JP2011129449A - Organic electronic element and manufacturing method therefor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrode having both a high conductivity and transparency through the restraint of current leakage or field concentration by one with high smoothness, or further, an organic electronic element with excellent efficiency and with an improved preservation property through reduction in its driving voltage. <P>SOLUTION: In the organic electronic element and its manufacturing method, provided with a first electrode having a transparent conductive layer made of metal nanoparticles on a substrate, a second electrode facing the same, and at least one organic function layer between the electrodes, the transparent conductive layer of the first electrode contains a conductive polymer and a nonconductive polymer, the nonconductive polymer is one in which hydroxyl groups themselves of the polymer equipped with a number of them are dehydrated and condensed, and moreover, with a dehydration condensation reaction ratio of 30% or more to 95% or less. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an organic electronic device such as an organic electroluminescence device (hereinafter referred to as an organic EL device) and an organic solar cell, and more particularly to an organic electronic device with improved performance such as driving voltage, efficiency, and life of the organic electronic device.

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

  Conventionally, a transparent electrode is an ITO transparent electrode obtained by forming a composite oxide (ITO) film of indium-tin on a transparent substrate such as glass or a transparent plastic film by a vacuum deposition method or a sputtering method. It has been mainly used from the viewpoint of performance such as transparency. However, a transparent electrode using a vacuum deposition method or a sputtering method has a problem in that the productivity is low and the manufacturing cost is high, and since it is inferior in flexibility, it cannot be applied to an element application requiring flexibility.

  In contrast, there is a method of forming a transparent conductor layer by coating or printing using a coating solution in which a conductive polymer typified by a π-conjugated polymer is dissolved or dispersed in an appropriate solvent (see, for example, Patent Document 1). Proposed. However, there is a problem that both transparency and conductivity are remarkably reduced as compared with a metal oxide transparent electrode such as ITO formed by a vacuum film formation method. Furthermore, when an organic electronic device such as an organic EL is formed using this, in addition to the low conductivity of the transparent conductor layer itself, a behavior that is considered to have a high interface resistance with the functional layer provided on the transparent conductor layer (For example, in organic EL, the drive voltage was increased), and there was a problem that the performance as an element was lowered.

  In addition, in the organic EL, the conductive polymer is often laminated as a hole injection material and a hole transport material on the ITO or ZnO electrode. At this time, if there is a protrusion on the ITO electrode, the element life may be reduced due to leakage between the electrodes or electric field concentration at that portion. Laminating conductive polymer also improves surface smoothness by filling such protrusions, but depending on the size of the protrusions, the conductive polymer layer required for embedding becomes thicker, and the transparency of the element is increased. From the point of view, it is difficult to achieve both. When a conductive layer made of metal nanoparticles is used as an electrode instead of ITO, it is more difficult to achieve both surface smoothing and transparency.

  On the other hand, the method (for example, refer patent document 2) using the coating layer which consists of a conductive polymer and binder resin is proposed. By adding the binder resin, the thickness of the layer necessary for embedding the protrusion can be obtained without impairing the transparency, but another problem arises that the conductivity of the layer is remarkably lowered due to the reduction of the conductive polymer ratio. Furthermore, when an organic EL element is formed using this electrode, an increase in driving voltage is observed and the element performance is reduced as in the above-described method.

  In order to solve the problem of the decrease in conductivity due to the addition of the binder resin, a method of adding a cross-linking point forming compound having a specific structure to the conductive polymer (for example, see Patent Document 3) has been proposed. However, this method can suppress the decrease in conductivity of the electrode itself, but the effect of embedding the protrusion is low, resulting in the formation of an electrode with low surface smoothness. Furthermore, in an organic EL device using this electrode, driving There is no effect to suppress the voltage rise.

  In the present invention, a conductive polymer having absorption in the visible part on the first conductive layer made of metal nanoparticles, and non-conductivity of a specific structure having conductivity enhancing effect and no absorption in the visible part By forming the second conductive layer made of a polymer, both high transparency and high conductivity can be achieved at a film thickness necessary for smoothing the first conductive layer.

JP-A-6-273964 JP 2006-198805 A JP 2006-143922 A

  The object of the present invention has been made in view of the above circumstances, and in organic electronic elements such as organic EL elements and organic solar cells, current leakage and electric field concentration are suppressed by highly smooth electrodes, and high conductivity and transparency are achieved. Another object of the present invention is to provide an organic electronic device which has an excellent performance and further has a reduced driving voltage of the device, an excellent efficiency, and an improved storage property.

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

  1. In an organic electronic device having a first electrode having a transparent conductive layer made of metal nanoparticles on a substrate, a second electrode facing the first electrode, and at least one organic functional layer between the electrodes, the first electrode The transparent conductive layer contains a conductive polymer and a non-conductive polymer, and the non-conductive polymer is a polymer obtained by dehydrating and condensing the hydroxyl groups of a polymer having a large number of hydroxyl groups. An organic electronic device having a dehydration condensation reaction rate of 30% to 95%.

  2. 2. The organic electronic device as described in 1 above, wherein the non-conductive polymer has a dehydration condensation reaction rate of 50% to 95%.

  3. 3. The organic electronic device as described in 1 or 2 above, wherein the nonconductive polymer contains a polymer (A) having the following three polymer chains.

(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 indicate the composition ratio (mol%), 50 ≦ l + m + n ≦ 100, and l, m, and n are each 0-100.)
4). 4. The organic electronic device according to any one of 1 to 3, wherein the conductive polymer includes a sulfo group-containing polyanion.

  5. 5. The organic electronic device according to any one of 1 to 4, wherein the transparent conductive layer contains a catalyst for dehydration condensation reaction.

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

  7. 7. The method for producing an organic electronic device according to any one of 1 to 6, wherein a step of providing metal nanoparticles on a substrate, and a non-conductive polymer having a conductive polymer and a hydroxyl group on the metal nanoparticle layer A method for producing an organic electronic device, comprising: a step of providing a mixture layer of a dehydration condensation reaction catalyst; a step of heat treatment; and a step of forming an organic functional layer after the heat treatment.

  8). 8. The method for producing an organic electronic device according to 7, wherein the heat treatment is performed at a temperature of 50 ° C. or higher and 200 ° C. or lower.

  9. The organic electronic device according to any one of 1 to 6 is an organic electroluminescence device or an organic solar cell device.

  According to the present invention, in an organic electronic element such as an organic EL element and an organic solar cell, an electrode having high conductivity and transparency is provided by suppressing current leakage and electric field concentration by a highly smooth electrode, and further, It is possible to provide an organic electronic device with reduced driving voltage of the device, excellent efficiency, and improved lifetime.

It is sectional drawing of the organic electronic element of this invention. It is sectional drawing of the shape of the auxiliary electrode which concerns on this invention. It is a figure which shows the representative example of the shape of the auxiliary electrode which concerns on this invention. It is a figure which shows the manufacturing method of the organic electronic element of this invention.

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

  The present inventors tried a method of forming a transparent conductive layer made of a conductive polymer and a non-conductive polymer having a hydroxyl group on the transparent conductive layer made of metal nanoparticles as the first electrode. Thereby, the surface smoothness, transparency, and conductivity of the electrode can be satisfied at the same time, and further, the current-carrying characteristics such as the driving voltage and efficiency of the organic electronic element such as the organic EL can be improved. However, this method has a problem that the storage stability of the device, particularly storage stability at high temperatures, is lowered due to the dehydration condensation reaction of the hydroxyl group of the non-conductive polymer.

  On the other hand, the present inventors formed a transparent conductive layer made of a conductive polymer and a non-conductive polymer having a hydroxyl group on the transparent conductive layer made of metal nanoparticles as the first electrode, and the non-conductive polymer It has been found that the storage stability can be improved by dehydration condensation of hydroxyl groups.

  In the present invention, a conductive polymer having absorption in the visible part on the first conductive layer made of metal nanoparticles, and non-conductivity of a specific structure having conductivity enhancing effect and no absorption in the visible part By forming the second conductive layer made of a polymer, both high transparency and high conductivity can be achieved at a film thickness necessary for smoothing the first conductive layer. Furthermore, the hydroxyl group of the non-conductive polymer forms a crosslinked structure by dehydration condensation, so that the water resistance and solvent resistance of the electrode can be obtained, and process suitability can be improved. The storage stability of the device could be improved by setting the reaction rate of the dehydration condensation of the hydroxyl portion to 30% or more.

  Further, by adding an acid catalyst in the second conductive layer or by applying and drying the electrode, heat treatment is performed to promote the reaction, and the reaction rate can be increased to 30% or more in a short time. Device performance can be improved.

  Hereinafter, the present invention and its components will be described in detail.

<Board>
In the present invention, a plastic film, a plastic plate, glass or the like can be used as the transparent substrate, and it is preferable to use a transparent plastic film from the viewpoint of lightness and flexibility.

  Examples of raw materials for plastic films and plastic plates include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate, polyolefins such as polyethylene (PE), polypropylene (PP), polystyrene, and EVA, polyvinyl chloride, and polychlorinated chloride. Use vinyl resins such as vinylidene, polyether ether ketone (PEEK), polysulfone (PSF), polyether sulfone (PES), polycarbonate (PC), polyamide, polyimide, acrylic resin, triacetyl cellulose (TAC), etc. Can do.

  In the transparent electrode and the organic electronic device according to the present invention, the substrate is preferably excellent in surface smoothness. The smoothness of the surface is preferably an arithmetic average roughness Ra of 5 nm or less and a maximum height Rz of 50 nm or less, more preferably Ra of 2 nm or less and Rz of 30 nm or less, and still more preferably Ra of 1 nm or less. Rz is 20 nm or less. The surface of the substrate may be smoothed by applying an undercoat layer such as a thermosetting resin, an ultraviolet curable resin, an electron beam curable resin, or a radiation curable resin, or may be smoothed by mechanical processing such as polishing. You can also. Here, the smoothness of the surface can be determined according to the surface roughness standard (JIS B 0601-2001) from measurement by an atomic force microscope (AFM) or the like.

  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, it is preferable to provide a gas barrier layer for the purpose of blocking oxygen and moisture in the atmosphere. As a material for forming the gas barrier layer, metal oxides such as silicon oxide, silicon nitride, silicon oxynitride, aluminum nitride, and aluminum oxide, and metal nitrides can be used. These materials have an oxygen barrier function in addition to a water vapor barrier function. In particular, silicon nitride and silicon oxynitride having favorable barrier properties, solvent resistance, and transparency are preferable. In addition, the barrier layer may have a multilayer structure as necessary. As a method for forming the gas barrier layer, a resistance heating vapor deposition method, an electron beam vapor deposition method, a reactive vapor deposition method, an ion plating method, or a sputtering method can be used depending on the material. The thickness of each inorganic layer constituting the gas barrier layer is not particularly limited, but typically it is preferably in the range of 5 nm to 500 nm per layer, more preferably 10 nm to 200 nm per layer. The gas barrier layer is provided on at least one surface of the substrate, and more preferably on both surfaces.

<Conductive layer>
The conductive layer in the present invention includes a first conductive layer made of metal nanoparticles and a second conductive layer made of a conductive polymer and a hydroxyl group-containing nonconductive polymer.

  As a method for forming a conductive layer, first, a first conductive layer composed of metal nanoparticles and a binder is coated on a support, dried to form a film, and further composed of a conductive polymer and a hydroxyl group-containing non-conductive polymer. A second conductive layer is applied and dried to form a film. Further, as long as the function of the organic electronic element is not impaired, a third layer may be further provided between the first conductive layer and the second conductive layer, or on the second conductive layer. A conductive polymer may be included.

  The method for forming these conductive layers is not particularly limited as long as it is a liquid phase film forming method in which a metal nanoparticle-containing dispersion or a conductive polymer and a hydroxyl group-containing non-conductive polymer-containing dispersion is applied and dried to form a film. There is no. 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, ink jet method, etc. A coating method can be used. In addition, you may perform application | coating several times according to the density | concentration of a coating liquid and the target electroconductivity. Alternatively, direct pattern formation may be performed by a spray coating method, an inkjet method, or using a mask.

  By forming the conductive layer of the present invention, both the conductivity and transparency of the conductive layer can be achieved, and the protrusions in the lower layer of the conductive layer can be filled to smooth the electrode surface.

  As another method for forming the conductive layer, the first conductive layer may be transferred and formed. First, metal nanoparticles are applied to a smooth first support with releasability, dried to form a film, then transferred to the second support via a binder, and the gaps between the metal nanoparticles are filled with the binder The first support is peeled off to form a conductive layer. Next, the second conductive layer is applied and dried on the first conductive layer.

  The surface of the first support is preferably smoothed by a hard coat layer or the like. The surface smoothness (unevenness) of the first support is preferably such that the arithmetic average roughness Ra is 5 nm or less and the maximum height Rz is 50 nm or less, more preferably Ra is 1 nm or less and Rz is 30 nm or less. is there.

  Here, Ra and Rz representing surface smoothness mean Ra = arithmetic mean roughness and Rz = maximum height (the difference in height between the top and bottom of the surface), and are defined in JIS B601 (2001). It is a value according to the surface roughness. In the present invention, Ra, Rz, and the level difference can be measured by using a commercially available atomic force microscope (AFM), for example, by the following method.

  Using an SPI 3800N probe station and SPA400 multifunctional unit manufactured by Seiko Instruments Inc. as the AFM, set the sample cut to a size of about 1 cm square on a horizontal sample stage on the piezo scanner, and place the cantilever on the sample surface. When approaching and reaching the region where the atomic force works, scanning is performed in the XY direction, and the unevenness of the sample at that time is captured by the displacement of the piezo in the Z direction. A piezo scanner that can scan XY 150 μm and Z 5 μm is used. The cantilever is a silicon cantilever SI-DF20 manufactured by Seiko Instruments Inc., which has a resonance frequency of 120 to 150 kHz and a spring constant of 12 to 20 N / m, and is measured in a DFM mode (Dynamic Force Mode). A measurement area of 80 × 80 μm is measured at a scanning frequency of 0.1 Hz.

The attached amount of the metal nanoparticles in the first conductive layer is 5 mg / m ² or more and 500 mg / m ² or less, and preferably 10 mg / m ² or more and 200 mg / m ² or less. If the attached amount of metal nanoparticles is less than 5 mg / m ^2, the contact between the metal nanoparticles deteriorates and the conductivity is remarkably reduced, and if it exceeds 500 mg / m ² , the portion shielded from the metal nanoparticles increases. Transparency is greatly impaired.

  The surface specific resistance of the first conductive layer is preferably 100Ω / □ or less, and more preferably 10Ω / □ or less. 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.

  The ratio of the conductive polymer of the second conductive layer to the hydroxyl group-containing nonconductive polymer is preferably 30 to 900 parts by mass of the hydroxyl group-containing nonconductive polymer when the conductive polymer is 100 parts by mass. From the viewpoint of leakage prevention, the conductivity enhancing effect of the hydroxyl group-containing nonconductive polymer, and transparency, the hydroxyl group-containing nonconductive polymer is more preferably 100 parts by mass or more.

  The dry film thickness of the conductive layer is preferably 30 nm to 2000 nm. The conductive layer of the present invention is more preferably 100 nm or more from the viewpoint of conductivity, and further preferably 200 nm or more from the viewpoint of the surface smoothness of the electrode. Moreover, it is more preferable that it is 1000 nm or less from the point of transparency.

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

  In the present invention, after the drying is completed, the above crosslinking reaction can be promoted and completed by further heat treatment. Thereby, the cleaning resistance and solvent resistance of the electrode are remarkably improved, and the device performance is further improved. In particular, in an EL element, effects such as reduction in driving voltage and improvement in life can be obtained.

  The heat treatment is preferably performed at a temperature of 50 ° C. or higher and 200 ° C. or lower for 10 minutes or longer. If it is less than 50 ° C., the reaction promoting effect is small, and if it exceeds 200 ° C., thermal damage to the material increases, or the effect is small. The treatment temperature is more preferably 80 ° C. or more and 150 ° C. or less, and the treatment time is more preferably 10 minutes or more. The upper limit of the treatment time is not particularly limited, but is preferably 24 hours or less from the viewpoint of productivity.

  The moisture generated by the crosslinking reaction can be simultaneously dried in the heat treatment step of the present invention, but may be dried by a separate drying step before forming the organic functional layer. The heat treatment may be performed on-line or off-line after applying and drying the conductive layer. In the case of off-line, it is preferable to further perform under reduced pressure because it leads to promotion of drying of moisture generated by the crosslinking reaction.

  In the present invention, the reaction can be promoted and completed using an acid catalyst. As the acid catalyst, hydrochloric acid, sulfuric acid or ammonium sulfate can be used. Moreover, in the polyanion used as a dopant for a conductive polymer, a dopant and a catalyst can be used together by using a sulfo group-containing polyanion. In addition, the heat treatment described above can be performed in combination with the use of an acid catalyst, which is preferable because it shortens the treatment time.

  Various analysis methods can be used for the reaction rate of the dehydration condensation reaction. For example, in thermal analysis such as differential scanning calorimetry (DSC) and differential thermal-thermal mass simultaneous measurement (TG / DTA), it can be determined from the reaction heat and dehydration amount change accompanying the dehydration condensation reaction. Moreover, it can obtain | require from the change of a moisture content or the amount of hydroxyl groups by infrared spectroscopy.

  The dispersion containing the conductive polymer of the present invention and the hydroxyl group-containing non-conductive polymer further contains other transparent non-conductive polymers and additives as long as the conductivity, transparency and smoothness of the conductive layer are simultaneously satisfied. May be.

  As the transparent non-conductive polymer, a natural polymer resin or a synthetic polymer resin can be widely selected and used, and a water-soluble polymer or an aqueous polymer emulsion is particularly preferable. Examples of water-soluble polymers include natural polymers such as starch, gelatin, and agar, semi-synthetic polymers such as hydroxypropylmethylcellulose, carboxymethylcellulose, and hydroxyethylcellulose, cellulose derivatives, synthetic polymers such as polyvinyl alcohol, and polyacrylic acid polymers. , Polyacrylamide, polyethylene oxide, polyvinyl pyrrolidone, etc., and aqueous polymer emulsions include acrylic resins (acrylic silicon modified resins, fluorine modified acrylic resins, urethane modified acrylic resins, epoxy modified acrylic resins, etc.), polyester resins, urethane Resin, vinyl acetate resin and the like can be used.

  In addition, as the synthetic polymer resin, a transparent thermoplastic resin (for example, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polymethyl methacrylate, nitrocellulose, chlorinated polyethylene, chlorinated polypropylene, vinylidene fluoride) A transparent curable resin (for example, melamine acrylate, urethane acrylate, epoxy resin, polyimide resin, silicone resin such as acrylic-modified silicate) that can be cured by heat, light, electron beam, or radiation can be used.

  Examples of the additive include plasticizers, stabilizers such as antioxidants and sulfurization inhibitors, surfactants, dissolution accelerators, polymerization inhibitors, and colorants such as dyes and pigments. Furthermore, from the viewpoint of improving workability such as coating properties, solvents (for example, water, organic solvents such as alcohols, glycols, cellosolves, ketones, esters, ethers, amides, hydrocarbons, etc.) are used. May be included.

[Metal nanoparticles]
The metal nanoparticles of the present invention refer to fine metal particles having a particle diameter of from atomic scale to nm size. The average particle diameter of the metal nanoparticles is preferably 10 to 300 nm, and more preferably 30 to 200 nm. The metal used in the metal nanoparticles according to the present invention is preferably silver or copper from the viewpoint of conductivity, and may be silver or copper alone, or a combination of them, either silver and copper alloy, silver or copper. It may be plated with any metal.

  In the metal nanoparticles of the present invention, if the minor axis of the particle diameter is nm size, the shape may be particulate, rod or wire, but from the viewpoint of conductivity and transparency A wire-like metal nanowire is preferable.

  In general, a metal nanowire refers to a linear structure having a diameter from the atomic scale to the nm size, which contains a metal element as a main component.

  As the metal nanowire used in the present invention, in order to form a long conductive path with one metal nanowire, the average length is preferably 3 μm or more, more preferably 3 to 500 μm, and particularly preferably 3 to 300 μm. It is preferable. In addition, the relative standard deviation of the length is preferably 40% or less. Moreover, although there is no restriction | limiting in particular in an average breadth, it is preferable that it is small from a transparency viewpoint, and the larger one is preferable from a conductive viewpoint. In the present invention, the average minor axis of the metal nanowire is preferably 10 to 300 nm, and more preferably 30 to 200 nm. In addition, the relative standard deviation of the minor axis is preferably 20% or less. The metal nanowires of the conductive layer are preferably in contact with each other, and more preferably in mesh form. A conductive layer in which metal nanowires are brought into contact with each other or in a mesh form can be easily obtained by using the above liquid phase film forming method.

  In the present invention, the means for producing the metal nanowire is not particularly limited, and for example, known means such as a liquid phase method and a gas phase method can be used. Moreover, there is no restriction | limiting in particular in a specific manufacturing method, A well-known manufacturing method can be used. For example, as a method for producing silver nanowires, Adv. Mater. , 2002, 14, 833-837; Chem. Mater. 2002, 14, 4736-4745, and Japanese Patent Application Laid-Open No. 2002-266007 as a method for producing copper nanowires. The method for producing silver nanowires can be easily produced in an aqueous solution, and since the conductivity of silver is the highest in metals, it is preferably applied as a method for producing metal nanowires according to the present invention. Can do.

  As a method for forming a conductive layer other than metal nanowires, as described in Patent Document 4, the conductive layer may be formed by a random network structure of self-assembled silver fine particles.

<Conductive polymer>
The conductive polymer of the present invention is 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, polyfurans. , Polyparaphenylene vinylenes, polyazulenes, polyparaphenylenes, polyparaphenylene sulfides, polyisothianaphthenes, polythiazyl chain conductive polymers can be used. Of these, polythiophenes and polyanilines are preferable from the viewpoints of conductivity, transparency, stability, and the like. Most preferred is polyethylene dioxythiophene.

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

(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 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 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. Examples include 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. Moreover, the polyanion which has a fluorine in a compound may be sufficient. 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 the compound having a sulfo group is formed by applying and drying the conductive polymer-containing layer, the heat resistance of the applied film is obtained when heat treatment is performed at a temperature of 50 ° C. or higher and 200 ° C. or lower. And the solvent resistance is remarkably improved. Furthermore, among these, polystyrene sulfonic acid, polyisoprene sulfonic acid, polyacrylic acid ethylsulfonic acid, and polyacrylic acid butylsulfonic acid are preferable. These polyanions have high compatibility with the binder resin, 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 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 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.

  A commercially available material can be preferably used for such a conductive polymer. For example, a conductive polymer (abbreviated as PEDOT: PSS) made of poly (3,4-ethylenedioxythiophene) and polystyrene sulfonic acid is H.264. 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.

  2nd. A water-soluble organic compound may be contained as a dopant. There is no restriction | limiting in particular in the water-soluble organic compound which can be used by this invention, It can select suitably from well-known things, For example, an oxygen containing compound is mentioned suitably. The oxygen-containing compound is not particularly limited as long as it contains oxygen, and examples thereof include a 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, and glycerin. 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.

<Aqueous solvent>
In the present invention, 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.

<Hydroxyl-containing non-conductive polymer>
In the present invention, the hydroxyl group-containing non-conductive polymer 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 polymer (A) of the present invention, 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 number average molecular weight of 1000 or less in a content of 0 to 5%. When there are few low molecular components, the preservation | save property of an element and the behavior which has a barrier in the electroconductivity of a perpendicular | vertical direction with respect to a conductive layer can be reduced more.

  As a method for adjusting the content of the polymer (A) having a number average molecular weight of 1000 or less to 0 to 5%, a low molecular weight component is obtained by synthesizing a monodisperse polymer by living polymerization in a reprecipitation method or preparative GPC. A method of removing or suppressing the generation of low molecular weight components 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 Nihon Analytical Industrial Co., Ltd.), polystyrene gel column, and the polymer dissolved solution can be separated by molecular weight to cut the desired low molecular weight. This is how you can do it. In the living polymerization, the generation of the starting species does not change with time, and there are few side reactions such as termination reaction, and a polymer having a 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 of the polymer (A) 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 distribution of the polymer (A) of the present invention is preferably from 1.01 to 1.30, more preferably from 1.01 to 1.25. In the distribution obtained by GPC, the content having a number average molecular weight of 1000 or less was converted by multiplying the area having a number average molecular weight of 1000 or less and dividing by the area of the entire distribution. The living radical 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 radical polymerization temperature varies depending on the initiator used, but is generally -10 to 250 ° C, preferably 0 to 200 ° C, more preferably 10 to 100 ° C.

<Configuration of organic electronic device>
The configuration of the organic electronic element will be described with reference to the drawings. In FIG. 1, it has the 1st electrode (11) and 2nd electrode (12) which oppose on a board | substrate (10), and at least 1 layer of organic is between a 1st electrode (11) and a 2nd electrode (12) electrode. It has a functional layer (13). In the present invention, the first electrode (11) includes a first conductive layer (14) made of metal nanoparticles, and a second conductive layer (15) made of a conductive polymer and a hydroxyl group-containing non-conductive polymer. The second conductive layer made of a polymer and a hydroxyl group-containing non-conductive polymer is filled in the gap between the first conductive layer made of metal nanoparticles.

  Examples of the organic functional layer (13) of the present invention include an organic light emitting layer, an organic photoelectric conversion layer, and a liquid crystal polymer layer without any particular limitation. However, the present invention is an element of a current drive system in which the functional layer is a thin film. This is particularly effective in the case of a certain organic light emitting layer or organic photoelectric conversion layer.

<Auxiliary electrode>
In order to cope with an increase in area, the first electrode having a conductive layer made of metal nanoparticles, a conductive polymer and a hydroxyl group-containing nonconductive polymer is further provided with a light-impermeable conductive portion and a light-transmissive window portion. It is preferable to have an auxiliary electrode made of The auxiliary electrode only needs to be in electrical contact with the first electrode. For example, the auxiliary electrode is formed on the substrate, the first conductive layer made of metal nanoparticles is formed thereon, and the conductive polymer and the hydroxyl group are further formed. A second conductive layer composed of the containing non-conductive polymer can be formed (FIG. 2a). As another method, an auxiliary electrode is formed on a substrate, and a first conductive layer made of metal nanoparticles is formed thereon (FIG. 2b), or a first conductive layer made of metal nanoparticles is formed on the substrate. Then, an auxiliary electrode is formed thereon (FIG. 2c), this is transferred onto another substrate using a transparent adhesive resin, and then a second conductive layer is formed thereon (FIG. 2d, FIG. 2e). ) Further, after the auxiliary electrode is formed on the substrate and transferred to another substrate, the first conductive layer and the second conductive layer may be formed.

  The light-impermeable conductive portion of the auxiliary electrode is preferably a metal from the viewpoint of good conductivity, and examples of the metal material include gold, silver, copper, iron, nickel, and chromium. The metal of the conductive part may be an alloy, and the metal layer may be a single layer or a multilayer.

  The shape of the auxiliary electrode is not particularly limited, but for example, the conductive portion has a stripe shape, a mesh shape, or a random mesh shape (FIG. 3). There are no particular limitations on the method of forming the stripe-shaped or mesh-shaped auxiliary electrode with the conductive portion, 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 nanoparticles in a desired shape by screen printing, or a plating treatment after applying a catalyst ink that can be plated to a desired shape by gravure printing or an inkjet method. As another method, a method using silver salt photographic technology can also be used. About the method to which silver salt photography technology is applied, it can carry out with reference to 0076-0112 of Unexamined-Japanese-Patent No. 2009-140750 and an Example, for example. About the method of carrying out the gravure printing of catalyst ink and plating, it can carry out with reference to Unexamined-Japanese-Patent No. 2007-281290, for example.

<Random network structure>
As a random network structure, for example, a disordered network structure of conductive fine particles is spontaneously formed by applying and drying a liquid containing metal nanoparticles as described in JP-T-2005-530005. You can use the method. As another method, for example, a method of forming a random network structure of metal nanowires by applying and drying a coating solution containing metal nanowires as described in JP-T-2009-505358 can be used.

<Organic functional layer configuration>
(Organic EL device)
(Organic light emitting layer)
The organic electronic device having an organic light emitting layer in the present invention is used 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 in addition to the organic light emitting layer. Thus, a layer for controlling light emission may be provided. 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, 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. 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 of the present invention serves as a cathode in the organic EL device. The second electrode portion of the present invention 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 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, 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.

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

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

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

[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 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. Acene compounds substituted with trialkylsilylethynyl groups described in US Pat. No. 9,2706, etc., and pentacene precursors described in US Patent Application Publication No. 2003/136964, Japanese Patent Application Laid-Open No. 2007-224019, etc. And a precursor type compound (precursor) such as a porphyrin precursor.

  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), 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 which uses the photoelectric conversion element of this invention as photoelectric conversion materials, such as a solar cell, a photoelectric conversion element may be utilized by a single layer and may be laminated | stacked (tandem type) and may be utilized.

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

  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.

Synthesis Example <Living Radical Polymerization Using ATRP (Atom Transfer Radical Polymerization) Method>
"Synthesis of initiators"
Synthesis Example 1 (Synthesis of methoxy-capped oligoethylene glycol methacrylate 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 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 hydroxyl group-containing non-conductive polymers by living polymerization (ATRP)”
Synthesis Example 2 (Synthesis of poly (2-hydroxyethyl acrylate))
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%, 5 ml of methanol / water mixed solvent was put into a Schlenk tube, The Schlenk tube was immersed in liquid nitrogen under reduced pressure for 10 minutes. The Schlenk tube was taken out of liquid nitrogen and replaced with nitrogen after 5 minutes. After performing this operation three times, bipyridine (400 mg, 2.56 mmol) and CuBr (147 mg, 1.02 mmol) were added under nitrogen, and the mixture was stirred at 20 ° C. After 30 minutes, the reaction solution was dropped onto a 4 cm Kiriyama funnel with filter paper and silica, and the reaction solution was recovered under reduced pressure. The solvent was distilled off under reduced pressure using a rotary evaporator and then dried under reduced pressure at 50 ° C. for 3 hours. As a result, 2.60 g (yield 84%) of a hydroxyl group-containing non-conductive polymer P-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 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
Similarly, as a homopolymer of a hydroxyl group-containing nonconductive polymer, polyhydroxybutyl acrylate (P-2), polyhydroxyethyl vinyl ether (P-3), polyhydroxyethyl acrylamide (P-4) (number average molecular weight of about 2 P-5 was synthesized as a copolymer of hydroxyethyl acrylate (60 mol%) and methyl acrylate (40 mol%) with a number average molecular weight <1000 of 0%).

<Preparation of silver nanowire>
As metal nanoparticles, Adv. Mater. , 2002, 14, 833 to 837 with reference to PVP K30 (number average molecular weight 50,000; manufactured by ISP), silver nanowires having an average minor axis of 75 nm and an average length of 35 μm were prepared. After silver nanowires are filtered and washed with an ultrafiltration membrane, hydroxypropylmethylcellulose 60SH-50 (manufactured by Shin-Etsu Chemical Co., Ltd.) is redispersed in an aqueous solution containing 25% by mass of silver, and the silver nanowire dispersion liquid Was prepared.

<Preparation of the first conductive layer>
As a first conductive layer, the prepared silver nanowire dispersion liquid was applied on a 30 mm × 30 mm × 1.1 mm glass substrate using a spin coater so that the amount of silver nanowire applied was 0.06 g / m ^2. And dried to produce a silver nanowire layer.

  The viscosity of the metal nanoparticle removing solution is adjusted to 10 Pa · s with sodium carboxymethylcellulose (manufactured by SIGMA-ALDRICH; C5013 or less, CMC), and the reverse of FIG. Screen printing was performed with a pattern. After printing, the substrate was left for 1 minute, and then immersed in water for 30 seconds to perform a water washing treatment, thereby forming a silver nanowire layer (first conductive layer) 22 on the glass substrate 21.

<Preparation of metal nanoparticle removal solution>
60 g of ethylenediaminetetraacetic acid ferric ammonium salt
Ethylenediaminetetraacetic acid 2.0 g
Sodium metabisulfite 15g
70g ammonium thiosulfate
Maleic acid 5.0g
The metal nanowire remover was prepared by finishing to 1 L with pure water and adjusting the pH to 5.5 with sulfuric acid or ammonia water.

<Preparation of second conductive layer>
A mixed liquid of the conductive polymer and the nonconductive polymer shown in Table 1 was applied to the substrate on which the first conductive layer was patterned using a spin coater so as to have a predetermined dry film thickness. Next, using a cotton swab dipped in pure water, the region other than the second conductive layer 23 shown in FIG. 4b was removed and dried, and then heat treatment was performed at the temperature and time shown in Table 1, and from the first electrode 101 124 was produced. In addition, the polymer composition of Table 1 represents the mass ratio of the conductive polymer solid content to the total mass of the conductive polymer and the non-conductive polymer solid content.

Conductive polymer PH510: PEDOT: PSS dispersion PH510 (solid content 1.89%) (manufactured by HC Starck)
P4083: PEDOT: PSS dispersion Clevios P AI 4083 (solid content 1.5%) (manufactured by HC Starck)
Hydroxyl group-containing non-conductive polymer CMC: Carboxymethylcellulose low viscosity type (manufactured by Sigma-Aldrich)
PVA: polyvinyl alcohol PVA-235 (manufactured by Kuraray Co., Ltd.)
P-1: Polyhydroxyethyl acrylate P-2: Polyhydroxybutyl acrylate P-3: Polyhydroxyethyl vinyl ether P-4: Polyhydroxyethyl acrylamide P-5: Hydroxyethyl acrylate (60 mol%), Methyl acrylate (40 mol%) As the evaluation of the copolymer polymer electrode, the conductivity, transparency, smoothness of the portion where the first conductive layer and the second conductive layer overlap, and the dehydration condensation reaction rate of the second conductive layer were evaluated as follows.

(transparency)
As evaluation of transparency, the total light transmittance was measured using HAZE METER NDH5000 manufactured by Tokyo Denshoku Co., Ltd., and evaluated with the following indices. It is preferable that it is 70% or more from the optical loss in an element.

5: 80% or more 4: 70% or more and less than 80% 3: 60% or more and less than 70% 2: 50% or more and less than 60% 1: less than 50% (conductivity)
As conductivity evaluation, the surface resistance was measured using a resistivity meter (Loresta GP (MCP-T610 type): manufactured by Dia Instruments Co., Ltd.), and evaluated by the following indices. 4 or more is preferable, and 5 is more preferable.

5:10 ³ Ω / □ less than 4:10 ³ Ω / □ or more 10 ⁴ Ω / □ of less than 3:10 ⁴ Ω / □ or more 10 ⁵ Ω / □ under 2:10 ⁵ Ω / □ or more 10 ⁶ Ω / □ under 1:10 ⁶ Ω / □ or more (smoothness)
As an evaluation of smoothness, an atomic force microscope (AFM) SPI3800N probe station and a SPA400 multifunctional unit (manufactured by Seiko Instruments Inc.) were used to measure the surface roughness Ra. The cantilever uses SI-DF20 (manufactured by Seiko Instruments Inc.) and measures a 10 μm square measurement area at a scanning frequency of 1 Hz in a resonance frequency of 120 to 150 kHz, a spring constant of 12 to 20 N / m, and a DFM mode (Dynamic Force Mode). did. Using the arithmetic average roughness Ra determined according to JIS B601 (1994), the smoothness was evaluated using the following indices. The conductive polymer-containing layer alone is preferably 5 nm or less.

5: 0 μm or more and less than 1 μm 4: 1 μm or more and less than 5 μm 3: 5 μm or more but less than 10 μm 2:10 μm or more but less than 20 μm 1:20 μm or more (dehydration condensation reaction rate)
As an evaluation of the reaction rate, a differential scanning calorimeter (EXSTAR DSC6220 manufactured by SII Nanotechnology Co., Ltd.) was used to measure from 30 ° C. to 250 ° C. at a heating rate of 10 ° C./min in the atmosphere. The heat of reaction of the condensation reaction was measured. As the second conductive layer, coating and vacuum drying were performed at room temperature, and the reaction rate was calculated from the reaction heat C1 of each sample by the following formula using the reaction heat C0 of this sample as a reference for a reaction rate of 100%.
Reaction rate (%) = (C0−C1) / C0
The reaction rate was evaluated using the following indices.

5: Reaction rate of 50% to 100% 4: Reaction rate of 30% to less than 50% 3: Reaction rate of 20% to less than 30% 2: Reaction rate of 10% to less than 20% 1: Less than 10%

  From Table 1, smoothness cannot be satisfied only with the first conductive layer made of silver nanowires. If a non-conductive polymer is used alone as the second conductive layer, the smoothness and conductivity of the electrode cannot be compatible. When a conductive polymer is used alone as the second conductive layer, transparency, conductivity, and smoothness cannot be satisfied at the same time. The electrode of the present invention can simultaneously satisfy the above performance.

(Production of organic EL element)
(Production of organic functional layer (organic light-emitting layer))
The produced first electrode substrate was immersed in Semico Clean 56 (manufactured by Furuuchi Chemical Co., Ltd.), and subjected to ultrasonic cleaning treatment for 10 minutes using an ultrasonic cleaner Brandonic 3510J-MT. Subsequently, it was washed with running water for 5 minutes and then dried.

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. First, after reducing the vacuum to 1 × 10 ⁻⁴ Pa, the deposition crucible containing α-NPD was energized and heated, the deposition rate was 0.1 nm / second, and the second conductive layer in the pattern of FIG. A 30 nm hole transport layer was provided.

  Next, each light emitting layer was provided on the hole transport layer in the pattern of FIG.

  Ir-1, Ir-2, and A-1 were co-deposited at a deposition rate of 0.1 nm / sec so that the concentration of Ir-1 was 13% by mass and Ir-2 was 3.7% by mass. A green-red phosphorescent light emitting layer having a wavelength of 622 nm and a thickness of 10 nm was formed.

  Next, A-2 and A-1 are co-evaporated at a deposition rate of 0.1 nm / second so that A-2 is 10% by mass to form a blue phosphorescent light emitting layer having a maximum emission wavelength of 471 nm and a thickness of 15 nm. did.

  Thereafter, A-2 is deposited to a thickness of 5 nm to form a hole blocking layer, and CsF is co-deposited with A-3 so that the film thickness ratio is 10%, and an electron transport layer having a thickness of 45 nm is formed. Formed. Thus, an organic functional layer (organic light emitting layer) 24 was produced.

  Furthermore, as the second electrode, aluminum (film thickness: 110 nm) was deposited in the pattern of FIG.

<Formation of sealing film>
On the formed electron transport layer, a polyethylene terephthalate as a substrate, using a flexible sealing member which is deposited to a thickness 300nm of Al ₂ O _3. 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 the flexible sealing member 26 is shown in FIG. 4d (flexible sealing member). After bonding to the region, heat treatment was performed to cure the adhesive.

  Organic EL elements 201 to 224 were fabricated using ITO as an external extraction terminal for the anode and cathode electrodes.

(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.

  Five substrates were produced. Since there are two light emitting portions per substrate, a total of 10 light emitting portions were evaluated.

(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 increases with the influence of foreign matter and protrusions. When this ratio is 1, it is preferably completely leaked, preferably 100 or more, more preferably 1000 or more. The following indicators were used for evaluation. In order to cope with an increase in area, it is essential that the level is 3 or more, and 4 or more is preferable.

5: 8 or more is 1000 or more, less than 100 4: 5 or more is 1000 or more, less than 100 3: There is no element that does not emit light, but 1 is less than 100 2: 1 is less than 100, or 1 is an element that does not emit light 4: 1: Less than 100, or 5 or more elements that do not emit light (drive voltage)
The average value of the light-emitting elements was used as the drive voltage for each element, and the ratio of the element 204 to the drive voltage was determined and evaluated using the following indices. 3 or more is preferable, and 4 or more is more preferable.

5: Less than 80% 4: 80% or more and less than 90% 3: 90% or more and less than 110% 2: 110% or more and less than 130% 1: 130% or more or no light emission (storability)
The light-emitting element was left in an oven at 80 ° C. for 1 week, and then the drive voltage was measured. Similarly to the drive voltage evaluation described above, the ratio of the element 204 before the oven treatment to the drive voltage was obtained and evaluated using the following indices. .

5: Less than 80% 4: 80% or more and less than 90% 3: 90% or more and less than 110% 2: 110% or more and less than 130% 1: 130% or more or no light emission (lifetime)
Arbitrary elements were selected, continuous light emission was performed at an initial luminance of 5000 cd / m ² , and the time until the luminance was reduced by half was determined. The ratio of the element 204 to the driving voltage was obtained and evaluated using the following indices. 3 or more is preferable, and 4 or more is more preferable.

5: 90% or more 4: less than 90% 70% or more 3: less than 70% 50% or more 2: less than 50% 10% or more 1: less than 10%

  By including a non-conductive polymer having a specific structure having a hydroxyl group from Table 2, the device performance such as the rectification ratio of the device, the driving voltage, and the lifetime during continuous light emission is improved, and the dehydration condensation reaction rate of the non-conductive polymer is further improved. It can be seen that the storage stability can be drastically improved by setting it to 30% or more.

DESCRIPTION OF SYMBOLS 10 Substrate 11 First electrode 12 Second electrode 13 Organic functional layer 14 First conductive layer 15 Second conductive layer 16 Auxiliary electrode 21 Glass substrate 22 Silver nanowire layer (first conductive layer)
23 First conductive layer (conductive polymer and non-conductive polymer layer)
24 Organic functional layer (organic light-emitting layer)
25 Aluminum cathode

Claims (9)

  In an organic electronic device having a first electrode having a transparent conductive layer made of metal nanoparticles on a substrate, a second electrode facing the first electrode, and at least one organic functional layer between the electrodes, the first electrode The transparent conductive layer contains a conductive polymer and a non-conductive polymer, and the non-conductive polymer is a polymer obtained by dehydrating and condensing the hydroxyl groups of a polymer having a large number of hydroxyl groups. An organic electronic device having a dehydration condensation reaction rate of 30% to 95%.   2. The organic electronic device according to claim 1, wherein the non-conductive polymer has a dehydration condensation reaction rate of 50% to 95%. 3. The organic electronic device according to claim 1, wherein the non-conductive polymer includes a polymer (A) having the following three polymer chains.

(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 indicate the composition ratio (mol%), 50 ≦ l + m + n ≦ 100, and l, m, and n are each 0-100.)   The organic electronic device according to claim 1, wherein the conductive polymer includes a sulfo group-containing polyanion.   The organic electronic device according to claim 1, wherein the transparent conductive layer contains a catalyst for a dehydration condensation reaction.   The organic electronic device according to claim 5, wherein the catalyst is an acid catalyst.   The method for producing an organic electronic device according to any one of claims 1 to 6, wherein the step of providing metal nanoparticles on a substrate, and a non-conductive material having a conductive polymer and a hydroxyl group on the metal nanoparticle layer are provided. A method for producing an organic electronic device, comprising: a step of providing a mixture layer of a polymer and a dehydration condensation reaction catalyst; a step of heat treatment; and a step of forming an organic functional layer after the heat treatment.   The method for manufacturing an organic electronic device according to claim 7, wherein the heat treatment is performed at a temperature of 50 ° C. or more and 200 ° C. or less.   The organic electronic element of any one of Claims 1-6 is an organic electroluminescent element or an organic solar cell element, The organic electronic element characterized by the above-mentioned.

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