JP2019157226A - Production method of substrate with transparent conductive film, and substrate with transparent conductive film - Google Patents

Abstract

To provide a substrate with a transparent conductive film capable of obtaining excellently extraction efficiency of light.SOLUTION: A production method of a substrate with a transparent conductive film has a step for forming a transparent conductive film 70 over an organic layer 60 provided on a substrate S by using an ion beam sputtering method. In the step for forming the transparent conductive film 70, the transparent conductive film 70 having an amorphous region 72 and a crystal 73 dispersed in the amorphous region is formed by adjusting the position of the substrate S and the potential of a target.SELECTED DRAWING: Figure 2

Description

  The present invention relates to a method for producing a substrate with a transparent conductive film and a substrate with a transparent conductive film.

  In recent years, organic devices are known as devices having functions such as light emission, display, and imaging. In such an organic device structure, a transparent conductive film that scatters light is formed on the organic film. For example, an organic light emitting device in which light scattering is realized by forming voids inside a metal oxide thin film is known (see, for example, Patent Document 1).

JP 2014-37626 A

  The present invention has been made in view of such circumstances. Unlike a metal oxide thin film having a cavity, the present invention provides a method for producing a substrate with a transparent conductive film that can obtain good light extraction efficiency, and the method. It aims at providing the board | substrate with a transparent conductive film obtained.

  The manufacturing method of the substrate with a transparent conductive film according to the first aspect of the present invention includes a step of forming a transparent conductive film above the substrate using an ion beam sputtering method, and the step of forming the transparent conductive film. Adjusts the position of the substrate and the potential of the target to form a transparent conductive film having an amorphous region and crystals dispersed in the amorphous region.

  In the method for manufacturing a substrate with a transparent conductive film according to the first aspect of the present invention, the substrate includes an organic layer, and in the step of forming the transparent conductive film, the amorphous region is disposed above the organic layer. May be formed.

  In the method for manufacturing a substrate with a transparent conductive film according to the first aspect of the present invention, in the step of forming the transparent conductive film, a protective layer is formed on the organic layer, and the amorphous region is formed on the protective layer. It may be formed.

  In the method for manufacturing a substrate with a transparent conductive film according to the first aspect of the present invention, the potential of the target may be set to any one of a minus potential, a plus potential, a ground potential, and a floating.

  In the method for manufacturing a substrate with a transparent conductive film according to the first aspect of the present invention, the transparent conductive film is formed in a film formation space located above an opening of a shielding plate disposed between the target and the substrate. The film formation space includes a first film formation space, a second film formation space, and a third film formation space, and the first film formation space is closer to the ion gun than the target. Located above the first opening end of the opening, the second film formation space is located so as to correspond to the center of the opening, and the third film formation space is closer to the target than the ion gun. The substrate is positioned above the second opening end of the opening at a position close to the substrate so as to face any one of the first film formation space, the second film formation space, and the third film formation space. The position of the substrate may be adjusted by moving.

  A substrate with a transparent conductive film according to a second aspect of the present invention includes a substrate, an amorphous region, and a transparent conductive film positioned above the substrate, the crystal being dispersed in the amorphous region.

  In the substrate with a transparent conductive film according to the second aspect of the present invention, the substrate may include an organic layer, and the amorphous region may be provided above the organic layer.

  In the substrate with a transparent conductive film according to the second aspect of the present invention, the transparent conductive film is provided on the organic layer and includes a protective layer that protects the organic layer, and the amorphous region is provided on the protective layer. May be located.

  In the substrate with a transparent conductive film according to the second aspect of the present invention, the crystal may be dispersed in the amorphous region so that the crystal is exposed on an upper surface of the transparent conductive film.

  In the substrate with a transparent conductive film according to the second aspect of the present invention, the crystal is located in the amorphous region so that the crystal is located inside the transparent conductive film and the periphery of the crystal is covered with the amorphous region. May be dispersed.

  In the substrate with a transparent conductive film according to the second aspect of the present invention, the transparent conductive film is located on the first region constituted by the amorphous region, and the periphery of the crystal is the amorphous region. You may provide the 2nd area | region where the said crystal | crystallization disperse | distributes in the said amorphous area | region so that it may be covered with an area | region, and the 3rd area | region located on the said 2nd area | region and comprised by the said amorphous area | region.

  In the substrate with a transparent conductive film according to the second aspect of the present invention, the transparent conductive film is located on the third region, and the amorphous region is covered with the amorphous region so that the periphery of the crystal is covered with the amorphous region. A fourth region in which crystals are dispersed may be provided.

  In the substrate with a transparent conductive film according to the second aspect of the present invention, the crystal has a triangular shape that gradually decreases from the surface of the transparent conductive film toward the inside of the transparent conductive film in a cross-sectional view. Also good.

  According to the said aspect of this invention, the manufacturing method of the board | substrate with a transparent conductive film which can obtain the light extraction efficiency favorably, and the board | substrate with a transparent conductive film obtained by this method are realizable.

It is sectional drawing which shows schematic structure of the manufacturing apparatus of the board | substrate with a transparent conductive film which concerns on embodiment of this invention. It is an expanded sectional view showing a substrate with a transparent conductive film concerning an embodiment of the present invention. It is an expanded sectional view explaining the manufacturing process of the board | substrate with a transparent conductive film which concerns on embodiment of this invention. It is an expanded sectional view showing a substrate with a transparent conductive film concerning a modification of an embodiment of the present invention. It is a figure explaining the Example of this invention, Comprising: The film-forming rate and film quality of a transparent conductive film with respect to the position of the measurement point in an experiment board | substrate, It is a figure explaining the structure of a sputtering device. It is a figure explaining the Example of this invention, Comprising: It is a TEM image explaining the surface structure of a transparent conductive film. It is a figure explaining the Example of this invention, Comprising: It is a TEM image explaining the surface structure and cross-section of a transparent conductive film. It is a figure corresponding to the external shape outline of the crystal created based on the TEM image shown in FIG.

  A manufacturing method of a substrate with a transparent conductive film and a substrate with a transparent conductive film according to an embodiment of the present invention will be described with reference to the drawings. In each drawing used for explanation of the present embodiment, the scale of each member is appropriately changed in order to make each member a recognizable size.

(Sputtering equipment)
The manufacturing method of the board | substrate with a transparent conductive film which concerns on this embodiment is performed in the sputtering apparatus 1 (manufacturing apparatus of a board | substrate with a transparent conductive film) shown in FIG. The sputtering apparatus 1 is an ion beam sputtering apparatus that forms a film on an organic film formed on a substrate S in a chamber (not shown).
The sputtering apparatus 1 includes a target 10, an ion gun 20, a shielding plate 30, a substrate moving unit 40, and a potential control unit 50 that adjusts the potential of the target 10.
A gas supply device (not shown) that supplies argon (Ar) and oxygen (O ₂ ) into the chamber is connected to the sputtering apparatus 1.

(Target, ion gun)
The material constituting the target 10 is ITO (Indium Tin Oxide). The target 10 is irradiated with an ion beam emitted from the ion gun 20. The target 10 is sputtered by ion beam irradiation, and the material constituting the target 10 is formed as a film on the substrate S.

(Shield)
The shielding plate 30 is disposed between the target 10 and the substrate S and has an opening 31. The shielding plate 30 is grounded via a wiring (not shown), and the potential of the shielding plate 30 is zero. The shielding plate 30 includes an opening end 32 (first opening end) of the opening 31 located closer to the ion gun 20 than the target 10 and an opening end 33 (a first opening end) of the opening 31 located closer to the target 10 than the ion gun 20. Second opening end).

  Magnets may be arranged on the upper surface of the shielding plate 30 on both sides (opening ends 32 and 33) of the opening 31. The shielding plate 30 having such a configuration suppresses recoil argon generated by ion beam sputtering from flying toward the substrate S, and opens the sputtered particles SP generated from the target 10 by sputtering the target 10. 31 is transmitted. Further, since the magnet is arranged, electrons are attracted to the magnet, and introduction of electrons into the substrate S is suppressed.

(Substrate moving part)
The substrate moving unit 40 includes a holding unit 41 that holds the substrate S and a drive unit 42 that moves the holding unit 41 relative to the opening 31. The substrate moving unit 40 causes the driving unit 42 to reciprocate the holding unit 41 in the direction indicated by reference numeral D while the substrate S is held by the holding unit 41. As a result, the substrate moving unit 40 exposes the substrate S to the film formation space 43 located above the opening 31. That is, the substrate moving unit 40 can adjust the position of the substrate S in the film formation space 43.

As will be described later in FIG. 5, the film formation space 43 includes a first film formation space 43 </ b> A in which a transparent conductive film having an amorphous region can be formed on the substrate S while suppressing the formation of crystals, and crystals are dispersed. The second film formation space 43B in which a transparent conductive film having an amorphous region can be formed on the substrate S, and the transparent conductive film having an amorphous region in which the crystal generation frequency is higher than the film formation in the second film formation space 43B And a third film formation space 43C that can be formed on the substrate S.
Therefore, the substrate moving unit 40 adjusts the position of the substrate S, that is, the substrate is opposed to any one of the first film formation space 43A, the second film formation space 43B, and the third film formation space 43C. S can be moved, and the occurrence frequency of crystals formed in an amorphous region constituting the transparent conductive film can be controlled.

The first film formation space 43A, the second film formation space 43B, and the third film formation space 43C are arranged in this order along the direction from the ion gun 20 toward the target 10, and the shielding plate 30 and the substrate S (substrate movement). Part 40).
In other words, in the film forming space 43 located above the opening 31, the first film forming space 43 </ b> A is located above the opening end 32 (first opening end) of the opening 31 located closer to the ion gun 20 than the target 10. Is located. On the other hand, in the film forming space 43, the third film forming space 43 </ b> C is located above the opening end 33 (second opening end) of the opening 31 that is closer to the target 10 than the ion gun 20. In the film formation space 43, the second film formation space 43 </ b> B is located at a position corresponding to the center of the opening 31. That is, the second film formation space 43B is located between the first film formation space 43A and the third film formation space 43C.

The substrate moving part 40 is disposed at a position facing the first film formation space 43A, and sputtering is performed in this state, so that an amorphous region can be formed above the substrate S while suppressing the formation of crystals. It becomes possible.
By placing the substrate S at a position where the substrate moving unit 40 faces the second film formation space 43B and performing sputtering in this state, it is possible to form an amorphous region above the substrate S so as to include crystals. Become.
The substrate moving portion 40 is disposed at a position facing the third film formation space 43C, and sputtering is performed in this state, so that an amorphous region having a higher crystal generation frequency than the second film formation space 43B can be obtained. It becomes possible to form above.

(Potential control unit)
The potential control unit 50 can set the potential of the target 10 to any one of a minus potential 51 (minus bias), a plus potential 52 (plus bias), a ground potential 53 (GND), and a floating 54. The amount of potential at the minus potential 51 and the plus potential 52 can also be adjusted as appropriate.

Sputtering is performed with the potential control unit 50 setting the potential of the target 10 to the ground potential or negative potential, so that an amorphous region in which generation of crystals is suppressed can be formed above the substrate S.
Further, by performing sputtering with the potential control unit 50 setting the potential of the target 10 to be floating, it is possible to form an amorphous region having a high crystal generation frequency above the substrate S.

Specifically, when sputtering is performed under the condition where the potential of the target 10 is set to a negative potential such as −200 V (the potential of the substrate is set to a positive potential), the speed of Ar ⁺ is greatly reduced and electrons (e ^- speed of) is greatly accelerated, oxygen (O ^-, rate of oxygen ions) is greatly accelerated, in this state, the sputtering is performed. In this case, the sputtered particles as the target material fly toward the substrate S together with electrons and oxygen ions, and film formation is performed.

Further, when sputtering is performed under the condition that the potential of the target 10 is set to the ground potential (the substrate potential is set to a positive potential), the speed of Ar ⁺ is reduced to a small speed and the speed of electrons (e ⁻ ) is reduced to a small speed. Then, the speed of oxygen (O ⁻ , oxygen ions) is accelerated to a small extent, and sputtering is performed in this state. In this case, the sputtered particles as the target material fly toward the substrate S and film formation is performed. Electrons and oxygen ions are attracted to a magnet disposed on the upper surface of the shielding plate 30.

Further, when sputtering is performed under the condition where the potential of the target 10 is set to be floating (the potential of the substrate is set to a positive potential), Ar ⁺ is accelerated, the velocity of electrons (e ⁻ ) is greatly reduced, and oxygen ( The speed of (O ⁻ , oxygen ions) is greatly reduced, and sputtering is performed in this state. In this case, the sputtered particles as the target material fly toward the substrate S and film formation is performed. Electrons and oxygen ions are attracted to the target.

(Substrate with transparent conductive film)
As shown in FIG. 2, the substrate 100 with a transparent conductive film according to the present embodiment includes a substrate S including an organic layer 60 and a transparent conductive film 70 (TCO film, Transparent Conductive Oxide) positioned above the organic layer 60. Is provided. The transparent conductive film 70 includes a protective layer 71 that protects the organic layer 60, an amorphous region 72 located on the protective layer 71, and crystals 73 dispersed in the amorphous region 72.

(substrate)
The substrate S is made of a known material such as a resin material or an inorganic material.
Although FIG. 1 shows one substrate S having an end, the present invention does not limit the substrate S shown in FIG. For example, a film substrate may be used.

(Organic film)
The organic layer 60 is a film constituting an organic device having functions such as light emission, display, and imaging, and is made of a known material such as a low molecular material or a high molecular material.
In the present embodiment, a case where the organic layer 60 functions as a light emitting layer will be described.

(Protective layer)
The protective layer 71 is an initial layer that is first formed on the organic layer 60 in the method for manufacturing a substrate with a transparent conductive film. The protective layer 71 prevents the organic layer 60 from being damaged by a thermal load or the like by sputtering, and protects the organic layer 60. Regarding the thickness of the protective layer 71, it may be thin as long as the effect of suppressing damage to the organic layer 60 is obtained. The thickness of the protective layer 71 is smaller than that of the amorphous region 72, and is about 100 mm, for example.

(Amorphous region)
In the present embodiment, the refractive index of the amorphous region 72 is about 2.0 (n = 2.0). In the present invention, the refractive index of the amorphous region 72 is not limited, and the refractive index can be appropriately adjusted by changing the sputtering conditions.

(crystal)
In the present embodiment, the refractive index of the crystal 73 is approximately 1.7 (n = 1.7). In the present invention, the refractive index of the crystal 73 is not limited, and the refractive index can be appropriately adjusted by changing the sputtering conditions. The crystal 73 is partially formed in the amorphous region 72.

In cross-sectional view, the crystal 73 has a triangular shape that gradually becomes thinner from the transparent conductive film 70 toward the organic layer 60. In other words, it has a triangular shape that gradually decreases from the upper surface 70T (front surface) of the transparent conductive film 70 toward the inside of the transparent conductive film 70.
More specifically, in FIG. 2, the cross-sectional area of the crystal 73 along the XY direction (direction parallel to the light emitting surface (upper surface 70T) of the substrate 100 with transparent conductive film) is the Z direction (substrate 100 with transparent conductive film). It gradually decreases toward the light exit surface (direction perpendicular to the upper surface 70T). In the present embodiment, the crystals 73 are dispersed in the amorphous region 72 so that the crystals 73 are exposed on the upper surface 70 </ b> T of the transparent conductive film 70.

  The transparent conductive film 70 having the above-described structure has a first region 70A composed of an amorphous region 72 having no crystal 73, and a second region 70B in which the crystal 73 is dispersed in the amorphous region 72. The transparent conductive film 70 not only functions as a film having conductivity and light transmittance, but also functions as a light scattering layer having two layers having different refractive indexes.

  In the transparent conductive film 70 produced by the manufacturing method according to the present embodiment, the transmittance of the film in which the crystal 73 is dispersed in the amorphous region 72 is increased, and the refractive index is the refractive index of the amorphous amorphous material. Less than. It was confirmed that the ratio showed a correlation with the crystal volume ratio.

(Manufacturing method of substrate with transparent conductive film)
(Formation of protective layer)
As shown in FIG. 3A, first, a substrate S provided with an organic layer 60 is prepared, and a protective layer 71 is formed above the organic layer 60. As a method for forming the protective layer 71, an ion beam sputtering method using the sputtering apparatus 1 shown in FIG. 1 is used. As a film forming condition of the protective layer 71, sputtering is performed by setting a target potential to a ground potential or a negative potential. As the negative potential, for example, a potential of −200 V can be given.

(Formation of amorphous region with suppressed crystal generation)
Next, as shown in FIG. 3B, a first region 70 </ b> A composed of an amorphous region 72 is formed on the protective layer 71. As a method of forming the first region 70A, the sputtering apparatus 1 shown in FIG. 1 is used, and the first region 70A is formed by controlling the substrate moving unit 40 and the potential control unit 50. As film formation conditions for the first region 70A, sputtering is performed in a state where the potential of the target is set to be floating, for example. Note that, in the film formation condition of the amorphous region formed first on the protective layer 71, the target potential is not limited to floating, and may be set to a negative potential such as −200 V, or set to a ground potential. May be.

(Formation of amorphous region accompanied by crystal generation)
Next, as shown in FIG. 3C, a second region 70B in which the crystals 73 are dispersed in the amorphous region 72 is formed on the first region 70A. In the second region 70 </ b> B, the crystal 73 is dispersed in the amorphous region 72 so that the periphery of the crystal 73 is covered with the amorphous region 72. As a method of forming the second region 70B, an ion beam sputtering method using the sputtering apparatus 1 shown in FIG. 1 is used, and the second region 70B is formed by controlling the substrate moving unit 40 and the potential control unit 50. As a film forming condition for the second region 70B, sputtering is performed in a state where the potential of the target is set to be floating.
Further, by controlling the substrate moving unit 40 and the potential control unit 50, the frequency of occurrence of the crystals 73 in the amorphous region (the number of the crystals 73 per unit area) can be adjusted.

  By using the manufacturing method according to the present embodiment, the speed of sputtered particles that affects crystallization can be controlled. Thereby, the controllability of the occurrence frequency of the crystal 73 in the amorphous region 72 is obtained, and a desired light scattering layer can be easily formed according to the light scattering property required for the optical device including the transparent conductive film 70. it can.

Further, in the manufacturing method described above, processes such as etching and ion implantation are unnecessary, and it is not necessary to take out the substrate S from the sputtering apparatus 1. Using one sputtering apparatus 1, the first region 70A and the second region 70B can be formed continuously.
In addition, you may heat-process as needed.

  In the present embodiment, an example in which the second region 70B is positioned on the first region 70A has been described. However, no boundary is formed between the first region 70A and the second region 70B. The first region 70A and the second region 70B are continuously formed by the sputtering apparatus 1.

Next, an effect | action in the board | substrate 100 with a transparent conductive film which concerns on this embodiment is demonstrated.
As shown in FIG. 2, when a voltage is supplied from an unillustrated electrode to the organic layer 60, the organic layer 60 emits light, and light generated from the organic layer 60 enters the amorphous region 72. Part of the light that has passed through the amorphous region 72 is incident on the crystal 73. At this time, the light incident on the crystal 73 is refracted due to the difference in refractive index between the amorphous region 72 and the crystal 73. The light refracted by the crystal 73 is extracted as outgoing light L from the upper surface 70T of the transparent conductive film 70 to the outside of the substrate 100 with the transparent conductive film.

Such light refraction is performed between the first region 70A and the second region 70B, and the emitted light L is obtained on the entire upper surface 70T.
According to the present embodiment, in the first region 70A and the second region 70B, the light can be scattered by passing through the amorphous region and the crystal having different refractive indexes, and the light extraction efficiency is good. Can get to.
Further, by adjusting only the conditions of the ion beam sputtering method in the sputtering apparatus 1, a two-layered multilayer structure (first region 70A and second region 70B) can be formed, and the above effects can be obtained.

(Modified example of substrate with transparent conductive film)
Next, a substrate with a transparent conductive film according to a modification of the embodiment of the present invention will be described with reference to FIG. In FIG. 4, the same members as those in the above-described embodiment are denoted by the same reference numerals, and the description thereof is omitted or simplified. The modification described below is different from the above-described embodiment in terms of the structure of the transparent conductive film 70.

(Modification 1)
As shown in FIG. 4A, in the substrate 101 with a transparent conductive film according to Modification 1, the crystal 73 is located inside the transparent conductive film 70 and the periphery of the crystal 73 is covered with amorphous regions 72 and 74. As described above, the crystals 73 are dispersed in the amorphous regions 72 and 74.
In the following description, amorphous regions are indicated by different reference numerals 72 and 74, but the layer configuration is the same.

In the method for manufacturing the substrate 101 with the transparent conductive film according to the first modification, the third region 70C constituted by the amorphous region 74 is formed on the second region 70B shown in FIG. As a method of forming the third region 70C, the method described in FIG.
In the first modification, the example in which the third region 70C is located on the second region 70B has been described. However, no boundary is formed between the second region 70B and the third region 70C. . The first region 70A, the second region 70B, and the third region 70C are continuously formed by the sputtering apparatus 1.

Next, an effect | action in the board | substrate 101 with a transparent conductive film which concerns on this modification 1 is demonstrated.
When a voltage is supplied to the organic layer 60 from an electrode (not shown), the organic layer 60 emits light, and light generated from the organic layer 60 enters the amorphous region 72. Part of the light that has passed through the amorphous region 72 is incident on the crystal 73. At this time, the light incident on the crystal 73 is refracted due to the difference in refractive index between the amorphous region 72 and the crystal 73.

  The light refracted by the crystal 73 is further refracted due to the difference in refractive index between the crystal 73 and the amorphous region 74 when entering the amorphous region 74 (third region 70C). The light that has passed through the amorphous region 74 is extracted as outgoing light L from the upper surface 70T of the transparent conductive film 70 to the outside of the substrate 101 with the transparent conductive film. Such light refraction is performed between adjacent regions of the first region 70A, the second region 70B, and the third region 70C, and the emitted light L is obtained over the entire upper surface 70T.

According to the first modification, in the first region 70A, the second region 70B, and the third region 70C, light can be scattered by passing through the amorphous region and the crystal having different refractive indexes. The light extraction efficiency can be obtained well.
In addition, a three-layered structure (first region 70A, second region 70B, and third region 70C) can be formed simply by adjusting the conditions of the ion beam sputtering method in the sputtering apparatus 1, and the above-described effects can be obtained. be able to.

(Modification 2)
As shown in FIG. 4B, in the substrate 102 with a transparent conductive film according to the modified example 2, a fourth region 70D located on the third region 70C shown in FIG. 4A is formed. As the formation method of the fourth region 70D, the method described in FIG. In the fourth region 70D, the crystal 75 is dispersed in the amorphous region so that the periphery of the crystal 75 is covered with the amorphous region.
In the second modification, the crystals 73 and 75 are dispersed in the amorphous region so that the crystal 73 is located inside the transparent conductive film 70 and the crystal 75 is exposed on the upper surface 70T of the transparent conductive film 70. ing.
In the following description, crystals are indicated by different symbols 73 and 75, but the crystal structures are the same.

  In the second modification, an example is described in which the fourth region 70D is positioned on the third region 70C, but no boundary is formed between the third region 70C and the fourth region 70D. . The first region 70A, the second region 70B, the third region 70C, and the fourth region 70D are continuously formed by the sputtering apparatus 1.

Next, an effect | action in the board | substrate 102 with a transparent conductive film which concerns on this modification 2 is demonstrated.
When a voltage is supplied to the organic layer 60 from an electrode (not shown), the organic layer 60 emits light, and light generated from the organic layer 60 enters the amorphous region 72. Part of the light that has passed through the amorphous region 72 is incident on the crystal 73. At this time, the light incident on the crystal 73 is refracted due to the difference in refractive index between the amorphous region 72 and the crystal 73.

  The light refracted by the crystal 73 is further refracted due to the difference in refractive index between the crystal 73 and the amorphous region 74 when entering the amorphous region 74 (third region 70C). Part of the light that has passed through the amorphous region 74 is incident on the crystal 75. At this time, the light incident on the crystal 75 is further refracted due to the difference in refractive index between the amorphous region 74 and the crystal 75.

  The light refracted by the crystal 75 is extracted as outgoing light L from the upper surface 70T of the transparent conductive film 70 to the outside of the substrate 102 with the transparent conductive film. Such light refraction is performed between adjacent regions among the first region 70A, the second region 70B, the third region 70C, and the fourth region 70D, and the emitted light L is obtained over the entire upper surface 70T. It is done.

According to the second modification, in the first region 70A, the second region 70B, the third region 70C, and the fourth region 70D, light passes through an amorphous region and a crystal having different refractive indexes, thereby transmitting light. The light can be scattered and the light extraction efficiency can be obtained well.
Further, a four-layered structure (first region 70A, second region 70B, third region 70C, and fourth region 70D) can be formed simply by adjusting the conditions of the ion beam sputtering method in the sputtering apparatus 1. The above effects can be obtained.

  In the example shown in FIG. 4B, the transparent conductive film 70 has been described as having a structure including two layers (second region 70B and fourth region 70D) in which crystals are dispersed in the amorphous region. The number of layers in which crystals are dispersed is not limited to two. In three or more layers, crystals may be dispersed in the amorphous region.

(Modification 3)
In the embodiment and the modification described above, the transparent conductive film 70 includes the protective layer 71 that suppresses damage to the organic layer 60 due to sputtering, but the present invention does not limit the structure including the protective layer 71. You may apply the transparent conductive film 70 mentioned above to the structure which is not provided with the organic layer 60, for example, the texture structure of a solar cell.

(Modification 4)
The transparent conductive film 70 described above may be applied to a portion where light scattering properties are required even in an inorganic device without being limited to an organic device.
For example, in an optical device that requires good light transmittance and good light emission efficiency, the above-described transparent conductive film 70 may be formed in a portion where a light shielding part such as a wiring is disposed on the optical path. . In this case, conventionally, light that is blocked by the light blocking portion can be scattered, and an optical device having good light transmittance and good light emission efficiency can be realized.

  While preferred embodiments of the present invention have been described and described above, it should be understood that these are exemplary of the invention and should not be considered as limiting. Additions, omissions, substitutions, and other changes can be made without departing from the scope of the invention. Accordingly, the invention is not to be seen as limited by the foregoing description, but is limited by the scope of the claims.

  Next, the effects of the present invention will be described more specifically with reference to the examples based on FIGS.

(Deposition rate and film quality of transparent conductive film relative to position of measurement point on experimental substrate, and structure of sputtering apparatus)
FIG. 5 shows the result of forming a transparent conductive film on the experimental substrate ES using the sputtering apparatus 1 described above, and is a diagram for explaining the film formation rate and film quality of the transparent conductive film.

FIG. 5A shows the results obtained by the experiment. The position of the measurement point on the experimental substrate ES (0 mm to 400 mm, Position), the resistivity (μΩcm, Resistivity), and the film formation rate (nm / min). , Deposition Rate).
FIG. 5B is a diagram showing the relationship between the structure of the sputtering apparatus 1 described above, the film formation space 43, and the position of the measurement point on the experimental substrate ES. In FIG. 5B, the substrate is not moved by the substrate moving unit 40, that is, the sputtering is performed in a state where the experimental substrate ES is fixed.

  Regarding the correspondence between FIG. 5A and FIG. 5B, the position 120 mm shown in FIG. 5A corresponds to the point P1 on the experimental substrate ES shown in FIG. 5B, and FIG. ) Corresponds to a point P2 on the experimental substrate ES shown in FIG. 5B, and a position 300mm shown in FIG. 5A is a point P3 on the experimental substrate ES shown in FIG. 5B. Corresponding to

  The point P1 faces the first film formation space 43A in the film formation space 43. The point P <b> 2 faces the second film formation space 43 </ b> B in the film formation space 43. The point P3 faces the third film formation space 43C in the film formation space 43.

The film forming conditions are as follows.

Types of gases supplied into the chamber: argon (Ar), oxygen (O ₂ )
Pressure in the chamber before argon is supplied: 5.0 × 10 ⁻⁴ Pa
Pressure in the chamber when argon is supplied: 5.0 × 10 ⁻² Pa
Power supplied to ion gun: 2000V
Target type: ITO
Target potential: floating

As is generally known, when forming a transparent conductive film while supplying oxygen, the supply amount (partial pressure) of oxygen at which the resistance value of the transparent conductive film obtained by film formation is the lowest is Exists. Therefore, in this embodiment, an oxygen supply amount at which the resistance value of the transparent conductive film is lowest is obtained in advance by experiments, and this oxygen supply amount is applied (O ₂ Optimized).

The following points became clear from FIG.
(A1) Regarding the resistivity, the resistivity gradually decreases as the position of the measurement point on the experimental substrate ES changes from 10 mm to 120 mm (point P1). When the position is 120 mm, the resistivity is 9 × 10 ^2. It became clear that it became about μΩcm. Further, as the position of the measurement point on the experimental substrate ES changes from 120 mm to 300 mm (point P3), the resistivity gradually increases. When the position of the measurement point is 300 mm, the resistivity is 3.5 × 10 ^3. It became clear that it became about μΩcm.

(A2) Regarding the film formation rate, the film formation rate hardly changed when the position of the measurement point on the experimental substrate ES was 10 mm to 30 mm, and the film formation rate was about 0.5 to 0.8 nm / min. It was. As the position of the measurement point on the experimental substrate ES changes from 30 mm to 220 mm, the film formation rate increases. When the position of the measurement point is 220 mm, it is clear that the film formation rate is about 4.5 nm / min. became. Further, as the position of the measurement point on the experimental substrate ES changes from 220 mm to 390 mm, the film formation rate decreases. When the position of the measurement point is 390 mm, the film formation rate may be about 0.8 nm / min. It became clear.

FIG. 6 is a TEM image for explaining the surface structure of the transparent conductive film formed on the experimental substrate ES shown in FIG. FIG. 6A shows the surface structure of the transparent conductive film at a point P1 on the experimental substrate ES (position in FIG. 5A: 120 mm, symbol (a)). FIG. 6B shows the surface structure of the transparent conductive film at the point P2 on the experimental substrate ES (position in FIG. 5A: 200 mm, symbol (b)). FIG. 6C shows the surface structure of the transparent conductive film at the point P3 on the experimental substrate ES (position in FIG. 5A: 300 mm, symbol (c)).
In FIG. 6, a portion indicated by a black dot is a crystal of a transparent conductive film. A region formed around the crystal is an amorphous region of the transparent conductive film.

The following points became clear from FIG.
(B1) At the point P1 on the experimental substrate ES, almost no crystals were confirmed, and it was revealed that an amorphous region was formed. In other words, in the first film formation space 43A in FIG. 5B, it can be seen that a transparent conductive film having an amorphous region can be formed on the substrate while suppressing the formation of crystals.
(B2) At point P2 on the experimental substrate ES, partial generation of crystals was confirmed, and it became clear that an amorphous region in which crystals were dispersed was formed. In other words, in the second film formation space 43B in FIG. 5B, it can be seen that a transparent conductive film having an amorphous region in which crystals are dispersed can be formed on the substrate.
(B3) Partial generation of crystals was confirmed at point P3 on the experimental substrate ES, and it became clear that an amorphous region having a higher frequency of crystal generation than point P2 was formed. In other words, in the third film formation space 43C in FIG. 5B, it is possible to form a transparent conductive film having an amorphous region in which crystals are generated more frequently than the film formation in the second film formation space 43B on the substrate. I understand that.
(B4) As described above, as a result of film formation in a state where the experimental substrate ES was fixed, it was revealed that the crystal generation frequency differs at points P1 to P3. That is, since the position of the substrate can be adjusted in the above-described embodiment, the surface structure shown in FIG. 6A is obtained by performing film formation with the substrate facing the first film formation space 43A. It is clear that a transparent conductive film can be formed on the substrate. Similarly, it is apparent that a transparent conductive film having the surface structure shown in FIG. 6B can be formed on the substrate by performing film formation with the substrate facing the second film formation space 43B. Further, it is apparent that a transparent conductive film having the surface structure shown in FIG. 6C can be formed on the substrate by performing film formation with the substrate facing the third film formation space 43C.

  FIG. 7 is an enlarged view showing a crystal formed on the transparent conductive film shown in FIG. FIG. 7A is a TEM image showing the surface structure of the crystal. FIG. 7B is a TEM image showing the cross-sectional structure of the crystal generated at the location indicated by the symbol A shown in FIG.

The following points became clear from FIG.
(C1) The black point shown in FIG. 7A is a crystal of the transparent conductive film, and it can be seen that an amorphous region of the transparent conductive film is formed around the crystal.
(C2) As shown in FIG. 7B, it can be seen that the crystal of the transparent conductive film has a triangular shape that gradually becomes thinner from the surface of the transparent conductive film toward the inside.

  FIG. 8 is a diagram corresponding to the outer contour of the crystal created based on the TEM image shown in FIG. FIG. 8A corresponds to FIG. 7A and is a TEM image showing the surface structure of the crystal. FIG. 8B is created using image processing software (ImageJ). The plurality of dot-like objects (polygons) shown in FIG. 8B are black dots (polygons) shown in FIG. Crystal).

The following points became clear from FIG.
(D1) It turns out that the shape of a crystal | crystallization is a polygon which has various shapes.
(D2) It can be seen that the crystals are dispersed in the amorphous region.

  INDUSTRIAL APPLICABILITY The present invention is applicable to a method for manufacturing a substrate with a transparent conductive film that can obtain good light extraction efficiency and a substrate with a transparent conductive film obtained by this method.

  DESCRIPTION OF SYMBOLS 1 Sputtering device, 10 Target, 20 Ion gun, 30 Shielding plate, 31 Opening part, 32 Opening end (first opening end), 33 Opening end (second opening end), 40 Substrate moving part, 41 Holding part, 42 Driving part 43 film formation space, 43A first film formation space (film formation space), 43B second film formation space (film formation space), 43C third film formation space (film formation space), 50 potential control unit, 51 negative potential , 52 plus potential, 53 ground potential, 60 organic layer, 70 transparent conductive film, 70A first region, 70B second region, 70C third region, 70D fourth region, 70T upper surface, 71 protective layer, 72, 74 amorphous region 73, 75 crystal, 100, 101, 102 substrate with transparent conductive film, GND ground potential, L outgoing light, P1, P2, P3 point, ES experimental substrate, S substrate, P sputtered particles.

Claims (13)

A method for manufacturing a substrate with a transparent conductive film,
Using an ion beam sputtering method to form a transparent conductive film above the substrate;
In the step of forming the transparent conductive film, a transparent conductive film having an amorphous region and crystals dispersed in the amorphous region is formed by adjusting the position of the substrate and the potential of the target.
A method for producing a substrate with a transparent conductive film. The substrate comprises an organic layer;
In the step of forming the transparent conductive film, the amorphous region is formed above the organic layer.
The manufacturing method of the board | substrate with a transparent conductive film of Claim 1. In the step of forming the transparent conductive film, a protective layer is formed on the organic layer,
Forming the amorphous region on the protective layer;
The manufacturing method of the board | substrate with a transparent conductive film of Claim 2. The potential of the target is set to any one of a negative potential, a positive potential, a ground potential, and a floating.
The manufacturing method of the board | substrate with a transparent conductive film as described in any one of Claims 1-3. Forming the transparent conductive film in a film formation space located above an opening of a shielding plate disposed between the target and the substrate;
The film formation space includes a first film formation space, a second film formation space, and a third film formation space;
The first film formation space is located above the first opening end of the opening at a position closer to the ion gun than the target,
The second film formation space is located so as to correspond to the center of the opening,
The third film formation space is located above the second opening end of the opening at a position closer to the target than the ion gun,
Adjusting the position of the substrate by moving the substrate so as to face any of the first film formation space, the second film formation space, and the third film formation space;
The manufacturing method of the board | substrate with a transparent conductive film as described in any one of Claims 1-4. A substrate with a transparent conductive film,
A substrate,
A transparent conductive film having an amorphous region and a crystal dispersed in the amorphous region, and positioned above the substrate;
A substrate with a transparent conductive film. The substrate comprises an organic layer;
The amorphous region is provided above the organic layer,
The substrate with a transparent conductive film according to claim 6. The transparent conductive film includes a protective layer located on the organic layer and protecting the organic layer,
The amorphous region is located on the protective layer;
The substrate with a transparent conductive film according to claim 7. The crystal is dispersed in the amorphous region so that the crystal is exposed on the upper surface of the transparent conductive film.
The board | substrate with a transparent conductive film as described in any one of Claims 6-8. The crystal is dispersed in the amorphous region so that the crystal is located inside the transparent conductive film, and the periphery of the crystal is covered with the amorphous region.
The board | substrate with a transparent conductive film as described in any one of Claims 6-8. The transparent conductive film is
A first region composed of the amorphous region;
A second region that is located on the first region and in which the crystal is dispersed in the amorphous region such that the periphery of the crystal is covered with the amorphous region;
A third region located on the second region and composed of the amorphous region;
The board | substrate with a transparent conductive film as described in any one of Claims 6-10 provided with these. The transparent conductive film is
A fourth region located on the third region, wherein the crystal is dispersed in the amorphous region such that the periphery of the crystal is covered with the amorphous region;
The substrate with a transparent conductive film according to claim 11. In cross-sectional view, the crystal has a triangular shape that gradually narrows from the surface of the transparent conductive film toward the inside of the transparent conductive film.
The substrate with a transparent conductive film according to any one of claims 6 to 12.