JP2015127443A - Production method of transparent conductive film, production apparatus of transparent conductive film, and transparent conductive film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a production method of a transparent conductive film and a production apparatus of a transparent conductive film capable of obtaining a transparent conductive film having a low specific resistance in a low-temperature film deposition.SOLUTION: A production method of a transparent conductive film includes steps of: forming a transparent conductive film on a substrate by a sputtering method by repeating alternately a film deposition time zone α and a film non-deposition time zone β; and applying a post-heat treatment to the transparent conductive film formed on the substrate. Hereby, a transparent conductive film having a greatly reduced specific resistance can be produced.

Description

  The present invention relates to a method for producing a transparent conductive film having a low specific resistance in low-temperature film formation, a transparent conductive film production apparatus, and a transparent conductive film.

  In recent years, with the progress of flat panel displays (FPD) such as liquid crystal display devices (LCD), new demands have also been increasing for touch panels provided on the display surface of the flat panel display (FPD). New technologies have been developed and proposed to meet these requirements.

  A resistive film type touch panel is known as a kind of this touch panel. In this resistive film type touch panel, a pair of transparent substrates each having a transparent conductive film formed on the main surface are arranged facing each other at a predetermined interval so that the transparent conductive films face each other. A plurality of insulating spacers are arranged in a matrix between these transparent conductive films. This touch panel electrically connects a pair of transparent conductive films at the desired position when a desired position on the viewing-side transparent substrate is pressed toward the display surface, and information on the desired position. Is output to the outside as an electrical signal.

Conventionally, in this resistive film type touch panel, tin-added indium oxide (ITO: Indium Tin Oxide) in which 1 to 40 mass% of tin oxide (SnO ₂ ) is added to indium oxide (In ₂ O ₃ ) as a material of the transparent conductive film. Is used as a touch sensor (see, for example, Patent Document 1).

  In recent years, on-cell type, in-cell type, or OGS (One Glass Solution) type high-performance products have been demanded (see Non-Patent Document 1). These high-performance products are required to have high responsiveness, design, thin and light shape performance, and the like.

  When a touch sensor is formed adjacent to a color filter such as an on-cell type or an in-cell type, when ITO is used as the touch sensor, there is a problem of heat resistance of the color filter. It is difficult to employ a high-temperature film forming process that can reduce the resistance of the film.

  On the other hand, the OSG type is a method in which a touch sensor is built on a cover glass. Since the film formation target is glass, high-temperature film formation is possible. There are constraints.

  That is, recently, the demand for the design has increased, and the demand for increasing variations in the color of the bezel (frame) formed on the edge of the panel has increased. Conventionally, a black frame called BlackMatrix has been adopted for the bezel, but in recent years there are also demands for other colors such as white and blue as the color of the bezel. It's getting harder to adopt. That is, a new process development for producing a good product at a low temperature is indispensable for a high-functional product, but it has been difficult to produce a transparent conductive film having a sufficiently low resistance in a low-temperature film formation by a conventional technique.

JP 2008-071531 A

Koji Hattori, “Chassis Voltage Application Method Touch Sensor Panel”, October 8, 2013, New Technology Briefing (Industry-University Collaboration Center, Kyushu University), [online], [Search December 16, 2013], Internet <URL: http://jstshingi.jp/abst/p/13/1329/kyudai_1.pdf>

The present invention has been devised in view of such a conventional situation, and the first object is to provide a method for producing a transparent conductive film from which a transparent conductive film having a low specific resistance can be obtained in low-temperature film formation. Objective.
In addition, a second object of the present invention is to provide a transparent conductive film manufacturing apparatus in which a transparent conductive film having a low specific resistance can be obtained in low temperature film formation.
A third object of the present invention is to provide a transparent conductive film having a low specific resistance.

In the method for producing a transparent conductive film according to claim 1 of the present invention, the transparent conductive film is formed on the substrate by sputtering by alternately repeating the film formation time zone α and the non-film formation time zone β. It includes a step A and a step B in which post-heating treatment is performed on the transparent conductive film formed on the substrate.
The method for producing a transparent conductive film according to claim 2 of the present invention is the method according to claim 1, wherein the number of times of alternately repeating the film formation time zone α and the non-film formation time zone β in the step A is 2 or more. It is characterized by being.
The method for producing a transparent conductive film according to claim 3 of the present invention is the film forming method according to claim 1 or 2, wherein a metal film is formed on the substrate before forming the transparent conductive film in the step A. It has a time zone α and a non-film formation time zone β.
The method for producing a transparent conductive film according to claim 4 of the present invention is the method according to claim 1, wherein the substrate in the film formation time zone α is a temperature profile that increases with time, and the substrate in the non-film formation time zone β is The temperature of the substrate is controlled so that the temperature profile decreases with time.
The method for producing a transparent conductive film according to claim 5 of the present invention is characterized in that, in claim 4, forced cooling means is used to obtain a temperature profile of the substrate in the non-deposition time zone β. To do.
The method for producing a transparent conductive film according to claim 6 of the present invention is the method according to any one of claims 1 to 5, wherein the step A uses the target made of ITO on the substrate made of glass. A transparent conductive film is formed.
The method for producing a transparent conductive film according to claim 7 of the present invention is characterized in that, in claim 3, the maximum temperature Td [° C.] of the substrate in the film formation time zone α is less than 60 ° C. .
In the method for producing a transparent conductive film according to claim 8 of the present invention, when the temperature of the post-heating treatment is defined as Ta [° C.] in claim 1, the Td satisfies the relational expression Td ≦ Ta / 2. It is characterized by satisfying.
The method for producing a transparent conductive film according to claim 9 of the present invention is the method for producing a transparent conductive film according to claim 1, wherein the thickness [の] of the ultrathin transparent conductive film formed for each film formation time period α and the substrate The product [Å · m / min] with the conveyance speed [m / min] is 720 or less.
The method for producing a transparent conductive film according to claim 10 of the present invention is characterized in that, in claim 1, the thickness [Å] of the ultrathin transparent conductive film is 175 or more and 350 or less.

A manufacturing apparatus for a transparent conductive film according to an eleventh aspect of the present invention is a manufacturing apparatus for forming a transparent conductive film on a substrate using a sputtering method, wherein the substrate is disposed in a vacuum vessel and the vacuum vessel. Means for heating, a target disposed in the film-forming space such that a film-forming space and a non-film-forming space exist alternately along the direction in which the substrate travels in the vacuum vessel, and the target And a power source for applying a sputtering voltage to the vacuum vessel, wherein the vacuum container has means for introducing a process gas toward the film formation space.
A manufacturing apparatus for a transparent conductive film according to a twelfth aspect of the present invention is the apparatus for manufacturing a transparent conductive film according to the ninth aspect, further comprising a forced cooling means for the substrate disposed in the non-deposition space in the vacuum vessel. To do.

  A transparent conductive film according to a thirteenth aspect of the present invention is formed using the method for producing a transparent conductive film according to any one of the first to tenth aspects.

  In the method for producing a transparent conductive film of the present invention, in step A, the film formation time zone α and the non-film formation time zone β are alternately repeated to form a transparent conductive film using a sputtering method. The maximum temperature of the transparent conductive film itself can be kept at a low temperature (that is, low-temperature film formation is possible). Thereby, the deposited transparent conductive film is suppressed from microcrystallization during film formation and becomes amorphous. Thereafter, the transparent conductive film can be crystallized by performing post-heating treatment in Step B. Thereby, the transparent conductive film with which specific resistance was reduced significantly can be manufactured.

  The transparent conductive film manufacturing apparatus of the present invention is a manufacturing apparatus for forming a transparent conductive film on a (transparent) substrate using a sputtering method, and forms a film along the direction in which the substrate proceeds in the film forming space. The targets are arranged so that spaces and non-film formation spaces exist alternately. As a result, the substrate passes through the film formation space and the non-film formation space alternately, so that the substrate temperature that rises when the substrate passes through one film formation space can be suppressed to form a film at a low temperature. An apparatus for producing a transparent conductive film can be provided.

  Since the transparent conductive film of this invention is formed using the manufacturing method of the transparent conductive film of this invention as mentioned above, the transparent conductive film in which resistance was reduced significantly can be provided.

The figure which shows an example of a board | substrate with a transparent conductive film which has the transparent conductive film of this invention. The figure which shows the time change of base | substrate temperature in the film-forming time slot | zone (alpha) and the non-film-forming time slot | zone (beta). The figure which shows the characteristic mechanism of a transparent conductive film in the manufacturing method of this invention. The schematic block diagram which shows an example of the manufacturing apparatus of this invention. FIG. 5 is a cross-sectional view illustrating an example of a main part of a film forming chamber in the manufacturing apparatus of FIG. 4. The schematic block diagram which shows another example of the manufacturing apparatus of this invention. The figure which shows the temperature profile at the time of cooling a base | substrate. The figure which shows another example of the board | substrate with a transparent conductive film which has the transparent conductive film of this invention. The figure which shows the relationship between the oxygen flow rate at the time of film-forming, and the specific resistance of a transparent conductive film.

  Below, one embodiment of a manufacturing method of a transparent conductive film concerning the present invention, a manufacturing device of a transparent conductive film, and a transparent conductive film is described based on a drawing.

FIG. 1 is a diagram schematically showing a configuration example of a substrate with a transparent conductive film having the transparent conductive film of the present invention.
A substrate 1A (1) with a transparent conductive film is formed by forming a transparent conductive film 3 on a substrate 2.
As the substrate 2, a transparent substrate 2 such as a glass substrate is preferably used.
In FIG. 1 (and FIG. 9 described later), the transparent conductive film 3 is formed by laminating eight ultrathin transparent conductive films of the first transparent conductive film 3a to the eighth transparent conductive film 3h. Although shown as an example, the transparent conductive film 3 of the present invention is not particularly limited, and even if only one layer is formed, two or more ultrathin transparent conductive films are laminated. It may be.

Such a transparent conductive film 3 has a low specific resistance by being formed using the method for producing a transparent conductive film of the present invention, which will be described later.
The method for producing a transparent conductive film of the present invention comprises a step A in which a transparent conductive film 3 is formed on a substrate 2 by sputtering by alternately repeating a film formation time zone and a non-film formation time zone, and the substrate And a step B of performing a post-heating treatment on the transparent conductive film 3 formed on the substrate 2.

As shown in FIG. 2, in the method for producing a transparent conductive film of the present invention, the substrate 2 in the film formation time zone rises with time, and the substrate 2 in the non-film formation time zone falls with time. The temperature of the substrate 2 is controlled so as to obtain a temperature profile.
Although specifically described later, in the present invention, for example, the film is formed at a relatively low temperature such that the maximum temperature Td [° C.] of the substrate 2 is less than 60 ° C.

FIG. 3 is a diagram schematically showing the characteristic mechanism of the transparent conductive film 3.
For example, the transparent conductive film 3 is formed by sputtering using tin-added indium oxide (ITO) in which 1 to 10 mass% of tin oxide (SnO ₂ ) is added to indium oxide (In ₂ O ₃ ) as a target. Take as an example.
When a film is formed under conditions where the temperature is halfway, for example, 80 ° C. by plasma heat input, indium oxide (In ₂ O ₃ ) is microcrystallized. For this reason, when heat treatment is performed in a subsequent process, it is considered that Sn added as an impurity and In are not successfully replaced. That is, it is considered that the carrier density is lowered and becomes a factor that hinders the reduction in resistance.

On the other hand, by making it comparatively low temperature (less than 60 degreeC) like this invention, the microcrystallization of indium oxide during film-forming is suppressed and it exists in an amorphous state.
Furthermore, in the present invention, the transparent conductive film 3 is formed by alternately repeating the film formation time period and the non-film formation time period, whereby the transparent conductive film 3 is formed into the ultrathin transparent conductive film 3 (first film It becomes a multilayer structure of the transparent conductive film 3a to the eighth transparent conductive film 3h), and crystal growth during film formation in each ultrathin film can be suppressed.
Therefore, when heat treatment (annealing treatment) is performed as a post process, the substitution of Sn and In added as impurities is suitably performed, so that a decrease in carrier density is suppressed, and the transparent conductive film 3 Can be achieved.
This will be specifically described below.

  First, an example of a manufacturing apparatus suitable for forming the transparent conductive film 3 in the method for manufacturing a transparent conductive film of the present invention will be described.

(Sputtering equipment)
FIG. 4 is a schematic configuration diagram showing an example of a sputtering apparatus (manufacturing apparatus) used in the transparent conductive film manufacturing method of the present invention. FIG. 5 is a cross-sectional view showing the main part of the film forming chamber of the sputtering apparatus.
The sputtering apparatus 10 is an inter-back type sputtering apparatus. For example, a substrate 2 made of an alkali-free glass substrate and a loading / unloading chamber (L / UL) 11 for loading / unloading a tray 18 on which the substrate 2 is mounted; A heating chamber (H) 12 that heat-treats 2, a sputter loading chamber (Sin) 13 that functions as a front chamber for moving the heat-treated substrate 2 unloaded from the heating chamber 12 to the film forming chamber 14, and sputter loading A film forming chamber (S) 14 for forming the transparent conductive film 3 on the substrate 2 supplied from the chamber (Sin) 13 by sputtering is provided.

In the charging / unloading chamber 11, the plate-like substrate 2 is supported in a vertical type (the substrate 2 is supported so that the surface forming the plate thickness of the substrate 2 is in the vertical direction, and subsequent heating and film forming processes are performed on the substrate 2. A tray 18 for holding and transporting the main surface) is movably disposed.
In the heating chamber 12, a heater 19 for heating the base 2 is provided in a vertical shape (FIG. 4 is an example in which the heater 19 is individually provided facing both sides of the base 2, and may be provided only on one side). .
The preparation / removal chamber 11 is provided with a roughing exhaust means 11P such as a rotary pump for roughly vacuuming the chamber.

The sputter carry-in chamber 13 cools the substrate 2 before moving the heat-treated substrate 2 carried out of the heating chamber 12 to the film forming chamber 14 and transfers it to the subsequent film forming chamber 13. Is evacuated by the exhaust means 13P.
For this purpose, the sputter carry-in chamber 13 is provided with an exhaust means 13P such as a turbo molecular pump for evacuating the chamber.
Moreover, in order to cool the base | substrate 2 actively, it is good also as a structure provided with the forced cooling means 21i connected to the power supply 21Di.

Inside the film forming chamber 14, a temperature adjusting means 31 for adjusting the temperature of the substrate 2 as needed is provided on one side surface 14a as required, and a target made of an ITO material is provided on the other side surface 14b. A sputtering cathode mechanism 33 that holds 32 and applies a desired sputtering voltage is provided in a vertical type. A power supply 34 that supplies the sputtering voltage to the sputtering cathode mechanism 33 is disposed outside the film forming chamber 14. .
Further, the film forming chamber 14 is provided with a high vacuum exhaust means 14P such as a turbo molecular pump for evacuating the chamber, and a gas introducing means 35 for introducing a process gas into the chamber. The gas introduction means 35 is connected to a port (not shown) through which various gases can be introduced.

  The sputter cathode mechanism 33 is made of a plate-like metal plate, and is used for fixing the target 32 by bonding with a mouth material or the like. The power source 34 is for applying a DC voltage as a sputtering voltage to the target 32, and a DC power source is preferably used.

  The gas introduction means 35 is connected to a port through which various gases constituting the process gas can be introduced. Examples of various gases include inert gas (typically Ar gas), hydrogen gas, oxygen gas, and water vapor. Can be mentioned.

  The gas introduction means 35 includes ports connected to various gas supply sources, and may be freely selected and used as necessary. For example, it is good also as a structure connected to two ports simultaneously like hydrogen gas and oxygen gas, hydrogen gas and water vapor | steam.

  FIG. 5 is a schematic configuration diagram showing another example of a sputtering apparatus used in the method for producing a transparent conductive film according to the present invention, that is, a cross-sectional view showing the main part of a film forming chamber of an inter-back magnetron sputtering apparatus. It is.

  The sputter cathode mechanism 33 includes a back plate (not shown) in which the target 32 is bonded (fixed) with a brazing material or the like, and a magnetic circuit (not shown) arranged along the back surface of the back plate (not shown). Yes. This magnetic circuit (not shown) generates a horizontal magnetic field on the surface of the target 32, and is obtained by appropriately adjusting the shape and arrangement of magnets so that a desired horizontal magnetic field is generated on the surface of the target 32. is there.

  In the manufacturing apparatus shown in FIG. 5, since the sputtering cathode mechanism 33 that generates a desired magnetic field is provided on the one side surface 14 b of the film forming chamber 14 in a vertical type, the sputtering voltage is set to 250 V or less, By setting the maximum value of the horizontal magnetic field strength on the surface to 1000 gauss or more, the transparent conductive film 3 with a well-organized crystal lattice can be formed.

Next, as an example of the manufacturing method of the transparent conductive film of the present invention, a method of forming the transparent conductive film 3 on the transparent substrate 2 using the sputtering apparatus 10 shown in FIGS.
First, the transparent conductive film 3 is formed on the substrate 2 by sputtering by alternately repeating the film formation time zone α and the non-film formation time zone β (step A).

  Examples of the target material to be used include tin-added indium oxide (ITO) in which 1 to 10% by mass of tin oxide is added to indium oxide. In particular, indium oxide is capable of forming a thin film having a low specific resistance. ITO in which 1 to 10% by mass of tin oxide is added is preferable.

Next, the transparent substrate 2 made of glass (hereinafter also referred to as the substrate 2) is loaded into the heating chamber 12 from the loading / unloading chamber 11 while being mounted on the tray 18 of the loading / unloading chamber 11. The substrate 2 is placed in front of the heater 19 that is maintained at a desired temperature, and the substrate 2 is heated to a predetermined temperature (for example, 120 ° C.) by the heater 19.
When the substrate 2 is heated to a predetermined temperature, the substrate 2 is transferred from the heating chamber 12 to a sputter loading chamber 13 having a predetermined degree of vacuum (for example, 0.27 Pa (2.0 mTorr)).
The substrate 2 is retained in the sputter carry-in chamber 13, and the substrate 2 is cooled to a predetermined temperature (for example, 20 ° C. to 30 ° C.) by natural heat dissipation. At that time, if necessary, the forced cooling means 21i and the power source 21Di may be used to shorten the cooling time or change the cooling profile.

  Next, the substrate 2 cooled to a predetermined temperature in the sputter carrying-in chamber 13 is carried from the sputter carrying-in chamber 13 to the film forming chamber 14 while being mounted on the tray 18. At that time, the film forming chamber 14 is set to a degree of vacuum (for example, 0.27 Pa (2.0 mTorr)) almost the same level as the sputtering carry-in chamber 13.

Next, the film forming chamber 14 is evacuated by the high vacuum exhaust means 14 so that the film forming chamber 14 has a predetermined high vacuum, for example, 2.7 × 10 ⁻⁴ Pa (2.0 × 10 ⁻³ mTorr). After that, a sputtering gas such as Ar is introduced into the film forming chamber 14 by the sputtering gas introducing means 35, and the inside of the film forming chamber 14 is set to a predetermined pressure (sputtering pressure).

Next, a sputtering voltage, for example, a DC voltage is applied as a sputtering voltage to the target 32 by the power supply 34. By applying the sputtering voltage, ions of sputtering gas such as Ar excited by the generated plasma collide with the target 32, and atoms constituting the tin-added indium oxide (ITO) are ejected from the target 32. The tray 18 on which the base 2 is mounted is moved in the direction of the dotted arrow shown in FIG. 4 so as to pass through the front space of the target 32 in this state. By this operation, a very thin first transparent conductive film 3a made of ITO is formed on the substrate 2 (deposition time zone α).
In order to make the maximum temperature of the substrate 2 in the film formation time zone α less than a predetermined temperature (for example, less than 60 ° C.), the temperature adjusting means 31 disposed at a position facing the target 32 is used as necessary. May be.

As shown in FIG. 2, the temperature of the substrate 2 is controlled so that the substrate 2 in the film formation time zone α has a temperature profile that increases with time.
At that time, the maximum temperature Td of the substrate 2 in the film formation time zone α is preferably less than 60 ° C.
When the temperature of the substrate 2 in the film formation time zone α is relatively high, for example, 120 ° C., the resistance does not decrease so much even after heat treatment in a subsequent process, but the temperature of the substrate 2 is relatively low, ie, less than 60 ° C. By suppressing the resistance, the effect of reducing the resistance after the post-heat treatment becomes remarkable.

The product [Å · m / min] of “thickness of ultrathin transparent conductive film [Å]” and “substrate transport speed [m / min]” formed for each deposition time zone α is particularly limited. For example, it is preferably 720 or less. When film formation is performed while the substrate passes in front of the target, this product is a numerical value called “dynamic deposition rate (passage film formation speed)”.
If this product [Å · m / min] exceeds 720, the plasma damage will increase and the film quality of the transparent conductive film will be affected. Therefore, the product [Å · m / min] is preferably in the range of 720 or less.

The thickness [Å] of each of the ultrathin transparent conductive films (the first transparent conductive film 3a to the eighth transparent conductive film 3h) is not particularly limited, and is, for example, 175 or more and 350 or less. It is preferable.
If the ultrathin transparent conductive film is thinner than 175 [Å], impurities such as residual gas are easily taken into the film during film formation, and the film quality deteriorates. In addition, the number of times of lamination is increased to obtain a desired film thickness, and the number of sputter cathodes is increased, which is not preferable as a production apparatus. On the other hand, if the ultrathin transparent conductive film is thicker than 350 [Å], crystallization is likely to proceed during film formation. Therefore, the thickness [Å] of each of the ultrathin transparent conductive films (the first transparent conductive film 3a to the eighth transparent conductive film 3h) is preferably in the range of 175 to 350.
In addition, the total thickness of the transparent conductive film 3 is not particularly limited, but is preferably 350 [Å] or more and 1600 [Å] or less, for example.

  After the ultrathin first transparent conductive film 3a made of ITO is formed on the substrate 2 as described above, the substrate 2 is moved from the film formation chamber 14 to the sputter carry-in chamber 13 (shown in FIG. 4). (Return from the position of the mark to the position of the mark ◇). This time period is a time period during which film formation is not performed, that is, a non-film formation time period. At this time, by dissipating heat, the base body 2 is cooled and cooled. That is, as shown in FIG. 2, the temperature of the substrate 2 is controlled so that the substrate 2 has a temperature profile that decreases with time in the non-deposition time period.

When the substrate 2 is cooled by heat radiation to a predetermined temperature (for example, 20 ° C. to 30 ° C.), the substrate 2 is transferred from the sputter loading chamber 13 to the film forming chamber 14.
Then, the second transparent conductive film 3b is formed on the first transparent conductive film 3a in the same manner as in the case where the first transparent conductive film 3a is formed (deposition time zone α). At this time, the substrate 2 during film formation may be cooled using the temperature adjusting means 31 as necessary.

After the second transparent conductive film 3b is formed, the substrate 2 is returned from the film formation chamber 14 to the sputter carry-in chamber 13 to dissipate heat (non-film formation time zone β).
When the substrate 2 is cooled (heat radiation) to a predetermined temperature, the substrate 2 is transferred from the sputter loading chamber 13 to the film forming chamber 14, and the third transparent conductive film 3c is formed on the second transparent conductive film 3b. (Deposition time zone α). At this time, the substrate 2 during film formation may be cooled using the temperature adjusting means 31 as necessary.
Similarly, the fourth transparent conductive film 3d˜3d is repeatedly formed by alternately repeating heat dissipation (non-deposition time zone β) in the sputter carry-in chamber 13 and film formation (deposition time zone α) in the film formation chamber 14. The eighth transparent conductive film 3h is sequentially formed.

  As described above, in the process A, the film formation in the film formation chamber 14 (film formation time zone α) and the heat release in the sputter carry-in chamber 13 (non-film formation time zone β) are alternately repeated, thereby The first transparent conductive film 3a to the eighth transparent conductive film 3h are sequentially formed.

  The number of times of alternately repeating the film formation time zone α and the non-film formation time zone β is 2 or more. By setting it to 2 or more, the non-deposition time zone β can be provided before and after the deposition time zone α. In particular, 4 times or more is more preferable, and 8 times or more is more preferable. When the film thickness of the transparent conductive film 3 is constant by repeating the film formation time zone α and the non-film formation time zone β alternately 8 times or more and intermittently sputtering, the film formation time zone It is possible to form a transparent conductive layer 3 having a thinner transparent conductive layer made of α and having a more multilayered structure, and then to improve heat resistance (reduction) by performing post-heating treatment described later. Can be noticeable.

As described above, the transparent conductive film 3 is formed by sequentially laminating the ultrathin first transparent conductive film 3 a to the eighth transparent conductive film 3 h on the substrate 2.
Finally, after the substrate 2 is transferred from the film forming chamber 14 to the sputter loading chamber 13 and the preparation / removal chamber 11, the vacuum in the preparation / removal chamber 11 is broken and the transparent conductive film 3 (first transparent conductive film) made of this ITO is broken. The substrate 2 on which the films 3a to 8th transparent conductive film 3) are formed is taken out.

Next, post-heat treatment is performed on the transparent conductive film 3 formed on the substrate 2 (step B). Although the post-heating process with respect to the formed transparent conductive film 3 is performed in air | atmosphere, you may perform it in a vacuum (under pressure reduction) as needed. Subsequent heat treatment suitably replaces Sn and In added as impurities, and causes ITO to crystallize. As a result, a decrease in carrier density is suppressed, and a transparent conductive film 3 having a low resistance is obtained.
When the temperature of the post-heating treatment at this time is defined as Ta [° C.], it is preferable that the maximum temperature Td of the substrate 2 in the film formation time zone satisfies the relational expression Td ≦ Ta / 2. For example, when the post-heat treatment temperature Ta is 120 [° C.], the maximum temperature Td of the substrate 2 may be less than 60 [° C.]. By satisfying this relationship, stable crystallization of the transparent conductive film 3 can be obtained.

In this way, a substrate 1A (1) with a transparent conductive film in which the transparent conductive film 3 made of ITO is formed on the substrate 2 is obtained.
In the present invention, the transparent conductive film 3 having a low resistance can be formed (manufactured) even at a low temperature of, for example, less than 60 ° C. In this manufacturing method, in addition to the base 2 made of a glass substrate (single unit), even if the base 2 has another thin film already formed on the glass substrate, the specific resistance does not adversely affect the cracking or thin film due to high temperature. Can be formed.

  As the substrate 2 on which another thin film has already been formed, a substrate 2 on which a metal film that does not affect the conductive properties of the transparent conductive film 3 is disposed in advance is suitable. In the present invention, the transparent conductive film 3 can be formed in a lower temperature range (less than 60 ° C.) as compared with a conventional process (a process at a film forming temperature of at least 80 ° C., usually 100 ° C. or more). Even if a metal film and a transparent conductive film are laminated in order on 2, cracks due to high temperature and adverse effects (adhesion, internal stress) on the thin film (interface and in the film) are remarkably eliminated.

In the film forming apparatus and the film forming method described above, it has been described that the film is formed by passing the tray 18 on which the substrate 2 is mounted in front of the target. However, in the case where a means for moving only the substrate 2 is provided. In this case, the tray 18 becomes unnecessary. In this case, since the base body 2 has only its own weight, there is an advantage that high-speed conveyance is possible.
On the other hand, when the tray 18 on which the substrate 2 is mounted is used, there is an advantage that the temperature and temperature of the substrate 2 can be suppressed by devising the material and shape of the tray 18 to take the temperature from the substrate 2.

FIG. 6 is a diagram showing another configuration example of the transparent conductive film manufacturing apparatus.
In the manufacturing apparatus 10 shown in FIG. 4, the tray 18 on which the substrate 2 is mounted repeatedly repeats the film formation chamber 14 and the sputter carry-in chamber 13 to repeat the film formation time zone and the non-film formation time zone. It was.
In contrast, in the manufacturing apparatus 100 shown in FIG. 6, a unit including a plurality of targets 132 a to 132 d (132) and a plurality of sputter cathode mechanisms 133 a to 133 d (133) corresponding to the targets 132 a to 132 d (132) is provided in the film forming chamber 14. It has been.

  FIG. 7 illustrates the case where the sputtering cathode mechanism 133 constituting each unit is provided with power supplies 134a to 134d (134). However, the power supplies are not necessarily arranged individually, and one unit is provided for each unit. You may arrange | position so that it may become one power supply.

  In this manufacturing apparatus 100, the tray 18 on which the substrate 2 is mounted moves in the film forming chamber 14, thereby repeating the film formation time period α and the non-film formation time period β. When the substrate 2 is opposed to the sputtering cathode mechanism 133 (that is, at a position passing in front of each of the targets 132a to 132d (132)), film formation is performed (film formation time zone α), and sputtering is performed. When moving between the cathode mechanism 133 and the next sputtering cathode mechanism 133 (for example, between 133a and 133b), heat is radiated from the substrate 2 (non-deposition time zone β).

  At this time, it is preferable to provide the forced cooling means 121 between the adjacent sputtering cathode mechanisms 133 which are non-deposition spaces. By providing the forced cooling means 121 to forcibly cool the substrate 2, the temperature is rapidly taken away from the substrate 2 in the non-deposition time zone β, and as a result, the temperature profile of the substrate 2 drops rapidly with time. The temperature of the substrate 2 can be controlled efficiently.

Such a forced cooling means 21 is not particularly limited, but for example, a cooling panel using a cryopanel is preferably used.
By using a cooling panel capable of adjusting the panel temperature in a low temperature region, the substrate temperature after film formation can be rapidly lowered by radiation cooling. By adjusting the panel temperature at about 150K, water vapor can be exhausted.

FIG. 7 is a schematic explanatory diagram showing a temperature profile when the substrate 2 after film formation is cooled. FIG. 7 shows a temperature profile (dotted line) when the base body 2 is cooled by natural heat radiation without using the forced cooling means 121 and a temperature profile when the base body 2 is forcibly cooled using the forced cooling means 121 ( It is shown with a solid line.
Even when there is no forced cooling means 121 (dotted line), a temperature profile in which the temperature of the base body 2 decreases with time due to natural heat dissipation is shown. However, by using the forced cooling means 121 (solid line), the temperature profile at which the substrate 2 descends with time can be changed to one that is steeper and falls to a lower temperature. Therefore, in the case where the forced cooling means 121 is present (solid line), the temperature of the base 2 can be lowered to a lower temperature in a shorter time, so that the forced cooling means 121 efficiently controls the temperature of the base 2. It is effective for.

  By using such a manufacturing apparatus (sputtering apparatus) 100, an extremely thin first transparent conductive film 3a to eighth transparent conductive film 3h made of ITO are sequentially stacked on the substrate 2 to form a film, The case where the transparent conductive film 3 is formed (step A) will be described.

  The sputtering apparatus 100 is an in-line type sputtering apparatus. For example, a charging chamber (L) 111 into which a base 2 made of an alkali-free glass substrate and a tray 118 on which the base 2 is mounted, and a heating chamber (H. H) 112, a sputter carry-in chamber (Sin) 113 that functions as a front chamber for moving the heat-treated substrate 2 carried out of the heating chamber 112 to the film forming chamber 114, and a sputter carry-in chamber (Sin) 113. A film forming chamber (S) 114 for forming the transparent conductive film 3 on the formed substrate 2 by sputtering, a sputter unloading chamber (Sout) 115 for unloading the substrate 2 after the film forming process from the film forming chamber 114, At least an unloading chamber (UL) 116 for unloading the substrate 2 moved from the sputter unloading chamber (Sout) 115 under atmospheric pressure is provided.

In the sputtering apparatus 100, the temperature profile of the substrate 2 when it reaches from the preparation chamber 111 through the heating chamber 112 to the sputtering carry-in chamber 113 may be the same as the temperature profile in the sputtering apparatus 10 described above.
For example, the base 2 that has been heat-treated (for example, 120 ° C.) in the heating chamber 112 is carried into the sputter carry-in chamber 113, and the base 2 is retained in the sputter carry-in chamber 113, so that the base 2 is heated to a predetermined temperature (natural heat dissipation). For example, it cools to 20 degreeC-30 degreeC. At that time, the cooling time may be shortened or the cooling profile may be changed using the forced cooling means 121i and the power source 121Di as necessary.

Next, the substrate 2 cooled to a predetermined temperature (for example, 20 ° C. to 30 ° C.) is carried from the sputtering carry-in chamber 113 to the film forming chamber 114.
Next, after a process gas (a sputtering gas such as Ar) is introduced into the film forming chamber 114 by the gas introduction means 135 and set to a predetermined pressure, the target 132a (of the sputtering cathode mechanism 133a (133) is set by the power supply 134a (134). 132), a sputtering voltage, for example, a DC voltage is applied as a sputtering voltage. By applying the sputtering voltage, ions of sputtering gas such as Ar excited by the generated plasma collide with the target 132a (132), and atoms constituting the tin-added indium oxide (ITO) jump out of the target 132a (132). Let The tray 118 on which the substrate 2 is mounted is moved in the direction of the dotted arrow shown in FIG. 6 so as to pass through the front space of the target 132a (132) in this state. By this operation, a very thin first transparent conductive film 3a made of ITO is formed on the substrate 2 (deposition time zone α).
In order to set the maximum temperature of the substrate 2 in the film formation time zone α to a temperature lower than a predetermined temperature (for example, lower than 60 ° C.), the temperature adjusting means 131 (131a) disposed at a position facing the target 132a (132) It may be used as necessary.

  In addition, you may arrange | position the temperature control means 131a-131d (131) in the position where each target 132a-132d (132) faces, as needed. In addition, although the case where four temperature control means and four units are provided is illustrated in FIG. 6, the present invention is not limited to this, and the number corresponding to the number of ultrathin transparent conductive films may be provided. For example, when the first transparent conductive film 3a to the eighth transparent conductive film 3h are stacked, eight units may be provided.

After the ultrathin first transparent conductive film 3a made of ITO is formed on the substrate 2, the substrate 2 is moved from a position facing the sputtering cathode mechanism 133a (133) to a position facing the sputtering cathode mechanism 133b (133). Move to. During this time period, no film formation is performed, and the (first time) non-film formation time period β becomes, and the base 2 is naturally radiated.
By disposing the forced cooling means 121 at a position corresponding to the non-deposition time zone β, that is, a position between the sputter cathode mechanism 133a and the sputter cathode mechanism 133b, the temperature of the substrate 2 is actively lowered. You may comprise as follows.

After the first transparent conductive film 3a is formed (first film formation time zone α), the base 2 that has spent the non-film formation time zone β is passed in front of the sputter cathode mechanism 133b (133). A second transparent conductive film 3b is formed on the first transparent conductive film 3a (second film formation time zone α).
After forming the second transparent conductive film 3b on the first transparent conductive film 3a provided on the substrate 2, the substrate 2 is moved from the position facing the sputtering cathode mechanism 133b (133) to the sputtering cathode mechanism 133c (133). And move it to a position facing it. The time zone during this period is a (second) non-film formation time zone β in which no film formation is performed.
By disposing the forced cooling means 121b (121) at a position corresponding to the non-deposition time zone β, that is, at a position between the sputter cathode mechanism 133a and the sputter cathode mechanism 133b, the substrate 2 is positively disposed. You may comprise so that temperature may be lowered | hung.

Similarly, the base body 2 is moved sequentially in front of the sputtering cathode mechanism 133c (133) and the sputtering cathode mechanism 133d (133), thereby forming the third transparent conductive film 3c and the fourth transparent conductive film 3d in a stacked manner. That is, for the third transparent conductive film 3c and the fourth transparent conductive film 3d, film formation by the sputtering cathode mechanism 32 (film formation time zone α) and the substrate 2 is naturally cooled or radiated by the forced cooling means 21 (non-formed). And the membrane time zone β) are alternately repeated.
Further, the substrate 2 is alternately operated by the same operation, that is, the film formation by the sputtering cathode mechanism 133 (film formation time zone α) and the substrate 2 is naturally cooled or radiated by the forced cooling means 21 (non-film formation time zone β). The fourth transparent conductive film 3d to the eighth transparent conductive film 3h are sequentially formed by repeating the above operations.

  By changing the moving speed (conveyance speed) of the substrate 2 in the film forming time zone α, the film thickness for one layer or “dynamic deposition rate (passing film forming speed) [Å · m / min]” is controlled. Can do.

As described above, the ultrathin first transparent conductive film 3a to the eighth transparent conductive film 3h are sequentially laminated on the substrate 2, thereby forming the transparent conductive film 3 shown in FIG. Is done.
After the substrate 2 is taken out from the manufacturing apparatus, the formed transparent conductive film 3 is subjected to post-heating treatment in the atmosphere (step B). Thereby, the transparent conductive film 3 has a low resistance.

FIG. 8 is a diagram schematically showing another configuration example of a substrate with a transparent conductive film.
A substrate 1B (1) with a transparent conductive film has a metal film 4 formed in advance on the base 2, and a plurality of ultrathin transparent conductive films 3 (first transparent conductive films 3a to 3a) are formed on the metal film 4. This is a configuration example in which a transparent conductive film 3) in which an eighth transparent conductive film 3h is laminated is formed.
The metal film 4 is not particularly limited. For example, when an index matching layer having an antireflection function is formed, a metal oxide such as niobium oxide or silicon oxide can be used.
The metal film 4 may be a single layer or a multilayer, and is not limited.

  In FIG. 8, a plurality of ultrathin transparent conductive films 3 (transparent conductive films 3 in which the first transparent conductive film 3 a to the eighth transparent conductive film 3 h are stacked) are formed on the metal film 4. However, the transparent conductive film 3 may be a single layer (that is, only the first transparent conductive film 3a formed first on the metal film 4). That is, before the first transparent conductive film 3a is formed, the base 2 on which the metal film 4 is previously provided is radiated by natural cooling or forced cooling means 21 (non-deposition time zone β), and then If the first transparent conductive film 3a is formed (deposition time zone α), the functions and effects of the present invention can be exhibited.

  In particular, in order to obtain such operations and effects stably, for example, in the manufacturing apparatus shown in FIGS. 4 and 6, a film formation chamber for the metal film 4 is provided as a front stage of the film formation chamber for the transparent conductive film 3. It is good also as an apparatus structure to provide. That is, when forming the substrate 1B (1) with a transparent conductive film, in step A, before forming the transparent conductive film 3, a film formation time zone α for forming the metal film 4 on the substrate 2 and non-film formation. And a time zone β.

(Experimental example)
Hereinafter, experimental examples performed for confirming the effects of the present invention will be described.
Using the manufacturing apparatus 10 as shown in FIG. 4, the substrate 2 is reciprocated between the film formation chamber 14 (the position marked with ◆) and the sputter carry-in chamber 13 (the position marked with ◇) to form a film (deposition). By repeating the film time zone α) and heat dissipation (non-film formation time zone β), a plurality of ultrathin transparent conductive films were laminated on the substrate.
The characteristics of the transparent conductive film were evaluated by changing the number of times the film formation time zone α and the non-film formation time zone β were alternately repeated.

(Sample 1)
First, the target 32 was attached to the sputtering cathode mechanism 33. As the target 32, a material (ITO) obtained by adding 5% by mass of SnO ₂ as an impurity to In ₂ O ₃ was used. Thereafter, the alkali-free glass substrate (base 2) was moved from the charging / unloading chamber 11 toward the heating chamber 12, and the base 2 was heat-treated by the heater 19.
The substrate 2 was loaded from the heating chamber 12 into the sputter loading chamber 13. The substrate 2 was retained in the sputter carry-in chamber 13 and cooled to a predetermined temperature (for example, 20 ° C. to 30 ° C.) by natural heat dissipation.
Then, the substrate 2 having a predetermined temperature (for example, 20 ° C. to 30 ° C.) was transferred to the film forming chamber 14. At this time, the inside of the film forming chamber 14 is maintained at a predetermined degree of vacuum by the high vacuum exhaust means 14P.

Ar gas is introduced as a process gas from the sputter gas introduction means 35 and adjusted to a desired sputtering pressure by a conductance valve (not shown), and then the sputtering cathode mechanism 33 is supplied with 2.0 [W / cm ² by a DC power source 34. ], A discharge state was obtained in which the ITO target 32 attached to the sputter cathode mechanism 33 was sputtered. And the 1st transparent conductive film 3a was formed by moving the base | substrate 2 so that it may pass in front of the target 32 made into this discharge state (film-forming time slot | zone (alpha)).
The voltage value at this time was 230 [V], and the current value was 27 [A]. The substrate transfer speed was 1980 [mm / min].

In addition, in the measurement of the substrate temperature in the film formation time zone α, the heat label (manufactured by Micron Corporation, type “6R-40”: http://www.microncorp.co.jp/heat_6r.html) The heat label shown) was used. The temperature range of this heat label is “40-43-46-49-54-60 [° C.]”.
When a film formation experiment was performed using this heat label, the label “40-43-46-49-54” sometimes changed color, but the label “60” did not change color. That is, it was confirmed that the maximum temperature Td of the substrate 2 was “lower than 60 ° C. (below 60 ° C.)”.

In this manner, an extremely thin first transparent conductive film 3a was formed on the substrate 2 to a thickness of 175 [Å] (deposition time zone α).
Thereafter, the substrate 2 is moved from the film formation chamber 14 to the sputter carry-in chamber 13 (returned from the position marked with ♦ to the position marked with ◇), and the substrate 2 is retained in the sputter carry-in chamber 13 from the substrate 2. By dissipating heat, the temperature of the substrate 2 was lowered (non-deposition time zone β).
When the substrate 2 is cooled (heat radiation) to a predetermined temperature (for example, 20 ° C. to 30 ° C.), the substrate 2 is transferred from the sputter loading chamber 13 to the film forming chamber 14 and passed in front of the target 32 in a discharged state. Thus, the second transparent conductive film 3b was formed on the first transparent conductive film 3a (deposition time zone α).

By repeating these operations as a series of 8 passes (that is, repeating the film formation time zone α and the non-film formation time zone β 8 times), the ultrathin first transparent conductive films 3a to 8th are repeated. The transparent conductive film 3h was sequentially laminated to form the transparent conductive film 3 on the substrate 2 so that the total film thickness was 1400 [４００]. Thereafter, the substrate 2 was taken out from the take-out chamber.
Finally, sample 1 was obtained by subjecting the transparent conductive film 3 formed on the substrate 2 to a post-heating treatment at 120 [° C.] for 1 hour.
In the case of the manufacturing conditions of Sample 1, the “dynamic deposition rate (passing film forming speed)” was 350 [Å · m / min].

(Sample 2)
In Sample 2, the number of times of alternately repeating the film formation time zone α and the non-film formation time zone β was set to 4 times.
At that time, the ultrathin first transparent conductive film 3a to the fourth transparent conductive film 3d were sequentially formed in the same manner as in the sample 1 except that the conveyance speed of the substrate 2 was set to 1060 [mm / min]. When the transparent conductive film 3 was formed so as to have a total film thickness of 1400 [Å] after being laminated, the temperature of the substrate 2 in the film formation time zone α was less than 60 ° C. After the film formation, the transparent conductive film 3 formed on the substrate 2 was subjected to a post-heating treatment at 120 [° C.] for 1 hour in the same manner as the sample 1.
In the case of the manufacturing conditions of Sample 2, the “dynamic deposition rate (passing film forming speed)” was 370 [Å · m / min].

(Sample 3)
In Sample 3, the number of times of alternately repeating the film formation time zone α and the non-film formation time zone β was set to once (one pass).
At that time, when the desired total film thickness (1400 [Å]) was formed once (one pass), the temperature of the substrate 2 in the film formation time zone α was 82 ° C. The conveyance speed of the substrate 2 was 255 [mm / min]. Except for these, the transparent conductive film 3 was formed in the same manner as in Sample 1 so that the film thickness was 1400 [Å]. After the film formation, the transparent conductive film 3 formed on the substrate 2 was subjected to a post-heating treatment at 120 [° C.] for 1 hour in the same manner as the sample 1.
When the production conditions of Sample 3 were adopted, the “dynamic deposition rate (passing film forming speed)” was 360 [Å · m / min].

(Sample 4)
In sample 4, the power applied to the sputter cathode mechanism 33 is 4.0 [W / cm ² ] and the transport speed of the substrate 2 is 2060 [mm / min] in the film formation time zone α, and the desired total film thickness ( 1400 [Å]) was formed four times (four passes), the temperature of the substrate 2 in the film formation time zone α was less than 60 ° C. Except for these, the transparent conductive film 3 was formed in the same manner as in the sample 2 so that the film thickness was 1400 [Å]. After the film formation, the transparent conductive film 3 formed on the substrate 2 was subjected to a post-heating treatment at 120 [° C.] for 1 hour in the same manner as the sample 1.
Note that when the manufacturing conditions of the sample 4 were used, the “dynamic deposition rate (passing film forming speed)” was 720 [Å · m / min].

(Sample 5)
In sample 5, the power applied to the sputter cathode mechanism 33 is 4.0 [W / cm ² ] and the conveyance speed of the substrate 2 is 477 [mm / min] in the film formation time period α, and the desired total film thickness ( 1400 [Å]) was formed once (one pass), the temperature of the substrate 2 in the film formation time zone α was 77 ° C. Except for these, the transparent conductive film 3 was formed in the same manner as the sample 3 so that the film thickness was 1400 [Å]. After the film formation, the transparent conductive film 3 formed on the substrate 2 was subjected to a post-heating treatment at 120 [° C.] for 1 hour in the same manner as the sample 1.
Note that when the manufacturing conditions of the sample 5 were used, the “dynamic deposition rate (passing film forming speed)” was 670 [Å · m / min].

  The specific resistance [μΩ · cm] of the transparent conductive film 3 formed as described above was measured. The results are shown in Table 1.

The following points became clear from Table 1.
(1A) As the number of repetitions (pass number) of the film formation time zone α and the non-film formation time zone β increases from 1 to 4 times to 8 times, the specific resistance of the transparent conductive film after annealing decreases. (Sample numbers: 3, 2, 1 are compared). When the rate of decrease is expressed by the “relative value of specific resistance”, when the number of passes is four, it is reduced by about 9% (0.913), and when the number of passes is eight, it is reduced by about 16% (0.838). It turns out that.
(1B) It was found that there was a similar tendency when the applied power was doubled (sample numbers: 5 and 4 were compared).
From the results of the above (1A) to (1B), it was found that the number of passes (the number of times of alternately forming the film formation time zone α and the non-film formation time zone β) is important as a factor for reducing the specific resistance.

FIG. 9 is a diagram showing the relationship between the oxygen flow rate during film formation and the specific resistance of the transparent conductive film. The following points became clear from FIG. In FIG. 9, □ represents the result of sample 1 (8 passes), 、 represents the result of sample 2 (4 passes), and ○ represents the result of sample 3 (1 pass).
(2A) There is an oxygen flow rate that minimizes the specific resistance without depending on the number of passes. In Sample 1 (marked with □ in the figure) and Sample 2 (marked with ◇ in the figure), a lower specific resistance was obtained when the oxygen flow rate was 2 [sccm].
(2B) The oxygen flow rate value at which the specific resistance is minimized tends to increase as the number of passes increases. At the same time, the minimum specific resistance tends to decrease.
(2C) When the number of passes was 8 (sample 1: □ in the figure), a specific resistance of 350 [μΩ / cm] or less was obtained when the oxygen flow rate was in the range of 2 to 3 [sccm].
From the above (2A) to (2C), it is understood that the number of passes (the number of times of alternately forming the film formation time zone α and the non-film formation time zone β) is important as a factor for reducing the specific resistance.

  In the production of Samples 1 to 5 described above, the product of “the thickness [Å] of the ultrathin transparent conductive film formed for each film formation time period α and the transport speed [m / min] of the substrate” is shown. It was found that [Å · m / min] ”, that is,“ dynamic deposition rate (passing film forming speed) ”should be 720 or less. It was found that when this product [Å · m / min] exceeds 720, the plasma damage increases and affects the film quality of the transparent conductive film. Therefore, the product [Å · m / min] is preferably in the range of 720 or less.

As mentioned above, although the manufacturing method of the transparent conductive film of this invention, the manufacturing apparatus of a transparent conductive film, and the transparent conductive film have been demonstrated, this invention is not limited to this, In the range which does not deviate from the meaning of invention, Changes can be made as appropriate.
For example, in the manufacturing apparatus shown in FIG. 4, in the non-deposition time zone β, the substrate temperature was lowered by naturally dissipating heat in the sputtering carry-in chamber, but the present invention is not limited to this, The substrate may be cooled by providing a forced cooling means.
In the above-described embodiment, the case where the transparent conductive film made of ITO is formed has been described as an example. However, the present invention is not limited to this. For example, a zinc oxide-based transparent conductive film is formed. It can also be applied when filming.

  The present invention is widely applicable to a transparent conductive film manufacturing method, a transparent conductive film manufacturing apparatus, and a transparent conductive film. Such a transparent conductive film is suitably used for the whole touch panel product, for example.

  1A, 1B (1) Substrate with a transparent conductive film, 2 substrate, 3 transparent conductive film, 3a to 3h 1st transparent conductive film to 8th transparent conductive film, 4 metal film.

Claims (13)

Step A for forming the transparent conductive film on the substrate by sputtering by alternately repeating the film formation time zone α and the non-film formation time zone β;
A step B of subjecting the transparent conductive film formed on the substrate to a post-heating treatment;
The manufacturing method of the transparent conductive film characterized by including.   2. The method for producing a transparent conductive film according to claim 1, wherein in the step A, the number of times of alternately repeating the film formation time period α and the non-film formation time period β is 2 or more.   The step A includes a film formation time zone α for forming a metal film on the substrate and a non-film formation time zone β before forming the transparent conductive film. The manufacturing method of the transparent conductive film of description.   The temperature of the substrate is controlled so that the substrate in the film formation time zone α has a temperature profile that increases with time, and the substrate in the non-film formation time zone β has a temperature profile that decreases with time. The manufacturing method of the transparent conductive film of Claim 1.   The method for producing a transparent conductive film according to claim 4, wherein forced cooling means is used to obtain a temperature profile of the substrate in the non-film formation time zone β.   The said process A forms the said transparent conductive film on the said base | substrate which consists of glass using the target which consists of ITO, The transparent conductive film as described in any one of Claim 1 thru | or 5 characterized by the above-mentioned. Production method.   The method for producing a transparent conductive film according to claim 5, wherein a maximum temperature Td [° C.] of the substrate in the film formation time period α is less than 60 ° C. 6. When the temperature of the post-heat treatment is defined as Ta [° C.]
The method for producing a transparent conductive film according to claim 1, wherein the Td satisfies a relational expression Td ≦ Ta / 2.   The product [Å · m / min] of the thickness [Å] of the ultrathin transparent conductive film formed for each film formation time zone α and the conveyance speed [m / min] of the substrate is 720 or less. The method for producing a transparent conductive film according to claim 1, wherein:   2. The method for producing a transparent conductive film according to claim 1, wherein the thickness [Å] of the ultrathin transparent conductive film is 175 or more and 350 or less. A manufacturing apparatus for forming a transparent conductive film on a substrate using a sputtering method,
A vacuum vessel;
Means for heating the substrate in the vacuum vessel;
In the vacuum vessel, a target disposed in the film formation space so that film formation spaces and non-film formation spaces exist alternately along the direction in which the substrate travels;
A power source for applying a sputtering voltage to the target,
The said vacuum vessel has a means to introduce | transduce process gas toward the said film-forming space, The manufacturing apparatus of the transparent conductive film characterized by the above-mentioned.   The apparatus for producing a transparent conductive film according to claim 11, further comprising forced cooling means for the base disposed in the non-deposition space in the vacuum container.   A transparent conductive film formed using the method for producing a transparent conductive film according to claim 1.

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