WO2011148931A1

WO2011148931A1 - Electrode for organic electronic device

Info

Publication number: WO2011148931A1
Application number: PCT/JP2011/061848
Authority: WO
Inventors: 博和小山; 宏明伊東
Original assignee: コニカミノルタホールディングス株式会社
Priority date: 2010-05-28
Filing date: 2011-05-24
Publication date: 2011-12-01
Also published as: JP5720680B2; JPWO2011148931A1

Abstract

Disclosed is an electrode for an organic electronic device, which can exhibit improved optical performance without causing leakage between electrodes, the disturbance in device performance around a pattern of a metal fine wire or the like. Specifically disclosed is an electrode for an organic electronic device, which comprises a base material, a pattern of an electrically conductive metal fine wire formed on the base material, and a layer containing an electrically conductive polymer (an electrically-conductive-polymer-containing layer) formed on the pattern. The electrode is characterized in that a part of the electrically-conductive-polymer-containing layer which lies on an area having the metal fine wire has a thickness of 100 to 2000 nm and the difference in level between the surface of a part of the electrically-conductive-polymer-containing layer which lies on an area having the metal fine wire and the surface of a part of the electrically-conductive-polymer-containing layer which lies on an area having no metal fine wire in the area having the pattern of the metal fine wire is 100 to 800 nm inclusive.

Description

Electrodes for organic electronic devices

The present invention relates to an electrode for an organic electronic device, and more particularly, to an electrode for an organic electronic device having improved optical performance without causing leakage between the electrodes or disturbance of the device performance around the pattern of the fine metal wire. .

A transparent conductive film in which a transparent conductive film is laminated on a fine metal wire pattern so as to be compatible with a device having a large area is known (see, for example, Patent Documents 1 and 2). However, when such a transparent conductive film is used for an organic electronic device such as organic electroluminescence (hereinafter referred to as organic EL) or an organic solar cell, leakage occurs between opposing electrodes, or in the organic EL, around the metal pattern. In some cases, the device performance may be abnormal in the vicinity of the thin metal wire pattern, for example, the light may only shine brightly or the life of the element may be reduced from the periphery of the metal pattern. This is because the pattern of the fine metal wire has a step, so that the thickness of the conductive layer on the fine metal wire pattern becomes thin when the transparent conductive film is formed, and it is easy to leak from the grid. It seems that the step between the metal thin wire pattern and the portion not having the metal fine line pattern is large, and the organic device configuration is disturbed at the step portion, which makes it easy to leak. Furthermore, from only the functional layer at the step portion, the organic EL may shine brightly only around the metal pattern, or the lifetime of the element may decrease from around the metal pattern.

On the other hand, a technique of providing a transparent conductive layer after transferring a pattern of fine metal wires formed on a smooth surface to another support provided with an adhesive layer and forming a fine metal wire pattern without steps (for example, Patent Document 3) is known. This is a preferable mode because it is possible to prevent leakage due to the influence of the step as described above.

On the other hand, in organic electronic devices such as organic EL and organic solar cells in which a large number of highly smooth layers having different refractive indexes are stacked, for example, in organic EL, light emitted by the influence of interface reflection cannot be extracted. There is a problem that light cannot be taken in. The technique of Patent Document 3 in which leakage is prevented by smoothing is considered disadvantageous for such a problem.

JP 2005-302508 A JP 2009-87843 A JP 2009-146640 A

An object of the present invention is to provide an electrode for an organic electronic device with improved optical performance without causing leakage between the electrodes or disorder of the device performance around the pattern of the fine metal wire.

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

1. An electrode for an organic electronic device in which a conductive fine metal wire pattern is provided on a substrate and a conductive polymer-containing layer is further provided thereon, and the conductive polymer-containing layer film on a portion where the fine metal wire is present The surface of the conductive polymer-containing layer having a thickness of 100 nm to 2000 nm and on the portion with the fine metal wire, and the conductive polymer in the portion without the fine metal wire in the region provided with the pattern of the fine metal wire An electrode for an organic electronic device, wherein a level difference from the surface of the containing layer is 100 nm or more and 800 nm or less.

2. The level difference between the outermost surface of the conductive polymer-containing layer above the portion with the fine metal wire and the outermost surface of the conductive polymer-containing layer at the portion without the fine metal wire pattern is 150 nm or more and 600 nm or less, 2. The electrode for an organic electronic device according to 1 above.

3. 3. The electrode for an organic electronic device according to 1 or 2 above, wherein the conductive polymer-containing layer in a portion without the thin metal wire has a thickness of 200 nm to 1500 nm.

4. 4. The organic electronic device electrode according to any one of 1 to 3, wherein a height of the outermost surface of the fine metal wire from the base material surface is 200 nm or more and 2000 nm or less.

5. 5. The electrode for an organic electronic device according to any one of 1 to 4, wherein the conductive polymer-containing layer further contains a water-soluble polymer.

6. 6. The electrode for an organic electronic device as described in 5 above, wherein the water-soluble polymer is the following polymer (A).

(Wherein X ₁ , X ₂ and X ₃ each independently represents a hydrogen atom or a methyl group, and R ₁ , R ₂ and R ₃ each independently represents an alkylene group having 5 or less carbon atoms. , M, and n represent the composition ratio (mol%), where 50 ≦ l + m + n ≦ 100, and l, m, and n are 0 to 100, respectively.
7). 7. The electrode for an organic electronic device according to any one of 1 to 6, wherein the pattern of the fine metal wire and the conductive polymer-containing layer are formed by a wet film forming method.

According to the present invention, it is possible to provide an electrode for an organic electronic device with improved optical performance without causing leakage between the electrodes or disorder of the device performance around the pattern of the fine metal wire.

It is a figure which shows the 1st process in the case of manufacture of the electrode for organic electronic devices of this invention. It is a figure which shows the 2nd process in the case of manufacture of the electrode for organic electronic devices of this invention. It is a figure which shows the 3rd process in the case of electrode manufacture for organic electronic devices of this invention. It is a figure which shows the cathode electrode of the organic EL element using the electrode for organic electronic devices of this invention.

In the present invention, in order to cope with a device having a large area, a conductive fine metal wire pattern is used to suppress a voltage drop at the electrode. Furthermore, a conductive polymer-containing layer is provided on at least a part of the portion without the metal fine wire pattern so that electricity flows also through the portion without the metal fine wire pattern. Thereby, it can function as a surface electrode.

Organic electronic devices such as organic EL and organic solar cells are usually thin films with a functional layer of several hundred nm or less. For this reason, if there is a convex portion such as a pattern of a fine metal wire, it may cause a leak. Therefore, it is conceivable to smooth the pattern portion of the fine metal wire as in Patent Document 3 described above. In addition, the fine metal wire portion is not completely smoothed, and the upper portion of the conductive polymer-containing layer on the fine metal wire pattern portion is made higher than the upper portion of the conductive polymer-containing layer in the portion without the fine metal wire pattern by 100 nm or more. . Thereby, it discovered that it was effective in optical characteristics, such as light extraction of the pattern of the metal fine wire which is another subject of organic electronic devices, such as organic EL and an organic solar cell, and light uptake | capture. This is because, for example, in organic EL, the total reflection between the front and back surfaces of the light emitting layer having a high refractive index is repeated, and the incident angle of the confined light on the front and back surfaces changes greatly around the pattern portion of the thin metal wire. It is thought that light extraction performance is manifested by the effect of surface scattering. Further, the step between the upper portion of the conductive polymer-containing layer on the fine metal wire pattern portion and the upper portion of the conductive polymer-containing layer in the portion without the thin metal wire pattern is set to 800 nm or less, and further, the conductivity on the fine metal wire pattern portion is further reduced. It has been found that by setting the film thickness of the conductive polymer-containing layer to 100 nm to 2000 nm, it is possible to prevent leakage and disturbance of device performance around the pattern portion of the fine metal wire while maintaining the efficiency of the electronic device. I went to.

<< Method for Producing Electrode for Organic Electronic Device of the Present Invention >>
The manufacturing method of the electrode for organic electronic devices of this invention is demonstrated using figures. In FIG. 1, the ink containing metal fine particles for inkjet is printed on an easily contacted substrate as follows using an inkjet coating apparatus. Extraction electrodes (1) and (4) of the solid metal portion, a pattern (2) of the fine metal wire in contact with the extraction electrode (1), and a fine metal wire between the pattern (2) of the fine metal wire and the extraction electrode (4) A blank part (3) having no pattern is provided. The pattern of fine metal wires is fixed by heat treatment.

Next, as shown in FIG. 2, a conductive polymer-containing layer (5) is provided on the fine metal wire pattern (2) by coating.

Next, as shown in FIG. 3, the conductive polymer-containing layer (5), which has no fine metal wire pattern, is wiped away with pure water to remove the conductive polymer-containing layer ( 5 '). The conductive polymer-containing layer (5 ′) is also fixed by heat treatment to obtain an electrode for organic electronic devices (10).

FIG. 4 shows a cathode electrode (6) finally produced after an organic layer necessary as an organic EL element is formed on the electrode for organic electronic devices (10) of the present invention.

Hereinafter, the best mode for carrying out the present invention will be described in detail, but the present invention is not limited thereto.

<< Conductive polymer >>
The conductive polymer according to the present invention is preferably a conductive polymer comprising a π-conjugated conductive polymer and a polyanion. Such a conductive polymer can be easily produced by chemically oxidatively polymerizing 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, A chain conductive polymer of polyfurans, polyparaphenylene vinylenes, polyazulenes, polyparaphenylenes, polyparaphenylene sulfides, polyisothianaphthenes, polythiazyl compounds 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, and the like.

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 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 anion 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 anion group of the polyanion may be a functional group capable of undergoing 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 sufficient and 2 or more types of copolymers may be sufficient.

Further, it may be a polyanion having F in the compound. Specific examples include Nafion containing a perfluorosulfonic acid group (manufactured by Dupont), Flemion made of perfluoro vinyl ether containing a carboxylic acid group (manufactured by Asahi Glass Co., Ltd.), and the like.

Among these, when a compound having a sulfonic acid is formed by applying and drying a conductive polymer-containing layer, when subjected to a heat treatment 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 methods for producing polyanions 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, and anionic group-containing polymerization. And a method of production by polymerization of a functional monomer.

Examples of the method for producing an anion group-containing polymerizable monomer by polymerization include a method for producing an anion 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. Specifically, a predetermined amount of the anionic group-containing polymerizable monomer is dissolved in a solvent, kept at a constant temperature, and a solution in which a predetermined amount of an oxidizing agent and / or a polymerization catalyst is dissolved in the solvent is added to the predetermined amount. React with time. The polymer obtained by the reaction is adjusted to a certain concentration by the solvent. In this production method, an anionic group-containing polymerizable monomer may be copolymerized with a polymerizable monomer having no anionic group.

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) made of poly (3,4-ethylenedioxythiophene) and polystyrenesulfonic acid is H.264. C. It is commercially available from Starck as the CLEVIOS series, from Aldrich as PEDOT-PASS 483095, 560598, 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.

When the polyanion is used as the first dopant, a water-soluble organic compound may be contained as the second 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.

《Water-soluble polymer》
In the present invention, by using a water-soluble polymer in combination with the conductive polymer-containing layer, it becomes possible to increase the film thickness without reducing the transmittance, and to embed foreign matter attached to the surface, etc. This is a preferred embodiment. The water-soluble polymer used in the present invention is not particularly limited as long as it is a polymer that can be dissolved or dispersed in an aqueous solvent (described later). For example, a polyester resin, an acrylic resin, a polyurethane resin, an acrylic urethane resin, Examples thereof include polycarbonate resins, cellulose resins, polyvinyl acetal resins, polyvinyl alcohol resins, and the like. Specific examples of the compound include Vylonal MD1200, MD1400, MD1480 (manufactured by Toyobo Co., Ltd.) as polyester resins.

As the water-soluble polymer according to the present invention, a compound having a group that reacts with a crosslinking agent described later is more preferable because it forms a stronger film. As such a water-soluble polymer, the group that reacts with the crosslinking agent varies depending on the crosslinking agent, and examples thereof include a hydroxy group, a carboxyl group, and an amino group. Among these, it is most preferable to have a hydroxy group in the side chain.

Specific compounds of the water-soluble polymer according to the present invention include polyvinyl alcohol PVA-203, PVA-224, PVA-420 (manufactured by Kureha), hydroxypropyl methylcellulose 60SH-06, 60SH-50, 60SH-4000. , 90SH-100 (above, manufactured by Shin-Etsu Chemical Co., Ltd.), methylcellulose SM-100 (produced by Shin-Etsu Chemical Co., Ltd.), cellulose acetate L-20, L-40, L-70 (above, manufactured by Daicel Chemical Industries, Ltd.), carboxy Methylcellulose CMC-1160 (manufactured by Daicel Chemical Industries), hydroxyethylcellulose SP-200, SP-600 (above, manufactured by Daicel Chemical Industries), alkyl acrylate copolymer Jurimer AT-210, AT-510 (above, Toagosei Co., Ltd.) , Polyhydroxyethyl acrylate Polyhydroxyethyl methacrylate, and the like.

Among them, when the water-soluble polymer contains a certain amount of the polymer (A), it is possible to improve the conductivity of the conductive polymer-containing layer by using this compound without using the second dopant. Furthermore, compatibility with a conductive polymer is also good, and high transparency and smoothness can be achieved. Further, when the polyanion has a sulfo group, if the polymer (A) is used, the sulfo group effectively acts as a dehydration catalyst, and a dense cross-linked layer can be formed without using an additional agent such as a cross-linking agent. This is a more preferred embodiment because it can be formed.

In the present invention, the water-soluble polymer (A) is composed mainly of the following monomers M1, M2, and M3, and 50 mol% or more of the copolymer components are any of the monomers, or the total is 50 mol% or more. It is a copolymer. The total of the monomer components is more preferably 80 mol% or more, and it may be a homopolymer formed from any single monomer, which is a preferred embodiment.

In the formula, X ₁ , X ₂ , and X ₃ each independently represent a hydrogen atom or a methyl group, and R ₁ , R ₂ , and R ₃ each independently represent an alkylene group having 5 or less carbon atoms.

In the polymer (A), other monomer components may be copolymerized as long as they are soluble in an aqueous solvent, but a monomer component having high hydrophilicity is more preferable.

The polymer (A) preferably has a content of 1000 or less in the number average molecular weight of 0 to 5%.

In the number average molecular weight of the polymer (A), the content of 1000 or less is 0 to 5% or less, such as reprecipitation method, preparative GPC, or synthesis of monodisperse polymer by living polymerization, etc. A method of removing the low molecular weight component or suppressing the generation of the low molecular weight component can be used.

In the reprecipitation method, the polymer is dissolved in a solvent in which the polymer can be dissolved and dropped into a solvent having a lower solubility than the solvent in which the polymer is dissolved, thereby precipitating the polymer and removing low molecular weight components such as monomers, catalysts, and oligomers. It is a method to do.

In addition, preparative GPC is, for example, recycled preparative GPCLC-9100 (manufactured by Nippon Analytical Industrial Co., Ltd.), polystyrene gel column, and a polymer-dissolved solution can be separated by molecular weight to cut the desired low molecular weight. This is how you can do it.

Living polymerization does not change the generation of the starting species over time, and there are few side reactions such as termination reaction, and a polymer with uniform molecular weight can be obtained. Since the molecular weight can be adjusted by the addition amount of the monomer, for example, if a polymer having a molecular weight of 20,000 is synthesized, the formation of a low molecular weight body can be suppressed. The reprecipitation method and living polymerization are preferable from the viewpoint of production suitability.

The number average molecular weight and the weight average molecular weight of the water-soluble polymer of the present invention can be measured by a generally known gel permeation chromatography (GPC). The molecular weight distribution can be expressed by a ratio of (weight average molecular weight / number average molecular weight). The solvent to be used is not particularly limited as long as the water-soluble binder resin dissolves, and THF, DMF, and CH ₂ Cl ₂ are preferable, THF and DMF are more preferable, and DMF is more preferable. The measurement temperature is not particularly limited, but 40 ° C. is preferable.

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 number average molecular weight distribution of the polymer (A) according to the present invention is preferably 1.01 to 1.30, more preferably 1.01 to 1.25.

In the distribution obtained by GPC, the content with a number average molecular weight of 1000 or less was converted to a ratio by integrating the area with a number average molecular weight of 1000 or less and dividing by the area of the entire distribution.

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

[Formation of conductive polymer-containing layer]
The conductive polymer-containing layer contains, for example, at least a conductive polymer containing a π-conjugated conductive polymer component and a polyanion component and a solvent, more preferably a coating solution containing a water-soluble polymer. Can be formed by coating and drying.

As the solvent, an aqueous solvent can be preferably used. Here, the aqueous solvent represents 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.

As coating methods, roll coating method, bar coating method, dip coating method, spin coating method, casting method, die coating method, blade coating method, bar coating method, gravure coating method, curtain coating method, spray coating method, doctor coating method A letterpress (letter) printing method, a stencil (screen) printing method, a lithographic (offset) printing method, an intaglio (gravure) printing method, a spray printing method, an ink jet printing method, and the like can be used.

The dry film thickness of the conductive polymer-containing layer needs to be 100 nm or more on the portion where the fine metal wire is present in order to prevent leakage between the fine metal wire and the counter electrode. Moreover, it is preferable that the film thickness of the conductive polymer content layer of a part without a metal fine wire is 200 nm or more and 1500 nm or less. By setting the thickness to 200 nm or more, it is possible to prevent leakage due to foreign matter or the like. On the other hand, if the thickness exceeds 1500 nm, the influence of coloring of the conductive polymer and the scattering effect of the fine metal wire pattern become small, and the optical effect of the present invention becomes small. For higher effects, the thickness is more preferably 300 nm or more and 1000 nm or less.

The outermost surface of the conductive polymer-containing layer on the portion with the fine metal wire is 100 nm or more higher than the outermost surface of the conductive polymer-containing layer on the portion without the fine metal wire, more preferably 150 nm or more. Thereby, optical characteristics such as light extraction and light capture of organic electronic devices such as organic EL and organic solar cells can be improved. Moreover, as an upper limit, it is 800 nm or less, Preferably it is 600 nm or less. By doing so, it is possible to minimize the disturbance of the functional layer at the stepped portion, and to suppress leakage and abnormal light emission around the pattern portion of the fine metal wire and a decrease in the lifetime.

The conductive polymer-containing layer where there is no fine metal wire can be adjusted by the solid content and amount of coating solution. Furthermore, by adjusting the viscosity of the coating solution, the film thickness of the conductive polymer-containing layer on the portion with the thin metal wire, and the outermost surface of the conductive polymer-containing layer on the portion with the thin metal wire, The level | step difference with the outermost surface of the conductive polymer content layer on the part without a metal fine wire can be adjusted. When the viscosity is increased, the thickness of the conductive polymer-containing layer on the portion where the fine metal wire is present is increased, and the level difference is increased. On the contrary, when the viscosity is lowered, the film thickness of the conductive polymer-containing layer on the portion where the fine metal wire is present is thin, and the step is reduced. The viscosity of the coating solution is increased by increasing the solid content, using a water-soluble polymer together, increasing the number average molecular weight of the water-soluble polymer used together, adding a water-soluble solvent having a hydroxyl group, such as an alcohol, etc. It can be raised and vice versa. Furthermore, it can be adjusted according to the drying conditions described later. When drying is strengthened, the upper part of the conductive polymer-containing layer on the portion with the fine metal wires is thickened. It is.

After coating, a drying process is appropriately performed to volatilize the solvent. 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 board | substrate 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.

(Metallic thin wire pattern)
In the pattern of fine metal wires of the present invention, the pattern shape is not particularly limited, but for example, a triangle, a square, a rectangle, a rhombus, a parallelogram, a trapezoid or other quadrangle, a (regular) hexagon, a (positive) octagon It is possible to raise a mesh-like pattern composed of geometric figures combining the above. Alternatively, a stripe shape composed of a plurality of parallel lines may be used. For example, stripes or lattices having a line width of 10 to 200 μm and a line interval of 200 to 3000 μm can be given. The height of the fine metal wire pattern is not particularly limited as long as the relationship of the conductive polymer-containing layer can be satisfied. However, in order to easily satisfy the relationship of the present invention, it is preferably 200 nm or more and 2000 nm or less, and 300 nm or more. More preferably, it is 1000 nm or less.

The pattern of the fine metal wire does not use the conductive polymer-containing layer, and preferably has a conductivity of 30Ω / □ or less as a single film, more preferably 5Ω / □ or less, and preferably 1Ω / □ or less. Most preferred.

Examples of the metal material include gold, silver, copper, iron, nickel, and chromium. Moreover, the metal may be an alloy, and the pattern of the fine metal wire may be a single layer or multiple layers.

There is no particular limitation on the method for forming the auxiliary electrode having a conductive portion having a stripe shape or a mesh shape, and a conventionally known method can be used. For example, a metal layer can be formed on the entire surface of the substrate and formed by a known photolithography method. Specifically, a conductor layer is formed on the entire surface of the substrate using one or more physical or chemical forming methods such as vapor deposition, sputtering, and plating, or a metal foil is formed with an adhesive. After being laminated on the material, it can be processed into a desired stripe shape or mesh shape by etching using a known photolithography method.

As another method, a method of printing an ink containing metal fine particles in a desired shape by various printing methods such as screen printing, flexographic printing, gravure printing, or an ink jet method, and various similar catalytic inks that can be plated are used. A method of applying a silver salt photographic technique can be used as a method of applying a desired shape by a printing method and then performing a plating treatment, and as another method. Among these methods, the method of printing ink containing metal fine particles in a desired shape by various printing methods can be manufactured in a simple process, so that it is possible to reduce the entrainment of foreign matters that may cause leakage at the time of manufacture. Since ink is used only at the location, there is little loss of liquid, and since there is no need for special chemical treatment such as plating, there is no concern about contamination of chemicals that cannot be removed. This is the most preferred embodiment.

(Ink containing fine metal particles)
As the metal fine particle-containing ink, known inks can be used. Examples of the metal fine particles include metal fine particles containing any one of silver, gold, copper, palladium, platinum, aluminum and nickel, or alloy fine particles containing these metals.

These metal fine particles are coated with a film (coating material) such as an organic substance on the surface in order to improve dispersibility.

The particle diameter of the metal fine particles is preferably 1 nm or more and 1 μm or less, and more preferably 0.1 μm or less. When the thickness exceeds 1 μm, the unevenness of the pattern portion of the fine metal wire is large, which is disadvantageous for leakage. When the thickness is 0.1 μm or less, fusion between particles proceeds even at low temperature firing, and high conductivity is obtained. It is also preferable to use particles having a size of 0.1 μm or less and particles having a size of 0.1 μm or more as described in JP-A-2008-091250.

In order to use metal fine particles of 0.1 μm or less, it is preferable to use the fine particles coated with an organic protective colloid. As this organic protective colloid, one having a decomposition temperature or boiling point in the range of 70 to 250 ° C. is used. This decomposition temperature or boiling point means the lower one of the decomposition temperature and boiling point. If the decomposition temperature or boiling point of the organic protective colloid exceeds 250 ° C., the organic protective colloid cannot be decomposed or evaporated by low-temperature heat treatment, and low-temperature firing cannot be performed. If the decomposition temperature or boiling point of the organic protective colloid is less than 70 ° C., the organic protective colloid may be decomposed or evaporated during storage of the silver paste, which causes a problem in storage stability of the silver paste.

Further, as the organic protective colloid, it is preferable to use hydrocarbons having 3 to 18 carbon atoms. If the carbon number is 19 or more, the decomposition temperature or boiling point becomes high, and the organic protective colloid may not be decomposed or evaporated by low-temperature heat treatment, and if the carbon number is 2 or less, the decomposition temperature Alternatively, the boiling point becomes too low, which may cause a problem in the storage stability of the silver paste.

The organic protective colloid satisfying the above conditions is not particularly limited, but includes octylamine (boiling point 178 to 179 ° C.), 6-methyl-2-heptylamine (boiling point 154 to 156 ° C.), dibutylamine ( Boiling point 160-162 ° C), hexylamine (boiling point 130-132 ° C), dipropylamine (boiling point 105 ° C), diisopropylamine (boiling point 83-84 ° C), butylamine (boiling point 76-78 ° C), stearic acid (boiling point 232) 19.95 hPa), palmitic acid (boiling point 271.4 ° C; 133 hPa), myristic acid (boiling point 250 ° C; 133 hPa), lauric acid (boiling point 131 ° C; 1.3 hPa), octanoic acid (boiling point 238 ° C), hexane Acid (boiling point 206 ° C), butyric acid (boiling point 162-165 ° C), octadecadienoic acid (229-23) ° C.) can be exemplified a, except for using these alone, but can also be used in combination of two or more.

Among these, as the organic protective colloid, those containing an amine (amino group) are particularly preferable. By including amines, it is possible to obtain a high effect of protecting metal nanoparticles with an organic protective colloid, and the organic protective colloid does not remain during firing, and the organic residue has an adverse effect on the specific resistance. It is possible to prevent the effect.

The method of coating the surface of the metal nanoparticles with the organic protective colloid can adopt any method. For example, the surface of the metal nanoparticles can be prepared by making the organic protective colloid coexist when preparing the metal nanoparticles. Can be easily coated with an organic protective colloid. The coating amount of the metal nanoparticles with the organic protective colloid is not particularly limited, but is preferably set in the range of 1 to 40 parts by mass with respect to 100 parts by mass of the metal nanoparticles.

As the dispersion medium, one having a decomposition temperature or boiling point in the range of 70 to 250 ° C. is used, and the decomposition temperature or boiling point is a lower one of the decomposition temperature and the boiling point. If the decomposition temperature or boiling point of the dispersion medium exceeds 250 ° C., the dispersion medium cannot be decomposed or evaporated by low-temperature heat treatment, and low-temperature firing cannot be performed. If the decomposition temperature or boiling point of the dispersion medium is less than 70 ° C., the dispersion medium may decompose or evaporate during storage of the silver paste, which causes a problem in storage stability of the silver paste.

Further, as the dispersion medium, hydrocarbons having 3 to 18 carbon atoms are preferably used. If the carbon number is 19 or more, the decomposition temperature or boiling point becomes high, and there is a possibility that the dispersion medium cannot be decomposed or evaporated by low-temperature heat treatment, and if the carbon number is 2 or less, the decomposition temperature or The boiling point becomes too low, which may cause a problem in the storage stability of the silver paste.

Such a dispersion medium is not particularly limited, but myristyl alcohol (boiling point 167 ° C .; 20 hPa), lauryl alcohol (boiling point 258 to 265 ° C.), undecanol (boiling point 129 to 131 ° C .; 16 hPa), decanol ( Examples include boiling point 220 to 235 ° C., nonanol (boiling point 214 to 216 ° C.), octanol (boiling point 188 to 198 ° C.), and the like. These may be used alone or in combination of two or more. It is.

Among these, it is particularly preferable to use decanol as a dispersion medium. By using decanol as a dispersion medium, a silver paste suitable for drawing by screen printing or the like can be obtained.

The silver paste according to the present invention can be prepared by mixing and mixing the metal nanoparticles covered with the organic protective colloid, the silver filler, and the dispersion medium. Since the organic protective colloid covering the metal nanoparticles also serves as a binder, it is not necessary to add a binder. Therefore, a silver paste is prepared with only the three components of the metal nanoparticles, the silver filler, and the dispersion medium. It is something that can be done.

The amount of the dispersion medium in the silver paste varies depending on the silver paste application method, and is appropriately set so as to obtain viscosity and fluidity according to the application method.

The silver paste thus prepared can be applied to the surface of a substrate or the like by a conventionally known method such as screen printing, ink jet printing, dipping, applicator application, spin coat application. As described above, the organic protective colloid covering the metal nanoparticles also plays a role as a binder, so that a coating film can be formed by printing a silver paste without the need for blending a binder.

The dispersoid concentration when the metal fine particles are dispersed in a dispersion medium is 1% by mass or more and 80% by mass or less, and can be adjusted according to a desired film thickness of the conductive film. If it exceeds 80% by mass, aggregation tends to occur and it is difficult to obtain a uniform film.

(Catalyst ink)
For the catalyst ink, a catalyst ink containing a binder resin and an electroless plating catalyst is used. The electroless plating catalyst is not particularly limited as long as the metal can be grown by electroless plating, but precious metal colloidal particles are preferably used. As the noble metal colloidal particles, known catalyst particles used for electroless plating, for example, colloidal fine particles of noble metals such as palladium, gold, silver, and platinum can be used. Of these, palladium is a typical noble metal. When noble metal colloidal particles are used, it is desirable to use the noble metal colloidal particles supported on a catalyst carrier such as fine alumina gel or silica gel as particles having a surface charge opposite to that of the particles. By using the catalyst carrier, the precious metal colloidal particles are easily exposed on the surface of the catalyst ink pattern, and these catalyst carriers can give thixotropy to the catalyst ink, and the ink breaks at the contour of the image area. Sharpens and makes it difficult for bleeding and fatness to occur.

In addition, as the binder resin of the catalyst ink, for example, urethane resin such as two-component curable urethane resin, epoxy resin, acrylic resin, alkyd resin, polyester resin, or the like is used as one or two or more mixed resins. Further, the catalyst ink is composed of such a binder resin, an electroless plating catalyst composed of the above-mentioned noble metal, and an appropriate solvent. In addition to this, for the purpose of adjusting printability, etc. You may contain additives, such as a pigment, surfactant, and a coloring agent. As extender pigments, for example, powders such as calcium carbonate, barium sulfate, and silica are used. By adding a colorant, it is possible to easily check the quality of the catalyst ink pattern printed and formed in a pattern before electroless plating. A known colorant such as carbon black may be used as the colorant. Further, the catalyst ink may be any of organic solvent type, water type, emulsion type and the like.

[Plating treatment]
In the present invention, a plating treatment may be performed in order to increase conductivity. When the above-described plating catalyst is applied by an electrostatic ink jet method or a printing method, electroless plating is performed, or electrolytic plating is performed following electroless plating.

In the present invention, conventionally known various plating methods can be used for the plating treatment. For example, electrolytic plating and electroless plating can be carried out alone or in combination. As metals that can be used for plating, For example, copper, nickel, cobalt, tin, silver, gold, platinum, and other various alloys can be used. For example, electrolytic copper sulfate plating can be preferably used.

(Pressure or pressure heat treatment)
In the present invention, when higher smoothness is required or for the purpose of improving the conductivity of the mesh portion, it is also preferable to apply pressure or pressure heat treatment, and it is preferable to carry out at least before setting the transparent conductive film. . By this treatment, it is possible to smooth the resin surface of the upper part of the conductive metal pattern and the transparent window part, and further reduce the step between the conductive metal pattern and the resin of the transparent window part. It becomes. Furthermore, since the metal particle density of the conductive metal pattern portion is increased and the particle interface adhesion is improved, the conductivity can be improved.

In pressurization, the surface is pressed on the plate with the plate / surface pressurization, the nip roll pressurization is performed while passing the base film between the rolls, and the combined pressurization is performed on the plate with the roll. Can be adopted. The magnitude of the pressurization is arbitrarily possible in the range of 1 kPa to 100 MPa, preferably 10 kPa to 10 MPa, more preferably 50 kPa to 5 MPa. When the pressure is less than 1 kP, the effect of contact between the particles cannot be obtained, and when the pressure is 100 MPa or more, it is difficult to keep the surface smooth, and the haze increases. Further, since heating is effective when heated, it is preferable to heat in the range of 40 ° C to 300 ° C. In particular, for the smoothness of the resin surface of the translucent window portion and the reduction in the level difference with the metal pattern, it is preferable to heat to a temperature equal to or higher than the Tg of the resin. The heating time is adjusted in relation to the temperature and can be short at a high temperature and long at a low temperature. In the case of a nip roll, the heating method includes a method in which the roll is heated to a predetermined temperature in advance and a method in which heating is performed in a heating chamber such as an autoclave chamber. A method of laminating a plurality of samples of a predetermined size and heating them at a time is preferable because of high productivity.

〔Base material〕
The substrate used for the electrode for organic electronic devices of the present invention is preferably a transparent substrate. The transparent substrate is not particularly limited as long as it has high light transmittance. For example, a glass substrate, a resin substrate, a resin film, and the like are preferable in terms of excellent hardness as a base material and ease of formation of a conductive layer on the surface. From the viewpoint, it is preferable to use a transparent resin film.

The transparent resin film that can be preferably used as the transparent substrate in the present invention is not particularly limited, and the material, shape, structure, thickness and the like can be appropriately selected from known ones. For example, polyolefins such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyester resin film such as modified polyester, polyethylene (PE) resin film, polypropylene (PP) resin film, polystyrene resin film, cyclic olefin resin, etc. Resin films, vinyl resin films such as polyvinyl chloride and polyvinylidene chloride, polyether ether ketone (PEEK) resin films, polysulfone (PSF) resin films, polyether sulfone (PES) resin films, polycarbonate (PC) resin films , Polyamide resin film, polyimide resin film, acrylic resin film, triacetyl cellulose (TAC) resin film, and the like. If the resin film transmittance of 80% or more at 0 ~ 780 nm), can be preferably applied to a transparent resin film according 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 substrate 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. The easy adhesion layer may be a single layer, but may be composed of two or more layers in order to improve adhesion.

The electrode for organic electronic devices of the present invention can be used as an electrode for organic electronic devices. Hereinafter, the organic EL element will be described.

[Organic EL device]
In addition to the organic light emitting layer, the organic EL device of the present invention controls light emission in combination with an organic light emitting layer such as a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, a hole block layer, and an electron block layer. You may have a layer to do. Since the conductive polymer-containing layer 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.

Although the preferable specific example of a structure is shown below, this 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.

(Second electrode part)
The second electrode serves as a cathode in the organic EL element. The second electrode portion may be a single conductive material layer, but in addition to a conductive material, a resin that holds these may be used in combination. As the conductive material of the second electrode portion, a material having a small work function (4 eV or less) metal (referred to as an electron injecting metal), an alloy, an electrically conductive compound, and a mixture thereof 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, etc., a mixture of an electron injecting metal and a second metal which is a stable metal having a larger work function 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.

[Organic photoelectric conversion element]
The organic photoelectric conversion element has a structure in which a first electrode part, 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 part 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 like 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, thiophene hexamer α-seccithiophene α, ω-dihexyl-α-sexualthiophene, 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 those described in J. Org. Amer. Chem. Soc. , Vol. 123, p9482; Amer. Chem. Soc. , Vol. 130 (2008), no. Acene-based compounds substituted with trialkylsilylethynyl groups described in US Pat. No. 9,2706, etc., pentacene precursors 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. Of these, compounds that cause a chemical 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 material 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, the photoelectric conversion material is preferably sealed by a known method so as not to be deteriorated by oxygen, moisture, etc. in the environment.

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.

(Production of organic electronic device electrode D001)
A polyethylene naphthalate film having a film thickness of 125 μm (manufactured by Teijin DuPont Films Ltd., extremely low heat yield PEN Q83) was cut into 4 cm × 4 cm. The following <Easily Adhesive Layer Coating Solution-1> is applied as an easy-adhesion layer by a spin coater with the rotational speed adjusted to a dry film thickness of 50 nm, and subjected to a heat treatment at 110 ° C. for 3 minutes. A finished substrate was obtained.

<Easily adhesive layer coating solution-1>
Bironal MD1200 (Toyobo Co., Ltd.) 0.6g
4.7 g of H ₂ O
Isopropyl alcohol 4.7g
Inkjet silver nanopaste NPS-JL (manufactured by Harima Kasei Co., Ltd.) has a pressure applying means and an electric field applying means as an ink jet recording head. 1 represents the number of dots per inch, that is, 2.54 cm), and loaded on an ink jet printing apparatus equipped with a piezo-type head, and printed on the easily contacted substrate as shown in FIG.

(1) and (4) in FIG. 1 are used as extraction electrodes with a silver solid portion of 1.2 cm × 5 mm. (2) in FIG. 1 is in contact with (1) at a metal mesh pattern portion having a line width of 50 μm and a line interval of 950 μm printed in a range of 1.2 cm × 1.2 cm. (3) is a 1.2 cm × 2 mm silver-free portion. The formed fine metal wire pattern was heat-treated at 130 ° C. for 60 minutes. The height of the metal fine wire pattern from the base material (hereinafter referred to as metal fine wire height) was 600 nm.

Next, using an applicator having a coating width of 1.2 cm and a gap interval of 100 μm, passing over the metal fine line pattern of FIG. 1 (2) at a speed of 110 cm / min, the (5) of FIG. The following conductive polymer containing coating liquid 1 was apply | coated to the area | region. Dry the coated polymer sample for 1 minute with hot air at 80 ° C, and remove the conductive polymer-containing layer by wiping and removing the area without the fine metal wire pattern (area other than (2)) with pure water (2) A conductive polymer-containing layer was provided in the region ((5 ′) in FIG. 3). Further, heat treatment was performed for 30 minutes in an oven at 130 ° C. to obtain an organic electronic device electrode D001.

The film thickness of the conductive polymer-containing layer on the portion of the obtained organic electronic device electrode where the fine metal wire pattern is located (hereinafter referred to as the thickness of the fine metal wire portion) is 200 nm. The film thickness of the conductive polymer-containing layer in the portion not present (hereinafter referred to as the film thickness of the metal-free portion) was 500 nm.

Conductive polymer-containing coating solution 1
PEDOT-PSS CLEVIOS PH510
(Solid content 1.89%) (manufactured by HC Starck) 1.59 g
Polyhydroxyethyl acrylate (Synthesis Example 2, 20% solid content aqueous solution)
0.35g
Dimethyl sulfoxide (DMSO) 0.08g
"Synthesis of initiators"
Synthesis example 1
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.

"Synthesis of water-soluble polymer resin by living polymerization (ATRP)"
Synthesis Example 2 (Synthesis of poly (2-hydroxyethyl acrylate))
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, and the pressure was reduced. The Schlenk tube was immersed in the lower liquid nitrogen 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 polymer resin 1 having a number average molecular weight of 13100, a molecular weight distribution of 1.17, and a content of number average molecular weight <1000 of 0% was obtained.

The structure and number average 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
(Production of organic electronic device electrode D002)
An organic electronic device electrode D002 was prepared in the same manner except that when the organic electronic device electrode D001 was produced, the applicator speed was changed to 125 cm / min and the amount of the conductive polymer-containing coating solution 1 was increased.

(Preparation of electrodes D003 to D005 for organic electronic devices)
During the production of the organic electronic device electrode D002, pure water is added to the conductive polymer-containing coating solution 1 to reduce the solid content by 10%, 20%, 30%, respectively, thereby reducing the viscosity of the coating solution, In the same manner, except that the film thickness of the metal-free portion is not changed by increasing the speed of the applicator, the thickness of the metal-free portion is the same, and the electrode D003 for organic electronic devices having a different thickness of the metal thin wire portion is different. , D004 and D005 were produced.

(Preparation of electrodes D006 to D008 for organic electronic devices)
Conductive polymer-containing coating in which the viscosity of the coating solution is increased by changing polyhydroxyethyl acrylate to polyhydroxyethyl acrylate with a solid content of 40% by weight and a number average molecular weight of about 100,000 when producing electrode D001 for organic electronic devices Except for using liquid 2 and changing the applicator speeds to 120 cm / min, 130 cm / min, and 140 cm / min, respectively, to increase both the thickness of the metal-free portion and the thickness of the thin metal wire portion. Similarly, electrodes D006 to D008 for organic electronic devices were produced.

(Preparation of organic electronic device electrodes D009 to D011)
PEDOT-PSS in which the solid content is increased to 2.64 mass% by placing PH510 (manufactured by HC Starck) under vacuum in the conductive polymer-containing coating liquid 1 in the conductive polymer-containing coating liquid 1. In addition, by using the electropolymer-containing coating solution 3 excluding polyhydroxyethyl acrylate, and changing the applicator speed to 140 cm / min, 120 cm / min, and 115 cm / min, otherwise, for organic electronic devices Organic electronic device electrodes D009 to D011 were fabricated in the same manner as the electrode D001.

(Preparation of electrode D012 for organic electronic devices)
From D011, the ink discharge amount of the ink jet is increased, the height of the fine metal wire pattern is increased to 800 nm, and the applicator speed is changed to 105 cm / min. An organic electronic device electrode D012 was produced in the same manner except that the amount was lowered.

(Preparation of electrode D013 for organic electronic devices)
In D012, the electrode D013 for organic electronic devices was produced by changing to the coating liquid 2 containing a conductive polymer and changing the applicator speed to 80 cm / min.

(Preparation of electrode D014 for organic electronic devices)
In D013, except that the solid content was reduced by adding 30% of pure water to the conductive polymer-containing coating solution 2 and the speed of the applicator was increased so that the film thickness of the metal-free portion was not changed. Thus, an organic electronic device electrode D014 was produced.

(Preparation of organic electronic device electrodes D015 to D017)
When producing the electrode D013 for organic electronic devices, the height of the metal fine wire pattern is changed by increasing the ink ejection amount of the ink jet, and the solid content is reduced by adding 30% of pure water to the conductive polymer-containing coating solution 2 Further, an organic electronic device electrode D015 was produced in the same manner except that the applicator speed was increased so that the film thickness of the metal-free portion was not changed.

Further, D016 was produced in the same manner as D015 except that the height of the metal fine line pattern was changed by increasing the ink discharge amount of the inkjet. Further, when the organic electronic device electrode D016 was manufactured, the speed of the applicator was increased so that the film thickness of the metal-free portion became the value shown in Table 1, and D017 was manufactured.

(Production of organic electronic device electrodes D018 and D019)
When producing the organic electronic device electrode D001, the ink discharge amount of the ink jet is decreased to change the height of the fine metal wire pattern, and the speed of the applicator is changed to 90 cm / min. Organic electronic device electrodes D018 and D019 were produced in the same manner except that the attached amount of was reduced.

(Preparation of electrode D020 for organic electronic devices)
An organic electronic device electrode D001 was prepared except that a silver fine particle paste MDot-SLP manufactured by Mitsuboshi Belting Co., Ltd. was gravure printed using a K303 multicoater manufactured by Matsuo Sangyo Co., Ltd. In the same manner, an electrode D020 for organic electronic devices was produced.

(Preparation of organic electronic device electrode D021)
Upon production of the electrode D001 for an organic electronic device, the pattern of the fine metal wire was gravure-printed with the following <electroless plating catalyst-containing ink>, and subsequently subjected to electroless copper plating at 45 ° C. using the following <electroless plating solution> An organic electronic device electrode D021 was produced in the same manner as the organic electronic device electrode D001 except that the plating was performed.

<Catalyst-containing ink for electroless plating>
0.03 parts by mass of potassium chloride is dissolved in 100 parts by mass of water with stirring, and 0.015 parts by mass of palladium chloride is further dissolved therein. After adding 0.06 part by mass of trisodium citrate to the obtained palladium ion-containing aqueous solution and dissolving it, an aqueous solution in which 0.003 part by mass of sodium borohydride was further dissolved with respect to 10 parts by mass of water. Was added to obtain a palladium colloid dispersion. This palladium colloidal solution was desalted by ultrafiltration, and 5 parts by mass of alumina was added to the filtered colloidal solution, and the heteroaggregated and precipitated portion was filtered and crushed to obtain alumina-supported palladium particles. Next, 8 parts by mass of ethyl cellulose resin was dissolved in 100 parts by mass of toluene, and 1 part by mass of the palladium particles prepared earlier was added to the liquid to obtain a catalyst-containing ink for electroless plating.

<Electroless plating solution>
Copper sulfate 0.04 mol Formaldehyde (37%) 0.08 mol Sodium hydroxide 0.10 mol Triethanolamine 0.05 mol Polyethylene glycol 100 ppm
Add water to bring the total volume to 1 liter.

(Preparation of electrode D022 for organic electronic devices)
An organic electronic device electrode D022 was prepared in the same manner as the organic electronic device electrode D001, except that when the organic electronic device electrode D001 was produced, the fine metal wire pattern was a line having a line width of 50 μm and a line interval of 950 μm.

(Preparation of electrode D030 for organic electronic devices)
The following solution A was kept at 34 ° C. in a reaction vessel, and the pH was adjusted to 2.95 using nitric acid (concentration 6%) while stirring at high speed using a mixing and stirring apparatus described in JP-A-62-160128. It was adjusted. Subsequently, the following solution B and the following solution C were added at a constant flow rate over 8 minutes and 6 seconds using the double jet method. After completion of the addition, the pH was adjusted to 5.90 using sodium carbonate (concentration 5%), and then the following solution D and solution E were added.

(Solution A)
Alkali-treated inert gelatin (average molecular weight 100,000) 18.7g
Sodium chloride 0.31g
Solution I (below) 1.59ml
Pure water 1246ml
(Solution B)
169.9g of silver nitrate
Nitric acid (concentration 6%) 5.89ml
Finish to 317.1 ml with pure water.

(Solution C)
Alkali-treated inert gelatin (average molecular weight 100,000) 5.66 g
Sodium chloride 58.8g
13.3 g of potassium bromide
Solution I (below) 0.85ml
Solution II (below) 2.72 ml
Finish to 317.1 ml with pure water.

(Solution D)
2-Methyl-4-hydroxy-1,3,3a, 7-tetraazaindene 0.56 g
112.1 ml of pure water
(Solution E)
Alkali-treated inert gelatin (average molecular weight 100,000) 3.96 g
Solution I (below) 0.40ml
128.5 ml of pure water
(Solution I)
Surfactant: 10% by weight methanol solution of polyisopropylene polyethylene oxydisuccinate sodium salt (Solution II)
10% by weight aqueous solution of rhodium hexachloride complex After the above operation is completed, desalting and water washing are performed using a flocculation method at 40 ° C. according to a conventional method. The pH was adjusted to 5.90 at 40 ° C., and finally a silver chlorobromide cubic grain emulsion containing 10 mol% of silver bromide and having an average grain size of 0.09 μm and a coefficient of variation of 10% was obtained.

(Solution F)
Alkali-treated inert gelatin (average molecular weight 100,000) 16.5g
Pure water 139.8ml
The silver halide emulsion was chemically sensitized with 20 mg of sodium thiosulfate per mole of silver halide at 40 ° C. for 80 minutes, and 4-hydroxy-6-methyl-1,3, after completion of chemical sensitization. 500 mg of 3a, 7-tetrazaindene (TAI) per mol of silver halide and 150 mg of 1-phenyl-5-mercaptotetrazole per mol of silver halide were added to obtain a silver halide emulsion EM-1. In this silver halide emulsion EM-1, the volume ratio of silver halide grains to gelatin (silver halide grains / gelatin) was 0.625. Further, a hardening agent (H-1: tetrakis (vinylsulfonylmethyl) methane) was added at a ratio of 200 mg per 1 g of gelatin, and a surfactant (SU-2: sulfosuccinate disulfate) was applied as a coating aid. (2-ethylhexyl) .sodium) was added to adjust the surface tension. The coating solution thus obtained was applied on one side of the substrate, and then cured at 50 ° C. for 24 hours.

The substrate prepared as described above is exposed using an ultraviolet lamp through a 1 cm square grid photomask having a line width of 6 μm and a distance between lines of 244 μm, and the following developer ( After developing for 60 seconds at 25 ° C. using DEV-1), the fixing treatment for 120 seconds was performed at 25 ° C. using the following fixer (FIX-1). Further, physical development was performed at 25 ° C. for 10 minutes using the following physical developer (PDEV-1), followed by washing with water and drying treatment to form a fine metal wire pattern. Thereafter, an electrode D030 was prepared in the same manner as the electrode D012 for an organic electronic device.

(DEV-1)
500 ml of pure water
Metol 2g
80 g of anhydrous sodium sulfite
Hydroquinone 4g
4g borax
Sodium thiosulfate 10g
Potassium bromide 0.5g
Add water to bring the total volume to 1 liter.

(FIX-1)
750 ml of pure water
Sodium thiosulfate 250g
Anhydrous sodium sulfite 15g
Glacial acetic acid 15ml
Potash alum 15g
Add water to bring the total volume to 1 liter.

(PDEV-1)
The following A liquid and B liquid are mixed immediately before a process.

(Liquid A)
400ml of pure water
Citric acid 10g
Disodium hydrogen phosphate 1g
Ammonia water (28% aqueous solution) 1.2ml
Hydroquinone 3g
(Liquid B)
10ml of pure water
0.4 g of silver nitrate
(Preparation of electrode D031 for organic electronic devices)
The aluminum fine wire pattern was vapor-deposited on the substrate by vacuum vapor deposition in the region of the fine metal wire pattern 2 in FIG. 1 so as to have the same pattern as D001 with a width of 5 microns and a height of 2.5 μm. Further, aluminum was uniformly deposited on the entire surface of the

extraction electrodes

1 and 4 in FIG. 1 so as to have a height of 2.5 μm. Next, instead of the conductive polymer-containing layer, an ITO layer as a transparent conductive film layer is deposited uniformly on the entire surface of the area where the pattern of the aluminum thin wire is deposited by sputtering to a thickness of 40 nm, thereby forming an electrode D031 for organic electronic devices. Was made.

In D031, the film thickness and level difference of the conductive polymer-containing layer were obtained in the same manner by replacing the ITO layer with the conductive polymer-containing layer.

(Preparation of electrode D032 for organic electronic devices)
On one side of a 100 μm thick polyethylene terephthalate film support with a 50 nm thick silicon nitride film formed on both sides, a 30 μm thick UV curable resin (UVPOT Medium 0, manufactured by Teikoku Inc.) is used as an adhesive layer. Then, an adhesive substrate was produced.

The produced adhesive substrate and the metallic silver pattern produced in the same manner as D030 were pressure-bonded so that the adhesive layer and the metallic silver pattern faced to form a laminate. Next, ultraviolet rays were irradiated from the adhesive substrate side to cure the ultraviolet curable resin, and the adhesive substrate and the metal silver pattern were joined.

The bonded adhesive substrate and the metal silver pattern were immersed in the following enzyme solution at 40 ° C. for 5 minutes, washed with water and dried. The pH of the enzyme solution was 7.0.

(Enzyme solution)
900ml water
7.4 g of 85% orthophosphoric acid
20g triethanolamine
Proteolytic enzyme * 2g
Add water to bring the total volume to 1000 ml.

* Bacterial proteinase: Nagase Sangyo Co., Ltd. Biolase AL15
After the enzyme solution treatment, the polyethylene terephthalate film support on the metal silver pattern side was peeled off to produce a metal silver pattern. The metallic silver pattern was embedded in the adhesive substrate and was smooth. Thereafter, an electrode D032 for organic electronic device was manufactured in the same manner as the electrode D012 for organic electronic device.

Table 1 shows the metal wire height, the metal wire portion thickness, and the metal-free portion film thickness of the organic electronic device electrodes D002 to D022 and D030 to D032 obtained as described above. When the conductive polymer-containing coating solution 1 is applied, since the viscosity of the coating solution is low, the coating solution flows from the metal thin wire portion having a high height to the portion having no metal having a low height. It became the number of.

The obtained organic electronic device electrodes D001 to D022 and D030 to D032 were used as electrodes of organic EL elements.

(Preparation of organic EL element 1)
The obtained organic electronic device electrode D001 was formed as the organic EL element 1 by forming the following layers on the metal fine wire pattern.

<Formation of hole injection layer>
PEDOT-PSS CLEVIOS P AI 4083 (solid content 1.5%) (manufactured by HC Starck) was made into the same region as the conductive polymer-containing coating solution using a bar coater with a gap gap of 40 μm, and the dry film thickness Was applied to a thickness of 30 nm, and unnecessary areas were wiped off in the same manner as the conductive polymer-containing coating solution. Further, heat treatment was performed at 130 ° C. for 30 minutes on a hot plate to form a hole injection layer.

<Formation of hole transport layer>
Each of the vapor deposition crucibles in a commercially available vacuum vapor deposition apparatus was filled with the optimum amount of the constituent material of each layer for device fabrication. The evaporation crucible used was made of a resistance heating material made of molybdenum or tungsten.

After depressurizing to a vacuum of 1 × 10 ⁻⁴ Pa, the deposition crucible containing compound 1 was energized and heated, and deposited at a deposition rate of 0.1 nm / second on a region with a pattern of fine metal wires. A hole transport layer was provided.

<Formation of light emitting layer>
Next, each light emitting layer was provided in the following procedures.

On the formed hole transport layer, the compound 2, the compound 3 and the compound 5 were deposited at a deposition rate of 0.1 nm / second so that the concentration of the compound 2 was 13% by mass and the compound 3 was 3.7% by mass. A green-red phosphorescent light emitting layer having a maximum emission wavelength of 622 nm and a thickness of 10 nm was formed by co-evaporation in a region having the above pattern.

Next, the compound 4 and the compound 5 are co-deposited on a region having a pattern of fine metal wires at a deposition rate of 0.1 nm / second so that the compound 4 becomes 10% by mass, and a blue light having a maximum emission wavelength of 471 nm and a thickness of 15 nm. A phosphorescent light emitting layer was formed.

<Formation of hole blocking layer>
Further, the hole blocking layer was formed by depositing the compound 6 in a film thickness of 5 nm on the formed light emitting layer in a region having a pattern of fine metal wires.

<Formation of electron transport layer>
Subsequently, on the formed hole blocking layer, CsF was co-evaporated with compound 6 so as to have a film thickness ratio of 10% in a region having a fine metal wire pattern, thereby forming an electron transport layer having a thickness of 45 nm.

<Formation of cathode electrode>
On the formed electron transport layer, Al was evaporated in a region of 6 (1.0 × 1.4 cm) in FIG. 4 under a vacuum of 5 × 10 ⁻⁴ Pa to form a cathode electrode having a thickness of 100 nm. Thus, an organic EL element 1 was produced.

In addition, the organic EL element was subjected to the subsequent evaluation under nitrogen without being exposed to the atmosphere even after vapor deposition.

(Preparation of organic EL elements 2 to 32)
In the same manner as in the organic EL element 1, the organic electronic device electrodes 1 were changed to the organic electronic device electrodes D002 to D022 and D030 to D032, and organic EL elements 2 to 22 and 30 to 32 were produced.

(EL element evaluation)
About each obtained organic EL element, DC voltage was applied and light-emitted at 1000 cd / m < ² > using the source measure unit 2400 type made from KEITHLEY.

(Rectification ratio)
Inverts the plus or minus of the applied voltage. The rectification ratio was defined as (absolute value of current during light emission) / (absolute value of current during inversion). This ratio decreases if there is an influence of foreign matter or protrusions, or if the level difference at the grid portion is too large. When this ratio is 1, the leakage state is complete, and the EL element is preferably 100 or more, more preferably 1000 or more. The following indicators were used for evaluation.

4: 1000 or more 3: 500 or more and less than 1000 2: 100 or more and less than 500 1: 100 or less (light emission unevenness)
The light emission state was observed visually and with a 50 × optical microscope, and evaluated with the following indices. Level 2 is the minimum and 3 or more is preferable.

4: Even the optical microscope appears to emit light uniformly over the entire surface 3: The optical microscope shows that the periphery of the pattern part of the fine metal wire is brighter than the others, but the whole surface appears to emit light uniformly 2: The entire surface emits light However, it can be seen by visual observation that the peripheral part of the pattern part of the fine metal wire is high in luminance. 1: Only the peripheral part of the pattern part of the fine metal wire emits light. Luminous (luminous efficiency)
Using a KEITHLEY source measure unit 2400 type, the luminous efficiency (lumen / W) when a direct current voltage was applied and light was emitted at 300 cd was measured, and evaluated according to the following index at the level with respect to the luminous efficiency of the organic EL element 32. .

3: Improvement range 15% or more 2: Improvement range 10% or more and less than 15% 1: Improvement range 3% or more and 10% or less 0: Improvement range 3% or less

It can be seen that the organic EL element using the electrode of the present invention has improved luminous efficiency without breaking performance such as rectification ratio and uneven emission.

In particular, an electrode in which a step between the outermost surface of the conductive polymer-containing layer on the portion with the fine metal wire pattern and the outermost surface of the conductive polymer-containing layer on the portion without the fine metal wire pattern is 150 nm or more and 600 nm or less It can be seen that the light emission efficiency is improved without using light emission unevenness.

In addition, it can be seen that when the film thickness of the conductive polymer-containing layer in the portion without the metal fine line pattern exceeds 1500 nm, the improvement width of the light emission efficiency slightly decreases, and when the thickness is less than 200 nm, the rectification ratio decreases. I can see it coming.

It can be seen that when the conductive polymer-containing layer further contains a water-soluble polymer, the rectification ratio can be improved without reducing the improvement in luminous efficiency.

DESCRIPTION OF

SYMBOLS

1, 4 Extraction electrode 2 Metal fine wire pattern 3 Blank part 5, 5 'Conductive polymer content layer 6 Cathode electrode 10 Electrode for organic electronic devices

Claims

An electrode for an organic electronic device in which a pattern of a conductive fine metal wire is provided on a substrate and a conductive polymer-containing layer is further provided thereon, and a film of the conductive polymer-containing layer on the portion where the fine metal wire is provided The surface of the conductive polymer-containing layer having a thickness of 100 nm to 2000 nm and on the portion with the fine metal wire, and the conductive polymer in the portion without the fine metal wire in the region provided with the pattern of the fine metal wire An electrode for an organic electronic device, wherein a step with respect to the surface of the containing layer is 100 nm or more and 800 nm or less.
The level difference between the outermost surface of the conductive polymer-containing layer above the portion with the fine metal wire and the outermost surface of the conductive polymer-containing layer at the portion without the metal fine wire pattern is 150 nm or more and 600 nm or less, The electrode for organic electronic devices according to claim 1.
The electrode for an organic electronic device according to claim 1 or 2, wherein a film thickness of the conductive polymer-containing layer in a portion without the thin metal wire is 200 nm or more and 1500 nm or less.
The electrode for organic electronic devices according to any one of claims 1 to 3, wherein the height from the base material surface of the outermost surface of the fine metal wire is 200 nm or more and 2000 nm or less.
The electrode for organic electronic devices according to any one of claims 1 to 4, wherein the conductive polymer-containing layer further contains a water-soluble polymer.
The said water-soluble polymer is the following polymer (A), The electrode for organic electronic devices of Claim 5 characterized by the above-mentioned.

(Wherein X 1 , X 2 and X 3 each independently represents a hydrogen atom or a methyl group, and R 1 , R 2 and R 3 each independently represents an alkylene group having 5 or less carbon atoms. , M, and n represent the composition ratio (mol%), where 50 ≦ l + m + n ≦ 100, and l, m, and n are 0 to 100, respectively.
The organic electronic device electrode according to any one of claims 1 to 6, wherein the pattern of the fine metal wires and the conductive polymer-containing layer are formed by a wet film forming method.