate resins, polyolefin resins and the like are particularly preferable.

As the transparent film substrate used for the transparent conductive film, one transparent film-like sheet is used, or a laminate in which two or more transparent film-like sheets are bonded together via an adhesive layer is used. .

The thickness of the transparent film substrate is preferably about 20 to 300 μm. More preferably, it is 20-200 micrometers. By setting the thickness of the transparent film substrate to 20 μm or more, the reliability and workability in a high-temperature and high-humidity environment can be improved. Also,
When the thickness of the transparent film substrate is 300 μm or less, the touch panel portion can be reduced when employed for a touch panel, and light weight can be applied as touch panel input characteristics.

Further, when the transparent film substrate is a laminate of two or more transparent film-like sheets, the thickness and material of each film-like sheet can be appropriately selected, but at least one of the 20 It is preferable that it is -125 micrometers.

As the pressure-sensitive adhesive layer used when the transparent film substrate is a laminate of transparent film-like sheets, a transparent layer can be used without particular limitation. For example, acrylic adhesive,
Silicone adhesives, rubber adhesives and the like are used. The pressure-sensitive adhesive layer has a function of improving the scratch resistance of the transparent conductive thin film provided on one surface of the film-like sheet and the hitting characteristics for a touch panel due to the cushion effect after the transparent substrate is bonded. From the viewpoint of better performing this function, the elastic modulus of the pressure-sensitive adhesive layer is in the range of 1 to 100 N / cm ² and the thickness is 1 μm.
m or more, and preferably in the range of 5 to 100 μm.

The said transparent conductive thin film may be provided in the said film base material through the anchor layer. One or two or more anchor layers can be provided. The anchor layer is formed of an inorganic material, an organic material, or a mixture of an inorganic material and an organic material. The anchor layer is effective in improving the adhesion between the film substrate and the transparent conductive thin film, as well as improving the scratch resistance and bending resistance of the transparent conductive thin film, and improving the dot characteristics for touch panels. is there.

Examples of the inorganic material forming the anchor layer include, for example, SiO ₂ , MgF ₂ ,
A1 ₂ O ₃ or the like is preferably used. Organic materials include acrylic resin, urethane resin,
Organic substances such as a melamine resin, an alkyd resin, and a siloxane polymer can be used. In particular,
As the organic substance, it is desirable to use a thermosetting resin made of a mixture of a melamine resin, an alkyd resin, and an organosilane condensate.

The anchor layer can be formed using the above materials by vacuum deposition, sputtering, ion plating, coating, or the like.

In addition, when attaching the transparent conductive thin film, the film surface of the film substrate is subjected to appropriate adhesion treatment such as corona discharge treatment, ultraviolet irradiation treatment, plasma treatment, sputter etching treatment, etc. Can also be increased.

In the film substrate, a hard coat layer can be formed on the surface on which the transparent conductive thin film is not provided. The hard coat treatment can be performed, for example, by a method of applying a hard resin such as an acrylic urethane resin or a siloxane resin and performing a curing treatment. In the hard coat treatment, the surface can be roughened by blending a silicone resin or the like with a hard resin such as acrylic urethane resin or siloxane resin to prevent reflection due to mirror action when used as a touch panel or the like. A non-glare surface can be formed simultaneously. An antifouling layer can also be formed on the hard coat layer.

When forming the hard coat layer, if the thickness is small, the hardness is insufficient, while if it is too thick, cracks may occur. In consideration of curling prevention characteristics and the like, the preferred thickness of the hard coat layer is preferably about 0.1 to 30 μm.

The light transmittance of the transparent conductive film according to this embodiment is preferably 86% or more.
More preferably, it is 88% or more. By setting the light transmittance of the transparent conductive film to 86% or more, when the touch panel is formed using the transparent conductive film of the present embodiment, the display can be brightened and the optical characteristics are improved.

The transparent conductive film which concerns on this embodiment can be applied suitably as a panel board of a touch panel. Examples of the touch panel include a resistance film type touch panel and a capacitance type touch panel. That is, in a touch panel in which a pair of panel plates having a transparent conductive thin film are arranged to face each other through spacers so that transparent conductive thin films formed in stripes orthogonal to each other face each other, as one panel plate The transparent conductive film can be used (usually the upper panel plate to be pressed). This touch panel
When pressed against the elastic force of the spacer from the upper panel plate side, the transparent conductive thin films come into contact with each other and the electric circuit is turned on.When the pressure is released, the original OFF state is restored. Functions as a transparent switch structure. The panel plate used for the touch panel can use the transparent conductive film of the present embodiment on either the upper or lower side, but the other panel plate is
What provided the transparent conductive thin film in the transparent base | substrate which consists of a plastic film, a glass plate, etc. can be used. The transparent conductive film according to this embodiment may be used for both the upper and lower sides.

Hereinafter, examples of the present invention will be described in comparison with comparative examples, and will be described more specifically. In addition,
In the following, “parts” means parts by weight.

Example 1
(Film substrate)
A transparent film-like sheet made of a polyethylene terephthalate film (hereinafter referred to as a first PET film) having a thickness of 25 μm was used.

(Formation of anchor layer)
On one side of the first PET film, melamine resin: alkyd resin: organosilane condensate =
A cured film of a thermosetting resin composition comprising 2: 2: 1 (weight ratio) (refractive index 1.54, thickness 1
50 nm).

(Formation of transparent conductive thin film)
For the anchor layer, indium oxide / tin oxide (97% by weight of indium oxide, 3% by weight of tin oxide) was used as a target, and an argon atmosphere of 4 × 10 ⁻¹ Pa (argon gas: oxygen gas = 100: 1 (capacity ratio). ), Nitrogen gas containing 6000 ppm with respect to argon gas (capacity ratio), water vapor gas containing within a range of 1500 to 2000 ppm with respect to argon gas (capacity ratio)), and a thickness of 25 nm by sputtering. Transparent conductive thin film (IT
O thin film) was formed. The water vapor gas content during sputtering was controlled as follows. Specifically, a water supply device that supplies water vapor gas and an exhaust device that exhausts water vapor gas in the film formation chamber are provided in the film formation chamber of the film formation device, and the water vapor gas that measures the concentration of water vapor gas in the film formation chamber A concentration measuring device was provided. And based on the density | concentration of the water vapor | steam gas obtained by the water vapor | steam gas concentration measuring apparatus, it performed by supplying water vapor | steam gas with a water supply apparatus, or exhausting water vapor | steam gas with an exhaust device.

Next, heat treatment is performed at 150 ° C. at a crystallization rate of 1 hour to obtain a crystalline transparent conductive thin film,
A transparent conductive film was obtained.

(Formation of hard coat layer)
On one surface of a 125 μm thick PET film (hereinafter referred to as a second PET film),
Acrylic / urethane resin (trade name “Unidic 17-8 manufactured by Dainippon Ink & Chemicals, Inc.”
06 ") 5 parts of hydroxycyclohexyl phenyl ketone (trade name" Irgacure 184 "manufactured by Ciba Specialty Chemicals) as a photopolymerization initiator,
A toluene solution diluted to a concentration of wt% was applied, dried at 100 ° C. for 3 minutes, and then immediately irradiated with two ozone-type high-pressure mercury lamps (80 W / cm, 15 cm condensing type), and the thickness was 5 μm.
m hard coat layers were formed.

(Preparation of transparent conductive laminate)
Next, the elastic coefficient is 10 N / c on the other side of the hard coat layer of the second PET film.
A transparent acrylic pressure-sensitive adhesive layer adjusted to m ² (an isocyanate cross-linking agent was added to 100 parts of a copolymer of a monomer mixture having a weight ratio of butyl acrylate: acrylic acid: vinyl acetate of 100: 2: 5). A partly blended acrylic pressure-sensitive adhesive) was formed to a thickness of about 20 μm. Furthermore, the surface of the transparent conductive film on the first PET film side (surface on which no ITO thin film is formed) was bonded to the surface of the pressure-sensitive adhesive layer to prepare a transparent conductive laminate.

Examples 2-5, Comparative Examples 1-5
In the formation of the crystalline transparent conductive thin film of Example 1, the transparent conductive film was formed in the same manner as in Example 1 except that the nitrogen gas ratio and the water vapor gas ratio in the argon atmosphere were changed as shown in Table 1. A conductive laminate was produced.

The following evaluation was performed about the transparent conductive film and transparent conductive laminated body which were obtained by said Example and comparative example. The results are shown in Table 1.

<Film resistance>
Using the four-terminal method, the surface electrical resistance (Ω / □) of the transparent conductive laminate was measured. Measurement is
Each transparent conductive laminate was subjected to 5 points at random. Table 1 shows the maximum surface electrical resistance,
The minimum value, the average value, and the difference between the maximum value and the minimum value are shown.

<Total light transmittance>
The visible light transmittance at a light wavelength of 550 nm was measured using a spectroscopic analyzer UV-240 manufactured by Shimadzu Corporation.

<Etching test>
The transparent conductive laminate is immersed in 5% by weight hydrochloric acid for 15 minutes, and the resistance value (Ω) between two points 15 mm apart is measured by a tester (made by Custom, product name “Digital Tester (M-04)”, measurement limit. Value 2 MΩ), and it was determined whether or not the crystalline transparent conductive thin film was crystallized.
When the resistance value was detected, it was determined that the transparent conductive laminate was crystallized.

In the examples, a crystalline transparent conductive film having a surface electrical resistance of 300Ω / □ or more and a small variation in resistance value (difference between the maximum value and the minimum value of 50Ω / □ or less) was obtained. On the other hand, the comparative example does not have the above characteristics.

Claims (5)

A transparent film substrate;
On the transparent film substrate,
Using a target mainly composed of indium oxide and tin oxide,
Argon gas, nitrogen gas, and water vapor gas are included, the nitrogen gas content is in the range of 2500 ppm to 8500 ppm with respect to the argon gas, and the water vapor gas content is between 1450 ppm and 13500 ppm with respect to the argon gas. A transparent conductive thin film formed by forming a film by a vapor phase method in an argon atmosphere within the range of
Transparent conductive thin film contains nitrogen, is crystalline, surface electrical resistance of 300 [Omega / □ or more, the transparent conductive film.
The transparent conductive film according to claim 1, wherein the target contains tin oxide within a range of 1 to 9 wt% with respect to the total of indium oxide and tin oxide . The transparent conductive film according to claim 1 or 2, wherein a difference between the maximum value and the minimum value of the surface electrical resistance of the transparent conductive thin film is 50 Ω / □ or less. The said transparent conductive thin film is a transparent conductive film in any one of Claims 1-3 which is a film | membrane crystallized through the crystallization process which heat-processes an amorphous transparent conductive thin film. The transparent conductive film according to claim 4, wherein the heat treatment conditions in the crystallization step are 120 to 155 ° C. and 2.5 hours or less .