JP2012190659A - Transparent conductive film, base material with transparent conductive film and organic electroluminescent element including the same - Google Patents

Abstract

In a transparent conductive film, a substrate with a transparent conductive film, and an organic electroluminescence device using the same, irregular reflection of light by a thin metal wire is suppressed and occurrence of migration is prevented.
A substrate 6 with a transparent conductive film includes a substrate 2 and a transparent conductive film 3 formed on the substrate 2. The transparent conductive film 3 includes a thin metal wire 3a having conductivity and a transparent resin layer 3b as a binder. The fine metal wire 3a is bonded onto the base material 2 by the transparent resin layer 3b. The surface of the metal thin wire 3a is oxidized or sulfided, and the oxidized or sulfided portion 3c is blackened to lose the metallic luster, so that irregular reflection of light can be suppressed. Further, since the oxidized or sulfurized portion 3c becomes a nonconductor and is chemically stable, the occurrence of migration can be prevented.
[Selection] Figure 2

Description

  The present invention relates to a transparent conductive film used for various optical devices, a substrate with a transparent conductive film, and an organic electroluminescence element using the same.

  Conventionally, a general organic electroluminescence (hereinafter referred to as organic EL) element is an organic light emitting layer sandwiched between a pair of electrodes formed on a transparent substrate, and the light from the organic light emitting layer is It passes through one electrode and is taken out from the substrate side. In this type of organic EL element, a material having conductivity and translucency is used as an electrode material on the substrate side, and indium tin oxide (hereinafter referred to as ITO) is widely used. However, an electrode using ITO as a material is vulnerable to bending and physical stress and is fragile. Moreover, in order to improve the electroconductivity of the electrode using ITO, high vapor deposition temperature and / or high annealing temperature are needed, and there exists a possibility that it may become high cost in manufacture of the device using an organic EL element.

  Therefore, a technique using a transparent conductive film including a plurality of fine metal wires as an electrode instead of ITO is known (for example, see Patent Document 1). A configuration example of this type of substrate with a transparent conductive film will be described with reference to FIG. The base material 101 with a transparent conductive film includes a base material 102 having translucency and a transparent conductive film 103 formed on the base material 102. The transparent conductive film 103 includes a plurality of fine metal wires (silver nanowires) 103a and a transparent resin layer 103b as a binder. The plurality of fine metal wires 103a are bonded onto the base material 102 by the transparent resin layer 103b.

Special table 2009-505358

  However, in such a substrate 101 with a transparent conductive film, the silver nanowires used as the fine metal wires 103a have a high reflectance, and the highly reflective fine metal wires 103a exist so as to be intricately entangled three-dimensionally. Therefore, irregular reflection of light is likely to occur. Therefore, the transparent conductive film 103 may appear cloudy, and further, the light extraction efficiency of the organic EL element may be reduced. Further, since the metal thin wire 103a is made of nano-order thin linear silver, migration easily occurs. Therefore, silver may melt and insulation failure may occur. Since the organic EL element has a configuration in which nano-order thin layers are stacked, an insulation failure may occur due to the migration described above.

  The present invention has been made to solve the above-described problems, and can suppress irregular reflection of light due to a fine metal wire and can prevent migration from occurring, and a substrate with a transparent conductive film And an organic electroluminescence device using the same.

  The transparent conductive film of the present invention is a transparent conductive film provided on a substrate and provided with a transparent resin layer containing fine metal wires, wherein the surface of the fine metal wires is oxidized or sulfided. .

  In this transparent conductive film, the fine metal wire preferably contains silver.

  In this transparent conductive film, the surface of the fine metal wire is preferably sulfided.

  In this transparent conductive film, the ratio of the sulfur element contained in the thin metal wire to the silver element contained in the fine metal wire is preferably more than 10% and less than 50%.

  In this transparent conductive film, the fine metal wire is preferably a metal nanowire.

  It is preferable that this transparent conductive film is formed on a base material, and is comprised as a base material with a transparent conductive film.

  It is preferable that this base material with a transparent conductive film is used for an organic electroluminescent element.

  According to the transparent conductive film of the present invention, the surface of the fine metal wire is oxidized or sulfided to become black and lose its metallic luster, so that it is possible to suppress irregular reflection of light. Moreover, since the surface of the fine metal wire is oxidized or sulfided to become a nonconductor and chemically stable, the occurrence of migration can be prevented.

Sectional drawing of the organic electroluminescent element provided with the base material with a transparent conductive film which concerns on one Embodiment of this invention. Sectional drawing of the base material with the said transparent conductive film, and partial expanded sectional view of the metal fine wire contained in the base material with the said transparent conductive film. Sectional drawing of the base material with the conventional transparent conductive film.

  Hereinafter, a transparent conductive film according to an embodiment of the present invention will be described with reference to the drawings. The transparent conductive film of the present embodiment is formed on a light-transmitting substrate and is configured as a substrate with a transparent conductive film, and is used for, for example, an organic electroluminescence (hereinafter referred to as organic EL) element. FIG. 1 shows a cross-sectional configuration of an organic EL element. The organic EL element 1 includes a base material 2, a transparent conductive film 3, an organic light emitting layer 4, and a conductor layer 5, and the transparent conductive film 3, the organic light emitting layer 4, and the conductor layer 5 are provided on the base material 2. Are sequentially stacked. The base material 2 and the transparent conductive film 3 constitute a base material 6 with a transparent conductive film. The transparent conductive film 3 functions as an anode of the organic EL element 1 and injects holes into the organic light emitting layer 4. On the other hand, the conductor layer 5 functions as a cathode of the organic EL element 1 and injects electrons into the organic light emitting layer 4.

  In the organic light emitting layer 4, it is preferable that a hole injection layer that promotes injection of holes from the transparent conductive film 3 is provided between the organic light emitting layer 4 and the transparent conductive film 3, and promotes injection of electrons from the conductor layer 5. An electron injection layer is preferably provided between the conductor layer 5. Furthermore, a hole transport layer that efficiently transports holes or an electron transport layer that efficiently transports electrons may be provided.

  In the organic EL element 1 configured as described above, when a voltage is applied between the transparent conductive film 3 and the conductor layer 5 with the transparent conductive film 3 side as a positive potential, holes are emitted from the transparent conductive film 3 to organic light emission. Electrons are injected into the layer 4 and electrons are injected from the conductor layer 5 into the organic light emitting layer 4. Then, the holes and electrons injected into the organic light emitting layer 4 are recombined in the organic light emitting layer 4 so that the organic light emitting layer 4 emits light. The light emitted from the organic light emitting layer 4 passes through the substrate 6 with the transparent conductive film (the transparent conductive film 3 and the substrate 2), and is taken out of the organic EL element 1. The light irradiated on the conductor layer 5 is reflected on the surface of the conductor layer 5, passes through the substrate 6 with a transparent conductive film, and is taken out of the organic EL element 1.

  In addition, the material of the base material 2 will not be specifically limited if it has translucency. As such a base material 2, for example, a rigid transparent glass plate such as soda glass or non-alkali glass, or a flexible transparent plastic plate such as polycarbonate or ethylene terephthalate is used. When a rigid transparent glass plate is used as the substrate 2, the strength of the device using the substrate 2 is excellent, and the formation of the transparent conductive film 3 on the substrate 2 can be facilitated. When a flexible transparent plastic plate is used as the substrate 2, the device using the substrate 2 can be reduced in weight, and the device can have flexibility.

  Examples of the material of the organic light emitting layer 4 include anthracene, naphthalene, pyrene, tetracene, coronene, perylene, phthaloperylene, naphthaloperylene, diphenylbutadiene, tetraphenylbutadiene, coumarin, oxadiazole, bisbenzoxazoline, bisstyryl, and cyclopentadiene. , Coumarin, oxadiazole, bisbenzoxazoline, bisstyryl, cyclopentadiene, quinoline metal complex, tris (8-hydroxyquinolinato) aluminum complex, tris (4-methyl-8-quinolinato) aluminum complex, tris (5- Phenyl-8-quinolinato) aluminum complex, aminoquinoline metal complex, benzoquinoline metal complex, tri- (p-terphenyl-4-yl) amine, pyran, quinacridone, rubrene, Or a group consisting of these derivatives, 1-aryl-2,5-di (2-thienyl) pyrrole derivatives, distyrylbenzene derivatives, styrylarylene derivatives, styrylamine derivatives, or these luminescent compounds as part of the molecule. The compound or polymer which has is used. In addition, for example, a light-emitting material such as an iridium complex, an osmium complex, a platinum complex, or a europium complex, or a phosphorescent light-emitting material such as a compound or polymer having these in a molecule can be used. These materials can be appropriately selected and used as necessary.

Moreover, as a material of the conductor layer 5, for example, aluminum or the like is used. Alternatively, a laminated structure may be formed by combining aluminum and another material. Examples of such combinations include a laminate of an alkali metal and aluminum, a laminate of an alkali metal and silver, a laminate of an alkali metal halide and aluminum, a laminate of an alkali metal oxide and aluminum, and an alkali. A laminate of an earth metal or rare earth metal and aluminum, or an alloy of these metal species with another metal can be used. Specifically, sodium, an alloy of sodium and potassium, a laminate of lithium or magnesium or the like and aluminum, a mixture of magnesium and silver, a mixture of magnesium and indium, an alloy of aluminum and lithium, lithium fluoride And a laminated body of a mixture of aluminum and aluminum, or a laminated body of a mixture of aluminum and aluminum oxide (Al ₂ O ₃ ).

  Next, the detail of the base material 6 with a transparent conductive film is demonstrated with reference to FIG. The substrate 6 with a transparent conductive film includes a substrate 2 and a transparent conductive film 3 formed on the substrate 2. The transparent conductive film 3 includes a plurality of fine metal wires 3a having conductivity and a transparent resin layer 3b as a binder. These fine metal wires 3a are bonded onto the base material 2 by the transparent resin layer 3b in a state in which a part thereof protrudes from the transparent resin layer 3b. For this reason, on the base material 2, a three-dimensional conductive network of a plurality of fine metal wires 3 a is formed. Thereby, the transparent conductive film 3 has electroconductivity. Here, the three-dimensional conductive network of the plurality of fine metal wires 3a indicates a state in which the plurality of fine metal wires 3a are in contact with or close to each other three-dimensionally.

  When the substrate 6 with a transparent conductive film is used for the organic EL element 1, when the plurality of fine metal wires 3 a protruding from the transparent resin layer 3 b come into contact with the organic light emitting layer 4 and a voltage is applied to the organic EL element 1. Then, holes are injected into the organic light emitting layer 4 from the plurality of fine metal wires 3a.

  In the present embodiment, the surface of the substrate 6 with a transparent conductive film is oxidized or sulfided, and the surfaces of the plurality of fine metal wires 3a are oxidized or sulfided. In this case, not only the surface of the fine metal wire 3a protruding from the transparent resin layer 3b but also the surface of the fine metal wire 3a in the transparent resin layer 3b is oxidized or sulfided. Therefore, the oxidized or sulfided portion 3c is blackened and becomes a nonconductor. Examples of the method for sulfiding the surface of the substrate 6 with a transparent conductive film include a method in which the substrate 6 with a transparent conductive film is placed in water and hydrogen sulfide generated by iron sulfide and hydrochloric acid is passed through the water. . Moreover, as a method of oxidizing the surface of the base material 6 with a transparent conductive film, the method of performing the surface treatment for oxidizing the surface of the base material 6 with a transparent conductive film, for example using a tabletop type optical surface treatment apparatus is mentioned. It is done.

  By adjusting these treatment times and concentrations, the degree of oxidation or sulfidation on the surface of the thin metal wire 3a can be controlled. In the present embodiment, a predetermined proportion of the surface of the thin metal wire 3a may be oxidized or sulfided. Since the metal thin wire 3a using silver nanowires has extremely high conductivity compared to ITO or the like, even if a predetermined proportion of its surface is oxidized or sulfided, it has sufficient conductivity for the portion that is not oxidized or sulfided. Can be held.

The fine metal wire 3a is made of a fibrous metal, metal, or metal fine particle having a line width of several nm to several tens of μm. The length of the fine metal wire 3a is sufficiently longer than the diameter of the cross section perpendicular to the length direction of the fine metal wire 3a. The amount of fine metal wire 3a to be adhered on the substrate 2 is more preferably is preferably 0.1 mg / ^{m 2} or more 1000 mg / ^{m 2,} a 1 mg / ^{m 2} or more 100 mg / ^{m 2.} Each length of the fine metal wires 3a is preferably 300 nm or less in consideration of the translucency of the transparent conductive film 3, and the average diameter of the fine metal wires 3a is preferably 0.3 nm or more and 200 nm or less. . Similarly, the average aspect ratio of the fine metal wires 3a is preferably 10 or more and 10,000 or less. Furthermore, the thickness of the transparent resin layer 3b is preferably not less than the average diameter of the fine metal wires 3a and not more than 500 nm in consideration of the conductivity of the transparent conductive film 3.

  As a material of the metal fine wire 3a, for example, a metal mesh, a metal nanowire, an aggregate of metal fine particles, or the like is used. Examples of the metal used for the thin metal wire 3a include gold, silver, copper, aluminum, zinc, cobalt, nickel, and tungsten. Among such metals, gold, silver, or copper having high conductivity is preferably used, and silver having the highest conductivity is more preferably used.

  When metal nanowires are used as the thin metal wires 3a, the length of the metal nanowires is preferably 3 μm or more, more preferably 3 μm or more and 500 μm or less, considering the conductivity of the transparent conductive film 3. More preferably, it is 300 μm or less. The average diameter of the metal nanowires is preferably 10 nm or more and 300 nm or less, and more preferably 30 nm or more and 200 nm or less in consideration of the translucency and conductivity of the transparent conductive film 3. The manufacturing method of metal nanowire is not specifically limited, For example, well-known methods, such as a liquid phase method or a gaseous-phase method, are used.

  When silver is used as the metal used for the fine metal wire 3a, the surface of the fine metal wire 3a is preferably sulfided. Since silver is more easily sulfided than chemically oxidized, the surface treatment of the fine metal wires 3a can be facilitated by sulfidation. Further, when the surface of the fine metal wire 3a is sulfided, if the ratio of the sulfur element contained in the fine metal wire 3a to the silver element contained in the fine metal wire 3a is 10% or less, irregular reflection of light occurs, and the fine metal wire 3a. When the ratio of the sulfur element contained in the metal fine wire 3a to the silver element contained in the metal element is 50% or more, the metal fine wire 3a cannot conduct electricity. Therefore, it is preferable that the ratio of the sulfur element contained in the metal fine wire 3a to the silver element contained in the metal fine wire 3a is more than 10% and less than 50%, specifically, 15% to 45%. It is preferable.

  Examples of the material of the transparent resin layer 3b include polyethylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer and a saponified product thereof, or an ethylene-ethyl acrylate copolymer, ethylene-methyl methacrylate copolymer. Polymers, olefin resins such as ethylene-vinyl acetate-methyl methacrylate copolymer, polypropylene, propylene-α-olefin copolymer, vinyl chloride resins such as polyvinyl chloride resin, acrylonitrile such as acrylonitrile-styrene copolymer Resins, polystyrene, styrene resins such as styrene-methyl methacrylate copolymer, acrylate polymers such as polyethyl acrylate, methacrylate polymers such as polymethyl methacrylate, copolymers thereof and others (Meth) acrylic acid with added copolymer component Ester resins, polyester resins such as polyethylene terephthalate, polyamide resins such as nylon, polycarbonate resin, ethyl cellulose, cellulose resins such as acetyl cellulose, polyurethane resins, and silicone resins.

  Further, for example, thermosetting resins such as phenol resin, urea resin, diallyl phthalate resin, melamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, aminoalkyd resin, silicon resin, or polysiloxane resin can be given. Furthermore, you may add a crosslinking agent, a polymerization initiator, a hardening | curing agent, a hardening accelerator, or a solvent to these thermosetting resins as needed.

  The ionizing radiation curable resin preferably has an acrylate functional group, for example, a relatively low molecular weight polyester resin, polyether resin, acrylic resin, epoxy resin, urethane resin, alkyd resin, spiroacetal. Resins, polybutadiene resins, polythiol polyene resins, oligomers such as (meth) acrylates of polyfunctional compounds such as polyhydric alcohols, prepolymers, and reactive diluents such as ethyl (meth) acrylate, ethylhexyl (meth) acrylate, styrene, methyl Monofunctional monomers such as styrene and N-vinylpyrrolidone, as well as polyfunctional monomers such as trimethylolpropane tri (meth) acrylate, hexanediol (meth) acrylate, tripropylene glycol di (meth) acrylate, Relatively large amounts of ethylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, etc. Can be used. Furthermore, in order to make the ionizing radiation curable resin an ultraviolet curable resin, it is preferable to mix a photopolymerization initiator in the ionizing radiation curable resin. As the photopolymerization initiator, acetophenones, benzophenones, α-amyloxime esters, thioxanthones or the like are used. In addition to the photopolymerization initiator, a photosensitizer may be used. As the photosensitizer, n-butylamine, triethylamine, tri-n-butylphosphine, thioxanthone, or the like is used.

  The coating method of the transparent conductive film 3 is not particularly limited, and a known coating method such as spin coating, screen printing, dip coating, die coating, casting, spray coating, or gravure coating is used. Moreover, in order to smooth the surface of the transparent conductive film 3 and stabilize the surface resistance value of the transparent conductive film 3, a pressurizing step using, for example, a roller press or the like may be performed.

  According to the substrate 6 with a transparent conductive film of the present embodiment, the oxidized or sulfided portion 3c on the surface of the fine metal wire 3a is blackened and the metallic luster is lost, so that irregular reflection of light can be suppressed. . Moreover, the light extraction efficiency of the organic EL element 1 can be improved by using this base material 6 with a transparent conductive film as a substrate of the organic EL element 1. Further, since the oxidized or sulfided portion 3c on the surface of the metal fine wire 3a becomes a non-conductor and is chemically stable, the occurrence of migration can be prevented. Moreover, by using this base material 6 with a transparent conductive film as a substrate of the organic EL element 1, it is possible to prevent an insulation failure of the organic EL element 1 and to realize a highly reliable device. .

  Next, Examples 1 to 5 and Comparative Examples 1 to 4 will be described.

  As shown below, first, silver nanowires were produced as thin metal wires, and then samples of Examples 1 to 5 and Comparative Examples 1 to 4 were produced.

(Metal fine wire)
Silver nanowires were produced as fine metal wires according to a known paper “Materials Chemistry and Physics vol. 114 p333-338“ Preparation of Ag nanorods with high yield by polyol process ””. In this case, the average diameter of the silver nanowire was 50 nm, and the average length of the silver nanowire was 5 μm.

Example 1
3 parts by mass of methyl cellulose (M7140) manufactured by Sigma-Aldrich was dissolved in 200 parts by mass of water to prepare a methyl cellulose solution. Next, a dispersion liquid in which the above-mentioned silver nanowire was dispersed as a metal thin wire and water was used as a dispersion medium at a solid content of 3.0% by mass was prepared. Next, 100 parts by mass of this dispersion was added to the methylcellulose solution and mixed well. Thereby, a coating agent composition was produced.

  Subsequently, the coating composition was applied on a glass substrate (BK7) having dimensions of 100 mm in length, 100 mm in width, and 0.7 mm in height by a spin coater so as to have a thickness of 100 nm. And after drying the glass base material with which this coating agent composition was apply | coated at 23 degreeC normal temperature for 3 minutes, it heated at 120 degreeC for 5 minutes, and was dried. Thereby, the transparent conductive film was formed on the glass base material, and the base material with a transparent conductive film was produced.

  Next, this base material with a transparent conductive film was placed in an aqueous solution, and hydrogen sulfide generated by iron sulfide and hydrochloric acid was passed through the aqueous solution for 20 minutes. Thereby, the surface of the silver nanowire was sulfided. Thus, the sample of Example 1 was produced.

(Example 2)
A sample of Example 2 was produced in the same manner as in Example 1 except that the time for passing hydrogen sulfide was 30 minutes.

(Example 3)
A sample of Example 3 was produced in the same manner as in Example 1 except that the time for passing hydrogen sulfide was 40 minutes.

Example 4
Instead of sulfidizing silver nanowires, PL16-110 manufactured by Sen Special Light Source Co., Ltd. was used for surface treatment for oxidizing the substrate with a transparent conductive film for 30 minutes, except that the surface of the silver nanowires was oxidized Then, a sample of Example 4 was produced in the same manner as in Example 1 above.

(Example 5)
A mesh consisting of a plurality of fine metal wires having a width of 50 mm and a height of 100 nm is formed on a glass substrate (BK7) having dimensions of 100 mm in length, 100 mm in width, and 0.7 mm in height by vapor deposition, and transparent. A substrate with a conductive film was prepared. In this case, silver was used as the material for the fine metal wire, and the size of the rectangular holes of the mesh was 250 μm in length and 250 μm in width. A sample of Example 5 was produced in the same manner as Example 1 except for these points.

(Comparative Example 1)
A sample of Comparative Example 1 was produced in the same manner as in Example 1 except that the substrate with a transparent conductive film was not sulfided.

(Comparative Example 2)
A sample of Comparative Example 2 was prepared in the same manner as in Example 1 except that hydrogen sulfide was passed for 10 minutes in an aqueous solution in which a substrate with a transparent conductive film was placed.

(Comparative Example 3)
A sample of Comparative Example 3 was produced in the same manner as in Example 1 except that hydrogen sulfide was passed through the aqueous solution having the transparent conductive film-coated substrate for 50 minutes.

(Comparative Example 4)
A sample of Comparative Example 4 was produced in the same manner as in Example 5 except that the substrate with a transparent conductive film was not sulfided.

  The samples of Examples 1 to 5 and Comparative Examples 1 to 4 were measured for haze value, transmittance, surface resistance value, sulfidity and oxidation degree, and migration. Hereinafter, these measurements will be described in order.

(Measurement of haze value)
The haze value of each sample was measured using NDH-2000 manufactured by Nippon Denshoku Industries Co., Ltd.

(Measurement of transmittance)
The transmittance of each sample was measured using NDH-2000 manufactured by Nippon Denshoku Industries Co., Ltd.

(Measurement of surface resistance)
The surface resistance value of each sample was measured using Loresta EP MCP-T360 manufactured by Mitsubishi Chemical Corporation.

(Measurement of sulfidity or oxidation)
Elemental analysis by energy dispersive X-ray spectroscopy (hereinafter referred to as EDX) was performed on an image (hereinafter referred to as TEM image) of the surface of each sample obtained by a transmission electron microscope (hereinafter referred to as TEM). In EDX, an image showing the distribution of elements on the surface of each sample (hereinafter referred to as an EDX mapping image) was obtained. In the TEM image and the EDX mapping image, the quantitative analysis by the thin film quantification method was performed within the range where the element contained in the fine metal wire was detected. Accordingly, the ratio of the number of sulfur elements contained in the metal thin wire to the number of silver elements contained in the metal thin wire, or the ratio of the number of oxygen elements contained in the metal thin wire to the number of silver elements is calculated, and The degree of sulfidation or oxidation was measured.

(Measurement of migration)
Vacuum of N, N-diphenyl-N, N-bis3-methyl-phenyl-1,1-diphenyl-4,4 diamine manufactured by Doujin Chemical Laboratory Co., Ltd. at a thickness of 50 nm on the transparent conductive film of each sample produced. Vapor deposited. This formed the positive hole transport layer on the transparent conductive film of each sample. Next, an aluminum quinolinol complex (Tris (8-hydroquinoline) aluminum) manufactured by Doujin Chemical Laboratory Co., Ltd. was vacuum-deposited with a thickness of 50 nm on the hole transport layer. This formed the organic light emitting layer on the positive hole transport layer. Next, aluminum was vacuum-deposited with a thickness of 150 nm on the organic light emitting layer. This formed the conductor layer which consists of aluminum on the organic light emitting layer. Thus, an organic EL element provided with each sample was produced. Subsequently, a steady voltage of 5 V was continuously applied to these organic EL elements for 500 hours. And the presence or absence of migration was confirmed by the current value and TEM image which flowed through the organic EL element before applying the voltage of 5V, and after holding said state.

  The results of the above measurements are shown in Table 1.

  As shown in Table 1, in Examples 1 to 5 in which the degree of sulfidation or oxidation was more than 10% and less than 50%, the haze value was low and no migration occurred. Further, the surface resistance values of Examples 1 to 5 were low, and the transmittances of Examples 1 to 5 were high. On the other hand, Comparative Example 1 and Comparative Example 4 in which the metal thin wire was not subjected to the oxidation or sulfurization surface treatment and Comparative Example 2 in which the degree of sulfuration was 10% had a high haze value and migration occurred. . In Comparative Example 3 in which the degree of sulfidation was 50%, the surface resistance value was extremely high at 120Ω / □. This result indicates that the degree of sulfidation or oxidation is preferably greater than 10% and less than 50%. Specifically, from the comparison between Example 1 and Comparative Example 2 and the comparison between Example 3 and Comparative Example 3, the degree of sulfidation or oxidation is preferably 15% to 45%.

The present invention is not limited to the configuration of the embodiment described above, and various modifications can be made without departing from the spirit of the invention. For example, the transparent conductive film 3 can be used as a transparent electrode such as a liquid crystal display, a plasma display, or a solar organic battery. In addition, carbon nanotubes may be used as the material for the fine metal wires 3a, and conductive polymers may be used as the material for the transparent resin layer 3b.

DESCRIPTION OF SYMBOLS 1 Organic EL element 2 Base material 3 Transparent conductive film 3a Metal fine wire (metal nanowire)
3b Transparent resin layer 6 Substrate with transparent conductive film

Claims (7)

A transparent conductive film provided on a substrate and provided with a transparent resin layer containing a thin metal wire,
The surface of the said metal fine wire is oxidized or sulfided, The transparent conductive film characterized by the above-mentioned.   The said thin metal wire contains silver, The transparent conductive film of Claim 1 characterized by the above-mentioned.   The transparent conductive film according to claim 2, wherein the surface of the fine metal wire is sulfided.   4. The transparent conductive film according to claim 3, wherein a ratio of a sulfur element contained in the thin metal wire to a silver element contained in the fine metal wire is more than 10% and less than 50%.   The transparent conductive film according to claim 1, wherein the thin metal wire is a metal nanowire.   A substrate with a transparent conductive film, wherein the transparent conductive film according to any one of claims 1 to 5 is formed on the substrate.   An organic electroluminescence device using the substrate with a transparent conductive film according to claim 6.

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