JP6032271B2 - Method for producing transparent electrode and method for producing organic electronic device - Google Patents

Description

  The present invention relates to a method for producing a transparent electrode, a transparent electrode, and an organic electronic element used in an organic electronic device such as an organic EL (electroluminescence) element and a solar cell using the transparent electrode.

  In recent years, organic electronic devices such as organic EL elements and organic solar cells have attracted attention, and in such devices, transparent electrodes have become an essential constituent technology.

  In organic electronic devices, there is an increasing demand for an increase in area. In the case of transparent electrodes such as ITO and conductive polymers that have been used in the past, the film formation cost is drastically increased especially in large-area applications where low surface resistance is required, and practically low enough Obtaining surface resistance is very difficult.

  In order to achieve both current surface uniformity and conductivity, a transparent electrode is disclosed in which a transparent conductive film of indium tin oxide (ITO) and a metal conductive layer formed in a pattern are combined (for example, Patent Documents) 1), no mention is made of organic electronic devices that require high smoothness.

  Moreover, in order to improve the transparency of the transparent electrode which combined the transparent conductive film and the metal conductive layer, it is essential to refine the metal conductive layer pattern. When forming a miniaturized metal conductive pattern, for example, a patterning method by etching using a photolithography method, or after exposing and developing a photosensitive material having a silver salt-containing layer, a plating process is performed to form a metal conductive pattern (For example, refer to Patent Document 2). However, the photolithography method and the silver salt method are costly and have a problem that the process is complicated.

Therefore, as a simple method for forming a conductive pattern at a low cost, a method of directly forming a metal conductive pattern that has been miniaturized by a printing method has recently been attracting attention. The formation of the conductive pattern by the printing method has a feature that the process is simple and can be performed at low cost.
In the formation of a conductive pattern by a printing method, a method of forming a conductive pattern with an ink containing a conductor such as metal nanoparticles on a substrate on which the conductive pattern is formed is employed. The conductivity of the conductive pattern is improved by heating and baking at a high temperature.

  In order to give flexibility to organic electronic devices, films such as PET (polyethylene terephthalate) and PEN (polyethylene naphthalate) are used for the substrate, but in order not to damage the substrate, the conductive material formed from metal nanoparticles. It is known that a fine metal wire pattern is fired by local heating. For example, an example of firing by irradiation with pulsed light (flash) is disclosed (for example, see Patent Document 3).

JP 2005-302508 A JP 2006-352073 A Special table 2008-522369

  However, if the accumulated energy of the pulsed light (that is, the product of the illuminance of the pulsed light and the pulse width) is increased in order to make the resistance value of the fine metal wire pattern sufficiently low, surface irregularities and disconnections will occur in the fine metal wire pattern. Defects such as disappearance due to ablation occur, or if the fine metal wire pattern is baked on the resin substrate, the resin substrate surface may be deformed or melted along the fine metal wire pattern, resulting in defects such as the substrate. Therefore, it was difficult to obtain a sufficient effect even if the resistance value was reduced.

In addition, as described above, it is included in the metal wire pattern before firing as one of the causes of defects such as surface irregularities, disconnection, disappearance due to ablation, etc. in the metal wire pattern generated when the accumulated energy of pulsed light is increased It is mentioned that the solvent to be evaporated rapidly evaporates and diffuses simultaneously with the irradiation (firing) of pulsed light.
Therefore, as a means for preventing defects in the fine metal line pattern, it is conceivable to heat and dry the fine metal line pattern prior to firing by irradiation with pulsed light. Heating and drying at a high temperature in order to sufficiently remove the high-boiling organic solvent necessary for the enhancement may cause deformation of the substrate when using a resin substrate, particularly a relatively inexpensive PET film, PEN film or the like. is there. Therefore, it is actually difficult to heat and dry at high temperature in order to avoid substrate deformation.

  Furthermore, as a method for achieving a reduction in resistance while preventing the defects of the fine metal line pattern and the substrate described above, it is also known that the pulsed light irradiation is divided into a plurality of times and firing is performed a plurality of times. (For example, refer to Patent Document 3) However, in these methods of irradiating pulsed light of the same energy a plurality of times, the effect of lowering resistance almost reaches its peak by the first pulsed light irradiation, and the pulsed light irradiation is performed a plurality of times. It is considered difficult to obtain the effect of lowering resistance even if it is divided.

  Therefore, the main object of the present invention is to provide a method for producing a transparent electrode capable of reducing the resistance value while preventing defects in the fine metal wire pattern and the substrate.

In order to solve the above-mentioned problems, the present inventor has examined the cause of the above-mentioned problem and the like. As a result, firing by light irradiation of the fine metal wire pattern is performed by preliminary firing (first firing step) and main firing (second firing step). ) And the firing is performed so that the integrated energy of the irradiation light in the first baking step is larger than the integrated energy of the irradiation light in the second baking step, so that the defects of the metal fine line pattern described above are obtained. And found that resistance can be reduced while preventing defects in the substrate.
This is because it is possible to form a situation in which the solvent contained in the fine metal wire pattern is removed in the pre-firing, and the integrated energy of the irradiation light in the pre-firing is an amount of energy that can be expected to reduce the resistance. Since the amount of energy is relatively low and has not reached, it is assumed that defects in the metal fine line pattern due to rapid solvent evaporation / diffusion are unlikely to occur.

  Further, by performing the second firing process (light irradiation), which is positioned as the main firing in a situation where the residual solvent in the metal fine wire pattern is reduced by the pre-firing, integration of irradiation light in the second firing process is performed. In energy, the efficiency used to fuse metal nanoparticles is expected to increase. Therefore, the integrated energy of the irradiation light in the second baking step is more efficient than the case where baking is performed with a single pulse light so far, that is, the effect of lowering resistance is obtained with lower energy. In addition, since the energy is lower, it is assumed that defects in the substrate are less likely to occur.

  Further, in the method for producing a transparent electrode in which the light irradiation processes in the first baking step and the second baking step are each composed of one or a plurality of times of pulsed light, the integrated energy in the first baking step is maximum. E-P1m (max) is the integrated energy amount of a single pulse, and E-P2m (max) is the single pulse integrated energy amount that maximizes the integrated energy in the second firing process. It has been found that the above-described effect is further increased by performing firing by light irradiation so that the value of P2m (max) / E-P1m (max) is 1.5 or more.

That is, the above-mentioned problem according to the present invention is solved by the following means:
According to the present invention,
In the method for producing a transparent electrode having a transparent substrate and a conductive fine metal wire pattern,
Forming the metal fine line pattern with metal nanoparticles on the transparent substrate;
A step of firing the fine metal wire pattern by light irradiation,
In the step of firing the fine metal wire pattern,
A first firing step of pre-firing the metal fine wire pattern;
A second firing step of subjecting the fine metal wire pattern to a main firing,
The integrated energy of the irradiation light in the second baking step is larger than the integrated energy of the irradiation light in the first baking step ;
Furthermore, in the first baking step and the second baking step, the light irradiation of each step is constituted by one or a plurality of times of pulsed light,
The integrated energy amount of a single pulse that maximizes the integrated energy in the first firing step is E-P1m (max),
When the accumulated energy amount of a single pulse that maximizes the accumulated energy in the second firing step is E-P2m (max),
E-P2m (max)> E-P1m (max)
A method for producing a transparent electrode is provided.

Preferably ,
The value of E−P2m (max) / E−P1m (max) is preferably 1.5 or more and 40 or less.

  ADVANTAGE OF THE INVENTION According to this invention, resistance value can be reduced, preventing a metal fine line pattern and a board | substrate from producing a defect.

It is drawing for demonstrating schematically the content of the process of baking a metal fine wire pattern by light irradiation.

  Hereinafter, the present invention, its components, and modes and modes for carrying out the present invention will be described in detail. In addition, in this application, "-" which shows a numerical range is used in the meaning which includes the numerical value described before and behind that as a lower limit and an upper limit.

The transparent electrode according to a preferred embodiment of the present invention has at least a transparent substrate and a conductive fine metal wire pattern, and the fine metal wire pattern is formed on the transparent substrate. In the transparent electrode, a conductive polymer layer is preferably formed on the fine metal wire pattern.
Hereinafter, the configuration and characteristics of each member of the transparent electrode, the manufacturing method, and the like will be described.

[Transparent substrate]
The transparent substrate used for the transparent electrode of the present invention is not particularly limited as long as it is a resin substrate having high light transparency. For example, although a resin substrate and a resin film are mentioned suitably, it is preferable to use a transparent resin film from a viewpoint of productivity, a viewpoint of performance, such as lightness and a softness | flexibility.

  There is no restriction | limiting in particular in the transparent resin film which can be used preferably, About the material, a shape, a structure, thickness, etc., it can select suitably from well-known things. 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 in 80~780nm), can be preferably applied to a transparent resin film according to the present invention. Among them, biaxial stretching of biaxially stretched polyethylene terephthalate resin film, biaxially stretched polyethylene naphthalate resin film, polyethersulfone resin film, polycarbonate resin film, etc. from the viewpoint of transparency, heat resistance, ease of handling, strength and cost It is preferably a polyester resin film, more preferably a biaxially stretched polyethylene terephthalate resin film or a biaxially stretched polyethylene naphthalate resin film.

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 adhesiveness 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.
Examples of the easy adhesion layer include polyester, polyamide, polyurethane, vinyl copolymer, butadiene copolymer, acrylic copolymer, vinylidene copolymer, and epoxy copolymer. The easy adhesion layer may be a single layer, but may be composed of two or more layers in order to improve adhesion.

In addition, an inorganic or organic film or a hybrid film of both may be formed on the front or back surface of the transparent substrate, and the water vapor transmission rate (25 ± 0) measured by a method according to JIS K 7129-1992. .5 ° C., relative humidity (90 ± 2)% RH) is preferably a barrier film of 1 × 10 ⁻³ g / (m ² · 24 h) or less, and further conforms to JIS K 7126-1987. The oxygen permeability measured by the above method is 1 × 10 ⁻³ ml / m ² · 24 h · atm or less (1 atm is 1.01325 × 10 ⁵ Pa), water vapor permeability (25 ± 0.5 ° C. , Relative humidity (90 ± 2)% RH) is preferably a high barrier film having 1 × 10 ⁻³ g / (m ² · 24 h) or less.

  As a material for forming a barrier film formed on the front or back surface of the film substrate in order to obtain a high barrier film, any material may be used as long as it has a function of suppressing intrusion of elements that cause deterioration of elements such as moisture and oxygen. For example, silicon oxide, silicon dioxide, silicon nitride, or the like can be used. Further, in order to improve the brittleness of the film, it is more preferable to have a laminated structure of these inorganic layers and organic material layers. Although there is no restriction | limiting in particular about the lamination | stacking order of an inorganic layer and an organic layer, It is preferable to laminate | stack both alternately several times.

[Metallic fine wire pattern]
The fine metal wire pattern of the present invention is formed from metal nanoparticles.
The metal material of the metal nanoparticles is not particularly limited as long as it has excellent conductivity. For example, an alloy other than a metal such as gold, silver, copper, iron, nickel, and chromium may be used. Silver is preferred from the viewpoint.

  Here, the average particle size of the metal nanoparticles is preferably 1 nm to 100 nm, more preferably 1 nm to 50 nm, and even more preferably 1 nm to 30 nm.

  The average particle diameter of the metal nanoparticles in the present invention is determined by observing 200 or more metal nanoparticles that can be observed as a circle, an ellipse, or a substantially circle or ellipse at random from an electron microscope observation of the metal nanoparticles. It is obtained by determining the particle size of the nanoparticles and determining the number average value thereof. Here, the average particle diameter according to the present invention refers to the minimum distance among the distances between the outer edges of the metal nanoparticles that can be observed as a circle, an ellipse, or a substantially circle or ellipse, between two parallel lines. . When measuring the average particle diameter, the ones that clearly represent the side surfaces of the metal nanoparticles are not measured.

  The pattern shape of the fine metal wire pattern in the present invention is not particularly limited. For example, the pattern shape may be a stripe shape or a mesh shape, but the aperture ratio is preferably 80% or more from the viewpoint of transparency. . An aperture ratio is the ratio which the electroconductive part which has translucency accounts to the whole. For example, when the light-impermeable metal fine line pattern has a stripe shape, the aperture ratio of the stripe pattern having a line width of 100 μm and a line interval of 1 mm is about 90%. The line width of the pattern is preferably 10 to 200 μm. When the line width of the thin wire is 10 μm or more, desired conductivity is obtained, and when it is 200 μm or less, sufficient transparency as a transparent electrode is obtained. The height of the fine wire is preferably 0.1 to 5 μm. If the height of the fine wire is 0.1 μm or more, desired conductivity is obtained, and if it is 5 μm or less, the unevenness difference does not affect the film thickness distribution of the functional layer in the formation of the organic electronic element.

As a method of forming an electrode having a conductive or striped conductive portion, a method of printing an ink containing metal nanoparticles in a desired shape is preferable. There is no restriction | limiting in particular as a printing method, It can print and form in a desired shape with well-known printing methods, such as gravure printing, flexographic printing, offset printing, screen printing, and inkjet printing.
Further, the pattern of the thin wire electrode is not limited to the regular pattern as described above, and may have a random network structure. As a random network structure, for example, a method for spontaneously forming a disordered network structure of conductive fine particles by applying and drying a liquid containing metal fine particles as described in JP-T-2005-530005 Can be used.

[Conductive polymer-containing layer]
The transparent electrode according to the present invention is preferably coated with a conductive polymer-containing layer so as to cover the fired fine metal wire pattern formed on the transparent substrate, depending on the application. That is, the case where it uses as transparent electrodes, such as organic electroluminescent (EL) element, organic electronic elements, such as a solar cell, etc. corresponds.
Here, the configuration of the conductive polymer-containing layer is arbitrary, but a configuration formed from a conductive polymer including a π-conjugated conductive polymer and a polyanion is preferable.
In the transparent electrode of the present invention, the conductive polymer-containing layer includes a conductive polymer containing at least a π-conjugated conductive polymer and a polyanion and a structural unit represented by the following general formula (I). It is preferable that it is formed from a water-soluble binder resin from the viewpoint of obtaining high surface smoothness while maintaining high transparency and conductivity.

In general formula (I), R represents a hydrogen atom or a methyl group, and Q represents —C (═O) O— or —C (═O) NRa—. Ra represents a hydrogen atom or an alkyl group, and A represents a substituted or unsubstituted alkylene group, — (CH ₂ CHRbO) _x CH ₂ CHRb—. Rb represents a hydrogen atom or an alkyl group, and x represents the average number of repeating units.

  The dry film thickness of the conductive polymer-containing layer is preferably 30 to 2000 nm. From the viewpoint of conductivity, the thickness is more preferably 100 nm or more, and from the viewpoint of the surface smoothness of the electrode, it is more preferably 300 nm or more. Further, from the viewpoint of transparency, the thickness is more preferably 1000 nm or less, and further preferably 800 nm or less.

  In addition to the above-described printing methods such as gravure printing, flexographic printing, and screen printing, the conductive polymer-containing layer is applied in roll coating, bar coating, dip coating, spin coating, casting, and die coating. Coating methods such as a method, a blade coating method, a bar coating method, a gravure coating method, a curtain coating method, a spray coating method, a doctor coating method, and an ink jet method can be used.

(1) Conductive polymer The conductive polymer according to the present invention comprises a π-conjugated conductive polymer and a polyanion. Such a conductive polymer can be easily produced by chemical oxidative polymerization of a precursor monomer that forms a π-conjugated conductive polymer described later in the presence of an appropriate oxidizing agent, an oxidation catalyst, and a poly anion described later. .

(1.1) π-conjugated conductive polymer The π-conjugated conductive polymer used in the present invention is not particularly limited, and includes polythiophenes (including basic polythiophene, the same shall apply hereinafter), polypyrroles, and polyindoles. A chain conductive polymer of polycarbazoles, polyanilines, polyacetylenes, polyfurans, polyparaphenylene vinylenes, polyazulenes, polyparaphenylenes, polyparaphenylene sulfides, polyisothianaphthenes, polythiazils Can be used. Of these, polythiophenes and polyanilines are preferred from the viewpoints of conductivity, transparency, stability, and the like, and ease of adsorption to metal nanoparticles. Most preferred is polyethylene dioxythiophene.

(1.1.1) π-Conjugated Conductive Polymer Precursor Monomer The precursor monomer used to form the π-conjugated conductive polymer has a π-conjugated system in the molecule and acts as an appropriate oxidizing agent. Even when the polymer is polymerized by π, a π-conjugated system is formed in the main chain. 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-hexylchi Phen, 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-diethoxythiol 3,4-dipropoxythiophene, 3,4-dibutoxythiophene, 3,4-dihexyloxythiophene, 3,4-diheptyloxythiophene, 3,4-dioctyloxythiophene, 3,4-didecyloxy Thiophene, 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-isobutyl Aniline, 2-aniline sulfonic acid, 3-aniline A sulfonic acid etc. are mentioned.

(1.2) Poly anion The poly anion used in the present invention is an acidic polymer in a free acid state, a polymer of a monomer having an anionic group, or a monomer having an anionic group and a monomer having no anionic group. It is a copolymer. The free acid may be in the form of a partially neutralized salt.

  This poly anion is a solubilized polymer that solubilizes the 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 any functional group capable of causing chemical oxidation doping to the π-conjugated conductive polymer. Among them, from the viewpoint of ease of production and stability, a monosubstituted sulfate ester Group, monosubstituted phosphate group, phosphate group, carboxy group, 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, poly Isoprene sulfonic 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, etc. Can be mentioned. These homopolymers may be sufficient and 2 or more types of copolymers may be sufficient.

Further, it may be a poly anion further having F (fluorine atom) in the compound. Specifically, Nafion (made by Dupont) containing a perfluorosulfonic acid group, Flemion (made by Asahi Glass Co., Ltd.) made of perfluoro vinyl ether containing a carboxylic acid group, and the like can be mentioned.
Among these, the compound having a sulfonic acid may be formed by applying and drying the conductive polymer-containing layer, and then subjected to a heat drying treatment at 100 to 120 ° C. for 5 minutes or more. This promotes the crosslinking reaction, which is preferable since the washing resistance and solvent resistance of the coating film are remarkably improved.

  Furthermore, among these, polystyrene sulfonic acid, polyisoprene sulfonic acid, polyacrylic acid ethylsulfonic acid, and polyacrylic acid butylsulfonic acid are preferable. These poly anions have high compatibility with the hydroxyl group-containing non-conductive polymer, and can further increase the conductivity of the obtained conductive polymer.

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

  Examples of the method for producing a polyanion include a method of directly introducing an anionic group into a polymer having no anionic group using an acid, a method of sulfonating a polymer having no anionic group with a sulfonating agent, and an anionic group containing The method of manufacturing by superposition | polymerization of a polymerizable monomer is mentioned.

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

  The ratio of π-conjugated conductive polymer and polyanion contained in the conductive polymer, “π-conjugated conductive polymer”: “polyanion” is preferably 1: 1 to 1:20 by mass ratio. The range of 1: 2 to 1:10 is more preferable from the viewpoint of conductivity and dispersibility.

The oxidant used when the precursor monomer forming the π-conjugated conductive polymer is chemically oxidatively polymerized in the presence of the polyanion to obtain the conductive polymer according to the present invention is, for example, J. Org. Am. Soc. 85, 454 (1963), which is suitable for the oxidative polymerization of pyrrole. For practical reasons, cheap and easy to handle oxidants such as iron (III) salts, eg FeCl ₃ , Fe (ClO ₄ ) ₃ , organic acids and iron (III) salts of inorganic acids containing organic residues Or use hydrogen peroxide, potassium dichromate, alkali persulfate (eg potassium persulfate, sodium persulfate) or ammonium, alkali perborate, potassium permanganate and copper salts such as copper tetrafluoroborate preferable. In addition, air and oxygen in the presence of catalytic amounts of metal ions such as iron, cobalt, nickel, molybdenum and vanadium ions can be used as oxidants at any time. The use of persulfates and the iron (III) salts of inorganic acids containing organic acids and organic residues has great application advantages because they are not corrosive.

  Examples of iron (III) salts of inorganic acids containing organic residues include iron (III) salts of sulfuric acid half esters of alkanols having 1 to 20 carbon atoms, such as lauryl sulfate; alkyl sulfonic acids having 1 to 20 carbon atoms, For example, methane or dodecanesulfonic acid; aliphatic carboxylic acids having 1 to 20 carbon atoms such as 2-ethylhexylcarboxylic acid; aliphatic perfluorocarboxylic acids such as trifluoroacetic acid and perfluorooctanoic acid; aliphatic dicarboxylic acids such as sulphur Mention may be made of acids and in particular aromatic, optionally alkyl-substituted sulphonic acids having 1 to 20 carbon atoms, such as the Fe (III) salts of benzenecene sulphonic acid, p-toluenesulphonic acid and dodecylbenzenesulphonic acid. Furthermore, oxidation polymerization can be performed using a known oxidation catalyst.

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

(2) Second dopant The conductive polymer-containing layer may contain a water-soluble organic compound 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 hydroxyl group-containing compound, a carbonyl group-containing compound, an ether group-containing compound, and a sulfoxide group-containing compound. Examples of the hydroxyl 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.

(3) Water-soluble binder resin The conductive polymer-containing layer of the present invention preferably contains a water-soluble binder resin containing at least the structural unit represented by the general formula (I). Since such a resin can be easily mixed with a conductive polymer and also has the above-mentioned second dopant effect, by using this water-soluble binder resin in combination, the conductivity and transparency are not reduced. The film thickness of the conductive polymer-containing layer can be increased. By increasing the film thickness, high surface smoothness can be obtained, and the metal fine wire pattern can be sufficiently covered with the conductive polymer-containing layer, even when used for electrodes such as organic light-emitting devices and organic solar cell devices. The rectification ratio is excellent, and it becomes possible to prevent leakage between the electrodes.
The water-soluble binder resin is a water-soluble binder resin and means a binder resin in which 0.001 g or more of the resin component is dissolved in 100 g of water at 25 ° C. The dissolution can be measured with a haze meter or a turbidimeter.

  The water-soluble binder resin is preferably transparent.

  The water-soluble binder resin preferably has a structure including the structural unit represented by the general formula (I). The homopolymer represented by the general formula (I) may be used, or other components may be copolymerized. When copolymerizing other components, the structural unit represented by the general formula (I) is preferably contained in an amount of 10 mol% or more, more preferably 30 mol% or more, and more preferably 50 mol% or more. More preferably.

  The water-soluble binder resin is preferably contained in the conductive polymer-containing layer in an amount of 40% by mass to 95% by mass, and more preferably 50% by mass to 90% by mass.

In the structural unit having a hydroxyl group represented by formula (I), R represents a hydrogen atom or a methyl group. Q represents -C (= O) O-, -C (= O) NRa-, and Ra represents a hydrogen atom or an alkyl group. The alkyl group is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group. Moreover, these alkyl groups may be substituted with a substituent.
Examples of these substituents include alkyl groups, cycloalkyl groups, aryl groups, heterocycloalkyl groups, heteroaryl groups, hydroxyl groups, halogen atoms, alkoxy groups, alkylthio groups, arylthio groups, cycloalkoxy groups, aryloxy groups, acyls. Group, alkylcarbonamide group, arylcarbonamide group, alkylsulfonamide group, arylsulfonamide group, ureido group, aralkyl group, nitro group, alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, alkylcarbamoyl group, aryl Rucarbamoyl group, alkylsulfamoyl group, arylsulfamoyl group, acyloxy group, alkenyl group, alkynyl group, alkylsulfonyl group, arylsulfonyl group, alkyloxysulfonyl group, Lumpur oxysulfonyl group, an alkylsulfonyloxy group, may be substituted with an aryl sulfonyloxy group. Of these, a hydroxyl group and an alkyloxy group are preferable.

  The halogen atom includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

  The alkyl group may have a branch, and the number of carbon atoms is preferably 1 to 20, more preferably 1 to 12, and still more preferably 1 to 8. Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, hexyl group, octyl group and the like.

  The number of carbon atoms in the cycloalkyl group is preferably 3-20, more preferably 3-12, and even more preferably 3-8. Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

  The alkoxy group may have a branch, the number of carbon atoms is preferably 1-20, more preferably 1-12, still more preferably 1-6, and 1-4 Most preferably. Examples of the alkoxy group include a methoxy group, an ethoxy group, a 2-methoxyethoxy group, a 2-methoxy-2-ethoxyethoxy group, a butyloxy group, a hexyloxy group and an octyloxy group, and preferably an ethoxy group.

  The number of carbon atoms of the alkylthio group may be branched, and the number of carbon atoms is preferably 1-20, more preferably 1-12, even more preferably 1-6, Most preferably, it is 1-4. Examples of the alkylthio group include a methylthio group and an ethylthio group.

  The arylthio group preferably has 6 to 20 carbon atoms, and more preferably 6 to 12 carbon atoms. Examples of the arylthio group include a phenylthio group and a naphthylthio group.

  The number of carbon atoms of the cycloalkoxy group is preferably 3-12, more preferably 3-8. Examples of the cycloalkoxy group include a cyclopropoxy group, a cyclobutoxy group, a cyclopentyloxy group, and a cyclohexyloxy group.

  The aryl group preferably has 6 to 20 carbon atoms, and more preferably 6 to 12 carbon atoms. Examples of the aryl group include a phenyl group and a naphthyl group.

  The aryloxy group preferably has 6 to 20 carbon atoms, and more preferably 6 to 12 carbon atoms. Examples of the aryloxy group include a phenoxy group and a naphthoxy group.

  The number of carbon atoms of the heterocycloalkyl group is preferably 2 to 10, and more preferably 3 to 5. Examples of the heterocycloalkyl group include a piperidino group, a dioxanyl group, and a 2-morpholinyl group.

  The number of carbon atoms in the heteroaryl group is preferably 3-20, and more preferably 3-10. Examples of the heteroaryl group include a thienyl group and a pyridyl group.

  The acyl group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. Examples of the acyl group include a formyl group, an acetyl group, and a benzoyl group.

  The alkylcarbonamide group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. Examples of the alkylcarbonamide group include an acetamide group.

  The arylcarbonamide group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. Examples of the arylcarbonamide group include a benzamide group and the like.

  The alkylsulfonamide group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. Examples of the sulfonamide group include a methanesulfonamide group.

  The arylsulfonamide group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. Examples of the arylsulfonamide group include a benzenesulfonamide group and p-toluenesulfonamide group.

  The aralkyl group preferably has 7 to 20 carbon atoms, and more preferably 7 to 12 carbon atoms. Examples of the aralkyl group include a benzyl group, a phenethyl group, and a naphthylmethyl group.

  The alkoxycarbonyl group preferably has 1 to 20 carbon atoms, more preferably 2 to 12 carbon atoms. Examples of the alkoxycarbonyl group include a methoxycarbonyl group.

  The aryloxycarbonyl group preferably has 7 to 20 carbon atoms, and more preferably 7 to 12 carbon atoms. Examples of the aryloxycarbonyl group include a phenoxycarbonyl group.

  The aralkyloxycarbonyl group preferably has 8 to 20 carbon atoms, and more preferably 8 to 12 carbon atoms. Examples of the aralkyloxycarbonyl group include a benzyloxycarbonyl group.

  The acyloxy group preferably has 1 to 20 carbon atoms, more preferably 2 to 12 carbon atoms. Examples of the acyloxy group include an acetoxy group and a benzoyloxy group.

  The alkenyl group has preferably 2 to 20 carbon atoms, and more preferably 2 to 12 carbon atoms. Examples of the alkenyl group include vinyl group, allyl group and isopropenyl group.

  The alkynyl group preferably has 2 to 20 carbon atoms, and more preferably 2 to 12 carbon atoms. Examples of the alkynyl group include an ethynyl group.

  The alkylsulfonyl group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. Examples of the alkylsulfonyl group include a methylsulfonyl group and an ethylsulfonyl group.

  The arylsulfonyl group preferably has 6 to 20 carbon atoms, and more preferably 6 to 12 carbon atoms. Examples of the arylsulfonyl group include a phenylsulfonyl group and a naphthylsulfonyl group.

  The alkyloxysulfonyl group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. Examples of the alkyloxysulfonyl group include a methoxysulfonyl group and an ethoxysulfonyl group.

  The aryloxysulfonyl group preferably has 6 to 20 carbon atoms, and more preferably 6 to 12 carbon atoms. Examples of the aryloxysulfonyl group include a phenoxysulfonyl group and a naphthoxysulfonyl group.

  The alkylsulfonyloxy group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. Examples of the alkylsulfonyloxy group include a methylsulfonyloxy group and an ethylsulfonyloxy group.

  The arylsulfonyloxy group preferably has 6 to 20 carbon atoms, and more preferably 6 to 12 carbon atoms. Examples of the arylsulfonyloxy group include a phenylsulfonyloxy group and a naphthylsulfonyloxy group. The substituents may be the same or different, and these substituents may be further substituted.

In the structural unit having a hydroxyl group represented by formula (I) of the present invention, A represents a substituted or unsubstituted alkylene group, — (CH ₂ CHRbO) _x —CH ₂ CHRb—. The alkylene group preferably has, for example, 1 to 5 carbon atoms, more preferably an ethylene group or a propylene group. These alkylene groups may be substituted with the substituent described above. Rb represents a hydrogen atom or an alkyl group. The alkyl group is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group. Moreover, these alkyl groups may be substituted with the above-mentioned substituent. Furthermore, x represents the average number of repeating units, preferably 0 to 100, more preferably 0 to 10. The number of repeating units has a distribution, and the notation indicates an average value and may be expressed with one decimal place.

  Hereinafter, typical specific examples of the structural unit represented by the general formula (I) are shown, but the present invention is not limited thereto.

The water-soluble binder resin of the present invention can be obtained by radical polymerization using a general-purpose polymerization catalyst. Examples of the polymerization mode include bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization and the like, preferably solution polymerization. The 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.
The number average molecular weight of the water-soluble binder resin of 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 5,000 to 100,000.
The number average molecular weight and molecular weight distribution (weight average molecular weight / number average molecular weight = Mw / Mn) of the water-soluble binder resin of the present invention can be measured by a generally known gel permeation chromatography (GPC). it can. The solvent to be used is not particularly limited as long as the binder resin dissolves, and THF (tetrahydrofuran), DMF (dimethylformamide), and CH ₂ Cl ₂ are preferable, more preferably THF and DMF, and still more preferably DMF. The measurement temperature is not particularly limited, but 40 ° C. is preferable.

[Characteristics of transparent electrode]
The total light transmittance of the transparent electrode in the present invention is 70% or more, preferably 80% or more. The total light transmittance can be measured according to a known method using a spectrophotometer or the like.
As the electric resistance value of the conductive portion of the transparent electrode in the present invention, the surface specific resistance is preferably 100Ω / □ or less, more preferably 20Ω / □ or less, for use in a large-area organic electronic device. preferable. The surface specific resistance can be measured based on, for example, JIS K6911, ASTM D257, etc., and can be easily measured using a commercially available surface resistivity meter.

[Method for producing transparent electrode]
In the method for producing a transparent electrode according to a preferred embodiment of the present invention, mainly,
(I) forming a fine metal wire pattern with metal nanoparticles on a transparent substrate;
(Ii) a step of firing the metal fine wire pattern by light irradiation;
It has.

In particular, the heating and firing by light irradiation of (ii) is realized, for example, by irradiation of pulsed light using a flash lamp, and a conductive metal fine wire pattern formed from metal nanoparticles is fired, This is performed in order to improve conductivity.
More specifically, as shown in FIG. 1, heating and baking by light irradiation with pulsed light is divided into a first baking step (10) for performing preliminary baking and a second baking step (20) for performing main baking. And the total of the integrated energy of the irradiation light in the 2nd baking process is made larger than the total of the integrated energy of the irradiation light in the 1st baking process.
Among these, as a preferable condition, the light irradiation in each step in the first baking step and the second baking step is constituted by one or a plurality of times of pulse light irradiation, and integration of irradiation light in the first baking step. E-P1m (max) is the integrated energy amount of the single pulse that maximizes the energy, and E-P2m (max) is the integrated energy amount of the single pulse that maximizes the integrated energy of the irradiation light in the second firing process. The value of E-P2m (max) / E-P1m (max) is 1.5 or more and 40 or less.

As the range of the amount of light irradiation energy, the total amount of light irradiation energy in the first baking step in which preliminary baking is performed is preferably 0.1 to 10 J / cm ² . 0.1 J / cm hardly effect of precalcination is obtained is less than ^2, exceeds 10J / cm ^2, it is more likely to result in an adverse effect on the shape of the metal thin wire pattern. More preferably, it is the range of 0.1-3J / cm < ² >.
The light irradiation time, that is, the pulse width is preferably from 10 μsec to 100 msec, and more preferably from 100 μsec to 10 msec.
The number of times of light irradiation may be one time or a plurality of times, and it is preferably performed in the range of 1-50 times. The pulse interval in the case of performing multiple irradiations is arbitrary. A preferable range of the integrated energy amount E-P1m (max) of the single pulse that maximizes the integrated energy of the irradiation light in the first firing step is 0.1 to 3 J / cm ² . If it is 0.1 J / cm ² or more, the effect of pre-firing can be easily obtained, and if it is ³ J / cm ² or less, the possibility of adversely affecting the shape of the metal fine line pattern is lowered.

On the other hand, the total amount of light irradiation energy in the second baking step for performing the main baking is preferably 0.3 to 50 J / cm ² . If it is 0.3 J / cm ² or more, the firing effect is easily obtained, and if it is 50 J / cm ² or less, the possibility of adversely affecting the shape of the fine metal wire pattern is lowered. More preferably, it is the range of 0.3-10 J / cm < ² >.
The light irradiation time, that is, the pulse width is preferably from 10 μsec to 100 msec, and more preferably from 100 μsec to 10 msec.
The number of times of light irradiation may be one time or a plurality of times, and it is preferably performed in the range of 1-50 times. The pulse interval in the case of performing multiple irradiations is arbitrary. A preferable range of the integrated energy amount E-P1m (max) of the single pulse that maximizes the integrated energy of the irradiation light in the second firing step is 0.3 to 4 J / cm ² . If it is 0.3 J / cm ² or more, it is easy to obtain the effect of preliminary firing, and if it is 4 J / cm ² or less, the possibility of adversely affecting the shape of the metal fine line pattern is lowered. However, as a matter of course, the relationship between the total light irradiation energy of the first baking step and the total light irradiation energy of the second baking step is large in the total light irradiation energy of the latter second baking step. Is the premise.

The interval between the first baking step and the second baking step is arbitrary, but is preferably 5 milliseconds or more. If it is 5 ms or more, the effect of separating the pre-firing and the main firing is easily obtained. More preferably, it is 10 milliseconds or more. On the contrary, there is no particular effect on the length of the interval and influence on the performance of the transparent electrode, but it is advantageous in terms of the production rate of the transparent electrode, and it is preferably within 1 minute.
The discrimination between the first firing step and the second firing step will be described in accordance with, for example, the contents shown in FIG. 1. When the pulsed light in each step is “pulsed light 11-13, 21-23” In addition, the amount of energy of the pulsed light tends to attenuate in each step. In such a case, when the pulse light 21 exceeding the energy amount of the pulse light 13 having the minimum energy amount among the pulse lights 11 to 13 in the first firing step is newly irradiated, the pulse light 13 and the pulse light 13 It is assumed that the first baking step and the second baking step are divided with the point between the light 21 as a boundary.

  Table 1 shows examples of more specific firing conditions by light irradiation.

  Xenon, helium, neon, and argon can be used as the discharge tube of the flash lamp of the present invention, but xenon is preferably used.

The preferred spectral band of the flash lamp in the present invention is preferably 240 nm to 2000 nm, because the conductive polymer-containing layer of the present invention is not damaged by light irradiation, such as a decrease in conductivity.
When the material of the substrate is a transparent body, the light irradiation of the flash lamp to the substrate may be performed not only from the front side on which the metal fine line pattern is printed, but also from the back side or from both sides. .

The light irradiation using the flash lamp of the present invention may be performed in the air, but can also be performed in an inert gas atmosphere such as nitrogen, argon, helium or the like, if necessary.
The substrate temperature at the time of light irradiation is the boiling point (vapor pressure) of the dispersion medium of the ink containing the metal nanoparticles, the type and pressure of the atmospheric gas, the thermal behavior such as the dispersibility and oxidation of the metal nanoparticles, the substrate It may be determined in consideration of the heat-resistant temperature of the film, and is preferably performed at room temperature or higher and 150 ° C. or lower. Note that the substrate on which the fine metal wire pattern has been formed may be subjected to heat treatment in advance before performing light irradiation using a flash lamp.
As long as the light irradiation device of the flash lamp satisfies the above irradiation energy and irradiation time, any device can be used.

[Organic electronic devices]
The organic electronic device in the present invention has a transparent electrode and an organic functional layer produced by the method of the present invention.

  For example, the transparent electrode formed by the method of the present invention is used as a first electrode portion, an organic functional layer is formed on the first electrode portion, and a second electrode portion is formed on the organic functional layer as a counter electrode. By forming it, an organic electronic device can be obtained.

  Examples of the organic functional layer include an organic light emitting layer, an organic photoelectric conversion layer, a liquid crystal polymer layer, and the like without any particular limitation, but the present invention includes an organic light emitting layer in which the organic functional layer is a thin film and a current-driven system, This is particularly effective in the case of an organic photoelectric conversion layer.

  Hereinafter, the component in case the organic electronic element of this invention is an organic EL element and an organic photoelectric conversion element is demonstrated.

(1) Organic EL element (1.1) Organic functional layer structure (organic light emitting layer)
In the present invention, an organic EL device having an organic light emitting layer as an organic functional layer includes a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, a hole block layer, an electron block layer, etc. in addition to the organic light emitting layer. A layer for controlling the light emission may be used in combination with the organic light emitting layer.

  Since the conductive polymer layer on the transparent electrode of the present invention can also serve 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 transport layer / light emitting layer / hole block layer / electron transport 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, quinacridone 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.

(1.2) Electrode The transparent electrode of the present invention is used in the first or second electrode portion described above. In a preferred embodiment, the first electrode portion is an anode and the second electrode portion is a cathode.

  The second electrode portion may be a 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 low work function (4 eV or less) metal (referred to as an electron injecting metal), an alloy, an electrically conductive compound, and a mixture thereof as an electrode material is used.

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

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

  If a metal material is used as the conductive material of the second electrode part, the light coming to the second electrode side is reflected and returns to the first electrode part side. By using a metal material as the conductive material of the second electrode portion, this light can be reused and the extraction efficiency is further improved.

(2) Organic photoelectric conversion element The organic photoelectric conversion element includes a first electrode part, a photoelectric conversion layer having a bulk heterojunction structure (p-type semiconductor layer and n-type semiconductor layer) (hereinafter also referred to as a bulk heterojunction layer), and a second electrode. It is preferable to have a structure in which the portions are laminated. The transparent electrode of the present invention is used at least on the incident light side.

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

(2.1) 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. It is preferable. The p-type semiconductor material functions relatively as an electron donor (donor), and the n-type semiconductor material functions relatively as an electron acceptor (acceptor).

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

  Examples of the p-type semiconductor material 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. Org. 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.

  Furthermore, 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, Japanese Patent Application Laid-Open No. 2004-107216, and the like. 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 have high solubility in organic solvents to the extent that solution processing is possible, 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. 9, 2706 and the like, and acene-based compounds substituted with a trialkylsilylethynyl group, a pentacene precursor described in U.S. Patent Application Publication No. 2003/136964, etc., and Japanese Patent Application Laid-Open No. 2007-224019 Examples include precursor type compounds (precursors) such as porphyrin precursors.

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

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

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

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

  Among these, fullerene-containing polymer compounds are preferable. 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 type), etc. Examples include high molecular compounds 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 which uses the photoelectric conversion element of this invention as photoelectric conversion devices, such as a solar cell, a photoelectric conversion element may be utilized by a single layer and may be laminated | stacked and utilized (tandem type).

  In addition, since the photoelectric conversion device is not deteriorated by oxygen, moisture, or the like in the environment, the photoelectric conversion device is preferably sealed by a known method.

According to the present embodiment described above, it is possible to manufacture a transparent electrode capable of reducing the resistance value while preventing defects in the fine metal wire pattern and the substrate (see the following examples).
Such a transparent electrode is excellent in transparency and conductivity, and also has a flexible characteristic by using a transparent resin substrate.
In addition, if the transparent electrode is used, it is possible to provide an organic electronic device that can be driven at a low voltage in response to an increase in area. In addition, by using a flexible resin substrate, it has become possible to provide a high-speed and mass production form by a roll-to-roll process, and to provide an inexpensive and high-performance transparent electrode.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to 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.

(1) Production of transparent substrate with gas barrier layer A polyethylene terephthalate film substrate having a thickness of 100 μm and a size of 180 mm × 180 mm was prepared, and a gas barrier layer was formed on both sides thereof by the following method.
(1.1) Coating A 20% by weight dibutyl ether solution of perhydropolysilazane (PHPS, AZ Electronic Materials Co., Ltd. Aquamica NN320) was dried with a wireless bar, and the (average) film thickness after drying was 0.30 μm. It apply | coated so that a coating sample might be obtained.
(1.2) Drying and dehumidification (first step; drying treatment)
The obtained coated sample was treated for 1 minute in an atmosphere having a temperature of 85 ° C. and a humidity of 55% RH to obtain a dried sample.
(Second step; dehumidification treatment)
The dried sample was further held for 10 minutes in an atmosphere of a temperature of 25 ° C. and a humidity of 10% RH (dew point temperature −8 ° C.) to perform dehumidification.
(1.3) Modification (reforming treatment)
The sample subjected to the dehumidification treatment was modified under the following conditions to form a gas barrier layer. The dew point temperature during the reforming treatment was -8 ° C.
(Modification equipment)
An excimer irradiation apparatus MODEL: MECL-M-1-200 manufactured by M.D.Com Co., Ltd., a wavelength of 172 nm, and a lamp-filled gas Xe were used.
A sample was fixed on the operation stage, and the sample was modified under the following conditions.
(Reforming treatment conditions)
Excimer light intensity 60 mW / cm ² (172 nm)
1mm distance between sample and light source
Stage heating temperature 70 ℃
Oxygen concentration in irradiation device 1%
Excimer irradiation time 3 seconds

(2) Preparation of transparent electrode (sample) (2.1) Preparation of transparent electrode TCF-1 On the transparent substrate with the gas barrier layer prepared above, silver nanoparticle ink 1 (TEC-PA-010; manufactured by InkTec) Was used to print a metal fine line pattern by a screen printing method so that the height of the fine line after firing was 800 nm with a screen plate pattern of 50 μm width, 1 mm pitch and square lattice shape.
A small thick film semi-automatic printing machine STF-150IP (manufactured by Tokai Shoji Co., Ltd.) was used as a printing apparatus. The area of the pattern printing area was 150 mm × 150 mm.
Thereafter, the resin film substrate on which the fine metal wire pattern obtained above was formed was baked by light irradiation under the baking conditions (light irradiation pattern A) in Table 1 described above to produce “transparent electrode TCF-1”. .
As the flash lamp, a xenon lamp 2400WS (made by COMET) equipped with a short wavelength cut filter of 250 nm or less was used.

(2.2) Production of Transparent Electrodes TCF-2 to TCF-8 In production of the transparent electrode TCF-1, the firing conditions were changed to the light irradiation patterns B to H in Table 1 described above. Others were processed in the same manner as the transparent electrode TCF-1 to produce “transparent electrodes TCF-2 to TCF-8”.

(2.3) Production of Transparent Electrode TCF-R1 (Comparative) In production of transparent electrode TCF-1, the firing conditions were an energy amount of 4 J / cm ² and a pulse width of 2 msec. Others were processed in the same manner as the transparent electrode TCF-1, and a comparative “transparent electrode TCF-R1” was produced.
(2.4) Production of Transparent Electrode TCF-R2 (Comparative) In production of transparent electrode TCF-1, the firing conditions were an energy amount of 1.5 J / cm ² and a pulse width of 3 milliseconds. Others were processed in the same manner as the transparent electrode TCF-1, and a comparative “transparent electrode TCF-R2” was produced.
(2.5) Production of Transparent Electrode TCF-R3 (Comparative) In production of transparent electrode TCF-1, the firing conditions were an energy amount of 1.5 J / cm ² , a pulse width of 3 ms, and a pause of 1 second, Two irradiations were performed. Others were processed in the same manner as the transparent electrode TCF-1, and a comparative “transparent electrode TCF-R3” was produced.

(2.6) Production of Transparent Electrode TCF-R4 (Comparative) In production of transparent electrode TCF-1, the firing conditions were as follows. In other respects, the same processes as those of the transparent electrode TCF-1 were performed to produce a comparative “transparent electrode TCF-R4”.
(Baking conditions of transparent electrode TCF-R4)
Pulse energy 2J / cm ² irradiation the pulse width 1m sec → 2m sec pause → in energy 1.4 J / cm ² irradiation the pulse width 1m sec → 2m sec pause → energy 1.0 J / cm ² Light irradiation with a width of 1 msec → Pause for 2 msec → Light irradiation with a pulse width of 1 msec with an energy amount of 0.7 J / cm ²

(3) Evaluation of sample About the transparent electrodes TCF-1 to TCF8 and TCF-R1 to TCF-R4 produced as described above, surface specific resistance measurement on a grid and surface observation by SEM were performed. For the surface resistivity, the surface resistivity of the transparent electrode was measured by a four-terminal method using a resistivity meter Loresta GP manufactured by Dia Instruments.
Table 2 shows the measurement results of the surface specific resistance and the observation results by SEM.

(3) Summary As shown in Table 2, when the transparent electrodes TCF-1 to TCF-8 and the transparent electrodes TCF-R1 to TCF-R4 are compared, the former sample in which the firing conditions are the conditions described in Table 1, The surface resistivity was low, no defects were observed in the fine metal wire pattern and the substrate, and the observation results were good.
From the above, in reducing the resistance value while preventing the occurrence of defects in the fine metal wire pattern and the substrate, the firing process by light irradiation is divided into two stages, and the integrated energy of the irradiation light in the second firing process, It turns out that it is useful to make it larger than the integrated energy of the irradiation light in the 1st baking process.

(1) Production of transparent electrode with conductive polymer-containing layer for organic EL device (1.1) Synthesis of water-soluble binder resin 1 200 ml of THF was added to a 300 ml three-necked flask and heated to reflux for 10 minutes, and then brought to room temperature under nitrogen. Cooled down. 2-hydroxyethyl acrylate (10.0 g, 86.2 mmol, molecular weight 116.12) and AIBN (2.8 g, 17.2 mmol, molecular weight 164.11) were added, and the mixture was heated to reflux for 5 hours. After cooling to room temperature, the reaction solution was dropped into 2000 ml of MEK and stirred for 1 hour. After decantation of MEK, the polymer was washed 3 times with 100 ml of MEK, and then the polymer was dissolved in THF and transferred to a 100 ml flask. THF 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, 9.0 g (yield 90%) of “water-soluble binder resin 1” having a number average molecular weight of 22100 and a molecular weight distribution of 1.42 was obtained.
The structure and molecular weight were measured by ¹ H-NMR (400 MHz, manufactured by JEOL Ltd.) and GPC (Waters 2695, manufactured by Waters), respectively.

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

(1.2) Preparation of conductive polymer liquid CP-1 Next, the following compounds were mixed to prepare a conductive polymer liquid CP-1.
Water-soluble binder resin 1 aqueous solution (20% solid content aqueous solution) 0.40 g
PEDOT-PSS CLEVIOS PH750 (solid content 1.03%) (made by Heraeus) 1.90 g
Dimethyl sulfoxide 0.10g

(1.3) Application and drying Among the transparent electrodes produced in Example 1, except for TCF-R1 whose surface specific resistance could not be measured, the above-described metal thin line pattern on each transparent electrode was printed according to the printing width. The conductive polymer liquid CP-1 prepared by the above method is applied as a conductive polymer-containing layer on a resin film substrate so as to have a dry film thickness of 500 nm using an applicator having a coating width of 150 mm, and printing of a fine metal wire pattern After wiping off unnecessary peripheral portions so as to be the same as the region, heat treatment was performed at 120 ° C. for 30 minutes using a hot plate, and “transparent electrodes TCF-1P to TCF-8P with conductive polymer-containing layer, TCF- R2P to TCF-R4P "were produced.

(2) Preparation of organic EL element (sample) Using each transparent polymer-containing transparent electrode as a first electrode (anode), “organic EL elements OLED-1-8, OLED-R2— R4 "was produced.

  On the first electrode, PEDOT-PSS CLEVIOS P AI 4083 (solid content 1.5%) (manufactured by Heraeus) is applied on a glass substrate using an applicator having a coating width of 150 mm so that the dry film thickness becomes 30 nm. It was applied and wiped off unnecessary peripheral parts so as to have an area of 150 mm × 150 mm, and then dried.

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

Subsequently, each light emitting layer was provided in the following procedures.
First, after depressurizing to a vacuum degree of 1 × 10 ⁻⁴ Pa, the energization crucible containing the following α-NPD was energized and heated, evaporated at a deposition rate of 0.1 nm / second, and a 30 nm hole transport layer. Was provided.
Thereafter, Ir-1, Ir-14 and the following compound 1-7 were added at a deposition rate of 0.1 nm / second so that the following Ir-1 had a concentration of 13% by mass and the following Ir-14 had a concentration of 3.7% by mass. Co-evaporation was performed to form a green-red phosphorescent layer having a maximum emission wavelength of 622 nm and a thickness of 10 nm.
Thereafter, E-66 and compound 1-7 are co-evaporated at a deposition rate of 0.1 nm / second so that the following E-66 is 10% by mass, and a blue phosphorescent light emitting layer having a maximum emission wavelength of 471 nm and a thickness of 15 nm. Formed.
Thereafter, the following M-1 was vapor-deposited to a thickness of 5 nm to form a hole blocking layer, and CsF was co-deposited with M-1 so that the film thickness ratio was 10%, and an electron transport layer having a thickness of 45 nm. Formed.

  The compounds used for forming each layer are shown below.

On the formed electron transport layer, Al was mask-deposited under a vacuum of 5 × 10 ⁻⁴ Pa as a material for forming an external lead terminal for the first electrode and a second electrode (cathode) of 150 mm × 150 mm. A 100 nm second electrode was formed.

Further, an adhesive is applied to the periphery of the second electrode except for the end portions so that external lead terminals of the first electrode and the second electrode can be formed, and a polyethylene terephthalate resin film is used as a substrate to form Al ₂ O ₃ with a thickness of 300 nm. After bonding the vapor-deposited flexible sealing member, the adhesive was cured by heat treatment to form a sealing film, and an organic EL element having a light emitting area of 150 mm × 150 mm was produced.
As the adhesive, a two-component epoxy compounded resin (manufactured by Three Bond) 2016B and 2103 were blended at a ratio of 100: 3.

(3) Measurement and evaluation of sample By the following method, the rectification ratio, light emission unevenness, and voltage value of each organic EL element produced as described above were measured, and the light emission uniformity and drive voltage of the organic EL element were evaluated.

(3.1) Rectification ratio The current value when a voltage of +4 V / -4 V was applied to each organic EL element was measured, the rectification ratio was determined by the following calculation formula, and evaluated according to the following criteria. If there is leakage between electrodes, the rectification ratio becomes a low value. It is practical range is 10 ² or more.

Rectification ratio = current value when +4 V is applied / current value when −4 V is applied ◎: Rectification ratio 10 ³ or more ○: Rectification ratio 10 ² or more and less than 10 ³ Δ: Rectification ratio 10 ¹ or more and less than 10 ² ×: Rectification ratio 10 ¹ Less than

(3.2) Light emission unevenness Using a KEITHLEY source measure unit type 2400, a direct current voltage was applied to each organic EL element to emit light so that the luminance became 1000 cd / m ² , and the light emission state was visually evaluated according to the following criteria. .
◎: Completely uniform light emission, no problem at all ○: Almost uniform light emission, no problem in practical use △: Uneven light emission is partially observed and practically unacceptable ×: Light emission over the entire surface Unevenness is seen and not acceptable at all

(3.3) using a driving voltage KEITHLEY source measure unit MODEL 2400, manufactured by luminance by applying a DC current to each organic EL element to emit light so as to be 1000 cd / ^{m 2,} the voltage values at 1000 cd / ^{m 2} It was measured. The lower the voltage value, the lower the driving voltage. 5V or less is a practical range.

  The evaluation results are shown in Table 3.

(4) Summary As shown in Table 3, when the organic EL elements OLED-1 to OLED-8 and the organic EL elements OLED-R2 to R4 are compared, the former using the transparent electrodes TCF-1 to TCF8 according to the examples of the present invention. This sample had excellent device performance.
From the above, in order to improve the element performance of the organic EL element, the baking process by light irradiation is divided into two stages in the manufacturing process of the transparent electrode, and the integrated energy of the irradiation light in the second baking process is divided into the first baking process. It turns out that it is useful to make it larger than the integrated energy of the irradiation light in a process.

  The present invention relates to a method for producing a transparent electrode, and can be particularly suitably used for reducing a resistance value while preventing defects in a fine metal wire pattern or a substrate.

10 1st baking process 11-13 Pulse light 20 2nd baking process 21-23 Pulse light

Claims (5)

In the method for producing a transparent electrode having a transparent resin substrate and a conductive fine metal wire pattern,
Forming the metal fine line pattern with metal nanoparticles on the transparent substrate;
A step of firing the fine metal wire pattern by light irradiation,
In the step of firing the fine metal wire pattern,
A first firing step of pre-firing the metal fine wire pattern;
A second firing step of subjecting the fine metal wire pattern to a main firing,
The integrated energy of the irradiation light in the second baking step is larger than the integrated energy of the irradiation light in the first baking step ;
Furthermore, in the first baking step and the second baking step, the light irradiation of each step is constituted by one or a plurality of times of pulsed light,
The integrated energy amount of a single pulse that maximizes the integrated energy in the first firing step is E-P1m (max),
When the accumulated energy amount of a single pulse that maximizes the accumulated energy in the second firing step is E-P2m (max),
E-P2m (max)> E-P1m (max)
A method for producing a transparent electrode, characterized in that In the manufacturing method of the transparent electrode of Claim 1 ,
A method for producing a transparent electrode, wherein a value of E-P2m (max) / E-P1m (max) is 1.5 or more and 40 or less. In the manufacturing method of the transparent electrode of Claim 1 or 2,
The method for producing a transparent electrode, wherein the metal nanoparticles are silver nanoparticles. In the manufacturing method of the transparent electrode of Claim 1,
A method for producing a transparent electrode, comprising a step of forming a conductive polymer layer by coating a conductive polymer on the fine metal wire pattern after firing. An organic compound layer is formed on the transparent electrode produced by the method for producing a transparent electrode according to any one of claims 1 to 4 , and
A method for producing an organic electronic element , comprising forming the second electrode as a counter electrode on the organic compound layer .

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