WO2015118724A1 - Transparent conductive laminate, method for producing transparent conductive laminate, and electronic device formed using transparent conductive laminate - Google Patents

Abstract

The present invention provides a transparent conductive laminate having excellent moist heat characteristics, a method for producing said transparent conductive laminate, and an electronic device formed using such a transparent conductive laminate. Provided is a transparent conductive laminate formed by forming a transparent conductive layer on at least one side of a substrate, said laminate being characterized in that the transparent conductive layer includes zinc oxide and constitutes a zinc oxide film formed by doping gallium and indium, and the zinc oxide film includes a plurality of regions having non-uniform concentration distributions of zinc content, gallium content, oxygen content, and indium content measured by XPS analysis in the depth direction, said plurality of regions including a first region and a second region having different [In]/[Ga] values.

Description

Transparent conductive laminate, method for producing transparent conductive laminate, and electronic device using transparent conductive laminate

The present invention relates to a transparent conductive laminate, a method for producing a transparent conductive laminate, and an electronic device using the transparent conductive laminate, and in particular, a transparent conductive laminate and a transparent conductive laminate excellent in wet heat characteristics. And an electronic device using such a transparent conductive laminate.

Conventionally, in an image display device provided with a liquid crystal device or an organic electroluminescence device (organic EL element), a transparent conductive laminate using tin-doped indium oxide as a material for forming a transparent conductive layer has been widely used.
On the other hand, a transparent conductive laminate using zinc oxide with excellent transparency and surface smoothness has been proposed as an alternative to a transparent conductive layer using tin-doped indium oxide containing a large amount of indium, which is an expensive and rare metal. Yes.
More specifically, a transparent conductive film is proposed in which an Al ₂ O ₃ thin film is formed on an organic polymer laminate substrate, and a GZO thin film of ZnO doped with Ga is formed thereon. (For example, refer to Patent Document 1).

In addition, a low-resistivity transparent conductor has been proposed which has a zinc oxide as a main component and a dopant whose concentration can be easily controlled.
That is, a transparent conductor made of zinc oxide, indium oxide, and gallium oxide, and a low-resistance transparent conductor in which the element concentrations of indium and gallium are each within a predetermined range has been proposed (for example, Patent Documents). 2).

On the other hand, a transparent conductive zinc oxide film doped with a specific element has been proposed for the purpose of obtaining excellent moisture and heat resistance characteristics even at an extremely thin film level.
That is, a first element composed of Ga and / or Al and a second element composed of at least one selected from the group consisting of In, Bi, Se, Ce, Cu, Er, and Eu are added to zinc oxide. A transparent conductive zinc oxide film having a specific resistance value within a predetermined range before and after a predetermined wet heat test, and a transparent value in which the atomic quantity ratio and film thickness of zinc and the second element are specified within the predetermined range. A conductive zinc oxide film has been proposed (for example, Patent Document 3).

Japanese Patent No. 4917897 (Claims etc.) JP 2006-147325 A (Claims etc.) JP 2013-147727 A (Claims etc.)

However, although the transparent conductive laminate disclosed in Patent Document 1 requires an Al ₂ O ₃ thin film as an undercoat layer, a zinc oxide film doped only with gallium still has poor moisture and heat resistance characteristics. There was a problem of being sufficient.
Moreover, although the low resistivity transparent conductor disclosed in Patent Document 2 has improved the resistivity, there has been a problem that no consideration has been given to the wet heat characteristics.
Moreover, although the transparent conductive zinc oxide film disclosed in Patent Document 3 has some wet heat characteristics, the film forming conditions are relatively severe, and the film thickness must be 140 nm or less. However, there has been a problem that the application is relatively narrow and limited.

Therefore, as a result of intensive studies on such problems, the present inventors are a transparent conductive laminate in which a transparent conductive layer is formed on at least one side of a substrate, and the zinc oxide film contains zinc oxide. A zinc oxide film doped with gallium and indium, the zinc oxide film having a non-uniform concentration distribution with respect to zinc content, gallium content, oxygen content, and indium content measured by XPS analysis It has been found that by forming a transparent conductive laminate including a plurality of regions having a configuration, it has excellent wet heat characteristics, and the present invention has been completed.
That is, an object of the present invention is to provide a transparent conductive laminate excellent in wet heat characteristics, a method for producing the transparent conductive laminate, and an electronic device using such a transparent conductive laminate.

According to the present invention, there is provided a transparent conductive laminate formed by forming a transparent conductive layer on at least one surface on a substrate, the transparent conductive layer containing zinc oxide and being doped with gallium and indium. A zinc film, the zinc oxide film including a plurality of regions having a non-uniform concentration distribution with respect to zinc content, gallium content, oxygen content, and indium content measured by XPS analysis in a depth direction; and The transparent conductive laminate is characterized in that the plurality of regions include a first region and a second region having different values of [In] / [Ga] in the film thickness direction from the transparent conductive layer toward the substrate. Provided and can solve the above-mentioned problems.
That is, the transparent conductive layer of the present invention is a zinc oxide film containing zinc oxide and doped with gallium and indium, and has a non-uniform concentration distribution with respect to zinc content, gallium content, oxygen content and indium content. Since it contains a plurality of regions, the wet heat characteristics of the transparent conductive layer can be improved.
More specifically, each region of the first region to the second region included in the transparent conductive layer satisfies the above-described element amount relationship, whereby a transparent conductive layer having excellent wet heat characteristics can be obtained. it can.
In addition, by specifying the blending composition of the first region to the second region by XPS measurement, it is possible to easily control the blending composition to a predetermined amount and satisfy a predetermined relationship with high accuracy. A transparent conductive laminate having stable performance can be obtained.
However, the interface between the first region and the second region included in the transparent conductive layer is not necessarily clear, but in a state where the composition ratio of each region changes continuously or in steps. Preferably there is.
In other words, in the transparent conductive layer, the internal composition ratio changes continuously or stepwise in the thickness direction, and the first region to the second region having different composition ratios are formed in the XPS measurement. It may be a grade which is confirmed.

In configuring the present invention, the value of [In] / [Ga] gradually decreases in the first region, and the value of [In] / [Ga] becomes a constant value in the second region. It is preferable to show.
As described above, when each region of the first region to the second region included in the transparent conductive layer satisfies the above-described element amount relationship, a transparent conductive layer having excellent wet heat characteristics can be obtained.

In constituting the present invention, in the transparent conductive layer, the amount of indium is 0.01 to about the total amount (100 atom%) of zinc amount, gallium amount, oxygen amount and indium amount by XPS elemental analysis measurement. It is preferable to set the value within the range of 8 atom% and the gallium content within the range of 0.1 to 10 atom%.
Thus, wet heat characteristics can be improved by setting the indium and gallium concentrations of the transparent conductive layer to values within a predetermined range.

Further, in constituting the present invention, in the first region, the zinc amount is 20 to 60 atom% with respect to the total amount (100 atom%) of zinc amount, gallium amount, oxygen amount and indium amount by XPS elemental analysis measurement. The amount of gallium is a value within the range of 0.1 to 10 atom%, the amount of oxygen is within the range of 22 to 79.89 atom%, and the amount of indium is 0.01 to 8 atom%. It is preferable to set the value within the range.
Thus, the further excellent wet heat characteristic can be acquired by comprising a transparent conductive laminated body in consideration of each composition amount of the 1st field.

In constructing the present invention, in the second region, the zinc amount is 35 to 65 atom% with respect to the total amount (100 atom%) of zinc amount, gallium amount, oxygen amount and indium amount by XPS elemental analysis measurement. The amount of gallium is a value within the range of 0.1 to 10 atom%, the amount of oxygen is within the range of 17 to 64.89 atom%, and the amount of indium is 0.01 to 8 atom%. It is preferable to set the value within the range.
Thus, the further excellent wet heat characteristic can be acquired by comprising a transparent conductive laminated body in consideration of each composition amount of the 2nd field.

In configuring the present invention, the value of [In] / [Ga] in the first region is preferably larger than the value of [In] / [Ga] in the second region.
By configuring the first region and the second region in this way, further excellent wet heat characteristics can be obtained.

In configuring the present invention, the initial specific resistance of the transparent conductive layer represented by ρ ₀ is set to a value in the range of 1 × 10 ⁻⁴ to 1 × 10 ⁻¹ Ω · cm, and the film thickness is set to A value in the range of 10 to 300 nm is preferable.
By comprising in this way, the productivity of the transparent conductive layer which has a predetermined film thickness and a low specific resistance can be improved.

In constructing the present invention, the initial specific resistance of the transparent conductive layer is ρ _0, and the specific resistance after storage for 500 hours at 60 ° C. and relative humidity of 95% is ρ _1. The ratio represented by ρ ₁ / ρ ₀ is preferably set to a value of 1.5 or less.
By comprising in this way, the transparent conductive laminated body which is excellent in wet heat characteristics can be obtained.

Another embodiment of the present invention is an electronic device characterized by using any of the transparent conductive laminates described above as a transparent electrode.
Thus, the long-term stability of an electronic device can be suitably achieved by using the transparent conductive laminated body excellent in wet heat characteristics for a transparent electrode.

Still another embodiment of the present invention is a method for producing a transparent conductive laminate in which a transparent conductive layer is formed on at least one surface on a substrate, and includes the following steps (1) to (2): Is a method for producing a transparent conductive laminate.
(1) Step of preparing a base material and a sintered body (2) At least one surface on the base material is doped with gallium and indium while containing zinc oxide from the sintered body by sputtering or vapor deposition. A zinc oxide film, which includes a plurality of regions having a non-uniform concentration distribution with respect to zinc amount, gallium amount, oxygen amount, and indium amount measured by XPS analysis in the depth direction, and the plurality of regions However, in the thickness direction from the transparent conductive layer to the substrate, a step of forming a transparent conductive layer composed of a zinc oxide film including a first region and a second region having different values of [In] / [Ga] By producing in this way, a transparent conductive laminate excellent in wet heat characteristics can be produced stably.

In practicing the present invention, it is preferable that the temperature of the substrate when forming the transparent conductive layer on the substrate is set to a value within the range of 10 to 150 ° C.
Manufacturing in this way increases the types of base materials that can be used, so that it is possible not only to manufacture a transparent conductive laminate that can be used for many purposes, but it is also economically advantageous.

FIG. 1A illustrates the amounts of elements (zinc content, oxygen content, gallium content and indium content) measured by XPS analysis in the depth direction of the transparent conductive layer in the transparent conductive laminate of Example 2. FIG. 1B is an enlarged view of the distribution curve of the gallium content and the indium content, and FIG. 1C is a diagram for explaining a change in the value of [In] / [Ga]. FIG. FIGS. 2A to 2C are views for explaining a cross section of a transparent conductive laminate including a transparent conductive layer including a plurality of regions having a non-uniform concentration distribution according to the present invention. FIG. 3 is an X-ray diffraction chart by an In Plane method of a zinc oxide film containing the zinc oxide of the present invention and doped with gallium and indium. FIG. 4 is an X-ray diffraction chart on the 002 plane of the zinc oxide film of the present invention by the Out of Plane method. FIG. 5 is a photograph provided to explain the crystal structure of the GZO film. FIG. 6 is a diagram provided for explaining the wet heat characteristics of the transparent conductive laminate of the present invention. FIG. 7A illustrates the element amounts (zinc amount, oxygen amount, gallium amount and indium amount) of the transparent conductive layer in the transparent conductive laminate of Example 1 measured by XPS analysis in the depth direction. FIG. 7B is an enlarged view of the distribution curve of the gallium content and the indium content, and FIG. 7C is a diagram for explaining a change in the value of [In] / [Ga]. FIG. FIG. 8A illustrates the amounts of elements (zinc content, oxygen content, gallium content and indium content) measured by XPS analysis in the depth direction of the transparent conductive layer in the transparent conductive laminate of Example 3. FIG. 8B is an enlarged view of the distribution curve of the gallium content and the indium content, and FIG. 8C is a diagram for explaining the change in the value of [In] / [Ga]. FIG. FIG. 9A illustrates the amounts of elements (zinc content, oxygen content, gallium content and indium content) measured by XPS analysis in the depth direction of the transparent conductive layer in the transparent conductive laminate of Example 4. FIG. 9B is an enlarged view of the distribution curve of the gallium content and the indium content, and FIG. 9C is a diagram for explaining the change in the value of [In] / [Ga]. FIG. FIG. 10A illustrates the element amounts (zinc amount, oxygen amount, gallium amount, and indium amount) measured by XPS analysis in the depth direction of the transparent conductive layer in the transparent conductive laminate of Comparative Example 1. FIG. 10B is an enlarged view of the distribution curves of the gallium content and the indium content.

[First embodiment]
The first embodiment is a transparent conductive laminate in which a transparent conductive layer is formed on at least one surface on a substrate, and the transparent conductive layer contains zinc oxide and is doped with gallium and indium. A zinc oxide film, the zinc oxide film including a plurality of regions having a non-uniform concentration distribution with respect to zinc amount, gallium amount, oxygen amount, and indium amount measured by XPS analysis in a depth direction; And the said several area | region contains the 1st area | region and the 2nd area | region from which the value of [In] / [Ga] differs in the film thickness direction which goes to a base material from a transparent conductive layer, The transparent conductive laminated body characterized by the above-mentioned It is.
Hereinafter, the transparent conductive laminate of the first embodiment will be specifically described with reference to the drawings as appropriate.

1. Transparent conductive layer The transparent conductive layer is a zinc oxide film in which the transparent conductive layer 10 contains zinc oxide and is doped with gallium and indium, as shown in FIG. In the thickness direction, it includes a plurality of regions having non-uniform concentration distribution with respect to zinc amount, gallium amount, oxygen amount and indium amount measured by XPS analysis in the depth direction, and the plurality of regions are transparent It includes a first region 10a and a second region 10b having different values of [In] / [Ga] in the film thickness direction from the conductive layer toward the substrate.
That is, when each region of the first region to the second region included in the transparent conductive layer satisfies the above element distribution relationship, a transparent conductive layer excellent in wet heat characteristics and transparency can be obtained.

(1) Crystal structure The zinc oxide film has a hexagonal wurtzite crystal structure, and a zinc oxide film doped with gallium (hereinafter referred to as a GZO film) is also shown in FIG. It is known to be a thin film having a hexagonal wurtzite crystal structure and a strong c-axis orientation.
The zinc oxide film in the present invention is a zinc oxide film containing zinc oxide and doped with gallium and indium (hereinafter sometimes referred to as an In-GZO film). Since the indium content is relatively small, it is understood that a columnar structure having a high c-axis orientation is taken as shown in FIGS.
More specifically, FIG. 3 shows an X-ray diffraction chart by the In plane method when the concentration of indium is changed. Here, the characteristic curve A is an X-ray of an In-GZO film obtained from a sintered body having a weight ratio of ZnO: Ga ₂ O ₃ : In ₂ O ₃ = 94.0: 5.7: 0.3. It is a diffraction chart, and the characteristic curve B shows an In-GZO film obtained from a sintered body having a weight ratio of ZnO: Ga ₂ O ₃ : In ₂ O ₃ = 93.5: 5.7: 1.0. It is an X-ray diffraction chart, and a characteristic curve C shows In-GZO obtained from a sintered body having a weight ratio of ZnO: Ga ₂ O ₃ : In ₂ O ₃ = 89.3: 5.7: 5.0. It is an X-ray diffraction chart of the film, and the characteristic curve D shows the In obtained from the sintered body whose weight ratio is ZnO: Ga ₂ O ₃ : In ₂ O ₃ = 84.3: 5.7: 10.0. -GZO film X-ray diffraction chart, characteristic curve E does not contain indium, that is, GZO film X-ray diffraction chart.

FIG. 4 shows an X-ray diffraction chart of the 002 plane by the out of plane method. Here, as in FIG. 3, the characteristic curve A is an In obtained from a sintered body having a weight ratio of ZnO: Ga ₂ O ₃ : In ₂ O ₃ = 94.0: 5.7: 0.3. -GZO film X-ray diffraction chart, characteristic curve B obtained from a sintered body having a weight ratio of ZnO: Ga ₂ O ₃ : In ₂ O ₃ = 93.5: 5.7: 1.0 3 is an X-ray diffraction chart of an In-GZO film, and a characteristic curve C is obtained from a sintered body having a weight ratio of ZnO: Ga ₂ O ₃ : In ₂ O ₃ = 89.3: 5.7: 5.0. It is an X-ray diffraction chart of the obtained In-GZO film, and the characteristic curve D shows that the weight ratio is ZnO: Ga ₂ O ₃ : In ₂ O ₃ = 84.3: 5.7: 10.0. 2 is an X-ray diffraction chart of an In—GZO film obtained from the body, and a characteristic curve E is an X-ray diffraction chart of the GZO film that does not contain indium.
3 to 4, it can be understood that the In-GZO film shows the same diffraction peak as that of the GZO film, and the crystal structure is similar.

(2) Configuration Further, in the transparent conductive layer, the indium content is 0.01 to 8 atom% with respect to the total amount (100 atom%) of zinc content, gallium content, oxygen content and indium content by XPS elemental analysis measurement. It is preferable to set the value within the range and the gallium content within the range of 0.1 to 10 atom%.
That is, in the transparent conductive layer, when the amount of indium is less than 0.01 atom%, suitable wet heat characteristics may not be obtained. On the other hand, when the amount of indium exceeds 8 atom%, the electrical characteristics deteriorate. It is because there is a case to do.
Moreover, it is because an electrical property may be inferior when the amount of gallium becomes a value outside the above range.
Therefore, in order to improve the wet heat characteristics, in the transparent conductive layer, the indium concentration is set to the total amount (100 atom%) of zinc amount, gallium amount, oxygen amount and indium amount by XPS elemental analysis measurement. More preferably, the value is in the range of 0.02 to 7 atom%, and the gallium concentration is in the range of 0.5 to 10 atom%.
In addition, each element amount by the elemental analysis measurement of XPS means the average value of the element amount in each depth measured by the XPS analysis of the depth direction in the whole transparent conductive layer.

(3) First Region As shown in FIGS. 1 (a) to 1 (c) and FIG. 2 (a), the first region 10a in the transparent conductive layer 10 has a zinc content, a gallium content, an oxygen content, and an indium content. , One of a plurality of regions having a non-uniform concentration distribution and formed farthest from the substrate surface, and in XPS analysis in the depth direction, indium content / gallium content ([In] / [Ga ]) Is preferably gradually reduced.
Here, the results of the transparent conductive layer 10 measured by XPS analysis in the depth direction are shown, for example, in FIGS.
FIG. 1C shows the result of calculating [In] / [Ga] from FIGS. 1A to 1B.
That is, it can be understood from FIG. 1 that in the first region, the amount of gallium is greatly increased toward the base material compared to the amount of indium.
In the first region, it is preferable that the amount of oxygen and the amount of indium decrease, and the amount of gallium and the amount of zinc increase.
The reason is that good wet heat characteristics can be obtained when each element has such a structure.

Further, in the first region, the zinc amount is set to a value in the range of 20 to 60 atom% with respect to the total amount (100 atom%) of zinc amount, gallium amount, oxygen amount and indium amount by XPS elemental analysis measurement, The amount of gallium is set to a value within the range of 0.1 to 10 atom%, the amount of oxygen is set to a value within the range of 22 to 79.89 atom%, and the amount of indium is set to a value within the range of 0.01 to 8 atom%. It is preferable.

That is, when the amount of indium in the first region is less than 0.01 atom%, the wet heat characteristics may be significantly deteriorated.
On the other hand, when the amount of indium in the first region exceeds 8 atom%, the amount of zinc and the amount of gallium are relatively decreased, and the balance of the blending components may be lost to change the crystal structure.
Therefore, in order to improve the wet heat characteristics, in the first region, the zinc amount is set to the total amount (100 atom%) of zinc amount, gallium amount, oxygen amount, and indium amount by XPS elemental analysis measurement. The value is in the range of 25 to 55 atom%, the gallium amount is in the range of 0.1 to 5 atom%, the oxygen amount is in the range of 33 to 74.88 atom%, and the indium amount is 0.8. A value in the range of 02 to 7 atom% is more preferable.
In addition, each element amount in the first region by XPS elemental analysis measurement means an average value of element amounts in a range where the value of [In] / [Ga] gradually decreases in the measurement by XPS analysis in the depth direction. However, since the first region is an extremely thin film, when the measured value is only one point, that value is meant.

(4) Second region As shown in FIGS. 1 (a) to 1 (c) and FIG. 2 (a), the second region 10b in the transparent conductive layer 10 has an amount of zinc measured by XPS analysis in the depth direction, One of a plurality of regions having a non-uniform concentration distribution with respect to the amount of gallium, the amount of oxygen, and the amount of indium, located on the substrate side, and the total amount of zinc, gallium, oxygen, and indium (100 atoms) %), The value of [In] / [Ga] preferably represents a constant value.
The reason for this is that good wet heat characteristics can be obtained when the second region becomes a region in which the composition ratio does not change significantly in the film thickness direction.
Note that the value of [In] / [Ga] being a constant value means that the increase / decrease in the value of [In] / [Ga] is a value within a range of ± 0.5.

Therefore, in the second region, the zinc amount is set to a value within the range of 35 to 65 atom% with respect to the total amount (100 atom%) of zinc amount, gallium amount, oxygen amount and indium amount by XPS elemental analysis measurement, The amount of gallium is set to a value within the range of 0.1 to 10 atom%, the amount of oxygen is set to a value within the range of 17 to 64.89 atom%, and the amount of indium is set to a value within the range of 0.01 to 8 atom%. It is preferable.

That is, when the amount of indium in the second region is less than 0.01 atom%, the wet heat characteristics may be significantly deteriorated.
On the other hand, when the amount of indium in the second region exceeds 8 atom%, the amount of zinc and the amount of gallium are relatively decreased, and the balance of the blending components may be lost to change the crystal structure.
Therefore, in order to improve the wet heat characteristics, in the second region, the zinc amount is set to the total amount (100 atom%) of zinc amount, gallium amount, oxygen amount and indium amount by XPS elemental analysis measurement. The value is in the range of 40 to 60 atom%, the gallium amount is in the range of 0.5 to 10 atom%, the oxygen amount is in the range of 23 to 59.48 atom%, and the indium amount is 0.8. A value in the range of 02 to 7 atom% is more preferable.
In addition, each element amount in the second region by XPS elemental analysis measurement means an average value of element amounts in a range in which the value of [In] / [Ga] shows a constant value in measurement by XPS analysis in the depth direction. To do.

(5) [In] / [Ga]
In the first region and the second region, the value of [In] / [Ga] in the first region is preferably larger than the value of [In] / [Ga] in the second region.
That is, as the amount of gallium and the amount of indium change from the first region toward the second region, the value of [In] / [Ga] in the first region is changed to [In] in the second region as described above. ] / [Ga] is preferably larger.
More specifically, it is preferable that the amount of gallium increases greatly and the amount of indium decreases or any one of them as described above from the first region toward the second region.
Further, it is more preferable that the value of [In] / [Ga] in the first region is 0.03 or more larger than the value of [In] / [Ga] in the second region.
The reason for this is that good wet heat characteristics can be obtained when the first region and the second region have such a configuration.

(6) Film thickness In the present invention, it is preferable that the film thickness of the transparent conductive layer including the first region to the second region is a value within the range of 10 to 300 nm.
This is because when the thickness of the transparent conductive layer is less than 10 nm, stable formation of the transparent conductive layer including the first region to the second region may become difficult, and the wet heat characteristics are remarkably increased. This is because it may decrease.
On the other hand, when the film thickness of the transparent conductive layer exceeds 300 nm, it takes an excessive amount of time to form the transparent conductive layer, which may reduce productivity.
Accordingly, the thickness of the transparent conductive layer including the first region to the second region is more preferably in the range of 20 to 250 nm, and still more preferably in the range of 30 to 200 nm.

Furthermore, regarding the film thickness in each region of the transparent conductive layer of the present invention, the film thickness in the first region is preferably 15 nm or less.
This is because excellent wet heat characteristics and the like can be obtained by setting the film thickness of each region in such a range.
Therefore, the film thickness in the first region is more preferably 10 nm or less, and even more preferably 5 nm or less.
In addition, the minimum of the film thickness in a 1st area | region is 0.1 nm or more normally.

(7) Humid heat characteristics In addition, the initial specific resistance of the transparent conductive layers 10 and 10 ′ illustrated in FIGS. 2A to 2C is ρ ₀ , and is 500 under the conditions of 60 ° C. and relative humidity 95%. It is preferable to set the ratio represented by ρ ₁ / ρ ₀ to a value of 1.5 or less, where ρ ₁ is the specific resistance after storage for hours.
In addition, the specific resistance (ρ ₀ , ρ ₁ ) of the transparent conductive layer can be measured using a surface resistance measuring device as specifically described in Example 1.

Here, with reference to FIG. 6, the relationship between the structure of a transparent conductive layer in a transparent conductive laminated body and the change of the specific resistance before and behind an environmental test is demonstrated.
That is, the horizontal axis of FIG. 6 shows the elapsed storage time under conditions of 60 ° C. and 95% relative humidity, and the vertical axis shows the ratio represented by ρ ₁ / ρ _0. .
The characteristic curve A shows the wet heat characteristics of the In-GZO film obtained from the sintered body having a weight ratio of ZnO: Ga ₂ O ₃ : In ₂ O ₃ = 94.0: 5.7: 0.3. The characteristic curve B shows an In-GZO film obtained from a sintered body having a weight ratio of ZnO: Ga ₂ O ₃ : In ₂ O ₃ = 93.5: 5.7: 1.0. The characteristic curve C is a curve showing wet heat characteristics, and the characteristic curve C is an In − obtained from a sintered body having a weight ratio of ZnO: Ga ₂ O ₃ : In ₂ O ₃ = 89.3: 5.7: 5.0. is a curve showing the moist heat characteristics of the GZO film, the characteristic curve D, the weight ratio of _{ZnO: Ga 2 O 3: in} 2 O 3 = 84.3: 5.7: obtained a sintered body which is a 10.0 The characteristic curve E is a curve that does not contain indium, that is, a characteristic curve that indicates the wet heat characteristics of the GZO film.
From these characteristic curves A to E, it is understood that the wet heat characteristics are dramatically improved by adding a small amount of indium to the transparent conductive layer which is a GZO film.
Moreover, the tendency for a wet heat characteristic to improve more by the increase in the compounding quantity of an indium amount is seen.
Therefore, it can be understood that the In-GZO film is superior in wet heat characteristics over time because the rate of change in specific resistance in a wet heat environment is low over a long period of time compared to the GZO film.

(8) Specific Resistance The initial specific resistance (ρ ₀ ) of the transparent conductive layers 10 and 10 ′ illustrated in FIGS. 2A to 2C is 1 × 10 ⁻⁴ to 1 × 10 ⁻¹ Ω · A value in the range of cm is preferable.
The specific resistance (ρ) of the transparent conductive layer should be calculated from the film thickness (d) of the transparent conductive laminate and the measured surface resistivity (R), as specifically described in Example 1. Can do.

2. Type of base material (1) The base material 12 illustrated in FIG. 1 is not particularly limited as long as it is excellent in transparency, and examples thereof include glass, ceramics, and resin films. Resin film materials include polyimide, polyamide, polyamideimide, polyphenylene ether, polyetherketone, polyetheretherketone, polyolefin, polyester, polycarbonate, polysulfone, polyethersulfone, polyphenylene sulfide, polyarylate, acrylic resin, cyclohexane Examples thereof include olefin polymers, aromatic polymers, polyurethane polymers and the like.
In particular, in order for the transparent conductive laminate of the present invention to be excellent in flexibility, the substrate is preferably a resin film.
Among these resin films, since it is excellent in transparency and versatile, it is preferably at least one selected from the group consisting of polyester, polyimide, polyamide, and cycloolefin polymer. Olefin polymers are more preferred.
More specifically, examples of the polyester include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polyarylate.
Examples of the polyamide include wholly aromatic polyamide, nylon 6, nylon 66, nylon copolymer, and the like.
Examples of cycloolefin polymers include norbornene polymers, monocyclic olefin polymers, cyclic conjugated diene polymers, vinyl alicyclic hydrocarbon polymers, and hydrides thereof. Examples thereof include apell (an ethylene-cycloolefin copolymer manufactured by Mitsui Chemicals), arton (a norbornene polymer manufactured by JSR), zeonoa (a norbornene polymer manufactured by Nippon Zeon), and the like.

(2) Film thickness The film thickness of the substrate 12 illustrated in FIG. 2 may be determined according to the purpose of use and the like, but is within the range of 1 to 1000 μm from the viewpoint of flexibility and easy handling. The value is preferably in the range of 5 to 250 μm, more preferably in the range of 10 to 200 μm.

(3) Additives In addition to the resin component described above, the base material may contain various additives such as an antioxidant, a flame retardant, and a lubricant as long as transparency and the like are not impaired.

3. Other layers Furthermore, various other layers can be provided in the transparent conductive laminate of the present invention as necessary.
Examples of such other layers include gas barrier layers, primer layers, planarization layers, hard coat layers, protective layers, antistatic layers, antifouling layers, antiglare layers, color filters, adhesive layers, decorative layers, and printing. Layer and the like.
Here, a primer layer is a layer provided in order to improve the adhesiveness of a base material and a transparent conductive layer, As a material, a urethane type resin, an acrylic resin, a silane coupling agent, an epoxy resin, polyester, for example Known resins such as a resin and an ultraviolet curable resin can be used.

Further, the gas barrier layer is preferably provided between the base material and the transparent conductive layer, and the material constituting the gas barrier layer is not particularly limited as long as it prevents the permeation of oxygen and water vapor. It is preferable that the gas barrier property is good.
More specifically, examples of the constituent material include metals such as aluminum, magnesium, zirconium, titanium, zinc, and tin; silicon oxide, aluminum oxide, zinc oxide, zirconium oxide, titanium oxide, indium oxide, tin oxide, and oxide. Inorganic oxides such as zinc tin; inorganic nitrides such as silicon nitride; inorganic oxynitrides; inorganic carbides; inorganic sulfides; inorganic oxynitride carbides; at least one selected from polymer compounds and composites thereof Is preferred.
The gas barrier layer may contain other compounding components such as various polymer resins, curing agents, anti-aging agents, light stabilizers, and flame retardants.

In addition, the method for forming the gas barrier layer is not particularly limited. For example, a method for forming the above-described material on a substrate by a vapor deposition method, a sputtering method, an ion plating method, a thermal CVD method, a plasma CVD method, or the like. , A method in which a solution obtained by dissolving or dispersing the above material in an organic solvent is coated on a substrate by a known coating method, and the resulting coating film is appropriately dried to form an atmospheric pressure with respect to the resulting coating film. Examples thereof include a method of forming by surface modification such as plasma, ion implantation, and lamp annealing.

Further, the thickness of the gas barrier layer is not particularly limited, and is usually preferably a value within the range of 20 nm to 50 μm.
The reason for this is that by using such a gas barrier layer having a predetermined film thickness, further excellent gas barrier properties and adhesion can be obtained, and at the same time, both flexibility and coating strength can be achieved.
Therefore, the film thickness of the gas barrier layer is more preferably set to a value within the range of 30 nm to 1 μm, and further preferably set to a value within the range of 40 nm to 500 nm.

Further, 40 ° C. of the gas barrier layer, a water vapor permeability as measured in an atmosphere of 90% RH is preferably not more than the value ^{0.1g / m 2 / day, 0.05g} / m 2 / day or less of More preferably, the value is 0.01 g / m ² / day or less.
The reason for this is that by setting such a value of water vapor transmission rate, the transparent conductive layer can be prevented from deteriorating and gas barrier properties excellent in moisture and heat resistance can be obtained.
In addition, it can measure by a well-known method as a water vapor transmission rate of a gas barrier layer, For example, it can measure using a commercially available water vapor transmission rate measuring apparatus.

4). Transparent Conductive Laminate (1) Aspect The transparent conductive laminates 50, 50 ′, 50 ″ illustrated in FIGS. 2 (a) to 2 (c) are transparent conductive layers 10 on one side or both sides of the substrate 12. 10 'is a transparent conductive laminate, and the transparent conductive layer has the first region 10a and the second region 10b having a specific composition ratio measured by XPS analysis from the transparent conductive layer to the substrate. It is comprised including in the film thickness direction which goes.
Moreover, as shown in FIG.2 (c), it is a preferable aspect even if it is a case where the gas barrier layer 14 is included between the base material and the transparent conductive layer.
In the present invention, regarding the transparency of the transparent conductive layer, the light transmittance at a wavelength of 550 nm is preferably 70% or more at a predetermined thickness, for example, any of 20 to 600 nm, and 80% or more. More preferably, the value is 90% or more.
Further, regarding the transparency of the transparent conductive laminate, the light transmittance at a wavelength of 550 nm is preferably 50% or more at a predetermined thickness, for example, 10 μm to 1 mm, and is a value of 60% or more. More preferably, the value is more preferably 70% or more.

(2) Specific Resistance The specific resistance (ρ) of the transparent conductive laminates 50, 50 ′, 50 ″ illustrated in FIGS. 2 (a) to 2 (c) is substantially the same as that of the transparent conductive layers 10, 10 ′. Since it is the same as the specific resistance, the description thereof will be omitted.

[Second Embodiment]
The second embodiment is a method for producing a transparent conductive laminate in which a transparent conductive layer is formed on at least one surface on a substrate, and includes the following steps (1) to (2). It is a manufacturing method of a transparent conductive laminated body.
(1) Step of preparing a base material and a sintered body (2) At least one surface on the base material is doped with gallium and indium while containing zinc oxide from the sintered body by sputtering or vapor deposition. A zinc oxide film, which includes a plurality of regions having a non-uniform concentration distribution with respect to zinc amount, gallium amount, oxygen amount, and indium amount measured by XPS analysis in the depth direction, and the plurality of regions Forming a transparent conductive layer comprising a zinc oxide film including a first region and a second region having different values of [In] / [Ga] in the thickness direction from the transparent conductive layer toward the substrate. The manufacturing method of the transparent conductive laminated body of 2 embodiment is demonstrated concretely.

1. Step (1): Step of Preparing Substrate and Sintered Body The transparent conductive layer exemplified in FIGS. 2 (a) to (c) has zinc oxide as a main component and further contains gallium oxide and indium oxide. It is preferable to form a film from the sintered body.
In the sintered body forming the transparent conductive layer, the blending amount of zinc oxide is set to a value in the range of 70 to 99.98% by weight with respect to the total amount of the sintered body, and the blending amount of gallium oxide is It is preferable to set the value within the range of 0.01 to 15% by weight and the blending amount of indium oxide within the range of 0.01 to 15% by weight.
The reason for this is that by using a ternary sintered body of zinc oxide-gallium oxide-indium oxide in which the blending amount is controlled, a transparent conductive layer having excellent wet heat characteristics can be efficiently formed. This is because production efficiency can be improved.
More specifically, when the blending amount of indium oxide is less than 0.01% by weight with respect to the total amount of the sintered body, the amount of indium contained in the transparent conductive layer after film formation is significantly reduced. This is because sufficient wet heat characteristics may not be obtained.
On the other hand, when the amount of indium oxide exceeds 15% by weight, the amount of indium contained in the transparent conductive layer after film formation increases, so that the specific resistance may be a remarkably large value.
Accordingly, the zinc oxide content is in the range of 76 to 99.4% by weight and the gallium oxide content is in the range of 0.5 to 12% by weight with respect to the total amount of the sintered body. More preferably, the blending amount of indium oxide is set to a value within the range of 0.1 to 12 weights.
Further, the blending amount of zinc oxide is set to a value within the range of 80 to 98.7% by weight, and the blending amount of gallium oxide is set to a value within the range of 1 to 10% by weight with respect to the total amount of the sintered body. Further, it is more preferable that the blending amount of indium oxide is a value within the range of 0.3 to 10% by weight.
The details of the base material are the same as described above, and will be omitted.

2. Step (2): Method for forming transparent conductive layer As a method for forming a transparent conductive layer, for example, a physical production method represented by sputtering or vapor deposition, and a chemical production method represented by chemical vapor deposition Is mentioned.
Among these, a sputtering method or a vapor deposition method is preferable because a transparent conductor layer can be easily formed. That is, since the composition of the formed transparent conductive layer can be easily controlled by forming by sputtering or vapor deposition, the transparent conductive layer can be formed efficiently.

More specific sputtering methods include DC sputtering method, DC magnetron sputtering method, RF sputtering method, RF magnetron sputtering method, DC + RF superposition sputtering method, DC + RF superposition magnetron sputtering method, counter target sputtering method, ECR sputtering method, dual magnetron sputtering method. Etc.
More specific vapor deposition methods include a resistance heating method, an electron beam heating method, a laser heating method, an arc vapor deposition method, and an induction heating method.

The conditions for sputtering or vapor deposition are not particularly limited, but the back pressure is preferably 1 × 10 ⁻² Pa or less, and more preferably 1 × 10 ⁻³ Pa or less.
In addition, when a formation method in which argon gas is introduced into the system is selected, the internal pressure is preferably set to a value in the range of 0.1 to 5 Pa, more preferably 0.2 to 1 Pa.
Furthermore, it is preferable in terms of production cost that argon (Ar) or a mixed gas of argon (Ar) and oxygen (O ₂ ) is used as a gas species to be introduced into the system by sputtering or vapor deposition, but rare gases other than Ar are used. Gas, nitrogen (N ₂ ), or the like may be used. When a mixed gas is used, the mixing ratio (O ₂ / (Ar + O ₂ )) is preferably set to a value within the range of 0.01 to 20, and more preferably set to a value within the range of 0.1 to 10. preferable.
The reason for this is that, if the mixing ratio of argon and oxygen is in the above range, the composition of the transparent conductive layer to be formed can be easily controlled. Therefore, the specific resistance is low and the heat and moisture resistance is excellent. This is because a low conductive layer can be formed.

In addition, the temperature of the substrate when forming the transparent conductive layer on the substrate is preferably set to a value within the range of 10 to 150 ° C.
This is because, if the temperature of the substrate is a value within the range of 10 to 150 ° C., the transparent conductive film formed without changing the substrate even when a resin film is used as the substrate. This is because the composition of the layer can be easily controlled and a transparent conductive layer can be suitably formed.

[Third embodiment]
The third embodiment is an electronic device characterized by using any of the transparent conductive laminates described above as a transparent electrode.
More specifically, a liquid crystal display, an organic EL display, an inorganic EL display, an electronic paper, a solar cell, an organic transistor, an organic EL illumination, and an inorganic EL illumination each having a transparent electrode provided with a predetermined transparent conductive laminate. , Thermoelectric conversion devices, gas sensors and the like.

That is, since the electronic device of the present invention includes the transparent conductive laminate described in the first embodiment, it is excellent in transparency, has a sufficiently small specific resistance, and increases in specific resistance over a long period of time. Can exhibit conductivity that can be suppressed.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the following description shows the present invention by way of example, and the present invention is not limited to these descriptions.

[Example 1]
1. Production of transparent conductive laminate (1) Step 1: Step of preparing base material and sintered body As a base material, alkali-free glass (Corning Corp., Eagle XG, thickness: 700 μm) was prepared.
Also, a zinc oxide-gallium oxide-indium oxide ternary sintered body (ZnO: Ga ₂ O ₃ : In ₂ O ₃ = 94.0 wt%: 5.7 wt%: 0.3 wt%) was prepared. did.

(2) Step 2: Step of forming transparent conductive layer Next, a transparent conductive layer (film thickness) is formed on the alkali-free glass by the DC magnetron sputtering method using the ternary sintered body described above under the following sputtering conditions. : 100 nm) to form a transparent conductive laminate.
Substrate temperature: 20 ° C
DC output: 500W
Carrier gas: Argon (Ar)
Deposition pressure: 0.6Pa
Deposition time: 35 sec.

2. Evaluation of transparent conductive laminate The obtained transparent conductive laminate was measured and evaluated as follows.

(1) XPS analysis in the depth direction Using an XPS measurement analyzer (manufactured by ULVAC-PHI, Quantum 2000), zinc, gallium, indium, oxygen in the depth direction of the transparent conductive layer in the obtained transparent conductive laminate, and Elemental analysis of silicon was performed. FIG. 7 shows an element amount chart obtained by XPS measurement.
Moreover, from this element amount chart, it was confirmed whether or not a plurality of regions including a first region and a second region each having a predetermined composition ratio were formed in the transparent conductive layer.
That is, all of the first to second regions having a predetermined composition ratio are confirmed, and the first region in which the value of [In] / [Ga] decreases is confirmed in the film thickness direction from the transparent conductive layer toward the substrate. The case where the first region where the value of [In] / [Ga] decreases was not confirmed was evaluated as x evaluation. The obtained results are shown in Table 1.

(2) X-ray diffraction measurement Using an X-ray diffractometer (manufactured by Rigaku Corporation, fully automatic horizontal multi-purpose X-ray diffractometer Smart Lab), the crystal structure of the transparent conductive layer in the obtained transparent conductive laminate is obtained. This was confirmed by the In plane method and the Out of plane method. The obtained results are shown in the characteristic curve A of FIGS.

(3) Film thickness of transparent conductive layer (d)
The film thickness (d) in the transparent conductive layer of the obtained transparent conductive laminate was measured using a spectroscopic ellipsometer M-2000U (manufactured by JA Woollam Japan).

(4) Calculation of ρ ₁ / ρ ₀ The initial surface resistivity (R ₀ ) in the transparent conductive layer of the obtained transparent conductive laminate was used as a surface resistance measuring device as a LORESTA-GP MCP-T600 (Mitsubishi Chemical ( As a probe and a probe type ASP (manufactured by Mitsubishi Chemical Analytech Co., Ltd.), the measurement was performed under environmental conditions of a temperature of 23 ° C. and 50% RH.
Next, the obtained transparent conductive laminate was placed in an environment of 60 ° C. and 95% RH for 500 hours, taken out, and then subjected to temperature / humidity control in a 23 ° C. and 50% RH environment for 1 day. The surface resistivity (R ₁ ) was measured.
Next, from the obtained surface resistivity (R ₀ and R ₁ ) and film thickness (d), from the following formulas (1) and (2), the initial specific resistance (ρ ₀ ) and the specific resistance after the wet heat test (ρ ₁ ) was calculated to obtain a ratio of ρ ₁ / ρ ₀ . The obtained results are shown in Table 1.
FIG. 6 shows the relationship between the wet heat test elapsed time in Example 1 and the specific resistance ratio (ρ ₁ / ρ ₀ ) before and after the wet heat test.
R ₀ = ρ ₀ / d (1)
R ₁ = ρ ₁ / d (2)

[Example 2]
In Example 2, the weight ratio of the ternary sintered body used for sputtering was changed to ZnO: Ga ₂ O ₃ : In ₂ O ₃ = 93.3: 5.7: 1.0. A transparent conductive laminate was produced and evaluated in the same manner as in Example 1. The obtained results are shown in Table 1, the obtained element amount chart by XPS measurement is shown in FIG. 1, and the obtained X-ray diffraction peaks are shown in the characteristic curve B of FIG. 3 and FIG.

[Example 3]
In Example 3, except that the weight ratio of the ternary sintered body used for sputtering was changed to ZnO: Ga ₂ O ₃ : In ₂ O ₃ = 89.3: 5.7: 5.0 A transparent conductive laminate was produced and evaluated in the same manner as in Example 1. The obtained results are shown in Table 1, the obtained element amount chart by XPS measurement is shown in FIG. 8, and the obtained X-ray diffraction peaks are shown in the characteristic curve C of FIG. 3 and FIG.

[Example 4]
In Example 4, except that the weight ratio of the ternary sintered body used for sputtering was changed to ZnO: Ga ₂ O ₃ : In ₂ O ₃ = 84.3: 5.7: 10.0 A transparent conductive laminate was produced and evaluated in the same manner as in Example 1. The obtained results are shown in Table 1, the obtained element amount chart by XPS measurement is shown in FIG. 9, and the obtained X-ray diffraction peaks are shown in the characteristic curve D of FIG. 3 and FIG.

[Example 5]
In Example 5, the forming process is a DC arc plasma deposition method, and the weight ratio of the ternary sintered body is ZnO: Ga ₂ O ₃ : In ₂ O ₃ = 95.0: 4.0: 1.0. Except for the change, a transparent conductive laminate was produced and evaluated using non-alkali glass as a base material in the same manner as in Example 1. The obtained results are shown in Table 1. The film forming conditions were as follows.
Although not shown, the X-ray diffraction peak was a c-axis oriented hexagonal wurtzite crystal, similar to the film obtained by the sputtering method.
Substrate temperature: 20 ° C
Discharge current: 150A
Carrier gas: Argon (Ar), Oxygen (O ₂ )
Oxygen ratio: 6% of the total gas flow rate
Deposition pressure: 0.2Pa
Deposition time: 25 sec.

[Comparative Example 1]
In Comparative Example 1, the transparent conductive material was the same as in Example 1 except that a sintered body having a weight ratio of ZnO: Ga ₂ O ₃ = 94.3: 5.7 was used as the sintered body used for sputtering. The conductive laminate was manufactured and evaluated. The obtained results are shown in Table 1, the obtained element amount chart by XPS measurement is shown in FIG. 10, and the obtained X-ray diffraction peaks are shown in the characteristic curve E of FIGS.

From Table 1, the transparent conductive laminate obtained in the Examples includes a first region and a second region in which the transparent conductive layer has a predetermined crystal structure and different composition ratios by XPS analysis, and each It was confirmed that the region is a zinc oxide film having a specific configuration, and a transparent conductive laminate having extremely excellent wet heat characteristics can be obtained efficiently.
On the other hand, the transparent conductive laminate including the GZO film not containing indium in Comparative Example 1 did not include the predetermined first and second regions, and the specific resistance after the environmental test was significantly increased.

As described above in detail, according to the transparent conductive laminate of the present invention, it is a transparent conductive laminate formed by forming a transparent conductive layer on at least one surface on a substrate, and the transparent conductive layer is made of zinc. Is a zinc oxide film containing indium, gallium, and oxygen and doped with indium, and has a non-uniform concentration distribution with respect to zinc content, gallium content, oxygen content, and indium content measured by XPS analysis in the depth direction And a plurality of regions including the specific first region and the second region, a transparent conductive laminate having extremely excellent wet heat characteristics can be efficiently obtained. It was.
Moreover, according to the manufacturing method of the present invention, the transparent conductive layer including the first and second regions having different composition ratios can be easily and accurately manufactured stably by XPS measurement.
Therefore, the transparent conductive laminate of the present invention is an electric product, electronic component, or image display device (organic electroluminescence element, inorganic electroluminescence element, liquid crystal display device, electronic paper, etc.) solar cell in which a predetermined wet heat characteristic is desired. In various applications such as, it is expected to be used effectively as a transparent electrode.

10, 10 ': Transparent conductive layer 10a: First region, 10b: Second region 12: Base material 14: Gas barrier layer 20: GZO films 50, 50', 50 ": Transparent conductive laminate

Claims (11)

A transparent conductive laminate formed by forming a transparent conductive layer on at least one side of a substrate,
The transparent conductive layer contains zinc oxide and is a zinc oxide film doped with gallium and indium,
The zinc oxide film includes a plurality of regions having a non-uniform concentration distribution with respect to zinc amount, gallium amount, oxygen amount, and indium amount measured by XPS analysis in the depth direction,
And the said several area | region contains the 1st area | region and the 2nd area | region from which the value of [In] / [Ga] differs in the film thickness direction which goes to the said base material from the said transparent conductive layer, The transparent conductive lamination characterized by the above-mentioned. body. In the first region, the value of [In] / [Ga] gradually decreases,
2. The transparent conductive laminate according to claim 1, wherein in the second region, the value of [In] / [Ga] is a constant value. In the transparent conductive layer, the amount of indium is a value in the range of 0.01 to 8 atom% with respect to the total amount (100 atom%) of zinc amount, gallium amount, oxygen amount and indium amount by XPS elemental analysis measurement. The transparent conductive laminate according to claim 1 or 2, wherein the amount of gallium is set to a value within a range of 0.1 to 10 atom%. In the first region, with respect to the total amount (100 atom%) of zinc amount, gallium amount, oxygen amount and indium amount as measured by XPS elemental analysis, the zinc amount is set to a value within a range of 20 to 60 atom%, and gallium The amount is set to a value within the range of 0.1 to 10 atom%, the oxygen amount is set to a value within the range of 22 to 79.89 atom%, and the indium amount is set to a value within the range of 0.01 to 8 atom%. The transparent conductive laminate according to any one of claims 1 to 3, wherein: In the second region, with respect to the total amount (100 atom%) of zinc amount, gallium amount, oxygen amount and indium amount by XPS elemental analysis measurement, the zinc amount is set to a value within the range of 35 to 65 atom%, and gallium The amount is set to a value within the range of 0.1 to 10 atom%, the oxygen amount is set to a value within the range of 17 to 64.89 atom%, and the indium amount is set to a value within the range of 0.01 to 8 atom%. The transparent conductive laminate according to any one of claims 1 to 4, wherein: The value of [In] / [Ga] in the first region is larger than the value of [In] / [Ga] in the second region, according to any one of claims 1 to 5. Transparent conductive laminate. The initial specific resistance of the transparent conductive layer represented by ρ ₀ is a value in the range of 1 × 10 ⁻⁴ to 1 × 10 ⁻¹ Ω · cm, and the film thickness is in the range of 10 to 300 nm. The transparent conductive laminate according to any one of claims 1 to 6, wherein: The initial resistivity in the transparent conductive layer and [rho _0, 60 ° C., under a relative humidity of 95% for 500 hours, the specific resistance after storage when a [rho _1, represented by ρ ₁ / ρ ₀ The transparent conductive laminate according to any one of claims 1 to 7, characterized in that the ratio is 1.5 or less. An electronic device comprising the transparent conductive laminate according to any one of claims 1 to 8 as a transparent electrode. A method for producing a transparent conductive laminate comprising a transparent conductive layer formed on at least one surface of a substrate, comprising the following steps (1) to (2): Method.
(1) Step of preparing the base material and the sintered body (2) At least one surface on the base material contains zinc oxide and doped with gallium and indium from the sintered body by sputtering or vapor deposition. A zinc oxide film,
The zinc content, the gallium content, the oxygen content, and the indium content measured by XPS analysis in the depth direction include a plurality of regions having a non-uniform concentration distribution, and the plurality of regions are separated from the transparent conductive layer. Forming the transparent conductive layer made of the zinc oxide film including a first region and a second region having different values of [In] / [Ga] in a thickness direction toward the substrate; 11. The production of a transparent conductive laminate according to claim 10, wherein the temperature of the substrate when forming the transparent conductive layer on the substrate is set to a value within the range of 10 to 150 ° C. Method.

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