JP6984649B2 - Composition for manufacturing electronic devices, manufacturing method of composition for manufacturing electronic devices, manufacturing method of organic thin film and organic thin film - Google Patents

Description

The present invention relates to a composition for manufacturing an electronic device, a method for manufacturing a composition for manufacturing an electronic device, and a method for manufacturing an organic thin film and an organic thin film, and in particular, a selection range of solvents that can be used when manufacturing an electronic device such as an organic electronic device. The present invention relates to a composition for manufacturing an electronic device, which is excellent in solvent resistance and enables the manufacture of an electronic device having a laminated thin film without affecting the device performance and the like.

As a method for manufacturing an organic electronic device represented by an organic electroluminescence device (hereinafter, also referred to as an organic EL device), a thin film forming method by a vacuum vapor deposition method is widely used. However, the thin film forming method by the vacuum vapor deposition method requires a high vacuum and a high temperature for vapor deposition, and problems such as a limited molecular weight of a compound that can be used and an increase in the size of a manufacturing apparatus have become apparent.
As one of the methods for solving these problems, a method for manufacturing an organic EL device by a coating method using a solution containing an organic compound is being actively developed instead of the vacuum vapor deposition method.
However, when an organic EL element in which a plurality of organic thin films are laminated is formed by a coating method, an attempt is made to apply a solution containing another organic compound on the previously formed organic thin film containing an organic compound. In many cases, the previously formed organic thin film is destroyed.

Regarding an efficient method for forming an organic thin film in which organic EL elements are laminated, for example, Patent Document 1 discloses a method for manufacturing an organic EL element by a spin coating method, which is one of the coating methods. In Patent Document 1, all organic layers, which have been considered difficult in the past, are coated and formed by selecting an organic compound or a coating solvent constituting an organic EL device. That is, it can be considered that one method of imparting resistance to the solution used in the next step to the previously applied organic thin film has been proposed. As described above, Patent Document 1 makes it possible to manufacture an organic EL element by a coating method, but there are many restrictions such as the organic compound constituting each layer, the coating solvent, and the order of lamination, and further improvement is desired. ..

Further, as another method for laminating an organic thin film of an organic EL element by a coating method, Patent Document 2 discloses a laminating technique using a polymer material. This is a method utilizing the solvent resistance of the polymer thin film. However, since it is difficult to remove impurities derived from the polymer material in the thin film layer made of the polymer material, it is known that the device performance is deteriorated, and it is difficult to pursue the emission brightness and the like.
As described above, it is common to use a polymer or select a solvent that does not dissolve the adjacent layer in order to realize the lamination of the organic thin film. However, the solvent that can dissolve the organic compound contained in each organic thin film is limited, and if a polymer material is used, the device performance may be deteriorated, which is a big factor in the manufacturing process. There are challenges.

Japanese Patent No. 6052324 Japanese Unexamined Patent Publication No. 2016-115885

The present invention has been made in view of the above problems and situations, and the problem to be solved thereof is that the selection range of the solvent that can be used when manufacturing an electronic device is not limited, the solvent resistance is excellent, and the device performance is also affected. Provided are an electronic device manufacturing composition and a manufacturing method thereof, which makes it possible to manufacture an electronic device having a laminated thin film, and an organic thin film containing the electronic device manufacturing composition and a manufacturing method thereof. It is to be.

In the process of examining the cause of the above problem in order to solve the above-mentioned problem, the present inventor, when forming a plurality of laminated organic thin films, is applied to the previously formed organic thin film and then to the upper portion thereof. I thought that one of the solutions was to give solvent resistance to the solution. Therefore, we focused on cellulose nanofibers (CNF), which can effectively change the characteristics of the solution (composition) with the addition of a small amount.
The chicosis, which is one of the characteristics of CNF, makes it possible to impart solvent resistance, and when CNF is used to form an organic EL device, it imparts solvent resistance to an organic thin film that originally does not have solvent resistance. It has been found that this is possible and that laminated organic thin films can be easily formed. Furthermore, it was found that it is possible to form laminated organic thin films by adding a small amount of CNF, and it is epoch-making that it is possible to manufacture the desired organic EL element without sacrificing the characteristics of the organic EL element. We found a new method and came up with the present invention.
That is, the above-mentioned problem according to the present invention is solved by the following means.

1. 1. A composition for manufacturing an electronic device containing an organic material for an electronic device for forming an organic thin film.
A composition for producing an electronic device containing cellulose nanofibers.

2. 2. The composition for making an electronic device according to Item 1, wherein the cellulose nanofibers are contained in the range of 0.001 to 20000 mass ppm.

3. 3. The composition for manufacturing an electronic device according to item 1 or 2, which is an ink for inkjet.

4. Item 2. The electron according to any one of the items 1 to 3 , wherein the content of the cellulose nanofiber is in the range of 0.000001 to 5% by mass with respect to the mass of the organic material for an electronic device. Composition for device fabrication.

5. The composition for manufacturing an electronic device according to any one of items 1 to 4, wherein the organic material for an electronic device is a material for an organic electroluminescence device.

6. The method for producing a composition for manufacturing an electronic device according to any one of paragraphs 1 to 5.
A method for producing a composition for producing an electronic device, which comprises a step of mixing the organic material for an electronic device and the cellulose nanofibers.

7. An organic thin film containing the composition for manufacturing an electronic device according to any one of items 1 to 5.

8. The method for producing an organic thin film according to Item 7.
A method for producing an organic thin film, which comprises a step of applying the composition for producing an electronic device.

For manufacturing electronic devices having excellent solvent resistance, widening the selection range of solvents, and making it possible to manufacture electronic devices having laminated thin films without affecting device performance by the above means of the present invention. It is possible to provide a composition and a method for producing the same, an organic thin film containing the composition for producing the electronic device, and a method for producing the same.
Although the mechanism of expression or the mechanism of action of the effect of the present invention has not been clarified, it is inferred as follows.
By containing cellulose nanofibers, it is possible to effectively exert a thickening effect with a small amount of addition due to a special effect not found in other thickening agents such as thixophilicity. That is, the solvent resistance is improved by forming clusters of cellulose nanofibers by partial bonds between nanofibers via hydrogen bonds or the like. As a result, the organic thin film can be laminated without narrowing the selection range of the solvent, and since it is not necessary to use a polymer material or the like as the solvent, the device performance is not affected. Further, since the cellulose nanofibers are electrically inactive, the influence on the device performance is small.
Further, it is presumed that the cellulose nanofibers have an effect of amorphizing the state of the organic thin film by suppressing the crystallization of the film component and exhibiting the effect of dividing the layer (foreign matter mixing effect).

Schematic diagram showing an example of a display device composed of an organic EL element Schematic diagram of display unit A Schematic diagram showing a pixel circuit Schematic diagram of a passive matrix full-color display device Cross-sectional view showing a solar cell including a bulk heterojunction type organic photoelectric conversion element. Cross-sectional view showing a solar cell including an organic photoelectric conversion element provided with a tandem type bulk heterojunction layer.

The composition for manufacturing an electronic device of the present invention is a composition for manufacturing an electronic device containing an organic material for an electronic device, and contains cellulose nanofibers.
This feature is a technical feature common to or corresponding to the invention according to the present embodiment.
As an embodiment of the present invention, when the cellulose nanofibers are contained in the range of 0.001 to 20000 mass ppm, the viscosity can be easily adjusted and an electronic device having good performance can be produced. It is preferable in that it can be used.

The composition for producing an electronic device of the present invention is preferably an ink jet ink in terms of producing a variety of electronic devices.

When the content of the cellulose nanofibers is 5% by mass or less with respect to the mass of the organic material for electronic devices, the viscosity can be easily adjusted and an electronic device having good performance can be produced. It is preferable in that it can be used.

It is preferable that the organic material for an electronic device is a material for an organic electroluminescence element in that a long life of the light emitting element and high luminous efficiency can be effectively obtained.

A method for producing a composition for producing an electronic device of the present invention.
It has a step of mixing the organic material for an electronic device and the cellulose nanofibers.

The composition for manufacturing an electronic device of the present invention is suitably used for an organic thin film.
The method for producing an organic thin film of the present invention includes a step of applying the composition for producing an electronic device.

Hereinafter, the present invention, its constituent elements, and modes and embodiments for carrying out the present invention will be described in detail. In the present application, "~" is used to mean that the numerical values described before and after it are included as the lower limit value and the upper limit value. Further, in the present invention, the ratios such as "%" and "ppm" are based on mass.

[Outline of the composition for manufacturing an electronic device of the present invention]
The composition for manufacturing an electronic device of the present invention is a composition for manufacturing an electronic device containing an organic material for an electronic device, and contains cellulose nanofibers.
The composition for producing an electronic device of the present invention is preferably an inkjet ink applied by using an inkjet method.
When the composition for producing an electronic device is used for coating in the present invention, it is also referred to as a coating composition.

<Organic materials for electronic devices>
The organic material for an electronic device according to the present invention is an organic material used for an electronic device.
Examples of the electronic device include an organic EL element, a light emitting diode (LED), a liquid crystal element, a solar cell (photoelectric conversion element), a touch panel, a color filter of a liquid crystal display device, and the like. In particular, in the present invention, the electronic device is preferably an organic EL element, and the organic material for an electronic device is preferably an organic material for an organic EL element, from the viewpoint of exhibiting the effects of the invention.
In the present invention, the organic material for an electronic device means a solid component of the organic material and does not contain an organic solvent.

<Cellulose nanofibers>
The content of the cellulose nanofibers is preferably in the range of 0.001 to 20000 mass ppm with respect to the total mass of the composition for manufacturing an electronic device.
If it is contained in an amount of 0.001 mass ppm or more, the viscosity can be easily adjusted and the effect of solvent resistance can be sufficiently obtained. Does not occur. As a result, it is possible to manufacture an electronic device having good performance.
Further, the content of the cellulose nanofibers is preferably 5% by mass or less, more preferably 2% by mass or less, based on the mass of the organic material for electronic devices. The lower limit is 0.000001% by mass or more, more preferably 0.0001% by mass or more.
The cellulose nanofibers according to the present invention are cellulose microfibrils or cellulose microfibril aggregates, and are cellulose fibers having a width on the order of 2 to several hundred nm.
Cellulose nanofafibers can be produced from cellulosic materials. The cellulose material is not particularly limited, and natural cellulose such as various types of wood, non-wood pulp, microbially produced cellulose, baronia cellulose, and sea squirt cellulose can be used, and a pulping method, a purification method, a bleaching method, and the like can be used. Is not particularly limited. However, in order to further control the physical properties and improve the purity and reproducibility, it is preferable to use a highly purified cellulose material such as bleached pulp or dissolving pulp.
Cellulose nanofibers (chemically modified cellulose nanofibers) obtained by subjecting the cellulose material to a chemical treatment according to the purpose and then performing a defibration treatment can be used.
As the cellulose nanofiber, it is preferable to use Celish KY100G (manufactured by Daisel Finechem Co., Ltd.).

<Organic solvent>
The composition for producing an electronic device of the present invention preferably contains an organic solvent in addition to the organic material for the electronic device and cellulose nanofibers.
In the present invention, the organic solvent contained in the composition for producing an electronic device means a liquid medium composed of an organic compound capable of dissolving or dispersing the organic material for an electronic device.
The liquid medium for dissolving or dispersing the organic material for electronic devices according to the present invention includes ketones such as methylene chloride, methyl ethyl ketone, tetrahydrofuran (THF) and cyclohexanone, ethyl acetate, normal propyl acetate, isopropyl acetate, butyl acetate and isobutyl acetate. Fatty acid esters such as, chlorobenzene, dichlorobenzene, halogenated hydrocarbons such as 2,2,3,3-tetrafluoro-1-propanol (TFPO), aromatic hydrocarbons such as toluene, xylene, mesitylene, cyclohexylbenzene and the like. , Cyclohexane, decalin, dodecane and other aliphatic hydrocarbons, n-butanol, s-butanol, t-butanol alcohols, DMF (N, N-dimethyl formamide), DMSO (Dimethyl sulfoxide), ethers and the like. An organic solvent is mentioned, and a solvent having a boiling point in the range of 50 to 180 ° C. is preferable from the viewpoint of suppressing the amount of the solvent contained in the element.

[Manufacturing method of composition for manufacturing electronic devices]
The method for producing a composition for producing an electronic device of the present invention includes a step of mixing an organic material for an electronic device and cellulose nanofibers.
Specifically, the organic material for an electronic device is dissolved or dispersed in an organic solvent capable of dissolving or dispersing the organic material for the electronic device, and then filtered with, for example, a filter to prepare a solution, and then the solution is prepared. The composition for producing an electronic device of the present invention can be produced by adding and mixing cellulose nanofibers.

[Organic thin film]
The organic thin film of the present invention contains the above composition for manufacturing an electronic device.
The organic thin film of the present invention is preferably applied to, for example, at least one organic functional layer of an organic EL device.
As will be described later, examples of the organic functional layer include a plurality of organic functional layers such as an electron injection layer, an electron transport layer, a hole blocking layer, a light emitting layer, an electron blocking layer, a hole transport layer, and a hole injection layer. The organic thin film of the present invention may be used for at least one of these organic functional layers, and is not particularly limited. Among these organic functional layers, an electron transport layer, a hole blocking layer, a light emitting layer, and electron blocking. It is preferably either a layer or a hole transport layer, and more preferably one or more of a hole blocking layer, a light emitting layer, and an electron blocking layer. In particular, a light emitting layer is preferable from the viewpoint of luminous efficiency and durability.

Hereinafter, the details of the organic EL element will be described.
The organic EL element according to the present invention has an anode and a cathode, and one or more organic functional layers (also referred to as "organic EL layer" and "organic compound layer") sandwiched between these electrodes on a substrate. Have.

(substrate)
The substrate (hereinafter, also referred to as a substrate, a support substrate, a substrate, a support, etc.) that can be used for the organic EL element according to the present invention is not particularly limited, and a glass substrate, a plastic substrate, or the like can be used. , And may be transparent or opaque. When light is taken out from the substrate side, the substrate is preferably transparent. Examples of the transparent substrate preferably used include glass, quartz, and a transparent plastic substrate.

Further, as the substrate, to prevent oxygen and water from entering from the substrate side, JIS Z-0208 in test according to, the thickness of the water vapor permeability at 1μm or more ^{1g / (m 2 · 24h ·} atm ) (25 ° C.) or less is preferable.

Specific examples of the glass substrate include non-alkali glass, low-alkali glass, soda lime glass and the like. Non-alkali glass is preferable from the viewpoint of less adsorption of water, but any of these may be used as long as it is sufficiently dried.

Plastic substrates have been attracting attention in recent years because of their high flexibility, light weight, and resistance to cracking, and their ability to further reduce the thickness of organic EL elements.
The resin film used as the base material of the plastic substrate is not particularly limited, and is, for example, polyester such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyethylene, polypropylene, cellophane, cellulose diacetate, and cellulose triacetate (TAC). ), Cellulose acetate butyrate, Cellulose acetate propionate (CAP), Cellulose acetate phthalate, Cellulose acetate such as cellulose nitrate or derivatives thereof, Polyvinylidene chloride, Polypoly alcohol, Polyethylene vinyl alcohol, Syndiotactic polystyrene, Polycarbonate. , Norbornen resin, polymethylpentene, polyether ketone, polyimide, polyethersulfone (PES), polyphenylene sulfide, polysulfones, polyetherimide, polyetherketoneimide, polyamide, fluororesin, nylon, polymethylmethacrylate, acrylic or poly Examples thereof include allylates and organic-inorganic hybrid resins.

Examples of the organic-inorganic hybrid resin include those obtained by combining an organic resin with an inorganic polymer (for example, silica, alumina, titania, zirconia, etc.) obtained by a sol-gel reaction. Of these, norbornene (or cycloolefin-based) resins such as Arton (manufactured by JSR Corporation) or Appel (manufactured by Mitsui Chemicals, Inc.) are particularly preferable.

The plastic substrate usually produced has a relatively high moisture permeability, and may contain moisture inside the substrate. Therefore, when such a plastic substrate is used, it is preferable to provide a film (hereinafter referred to as "barrier film" or "steam sealing film") for suppressing the intrusion of water vapor, oxygen, etc. on the resin film.

The material constituting the barrier film is not particularly limited, and an inorganic substance, an organic film, or a hybrid of both thereof is used. A coating may be formed and the water vapor transmission rate (25 ± 0.5 ° C., relative humidity (90 ± 2)% RH) measured by a method according to JIS K 7129-1992 is 0.01 g / (. preferably m ² · 24h) or less of the barrier film, and further, the measured oxygen permeability by the method based on JIS K 7126-1987 ^{is, 1 × 10 -3 mL / (} m 2 · 24h · atm) or less, the water vapor permeability is preferably ^{1 × 10 -5 g / (m} 2 · 24h) or less of the high barrier film.

The material constituting the barrier film is not particularly limited as long as it is a material having a function of suppressing infiltration of a material that causes deterioration of the element such as moisture and oxygen, and is, for example, a metal oxide, a metal oxynitride, a metal nitride, or the like. Inorganic substances, organic substances, or hybrid materials of both can be used.
Examples of the metal oxide, metal oxynitride or metal nitride include metal oxides such as silicon oxide, titanium oxide, indium oxide, tin oxide, indium tin oxide (ITO) and aluminum oxide, and metal nitride such as silicon nitride. Examples thereof include metal oxynitrides such as aluminum oxynitrides and titanium oxynitrides.

Further, in order to improve the vulnerability of the film, it is more preferable to have a laminated structure of these inorganic layers and layers made of an organic material. The stacking order of the inorganic layer and the organic layer is not particularly limited, but it is preferable to stack the inorganic layer and the organic layer alternately a plurality of times.

Barrier film was measured by the method based on JIS K 7129-1992, the water vapor transmission rate (25 ± 0.5 ° C., relative humidity (90 ± 2)% RH) is 0.01g / (m ² · 24h) preferably less a barrier film, and further, the oxygen permeability measured in compliance with the method provided in JIS K 7126-1987 ^{is, 10 -3 mL / (m 2} · 24h · atm) or less, the water vapor permeability but it is preferably ^{10 -5 g / (m 2 ·} 24h) or less of the high barrier film.
The method for providing the barrier film on the resin film is not particularly limited, and any method may be used. For example, a vacuum vapor deposition method, a sputtering method, a reactive sputtering method, a molecular beam epitaxy method, a cluster ion beam method, or an ion plating method may be used. A method, a plasma polymerization method, an atmospheric pressure plasma polymerization method, a CVD method (chemical vapor deposition: for example, a plasma CVD method, a laser CVD method, a thermal CVD method, etc.), a coating method, a sol-gel method, or the like can be used. .. Of these, the method by plasma CVD treatment at atmospheric pressure or near atmospheric pressure is preferable from the viewpoint that a dense film can be formed.

Examples of the opaque substrate include a metal plate such as aluminum and stainless steel, a film or an opaque resin substrate, and a ceramic substrate.

(anode)
As the anode of the organic EL element, a metal having a large work function (4 eV or more), an electrically conductive compound of a metal, or a mixture thereof as an electrode material is preferably used.
Here, the "electrically conductive compound of a metal" means a compound having electric conductivity among compounds of a metal and another substance, and specifically, for example, an oxide of a metal, a halide, or the like. Refers to those having electrical conductivity.

Specific examples of such an electrode material include metals such as Au and conductive transparent materials such as _{CuI, indium tin oxide (ITO), SnO 2, and ZnO.} The anode can be produced by forming a thin film made of these electrode substances on the substrate by a known method such as thin film deposition or sputtering.
Further, a pattern having a desired shape may be formed on this thin film by a photolithography method, and if pattern accuracy is not required so much (about 100 μm or more), the desired shape may be formed during vapor deposition or sputtering of the electrode material. A pattern may be formed via a mask.
When extracting light from the anode, it is desirable to increase the transmittance to more than 10%. The sheet resistance as an anode is several hundred Ω / sq. The following is preferable. Further, the film thickness of the anode is usually selected in the range of 10 nm to 1 μm, preferably 10 to 200 nm, although it depends on the constituent material.

(Organic functional layer)
The organic functional layer (also referred to as "organic EL layer" or "organic compound layer") includes at least a light emitting layer, but the light emitting layer is broadly defined as when a current is passed through an electrode composed of a cathode and an anode. Specifically, it refers to a layer containing an organic compound that emits light when a current is passed through an electrode consisting of a cathode and an anode.

The organic EL device used in the present invention may have a hole injection layer, an electron injection layer, a hole transport layer and an electron transport layer in addition to the light emitting layer, if necessary, and these layers are cathodes. It has a structure sandwiched between an electron and an anode.
In particular,
(I) Anode / light emitting layer / cathode (ii) anode / hole injection layer / light emitting layer / cathode (iii) anode / light emitting layer / electron injection layer / cathode (iv) anode / hole injection layer / light emitting layer / electron Injection layer / cathode (v) anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode (vi) anode / hole transport layer / light emitting layer / electron transport layer / cathode, etc. The structure of.
Further, a cathode buffer layer (eg, lithium fluoride, etc.) may be inserted between the electron injection layer and the cathode, and an anode buffer layer (eg, copper phthalocyanine, etc.) may be inserted between the anode and the hole injection layer. ) May be inserted.

(Light emitting layer)
The light emitting layer according to the present invention is a layer in which electrons and holes injected from an electrode or an electron transport layer and a hole transport layer recombine and emit light, and the light emitting portion is in the layer of the light emitting layer. May also be the interface between the light emitting layer and the adjacent layer. The light emitting layer may be a layer having a single composition, or may have a laminated structure composed of a plurality of layers having the same or different compositions.
The light emitting layer itself may be provided with functions such as a hole injection layer, an electron injection layer, a hole transport layer, and an electron transport layer. That is, (1) an injection function capable of injecting holes through an anode or a hole injection layer and electrons being injected from a cathode or an electron injection layer when an electric charge is applied to the light emitting layer, (2) injection. At least one of the transport function of moving charges (electrons and holes) by the force of an electric field, and (3) the light emitting function of providing a field of recombination of electrons and holes inside the light emitting layer and connecting this to light emission. Functions may be added. The light emitting layer may have a difference in the ease of injecting holes and the ease of injecting electrons, and may have different transport functions represented by the mobility of holes and electrons. , Those having a function of transferring at least one of the charges are preferable.

The type of light emitting material used for this light emitting layer is not particularly limited, and conventionally known light emitting materials for organic EL devices can be used. Such a light emitting material is mainly an organic compound, and depending on a desired color tone, for example, Macromol. Symp. Examples include the compounds described in Vol. 125, pp. 17-26. Further, the light emitting material may be a polymer material such as p-polyphenylene vinylene or polyfluorene, and further, a polymer material in which the light emitting material is introduced into a side chain or a polymer material in which the light emitting material is used as a main chain of a polymer may be used. You may use it. As described above, since the light emitting material may have a hole injection function and an electron injection function in addition to the light emission performance, most of the hole injection materials and electron injection materials described later can also be used as the light emitting material. Can be used.

In the layer constituting the organic EL element, when the layer is composed of two or more kinds of organic compounds, the main component is referred to as a host, the other components are referred to as a dopant, and the host and the dopant are used in combination in the light emitting layer of the present invention. The mixing ratio of the dopant of the light emitting layer (hereinafter, also referred to as light emitting dopant) with respect to the host compound as the main component is preferably less than 0.1 to 30% by mass in terms of mass.

The dopant used for the light emitting layer is roughly divided into two types: a fluorescent dopant that emits fluorescence and a phosphorescent dopant that emits phosphorescence.
Typical examples of fluorescent dopants are coumarin dyes, pyran dyes, cyanine dyes, croconium dyes, squalium dyes, oxobenzanthracene dyes, fluorescein dyes, rhodamine dyes, pyrylium dyes, and perylene dyes. , Fluorescein-based dyes, polythiophene-based dyes, rare earth complex-based phosphors, and other known fluorescent compounds.
In the present invention, it is preferable that at least one light emitting layer contains a phosphorescent compound.

In the present invention, the phosphorescent compound is a compound in which light emission from the excited triplet is observed, and is a compound having a phosphorescence quantum yield of 0.001 or more at 25 ° C.
The phosphorus photon yield is preferably 0.01 or more, more preferably 0.1 or more. The phosphorus photon yield can be measured by the method described on page 398 (1992 edition, Maruzen) of Spectroscopy II of the 4th edition Experimental Chemistry Course 7. The phosphorescent quantum yield in a solution can be measured using various solvents, but the phosphorescent compound used in the present invention may achieve the above-mentioned phosphorescent quantum yield in any of any solvents.

The phosphorescent dopant is a phosphorescent compound, and as a typical example thereof, it is preferably a complex compound containing a metal of Group 8 to 10 in the periodic table of elements, and more preferably an iridium compound or an osmium compound. , A rhodium compound, a palladium compound, or a platinum compound (platinum complex type compound), more preferably an iridium compound, a rhodium compound, and a platinum compound, and most preferably an iridium compound.

Examples of dopants are the compounds described in the following literature or patent gazettes. J. Am. Chem. Soc. Vol. 123, pp. 4304 to 4312, International Publication No. 2000/70655, No. 2001/93642, No. 2002/02714, No. 2002/15645, No. 2002/44189, No. 2002/081488, JP-A-2002-280178 No. 2001-181616, 2002-280179, 2001-181617, 2002-280180, 2001-247859, 2002-299060, 2001-313178. Publication No. 2002-302671, Publication No. 2001-345183, Publication No. 2002-324679, Publication No. 2002-332291, Publication No. 2002-50484, Publication No. 2002-332292, Publication No. 2002-836484. , Japanese Patent Application Laid-Open No. 2002-540572, JP-A-2002-117978, JP-A-2002-338588, JP-A-2002-170684, JP-A-2002-352960, JP-A-2002-50483, JP-A-2002-100476. No. 2002-173674, No. 2002-359082, No. 2002-175884, No. 2002-363552, No. 2002-184582, No. 2003-7469, No. 2002-525808. Japanese Patent Application Laid-Open No. 2003-7471, Japanese Patent Application Laid-Open No. 2002-525833, JP-A-2003-31366, JP-A-2002-226495, JP-A-2002-234894, JP-A-2002-23507, JP-A-2002- No. 241751, No. 2001-319779, No. 2001-319780, No. 2002-62824, No. 2002-100474, No. 2002-203679, No. 2002-343572, No. 2002-203678. Issue, etc.

Specific examples of phosphorescent dopants are given below, but the present invention is not limited thereto.

Only one type of light emitting dopant may be used, or a plurality of types may be used, and by simultaneously extracting light emitted from these dopants, a light emitting element having a plurality of light emission maximum wavelengths can be configured. Further, for example, both a phosphorescent dopant and a fluorescent dopant may be added. When a plurality of light emitting layers are laminated to form an organic EL element, the light emitting dopants contained in each layer may be the same or different, may be of a single type, or may be of a plurality of types. ..
Further, a polymer material in which the light emitting dopant is introduced into a polymer chain or the light emitting dopant is used as a main chain of a polymer may be used.

Examples of the host compound include those having a basic skeleton such as a carbazole derivative, a triarylamine derivative, an aromatic borane derivative, a nitrogen-containing heterocyclic compound, a thiophene derivative, a furan derivative, and an oligoarylene compound, which will be described later. Transport materials and hole transport materials are also examples of suitable examples.
When applied to blue or white light emitting elements, display devices and lighting devices, the fluorescence maximum wavelength of the host compound is preferably 415 nm or less, and when a phosphorescent dopant is used, the phosphorescence of the host compound is 0-. It is more preferable that the 0 band is 450 nm or less. As the light emitting host, a compound having hole transporting ability and electron transporting ability, preventing the wavelength of light emission from being lengthened, and having a high Tg (glass transition temperature) is preferable.

As a specific example of the light emitting host, for example, the compounds described in the following documents are suitable.
Japanese Patent Laid-Open Nos. 2001-257076, 2002-308855, 2001-313179, 2002-319491, 2001-357977, 2002-334786, 2002-8860, 2002-334787, 2002-15871, 2002-334788, 2002-43056, 2002-334789, 2002-75445, 2002-338579, 2002. 2002-105445, 2002-343568, 2002-141173, 2002-352957, 2002-203683, 2002-363227, 2002-231453, 2003. -3165, 2002-234888, 2003-27048, 2002-255934, 2002-260861, 2002-280183, 2002-299060, 2002- 302516, 2002-305083, 2002-305084, 2002-308837, etc.

The luminescent dopant may be dispersed throughout the layer containing the host compound, or may be partially dispersed. A compound having yet another function may be added to the light emitting layer.

A light emitting layer can be formed by thinning the above material by a known method such as a vapor deposition method, a spin coating method, a casting method, an LB method, an inkjet transfer method, or a printing method. It is particularly preferable that the light emitting layer formed is a molecular deposition film.
Here, the molecular deposition film is a thin film deposited and formed from the gas phase state of the compound, and a film solidified and formed from the molten state or the liquid phase state of the compound. Usually, this molecular deposition film and the thin film (molecular cumulative film) formed by the LB method can be distinguished from each other by the difference in aggregate structure, higher-order structure, and the functional difference caused by the difference.
In the present invention, it is preferable to use the phosphorescent dopant and the host compound, which are the above-mentioned light emitting materials, as the organic material for the electronic device according to the present invention. That is, the light emitting layer is a solution containing the phosphorescent dopant and the host compound, an organic solvent, and cellulose nanofibers (composition for manufacturing an electronic device) by spin coating method, casting method, inkjet method, spray method, printing. It is preferable to form by coating by a method, a slot type coater method or the like because a light emitting layer made of a molecular deposition film can be formed. Above all, the inkjet method is preferable from the viewpoint that a homogeneous film can be easily obtained and pinholes are less likely to be generated.
Then, in the coating liquid containing the phosphorescent dopant, the host compound, the organic solvent, and the cellulose nanofibers, the concentration of dissolved carbon dioxide in the organic solvent under atmospheric pressure conditions of 50 ° C. or lower is saturated from 1 ppm to the organic solvent. The concentration is preferably set. As a means for setting the dissolved carbon dioxide concentration in the above range, a method of bubbling carbon dioxide gas into a solution containing a phosphorescent dopant and a host compound and an organic solvent, or a supercritical fluid containing an organic solvent and carbon dioxide is used. Examples thereof include the supercritical chromatography method used.

(Hole injection layer and hole transport layer)
The hole injection material used for the hole injection layer has either hole injection or electron barrier property. Further, the hole transport material used for the hole transport layer has an electron barrier property and also has a function of transporting holes to the light emitting layer. Therefore, in the present invention, the hole transport layer is included in the hole injection layer.

The hole injection material and the hole transport material may be either an organic substance or an inorganic substance. Specifically, for example, triazole derivative, oxadiazole derivative, imidazole derivative, polyarylalkane derivative, pyrazoline derivative, pyrazolone derivative, phenylenediamine derivative, arylamine derivative, amino-substituted carcon derivative, oxazole derivative, styrylanthracene derivative, fluorenone derivative. , Hydrazone derivative, Stilben derivative, Silazan derivative, Aniline-based copolymer, Porphyrin compound, Conductive polymer oligomer such as thiophene oligomer. Of these, arylamine derivatives and porphyrin compounds are preferred.
Among the arylamine derivatives, aromatic tertiary amine compounds and styrylamine compounds are preferable, and aromatic tertiary amine compounds are more preferable.

Typical examples of the above aromatic tertiary amine compound and styrylamine compound are N, N, N', N'-tetraphenyl-4,4'-diaminophenyl; N, N'-diphenyl-N, N'. -Bis (3-methylphenyl)-[1,1'-biphenyl] -4,4'-diamine (TPD); 2,2-bis (4-di-p-tolylaminophenyl) propane; 1,1- Bis (4-di-p-tolylaminophenyl) cyclohexane; N, N, N', N'-tetra-p-tolyl-4,4'-diaminobiphenyl; 1,1-bis (4-di-p-) Trillaminophenyl) -4-phenylcyclohexane; bis (4-dimethylamino-2-methylphenyl) phenylmethane; bis (4-di-p-tolylaminophenyl) phenylmethane; N, N'-diphenyl-N, N ′ -Di (4-methoxyphenyl) -4,4'-diaminobiphenyl; N, N, N', N'-tetraphenyl-4,4'-diaminodiphenyl ether; 4,4'-bis (diphenylamino) biphenyl N, N, N-tri (p-tolyl) amine; 4- (di-p-tolylamino) -4'-[4- (di-p-tolylamino) styryl] stilben; 4-N, N-diphenylamino -(2-Diphenylvinyl) benzene; 3-methoxy-4'-N, N-diphenylaminostylben; N-phenylcarbazole, as well as the two condensed aromatics described in US Pat. No. 5,061569. Those having a ring in the molecule, for example, 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (hereinafter abbreviated as α-NPD), described in JP-A-4-308688. Examples include 4,4', 4 ″ -tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine (MTDATA) in which the triphenylamine units are linked in a three-star burst type. Further, inorganic compounds such as p-type-Si and p-type-SiC can also be used as the hole injection material.

Further, in the present invention, the hole transport material of the hole transport layer preferably has a fluorescence maximum wavelength of 415 nm or less. That is, the hole transporting material is preferably a compound having a hole transporting ability, preventing the wavelength of light emission from being lengthened, and having a high Tg.
As the hole injection layer and the hole transport layer, the hole injection material and the hole transport material are known, for example, vacuum deposition method, spin coating method, casting method, LB method, inkjet method, transfer method, printing method and the like. It can be formed by thinning the film according to the above method.
In the present invention, it is preferable to use the hole injection material and the hole transport material as the organic material for the electronic device according to the present invention. Then, the hole injection material, the hole transport material, the organic solvent, and the solution containing the cellulose nanofibers (composition for manufacturing an electronic device) are subjected to a spin coating method, a casting method, an inkjet method, a spray method, a printing method, and the like. It is preferably formed by coating by a slot type coater method or the like. Above all, the inkjet method is preferable from the viewpoint that a homogeneous film can be easily obtained and pinholes are less likely to be generated.

The thickness of the hole injection layer and the hole transport layer is not particularly limited, but is usually about 5 nm to 5 μm. The hole injection layer and the hole transport layer may have a one-layer structure composed of one or more of the above materials, respectively, or a laminated structure composed of a plurality of layers having the same composition or different compositions. May be good. When both the hole injection layer and the hole transport layer are provided, different materials are usually used among the above materials, but the same material may be used.

(Electron injection layer and electron transport layer)
The electron injection layer may have a function of transferring electrons injected from the cathode to the light emitting layer, and any conventionally known compound can be selected and used as the material thereof.
Examples of the material used for this electron-injected layer (hereinafter, also referred to as electron-injected material) include nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyrandioxide derivatives, heterocyclic tetracarboxylic acid anhydrides such as naphthalene perylene, and carbodiimide. , Freolenilidene methane derivative, anthraquinodimethane and anthron derivative, oxadiazole derivative and the like.
Further, a series of electron transporting compounds described in JP-A-59-194393 are disclosed as materials for forming a light emitting layer in the publication, but as a result of examination by the present inventors, electron injection is performed. It was found that it could be used as a material. Further, among the above oxadiazole derivatives, a thiadiazole derivative in which the oxygen atom of the oxadiazole ring is replaced with a sulfur atom, and a quinoxaline derivative having a quinoxaline ring known as an electron-withdrawing group can also be used as an electron injection material.

Also, metal complexes of 8-quinolinol derivatives such as tris (8-quinolinol) aluminum ( _{abbreviated as Alq 3} ), tris (5,7-dichloro-8-quinolinol) aluminum, tris (5,7-dibromo-8-). Kinolinol) aluminum, tris (2-methyl-8-quinolinol) aluminum, tris (5-methyl-8-quinolinol) aluminum, bis (8-quinolinol) zinc (Znq), etc. , Mg, Cu, Ca, Sn, Ga or Pb can also be used as the electron injection material.

In addition, metal-free or metal phthalocyanine, or those whose terminals are substituted with an alkyl group, a sulfonic acid group, or the like can also be preferably used as an electron injection material. Further, like the hole injection layer, inorganic semiconductors such as n-type-Si and n-type-SiC can also be used as the electron injection material.

The preferred compound used in the electron transport layer preferably has a fluorescence maximum wavelength of 415 nm or less. That is, the compound used for the electron transport layer is preferably a compound having an electron transport ability, preventing a long wavelength of light emission, and having a high Tg.
The electron injection layer is formed by thinning the electron injection material by a known method such as a vacuum vapor deposition method, a spin coating method, a casting method, an LB method, an inkjet method, a transfer method, or a printing method. Can be done.
In the present invention, it is preferable to use the electron injection material as an organic material for an electronic device according to the present invention. Then, the solution containing the electron injection material, the organic solvent, and the cellulose nanofibers (composition for manufacturing an electronic device) is subjected to a spin coating method, a casting method, an inkjet method, a spray method, a printing method, a slot type coater method, or the like. It is preferably formed by coating. Above all, the inkjet method is preferable from the viewpoint that a homogeneous film can be easily obtained and pinholes are less likely to be generated.
The thickness of the electron injection layer is not particularly limited, but is usually selected in the range of 5 nm to 5 μm. The electron injection layer may have a one-layer structure composed of one or more of these electron injection materials, or may have a laminated structure composed of a plurality of layers having the same composition or different compositions.

In the present specification, among the electron injection layers, when the ionization energy is larger than that of the light emitting layer, it is referred to as an electron transport layer. Therefore, in the present specification, the electron transport layer is included in the electron injection layer.
The electron transport layer is also referred to as a hole blocking layer (hole block layer), and examples thereof include International Publication No. 2000/706555, JP-A-2001-313178, and JP-A-11-204258. No. 11-204359, and those described in "Organic EL element and its forefront of industrialization (published by NTS Co., Ltd., November 30, 1998)", page 237, etc. can be mentioned. In particular, in a so-called "phosphorescent light emitting device" that uses an orthometal complex-based dopant for the light emitting layer, it is preferable to adopt a configuration having an electron transport layer (hole blocking layer) as described in (v) and (vi).

(Buffer layer)
A buffer layer (electrode interface layer) may be present between the anode and the light emitting layer or the hole injection layer, and between the cathode and the light emitting layer or the electron injection layer.
The buffer layer is a layer provided between the electrode and the organic layer in order to reduce the driving voltage and improve the luminous efficiency. "Organic EL element and its forefront of industrialization (November 30, 1998, published by NTS) ) ”, Volume 2, Chapter 2,“ Electrode Materials ”(pages 123 to 166), and includes an anode buffer layer and a cathode buffer layer.

The details of the anode buffer layer are also described in JP-A-9-45479, 9-2660062, 8-288569 and the like, and specific examples thereof include a phthalocyanine buffer layer typified by copper phthalocyanine and vanadium oxide. Examples thereof include an oxide buffer layer represented by the above, an amorphous carbon buffer layer, and a polymer buffer layer using a conductive polymer such as polyaniline (emeraldine) or polythiophene.

The details of the cathode buffer layer are described in JP-A-6-325871, No. 9-17574, No. 10-74586, etc., and specifically, a metal buffer layer typified by strontium, aluminum, or the like. Examples thereof include an alkali metal compound buffer layer typified by lithium fluoride, an alkaline earth metal compound buffer layer typified by magnesium fluoride, and an oxide buffer layer typified by aluminum oxide.

The buffer layer is preferably a very thin film, and the thickness thereof is preferably in the range of 0.1 to 100 nm, although it depends on the material. Further, in addition to the above basic constituent layers, layers having other functions may be appropriately laminated, if necessary.

(cathode)
As described above, the cathode of the organic EL element generally uses a metal (hereinafter referred to as an electron-injectable metal) having a small work function (less than 4 eV), an alloy, an electrically conductive compound of the metal, or a mixture thereof as an electrode material. Things are used.
Specific examples of such electrode materials include sodium, magnesium, lithium, aluminum, indium, rare earth metals, sodium-potassium alloys, magnesium / copper mixtures, magnesium / silver mixtures, magnesium / aluminum mixtures, magnesium / indium mixtures, and aluminum. / Aluminum oxide (Al ₂ O ₃ ) mixture, lithium / aluminum mixture and the like can be mentioned.

In the present invention, those listed above may be used as the electrode material of the cathode, but from the viewpoint of more effectively exerting the effect of the present invention, the cathode may contain a Group 13 metal element. preferable. That is, in the present invention, as will be described later, the surface of the cathode is oxidized with oxygen gas in a plasma state to form an oxide film on the surface of the cathode, thereby preventing further oxidation of the cathode and improving the durability of the cathode. Can be made to.
Therefore, the electrode material of the cathode is preferably a metal having preferable electron injection properties required for the cathode and capable of forming a dense oxide film.

Specific examples of the electrode material of the cathode containing the Group 13 metal element include aluminum, indium, magnesium / aluminum mixture, magnesium / indium mixture, and aluminum / aluminum oxide (Al ₂ O ₃ ) mixture. , Lithium / aluminum mixture and the like. The mixing ratio of each component of the mixture can be a conventionally known ratio as the cathode of the organic EL element, but the mixing ratio is not particularly limited to this. The cathode can be produced by forming a thin film on the organic compound layer (organic EL layer) by forming the electrode material on the organic compound layer (organic EL layer) by a method such as vapor deposition or sputtering.

The sheet resistance as a cathode is several hundred Ω / sq. The following is preferable, and the film thickness is usually selected in the range of 10 nm to 1 μm, preferably 50 to 200 nm. It is preferable to make either the anode or the cathode of the organic EL element transparent or translucent in order to transmit the emitted light because the luminous efficiency is improved.

[Manufacturing method of organic thin film]
The method for producing an organic thin film of the present invention includes a step of applying the composition for producing an electronic device.
A method for producing an organic thin film when the organic thin film of the present invention is used for the organic functional layer of the above-mentioned organic EL element, that is, a method for producing the organic EL element will be described.

As an example of a method for manufacturing an organic EL device, a method for manufacturing an organic EL device including an anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode will be described.
First, a thin film made of a desired electrode substance, for example, an anode substance, is formed on a suitable substrate by a method such as thin film deposition or sputtering so as to have a thickness of 1 μm or less, preferably 10 to 200 nm, to prepare an anode. do. Next, an organic compound thin film (organic thin film) of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a hole blocking layer, which are element materials, is formed on this.
As a method for thinning these organic thin films, as described above, there are a spin coating method, a casting method, an inkjet method, a spray method, a vapor deposition method, a printing method, a slot coating method and the like, and a uniform film can be obtained. The inkjet method is preferable in that it is easy and difficult to generate pinholes, and in the present invention, the composition for producing an electronic device according to the present invention can be used.
Further, a different film forming method may be applied to each layer. The case of employing an evaporation method in the deposition, the deposition conditions may vary due to kinds of materials used, generally boat temperature 50 to 450 ° C., vacuum of 10 ^-6 to 10 ^-2 Pa, the deposition rate 0.01 It is desirable to appropriately select in the range of ~ 50 nm / sec, substrate temperature -50 to 300 ° C., and thickness 0.1 nm to 5 μm.

After forming these layers, a thin film made of a cathode substance is formed on the thin film so as to have a thickness in the range of 1 μm or less, preferably 50 to 200 nm, for example, by a method such as thin film deposition or sputtering, and a cathode is provided. Therefore, a desired organic EL element can be obtained. The organic EL element is preferably manufactured from the hole injection layer to the cathode by one vacuuming, but it may be taken out in the middle and a different film forming method may be applied. At that time, consideration must be given to performing the work in a dry inert gas atmosphere.

[Seal of organic EL element]
The means for sealing the organic EL element is not particularly limited, but for example, after sealing the outer peripheral portion of the organic EL element with a sealing adhesive, a sealing member is provided so as to cover the light emitting region of the organic EL element. There is a method of arranging.

Examples of the sealing adhesive include acrylic acid-based oligomers, photocurable and thermosetting adhesives having a reactive vinyl group of methacrylic acid-based oligomers, and moisture-curable adhesives such as 2-cyanoacrylic acid ester. Can be mentioned. In addition, heat and chemical curing type (two-component mixing) such as epoxy type can be mentioned. Further, hot melt type polyamide, polyester and polyolefin can be mentioned. Further, a cation-curable type ultraviolet-curable epoxy resin adhesive can be mentioned.

As the sealing member, a polymer film and a metal film can be preferably used from the viewpoint that the organic EL element can be thinned.

In the gap between the sealing member and the light emitting region of the organic EL element, in addition to the sealing adhesive, in the gas phase and liquid phase, an inert gas such as nitrogen or argon, fluorinated hydrocarbon, silicon oil, etc. It is also possible to inject a non-active liquid. Further, the gap between the sealing member and the display region of the organic EL element can be evacuated, or the hygroscopic compound can be sealed in the gap.

[Display device]
In the multicolor display device using the organic EL element, a shadow mask is provided only when the light emitting layer is formed, and since the other layers are common, patterning of the shadow mask or the like is unnecessary, and the vapor deposition method, casting method, or spin coating method is performed on one surface. A film can be formed by a method, an inkjet method, a printing method, or the like.
When patterning only the light emitting layer, the method is not limited, but a vapor deposition method, an inkjet method, or a printing method is preferable. When the vapor deposition method is used, patterning using a shadow mask is preferable.
It is also possible to reverse the production order and produce the cathode, the electron injection layer, the electron transport layer, the light emitting layer, the hole transport layer, the hole injection layer, and the anode in this order.
When a DC voltage is applied to the multicolor display device thus obtained, light emission can be observed by applying a voltage of about 2 to 40 V with the anode as the positive polarity and the cathode as the negative polarity. Further, even if a voltage is applied with the opposite polarity, no current flows and no light emission occurs. Further, when an AC voltage is applied, light is emitted only when the anode is in the + state and the cathode is in the-state. The waveform of the alternating current to be applied may be arbitrary.

The multicolor display device can be used as a display device, a display, and various light emitting light sources. Full-color display is possible by using three types of organic EL elements of blue, red, and green emission in a display device and a display.
Examples of display devices and displays include televisions, personal computers, mobile devices, AV devices, teletext displays, information displays in automobiles, and the like. In particular, it may be used as a display device for reproducing a still image or a moving image, and the drive method when used as a display device for reproducing a moving image may be either a simple matrix (passive matrix) method or an active matrix method.

Light sources include household lighting, interior lighting, backlights for clocks and liquid crystals, signboard advertisements, traffic lights, light sources for optical storage media, light sources for electrophotographic copying machines, light sources for optical communication processors, light sources for optical sensors, etc. It can be mentioned, but it is not limited to this.
Further, the organic EL element according to the present invention may be used as an organic EL element having a resonator structure.
The purpose of using the organic EL element having such a resonator structure includes a light source of an optical storage medium, a light source of an electrophotographic copying machine, a light source of an optical communication processor, a light source of an optical sensor, and the like. Not limited. Further, it may be used for the above-mentioned applications by oscillating a laser.

The organic EL element according to the present invention may be used as a kind of lamp such as for lighting or an exposure light source, a projection device of a type for projecting an image, or a display of a type for directly visually recognizing a still image or a moving image. It may be used as a device (display). When used as a display device for video reproduction, the drive method may be either a simple matrix (passive matrix) method or an active matrix method. Alternatively, a full-color display device can be manufactured by using two or more kinds of organic EL elements of the present invention having different emission colors.

An example of a display device composed of an organic EL element according to the present invention will be described below with reference to the drawings.
FIG. 1 is a schematic diagram showing an example of a display device composed of an organic EL element.
It is a schematic diagram of a display such as a mobile phone which displays image information by light emission of an organic EL element. The display 41 includes a display unit A having a plurality of pixels, a control unit B that scans an image of the display unit A based on image information, and the like. The control unit B is electrically connected to the display unit A, sends a scanning signal and an image data signal to each of a plurality of pixels based on image information from the outside, and the scanning signal converts the pixels of each scanning line into an image data signal. In response to this, light is emitted in sequence, image scanning is performed, and image information is displayed on the display unit A.

FIG. 2 is a schematic diagram of the display unit A. The display unit A has a wiring unit including a plurality of scanning lines 55 and data lines 56, a plurality of pixels 53, and the like on the substrate. The main members of the display unit A will be described below.
FIG. 2 shows a case where the light emitted from the pixel 53 is taken out in the direction of the white arrow (downward). The scanning line 55 and the plurality of data lines 56 of the wiring portion are each made of a conductive material, and the scanning line 55 and the data line 56 are orthogonal to each other in a grid pattern and are connected to the pixel 53 at orthogonal positions (details are shown in the figure). Not shown). When a scanning signal is applied from the scanning line 55, the pixel 53 receives an image data signal from the data line 56 and emits light according to the received image data. Full-color display is possible by appropriately arranging pixels in the red region, pixels in the green region, and pixels in the blue region of the emission color on the same substrate.

Next, the light emitting process of the pixel will be described.
FIG. 3 is a schematic diagram showing a pixel circuit. The pixel includes an organic EL element 60, a switching transistor 61, a drive transistor 62, a capacitor 63, and the like. As the organic EL element 60 for a plurality of pixels, red, green, and blue light emitting organic EL elements are used, and by arranging them side by side on the same substrate, full-color display can be performed.
In FIG. 3, an image data signal is applied from the control unit B (not shown in FIG. 3 but shown in FIG. 1) to the drain of the switching transistor 61 via the data line 56. Then, when a scanning signal is applied from the control unit B to the gate of the switching transistor 61 via the scanning line 55, the driving of the switching transistor 61 is turned on, and the image data signal applied to the drain is the condenser 63 and the driving transistor 62. It is transmitted to the gate of.
By transmitting the image data signal, the condensate 63 is charged according to the potential of the image data signal, and the drive transistor 62 is driven on. In the drive transistor 62, the drain is connected to the power supply line 67, the source is connected to the electrode of the organic EL element 60, and the power supply line 67 is connected to the organic EL element 60 according to the potential of the image data signal applied to the gate. Current is supplied.

When the scanning signal is transferred to the next scanning line 55 by the sequential scanning of the control unit B, the driving of the switching transistor 61 is turned off. However, even if the drive of the switching transistor 61 is turned off, the capacitor 63 holds the potential of the charged image data signal, so that the drive of the drive transistor 62 is kept on and the next scan signal is applied. The light emission of the organic EL element 60 continues until. When the scanning signal is next applied by the sequential scanning, the driving transistor 62 is driven according to the potential of the next image data signal synchronized with the scanning signal, and the organic EL element 60 emits light. That is, for the light emission of the organic EL element 60, the switching transistor 61 and the drive transistor 62, which are active elements, are provided for the organic EL element 60 of each of the plurality of pixels, and the plurality of pixels 53 (not shown in FIG. 3). (Fig. 2).) Each organic EL element 60 emits light. Such a light emitting method is called an active matrix method.

Here, the light emission of the organic EL element 60 may be light emission of a plurality of gradations by a multi-valued image data signal having a plurality of gradation potentials, or on / off of a predetermined light emission amount by a binary image data signal. But it may be.
Further, the potential of the capacitor 63 may be continuously maintained until the next scan signal is applied, or may be discharged immediately before the next scan signal is applied.

In the present invention, the present invention is not limited to the active matrix method described above, and may be a passive matrix type light emission drive in which the organic EL element emits light in response to the data signal only when the scanning signal is scanned.
FIG. 4 is a schematic diagram of a display device using a passive matrix method. In FIG. 4, a plurality of scanning lines 55 and a plurality of image data lines 56 are provided in a grid pattern so as to face each other with the pixel 53 interposed therebetween. When the scanning signal of the scanning line 55 is applied by the sequential scanning, the pixel 53 connected to the applied scanning line 55 emits light according to the image data signal. In the passive matrix method, the pixel 53 does not have an active element, and the manufacturing cost can be reduced.

[Photoelectric conversion element and solar cell]
The organic thin film of the present invention is preferably applied to, for example, the organic functional layer of a photoelectric conversion element.
Hereinafter, the details of the photoelectric conversion element and the solar cell will be described.
FIG. 5 is a cross-sectional view showing an example of a solar cell having a single configuration (a configuration in which a bulk heterojunction layer is one layer) composed of a bulk heterojunction type organic photoelectric conversion element.
In FIG. 5, the bulk heterojunction type organic photoelectric conversion element 200 has a transparent electrode (anode) 202, a hole transport layer 207, a photoelectric conversion portion 204 of the bulk heterojunction layer, and an electron transport layer (or an electron transport layer) on one surface of the substrate 201. (Also referred to as a buffer layer) 208 and a counter electrode (cathode) 203 are sequentially laminated.

The substrate 201 is a member that holds the transparent electrodes 202, the photoelectric conversion unit 204, and the counter electrode 203 that are sequentially laminated. In the present embodiment, since the light to be photoelectrically converted is incident from the substrate 201 side, the substrate 201 can transmit the photoelectrically converted light, that is, with respect to the wavelength of the light to be photoelectrically converted. It is preferably a transparent member. As the substrate 201, for example, a glass substrate, a resin substrate, or the like is used. The substrate 201 is not essential, and for example, the bulk heterojunction type organic photoelectric conversion element 200 may be configured by forming the transparent electrodes 202 and the counter electrode 203 on both sides of the photoelectric conversion unit 204.

The photoelectric conversion unit 204 is a layer that converts light energy into electrical energy, and is configured to have 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 described as "an electron donor that, when light is absorbed, electrons move from the electron donor to the electron acceptor to form a hole-electron pair (charge separation state). And electron acceptors, which donate or accept electrons by photoreaction, rather than simply donating or accepting electrons like electrodes.

In FIG. 5, the light incident from the transparent electrode 202 via the substrate 201 is absorbed by an electron acceptor or an electron donor in the bulk heterojunction layer of the photoelectric conversion unit 204, and electrons move from the electron donor to the electron acceptor. Then, a hole-electron pair (charge separation state) is formed. The generated charge is due to the internal electric field, for example, the potential difference between the transparent electrode 202 and the counter electrode 203 when the work functions of the transparent electrode 202 and the counter electrode 203 are different, so that electrons pass between the electron acceptors and holes are electron donors. The photocurrent is detected by being carried to different electrodes. For example, when the work function of the transparent electrode 202 is larger than the work function of the counter electrode 203, electrons are transported to the transparent electrode 202 and holes are transported to the counter electrode 203. If the magnitude of the work function is reversed, electrons and holes are transported in the opposite direction. Further, the transport direction of electrons and holes can be controlled by applying a potential between the transparent electrode 202 and the counter electrode 203.

Although not shown in FIG. 5, another layer such as a hole block layer, an electron block layer, an electron injection layer, a hole injection layer, or a smoothing layer may be provided.
Further, for the purpose of further improving the solar utilization rate (photoelectric conversion efficiency), a tandem type configuration (a configuration having a plurality of bulk heterojunction layers) in which such photoelectric conversion elements are laminated may be used.
FIG. 6 is a cross-sectional view showing a solar cell including an organic photoelectric conversion element provided with a tandem type bulk heterojunction layer. In the case of the tandem type configuration, the transparent electrode 202 and the first photoelectric conversion unit 209 are sequentially laminated on the substrate 201, the charge recombination layer (intermediate electrode) 205 is laminated, and then the second optical conversion unit 206, Next, by stacking the counter electrode 203, a tandem type configuration can be obtained.

Examples of the material that can be used for the layer as described above include the n-type semiconductor material and the p-type semiconductor material described in paragraphs 0045 to 0113 of JP2015-149483.

(Method of forming bulk heterojunction layer)
Examples of the method for forming the bulk heterojunction layer in which the electron acceptor and the electron donor are mixed include a thin film deposition method, a coating method (including a cast method and a spin coating method), and the like. Of these, the coating method is preferable in order to increase the area of the interface where the holes and electrons are charge-separated and to produce an element having high photoelectric conversion efficiency. The coating method is also excellent in manufacturing speed.
In the present invention, the n-type semiconductor material and the p-type semiconductor material constituting the bulk heterojunction layer can be used as the organic material for the electronic device according to the present invention. That is, it is preferable to form the bulk heterojunction layer by coating the n-type semiconductor material and the p-type semiconductor material, the organic solvent, and the solution containing the cellulose nanofibers, and the n-type semiconductor material and the p-type semiconductor material. In a coating solution containing an organic solvent and cellulose nanofibers, the concentration of dissolved carbon dioxide in the organic solvent under atmospheric pressure conditions of 50 ° C. or lower is preferably 1 ppm to the saturation concentration with respect to the organic solvent.
As a means for setting the dissolved carbon dioxide concentration in the above range, as described above, a method of bubbling carbon dioxide gas into a solution containing an n-type semiconductor material, a p-type semiconductor material, an organic solvent, and cellulose nanofibers, or an organic method. Examples thereof include a supercritical chromatography method using a supercritical fluid containing a solvent and carbon dioxide.

After coating, it is preferable to perform heating in order to remove residual solvent, water and gas, and to improve mobility and lengthen absorption by crystallization of the semiconductor material. When annealed at a predetermined temperature during the manufacturing process, a part of the bulk heterojunction layer is microscopically promoted to be arranged or crystallized, and the bulk heterojunction layer can have an appropriate phase separation structure. As a result, the carrier mobility of the bulk heterojunction layer is improved, and high efficiency can be obtained.

The photoelectric conversion unit (bulk heterojunction layer) 204 may be composed of a single layer in which an electron acceptor and an electron donor are uniformly mixed, but a plurality of electron acceptors and electron donors having different mixing ratios. It may be composed of layers.
Next, the electrodes constituting the organic photoelectric conversion element will be described.

In the organic photoelectric conversion element, the positive charge and the negative charge generated in the bulk heterojunction layer are taken out from the transparent electrode and the counter electrode, respectively, via the p-type organic semiconductor material and the n-type organic semiconductor material, respectively, and function as a battery. It is something to do. Each electrode is required to have characteristics suitable for a carrier passing through the electrode.

(Opposite pole)
In the present invention, the counter electrode (cathode) is preferably an electrode for extracting electrons. For example, when it is used as a cathode, it may be a single layer of a conductive material, but in addition to a material having conductivity, a resin holding these may be used in combination.

The counter electrode material is required to have sufficient conductivity, a work function close to the extent that it does not form a Schottky barrier when bonded to the n-type semiconductor material, and does not deteriorate. That is, it is preferable that the metal has a work function 0 to 0, 3 eV larger than that of the LUMO of the n-type semiconductor material used for the bulk heterojunction layer, and it is preferable that the work function is 4.0 to 5.1 eV. On the other hand, it is not preferable that the work function is deeper than that of the transparent electrode (anodee) that extracts holes, and a metal with a work function shallower than that of the n-type semiconductor material may cause interlayer resistance. It is preferably a metal having a work function of 4.8 eV. Therefore, oxide-based materials such as aluminum, gold, silver, copper, indium, or zinc oxide, ITO, and titanium oxide are also preferable. More preferably, it is aluminum, silver, copper, and even more preferably silver.

The work function of these metals can also be measured using ultraviolet photoelectron spectroscopy (UPS).
If necessary, an alloy may be used, and for example, a magnesium / silver mixture, a magnesium / aluminum mixture, a magnesium / indium mixture, an aluminum / aluminum oxide (Al ₂ O ₃ ) mixture, a lithium / aluminum mixture, aluminum and the like are preferable. Is. The counter electrode can be produced by forming a thin film of these electrode materials by a method such as thin film deposition or sputtering. The film thickness is usually selected in the range of 10 nm to 5 μm, preferably 50 to 200 nm.

When the counter electrode side is to be light transmissive, for example, a conductive material suitable for counter electrode such as aluminum and aluminum alloy, silver and silver compound is prepared thinly with a film thickness of about 1 to 20 nm, and then conductive light is applied. By providing a film of a transmissive material, a light transmissive counter electrode can be obtained.

(Transparent electrode)
In the present invention, the transparent electrode is preferably an electrode that extracts holes. For example, when used as an anode, it is preferably an electrode that transmits light of 380 to 800 nm. As the material, for example, transparent conductive metal oxides such as indium tin oxide (ITO), SnO ₂ , ZnO, metal thin films such as gold, silver and platinum, metal nanowires and carbon nanotubes can be used.

Further, it is selected from the group consisting of derivatives of polypyrrole, polyaniline, polythiophene, polythienylenebinylene, polyazulene, polyisothianaften, polycarbazole, polyacetylene, polyphenylene, polyphenylenebinylene, polyacetylene, polyphenylacetylene, polydiaacetylene and polynaphthalene. Conductive polymers and the like can also be used. Further, a plurality of these conductive compounds can be combined to form a transparent electrode.

(Intermediate electrode)
Further, as the material of the intermediate electrode required in the case of the tandem configuration, it is preferable that the layer uses a compound having both transparency and conductivity, and the material (ITO, AZO, FTO) as used in the transparent electrode is preferable. , Transparent metal oxides such as titanium oxide, very thin metal layers such as Ag, Al, Au, or layers containing nanoparticles / nanoparticles, PEDOT: PSS, conductive polymer materials such as polyaniline, etc.) Can be done.

In addition, among the hole transport layer and the electron transport layer described above, there is also a combination that works as an intermediate electrode (charge recombination layer) by appropriately combining and laminating, and with such a configuration, a step of forming one layer is performed. It can be omitted and is preferable.

Next, materials constituting other than the electrodes and the bulk heterojunction layer will be described.

(Hole transport layer and electron block layer)
Since the organic photoelectric conversion element of the present invention can take out the electric charge generated in the bulk heterojunction layer more efficiently, it has a hole transport layer / electron block layer between the bulk heterojunction layer and the transparent electrode. It is preferable to do.

As the material constituting these layers, for example, as the hole transport layer, PEDOT such as Clevious manufactured by Heraeus, polyaniline and a doping material thereof, a cyanide compound described in WO2006 / 09270 and the like can be used.
The hole transport layer having a LUMO level shallower than the LUMO level of the n-type semiconductor material used for the bulk heterojunction layer has a rectifying effect that prevents electrons generated in the bulk heterojunction layer from flowing to the transparent electrode side. The electronic block function is provided. Such a hole transport layer is also called an electron block layer, and it is preferable to use a hole transport layer having such a function. As such a material, a triarylamine-based compound described in JP-A-5-271166 or the like, a metal oxide such as molybdenum oxide, nickel oxide, or tungsten oxide can be used. Further, a layer made of a single p-type semiconductor material used for the bulk heterojunction layer can also be used. As a means for forming these layers, either a vacuum vapor deposition method or a solution coating method may be used, but a solution coating method is preferable. It is preferable to form a coating film on the lower layer before forming the bulk heterojunction layer because it has the effect of leveling the coated surface and reduces the influence of leaks and the like.

(Electron transport layer, hole block layer and buffer layer)
The organic photoelectric conversion element of the present invention forms an electron transport layer, a hole block layer, and a buffer layer between the bulk heterojunction layer and the counter electrode to more efficiently extract the electric charge generated in the bulk heterojunction layer. It is preferable to have these layers because it is possible.

Further, as the electron transport layer, octaazaporphyrin and a perfluoro compound of a p-type semiconductor (perfluoropentacene, perfluorophthalocyanine, etc.) can be used, but similarly, the p-type semiconductor material used for the bulk heterojunction layer can be used. The electron transport layer having a HOMO level deeper than the HOMO level is provided with a hole blocking function having a rectifying effect so as not to allow holes generated in the bulk heterojunction layer to flow to the opposite electrode side. Such an electron transport layer is also called a hole block layer, and it is preferable to use an electron transport layer having such a function. Examples of such materials include phenanthrene compounds such as vasocuproin, n-type semiconductor materials such as naphthalenetetracarboxylic acid anhydride, naphthalenetetracarboxylic acid diimide, perylenetetracarboxylic acid anhydride, and perylenetetracarboxylic acid diimide, and titanium oxide. It is also possible to use an n-type inorganic oxide such as zinc oxide or gallium oxide, a layer made of a single n-type semiconductor material used for the bulk heterojunction layer, or the like.

Further, alkali metal compounds such as lithium fluoride, sodium fluoride and cesium fluoride can be used.

Among these, it is preferable to use an alkali metal compound which is further doped with an organic semiconductor molecule and has a function of improving electrical bonding with the metal electrode (cathode). In the case of an alkali metal compound layer, it may be a buffer layer in particular.

(Other layers)
For the purpose of improving the energy conversion efficiency and the life of the device, various intermediate layers may be provided in the device. Examples of the intermediate layer include a hole block layer, an electron block layer, a hole injection layer, an electron injection layer, an exciton block layer, a UV absorption layer, a light reflection layer, a wavelength conversion layer and the like.

(substrate)
When the light to be photoelectrically converted is incident from the substrate side, the substrate is preferably a member capable of transmitting the photoelectrically converted light, that is, a member transparent to the wavelength of the light to be photoelectrically converted. .. As the substrate, for example, a glass substrate, a resin substrate, or the like is preferable, but it is desirable to use a transparent resin film from the viewpoint of lightness and flexibility.
The transparent resin film that can be preferably used as a transparent substrate in the present invention is not particularly limited, and the material, shape, structure, thickness, and the like thereof can be appropriately selected from known ones. For example, polyester resin films such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and modified polyester, polyethylene (PE) resin film, polypropylene (PP) resin film, polystyrene resin film, and polyolefins such as cyclic olefin resin. Vinyl-based resin film such as resin film, polyvinyl chloride, polyvinylidene chloride, polyether ether ketone (PEEK) resin film, polysulfone (PSF) resin film, polyether sulfone (PES) resin film, polycarbonate (PC) resin film , Polyamitone resin film, polyimide resin film, acrylic resin film, triacetylcellulose (TAC) resin film, etc., but the resin film having a transmittance of 80% or more in the visible wavelength range (380 to 800 nm). If there is, it can be preferably applied to the transparent resin film according to the present invention. Among them, biaxially stretched polyethylene terephthalate film, biaxially stretched polyethylene naphthalate film, polyether sulfone film, and polycarbonate film are preferable from the viewpoint of transparency, heat resistance, ease of handling, strength, and cost, and biaxially stretched. More preferably, it is a polyethylene terephthalate film or a biaxially stretched polyethylene naphthalate film.

The transparent substrate used in the present invention may be surface-treated or provided with an easy-adhesion layer in order to ensure the wettability and adhesiveness of the coating liquid. Conventionally known techniques can be used for the surface treatment and the easy-adhesion layer. For example, examples of the surface treatment include surface activation treatments 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-based copolymer, butadiene-based copolymer, acrylic-based copolymer, vinylidene-based copolymer, and epoxy-based copolymer.

Further, a barrier coat layer may be preliminarily formed on the transparent substrate for the purpose of suppressing the permeation of oxygen and water vapor.

(Optical functional layer)
The organic photoelectric conversion element according to the present invention may have various optical functional layers for the purpose of receiving sunlight more efficiently. As the optical functional layer, for example, an antireflection film, a condensing layer such as a microlens array, a light diffusion layer capable of scattering light reflected by the counter electrode and making it incident on the bulk heterojunction layer again may be provided. good.

As the antireflection layer, various known antireflection layers can be provided. For example, when the transparent resin film is a biaxially stretched polyethylene terephthalate film, the refractive index of the easy-adhesion layer adjacent to the film is 1.57. It is more preferable to set the value to ~ 1.63 because the interfacial reflection between the film substrate and the easy-adhesion layer can be reduced and the transmittance can be improved. The method of adjusting the refractive index can be carried out by appropriately adjusting the ratio of the oxide sol having a relatively high refractive index such as tin oxide sol or cerium oxide sol to the binder resin and applying the mixture. The easy-adhesion layer may be a single layer, but may be composed of two or more layers in order to improve the adhesiveness.

As the light collecting layer, for example, the light receiving amount from a specific direction may be increased by processing the support substrate so as to provide a structure on the microlens array on the sunlight receiving side, or by combining with a so-called light collecting sheet. On the contrary, it is possible to reduce the dependence of sunlight on the incident angle.

As an example of a microlens array, a quadrangular pyramid having a side of 30 μm and an apex angle of 90 degrees is arranged two-dimensionally on the light extraction side of the substrate. One side is preferably in the range of 10 to 100 μm. If it is smaller than this, the effect of diffraction occurs and it is colored, and if it is too large, the thickness becomes thick, which is not preferable.

Examples of the light scattering layer include various anti-glare layers, layers in which nanoparticles / nanowires such as metals or various inorganic oxides are dispersed in a colorless and transparent polymer.

(Patterning)
The method and process for patterning the electrodes, power generation layer, hole transport layer, electron transport layer and the like according to the present invention are not particularly limited, and known methods can be appropriately applied.

If it is a soluble material such as a bulk heterojunction layer or a transport layer, it is possible to wipe off only unnecessary parts after applying the entire surface such as die coat or dip coat, or to directly pattern at the time of application using a method such as inkjet method or screen printing. You may.

In the case of an insoluble material such as an electrode material, the electrode can be mask-deposited at the time of vacuum deposition, or patterned by a known method such as etching or lift-off. Further, the pattern may be formed by transferring the pattern formed on another substrate.

(Sealing)
Further, since the produced organic photoelectric conversion element is not deteriorated by oxygen, moisture, etc. in the environment, it is preferable to seal not only the organic photoelectric conversion element but also the organic electroluminescence element or the like by a known method. For example, a method of sealing a cap made of aluminum or glass by adhering it with an adhesive, a plastic film on which a gas barrier layer such as aluminum, silicon oxide, or aluminum oxide is formed, and an organic photoelectric conversion element with an adhesive. Adhesive method, spin-coating method of organic polymer material with high gas barrier property (polyvinyl alcohol, etc.), inorganic thin film (silicon oxide, aluminum oxide, etc.) or organic film (parylene, etc.) with high gas barrier property under vacuum A method of depositing in the above, a method of laminating these in a composite manner, and the like can be mentioned.

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. Although the display of "parts" or "%" is used in the examples, it represents "parts by mass" or "% by mass" unless otherwise specified.

The compounds used in the examples are shown below.

[Example 1]
<< Preparation of coating composition 1-1-1-7, 1-11-1-20 >>
The solid components (organic materials for electronic devices) shown in Table I below are dissolved in the solvent shown in Table I, and then filtered through a hydrophobic PVDF (polyvinylidene fluoride) 0.45 μm filter (manufactured by Whatman Co., Ltd.) at room temperature. , The coating compositions 1-1 to 1-7 were prepared in an air atmosphere.
Next, 2 mg of cellulose nanofibers (Cerish KY100G, manufactured by Dycel Finechem Co., Ltd.) were added to each of the coating compositions 1-1 to 1-7 to obtain coating compositions 1-11-1-17, respectively.
Further, the amount of cellulose nanofibers added was changed as shown in Table I below to obtain coating compositions (compositions for producing electronic devices) 1-18 to 1-20, respectively. The content (mass ppm) of the cellulose nanofibers in the entire coating composition is the value obtained by rounding off the values on the order of ppm or less.

<< Formation of thin film >>
A substrate (NA-45 manufactured by NH Technoglass Co., Ltd.) having a 150 nm film of indium tin oxide (ITO) formed on 50 mm × 50 mm glass was ultrasonically cleaned with iso-propyl alcohol, dried with dry nitrogen gas, and dried. UV ozone cleaning was performed for 5 minutes to obtain a transparent support substrate.
The coating compositions 1-1 to 1-7 and 1-11 to 1-20 are formed on this substrate by an inkjet method using an inkjet drawing device equipped with an ink jet head (“KM512L” manufactured by Konica Minolta). The film was formed and heated in vacuum at 150 ° C. for 3 hours to obtain thin film pre-rinse evaluation samples 1-1-1-7 and 1-11-1-19, but when the coating composition 1-20 was used. Since the head was clogged and the film could not be formed, the film was formed by extrusion coating.

<< Solvent resistance evaluation of thin film >>
Next, the thin film pre-rinse evaluation sample 1-1 was set in a spin coater, rinsed with the solvent by the spin coating method under the conditions of 1000 rpm and 300 seconds using 6 ml of the solvent shown in Table I, and vacuumed. The mixture was heated at 150 ° C. for 3 hours to obtain a post-rinse evaluation sample 1-1 after rinsing. The same treatment was carried out for the pre-rinse evaluation samples 1-2-1-7 and 1-11-1-20 to obtain post-rinse evaluation samples 1-2-1-7 and 1-11-1-20.
The absorbance at 360 nm before and after the rinsing treatment was measured with a spectrophotometer (Hitachi UV-3300), and the residual ratio of the thin film after rinsing of each sample was calculated by the following formula to determine the durability (solvent resistance) of the thin film. It was used as an index to show.
Here, the rinsing treatment refers to a treatment in which a solvent is applied onto a thin film set for evaluation of solvent resistance, the compounds constituting the thin film are dissolved, and the compound is washed off.
Residual rate = (absorbance after rinsing) / (absorbance before rinsing) x 100
Table I shows the results as “x” for those with a residual rate of less than 10%, “Δ” for those with a residual rate of 10% or more and less than 60%, and “◯” for those with a residual rate of 60% or more.

From the results shown in Table I, it can be seen that the thin film (organic thin film) produced from the coating composition (composition for producing an electronic device) of the present invention has excellent solvent resistance.

[Example 2]
<< Fabrication of organic EL element 2-1 >>
(1.1) Preparation of Gas Barrier Flexible Film As a flexible film, the entire surface of a polyethylene naphthalate film (film manufactured by Teijin DuPont Film Co., Ltd., hereinafter abbreviated as PEN) on the side where the first electrode is formed. In addition, using the atmospheric pressure plasma discharge processing apparatus having the configuration described in JP-A-2004-68143, an inorganic gas barrier film made of SiOx is continuously formed on a flexible film so as to have a thickness of 500 nm. formed, oxygen permeability ^{0.001mL / (m 2 · 24h ·} atm) or less, to produce a water vapor permeability of 0.001g / (m ² · 24h) the following gas barrier properties of the flexible film.

(1.2) Formation of First Electrode Layer Indium tin oxide (ITO) having a thickness of 120 nm is formed on the prepared flexible film having a gas barrier property by a sputtering method, and patterning is performed by a photolithography method. , The first electrode layer (anode) was formed. The pattern was set so that the light emitting area was 50 mm square.

(1.3) Formation of hole injection layer The indium tin oxide (ITO) substrate after patterning was ultrasonically washed with isopropyl alcohol, dried with dry nitrogen gas, and washed with UV ozone for 5 minutes. On this substrate, a solution of poly (3,4-ethylenedioxythiophene) -polystyrene sulfonate (abbreviated as PEDOT / PSS, Clevious P VP AI 4083 (manufactured by Heleus)) diluted to 70% with pure water was diluted at 3000 rpm. After forming a film by the spin coating method in 30 seconds, the solution was dried at 200 ° C. for 1 hour to provide a hole injection layer having a thickness of 30 nm.

(1.4) Formation of Hole Transport Layer The substrate after the hole injection layer is formed is transferred to a nitrogen atmosphere using nitrogen gas (grade G1), and the coating composition 1-1 prepared in Example 1 above is used. After forming a film by an inkjet method, the film was held at 160 ° C. for 30 minutes to form a hole transport layer having a thickness of 30 nm.

(1.5) Formation of Light-emitting Layer Next, the coating composition 1-4 prepared in Example 1 was formed into a film by an inkjet method, and then held at 120 ° C. for 30 minutes to form a light-emitting layer having a thickness of 40 nm. ..

(1.6) Formation of Electron Transport Layer Subsequently, the coating composition 1-6 produced in Example 1 was formed into a film by an inkjet method, and then held at 120 ° C. for 30 minutes to have an electron having a thickness of 30 nm. It was used as a transportation layer.

(1.7) Formation of electron injection layer and cathode Subsequently, the substrate was attached to a vacuum vapor deposition apparatus without exposure to the atmosphere. In addition, a molybdenum resistance heating boat containing sodium fluoride and potassium fluoride was attached to a vacuum vapor deposition device, the vacuum tank ^{was depressurized to 4 × 10 -5} Pa, and then the boat was energized and heated. Sodium fluoride was applied to form a 1 nm thick thin film on the electron transport layer at 0.02 nm / sec, followed by potassium fluoride at 0.02 nm / sec on sodium fluoride with a thickness of 1.5 nm. An electron injection layer was formed.
Subsequently, 100 nm of aluminum was vapor-deposited to form a cathode.

(1.8) Sealing Subsequently, a sealing member was bonded using a commercially available roll laminating device to produce an organic EL element (2-1).
As a sealing member, a flexible aluminum foil (manufactured by Toyo Aluminum Co., Ltd.) with a thickness of 30 μm is covered with a polyethylene terephthalate (PET) film (12 μm thickness) as an adhesive for dry lamination (two-component reaction type urethane). A laminated adhesive (thickness of the adhesive layer 1.5 μm) was used.
As a sealing adhesive, a thermosetting adhesive was uniformly applied to the aluminum surface along the adhesive surface (glossy surface) of the aluminum foil with a thickness of 20 μm using a dispenser. This was dried under a vacuum of 100 Pa or less for 12 hours. Further, the dew point temperature was moved to −80 ° C. or lower and a nitrogen atmosphere having an oxygen concentration of 0.8 ppm or more, and the mixture was dried for 12 hours or more to adjust the water content of the sealing adhesive to 100 ppm or less.
As the thermosetting adhesive, an epoxy-based adhesive in which the following (A) to (C) were mixed was used.
(A) Bisphenol A Diglycidyl Ether (DGEBA)
(B) Dicyanodiamide (DICY)
(C) Epoxy adduct-based curing accelerator As described above, the sealing substrate is closely adhered and arranged so as to cover the joint portion of the take-out electrode and the electrode lead, and the thick coating condition and the crimping roll temperature are used using a crimping roll. The organic EL element 2-1 was manufactured by tightly sealing at 120 ° C., a pressure of 0.5 MPa, and a device speed of 0.3 m / min.

[Manufacturing of organic EL elements 2-2-2-11]
The coating compositions 1-1, 1-4, and 1-6 used in the hole transport layer, the light emitting layer, and the electron transport layer in the production of the organic EL element 2-1 are combined with each other in Table II. The organic EL element 2-2-2-11 was manufactured by changing to.

<< Evaluation of organic EL elements >>
The following evaluations were performed on each of the organic EL elements manufactured above.
(1) Measurement of emission brightness Each organic EL element is ^{lit at room temperature (about 23 to 25 ° C) under a constant brightness condition of 1000 cd / m 2} , and the spectral radiance meter CS-2000 (manufactured by Konica Minolta) is lit. ) Was used to measure the radiance of each organic EL element, and the radiance (current is constant) at a ^{radiance of 1000 cd / m 2 was determined.}
In Table II, the emission luminance of the organic EL element 2-1 is set to 100, and the emission luminance of the organic EL elements 2-1 to 2-11 is shown as a relative value.

From the results shown in Table II, it can be seen that the organic EL device using the coating composition of the present invention to which cellulose nanofibers are added has high emission brightness.

[Example 3]
<< Fabrication of Organic Photoelectric Conversion Element 3-1 >>
An indium tin oxide (ITO) transparent conductive film deposited at 140 nm on a glass substrate was patterned to a width of 2 mm by using ordinary photolithography technology and hydrochloric acid etching to form a transparent electrode.
The transparent electrode having the pattern formed was washed in the order of ultrasonic cleaning with a surfactant and ultrapure water, and ultrasonic cleaning with ultrapure water, dried with a nitrogen blow, and finally subjected to ultraviolet ozone cleaning. Clevious P VP AI 4083 (manufactured by Heleus), which is a conductive polymer, was spin-coated on this transparent substrate to a thickness of 60 nm, and then heated and dried in the air at 140 ° C. for 10 minutes.
After that, I brought the board into the glove box and worked in a nitrogen atmosphere. First, the substrate was heat-treated at 140 ° C. for 10 minutes in a nitrogen atmosphere.
PCPDTBT (Nature Mat. Vol. 6 (2007), polythiophene copolymer according to p497) is 1.0% by mass as a p-type semiconductor material for chlorobenzene, and PCBM (frontier carbon, NANOM SPECTRAE100H) is used as an n-type semiconductor material. 2.0% by mass of cellulose nanofiber (Cerish KY100G, manufactured by Daisel Finechem Co., Ltd.) 0.01% by mass, and 2.4% by mass of 1,8-octanedithiol were dissolved to prepare a solution of 0. After filtering with a filter of 45 μm, a thin film of 100 nm was formed by an inkjet method and dried at room temperature for 30 minutes to obtain a photoelectric conversion layer.
Next, the substrate on which the photoelectric conversion layer was formed was installed in the vacuum vapor deposition apparatus. The element was set so that the shadow mask having a width of 2 mm was orthogonal to the transparent electrode, and the ^{pressure inside the vacuum vapor deposition machine was reduced to 10 -3} Pa or less, and then lithium fluoride was vapor-deposited at 0.5 nm and Al was vapor-deposited at 80 nm. Finally, heating was performed at 120 ° C. for 30 minutes to obtain an organic photoelectric conversion element. The vapor deposition rate was 2 nm / sec, and the size was 2 mm square.
The obtained organic photoelectric conversion element was sealed with an aluminum cap and a UV curable resin (UV RESIN XNR5570-B1 manufactured by Nagase ChemteX Corporation) under a nitrogen atmosphere. This was designated as an organic photoelectric conversion element 3-1.

<< Evaluation of organic photoelectric conversion element >>
When the organic photoelectric conversion element produced above ^{was irradiated with light having an intensity of 100 mW / cm 2} of a solar simulator (AM1.5G filter), it was confirmed that the organic photoelectric conversion element had a sufficient function as a photoelectric conversion element.

INDUSTRIAL APPLICABILITY The present invention has excellent solvent resistance without limiting the selection range of solvents that can be used when manufacturing electronic devices such as organic electronic devices, and does not affect device performance, and has electrons having laminated thin films. It can be used in a composition for manufacturing an electronic device that enables the manufacture of a device.

41 Display 53 Pixel 55 Scanning line 56 Data line 60 Organic EL element 61 Switching transistor 62 Drive transistor 63 Capacitor 67 Power supply line 101 Glass substrate 102 ITO transparent electrode 103 Barrier 104 Hole injection layer 105B, 105G, 105R Light emitting layer 106 Electron transport layer 107 Cathode (Al)
200 Bulk heterojunction type organic photoelectric conversion element 201 Substrate 202 Transparent electrode (anode)
203 Counter electrode (cathode)
204 Photoelectric conversion unit (bulk heterojunction layer)
205 Charge recombination layer 206 Second photoelectric conversion unit 207 Hole transport layer 208 Electron transport layer 209 First photoelectric conversion unit A Display unit B Control unit

Claims (8)

A composition for manufacturing an electronic device containing an organic material for an electronic device for forming an organic thin film.
A composition for producing an electronic device containing cellulose nanofibers. The composition for manufacturing an electronic device according to claim 1, wherein the cellulose nanofibers are contained in the range of 0.001 to 20000 mass ppm. The composition for manufacturing an electronic device according to claim 1 or 2, which is an ink for inkjet. The electron according to any one of claims 1 to 3 , wherein the content of the cellulose nanofibers is in the range of 0.000001 to 5% by mass with respect to the mass of the organic material for an electronic device. Composition for device fabrication. The composition for manufacturing an electronic device according to any one of claims 1 to 4, wherein the organic material for an electronic device is a material for an organic electroluminescence device. The method for producing an electronic device-making composition according to any one of claims 1 to 5.
A method for producing a composition for producing an electronic device, which comprises a step of mixing the organic material for an electronic device and the cellulose nanofibers. An organic thin film containing the composition for producing an electronic device according to any one of claims 1 to 5. The method for producing an organic thin film according to claim 7.
A method for producing an organic thin film, which comprises a step of applying the composition for producing an electronic device.

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