WO2011136022A1

WO2011136022A1 - Method for manufacturing transparent electrode, transparent electrode and organic electronic element

Info

Publication number: WO2011136022A1
Application number: PCT/JP2011/059149
Authority: WO
Inventors: 昌紀後藤; 博和小山
Original assignee: コニカミノルタホールディングス株式会社
Priority date: 2010-04-26
Filing date: 2011-04-13
Publication date: 2011-11-03
Also published as: JP5673675B2; JPWO2011136022A1

Abstract

Disclosed is a method for manufacturing a transparent electrode, which provides an organic electronic element that has excellent durability and is excellent in terms of uniformity of the performance of an organic functional layer while high transparency and conductivity are also maintained. The method for manufacturing a transparent electrode includes: step (1) for forming, on a transparent support body, a conductive metal layer that has a metal fine wire structure; step (2), subsequent to step (1), for manufacturing a transparent electrode plate by forming, on the conductive metal layer, a conductive polymer layer that contains a polymer (A) and a conductive polymer having polyanions and π-conjugated conductive polymer molecules; and step (3), subsequent to step (2), for manufacturing a transparent electrode by performing chemical etching treatment on the transparent electrode plate. A transparent electrode which is obtained by the method for manufacturing a transparent electrode, and an organic electronic element which uses the transparent electrode, are also disclosed.

Description

Method for producing transparent electrode, transparent electrode and organic electronic device

The present invention relates to a method for producing a transparent electrode used in an organic electronic element used in organic electronic devices such as organic EL (electroluminescence) and solar cells.

In recent years, organic electronic devices such as organic EL elements and organic solar cells have attracted attention. In such devices, transparent electrodes have become an essential component technology. In organic electronic devices, the demand for larger areas is increasing, and in the case of transparent electrodes such as ITO and conductive polymers that have been used in the past, particularly low surface resistance is required. In the area use, not only the film formation cost is remarkably increased, but it is very difficult to obtain a surface resistance sufficiently low in practical use.

Other transparent electrodes include metal fibers such as metal nanowires described in US Patent Application Publication No. 2007 / 0074316A1, and metals typified by electromagnetic wave shielding films for plasma displays described in Japanese Patent Application Laid-Open No. 2000-149773. The transparent electrode which formed the fine mesh structure with the grid pattern is mentioned.

Among these, metal grids using silver, in particular, can achieve both good conductivity and transparency due to the inherent high conductivity of silver. However, because of the grid structure, the portion that transmits light is electrically conductive. The current cannot be uniform over the entire transparent electrode surface. In order to achieve both current surface uniformity and conductivity, a transparent electrode in which a transparent conductive film such as ITO or a conductive polymer is combined with a thin metal wire structure is disclosed (for example, see Patent Documents 1 and 2).

On the other hand, for organic electronic devices having organic EL elements, high smoothness is required for the transparent electrode. If there are protrusions on the transparent electrode, the element life may be reduced due to inter-electrode leakage or electric field concentration at that portion. Laminating conductive polymer also improves surface smoothness by filling such protrusions, but depending on the size of the protrusions, the conductive polymer layer required for embedding becomes thick, and the transparency of the device Therefore, it is difficult to achieve both.

As another method for filling the protrusions, a method of laminating an organic functional layer such as a light emitting layer after laminating a transparent conductive film and a metal grid in this order on the substrate, and further covering the metal grid completely with an insulating layer. However, there is a problem that the width of the insulating layer must be wider than the line width of the metal grid, and the light emitting region is reduced.

In order to eliminate protrusions on the transparent electrode combining the transparent conductive film and the metal grid, it is desirable that the metal grid itself has high surface smoothness.

Examples of methods for improving the surface smoothness of the metal grid include a method of etching the metal grid surface (see Patent Document 4), a method of polishing the grid surface (see Patent Document 5), and the like. As a result, there is a problem that the conductivity of the metal grid is lowered, and particles themselves generated by polishing cause leakage between electrodes.

JP 2005-302508 A Special table 2009-505358 International Publication No. 10/38181 Pamphlet JP-A-10-70354 JP 2007-233304 A

The object of the present invention has been made in view of the above circumstances, and provides a transparent electrode that provides an organic electronic device that is excellent in uniformity of the performance of the organic functional layer while maintaining high transparency and conductivity and excellent in durability. A manufacturing method to be manufactured, a transparent electrode obtained thereby, and an organic electronic device using the same can be provided. Furthermore, the performance of the organic functional layer is excellent in uniformity, excellent in durability, and can cope with a large area. The manufacturing method which manufactures the transparent electrode which gives an organic electronic device, the transparent electrode obtained by it, and the organic electronic device using the same can be provided.

The above object of the present invention can be achieved by the following configuration.

1. Forming a conductive metal layer having a fine metal wire structure on the transparent support (1);
A conductive polymer layer comprising a conductive polymer having a π-conjugated conductive polymer and a polyanion on the conductive metal layer and the following polymer (A), which is a step subsequent to the step (1). Forming a transparent electrode plate (2),
A step (3) after the step (2), in which the transparent electrode plate is subjected to a chemical etching treatment to produce a transparent electrode;
The manufacturing method of the transparent electrode characterized by having.
[Polymer (A): A polymer having at least one of the polymerization units (repeating units) represented by the following general formula 1, general formula 2 and general formula 3 as a polymerization unit under the following conditions.

[In each formula, X ¹ to X ³ each independently represents a hydrogen atom or a methyl group. R ¹ to R ³ each independently represents an alkylene group having 5 or less carbon atoms. Conditions: l (mol%) of the polymerized units of the above general formula 1 in the total polymerized units of the polymer (A), and ratios (mol%) of the polymerized units of the above general formula 2 in all polymerized units of the polymer (A). ) Is m, and the ratio (mol%) of the polymerized units of the above general formula 3 to the total polymerized units of the polymer (A) is n. 50 ≦ l + m + n ≦ 100, 0 ≦ l ≦ 100, 0 ≦ m ≦ 100 0 ≦ n ≦ 100. ]
2. 2. The method for producing a transparent electrode according to 1 above, wherein the thin metal wire structure is a metal grid pattern.

3. 2. The method for producing a transparent electrode according to 1 above, wherein the conductive metal layer contains metal nanowires.

4. 4. A transparent electrode manufactured by the method for manufacturing a transparent electrode according to any one of 1 to 3 above.

5. 5. An organic electronic device comprising the transparent electrode as described in 4 above.

6. 6. The organic electronic device as described in 5 above, wherein the organic electronic device is an organic electroluminescence device.

7. 7. The organic electronic device as described in 6 above, wherein the organic functional layer of the organic electroluminescent device has a thickness of 1 nm to 200 nm.

Manufacture of a transparent electrode that provides an organic electronic device with excellent uniformity in performance of organic functional layer and excellent durability by maintaining smoothness and conductivity while maintaining high transparency and conductivity. Method, transparent electrode obtained by the method, organic electronic device using the same, and organic electronic device having excellent performance uniformity of organic functional layer, excellent durability, and adaptable to large area The manufacturing method which manufactures the transparent electrode which gives can, the transparent electrode obtained by it, and an organic electronic device using the same can be provided.

This invention is a manufacturing method of a transparent electrode, Comprising: The process (1) and the process after a process (1) which form the electroconductive metal layer which has a metal fine wire structure on a transparent support body, an electroconductive metal Forming a conductive polymer layer containing a conductive polymer having a π-conjugated conductive polymer and a polyanion and the polymer (A) on the layer to produce a transparent electrode plate (2), step (2) A subsequent step (3), in which the transparent electrode plate is subjected to a chemical etching treatment to produce a transparent electrode.

In the present invention, in particular, the conductive polymer layer contains the above specific polymer, and after the conductive polymer layer is provided, a chemical etching treatment is performed to maintain high transparency and conductivity while maintaining smoothness. As a result, a transparent electrode that provides an organic electronic device with excellent uniformity in performance of the organic functional layer and excellent durability can be obtained.

DETAILED DESCRIPTION The components of the present invention will be described in detail.

(Process (1))
In the step (1), a conductive metal layer having a fine metal wire structure is formed on the transparent support.

(Transparent support)
The transparent support according to the present invention is a visible light wavelength region measured by a method in accordance with JIS K 7361-1 (corresponding to ISO 13468-1) “Plastic—Test method for total light transmittance of transparent material”. A substrate having a total light transmittance of 60% or more.

The transparent support used in the present invention is not particularly limited, and the material, shape, structure, thickness, hardness and the like can be appropriately selected from known materials, but have high light transmittance. Preferably it is.

For example, polyester resin films such as polyethylene terephthalate (PET), polyethylene naphthalate, modified polyester, polyethylene (PE) resin films, polypropylene (PP) resin films, polystyrene resin films, polyolefin resin films such as cyclic olefin resins, Vinyl resin films such as polyvinyl chloride and polyvinylidene chloride, polyvinyl acetal resin films such as polyvinyl butyral (PVB), polyether ether ketone (PEEK) resin films, polysulfone (PSF) resin films, polyether sulfone (PES) Resin film, polycarbonate (PC) resin film, polyamide resin film, polyimide resin film, acrylic resin film, triacetyl cellulose (T C) can be exemplified a resin film or the like.

A resin film having a transmittance of 80% or more at a visible wavelength (380 to 780 nm) can be particularly preferably applied to the present invention. Among these, from the viewpoint of transparency, heat resistance, ease of handling, strength and cost, it is preferably a biaxially stretched polyethylene terephthalate film, a biaxially stretched polyethylene naphthalate film, a polyethersulfone film, or a polycarbonate film, and biaxially stretched. More preferred are polyethylene terephthalate films and biaxially stretched polyethylene naphthalate films.

The transparent support used in the present invention can be subjected to a surface treatment or an easy adhesion layer in order to ensure the wettability and adhesion of the coating solution. A conventionally well-known technique can be used about a surface treatment or an easily bonding layer. For example, the surface treatment includes surface activation treatment such as corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, and laser treatment.

Also, examples of the easy adhesion layer include polyester, polyamide, polyurethane, vinyl copolymer, butadiene copolymer, acrylic copolymer, vinylidene copolymer, epoxy copolymer and the like.

When the transparent support is a biaxially stretched polyethylene terephthalate film, the refractive index of the easy-adhesion layer adjacent to the film is set to 1.57 to 1.63 so that the interface reflection between the film substrate and the easy-adhesion layer can be reduced. Since it can reduce and can improve the transmittance | permeability, it is more preferable. The method for adjusting the refractive index can be carried out by appropriately adjusting the ratio of the oxide sol having a relatively high refractive index such as tin oxide sol or cerium oxide sol and the binder resin.

The easy adhesion layer may be a single layer, but may be composed of two or more layers in order to improve adhesion.

In addition, a gas barrier layer may be formed in advance on the transparent support, if necessary, or a hard coat layer may be formed in advance. As a material for forming the gas barrier layer, metal oxides such as silicon oxide, silicon nitride, silicon oxynitride, aluminum nitride, and aluminum oxide, and metal nitrides can be used.

These materials have an oxygen barrier function in addition to a water vapor barrier function. In particular, silicon nitride and silicon oxynitride having good gas barrier properties, solvent resistance, and transparency are preferable. Further, the gas barrier layer may have a multilayer structure as necessary. As a method for forming the gas barrier layer, a resistance heating vapor deposition method, an electron beam vapor deposition method, a reactive vapor deposition method, an ion plating method, or a sputtering method can be used depending on the material.

The thickness of each inorganic layer constituting the gas barrier layer is not particularly limited, but typically it is preferably in the range of 5 nm to 500 nm per layer, more preferably 10 nm to 200 nm per layer. The gas barrier layer is provided on at least one surface of the transparent support. The gas barrier layer is preferably provided on the electrode layer side, and more preferably provided on both sides.

[Conductive metal layer]
The conductive metal layer according to the present invention has a fine metal wire structure.

The metal thin wire structure is a structure in which linear metals are gathered, and includes a structure in which a metal grid is patterned and a structure in which metal nanowires are gathered.

The thin metal wire structure of the conductive metal layer according to the present invention may be either a structure that is a metal grid pattern, a structure in which metal nanowires are aggregated, or a structure that includes both. As the metal material of the metal grid pattern, the metal may be a simple substance or an alloy, and may be a single layer or a multilayer, but silver is preferably used from the viewpoint of conductivity.

The shape of the metal grid pattern is not particularly limited and may be, for example, a stripe shape, a lattice shape, or a random network structure, but the aperture ratio is preferably 80% or more from the viewpoint of transparency. The aperture ratio is a ratio of the portion without the thin lines forming the metal grid pattern to the whole. For example, the aperture ratio of the striped grid pattern having a line width of 100 μm and a line interval of 1 mm is approximately 90%.

The line width of the metal grid pattern is preferably 10 to 200 μm from the viewpoint of conductivity and transmittance. The height of the fine wire (thickness of the conductive metal layer) is preferably 0.1 to 10 μm from the viewpoints of conductivity, current leakage prevention, and fine wire distribution uniformity.

The method for forming the metal grid pattern is not particularly limited, and a conventionally known method can be used. For example, the ink containing metal fine particles can be formed by a method of printing in a desired shape by a known printing method such as gravure printing, flexographic printing, offset printing, screen printing, and inkjet printing.

As another method, a metal layer is formed on the entire surface of the substrate and formed by a known photolithographic method, a method of performing plating after printing a catalyst ink that can be plated in a desired shape, and another method include A method using silver salt photography technology can also be used.

The method using silver salt photographic technology can be carried out, for example, referring to paragraph number 0076-0112 of JP2009-140750A and examples.

As a random network structure, for example, a method for spontaneously forming a disordered network structure of conductive fine particles by applying and drying a liquid containing metal fine particles as described in JP-T-2005-530005 Can be used.

In the present invention, the metal nanowire refers to a linear structure having a diameter from the atomic scale to the nm size, the main component being a metal element.

As the metal nanowire, in order to form a long conductive path with one metal nanowire, the average length is preferably 3 μm or more, more preferably 3 to 500 μm, and particularly preferably 3 to 300 μm. In addition, the relative standard deviation of the length is preferably 40% or less. Moreover, although there is no restriction | limiting in particular in an average breadth, it is preferable that it is small from a transparency viewpoint, and the larger one is preferable from a conductive viewpoint.

In the present invention, the average minor axis of the metal nanowire is preferably 10 to 300 nm, more preferably 30 to 200 nm. In addition, the relative standard deviation of the minor axis is preferably 20% or less.

In the metal thin wire structure in which metal nanowires are assembled, the metal nanowires are preferably in contact with each other, and more preferably in mesh form. Conductive metal layers in which metal nanowires are brought into contact with each other or in mesh form are prepared by applying a dispersion containing metal nanowires to a roll coating method, a bar coating method, a dip coating method, a spin coating method, a casting method, a die coating method, It can be easily obtained by coating and drying to form a film using a liquid phase film forming method such as a blade coating method, a bar coating method, a gravure coating method, a curtain coating method, a spray coating method, or a doctor coating method.

The basis weight of the metal nanowire is preferably 5 mg / m ² or more and 500 mg / m ² or less, more preferably 10 mg / m ² or more and 200 mg / m ² or less. When the amount of metal nanowires is 5 mg / m ² or more, the contact between the metal nanowires is improved and the conductivity is improved, and when the amount is 500 mg / m ² or less, the portion shielded from light by the metal nanowires is reduced. Transparency is improved.

There are no particular restrictions on the means for producing the metal nanowire, and for example, known means such as a liquid phase method or a gas phase method can be used. Moreover, there is no restriction | limiting in particular in a specific manufacturing method, A well-known manufacturing method can be used. For example, as a method for producing silver nanowires, Adv. Mater. , 2002, 14, 833-837; Chem. Mater. 2002, 14, 4736-4745, and the like. The method for producing silver nanowires can be easily produced in an aqueous solution, and since the conductivity of silver is the highest in metals, it is preferably applied as a method for producing metal nanowires according to the present invention. Can do.

(Process (2))
In the step (2), a conductive polymer layer containing a conductive polymer having a π-conjugated conductive polymer and a polyanion and the polymer (A) is formed on the conductive metal layer formed as described above. And forming a transparent electrode plate.

The conductive polymer according to the present invention is a conductive polymer comprising a π-conjugated conductive polymer and a polyanion. The conductive polymer can be easily produced by chemical oxidative polymerization of a precursor monomer that forms a π-conjugated conductive polymer described later in the presence of an appropriate oxidizing agent, an oxidation catalyst, and a polyanion described later.

(Π-conjugated conductive polymer)
The π-conjugated conductive polymer used in the present invention is not particularly limited, and includes polythiophenes (including basic polythiophenes, the same applies hereinafter), polypyrroles, polyindoles, polycarbazoles, polyanilines, polyacetylenes, polyfurans. , Polyparaphenylene vinylenes, polyazulenes, polyparaphenylenes, polyparaphenylene sulfides, polyisothianaphthenes, polythiazyl chain conductive polymers can be used. Of these, polythiophenes and polyanilines are preferable from the viewpoints of conductivity, transparency, stability, and the like. Most preferred is polyethylene dioxythiophene.

(Π-conjugated conductive polymer precursor monomer)
The precursor monomer has a π-conjugated system in the molecule, and a π-conjugated system is formed in the main chain even when polymerized by the action of an appropriate oxidizing agent. Examples thereof include pyrroles and derivatives thereof, thiophenes and derivatives thereof, anilines and derivatives thereof.

Specific examples of the precursor monomer include pyrrole, 3-methylpyrrole, 3-ethylpyrrole, 3-n-propylpyrrole, 3-butylpyrrole, 3-octylpyrrole, 3-decylpyrrole, 3-dodecylpyrrole, 3, 4-dimethylpyrrole, 3,4-dibutylpyrrole, 3-carboxylpyrrole, 3-methyl-4-carboxylpyrrole, 3-methyl-4-carboxyethylpyrrole, 3-methyl-4-carboxybutylpyrrole, 3-hydroxypyrrole 3-methoxypyrrole, 3-ethoxypyrrole, 3-butoxypyrrole, 3-hexyloxypyrrole, 3-methyl-4-hexyloxypyrrole, thiophene, 3-methylthiophene, 3-ethylthiophene, 3-propylthiophene, 3 -Butylthiophene, 3-hexyl Offene, 3-heptylthiophene, 3-octylthiophene, 3-decylthiophene, 3-dodecylthiophene, 3-octadecylthiophene, 3-bromothiophene, 3-chlorothiophene, 3-iodothiophene, 3-cyanothiophene, 3-phenyl Thiophene, 3,4-dimethylthiophene, 3,4-dibutylthiophene, 3-hydroxythiophene, 3-methoxythiophene, 3-ethoxythiophene, 3-butoxythiophene, 3-hexyloxythiophene, 3-heptyloxythiophene, 3- Octyloxythiophene, 3-decyloxythiophene, 3-dodecyloxythiophene, 3-octadecyloxythiophene, 3,4-dihydroxythiophene, 3,4-dimethoxythiophene, 3,4-diethoxythio , 3,4-dipropoxythiophene, 3,4-dibutoxythiophene, 3,4-dihexyloxythiophene, 3,4-diheptyloxythiophene, 3,4-dioctyloxythiophene, 3,4-didecyl Oxythiophene, 3,4-didodecyloxythiophene, 3,4-ethylenedioxythiophene, 3,4-propylenedioxythiophene, 3,4-butenedioxythiophene, 3-methyl-4-methoxythiophene, 3- Methyl-4-ethoxythiophene, 3-carboxythiophene, 3-methyl-4-carboxythiophene, 3-methyl-4-carboxyethylthiophene, 3-methyl-4-carboxybutylthiophene, aniline, 2-methylaniline, 3- Isobutylaniline, 2-anilinesulfonic acid, 3-anili Sulfonic acid and the like.

(Polyanion)
The polyanion is a substituted or unsubstituted polyalkylene, a substituted or unsubstituted polyalkenylene, a substituted or unsubstituted polyimide, a substituted or unsubstituted polyamide, a substituted or unsubstituted polyester, and a copolymer thereof. It consists of a structural unit having a functional group and a structural unit having no anionic group.

This polyanion is a solubilized polymer that solubilizes a π-conjugated conductive polymer in a solvent. The anionic group of the polyanion functions as a dopant for the π-conjugated conductive polymer, and improves the conductivity and heat resistance of the π-conjugated conductive polymer.

The anionic group of the polyanion may be any functional group that can undergo chemical oxidation doping to the π-conjugated conductive polymer. Among them, from the viewpoint of ease of production and stability, a monosubstituted sulfate group A monosubstituted phosphate group, a phosphate group, a carboxy group, a sulfo group and the like are preferable. Furthermore, from the viewpoint of the doping effect of the functional group on the π-conjugated conductive polymer, a sulfo group, a monosubstituted sulfate group, and a carboxy group are more preferable.

Specific examples of polyanions include polyvinyl sulfonic acid, polystyrene sulfonic acid, polyallyl sulfonic acid, polyacrylic acid ethyl sulfonic acid, polyacrylic acid butyl sulfonic acid, poly-2-acrylamido-2-methylpropane sulfonic acid, polyisoprene sulfone. Acid, polyvinyl carboxylic acid, polystyrene carboxylic acid, polyallyl carboxylic acid, polyacryl carboxylic acid, polymethacryl carboxylic acid, poly-2-acrylamido-2-methylpropane carboxylic acid, polyisoprene carboxylic acid, polyacrylic acid and the like. .

These homopolymers may be used, or two or more kinds of copolymers may be used. Moreover, the polyanion which has a fluorine (F) in a compound may be sufficient. Specifically, Nafion (manufactured by Dupont) containing a perfluorosulfo group, Flemion (manufactured by Asahi Glass Co., Ltd.) made of perfluoro vinyl ether containing a carboxylic acid group, and the like can be mentioned.

Among these, when the compound having a sulfo group is formed by applying and drying the conductive polymer-containing layer, the heat treatment is performed at a temperature of 100 ° C. or more and 200 ° C. or less for 5 minutes or more. It is more preferable because the cleaning resistance and solvent resistance of the coating film are remarkably improved.

Further, among these, polystyrene sulfonic acid, polyisoprene sulfonic acid, polyacrylic acid ethyl sulfonic acid, and polybutyl acrylate sulfonic acid are preferable. These polyanions have high compatibility with the binder resin, and can further increase the conductivity of the obtained conductive polymer.

The polymerization degree of the polyanion is preferably in the range of 10 to 100,000 monomer units, and more preferably in the range of 50 to 10,000 from the viewpoint of solvent solubility and conductivity.

Examples of the method for producing a polyanion include a method of directly introducing an anionic group into a polymer having no anionic group using an acid, a method of sulfonating a polymer having no anionic group with a sulfonating agent, an anion And a method of producing the polymerizable group-containing polymerizable monomer by polymerization.

Examples of the method for producing an anionic group-containing polymerizable monomer by polymerization include a method for producing an anionic group-containing polymerizable monomer in a solvent by oxidative polymerization or radical polymerization in the presence of an oxidizing agent and / or a polymerization catalyst. It is done.

Specifically, a predetermined amount of the anionic group-containing polymerizable monomer is dissolved in a solvent, this is maintained at a constant temperature, and a solution in which a predetermined amount of an oxidizing agent and / or a polymerization catalyst is previously dissolved in the solvent is added thereto, The reaction is performed for a predetermined time.

The polymer obtained by the reaction is adjusted to a certain concentration by the solvent. In this production method, a polymerizable monomer having no anionic group may be copolymerized with the anionic group-containing polymerizable monomer. The oxidizing agent, oxidation catalyst, and solvent used in the polymerization of the anionic group-containing polymerizable monomer are the same as those used in the polymerization of the precursor monomer that forms the π-conjugated conductive polymer.

When the obtained polymer is a polyanion salt, it is preferably transformed into a polyanionic acid. Examples of the method for converting to an anionic acid include an ion exchange method using an ion exchange resin, a dialysis method, an ultrafiltration method, and the like. Among these, the ultrafiltration method is preferable from the viewpoint of easy work.

Such a conductive polymer is preferably a commercially available material. For example, a conductive polymer (abbreviated as PEDOT-PSS) composed of poly (3,4-ethylenedioxythiophene) and polystyrenesulfonic acid is described in H.C. C. It is commercially available from Starck as the Clevios series, from Aldrich as PEDOT-PSS 483095 and 560596, and from Nagase Chemtex as the Denatron series. Polyaniline is also commercially available from Nissan Chemical as the ORMECON series. In the present invention, such an agent can also be preferably used.

2nd. A water-soluble organic compound may be contained as a dopant. There is no restriction | limiting in particular in the water-soluble organic compound which can be used by this invention, It can select suitably from well-known things, For example, an oxygen containing compound is mentioned suitably. The oxygen-containing compound is not particularly limited as long as it contains oxygen, and examples thereof include a hydroxy group-containing compound, a carbonyl group-containing compound, an ether group-containing compound, and a sulfoxide group-containing compound. Examples of the hydroxy group-containing compound include ethylene glycol, diethylene glycol, propylene glycol, trimethylene glycol, 1,4-butanediol, glycerin and the like. Among these, ethylene glycol and diethylene glycol are preferable. Examples of the carbonyl group-containing compound include isophorone, propylene carbonate, cyclohexanone, and γ-butyrolactone. Examples of the ether group-containing compound include diethylene glycol monoethyl ether. Examples of the sulfoxide group-containing compound include dimethyl sulfoxide. These may be used alone or in combination of two or more, but at least one selected from dimethyl sulfoxide, ethylene glycol, and diethylene glycol is preferably used.

(Polymer (A))
The polymer (A) is a polymer having at least one polymerization unit (repeating unit) represented by the following general formula 1, general formula 2 and general formula 3 as unit polymerization under the following conditions.

In each formula, X ¹ to X ³ each independently represents a hydrogen atom or a methyl group. R ¹ to R ³ each independently represents an alkylene group having 5 or less carbon atoms. Conditions: l (mol%) of the polymerized units of the above general formula 1 in the total polymerized units of the polymer (A), and ratios (mol%) of the polymerized units of the above general formula 2 in all polymerized units of the polymer (A). ) Is m, and the ratio (mol%) of the polymerized units of the above general formula 3 to the total polymerized units of the polymer (A) is n. 50 ≦ l + m + n ≦ 100, 0 ≦ l ≦ 100, 0 ≦ m ≦ 100 0 ≦ n ≦ 100.

That is, in the polymer (A), the component of 50% by mole or more of the copolymer component is any one of the above general formulas 1 to 3, or the total of the components of the above general formulas 1 to 3 is 50% by mole or more. Copolymer. More preferably, the total of the components of the general formulas 1 to 3 is 80 mol% or more. Further, it may be a homopolymer formed from a single monomer of any one of the above general formulas 1 to 3, and is a preferred embodiment.

The polymer (A) in the present invention has the above (repeated) unit structure.

Examples of the alkylene group having 5 or less carbon atoms represented by R ¹ to R ³ include a methylene group, an ethylene group, a butylene group, a propylene group, and a pentylene group, and an ethylene group is preferably used.

Furthermore, in the polymer (A), the ratio m of the polymerized units is preferably in the range of 70 ≦ m ≦ 100. The polymer (A) is preferably soluble in an aqueous solvent. The aqueous solvent refers to a solvent in which 50% by mass or more is water.

Of course, pure water containing no other solvent may be used.

The component other than water in the aqueous solvent is not particularly limited as long as it is a solvent compatible with water, but an alcoholic solvent can be preferably used, and isopropyl alcohol having a boiling point relatively close to water can be used. This is advantageous for the smoothness of the film to be formed.

The number average molecular weight of the polymer (A) according to the present invention is preferably in the range of 3,000 to 2,000,000, more preferably 4,000 to 500,000, still more preferably in the range of 5,000 to 100,000. .

The molecular weight distribution (weight average molecular weight / number average molecular weight = Mw / Mn) of the polymer (A) according to the present invention is preferably 1.01 to 10, more preferably 1.1 to 5, and still more preferably 1.2 to 3. It is.

The number average molecular weight and the weight average molecular weight according to the present invention are measured using gel permeation chromatography (hereinafter abbreviated as “GPC”).

The measurement conditions are as follows.

Apparatus: Wagers 2695 (Separations Module)
Detector: Waters 2414 (Refractive Index Detector)
Column: Shodex Asahipak GF-7M HQ
Eluent: Dimethylformamide (20 mM LiBr)
Flow rate: 1.0 ml / min
Temperature: 40 ° C
The polymer (A) is obtained by radical polymerization, but is particularly preferably synthesized by living radical polymerization.

As monomers used for the polymerization, methyl (meth) acrylate, ethyl (meth) acrylate, styrene and the like can be used in addition to the monomers corresponding to the above general formula 1, general formula 2 and general formula 3.

The solvent used in the living radical polymerization is inactive under reaction conditions and is not particularly limited as long as the monomer and the polymer to be formed can be dissolved, but a mixed solvent of an alcohol solvent and water is preferable.

The living radical polymerization temperature varies depending on the initiator used, but is generally -10 to 250 ° C, preferably 0 to 200 ° C, more preferably 10 to 100 ° C.

Specific examples of the monomer and polymer (A) that give polymerization units represented by general formulas 1, 2, and 3 are given below.

Monomers giving structural units represented by general formula 1 a1: 2-hydroxyethyl vinyl ether b1: 3-hydroxypropyl vinyl ether c1: 4-hydroxybutyl vinyl ether d1: 5-hydroxypentyl vinyl ether Structural unit represented by general formula 2 Monomers to be provided a2: 2-hydroxyethyl acrylate b2: 2-hydroxyethyl methacrylate c2: 3-hydroxypropyl methacrylate d2: 4-hydroxybutyl acrylate e2: 5-hydroxypentyl acrylate Monomer to give a structural unit represented by the general formula 3 a3 : 2-hydroxyethyl acrylamide b3: 2-hydroxyethyl methacrylamide c3: 3-hydroxypropyl methacrylamide d3: 4-hydroxybutyl acrylamide e 3: 5-hydroxypentylacrylamide

(Conductive polymer layer)
The conductive polymer layer according to the present invention is obtained by applying a coating solution containing the above conductive polymer and polymer (A) onto the conductive metal layer as described below and drying.

The ratio of the conductive polymer to the polymer (A) is preferably from 30 to 900 parts by mass of the polymer (A) when the conductive polymer is 100 parts by mass in terms of transparency and conductivity. More preferably, it is at least part.

As a method for forming a conductive polymer layer, a coating solution containing at least a conductive polymer containing a π-conjugated conductive polymer and a polyanion, a polymer (A), and an aqueous solvent is used. It is preferably formed by applying and drying by a method.

The concentration of solid content in the coating solution containing the conductive polymer and the polymer (A) is preferably 0.5 to 30% by mass, and preferably 1 to 20% by mass. From the viewpoint of the smoothness of the coating film and the expression of the leak prevention effect, it is more preferable.

The coating dry film thickness of the conductive polymer layer containing the conductive polymer and the polymer (A) is preferably 30 to 2000 nm.

In the region of less than 100 nm, the decrease in conductivity is large, so that it is more preferably 100 nm or more, and more preferably 200 nm or more from the viewpoint of enhancing prevention of inter-electrode current leakage with the counter electrode. Further, it is more preferably 1000 nm or less from the viewpoint of maintaining high transmittance.

) After coating, dry treatment is performed as appropriate. Although there is no restriction | limiting in particular as conditions of a drying process, It is preferable to dry-process at the temperature of the range which does not damage a base material and a conductive polymer content layer. For example, a drying process can be performed at 80 to 150 ° C. for 10 seconds to 10 minutes.

In order to perform the chemical etching process in step (3) more efficiently, it is preferable to perform the following immobilization process on the conductive polymer layer.

As the immobilization treatment method, a method in which the conductive polymer layer is hardly soluble or insoluble by heat treatment is preferably used. This heat treatment may be performed simultaneously with the aforementioned drying treatment.

In particular, when the polyanion is a polyanion having a sulfo group as an anionic group, an additional heat treatment is performed for 5 minutes or more at a temperature in the range of 100 to 200 ° C. after forming a film by a drying treatment after coating. It is preferable. As a result, the conductive polymer layer is fixed, and the washing resistance and solvent resistance are remarkably improved.

(Process (3))
In step (3), the transparent electrode plate obtained by the above steps (1) and (2) having a conductive metal layer and a conductive polymer layer on the support is subjected to a chemical etching treatment to produce a transparent electrode. .

[Chemical etching treatment]
The chemical etching treatment according to the present invention refers to a treatment with an etching solution described below, which is a solution. The chemical etching treatment is performed by etching at least a surface (electrode layer surface) having a conductive polymer layer of a transparent electrode plate. It is performed by bringing the liquid into contact.

As the composition of the etching solution, a general processing solution for metal etching can be used. From the viewpoint of handling safety and etching property of the conductive metal layer using silver, a silver halide color photographic light-sensitive material is used. The bleach-fixing solution used in the development processing can be preferably used.

The solution is preferably an aqueous solution, but an organic solvent such as ethanol may be used as long as it can dissolve the bleaching agent and fixing agent described below. As a bleaching agent used in the bleach-fixing solution, a known bleaching agent can also be used. In particular, an organic complex salt of iron (III) (for example, a complex salt of an aminopolycarboxylic acid) or an organic compound such as citric acid, tartaric acid, malic acid or the like. Acid, persulfate, hydrogen peroxide and the like are preferable. Of these, an organic complex salt of iron (III) is particularly preferable from the viewpoint of rapid processing and prevention of environmental pollution.

Examples of aminopolycarboxylic acids useful for forming organic complex salts of iron (III), or salts thereof, include biodegradable ethylenediamine disuccinic acid (SS form), N- (2-carboxylate ethyl) -L-aspartic acid, β-alanine diacetic acid, methyliminodiacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1,3-diaminopropanetetraacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid In addition to glycol ether diamine tetraacetic acid, compounds represented by general formula (I) or (II) of European Patent 0789275 can be mentioned.

These compounds may be sodium, potassium, thylium or ammonium salts. Among these compounds, ethylenediamine disuccinic acid (SS form), N- (2-carboxylateethyl) -L-aspartic acid, β-alanine diacetic acid, ethylenediaminetetraacetic acid, 1,3-diaminopropanetetraacetic acid, methylimino The diacetic acid is preferably its iron (III) complex salt.

These ferric ion complex salts may be used in the form of complex salts or ferric salts such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, ferric phosphate. And a ferric ion complex salt may be formed in a solution using a chelating agent such as aminopolycarboxylic acid.

In addition, the chelating agent may be used in excess of the ferric ion complex salt. Among the iron complexes, aminopolycarboxylic acid iron complexes are preferable, and the addition amount is 0.01 to 1.0 mol / liter, preferably 0.05 to 0.50 mol / liter, and more preferably 0.10 to 0.00. 50 mol / liter, more preferably 0.15 to 0.40 mol / liter.

Fixing agents used in the bleach-fixing solution are known fixing agents, that is, thiosulfates such as sodium thiosulfate and ammonium thiosulfate, thiocyanates such as sodium thiocyanate and ammonium thiocyanate, ethylenebisthioglycolic acid, 3, These are water-soluble silver halide solubilizers such as thioether compounds such as 6-dithia-1,8-octanediol and thioureas, and these can be used alone or in combination.

A special bleach-fixing agent comprising a combination of a fixing agent described in JP-A-55-155354 and a large amount of a halide such as potassium iodide can also be used.

In the present invention, it is preferable to use thiosulfate, particularly ammonium thiosulfate. The amount of the fixing agent per liter is preferably 0.3 to 2 mol, and more preferably 0.5 to 1.0 mol.

The pH range of the bleach-fixing solution used in the present invention is preferably from 3 to 8, more preferably from 4 to 7. In order to adjust the pH, hydrochloric acid, sulfuric acid, nitric acid, bicarbonate, ammonia, caustic potash, caustic soda, sodium carbonate, potassium carbonate and the like can be added as necessary.

In the chemical etching treatment according to the present invention, the conductive metal layer that is not covered with the conductive polymer and is present on the surface of the conductive polymer layer is removed.

The chemical etching treatment time is not particularly limited as long as unnecessary protruding portions of the conductive metal layer are removed, but it is preferably 180 seconds or less from the viewpoint of productivity, and more preferably 5 seconds or more and 120 seconds or less. After the chemical etching treatment, washing is performed with water, and the etching solution is sufficiently washed away, and then the transparent electrode is dried.

In the present invention, the electrical resistance value of the conductive part of the transparent electrode is preferably 1000Ω / □ or less, more preferably 100Ω / □ or less, as the surface specific resistance. The surface specific resistance can be measured based on, for example, JIS K6911, ASTM D257, etc., and can be easily measured using a commercially available surface resistivity meter.

In the present invention, the conductive polymer layer contains the polymer (A) and is subjected to a chemical etching treatment, so that the conductive polymer layer blocks the etching treatment liquid and removes the conductive metal exposed on the surface. It can be efficiently removed, and as a result, it is presumed that it has excellent flatness and maintains high conductivity and transparency.

[Organic electronic devices]
The organic electronic device in the present invention has a transparent electrode and an organic functional layer produced by the method of the present invention. For example, a transparent electrode formed by the method of the present invention is used as a first electrode, an organic functional layer is formed on the first electrode, and a second electrode is formed on the organic functional layer as a counter electrode. Thus, an organic electronic device can be obtained.

Examples of the organic functional layer include an organic light emitting layer, an organic photoelectric conversion layer, a liquid crystal polymer layer, and the like, without any particular limitation. This is particularly effective in the case of an organic photoelectric conversion layer.

The transparent electrode of the present invention is particularly effective when the organic functional layer described below has a thickness of 1 nm to 500 nm, and further effective for an organic functional layer with a thickness of 1 to 200 nm.

Hereinafter, the components in the case where the organic electronic device of the present invention is an organic EL device and an organic photoelectric conversion device will be described.

(Organic EL device)
<Organic functional layer configuration>
(Organic light emitting layer)
In the present invention, an organic EL device having an organic light emitting layer as an organic functional layer includes a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, a hole block layer, an electron block layer, etc. in addition to the organic light emitting layer. A layer for controlling light emission may be used in combination with the organic light emitting layer.

Since the conductive polymer layer on the transparent electrode of the present invention can also function as a hole injection layer, it can also serve as a hole injection layer, but a hole injection layer may be provided independently.

Preferred specific examples of the configuration are shown below, but the present invention is not limited to these.

(I) (first electrode part) / light emitting layer / electron transport layer / (second electrode part)
(Ii) (first electrode part) / hole transport layer / light emitting layer / electron transport layer / (second electrode part)
(Iii) (first electrode part) / hole transport layer / light emitting layer / hole block layer / electron transport layer / (second electrode part)
(Iv) (first electrode part) / hole transporting layer / light emitting layer / hole blocking layer / electron transporting layer / cathode buffer layer / (second electrode part)
(V) (first electrode part) / anode buffer layer / hole transport layer / light emitting layer / hole block layer / electron transport layer / cathode buffer layer / (second electrode part)
Here, the light emitting layer may be a monochromatic light emitting layer having a light emission maximum wavelength in the range of 430 to 480 nm, 510 to 550 nm, and 600 to 640 nm, respectively, or by laminating at least three of these light emitting layers. A white light emitting layer may be used, and a non-light emitting intermediate layer may be provided between the light emitting layers. The organic EL device of the present invention is preferably a white light emitting layer.

In addition, as the light emitting material or doping material that can be used in the organic light emitting layer in the present invention, anthracene, naphthalene, pyrene, tetracene, coronene, perylene, phthaloperylene, naphthaloperylene, diphenylbutadiene, tetraphenylbutadiene, coumarin, oxadiazole, bisbenzo Xazoline, 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, 1-aryl-2,5-di (2-thienyl) pyrrole derivative, pyran, quinaclide , Rubrene, distyrylbenzene derivatives, di still arylene derivatives and various fluorescent dyes and rare earth metal complex, there are phosphorescent materials, but is not limited thereto. It is also preferable to include 90 to 99.5 parts by mass of a light emitting material selected from these compounds and 0.5 to 10 parts by mass of a doping material.

The organic light emitting layer is prepared by a known method using the above materials and the like, and examples thereof include vapor deposition, coating, and transfer. The thickness of the organic light emitting layer is preferably 0.5 to 500 nm, particularly preferably 0.5 to 200 nm.

〔electrode〕
The transparent electrode of the present invention is used in the first or second electrode part. In a preferred embodiment, the first electrode portion is an anode and the second electrode portion is a cathode.

The second electrode portion may be a conductive material single layer, but in addition to a conductive material, a resin for holding these may be used in combination. As the conductive material of the second electrode portion, a material having a low work function (4 eV or less) metal (referred to as an electron injecting metal), an alloy, an electrically conductive compound, and a mixture thereof as an electrode material is used.

Specific examples of such electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al ₂ O ₃ ) Mixtures, indium, lithium / aluminum mixtures, rare earth metals and the like.

Among these, from the point of durability against electron injection and oxidation, a mixture of an electron injecting metal and a second metal which is a stable metal having a larger work function value than this, for example, a magnesium / silver mixture, Magnesium / aluminum mixtures, magnesium / indium mixtures, aluminum / aluminum oxide (Al ₂ O ₃ ) mixtures, lithium / aluminum mixtures, aluminum and the like are preferred. The cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering. The sheet resistance as the cathode is preferably several hundred Ω / □ or less, and the film thickness is usually selected in the range of 10 nm to 5 μm, preferably 50 to 200 nm.

If a metal material is used as the conductive material of the second electrode part, the light coming to the second electrode side is reflected and returns to the first electrode part side. The metal nanowire of the first electrode part scatters or reflects part of the light backward, but by using a metal material as the conductive material of the second electrode part, this light can be reused and the extraction efficiency is improved. .

(Organic photoelectric conversion element)
The organic photoelectric conversion element has a structure in which a first electrode portion, a photoelectric conversion layer (hereinafter also referred to as a bulk heterojunction layer) having a bulk heterojunction structure (p-type semiconductor layer and n-type semiconductor layer), and a second electrode portion are stacked. Have.

An intermediate layer such as an electron transport layer may be provided between the photoelectric conversion layer and the second electrode part.

[Photoelectric conversion layer]
The photoelectric conversion layer is a layer that converts light energy into electric energy, and constitutes a bulk heterojunction layer in which a p-type semiconductor material and an n-type semiconductor material are uniformly mixed. The p-type semiconductor material functions relatively as an electron donor (donor), and the n-type semiconductor material functions relatively as an electron acceptor (acceptor).

Here, the electron donor and the electron acceptor are “an electron donor in which, when light is absorbed, electrons move from the electron donor to the electron acceptor to form a hole-electron pair (charge separation state)”. And an electron acceptor ”, which does not simply donate or accept electrons as in the case of an electrode, but donates or accepts electrons by a photoreaction.

Examples of p-type semiconductor materials include various condensed polycyclic aromatic compounds and conjugated compounds.

As the condensed polycyclic aromatic compound, for example, anthracene, tetracene, pentacene, hexacene, heptacene, chrysene, picene, fluorene, pyrene, peropyrene, perylene, terylene, quaterylene, coronene, ovalene, sarkham anthracene, bisanthene, zestrene, heptazelene, Examples thereof include compounds such as pyranthrene, violanthene, isoviolanthene, cacobiphenyl, anthradithiophene, and derivatives and precursors thereof.

Examples of the conjugated compound include polythiophene and its oligomer, polypyrrole and its oligomer, polyaniline, polyphenylene and its oligomer, polyphenylene vinylene and its oligomer, polythienylene vinylene and its oligomer, polyacetylene, polydiacetylene, tetrathiafulvalene compound, quinone Compounds, cyano compounds such as tetracyanoquinodimethane, fullerenes and derivatives or mixtures thereof.

In particular, among polythiophene and oligomers thereof, α-sexual thiophene α, ω-dihexyl-α-sexual thiophene, α, ω-dihexyl-α-kinkethiophene, α, ω-bis (3- An oligomer such as butoxypropyl) -α-sexithiophene can be preferably used.

Other examples of the polymer p-type semiconductor include polyacetylene, polyparaphenylene, polypyrrole, polyparaphenylene sulfide, polythiophene, polyphenylene vinylene, polycarbazole, polyisothianaphthene, polyheptadiyne, polyquinoline, polyaniline, and the like. Substituted-unsubstituted alternating copolymer polythiophenes such as JP-A-2006-36755, JP-A-2007-51289, JP-A-2005-76030, J. Pat. Amer. Chem. Soc. , 2007, p4112, J.A. Amer. Chem. Soc. , 2007, p7246, etc., polymers having a condensed ring thiophene structure, WO2008 / 000664, Adv. Mater. , 2007, p4160, Macromolecules, 2007, Vol. Examples thereof include thiophene copolymers such as 40 and p1981.

Further, porphyrin, copper phthalocyanine, tetrathiafulvalene (TTF) -tetracyanoquinodimethane (TCNQ) complex, bisethylenedithiotetrathiafulvalene (BEDTTTTF) -perchloric acid complex, BEDTTTF-iodine complex, TCNQ-iodine complex, etc. Organic molecular complexes of C60, C70, C76, C78, C84, fullerenes such as SWNT, carbon nanotubes such as SWNT, merocyanine dyes, dyes such as hemicyanine dyes, and σ-conjugated polymers such as polysilane and polygermane Organic / inorganic hybrid materials described in Kai 2000-260999 can also be used.

Among these π-conjugated materials, at least one selected from the group consisting of condensed polycyclic aromatic compounds such as pentacene, fullerenes, condensed ring tetracarboxylic acid diimides, metal phthalocyanines, and metal porphyrins is preferable. Further, pentacenes are more preferable.

Examples of pentacenes include substituents described in International Publication No. 03/16599, International Publication No. 03/28125, US Pat. No. 6,690,029, JP-A-2004-107216, etc. A pentacene derivative described in U.S. Patent Application Publication No. 2003/136964 and the like; Amer. Chem. Soc. , Vol127. Examples thereof include substituted acenes described in No. 14.4986 and the like and derivatives thereof.

Among these compounds, compounds that are highly soluble in an organic solvent to the extent that a solution process can be performed, can form a crystalline thin film after drying, and can achieve high mobility are preferable.

Such compounds include J.M. Amer. Chem. Soc. , Vol. 123, p9482; Amer. Chem. Soc. , Vol. 130 (2008), no. 9, 2706 and the like, and acene-based compounds substituted with a trialkylsilylethynyl group, a pentacene precursor described in US Patent Application Publication No. 2003/136964, etc., and Japanese Patent Application Laid-Open No. 2007-224019 Examples include precursor type compounds (precursors) such as porphyrin precursors.

Among these, the latter precursor type can be preferably used.

This is because the precursor type is insolubilized after conversion, so when forming the hole transport layer, electron transport layer, hole block layer, electron block layer, etc. on the bulk hetero junction layer by solution process, bulk hetero junction This is because the layer does not dissolve and the material constituting the layer and the material forming the bulk heterojunction layer are not mixed, and further improvement in efficiency and life can be achieved. .

The p-type semiconductor material is a compound that has undergone a chemical structural change by a method such as exposing the precursor of the p-type semiconductor material to vapor of a compound that causes heat, light, radiation, or a chemical reaction, and converted into a p-type semiconductor material. Preferably there is. Among them, compounds that cause a scientific structural change by heat are preferred.

Examples of n-type semiconductor materials include fullerene, octaazaporphyrin, p-type semiconductor perfluoro compounds (perfluoropentacene, perfluorophthalocyanine, etc.), naphthalenetetracarboxylic anhydride, naphthalenetetracarboxylic diimide, perylenetetracarboxylic acid Examples thereof include polymer compounds containing an anhydride, an aromatic carboxylic acid anhydride such as perylenetetracarboxylic acid diimide, or an imidized product thereof as a skeleton.

Of these, fullerene-containing polymer compounds are preferred. Fullerene-containing polymer compounds include fullerene C60, fullerene C70, fullerene C76, fullerene C78, fullerene C84, fullerene C240, fullerene C540, mixed fullerene, fullerene nanotubes, multi-walled nanotubes, single-walled nanotubes, nanohorns (conical), etc. Examples thereof include a polymer compound having a skeleton. As the fullerene-containing polymer compound, a polymer compound (derivative) having fullerene C60 as a skeleton is preferable.

The fullerene-containing polymers are roughly classified into polymers in which fullerene is pendant from a polymer main chain and polymers in which fullerene is contained in the polymer main chain. Fullerene is contained in the polymer main chain. Are preferred.

This is not because fullerene is contained in the main chain because the polymer does not have a branched structure, so that it can be packed with high density when solidified, resulting in high mobility. It is estimated that.

Examples of a method for forming a bulk heterojunction layer in which an electron acceptor and an electron donor are mixed include a vapor deposition method and a coating method (including a casting method and a spin coating method).

As a form in which the photoelectric conversion element of the present invention is used as a photoelectric conversion device such as a solar cell, the photoelectric conversion element may be used in a single layer or may be used by being laminated (tandem type). In addition, since the photoelectric conversion device is not deteriorated by oxygen, moisture, or the like in the environment, the photoelectric conversion device is preferably sealed by a known method.

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto. In addition, although the display of "%" is used in an Example, unless otherwise indicated, "mass%" is represented.

<< Preparation of transparent electrode >>
[Preparation of transparent electrode TCF-1; comparative example]
ITO was vapor-deposited with an average film thickness of 150 nm on a 100 μm-thick polyethylene terephthalate film support provided with a gas barrier layer on both sides, and then the vapor-deposited film was cut into 180 mm × 180 mm square to produce a transparent electrode TCF-1.

[Preparation of transparent electrode TCF-2; comparative example]
On a 100 μm thick polyethylene terephthalate film support with gas barrier layers on both sides, a silver nanoparticle-containing paste (manufactured by Mitsuboshi Belting Co., Ltd .; MDot-SLP) is formed into a line grid pattern with a print pattern width of 50 μm and a pattern interval of 1000 μm Screen printing is performed using the formed screen printing mesh (Mitani Micronics Co., Ltd .; MFT325), heated at 120 ° C. for 30 minutes, and then the printed film is cut into a 100 mm × 100 mm square, with a pattern width of 50 μm / pattern A transparent electrode TCF-2 having a silver grid pattern with a spacing of 1000 μm and a thickness of 1 μm was produced.

[Preparation of transparent electrode TCF-3; comparative example]
A conductive polymer solution CP-1 prepared by the following method is applied onto TCF-2 using a spin coater so as to have a dry film thickness of 500 nm, heat-treated at 120 ° C. for 20 minutes, and then applied. A transparent electrode TCF-3 was produced in the same manner as TCF-2 except that the film was cut into 100 mm × 100 mm square.

(Preparation of conductive polymer liquid CP-1)
(Synthesis of poly (2-hydroxyethyl acrylate))
2-Bromoisobutyryl bromide (7.3 g, 35 mmol), triethylamine (2.48 g, 35 mmol) and THF (20 ml) were added to a 50 ml three-necked flask, and the internal temperature was kept at 0 ° C. with an ice bath.

In this solution, 30 ml of a 33% THF solution of oligoethylene glycol (10 g, 23 mmol, ethylene glycol units 7-8, manufactured by Laporte Specialties) was added dropwise. After stirring for 30 minutes, the solution was brought to room temperature and further stirred for 4 hours.

After THF was removed under reduced pressure by a rotary evaporator, the residue was dissolved in diethyl ether and transferred to a minute funnel. Water was added and the ether layer was washed three times, and then the ether layer was dried with MgSO ₄ . The ether was distilled off under reduced pressure using a rotary evaporator to obtain 8.2 g (yield 73%) of initiator 1.

5 ml of initiator 1 (500 mg, 1.02 mmol), 2-hydroxyethyl acrylate (4.64 g, 40 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.), 50:50 v / v% methanol / water mixed solvent was put into a Schlenk tube, The Schlenk tube was immersed in liquid nitrogen under reduced pressure for 10 minutes.

The Schlenk tube was taken out of liquid nitrogen and replaced with nitrogen after 5 minutes. After performing this operation three times, bipyridine (400 mg, 2.56 mmol) and CuBr (147 mg, 1.02 mmol) were added under nitrogen, and the mixture was stirred at 20 ° C. After 30 minutes, the reaction solution was dropped onto a 4 cm Kiriyama funnel with filter paper and silica, and the reaction solution was recovered under reduced pressure.

The solvent was distilled off under reduced pressure using a rotary evaporator and then dried under reduced pressure at 50 ° C. for 3 hours. As a result, 2.60 g (yield 84%) of water-soluble binder resin 1 (polymer (A)) having a number average molecular weight of 13,100, a molecular weight distribution of 1.17, and a content of number average molecular weight <1000 of 0% was obtained.

The structure and molecular weight were measured by ¹ H-NMR (400 MHz, manufactured by JEOL Ltd.) and GPC (Waters 2695, manufactured by Waters), respectively.

<GPC measurement conditions>
Apparatus: Wagers 2695 (Separations Module)
Detector: Waters 2414 (Refractive Index Detector)
Column: Shodex Asahipak GF-7M HQ
Eluent: Dimethylformamide (20 mM LiBr)
Flow rate: 1.0 ml / min
Temperature: 40 ° C
The obtained water-soluble binder resin 1 was dissolved in pure water to prepare a water-soluble binder resin 1 aqueous solution having a solid content of 20%.

Next, a conductive polymer liquid CP-1 was prepared as follows.

(Conductive polymer liquid CP-1)
Water-soluble binder resin 1 aqueous solution (solid content 20% aqueous solution) 0.35 g
PEDOT-PSS CLEVIOS PH510 (solid content 1.89%) (manufactured by HC Starck) 1.59 g
[Preparation of Transparent Electrode TCF-4; Present Invention]
A transparent electrode TCF-4 was produced in the same manner as TCF-3 except that TCF-3 was immersed in an etching solution BF-1 prepared by the following method at 25 ° C. for 60 seconds, washed with water and dried. did.

<Preparation of etching solution BF-1>
Ethylenediaminetetraacetic acid ferric ammonium 60g
Ethylenediaminetetraacetic acid 2g
Sodium metabisulfite 15g
70g ammonium thiosulfate
Maleic acid 5g
Etching solution BF-1 was prepared by finishing to 1 L with pure water and adjusting the pH to 5.5 with sulfuric acid or ammonia water.

[Preparation of transparent electrode TCF-5; comparative example]
In TCF-3, instead of the conductive polymer liquid CP-1, PEDOT-PSS CLEVIOS PH510 (solid content 1.89%) (manufactured by HC Starck) was applied to a spin coater so that the dry film thickness was 150 nm. A transparent electrode TCF-5 was produced in the same manner as TCF-3, except that coating and drying were performed using

[Preparation of transparent electrode TCF-6; comparative example]
In TCF-4, the transparent electrode TCF-6 is the same as TCF-4 except that it is immersed in the etching solution BF-1 for 60 seconds before being coated with the conductive polymer solution CP-1, and then washed and dried. Was made.

[Preparation of Transparent Electrode TCF-7; Present Invention]
In TCF-4, a transparent electrode TCF-7 was produced in the same manner as TCF-4 except that a silver nanowire film produced as described below was used instead of the silver grid pattern.

(Preparation of silver nanowire film)
Adv. Mater. , 2002, 14, 833 to 837, a silver nanowire having an average minor axis of 75 nm and an average length of 35 μm was prepared using polyvinylpyrrolidone K30 (molecular weight: 50,000; manufactured by ISP). After silver nanowires are filtered and washed with an outer filtration membrane, hydroxypropylmethylcellulose 60SH-50 (manufactured by Shin-Etsu Chemical Co., Ltd.) is redispersed in an aqueous solution containing 25% by mass of silver, and the silver nanowire dispersion liquid is obtained. Prepared.

The prepared silver nanowire dispersion is applied to a silver terephthalate film support having a gas barrier layer on both sides and a polyethylene terephthalate film support having a thickness of 100 μm so that the weight of the silver nanowire is 50 mg / m ^2. It was applied and dried to produce a silver nanowire film.

[Preparation of Transparent Electrode TCF-8; Present Invention]
In TCF-7, a transparent electrode was formed in the same manner as TCF-7, except that a silver grid pattern having a pattern width of 50 μm, a pattern interval of 1000 μm, and a thickness of 1 μm was formed on the silver nanowire film by the same method as TCF-2. TCF-8 was produced.

[Production of Transparent Electrode TCF-9; Present Invention]
A transparent electrode TCF-9 was produced in the same manner as TCF-4 except that the conductive polymer liquid CP-1 was changed to the conductive polymer liquid CP-2 prepared as follows in TCF-4.

(Conductive polymer liquid CP-2)
Polyhydroxyethylacrylamide (number average molecular weight 20,000, solid content 50% aqueous solution) 0.14 g
PEDOT-PSS CLEVIOS PH510 (solid content 1.89%) (manufactured by HC Starck) 1.59 g
[Preparation of transparent electrode TCF-10; the present invention]
A transparent electrode TCF-10 was produced in the same manner as TCF-4 except that the conductive polymer liquid CP-1 in TCF-4 was changed to the conductive polymer liquid CP-3 prepared as follows.

(Conductive polymer liquid CP-3)
Polyhydroxyethyl vinyl ether (number average molecular weight 20,000, solid content 50% aqueous solution) 0.14 g
PEDOT-PSS CLEVIOS PH510 (solid content 1.89%) (manufactured by HC Starck) 1.59 g
[Preparation of transparent electrode TCF-11; comparative example]
TCF-4 was the same as TCF-4 except that the water-soluble binder resin 1 was a conductive polymer liquid CP-4 made of a copolymer of hydroxyethyl acrylate (49 mol%) and methyl acrylate (51 mol%). When the transparent electrode TCF-11 was produced, the entire conductive polymer layer eluted during immersion in the etching solution BF-1 for 60 seconds, and a transparent electrode could not be produced.

[Preparation of transparent electrodes TCF-12 to 15; the present invention]
Transparent electrodes TCF-12 to 15 were produced in the same manner as TCF-4 except that the conductive metal layer and the conductive polymer layer were those shown in Table 2.

<< Measurement and evaluation of transparent electrodes >>
By the following method, it measured and evaluated about the transmittance | permeability and surface specific resistance of the electroconductive part of each produced transparent electrode, and evaluated transparency and electroconductivity.

(Transmittance)
For the transmittance, the total light transmittance of the transparent electrode was measured using AUTOMATIC ZEMETER (MODEL TC-HIIIDP) manufactured by Tokyo Denshoku.

(Surface resistivity)
For the surface resistivity, the surface resistivity of the transparent electrode was measured by a four-terminal method using a resistivity meter Loresta GP manufactured by Dia Instruments.

<< Production of organic EL element >>
Using the produced transparent electrodes as the first electrode (anode), organic EL elements OLED-1 to -15 were produced in the following procedure.

On the electrode, PEDOT-PSS CLEVIOS PH510 (solid content 1.89%) (manufactured by HC Starck) was applied and dried using a spin coater so that the dry film thickness was 30 nm.

Next, the transparent electrode was set in a commercially available vacuum deposition apparatus, and each of the deposition materials in the vacuum deposition apparatus was filled with the constituent material of each layer in an optimum amount for device fabrication. The evaporation crucible used was made of a resistance heating material made of molybdenum or tungsten.

Next, each light emitting layer was provided by the following procedure.

First, after depressurizing to a vacuum of 1 × 10 ⁻⁴ Pa, the deposition crucible containing the following α-NPD was energized and heated, evaporated at a deposition rate of 0.1 nm / second, and a 30 nm hole transport layer Was established.

Ir-1, Ir-14 and the following compound 1-7 were co-deposited at a deposition rate of 0.1 nm / sec so that the following Ir-1 would be 13% by mass and the following Ir-14 would be 3.7% by mass: Then, a green-red phosphorescent light emitting layer having an emission maximum wavelength of 622 nm and a thickness of 10 nm was formed.

Subsequently, E-66 and compound 1-7 were co-evaporated at a deposition rate of 0.1 nm / second so that the following E-66 was 10% by mass, and a blue phosphorescent emitting layer having an emission maximum wavelength of 471 nm and a thickness of 15 nm. Formed.

Thereafter, M-1 below is deposited to a thickness of 5 nm to form a hole blocking layer, and CsF is co-deposited with M-1 so that the thickness ratio is 10%, and an electron transport layer having a thickness of 45 nm is formed. Formed.

The compounds used for forming each layer are shown below.

On the formed electron transport layer, Al was evaporated as a first electrode external take-out terminal and 80 mm × 80 mm second electrode (cathode) forming material under a vacuum of 5 × 10 ⁻⁴ Pa to obtain a thickness. A second electrode of 100 nm was formed. The thickness of the organic functional layer between the electrodes was 120 nm.

Furthermore, an adhesive is applied to the periphery of the second electrode except for the end portion so that external terminals for the first electrode and the second electrode can be formed, and Al ₂ O ₃ is vapor deposited at a thickness of 300 nm using polyethylene terephthalate as a base material. After pasting the flexible sealing member, the adhesive was cured by heat treatment to form a sealing film, and an organic EL device having a light emitting area of 80 mm × 80 mm was produced.

<< Measurement and evaluation of organic EL elements >>
By the following method, the light emission unevenness of each organic EL element produced as described above was evaluated, used as an index of performance uniformity of the organic functional layer, evaluated as a rectification ratio and a luminance change, and used as an index of durability.

(Light emission unevenness)
The light emission unevenness was evaluated by visually evaluating the light emission state according to the following criteria using a source measure unit 2400 type manufactured by KEITHLEY, applying a direct current voltage to each organic EL element to emit light with a luminance of 1000 cd / m ² .

A: Completely uniform light emission, no problem. ○: Almost uniform light emission, no problem. Δ: Some light emission unevenness is partially observed, but practically acceptable. X: Light emission unevenness over the entire surface. Seen and unacceptable (rectification ratio)
The rectification ratio was determined by measuring the current value when a voltage of +3 V / −3 V was applied to each organic EL element, obtaining the rectification ratio by the following formula, and evaluating it according to the following criteria. If there is leakage between electrodes, the rectification ratio becomes a low value. It is practical range is 10 ² or more.

Rectification ratio = current value when +3 V is applied / current value when −3 V is applied ◎: Rectification ratio 10 ³ or more ○: Rectification ratio 10 ² or more and less than 10 ³ Δ: Rectification ratio 10 ¹ or more and less than 10 ² ×: Rectification ratio 10 ¹ Less than (brightness change)
Each organic EL element was allowed to emit light continuously at a constant voltage so that the initial luminance was 5000 cd / m ² , and the time until the luminance was reduced by half was determined. The half time of OLED-1 was set to 100, and the relative value was evaluated. 120 or more is a practically good range.

Measured and evaluated results are shown in Tables 2 and 3.

From Tables 2 and 3, the transparent electrode obtained by the method of the present invention maintains high transparency and conductivity, and the organic EL device using the same has little unevenness in light emission and excellent performance uniformity of the organic functional layer. It can be seen that it has excellent durability.

Claims

Forming a conductive metal layer having a fine metal wire structure on the transparent support (1);
A conductive polymer layer comprising a conductive polymer having a π-conjugated conductive polymer and a polyanion on the conductive metal layer and the following polymer (A), which is a step subsequent to the step (1). Forming a transparent electrode plate (2),
A step (3) after the step (2), in which the transparent electrode plate is subjected to a chemical etching treatment to produce a transparent electrode;
The manufacturing method of the transparent electrode characterized by having.
[Polymer (A): A polymer having at least one of the polymerization units (repeating units) represented by the following general formula 1, general formula 2 and general formula 3 as a polymerization unit under the following conditions.

[In each formula, X 1 to X 3 each independently represents a hydrogen atom or a methyl group. R 1 to R 3 each independently represents an alkylene group having 5 or less carbon atoms. Conditions: l (mol%) of the polymerized units of the above general formula 1 in the total polymerized units of the polymer (A), and ratios (mol%) of the polymerized units of the above general formula 2 in all polymerized units of the polymer (A). ) Is m, and the ratio (mol%) of the polymerized units of the above general formula 3 to the total polymerized units of the polymer (A) is n. 50 ≦ l + m + n ≦ 100, 0 ≦ l ≦ 100, 0 ≦ m ≦ 100 0 ≦ n ≦ 100. ]
The method for producing a transparent electrode according to claim 1, wherein the metal fine wire structure is a metal grid pattern.
The method for producing a transparent electrode according to claim 1, wherein the conductive metal layer contains metal nanowires.
A transparent electrode manufactured by the method for manufacturing a transparent electrode according to any one of claims 1 to 3.
An organic electronic device comprising the transparent electrode according to claim 4.
The organic electronic device according to claim 5, wherein the organic electronic device is an organic electroluminescence device.
The organic electronic device according to claim 6, wherein the organic functional layer of the organic electroluminescence device has a thickness of 1 nm to 200 nm.