JP2021057588A - Organic electronic device and method of manufacturing the same - Google Patents

Abstract

To provide an organic electronic device excellent in durability.SOLUTION: An organic electronic device 10 includes an organic active layer 22 on a substrate 1 and also includes an extraction electrode 5 and an SiON layer 4. The organic electronic device has a portion where the substrate 1, the extraction electrode 5, and the SiON layer 4 are directly laminated.SELECTED DRAWING: Figure 1

Description

The present invention relates to an organic electronic device and a method for manufacturing the same.

Organic electronic devices such as organic electroluminescence (organic EL), organic thin-film solar cells, organic transistors, and organic capacitors tend to be easily deteriorated by moisture and oxygen in the atmospheric environment. Therefore, various sealing methods have been developed to protect organic electronic devices from moisture and oxygen.

Examples of the sealing method of the organic electronic device include a step of arranging the electronic element main body on the sealing base material, a step of applying a specific welding accelerator, and the electronic element main body and the upper part of the welding accelerator. A step of arranging a gas barrier film having a base material and a gas barrier layer so as to cover the welding accelerator, and irradiating the welding accelerator with a laser beam to attach the sealing base material and the gas barrier film to the welding accelerator via the welding accelerator. A method for manufacturing an electronic device (see, for example, Patent Document 1), which comprises a step of sealing the electronic element main body by joining with the electronic element, at least (1) a step of preparing the electronic element, and (2) with the electronic element. Step of coating the surrounding base material with an organic flattening resin layer and an inorganic layer in this order (3) The gas barrier layer and the inorganic layer of a sealing film having a gas barrier layer are joined by vacuum room temperature welding. A method for manufacturing a functional element having an electronic element on a flexible substrate having a step of joining, wherein the functional element can be bent with a radius of curvature of 2 mm or less (for example,). (See Patent Document 2), a step of forming an electrode on a base material, a step of preparing an electronic element main body on the base material on which the electrode is formed, a step of coating at least the electrode with a silicon-containing film, and the above. A metal film as a welding margin for joining the base material and the sealing base material that seals the electronic element main body is formed on at least the silicon-containing film of the base material and on the sealing base material, respectively. A method for manufacturing an electronic device (see, for example, Patent Document 3) has been proposed, which includes a step of forming the metal films and a step of bringing the metal films into contact with each other to form a joint portion by welding at room temperature.

Japanese Unexamined Patent Publication No. 2013-232320 International Publication No. 2016/0392337 Japanese Unexamined Patent Publication No. 2019-050196

In recent years, there has been an increasing demand for flexible devices that can be bent or curved, and even in organic electronic devices, studies on flexible devices that use a film as a base material are underway. However, it is difficult to apply the laser beam bonding method disclosed in Patent Document 1 to a flexible substrate having low heat resistance such as a film, and another method for improving durability is required. Was being done. Further, the room temperature bonding as disclosed in Patent Documents 2 to 3 has a problem that the durability is insufficient because a high flatness is required for the bonding surface and a metal film is required for the bonding. It was.

Therefore, it is an object of the present invention to provide an organic electronic device which is applicable to a film base material and has excellent durability.

The present invention is an organic electronic device body having an organic active layer, an extraction electrode, and an organic electronic device having a SiON layer on a base material, and has a portion in which the base material, the extraction electrode, and the SiON layer are directly laminated. It is an organic electronic device.

The organic electronic device of the present invention has excellent durability.

It is an enlarged sectional view which shows the main part of one aspect of the organic electronic device of this invention. FIG. 5 is an enlarged cross-sectional view showing a main part of another aspect of the organic electronic device of the present invention. It is a graph which shows the elapsed time and the normalized power generation amount in the durability evaluation of the organic thin-film solar cell device produced in an Example and a comparative example. It is sectional drawing which shows the organic thin-film solar cell device produced in Example 1. FIG. It is sectional drawing which shows the organic thin-film solar cell device produced in the comparative example 1. FIG.

The organic electronic device of the present invention is an organic electronic device main body having an organic active layer, an extraction electrode and an organic electronic device having a SiON layer on a base material, and the base material, the extraction electrode and the SiON layer are directly laminated. Has an electrode. The extraction electrode is an electrode for sending electrical energy from the main body of the organic electronic device to an external circuit. The main body of the organic electronic device has an organic active layer that is easily deteriorated by moisture and oxygen in the environment, but in the present invention, the portion having the SiON layer and the base material, the extraction electrode, and the SiON layer directly laminated is formed. By having the organic active layer, it is possible to suppress the exposure of the organic active layer to the environment, suppress the deterioration, and improve the durability of the organic electronic device. It is preferable to further have a protective resin layer between the organic electronic device main body and the SION layer, and by further suppressing the deterioration of the organic active layer or by filling and smoothing the unevenness and steps of the base material and the organic electronic device. , The SiON layer can be easily formed. From the viewpoint of further suppressing the deterioration of the organic active layer and further improving the durability of the organic electronic device, the entire surface of the organic electronic device body is covered with a base material, a lead-out electrode, a SiON layer and / or a protective resin layer. Is preferable.

The base material serves as a device forming surface for forming the organic electronic device body. The organic electronic device body may not be formed on the entire surface of the base material, and the area ratio between the portion where the device is formed and the portion where the device is not formed is not particularly limited.

The water vapor transmission rate of the base material ^{is preferably 1.0 × 10 -1} g / m ² / day or less. By lowering the water vapor transmittance, the internal organic electronic device body can be protected by the waterproof performance of the base material even when it is used outdoors. The total line transmittance of visible light of the base material is preferably 80% or more.

Examples of the material of the base material having the above-mentioned water vapor transmittance and full-line transmittance include glass, polyethylene terephthalate, polyethylene naphthalate, and polyethylene. As the base material, a glass substrate or a film such as polyethylene terephthalate, polyethylene naphthalate, or polyethylene is preferable. For flexible device applications, a flexible base material such as ultra-thin glass or the film is preferable, and a film is more preferable, because the base material has high selectivity of the installation location and can reduce the transportation cost.

The organic electronic device body has an organic active layer. Further, it may have another layer or member. Examples of the organic electronic device main body include an organic EL, an organic thin-film solar cell, an organic TFT, and an organic capacitor. Hereinafter, an organic thin-film solar cell will be described as an example as a typical embodiment.

The organic thin-film solar cell has a transparent electrode / an organic active layer / a counter electrode in this order from the base material side. As the organic active layer, it is preferable to have an electron transport layer / a power generation layer / a hole transport layer in order from the base material side and having a multilayer structure according to function. The thickness of the organic thin-film solar cell is preferably 1 μm or less.

The transparent electrode preferably has a light transmittance in the wavelength range of 400 to 700 nm of 80% or more. Examples of the material constituting the transparent electrode include indium oxide, zinc oxide, tin oxide, indium tin oxide (ITO), fluorine-topped tin oxide (FTO) containing fluorine, and aluminum zinc oxidation. Metal oxides such as substances (Aluminium Zinc Oxide: AZO) and gallium zinc oxide (GZO), gold, platinum, silver, copper, tin, aluminum, molybdenum, titanium, tungsten, manganese, nickel, cobalt. Examples thereof include metals such as graphite, graphite interlayer compounds, carbon nanotubes, graphene, polyaniline and its derivatives, polythiophene and its derivatives, and the like. Two or more of these may be contained, or a laminated structure of two or more layers composed of these materials may be provided. The thickness of the transparent electrode is preferably 100 to 300 nm.

Examples of the material for forming the electron transport layer include metal oxides such as zinc oxide and titanium oxide, and Poly [(9,9-bis (3'-(N, N-dimethylamino) propyl) -2,7-). Fluorene) -alt-2,7- (9,9-dioctylfluorene)]: Examples of organic materials having high electron transport properties such as PFN, Polyethyleneimine, and ethoxylated: PEIE. Two or more of these may be used. The thickness of the electron transport layer is preferably 0.5 to 50 nm.

The power generation layer contains at least an electron donating organic material and an electron accepting organic material. Two or more of these may be contained. The structure of the power generation layer is, for example, a structure composed of a layer containing a mixture of an electron-donating organic material and an electron-accepting organic material, and a structure in which a layer composed of an electron-donating organic material and a layer composed of an electron-accepting organic material are laminated. , A structure in which a layer made of a mixture of these is laminated between a layer made of an electron-donating organic material and a layer made of an electron-accepting organic material can be mentioned. Of these, a structure composed of a layer containing a mixture of an electron-donating organic material and an electron-accepting organic material is preferable. The content ratio of the electron-donating organic material and the electron-accepting organic material is not particularly limited, but the electron-donating organic material: the electron-accepting organic material (donor acceptor ratio) is in the range of 10:90 to 60:40. Is preferable.

The electron-donating organic material is not particularly limited as long as it is an organic compound exhibiting p-type semiconductor properties. For example, polythiophene-based polymer, benzothiasiasol-thiophene-based polymer, quinoxalin-thiophene-based copolymer, thiophene-benzodithiophene-based copolymer, poly-p-phenylene vinylene-based polymer, poly-p-phenylene-based polymer. Polymers, polyfluorene-based polymers, polypyrrole-based polymers, polyaniline-based polymers, polyacetylene-based polymers, conjugated polymers such as polythienylene vinylene-based polymers, and phthalocyanine derivatives such as H2 phthalocyanine, copper phthalocyanine, and zinc phthalocyanine. , Low molecular weight organic compounds such as porphyrin derivatives, triarylamine derivatives, carbazole derivatives, oligothiophene derivatives (tarthiophene, quarterthiophene, sexithiophene, octthiophene, etc.) and the like. Two or more of these may be used. Among the conjugated polymers having the above skeletal structure, since it has a wide light absorption wavelength region and a deep HOMO level, high photoelectric conversion characteristics can be obtained, and therefore, it has a structure represented by the following general formula (1). Conjugated polymers are preferred.

In the above general formula (1), n represents an integer of 1 or more. The number average molecular weight of the conjugated polymer having the structure represented by the general formula (1) is preferably 30,000 to 60,000.

The electron-accepting organic material is not particularly limited as long as it is an organic substance exhibiting n-type semiconductor properties. For example, a fullerene derivative, which is an n-type semiconductor that is stable and has high carrier mobility, is preferably used. Fullerene derivatives include, for example, _{non-substituted ones such as C 60} , C ₇₀ , C ₇₆ , C ₇₈ , C ₈₂ , C ₈₄ , C ₉₀ , and C ₉₄ , and substitutions having improved solubility in organic solvents. Examples of the derivative include [6,6] -Phyyl-C61-Butyric Acid Ester: 60 PCBM, [6,6] -Phyyl-C71-Butyric Acid Ester: 70 PCBM and the like. Two or more of these may be used.

The thickness of the power generation layer may be a thickness sufficient for the electron-donating organic material and the electron-accepting organic material to cause photoelectric conversion by light absorption, and varies depending on the material, but is preferably 50 nm to 500 nm.

Examples of the material for forming the hole transport layer include a polythiophene polymer, a poly-p-phenylene vinylene polymer, a polyfluorene polymer, a polypyrrole polymer, a polyaniline polymer, a polyfuran polymer, and a polypyridine polymer. and conductive polymers such as poly carbazole polymer, a phthalocyanine derivative (H 2 _Pc, CuPc, etc. ZnPc), porphyrin derivatives, acene-based compounds (tetracene, pentacene, etc.) a low molecular organic compounds showing p-type semiconductor properties, such as, Examples thereof include carbon compounds such as graphene and graphene oxide, and inorganic materials such as molybdenum oxide, tungsten oxide, nickel oxide, vanadium oxide, and zirconium oxide. Two or more of these may be used. Among these, PEDOT: PSS in which polystyrene sulfonic acid (PSS) is added to polyethylenedioxythiophene (PEDOT), which is a polythiophene-based polymer, is preferable. The thickness of the hole transport layer is preferably 0.5 to 50 nm.

The counter electrode does not have to have light transmittance, and from the viewpoint of improving the amount of power generation, a conductive material having a particularly high light reflectance in the visible light region and ohmic contact with the hole transport layer is preferable. For example, metals such as gold, platinum, silver, copper, iron, zinc, tin, aluminum, indium, chromium, nickel and cobalt, graphite, graphite interlayer compounds, carbon nanotubes, graphene, polyaniline and its derivatives, polythiophene and its derivatives. Etc. are preferable. Two or more of these may be used. The thickness of the counter electrode is sufficient as long as it has conductivity, and is not particularly limited.

The extraction electrode does not have to have light transmission, and may be made of the same material as the transparent electrode and / or the counter electrode, or may be made of a different material. From the viewpoint of contact with an external circuit, a conductive material having a particularly high electrical conductivity, a higher barrier property against moisture and oxygen, and ohmic contact with a transparent electrode and a counter electrode is preferable. For example, the metal exemplified as the material constituting the counter electrode is preferable. The thickness of the lead-out electrode is not particularly limited as long as it has conductivity and strength.

The SION layer has a high barrier property against moisture and oxygen in the environment, which is a main deterioration factor of the organic electronic device main body. Therefore, by having the SION layer, the durability of the organic electronic device can be improved. Further, in the present invention, by having a portion where the base material, the extraction electrode and the SION layer are directly laminated, the exposure of the organic active layer to the environment is suppressed to suppress deterioration, and the durability of the organic electronic device is suppressed. The sex can be improved.

It is preferable to further have a protective resin layer between the organic electronic device main body and the inorganic barrier layer, and the SiON layer can be easily formed by filling and smoothing the unevenness and steps of the base material and the organic electronic device. it can. The protective resin preferably covers the entire surface of the organic electronic device body on the opposite side to the base material, and flattens particles and dust generated in the manufacturing process, minute protrusions, steps of the organic electronic device body itself, and the SiON layer. It is possible to suppress the occurrence of unevenness and pinholes.

As the resin forming the protective resin layer, a cured product of a photocurable material or a thermosetting material is preferable. From the viewpoint of step coating property, a material having a low viscosity of 20 mPa · s or less at the time of forming the protective resin layer is preferable.

Examples of the photocurable material include epoxy resin, unsaturated polyester resin, vinyl ester resin, acrylic resin and the like. Two or more of these may be used. In the present invention, when the SiON layer is formed by conversion of polysilazane, which will be described later, an acrylic resin having high corrosion gas resistance is preferable from the viewpoint of protecting the organic electronic device from ammonia gas generated in the conversion process. Acrylic resin generates less gas during photocuring and has excellent light transmission.

Examples of the thermosetting material include urethane resin, phenol resin, urea melamine resin, epoxy resin, unsaturated polyester resin and the like. Two or more of these may be used. Among these, epoxy resin is preferable because it has excellent heat resistance.

The thickness of the protective resin layer is preferably 0.1 to 10 μm.

Further, the organic electronic device of the present invention may have an opposing substrate on the opposite side of the base material of the organic electronic device main body. By having the facing substrate, scratch resistance can be improved. The facing substrate may be made of, for example, the same material as the above-mentioned base material, or may be made of an opaque material such as a metal leaf such as aluminum. The thickness of the opposing substrate is preferably 0.05 mm to 1.0 mm.

An adhesive resin layer may be further provided between the organic electronic device main body and the facing substrate. Examples of the material constituting the adhesive resin layer include a thermosetting material and a photocurable material exemplified as the material constituting the protective resin layer. Among these, sheet-shaped or paste-shaped epoxy resins are preferable. The thickness of the adhesive resin layer is preferably 1.0 μm to 50 μm.

Hereinafter, the organic electronic device of the present invention will be described with reference to the drawings. The drawings are schematic, and for example, the relationship between the plane dimensions and the thickness, the ratio of the thickness of each layer, and the like may differ from the actual ones. Further, in the embodiment, substantially the same components are designated by the same reference numerals and the description thereof will be omitted.

FIG. 1 shows an enlarged cross-sectional view of a main part of one aspect of the organic electronic device of the present invention. The organic electronic device 10 includes an organic electronic device main body 2 having a pull-out electrode 5, a transparent electrode 21, an organic active layer 22, and a counter electrode 23 on a base material 1, and a part thereof includes a base material 1 and a pull-out electrode 5. It has a SiON layer 4 that is directly laminated, and has a protective resin layer 3 between the organic electronic device main body 2 and the SiON layer 4. Here, the extraction electrode 5 extends the transparent electrode 21 and the counter electrode 23 of the organic electronic device main body 2, respectively, and connects them to an external circuit (not shown). The protective resin layer 3 covers the entire surface of the organic electronic device main body 2 opposite to the base material 1.

FIG. 2 shows an enlarged cross-sectional view of a main part of another aspect of the organic electronic device of the present invention. In addition to the organic electronic device shown in FIG. 1, it has an adhesive resin layer 6 and an opposing substrate 7.

Next, the method for manufacturing the organic electronic device of the present invention will be described. The method for producing an organic electronic device of the present invention preferably includes at least (a) a step of forming an organic electronic device main body and a lead-out electrode on a base material, and (b) a step of forming a SiON layer. Further, when the organic electronic device has a protective resin layer, (a) a step of forming the organic electronic device main body and the extraction electrode on the base material, and (c) forming the protective resin layer on the organic electronic device main body. It is preferable to have a step and (b) a step of forming a SiON layer. The following is an example of an organic thin-film solar cell device in which the main body of the organic electronic device is an organic thin-film solar cell having an electron transport layer / power generation layer / hole transport layer as an organic active layer, and further having a transparent electrode and a counter electrode. explain.

First, (a) an organic thin-film solar cell and a lead-out electrode are formed on the base material.

Examples of the method for forming the lead-out electrode include a vacuum deposition method, a sputtering method, an ion plating method, a plating method, a coating method such as an inkjet method, and the like.

It is preferable to form a transparent electrode on the base material on which the extraction electrode is formed. Examples of the method for forming the transparent electrode include the method exemplified as the method for forming the lead-out electrode.

Next, an electron transport layer, a power generation layer, and a hole transport layer are formed. Examples of the method for forming the electron transport layer, power generation layer, and hole transport layer include spin coat method, dip coat method, casting method, bar coat method, spray method, screen printing, gravure printing method, flexographic printing method, and offset printing. Examples include the method, dispenser coating, slit coating method, and inkjet method. When the power generation layer is a mixture of an electron-donating organic material and an electron-accepting organic material, as a method of mixing these materials, for example, an electron-donating organic material and an electron-accepting organic material are used as a solvent in a desired ratio. After addition, a method of dissolving in a solvent by a method such as heating, stirring and / or ultrasonic irradiation can be mentioned. Examples of the solvent include toluene, xylene, tetralin, chlorobenzene, dichlorobenzene, trichlorobenzene, chloroform, dichloromethane, dichloroethane, tetrahydrofuran, tetrahydropyran and the like.

Next, it is preferable to form the counter electrode on the base material on which the transparent electrode, the electron transport layer, the power generation layer and the hole transport layer are formed. Examples of the method for forming the counter electrode include the method exemplified as the method for forming the lead-out electrode.

Next, if necessary, (c) a protective resin layer is formed on the organic thin-film solar cell which is the main body of the organic electronic device. Examples of the method for forming the protective resin layer include the methods exemplified as the method for forming the electron transport layer, the power generation layer, and the hole transport layer.

Next, (b) a SION layer is formed.

The method for forming the SION layer is not particularly limited. For example, a vacuum vapor deposition method, a sputtering method, a chemical vapor deposition (CVD) method, a plasma CVD method, a photoconversion method of a SiON precursor, a thermal conversion method, and the like can be mentioned. Among them, the plasma CVD method, the photoconversion method of the precursor of SiON, and the thermal conversion method are preferable because defects are less likely to occur and a dense thin film can be easily formed.

In the present invention, as the step (b) for forming the SION layer, it is preferable to form the SION layer by photoconversion of polysilazane. Such a method does not require a vacuum process such as plasma CVD or sputtering, and can form a SION layer in a general environment under normal temperature and atmospheric pressure, so that it can be applied to a production method such as roll-to-roll. is there. It is more preferable to have the following steps (b-1) to (b-3).
(B-1) A step of applying a polysilazane solution onto at least a part of the extraction electrode and the body of the organic electronic device.
(B-2) A step of irradiating the polysilazane layer with ultraviolet light to convert polysilazane into light, and
(B-3) A step of heating and drying the photoconverted polysilazane layer to form a SION layer.

In the step (b-1), polysilazane is a polymer having a silicon-nitrogen bond having a structural unit represented by the following general formula (2), and is a polymer of Si—N, Si—H, NH, etc. It is a precursor polymer of silicon nitride such as SiO2, Si3N4 having a bond and their intermediate SiOxNy.

In the general formula (2), R ¹ , R ² and R ³ may be the same or different, and may be the same or different, and may be a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkylsilyl group, an alkylamino group or an alkoxy group. Represents. From the viewpoint of transparency and gas barrier property, poly (perhydrosilazane) in which all of ^{R 1} , R ² , and R ^{3 are hydrogen atoms is more preferable.}

Examples of the polysilazane solution include AZ NAX120-20, AZ NL120A-20, and AZ NN120-20 (manufactured by Merck Performance Materials Co., Ltd.). Two or more of these may be used. The concentration of the polysilazane solution can be selected according to the thickness of the SION layer to be formed, but is preferably 0.1 to 20% by mass. The polysilazane solution may contain a catalyst that promotes photoconversion, but a catalyst-free polysilazane solution is preferable because it forms a high-purity SiON film from the viewpoint of reducing the influence on organic electronic devices.

Examples of the method for applying the polysilazane solution include methods exemplified as a method for forming an electron transport layer, a power generation layer, and a hole transport layer.

In the step (b-2), it is preferable to irradiate the polysilazane layer with vacuum ultraviolet rays (VUV). In the present invention, the wavelength of the vacuum ultraviolet light is preferably 10 to 200 nm, more preferably 100 to 200 nm, and even more preferably 150 to 180 nm. The photoconversion of polysilazane in this step means that polysilazane is converted to SION. The conversion proceeds from the surface of the polysilazane layer, but in the present invention, it is sufficient that a part of the polysilazane layer is converted, and it is not necessary that all of the polysilazane layer is converted to SION.

The illuminance and irradiation time of the vacuum ultraviolet rays are not particularly limited as long as polysilazane can be sufficiently converted, and can be appropriately set in consideration of the influence on the base material and the main body of the electronic device. For example, the illuminance of the vacuum ultraviolet rays on the outermost surface of the polysilazane layer is preferably ^{0.1 to 100 mW / cm 2.} The irradiation time of vacuum ultraviolet rays is preferably 1 to 60 minutes, more preferably 10 to 30 minutes.

In the step (b-3), the photoconverted polysilazane layer is heated and dried. In the method of photoconverting the polysilazane layer after heating and drying, the polysilazane solution applied on the protective resin layer tends to generate repellent during the heating and drying, especially when the SiON layer is formed on the protective resin layer. In the present invention, such cissing is suppressed and a uniform SION layer is easily formed by photoconverting in step (b-2) and immobilizing as a SION layer and then heating and drying in step (b-3). be able to.

Further, when forming the adhesive resin layer or the opposing substrate, it is preferable to apply a paste-like adhesive resin on the organic electronic device main body and bond the opposing substrate and the organic electronic device main body. Examples of the adhesive resin coating method include a printing method capable of pattern processing such as screen printing, gravure printing, offset printing, dispense coating, and inkjet coating.

The above embodiments are presented as examples and are not intended to limit the scope of the invention. The above-described embodiment can be implemented in various other forms, and various omissions, replacements, and changes can be made without departing from the gist of the invention. The above-described embodiment and its modifications are included in the scope and gist of the invention, and are also included in the scope of the invention described in the claims and the equivalent scope thereof.

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

The durability evaluation method in each Example and Comparative Example will be described. First, for the organic thin-film solar cell devices produced in each Example and Comparative Example, the amount of power generation per unit area of the neutral white LED 200 Lux was measured and used as the initial characteristics. The evaluated organic thin-film solar cell device was stored in an environment of a temperature of 60 ° C. and a humidity of 90% RH. The amount of power generated per unit area of the LED 200 Lux was evaluated in the same manner, and the ratio to the initial characteristics was calculated.

(Example 1)
An organic thin-film solar cell device having the structure shown in FIG. 4 was produced by the following procedure. The organic thin-film solar cell device, which is the organic electronic device 10, has a portion in which the base material 1 / extraction electrode 5 / SION layer 4 is directly laminated.

(Formation of lead-out electrode)
An ITO having a thickness of 125 nm was formed on a substrate 1 made of a non-alkali glass substrate having a thickness of 0.7 mm by a sputtering method, and patterned by a photolithography method to form a lead-out electrode 5.

(Formation of organic thin-film solar cells)
An ITO having a thickness of 125 nm was formed on the base material 1 on which the extraction electrode 5 was formed by a sputtering method, and patterning was performed by a photolithography method to form a transparent electrode 21. The substrate on which the transparent electrode was formed was ultrasonically cleaned with an alkaline cleaning solution (Furuuchi Chemical Co., Ltd., "Semicoclean" (registered trademark) EL56 (trade name)) for 10 minutes, and then washed with pure water. UV / ozone treatment was performed for an additional 30 minutes.

0.5 mL of ethanol solvent (manufactured by Wako Pure Chemical Industries, Ltd.) was added to a sample bottle containing 10 mg of zinc acetate dihydrate (manufactured by Wako Pure Chemical Industries, Ltd.) and dissolved by heat. Aminopropyltriethoxysilane (manufactured by Wako Pure Chemical Industries, Ltd.) was added at a ratio of 1.0% by volume to obtain a coating ink for forming an electron transport layer. A coating ink for forming a hole transport layer is applied on a substrate on which a transparent electrode is formed by a spin coating method under the condition of 3000 rpm for 30 seconds, and then heated on a hot plate at a temperature of 150 ° C. for 30 minutes to prepare a solvent. It was removed to form an electron transport layer. The film thickness of the electron transport layer after drying was 40 nm.

Conjugated polymer having the structure represented by the general formula (1) (number average molecular weight: 45,900, weight average molecular weight: 106,000, Z average molecular weight: 247,000) 12.15 mg, [6,6 ] -Phenyl C61 Butyric Acid Methyl Estel (PCBM) (manufactured by Frontier Carbon) 14.85 mg, 3,4,5-trimethoxytoluene (manufactured by Tokyo Chemical Industry Co., Ltd.) 60 mg, chlorobenzene 1.114 mL in a sample bottle. It was put in and irradiated with ultrasonic waves for 30 minutes in an ultrasonic cleaner (US-2 (trade name) manufactured by Inuchi Seieidou, output 120 W) to obtain a coating ink for forming a power generation layer. A coating ink for forming a power generation layer is applied to a substrate on which an electron transport layer is formed by a spin coating method under the condition of 1000 rpm for 60 seconds, and then heated under reduced pressure at a temperature of 100 ° C. for 1 minute using a vacuum heating oven. The solvent was removed to form a power generation layer. The film thickness of the power generation layer after drying was 100 nm.

40% by volume of polyethylene dioxythiophene polystyrene sulfonate (PEDOT: PSS, manufactured by Heraeus, "Clevios" (registered trademark) PAI 4083) is diluted with 45% by volume of pure water and 15% by volume of 2-propanol to provide surface activity. An agent (manufactured by Kao Co., Ltd., "Emargen" (registered trademark) 103 (trade name)) was added in an amount of 1.0% by volume to obtain a coating ink for forming a hole transport layer. A coating ink for forming a hole transport layer is applied on a substrate on which a power generation layer is formed by a spin coating method for 30 seconds under the condition of 2000 rpm, and then heated on a hot plate at a temperature of 100 ° C. for 1 minute to prepare a solvent. It was removed to form a hole transport layer. The film thickness of the hole transport layer after drying was 30 nm.

A base material 1 in which a lead-out electrode 5, a transparent electrode 21, an organic active layer 22 composed of an electron transport layer / a power generation layer / a hole transport layer, and an electrode mask are installed in a vacuum vapor deposition apparatus. The vacuum inside was exhausted until the degree of vacuum became 1 × 10 ^-3 Pa or less, and a counter electrode 23 made of a silver layer having a thickness of 200 nm was formed by vapor deposition by a resistance heating method. The effective power generation area of the organic thin-film solar cell is 5 mm × 5 mm where the transparent electrode and the counter electrode overlap. Further, the organic thin-film solar cell composed of the transparent electrode 21, the organic active layer 22, and the counter electrode 23 on the base material 1 is the organic electronic device main body 2.

(Formation of protective resin layer)
Next, a photocurable resin having a viscosity of about 10 mPa · s (XMF-FCIE011B (trade name) manufactured by Mitsui Chemicals, Inc.) is applied to a part of the base material 1 and the organic electronic device main body 2 as an inkjet device. After applying the pattern with a discharge dot liquid amount of 10 pL and a printing pattern pitch of 20 μm, the protective resin layer 3 having a thickness of 5 μm was formed by irradiating with ^{ultraviolet light (wavelength 365 nm, intensity 100 mW / cm 2) for 1 minute.}

(Formation of SION layer)
Next, a dibutyl ether solution (NN120-20 manufactured by AZ Electronic Materials Co., Ltd.) containing 20% by mass of non-catalytic poly (perhydrosilazane) was added onto the base material 1 and the protective resin layer 3 by a spin coating method. A 4: 1 (mass ratio) mixed solution with anhydrous dibutyl ether was applied for 30 seconds under the condition of 1000 rpm, and then ^{irradiated with vacuum ultraviolet rays (wavelength 184 nm, intensity 1 mW / cm-2} ) for 20 minutes for photoconversion. The solvent was removed by heating on a hot plate at a temperature of 120 ° C. for 1 minute in an active atmosphere to form a SiON layer 4 having a thickness of 0.2 μm.

(Example 2)
Using the inkjet device DMP-2850 (manufactured by FUJIFILM Corporation) on the base material 1, silver nanoparticle ink (OAG-IJ005 manufactured by Nagase ChemteX Corporation) was applied on the substrate 1 with a discharge dot liquid volume of 1 pL and a printing pattern pitch of 15 μm. After arbitrarily applying a pattern under the conditions, the solvent was removed by heating on a hot plate at a temperature of 100 ° C. for 3 minutes to form a drawing electrode 5.

(Formation of organic thin-film solar cells)
Silver nanowire ink (C3nano, "ActiveGlide" (registered trademark) Ink GJ5DX) was applied to the base material 1 on which the extraction electrode 5 was formed by a spin coating method under the condition of 500 rpm for 30 seconds, and then placed on a hot plate. , The solvent was removed by heating at a temperature of 100 ° C. for 10 minutes to form a transparent electrode 21. The film thickness of the transparent electrode after drying was 50 nm.

In order to form an insulating pattern on the transparent electrode 21 coated on the entire surface, trimming was performed using a laser (wavelength 355 nm, output 150 mW, sweep speed 600 mm / sec, frequency 60 kHz).

50 parts by weight of ethylene glycol was added to 100 parts by weight of zinc oxide nanoparticle ink (Helios ETL Slot Die manufactured by GENESINK), and the amount of discharged dot liquid was discharged using an inkjet device DMP-2850 (manufactured by FUJIFILM Corporation). After the pattern was applied under the conditions of 10 pL and a printing pattern pitch of 20 μm, the solvent was removed by heating at a temperature of 100 ° C. for 1 minute under a reduced pressure of 100 Pa or less to form an electron transport layer. The film thickness of the electron transport layer after drying was 40 nm.

A conjugated polymer having a structure represented by the general formula (1) (number average molecular weight: 45,900, weight average molecular weight: 106,000, Z average molecular weight: 247,000) 135 mg, [6,6]- Phenyl C61 Butyric Acid Methyl Estel (PCBM) (manufactured by Frontier Carbon) 165 mg, 3,4,5-trimethoxytoluene (manufactured by Tokyo Chemical Industry Co., Ltd.) 1000 mg, o-dichlorobenzene 19 mL are placed in a sample bottle and super A coating ink for forming a power generation layer was obtained by irradiating ultrasonic waves for 30 minutes in a sonic cleaner (US-2 (trade name) manufactured by Inuchi Seieidou, output 120 W). On the base material on which the electron transport layer is formed, an inkjet device DMP-2850 (manufactured by FUJIFILM Corporation) is used to pattern the coating ink for forming the power generation layer under the conditions of a discharge dot liquid volume of 10 pL and a printing pattern pitch of 20 μm. After coating, the solvent was removed by heating at a temperature of 100 ° C. for 1 minute under a reduced pressure of 100 Pa or less to form a power generation layer. The film thickness of the power generation layer after drying was 250 nm. The outermost surface of the formed power generation layer was hydrophilized at 40 W for 1 second in a reduced pressure atmosphere using a vacuum plasma processing apparatus (YHS-R manufactured by Kai Semiconductor Co., Ltd.).

Inkjet device DMP-2850 (Fujifilm) on a substrate on which a power generation layer is formed by hydrophilizing polyethylene dioxythiophene polystyrene sulfonate (PEDOT: PSS, manufactured by Agfa, "ORGACON" (registered trademark) IJ-005). A coating ink for forming a hole transport layer was applied with a pattern applied under the conditions of a discharge dot liquid volume of 10 pL and a printing pattern pitch of 20 μm, and then heated at a temperature of 100 ° C. for 1 minute under a reduced pressure of 100 Pa or less. The solvent was removed to form a hole transport layer. The film thickness of the hole transport layer after drying was 100 nm.

Using an inkjet device DMP-2850 (manufactured by FUJIFILM Corporation), silver nanoparticle ink (OAG-IJ005 manufactured by Nagase ChemteX Corporation) was applied onto a substrate on which a hole transport layer was formed, with a discharge dot liquid volume of 1 pL. After the pattern was applied in a grid pattern at 1.0 mm intervals under the condition of a print pattern pitch of 15 μm, the solvent was removed by heating at a temperature of 100 ° C. for 3 minutes on a hot plate to form a counter electrode 23. The film thickness of the counter electrode after drying was 2 μm. The effective power generation area of the organic thin-film solar cell is 5 mm × 5 mm where the transparent electrode and the counter electrode overlap. Further, the organic thin-film solar cell composed of the transparent electrode 21, the organic active layer 22, and the counter electrode 23 on the base material 1 is the organic electronic device main body 2.

(Comparative Example 1)
In (formation of a protective resin layer), a photocurable resin (manufactured by Mitsui Chemicals, Inc., XMF-FCIE011B (trade name)) is applied on the base material 1 and the organic electronic device main body 2 by a spin coating method at 1000 rpm. After coating on the entire surface for 30 seconds under the conditions of the above conditions, ultraviolet light (wavelength 365 nm, intensity 100 mW / cm ² ) was irradiated for 1 minute to form a protective resin layer 3 having a thickness of 5 μm. Next, in (formation of the SION layer), an organic thin-film solar cell device having the structure shown in FIG. 5 was produced in the same manner as in Example 1 except that the SION layer 4 was formed on the entire surface of the protective resin layer 3. ..

In the organic thin-film solar cell device, which is the organic electronic device 10, the extraction electrode 5 is coated with the protective resin layer 3 and is not directly laminated with the SION layer 4.

The results of evaluating the durability of the organic thin-film solar cell devices produced in each Example and Comparative Example by the above-mentioned method are shown in FIG. In FIG. 3, the horizontal axis shows the elapsed time, and the vertical axis shows the amount of power generation standardized by the initial characteristics. Reference numerals ◯ and Δ indicate the evaluation results of Example 1 and Comparative Example 1, respectively. Example 1 is 1.05 times the initial power generation amount when 93 hours have passed, and 0.96 times the initial power generation amount when 213 hours have passed, and Comparative Example 1 is 0 of the initial power generation amount when 72 hours have passed. It was .36 times.

From the graph of FIG. 3, it can be seen that the organic solar cell device of Example 1 having a portion in which the base material, the extraction electrode, and the SiON layer are directly laminated is excellent in durability. On the other hand, the organic solar cell device of Comparative Example 1 which does not have a portion where the base material, the extraction electrode, and the SiON layer are directly laminated has low durability, and moisture and oxygen are released through the protective resin layer 3 to the organic electronic device. It is considered to reach the main body 2.

1 Base material 2 Organic electronic device body 3 Protective resin layer 4 SiON layer 5 Drawer electrode 6 Adhesive resin layer 7 Opposing substrate 10 Organic electronic device 21 Transparent electrode 22 Organic active layer 23 Opposing electrode

Claims (4)

An organic electronic device main body having an organic active layer, an organic electronic device having an extraction electrode and a SiON layer on a base material, and having a portion in which the base material, the extraction electrode and the SiON layer are directly laminated. The organic electronic device according to claim 1, further comprising a protective resin layer between the organic electronic device main body and the SION layer. At least (a) a step of forming the organic electronic device body and the extraction electrode on the substrate, and
(B) It has a step of forming a SION layer, and has a step.
(B) The step of forming the SION layer is
(B-1) A step of applying a polysilazane solution onto at least a part of the extraction electrode and the body of the organic electronic device.
(B-2) A step of irradiating the polysilazane layer with ultraviolet light to convert polysilazane into light, and
(B-3) The method for producing an organic electronic device according to claim 1, further comprising a step of heating and drying the photoconverted polysilazane layer to form a SiON layer. At least (a) a step of forming the organic electronic device body and the extraction electrode on the substrate,
(C) A step of forming a protective resin layer on the main body of the organic electronic device, and
(B) It has a step of forming a SION layer, and has a step.
(B) The step of forming the SION layer is
(B-1) A step of applying a polysilazane solution onto at least a part of the extraction electrode and the body of the organic electronic device.
The second aspect of claim 2, further comprising (b-2) a step of irradiating the polysilazane layer with ultraviolet light to photoconvert the polysilazane, and (b-3) a step of heating and drying the photoconverted polysilazane layer to form a SiON layer. A method for manufacturing organic electronic devices.

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