JP2012000599A - Barrier film and method of manufacturing the same, organic electronic device, and method of manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of manufacturing an organic electronic device giving an organic electronic device with high suitability for production step and high barrier performance and excellent in durability, and to provide the organic electronic device obtained by the method.SOLUTION: There is provided a barrier film characterized in that a boiling point of an amine compound contained in a coating liquid used on a side closer to a base material is higher than a boiling point of an amine compound contained in a coating liquid used on a side further from the base material when the coating liquid containing a polysilazane compound and amine compound is applied on the base material 1 substantially without water vapor barrier performance, dried, and then, irradiated with a vacuum ultraviolet light to form at least two layers 2, 3 or more water vapor barrier layers including a silicon compound. Furthermore, there are provided a method for manufacturing the same, and moreover, the organic electronic device and the method of manufacturing the same.

Description

  The present invention relates to a barrier film and a manufacturing method thereof, an organic electronic device and a manufacturing method thereof. More specifically, the present invention is used for a display material such as a package of an electronic device or a plastic substrate such as an organic EL element, a solar battery, and a liquid crystal. The present invention relates to a barrier film, a barrier film manufacturing method, and an organic electronic device using the barrier film.

  Organic electronic devices such as solar cells and organic EL elements have an organic functional layer that has various functions such as a conversion function between light and electricity, but the organic functional layer is subject to performance degradation due to various gases such as oxygen and water. The gas barrier film (hereinafter referred to as “barrier film”) or the like is used, and is configured to avoid contact between the organic functional layer and harmful gas.

  In general, a barrier film in which a thin film of a metal oxide such as aluminum oxide, magnesium oxide, or silicon oxide is formed on the surface of a film substrate such as a plastic substrate is known as a barrier film, such as water vapor or oxygen. It is widely used for packaging of articles that need to block various types of gases, and for packaging of foods, industrial goods, pharmaceuticals, and the like. And these barrier films are used also for a liquid crystal display element, a solar cell, an organic EL (electroluminescence) element, etc. besides the said packaging use.

  As a method for forming the inorganic barrier layer, for example, a chemical deposition method (plasma CVD) in which an organic silicon compound typified by TEOS (tetraethoxysilane) is used to form a film on a substrate while being oxidized with oxygen plasma under reduced pressure. Also known is a sputtering method in which metal Si is evaporated using a semiconductor laser and deposited on a substrate in the presence of oxygen.

Since these methods can form a thin film with an accurate composition on a substrate, they have been preferably used for the formation of metal oxide thin films including SiO _2. It took a lot of time, and continuous production was difficult, and the equipment was enlarged.

  In order to solve these problems, for the purpose of improving productivity, a silicon-containing compound is applied, a method of forming a silicon oxide thin film by modifying the coating film, and plasma under atmospheric pressure even in the same CVD method Attempts to form films under atmospheric pressure have been made, and are being studied for barrier films.

  As a silicon oxide film that can be generally produced by a solution process, a technique of forming an alkoxide compound as a raw material by a method called a sol-gel method is known. This sol-gel method generally requires heating to a high temperature, and further, a large volume shrinkage occurs in the course of the dehydration condensation reaction, resulting in a large number of defects in the film.

  In order to prevent this, a technique of mixing organic substances that do not directly participate in the formation of oxides into the raw material solution has been found. However, when these organic substances remain in the film, the barrier property of the entire film is lowered. .

  For these reasons, it has been difficult to directly apply an oxide film produced by a sol-gel method to an organic electronic device.

  As another method, it has been proposed to produce silicon oxide using a silazane compound having a basic structure of silazane structure (Si-N) as a raw material. In this case, the reaction is not from dehydration condensation polymerization but from nitrogen to oxygen. Since this is a direct substitution reaction, it is known that a dense film having a mass yield before and after the reaction of 80% to 100% or more and few defects in the film due to volume shrinkage can be obtained.

  However, production of a silicon oxide thin film by substitution reaction of a silazane compound requires a high temperature of 450 ° C. or higher, and it was impossible to adapt to a flexible substrate such as plastic.

  As a means for solving such a problem, it is known that the heating temperature at the time of forming the silica coating can be lowered and the heating time can be shortened by subjecting the polysilazane coating to vacuum ultraviolet irradiation (Patent Document 1). reference).

However, a large amount of energy of vacuum ultraviolet light required to form the silica film is required, and the water vapor transmission rate in JIS K-7129 is less than 0.01 g / m ² / day at most, Solar cells, organic electroluminescence (EL) substrates, and the like have a problem that their performance and life are reduced, and it has not been possible to obtain sufficient barrier properties to ensure the durability of various electronic devices.

  As a technique for reducing the amount of energy of vacuum ultraviolet light required to form such a silica film, a technique for adding an organic or inorganic catalyst to a polysilazane compound coating solution is known. (See Patent Document 2).

  However, in the case of an inorganic substance, such a catalyst remains in the silica film, so that it is difficult to form a layer having a dense structure and a high barrier property, and an organic catalyst having a high volatility. In the case where is added, it tends to volatilize together with the coating solvent in the coating and drying steps, and a sufficient reaction promoting effect cannot be obtained.

  Moreover, in order to obtain a barrier film having a high barrier property as described above, it is effective to form a plurality of barrier layers. On the other hand, formation of a silica thin film with polysilazane using vacuum ultraviolet light It is known that because of the short wavelength of vacuum ultraviolet light, oxygen in the atmosphere is activated and the reaction proceeds from the surface side of the polysilazane film irradiated with ultraviolet light. (Refer nonpatent literature 1).

  Therefore, when a plurality of barrier layers are formed, a region that is not sufficiently modified into a silica film, which is sandwiched between layers having burr, remains inside the excimer modified layer of polysilazane on the upper layer side. However, it became clear by examination of the present inventors.

  In such a low reforming region on the upper layer side, a volatile component such as ammonia gas decomposed and produced from polysilazane is produced when the reforming reaction proceeds further by long-term storage or heating, or when exposed to a high temperature. It is believed that by vaporizing, the barrier layer is partially destroyed and the barrier property is lowered.

  On the other hand, in the case of a lower layer that is directly applied to a substrate that does not substantially have barrier properties and is modified from a polysilazane film to a silica film by irradiation with vacuum ultraviolet rays, volatile components generated from the low-modified region are Even if it exists, it is easily removed by diffusing to the substrate surface side that does not have barrier properties.

JP 2009-255040 A Special table 2009-503157

Journal of the Ceramic Society of Japan: (2004), 112, 599-603

  The objective of this invention is providing the manufacturing method of the organic electronic device which gives the organic electronic device which has high production process suitability, high barrier performance, and is excellent in durability, and the organic electronic device obtained by it.

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

  1. A coating solution containing a polysilazane compound and an amine compound is coated on a substrate that does not substantially have a water vapor barrier property, and at least two or more water vapor barrier layers composed of a silicon compound are irradiated by irradiating vacuum ultraviolet light after drying. When forming, a barrier film characterized in that the boiling point of the amine compound contained in the coating solution used on the side closer to the substrate is higher than the boiling point of the amine compound contained in the coating solution used on the side far from the substrate. Manufacturing method.

  2. 2. The method for producing a barrier film according to 1 above, wherein the amine compound has a higher boiling point than that of the coating solvent. However, regarding the boiling point of the amine compound, when two or more amine compounds are used, the boiling point of the amine compound showing the lowest boiling point among the amine compounds used is the boiling point of the amine compound.

  3. A barrier film manufactured by the method for manufacturing a barrier film according to 1 or 2 above.

  4). 4. A method for producing an organic electronic device, comprising: sealing an organic photoelectric conversion element through an adhesive using the barrier film described in 3 above.

  5. 5. An organic electronic device manufactured by the manufacturing method described in 4 above.

  INDUSTRIAL APPLICABILITY According to the present invention, a barrier film having high barrier performance, a method for producing an organic electronic device that provides an organic electronic device having excellent durability, and an organic electronic device obtained thereby can be provided.

It is sectional drawing of the barrier film which concerns on this invention.

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

  FIG. 1 is a cross-sectional view of a barrier film according to the present invention, in which a) shows a structure having two barrier layers 2 and 3 on a substrate 1. b) shows a configuration in which the smooth layer 4 and the bleed-out preventing layer 5 are provided on both surfaces of the substrate 1, and two barrier layers 2 and 3 are provided on the smooth layer 4.

(Barrier layer forming process)
(Barrier film)
The barrier film according to the present invention has a barrier layer on a substrate. The barrier film in the present invention refers to a film having a function of suppressing permeation of oxygen and / or water vapor gas. Using a water vapor permeability measuring device manufactured by MOCON in accordance with the measurement method shown in JIS K7129 B method and ASTM F1249-90, the water vapor transmission rate when measured under the condition of 40 ° C. × 90% RH is 1 × refers to a layer of less than ¹⁰ -2 g / ^{m 2} · day.

  Specific measurement methods include the JIS K7129 B method (infrared sensor method) and the isobaric method called the Mocon method shown in ASTM F1249-90, the Ca corrosion method described in JP-A-2006-250816, and As described in 2009-257994, there is a method of detecting a change in color difference due to moisture absorption.

The oxygen permeability was measured according to JIS K 7126 (Method B). Measurement was performed at an ambient temperature of 23 ° C. and a humidity of 75%. The measurement uses an oxygen permeability measuring device (“MOCON OX-TRAN” manufactured by Mocon, USA) and refers to a layer having a measured value of 5 × 10 ⁻² ml / m ² · day or less.

(Base material)
The base material having substantially no water vapor barrier property used in the present invention is not particularly limited as long as it is formed of a material capable of holding a barrier layer described later.

It has substantially no water vapor barrier property using the Mocon method, and the measurement is based on JIS standard K7129 method (temperature 40 ° C., humidity 90% RH) using PERMATRAN-W3 / 33 manufactured by MOCON. The measured water vapor transmission rate is defined as 0.5 g / m ² / day or more as measured by the Mocon method. The substrate having substantially no water vapor barrier property used in the present invention may be a resin film as described later, or a laminate of various functional layers such as an anchor coat layer, a smooth layer, and a bleed out prevention layer. Preferably used.

If the substrate has a water vapor barrier property of less than 0.01 g / m ² / day, diffusion removal of the amine compound in the low-modified region of the barrier layer in contact with the substrate is inhibited, as described later. , Long-term storage and heat resistance will be reduced.

(Resin film)
Examples of the resin film material include polyacrylate, polymethacrylate, polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate (PEN), polycarbonate (PC), polyarylate, polyvinyl chloride (PVC), polyethylene (PE), polypropylene (PP), polystyrene (PS), nylon (Ny), aromatic polyamide, polyetheretherketone, polysulfone, polyethersulfone, polyimide, polyetherimide film, organic-inorganic hybrid structure Heat-resistant transparent film (product name Sila-DEC, manufactured by Chisso Corporation) having silsesquioxane having a basic skeleton as well as a resin film obtained by laminating two or more layers of the above resin It can be.

  From the viewpoint of cost and availability, polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate (PEN), polycarbonate (PC) and the like are preferably used.

  Further, in terms of optical transparency, heat resistance, adhesion to the inorganic layer and the barrier layer, a heat resistant transparent resin film having silsesquioxane having an organic-inorganic hybrid structure as a basic skeleton can be preferably used.

  The thickness of the substrate is preferably about 5 μm to 500 μm, more preferably 25 μm to 250 μm.

  In the present invention, the substrate is preferably transparent.

  Here, the base material being transparent means that the light transmittance of visible light (400 nm to 700 nm) is 80% or more.

  Since the base material is transparent and the layer formed on the base material is also transparent, it becomes possible to make a transparent barrier film, so that it becomes possible to make a transparent substrate such as an organic EL element. is there.

  Further, the resin film using the above-described resins or the like may be an unstretched film or a stretched film.

  The resin film used in the present invention can be produced by a conventionally known general method.

  For example, an unstretched substrate (support) that is substantially amorphous and not oriented can be produced by melting a resin as a material with an extruder, extruding it with an annular die or a T-die, and quenching. it can.

  In addition, a stretched resin film can be produced by a known method such as uniaxial stretching, tenter-type sequential biaxial stretching, tenter-type simultaneous biaxial stretching, and tubular simultaneous biaxial stretching of an unstretched substrate.

  The draw ratio in this case can be appropriately selected according to the resin as the raw material of the resin film, but is preferably 2 to 10 times in the vertical axis direction and the horizontal axis direction, respectively.

  Furthermore, in order to improve dimensional stability in the stretched resin film, it is preferable to perform relaxation treatment after stretching.

  Moreover, the surface of the resin film according to the present invention may be corona-treated, and an anchor coat agent layer may be further formed on the surface.

《Anchor coating agent layer》
Examples of the anchor coating agent used in the anchor coating agent layer include polyester resins, isocyanate resins, urethane resins, acrylic resins, ethylene vinyl alcohol resins, vinyl modified resins, epoxy resins, modified styrene resins, modified silicon resins, alkyl titanates, and the like. Of the mixture.

  Conventionally known additives can be added to these anchor coating agents.

  The anchor coating agent layer can be formed by coating on a substrate by a known method such as roll coating, gravure coating, knife coating, dip coating or spray coating.

The amount of the anchor coating agent is preferably about 0.1 g / m ^{2 to} 5 g / m ² (dry state).

《Smooth layer》
The base material according to the present invention may have a smooth layer.

  The smooth layer is provided in order to flatten the surface of the substrate on which protrusions and the like are present.

  A uniform barrier layer with few defects can be formed by laminating and forming a barrier layer on the surface flattened by the smooth layer after interposing another layer as required. Furthermore, the structure laminated | stacked so that the surface in which the smooth layer was formed may be directly contacted is more preferable.

  Such a smooth layer is basically produced by curing a photosensitive resin.

  As the photosensitive resin of the smooth layer, for example, a resin composition containing an acrylate compound having a radical reactive unsaturated compound, a resin composition containing an acrylate compound and a mercapto compound having a thiol group, epoxy acrylate, urethane acrylate, Examples thereof include a resin composition in which a polyfunctional acrylate monomer such as polyester acrylate, polyether acrylate, polyethylene glycol acrylate, or glycerol methacrylate is dissolved.

  It is also possible to use an arbitrary mixture of the above resin compositions, and any photosensitive resin containing a reactive monomer having one or more photopolymerizable unsaturated bonds in the molecule can be used. There are no particular restrictions.

  The method for forming the smooth layer is not particularly limited, but is preferably formed by a wet coating method such as a spin coating method, a spray method, a blade coating method, or a dip method, or a dry coating method such as an evaporation method.

  In the formation of the smooth layer, additives such as an antioxidant, an ultraviolet absorber, and a plasticizer can be added to the above-described photosensitive resin as necessary.

  In addition, regardless of the position where the smooth layer is laminated, in any smooth layer, an appropriate resin or additive may be used for improving the film formability and preventing the generation of pinholes in the film.

  The smoothness of the smooth layer is a value expressed by the surface roughness specified in JIS B 0601 from the viewpoint of coating properties, etc., and the maximum cross-sectional height Rt (p) is 10 nm or more and 30 nm or less. preferable.

  When it has a smooth layer, it is preferable to have a bleed-out prevention layer further.

  The bleed-out prevention layer is a layer provided for the purpose of suppressing the phenomenon that, when a film having a smooth layer is heated, unreacted oligomers migrate from the resin film to the surface and contaminate the contact surface. And a base material may have this on the opposite surface of the base material which has a smooth layer.

  The bleed-out prevention layer may have the same configuration as the smooth layer as long as it has this function.

  The unsaturated organic compound having a polymerizable unsaturated group that can be included in the bleed-out prevention layer is a polyunsaturated organic compound having two or more polymerizable unsaturated groups in the molecule or 1 in the molecule. Examples thereof include monounsaturated organic compounds having a single polymerizable unsaturated group.

  The bleed-out prevention layer may contain a matting agent as an additive.

  As the matting agent, inorganic particles having an average particle diameter of about 0.1 μm to 5 μm are preferable.

  As the inorganic particles, one or more of silica, alumina, talc, clay, calcium carbonate, magnesium carbonate, barium sulfate, aluminum hydroxide, titanium dioxide, zirconium oxide and the like can be used in combination.

  The matting agent composed of inorganic particles is 2 parts by mass or more, preferably 4 parts by mass or more, more preferably 6 parts by mass or more and 20 parts by mass or less, preferably 18 parts by mass with respect to 100 parts by mass of the solid content of the bleed-out prevention layer. Or less, more preferably 16 parts by mass or less.

  In addition, the bleed-out prevention layer may contain a thermoplastic resin, a thermosetting resin, an ionizing radiation curable resin, a photopolymerization initiator, and the like as other components.

  The bleed-out prevention layer as described above is formulated as a coating solution with a hard coating agent, a matting agent, and other components as necessary, and appropriately prepared as a dilution solvent to support the coating solution. It can form by apply | coating to a body film surface by a conventionally well-known coating method, and then irradiating with ionizing radiation and making it harden | cure.

  In addition, as a method of irradiating with ionizing radiation, ultraviolet rays having a wavelength region of 100 to 400 nm, preferably 200 nm to 400 nm, emitted from an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a metal halide lamp or the like are irradiated or scanned. The irradiation can be performed by irradiating an electron beam having a wavelength region of 100 nm or less emitted from a type or curtain type electron beam accelerator.

  The thickness of the bleed-out prevention layer is from the viewpoint of improving the heat resistance of the film, facilitating the balance adjustment of the optical properties of the film, and preventing curling when the bleed-out prevention layer is provided only on one side of the barrier film. The range of 1 μm to 10 μm is preferable, and the range of 2 μm to 7 μm is more preferable.

(Barrier layer)
The barrier layer is a silicon-containing inorganic oxide film made mainly of a polysilazane compound. Specific examples include a silicon oxide film and a silicon oxynitride film. The structure of the barrier layer is a multilayer structure of at least two layers in order to obtain high barrier properties.

(Barrier layer forming process)
As a method for forming the barrier layer on the substrate, a film containing a polysilazane compound as a main component is formed by coating.

  Hereinafter, the formation process of the barrier layer will be described by taking as an example the case of forming a polysilazane compound film by coating.

<Coating film containing polysilazane>
The coating film containing polysilazane is formed by applying a coating solution containing at least one polysilazane compound on a substrate.

  Any appropriate method can be adopted as a coating method.

  Specific examples include a spin coating method, a roll coating method, a flow coating method, an ink jet method, a spray coating method, a printing method, a dip coating method, a casting film forming method, a bar coating method, and a gravure printing method.

  The coating thickness can be appropriately set according to the purpose.

  For example, the coating thickness can be set so that the thickness after drying is preferably about 1 nm to 100 μm, more preferably about 10 nm to 10 μm, and most preferably about 10 nm to 1 μm.

The “polysilazane” used in the present invention is a polymer having a silicon-nitrogen bond, and is composed of Si—N, Si—H, N—H or the like, such as SiO ₂ , Si ₃ N _4, or an intermediate solid solution SiOxNy or the like. It is a precursor inorganic polymer.

  In order not to damage the film substrate, a compound that is converted to silica by being converted to ceramic at a relatively low temperature as described in JP-A-8-112879 is preferable.

  Examples of polysilazane include those having a structural unit represented by the following formula.

—Si (R ₁ ) (R ₂ ) —N (R ₃ ) —
In the formula, R ₁ , R ₂ and R ₃ each represent 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.

In the present invention, perhydropolysilazane, in which all of R ₁ , R ₂ and R ₃ are hydrogen atoms, is particularly preferred from the viewpoint of the denseness of the resulting barrier layer.

  On the other hand, the organopolysilazane in which the hydrogen part bonded to Si is partially substituted with an alkyl group or the like has an alkyl group such as a methyl group, so that the adhesion to the base substrate is improved and the polysilazane is hard and brittle. The barrier layer can have toughness, and there is an advantage that generation of cracks can be suppressed even when the film thickness is increased. These perhydropolysilazane and organopolysilazane may be appropriately selected according to the application, and may be used in combination.

  Perhydropolysilazane is presumed to have a linear structure and a ring structure centered on 6- and 8-membered rings. The molecular weight is about 600 to 2000 (polystyrene conversion) in terms of number average molecular weight (Mn), is a liquid or solid substance, and varies depending on the molecular weight. These are marketed in a solution state dissolved in an organic solvent, and the commercially available product can be used as it is as a polysilazane-containing coating solution.

  As another example of polysilazane which is ceramicized at low temperature, silicon alkoxide-added polysilazane obtained by reacting polysilazane of the above formula with silicon alkoxide (Japanese Patent Laid-Open No. 5-238827), glycidol-added polysilazane obtained by reacting glycidol (JP-A-6-122852), an alcohol-added polysilazane obtained by reacting an alcohol (JP-A-6-240208), a metal carboxylate-added polysilazane obtained by reacting a metal carboxylate (JP-A-6-6 -299118), acetylacetonate complex-added polysilazane obtained by reacting a metal-containing acetylacetonate complex (Japanese Patent Laid-Open No. 6-306329), metal fine particle-added polysilazane obtained by adding metal fine particles (Japanese Patent Laid-Open No. 7-196 86 No.), and the like.

  As an organic solvent for preparing a coating liquid containing polysilazane, it is not preferable to use an alcohol or water-containing one that easily reacts with polysilazane.

  Specifically, hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons and aromatic hydrocarbons, ethers such as halogenated hydrocarbon solvents, aliphatic ethers and alicyclic ethers can be used.

  Specific examples include hydrocarbons such as pentane, hexane, cyclohexane, toluene, xylene, solvesso and turben, halogen hydrocarbons such as methylene chloride and trichloroethane, and ethers such as dibutyl ether, dioxane and tetrahydrofuran.

  These organic solvents may be selected according to purposes such as the solubility of polysilazane and the evaporation rate of the organic solvent, and a plurality of organic solvents may be mixed.

  The polysilazane concentration in the coating solution containing polysilazane is about 0.2% by mass to 35% by mass, although it varies depending on the target film thickness and the pot life of the coating solution.

  Polysilazane may be a derivative in which the hydrogen part bonded to Si is partially substituted with an alkyl group or the like. In this case, as the alkyl group, for example, by having a methyl group, the adhesion to the base substrate is improved, and the hard and brittle silica film can be toughened. Occurrence is suppressed.

(Amine compound)
In the present invention, it is important to add an amine compound to the coating liquid containing polysilazane in order to promote the modification of the coating film containing polysilazane to the film containing silicon oxide described below.

  Examples of the amine compound include alkyl-substituted or unsubstituted amine, monofunctional, diamine, and triamine. The amine used in the present invention is preferably liquid or solid at room temperature (25 ° C.). The boiling point of the amine is preferably 80 ° C. or higher and 350 ° C. or lower, more preferably 120 ° C. or higher and 250 ° C. or lower.

  The amine compound having low volatility is likely to remain in the polysilazane film after coating and drying, and easily contributes to the modification reaction. However, it is preferably not present because it is an unnecessary component after the vacuum ultraviolet modification.

  In addition, the barrier layer formed in contact with the base material is easily diffused and removed from the side of the base material that does not substantially have a barrier property, but the second and subsequent barrier layers formed on the barrier layer are If the amine compound remains in the low modified region inside, there is a concern that the barrier properties may be lowered, which is presumed to be caused by a decrease in the physical strength of the barrier layer when stored for a long time or in a high temperature environment. The

  Therefore, when the same coating solution configuration in which the volatility of the coating solvent and the volatility of the amine compound are optimally set in the base-side barrier layer is also applied to the second and subsequent layers, such a phenomenon is likely to occur.

  In the barrier film of the present invention, in order to solve this problem, the barrier layer is modified by irradiating vacuum ultraviolet light after coating and drying a coating liquid containing a polysilazane compound and an amine compound, and on the substrate. By making the boiling point of the amine compound contained in the near layer higher than the boiling point of the amine compound contained in the layer far from the substrate, both the efficiency of modification to the silica film and long-term heat-resistant storage stability are achieved. I was able to. Further, an amine compound having a boiling point higher than the boiling point of the amine compound contained in the layer on the side close to the base material to the extent that the effect of the present invention is not adversely affected. A small amount may be mixed in the layer far from the substrate, but the maximum amount is less than 50% in terms of the total amine mass ratio.

  Examples of amine compounds are shown below.

  The amine compound used in the present invention is preferably higher than the boiling point of the coating solvent and, in the case of a composite solvent, compared to the lowest boiling point. Immediately after the coating solution is applied to the substrate, the amine compound is gradually reformed into a silica film while reacting with moisture in the air, but the relationship between the coating solvent and the boiling point of the amine compound is as described above. As a result, a part or most of the amine compound remains in the polysilazane film after the coating and drying step, and the addition to the silica film in the subsequent vacuum ultraviolet reforming step can be efficiently advanced. Although an example of diamine which is an amine compound preferably used for this invention is shown, it is not limited to these.

(Modification of polysilazane film)
The coating film containing polysilazane and an amine compound becomes a silicon oxide film by the following modification treatment to form a barrier layer. As the modification treatment, a method using vacuum ultraviolet (VUV) can be preferably used.

(Modification treatment of coating film containing polysilazane using vacuum ultraviolet ray (VUV))
The barrier layer is obtained by applying a solution containing polysilazane on a base material and then subjecting the coating film containing polysilazane to irradiation with vacuum ultraviolet rays (VUV).

  The barrier layer is obtained by a method in which a polysilazane-containing solution is applied on a substrate, dried, and then irradiated with vacuum ultraviolet rays.

  As the vacuum ultraviolet rays, vacuum ultraviolet rays (VUV light) of 100 nm to 200 nm are preferably used.

In the irradiation with the vacuum ultraviolet ray, the irradiation intensity and / or the irradiation time is set within a range in which the substrate carrying the irradiated coating film is not damaged. Taking the case of using a plastic film as a base material as an example, the base material so that the intensity of the base material surface is ^{10mW / cm 2 ~300mW / cm 2} - sets the ramp distance, 0.1 second to 10 It is preferable to perform irradiation for a minute, preferably 0.5 seconds to 3 minutes.

  As the vacuum ultraviolet irradiation apparatus, a commercially available lamp (for example, manufactured by USHIO INC.) Can be used.

  Vacuum ultraviolet (VUV) irradiation can be applied to both batch processing and continuous processing, and can be appropriately selected depending on the shape of the substrate to be coated.

  For example, in the case of batch processing, a substrate (eg, silicon wafer) having a polysilazane coating film on the surface can be processed in a vacuum ultraviolet ray baking furnace equipped with a vacuum ultraviolet ray source. The vacuum ultraviolet baking furnace itself is generally known, and for example, Ushio Electric Co., Ltd. can be used. In addition, when the base material having a polysilazane coating film on the surface is in the form of a long film, vacuum ultraviolet rays are continuously irradiated in the drying zone equipped with the vacuum ultraviolet ray generation source as described above while being conveyed. Can be made into ceramics.

  Since the vacuum ultraviolet light is larger than the interatomic bonding force of most substances, it can be preferably used because the bonding of atoms can be cut directly by the action of only photons called photon processes.

  By using this action, the reforming process can be efficiently performed at a low temperature without requiring hydrolysis.

  As the vacuum ultraviolet light source, a rare gas excimer lamp using excimer emission is preferably used.

  In order to obtain excimer light emission, a method using dielectric barrier discharge is known.

  Dielectric barrier discharge refers to lightning generated in a gas space by arranging a gas space between both electrodes via a dielectric (transparent quartz in the case of an excimer lamp) and applying a high frequency high voltage of several tens of kHz to the electrode. When the micro discharge streamer reaches the tube wall (dielectric) in a similar very thin discharge called micro discharge, the electric charge accumulates on the dielectric surface, and the micro discharge disappears.

  This micro discharge spreads over the entire tube wall, and is a discharge that is repeatedly generated and extinguished. For this reason, flickering of light that can be seen with the naked eye occurs.

  Moreover, since a very high temperature streamer reaches a pipe wall directly locally, there is a possibility that deterioration of the pipe wall may be accelerated.

  As a method for efficiently obtaining excimer light emission, electrodeless field discharge can be used in addition to dielectric barrier discharge.

《Vacuum UV irradiation intensity》
If the irradiation intensity is high, the probability that the photons and chemical bonds in the polysilazane collide increases, and the modification reaction can be shortened. Further, since the number of photons penetrating to the inside increases, the modified film thickness can be increased and / or the film quality can be improved (densification).

  However, if the irradiation time is too long, the flatness may be deteriorated and other materials of the barrier film may be damaged. In general, the progress of the reaction is considered by the integrated light amount represented by the product of the irradiation intensity and the irradiation time, but the absolute value of the irradiation intensity may be important.

Therefore, in the present invention, in the VUV irradiation process, at least 1 is selected from the viewpoint of suppressing both damage to the base material and damage to the members of the lamp and the lamp unit, increasing the reforming efficiency, and improving the barrier performance. times, it is preferable to carry out the reforming process which gives the maximum irradiation intensity of ^{50mW / cm 2 ~200mW / cm 2} .

(Vacuum ultraviolet (VUV) irradiation time)
The irradiation time for irradiating the vacuum ultraviolet rays (VUV) can be arbitrarily set, but from the viewpoint of substrate damage and film defect generation and productivity, the irradiation time in the light irradiation process is 0.1 second to 1 second. Minutes are preferred, and more preferably 0.5 seconds to 0.5 minutes.

(Oxygen concentration during irradiation with vacuum ultraviolet rays (VUV))
The oxygen concentration at the time of irradiation with vacuum ultraviolet rays (VUV) is preferably 300 ppm to 10000 ppm (1%), more preferably 500 ppm to 5000 ppm.

  By adjusting the oxygen concentration within the above range, it is possible to prevent the generation of an excessive oxygen barrier film and to prevent the deterioration of the barrier property.

  As a gas other than oxygen at the time of irradiation with vacuum ultraviolet rays (VUV), a dry inert gas is preferable, and dry nitrogen gas is particularly preferable from the viewpoint of cost.

  The oxygen concentration can be adjusted by measuring the flow rate of oxygen gas and inert gas introduced into the irradiation chamber and changing the flow rate ratio.

(Sealing process)
About the sealing method of this invention, an organic electronic element is shown as an example. In the pasting process according to the present invention, the organic electronic element is sealed with the barrier film of the present invention in contact with the organic electronic element and the barrier layer.

(Organic electronic device)
The organic electronic element according to the present invention is an element having an organic functional layer and an electrode having a function of converting light into electricity or electricity into light.

  In the method for producing an organic electronic device of the present invention, the organic electronic device is produced by sealing the organic electronic device with the barrier film in contact with the organic electronic device and the barrier layer as described above.

  The organic electronic device has a configuration having the organic electronic element on a support, but the barrier film according to the present invention may be used as the support or as a sealing member for sealing the organic electronic element. May be.

  The example at the time of using a barrier film as a support body is shown below.

  On the barrier layer of the barrier film, for example, a transparent conductive thin film such as ITO is provided as a transparent electrode. In this case, the organic electronic element and the barrier layer are brought into contact with each other and sealed by providing electrodes directly on the barrier layer as described below.

  For example, an organic photoelectric conversion element which is an organic electronic element by forming a porous semiconductor layer on an ITO transparent conductive film provided on a barrier film (support) as an anode and further forming a cathode made of a metal film. The organic photoelectric conversion element is sealed by stacking another sealing material or a sealing material having the same composition as that of the barrier film, adhering the barrier film (support) to the periphery, and enclosing the element. Accordingly, it is possible to seal off the influence on the element due to the humidity of the outside air or gas such as oxygen.

  The transparent conductive film can be formed by using a vacuum deposition method, a sputtering method, or the like, or by a coating method such as a sol-gel method using a metal alkoxide such as indium or tin.

  Moreover, as a film thickness of a transparent conductive film, the transparent conductive film of the range of 0.1 nm-1000 nm is preferable.

  Next, an organic photoelectric conversion element used for a solar cell or the like will be described as an organic electronic element.

  There is no restriction | limiting in particular as an organic photoelectric conversion element, A power generation layer (a layer in which a p-type semiconductor and an n-type semiconductor are mixed, a bulk heterojunction layer, or an i layer) sandwiched between the anode and the cathode is at least one layer. Any element that generates current when irradiated with light may be used.

  The preferable specific example of the layer structure of an organic photoelectric conversion element (The preferable layer structure of a solar cell is also the same) is shown below.

  The preferable specific example of the layer structure of an organic photoelectric conversion element is shown below.

(I) Anode / power generation layer / cathode (ii) Anode / hole transport layer / power generation layer / cathode (iii) Anode / hole transport layer / power generation layer / electron transport layer / cathode (iv) Anode / hole transport layer / P-type semiconductor layer / power generation layer / n-type semiconductor layer / electron transport layer / cathode (v) anode / hole transport layer / first power generation layer / electron transport layer / intermediate electrode / hole transport layer / second power generation layer / Electron transport layer / cathode.

  Here, the power generation layer needs to contain a p-type semiconductor material capable of transporting holes and an n-type semiconductor material capable of transporting electrons, and even if these layers form a heterojunction with substantially two layers. Alternatively, a bulk heterojunction in a mixed state in one layer may be manufactured, but a bulk heterojunction configuration is preferable because of higher photoelectric conversion efficiency. A p-type semiconductor material and an n-type semiconductor material used for the power generation layer will be described later.

  Like the organic EL device, the efficiency of taking out holes and electrons to the anode / cathode can be increased by sandwiching the power generation layer between the hole transport layer and the electron transport layer, so that the structure having them ((ii), ( iii)) is preferred.

  Further, in order to improve the rectification of holes and electrons (selection of carrier extraction), the power generation layer itself is sandwiched between layers of a p-type semiconductor material and a single n-type semiconductor material as shown in (iv). A configuration (also referred to as a pin configuration) may be used.

  Moreover, in order to improve the utilization efficiency of sunlight, the tandem configuration (configuration (v)) in which sunlight of different wavelengths is absorbed by each power generation layer may be employed.

  Below, the material which comprises these layers is described.

(Material for organic photoelectric conversion element)
A material used for forming a power generation layer (also referred to as a photoelectric conversion layer) of an organic photoelectric conversion element will be described.

(P-type semiconductor material)
Examples of the p-type semiconductor material preferably used as the power generation layer (bulk heterojunction layer) of the organic photoelectric conversion element include various condensed polycyclic aromatic low molecular compounds and conjugated polymers / oligomers.

  Examples of the condensed polycyclic aromatic low-molecular compound include anthracene, tetracene, pentacene, hexacene, heptacene, chrysene, picene, fluorene, pyrene, peropyrene, perylene, terylene, quaterylene, coronene, ovalene, circumanthracene, bisanthene, zesulene, Compounds such as heptazeslen, pyranthrene, violanthene, isoviolanthene, circobiphenyl, anthradithiophene, porphyrin, copper phthalocyanine, tetrathiafulvalene (TTF) -tetracyanoquinodimethane (TCNQ) complex, bisethylenetetrathiafulvalene (BEDTTTTF ) -Perchloric acid complexes, and derivatives and precursors thereof.

  Examples of the derivative having the above condensed polycycle include International Publication No. 03/16599, International Publication No. 03/28125, US Pat. No. 6,690,029, Japanese Patent Application Laid-Open No. 2004-107216. A pentacene derivative having a substituent described in JP-A No. 2003-136964, a pentacene precursor described in US Patent Application Publication No. 2003/136964, and the like; Amer. Chem. Soc. , Vol127. No. 14.4986, J. MoI. Amer. Chem. Soc. , Vol. 123, p9482; Amer. Chem. Soc. , Vol. 130 (2008), no. 9, acene-based compounds substituted with a trialkylsilylethynyl group described in 2706 and the like.

  As the conjugated polymer, for example, a polythiophene such as poly-3-hexylthiophene (P3HT) and an oligomer thereof, or a technical group described in Technical Digest of the International PVSEC-17, Fukuoka, Japan, 2007, P1225. Polythiophene, Nature Material, (2006) vol. 5, p328, a polythiophene-thienothiophene copolymer, a polythiophene-diketopyrrolopyrrole copolymer described in WO08 / 000664, and a polythiophene-thiazolothiazole copolymer described in Adv Mater, 2007p4160 , Nature Mat. vol. 6 (2007), p497 described in PCPDTBT, etc., polypyrrole and its oligomer, polyaniline, polyphenylene and its oligomer, polyphenylene vinylene and its oligomer, polythienylene vinylene and its oligomer, polyacetylene, polydiacetylene, Examples thereof include polymer materials such as σ-conjugated polymers such as polysilane and polygermane.

  In addition, oligomeric materials instead of polymer materials include thiophene hexamer α-sexual thiophene α, ω-dihexyl-α-sexual thiophene, α, ω-dihexyl-α-kinkethiophene, α, ω-bis (3 Oligomers such as -butoxypropyl) -α-sexithiophene are preferably used.

  Among these compounds, a compound that is highly soluble in an organic solvent to the extent that a solution process is possible and that can produce a crystalline thin film and achieve high mobility after drying is preferable.

  In addition, when the electron transport layer is formed on the power generation layer by coating, there is a problem that the electron transport layer solution dissolves the power generation layer. Therefore, a material that can be insolubilized after coating by a solution process may be used. .

  Examples of such a material include materials that can be insolubilized by polymerizing and crosslinking the coating film after coating, such as polythiophene having a polymerizable group described in Technical Digest of the International PVSEC-17, Fukuoka, Japan, 2007, P1225. Or by applying energy such as heat as described in US Patent Application Publication No. 2003/136964 and Japanese Patent Application Laid-Open No. 2008-16834, the soluble substituent reacts to insolubilize ( And materials).

(N-type semiconductor material)
Although it does not specifically limit as n-type semiconductor material used for a bulk heterojunction layer, For example, perfluoro body (Perfluoropentacene, perfluorophthalocyanine, etc.) which substituted the hydrogen atom of the p-type semiconductor with the fluorine atom, such as fullerene and octaazaporphyrin ), Aromatic carboxylic acid anhydrides such as naphthalenetetracarboxylic acid anhydride, naphthalenetetracarboxylic acid diimide, perylenetetracarboxylic acid anhydride, perylenetetracarboxylic acid diimide, and polymer compounds containing the imidized product as a skeleton. be able to.

  However, fullerene derivatives that can perform charge separation efficiently with various p-type semiconductor materials at high speed (˜50 fs) are preferable. Fullerene derivatives include fullerene C60, fullerene C70, fullerene C76, fullerene C78, fullerene C84, fullerene C240, fullerene C540, mixed fullerene, fullerene nanotubes, multi-walled nanotubes, single-walled nanotubes, nanohorns (conical), and the like. Partially by hydrogen atom, halogen atom, substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, cycloalkyl group, silyl group, ether group, thioether group, amino group, silyl group, etc. Examples thereof include substituted fullerene derivatives.

  Among them, [6,6] -phenyl C61-butyric acid methyl ester (abbreviation PCBM), [6,6] -phenyl C61-butyric acid-nbutyl ester (PCBnB), [6,6] -phenyl C61- Butyric acid-isobutyl ester (PCBiB), [6,6] -phenyl C61-butyric acid-n-hexyl ester (PCBH), Adv. Mater. , Vol. 20 (2008), p2116, etc., aminated fullerenes such as JP-A 2006-199674, metallocene fullerenes such as JP-A 2008-130889, US Pat. No. 7,329,709, etc. It is preferable to use a fullerene derivative having a substituent and having improved solubility, such as fullerene having a cyclic ether group such as a calligraphy.

(Hole transport layer / electron block layer)
The organic photoelectric conversion element has a hole transport layer between the bulk heterojunction layer and the anode, and it is possible to extract charges generated in the bulk heterojunction layer more efficiently. It is preferable.

  Examples of the material constituting these layers include, as the hole transport layer, PEDOT such as StarkVutec, trade name BaytronP, polyaniline and its doped material, cyan described in WO06 / 19270, etc. Compounds, etc. can be used.

  Note that 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 anode 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 compound described in JP-A-5-271166 or a metal oxide such as molybdenum oxide, nickel oxide, or tungsten oxide can be used.

  A layer made of a single p-type semiconductor material used for the bulk heterojunction layer can also be used. As a means for producing 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 produce a coating film in the lower layer before producing the bulk heterojunction layer because it has the effect of leveling the application surface and reduces the influence of leakage and the like.

(Electron transport layer / hole blocking layer)
An organic photoelectric conversion device has an electron transport layer in the middle of the bulk heterojunction layer and the cathode, so that charges generated in the bulk heterojunction layer can be taken out more efficiently. It is preferable.

  As the electron transport layer, octaazaporphyrin and p-type semiconductor perfluoro (perfluoropentacene, perfluorophthalocyanine, etc.) can be used. Similarly, HOMO of p-type semiconductor material used for the bulk heterojunction layer. The electron transport layer having a HOMO level deeper than the level is given a hole blocking function having a rectifying effect so that holes generated in the bulk heterojunction layer do not flow to the cathode side.

  Such an electron transport layer is also called a hole blocking layer, and it is preferable to use an electron transport layer having such a function.

  Examples of such materials include phenanthrene compounds such as bathocuproine, n-type semiconductor materials such as naphthalenetetracarboxylic acid anhydride, naphthalenetetracarboxylic acid diimide, perylenetetracarboxylic acid anhydride, perylenetetracarboxylic acid diimide, and titanium oxide. N-type inorganic oxides such as zinc oxide and gallium oxide, and alkali metal compounds such as lithium fluoride, sodium fluoride, and cesium fluoride can be used.

  A layer made of a single n-type semiconductor material used for the bulk heterojunction layer can also be used. As a means for producing these layers, either a vacuum vapor deposition method or a solution coating method may be used, but a solution coating method is preferable.

(Other layers)
For the purpose of improving energy conversion efficiency and improving the lifetime of the element, a structure having various intermediate layers in the element may be employed. 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, and a wavelength conversion layer.

(Electrode (first electrode))
In the case of an organic photoelectric conversion element, at least one of the electrodes sandwiching the organic functional layer is preferably a transparent electrode.

  The transparent electrode is not particularly limited to a cathode and an anode, and can be selected depending on the element configuration. Preferably, the transparent electrode is used as an anode.

  For example, when used as an anode, it is preferably an electrode that transmits light of 380 nm to 800 nm.

As the material, for example, transparent conductive metal oxides such as indium tin oxide (ITO), SnO ₂ and ZnO, metal thin films such as gold, silver and platinum, metal nanowires and carbon nanotubes can be used.

  Also selected from the group consisting of derivatives of polypyrrole, polyaniline, polythiophene, polythienylene vinylene, polyazulene, polyisothianaphthene, polycarbazole, polyacetylene, polyphenylene, polyphenylene vinylene, polyacene, polyphenylacetylene, polydiacetylene and polynaphthalene. Conductive polymers can also be used. A plurality of these conductive compounds can be combined to form a transparent electrode.

(Counter electrode (second electrode))
The counter electrode may be a single layer of a conductive material, but in addition to a conductive material, a resin that holds these may be used in combination. As the conductive material for the counter electrode, a material having a small work function (4 eV or less) metal, an alloy, an electrically conductive compound, and a mixture thereof as an electrode material is used. Specific examples of such electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al ₂ O ₃ ) Mixtures, indium, lithium / aluminum mixtures, rare earth metals and the like.

Among these, from the viewpoint of electron extraction performance and durability against oxidation, etc., a mixture of these metals and a second metal which is a stable metal having a larger work function value than this, for example, a magnesium / silver mixture, magnesium / Aluminum mixtures, magnesium / indium mixtures, aluminum / aluminum oxide (Al ₂ O ₃ ) mixtures, lithium / aluminum mixtures, aluminum and the like are preferred.

  The counter electrode can be produced by producing a thin film of these electrode materials by a method such as vapor deposition or sputtering. The film thickness is usually selected in the range of 10 nm to 5 μm, preferably 50 nm to 200 nm.

  If a metal material is used as the conductive material of the counter electrode, the light coming to the counter electrode side is reflected and reflected to the first electrode side, and this light can be reused and absorbed again by the photoelectric conversion layer, and more photoelectric conversion is performed. Efficiency is improved and preferable.

  The counter electrode may be a metal (for example, gold, silver, copper, platinum, rhodium, ruthenium, aluminum, magnesium, indium, etc.), carbon nanoparticle, nanowire, or nanostructure. If the dispersion is, a transparent and highly conductive counter electrode can be produced by a coating method.

  Moreover, when making the counter electrode side light-transmitting, for example, after forming a thin conductive material suitable for the counter electrode such as aluminum and aluminum alloy, silver and silver compound with a film thickness of about 1 to 20 nm, By providing a film of the conductive light transmissive material mentioned in the description of the transparent electrode, a light transmissive counter electrode can be obtained.

(Intermediate electrode)
The intermediate electrode material required in the case of the tandem structure is preferably a layer using a compound having both transparency and conductivity, and the materials (ITO, AZO, FTO, etc.) used in the transparent electrode , Transparent metal oxides such as titanium oxide, very thin metal layers such as Ag, Al, Au, or layers containing nanoparticles / nanowires, conductive polymer materials such as PEDOT: PSS, polyaniline, etc.) Can do.

  In addition to the above, a conductive fiber can be used as the material used for the electrode.

  As the conductive fibers, organic fibers and inorganic fibers coated with metal, conductive metal oxide fibers, metal nanowires, carbon fibers, carbon nanotubes, and the like can be used, but metal nanowires are preferable.

  A metal nanowire means a linear structure having a diameter of nm size.

  As a metal nanowire, in order to produce a long conductive path with one metal nanowire and to express appropriate light scattering properties, the average length is preferably 3 μm or more, and more preferably 3 μm to 3 μm 500 μm is preferable, and 3 μm to 300 μm is particularly preferable. In addition, the relative standard deviation of the length is preferably 40% or less.

  Moreover, it is preferable that an average diameter is small from a transparency viewpoint, On the other hand, the larger one is preferable from an electroconductive viewpoint. In the present invention, the average diameter of the metal nanowire is preferably 10 nm to 300 nm, and more preferably 30 nm to 200 nm. In addition, the relative standard deviation of the diameter is preferably 20% or less.

  There is no restriction | limiting in particular as a metal composition of metal nanowire, Although it can comprise from the 1 type or several metal of a noble metal element and a base metal element, it is noble metal (For example, gold, platinum, silver, palladium, rhodium, iridium, ruthenium) And at least one metal belonging to the group consisting of iron, cobalt, copper, and tin, and more preferably at least silver from the viewpoint of conductivity.

  In order to achieve both conductivity and stability (sulfurization and oxidation resistance of metal nanowires and migration resistance), it is also preferable to include silver and at least one metal belonging to a noble metal other than silver. When the metal nanowire according to the present invention includes two or more kinds of metal elements, for example, the metal composition may be different between the inside and the surface of the metal nanowire, or the entire metal nanowire has the same metal composition. You may have.

  There is no restriction | limiting in particular in the manufacturing method of metal nanowire, For example, well-known means, such as a liquid phase method and a gaseous-phase method, can be used. Moreover, there is no restriction | limiting in particular in a specific manufacturing method, A well-known manufacturing method can be used.

  For example, as a manufacturing method of Ag nanowire, Adv. Mater. , 2002, 14, 833-837; Chem. Mater. , 2002, 14, 4736-4745, etc., as a method for producing Au nanowires, such as JP 2006-233252A, etc., as a method for producing Cu nanowires, JP 2002-266007 A, etc. For example, Japanese Patent Application Laid-Open No. 2004-149871 can be referred to. In particular, Adv. Mater. And Chem. Mater. The method for producing Ag nanowires reported in 1 can easily produce Ag nanowires in an aqueous system, and since the conductivity of silver is the highest among metals, the production of metal nanowires according to the present invention is possible. It can be preferably applied as a method.

  Metal nanowires come into contact with each other to create a three-dimensional conductive network, exhibiting high conductivity, and allowing light to pass through the conductive network window where no metal nanowire exists, Due to the scattering effect of the metal nanowires, it is possible to efficiently generate power from the organic power generation layer. If a metal nanowire is installed in the 1st electrode at the side close | similar to an organic electric power generation layer part, since this scattering effect can be utilized more effectively, it is more preferable embodiment.

(Optical function layer)
The organic photoelectric conversion element may have various optical function layers for the purpose of, for example, more efficient reception of sunlight. As the optical functional layer, for example, a light condensing layer such as an antireflection layer or a microlens array, or a light diffusion layer that can scatter light reflected by the cathode and enter the power generation layer again may be provided. .

  Various known antireflection layers can be provided as the antireflection layer. 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 it to ˜1.63 because the interface reflection between the film substrate and the easy adhesion layer can be reduced and the transmittance can be improved. The method for 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 and the binder resin. The easy adhesion layer may be a single layer, but may be composed of two or more layers in order to improve adhesion.

  As the condensing layer, for example, it is processed so as to provide a structure on the microlens array on the sunlight receiving side of the support substrate, or the amount of light received from a specific direction is increased by combining with a so-called condensing sheet. Conversely, the incident angle dependency of sunlight can be reduced.

  As an example of the microlens array, quadrangular pyramids having a side of 30 μm and an apex angle of 90 degrees are two-dimensionally arranged on the light extraction side of the substrate. One side is preferably 10 μm to 100 μm. If it is smaller than this, the effect of diffraction is generated and colored.

  Examples of the light diffusion layer include various antiglare layers, layers in which nanoparticles or nanowires such as metals or various inorganic oxides are dispersed in a colorless and transparent polymer, and the like.

(Film formation method / surface treatment method)
Examples of methods for producing a bulk heterojunction layer in which an electron acceptor and an electron donor are mixed, and a transport layer / electrode include a vapor deposition method and a coating method (including a cast method and a spin coating method). Among these, examples of the method for producing the bulk heterojunction layer include a vapor deposition method and a coating method (including a casting method and a spin coating method).

  Among these, the coating method is preferable in order to increase the area of the interface where charges and electrons are separated from each other as described above and to produce a device having high photoelectric conversion efficiency. Also, the coating method is excellent in production speed.

  Although there is no restriction | limiting in the coating method used in this case, For example, a spin coat method, the cast method from a solution, a dip coat method, a blade coat method, a wire bar coat method, a gravure coat method, a spray coat method etc. are mentioned. Furthermore, patterning can also be performed by a printing method such as an inkjet method, a screen printing method, a relief printing method, an intaglio printing method, an offset printing method, a flexographic printing method, or the like.

  After coating, heating is preferably performed in order to cause removal of residual solvent, moisture and gas, and increase mobility and absorption longwave by crystallization of the semiconductor material. When annealing is performed at a predetermined temperature during the manufacturing process, a part of the particles is microscopically aggregated 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 power generation layer (bulk heterojunction layer) 14 may be composed of a single layer in which an electron acceptor and an electron donor are uniformly mixed, but a plurality of layers in which the mixing ratio of the electron acceptor and the electron donor is changed. You may comprise. In this case, it can be manufactured by using a material that can be insolubilized after coating as described above.

(Patterning)
The electrode, the power generation layer, the hole transport layer, the electron transport layer, and the like are used by patterning, but the patterning method and process are not particularly limited, and known methods can be appropriately applied.

  If it is a soluble material such as a bulk heterojunction layer and a transport layer, only unnecessary portions may be wiped after the entire surface of die coating, dip coating, etc., or direct patterning at the time of coating using a method such as an ink jet method or screen printing. May be.

  In the case of an insoluble material such as an electrode material, the electrode can be patterned by a known method such as mask vapor deposition during vacuum deposition or etching or lift-off. Alternatively, the pattern may be produced by transferring a pattern produced on another substrate.

  Hereinafter, the present invention will be specifically described by way of examples of solar cells as one form of the organic electronic device, but the present invention is not limited thereto.

Example 1
<< Preparation of barrier film >>
As described below, first, a base film F1 was used, and then a barrier film was formed on the base material to prepare a barrier film.

<Production of base material>
The base material F1 is a 75 μm-thick polyester film (Cosmo Shine A4300, manufactured by Toyobo Co., Ltd.) that is a thermoplastic resin support and is easily bonded to both sides, and has a water vapor transmission rate K7129 method (temperature 40 ° C., (Humidity 90% RH) 10 g / m ² / day.

  Using the base material F1, as shown below, a bleed-out prevention layer on one side and a smooth layer on the opposite side were used as the base material.

(Formation of bleed-out prevention layer)
A UV curing type organic / inorganic hybrid hard coating material OPSTAR Z7535 manufactured by JSR Co., Ltd. is applied to one side of the above support, applied with a wire bar so that the film thickness after drying is 4 μm, and then curing conditions: 1.0 J / cm ² under air, a high pressure mercury lamp used, drying conditions; 80 ° C., subjected to cure for 3 minutes to form a bleedout-preventing layer.

(Formation of smooth layer)
Subsequently, a UV curable organic / inorganic hybrid hard coat material OPSTAR Z7501 manufactured by JSR Corporation is applied to the opposite surface of the support, and is applied with a wire bar so that the film thickness after drying is 4 μm, and then drying conditions; After drying at 80 ° C. for 3 minutes, a high pressure mercury lamp was used in an air atmosphere, curing conditions; 1.0 J / cm ² curing was performed to form a smooth layer.

  The obtained smooth layer had a surface roughness specified by JIS B 0601 and a maximum cross-sectional height Rt (p) of 16 nm.

  The surface roughness is calculated from an uneven cross-sectional curve continuously measured with an AFM (Atomic Force Microscope) and a detector having a stylus with a minimum tip radius, and the measurement direction is 30 μm with a stylus with a minimum tip radius. This is the average roughness for the amplitude of fine irregularities, measured many times in the section.

(Measurement of water vapor permeability of substrate)
About the said base material after humidity control, a water vapor transmission rate uses the Mocon method, and measurement uses PERMATRAN-W3 / 33 by MOCON, and is based on K7129 method (temperature 40 degreeC, humidity 90% RH) of JIS specification. It was measured. The measured water vapor transmission rate was a level exceeding 5 g / m ² / day.

<< Preparation of barrier layer >>
On the smooth layer surface of the base material obtained above, the following steps (a) and (b) were repeated twice to produce a barrier layer having a lower layer and an upper layer. This sample was designated as barrier film samples 1-11.

Step (a): Preparation of perhydropolysilazane layer A base material provided with the smooth layer and the bleed-out prevention layer was coated with a coating solution containing perhydropolysilazane and an amine compound shown below on the smooth layer surface. A perhydropolysilazane layer (also referred to as a layer containing perhydropolysilazane) was prepared.

(Coating liquid containing perhydropolysilazane)
The coating liquid containing perhydropolysilazane is a combination of amine compounds A to E used in the lower layer and the upper layer shown in Table 3 using a 20% by mass dibutyl ether solution (Aquamica NN120-20 manufactured by AZ Electronic Materials Co., Ltd.). The mixture was mixed at a ratio of 1% by mass with respect to the mass of solid content of perhydropolysilazane, and this solution was diluted with dibutyl ether (boiling point: 141 ° C.) to adjust the concentration, and then applied with a roll coater. Then, it dried, heating at 80 degreeC for 3 minutes with dry air with a dew point of -5 degreeC continuously, and produced the perhydropolysilazane layer with a film thickness of 170 nm after drying.

Step (b): Preparation of barrier layer by modification (oxidation) of perhydropolysilazane layer Vacuum ultraviolet (VUV) irradiation treatment conditions Stage movable xenon excimer irradiation apparatus MODEL manufactured by MD Excimer: MECL-M-1-200 ( Using a wavelength of 172 nm, the sample is fixed so that the irradiation distance between the lamp and the sample is 1 mm, and the sample is moved at a stage moving speed of 10 mm / sec while maintaining the sample temperature at 85 ° C. The sample was taken out after being reciprocated and irradiated for a total of 6 reciprocations.

(Adjustment of oxygen concentration)
The oxygen concentration at the time of vacuum ultraviolet (VUV) irradiation is determined by measuring the flow rate of nitrogen gas and oxygen gas introduced into the vacuum ultraviolet (VUV) irradiation chamber with a flow meter, and nitrogen gas / oxygen of the gas introduced into the irradiation chamber. It adjusted so that oxygen concentration might be in the range of 0.2 volume%-0.4 volume% by gas flow rate ratio.

  Sample No. Sample No. 1 was changed in the same manner except that the substrate F1 used in 1 to 11 was changed to the following substrate having a different water vapor transmission rate. 12 and 13 were produced and evaluated in the same manner.

Base material F2
Mitsubishi Plastics, Inc. Tech Barrier TXR
Water vapor transmission rate K7129 method (temperature 40 ° C., humidity 90% RH) 0.5 g / m ² / day
Base material F3
Mitsubishi Plastics Corporation Tech Barrier HX
Water vapor permeability K7129 method (temperature 40 ° C., humidity 90% RH) 0.05 g / m ² / day
The barrier film samples 1 to 13 thus obtained were measured for water vapor transmission rate by the following method.

(Measurement device of water vapor transmission rate)
Vapor deposition apparatus: Vacuum vapor deposition apparatus JEE-400 manufactured by JEOL Ltd.
Constant temperature and humidity oven: Yamato Humidic Chamber IG47M
(raw materials)
Metal that reacts with water and corrodes: Calcium (granular)
Water vapor-impermeable metal: Aluminum (φ3-5mm, granular)
(Preparation of water vapor barrier property evaluation cell)
Using a vacuum vapor deposition device (JEOL-made vacuum vapor deposition device JEE-400), masking the portions other than the portions (12 mm × 12 mm 9 locations) to be deposited on the barrier films 1 to 13 before attaching the transparent conductive film, and metal calcium Was evaporated.

  Thereafter, the mask was removed in a vacuum state, and aluminum was deposited from another metal deposition source on the entire surface of one side of the sheet. After aluminum sealing, the vacuum state is released, and immediately facing the aluminum sealing side through a UV-curable resin for sealing (made by Nagase ChemteX) on quartz glass with a thickness of 0.2 mm in a dry nitrogen gas atmosphere The cell for evaluation was produced by irradiating with ultraviolet rays.

  The obtained sample with both sides sealed is stored at 60 ° C. and 90% RH under high temperature and high humidity, and moisture permeated into the cell from the corrosion amount of metallic calcium based on the method described in JP-A-2005-283561. The amount was calculated.

(Rank evaluation)
Less than 5: 1 × 10 ⁻⁴ g / m ² / day 4: 1 × 10 ⁻⁴ g / m ² / day or more, less than 1 × 10 ⁻³ g / m ² / day 3: 1 × 10 ⁻³ g / day m ² / day or more, 1 × 10 ⁻² g / m ² / day or less 2: 1 × 10 ⁻² g / m ² / day or more, 1 × 10 ⁻¹ g / m ² / day or less 1: 1 × 10 ⁻¹ g / m ² / day or more In rank evaluation, a practical range is rank 3 or more.

(Heat resistance test of barrier film)
Each of the barrier film samples 1 to 13 immediately after the production was stored in an 85 ° C. environment for 7 days, and then the water vapor permeability was measured in the same manner as described above to evaluate deterioration (durability) due to heat.

(Durability test of barrier film)
The barrier property deterioration (durability) after repeating the bending of the barrier film samples 1 to 13 immediately after fabrication 100 times at an angle of 180 degrees so as to have a curvature of 10 mm in the same manner as above. The transmittance was evaluated.

Example 2
<< Production of Organic Photoelectric Conversion Elements 1-13 >>
Using each of the barrier film samples 1 to 13 immediately after production obtained in Example 1, 150 nm of an indium tin oxide (ITO) transparent conductive film deposited (sheet resistance 10Ω / □) A first electrode was formed by patterning to a width of 2 mm using a photolithography technique and wet etching.

  The patterned first electrode was washed in the order of ultrasonic cleaning with a surfactant and ultrapure water, followed by ultrasonic cleaning with ultrapure water, dried with nitrogen blow, and finally subjected to ultraviolet ozone cleaning.

  On this transparent substrate, Baytron P4083 (manufactured by Starck Vitec), which is a conductive polymer, was applied and dried to a film thickness of 30 nm, and then heat treated at 150 ° C. for 30 minutes to form a hole transport layer. .

  Thereafter, the substrate was brought into a nitrogen chamber and manufactured in a nitrogen atmosphere.

  First, the substrate was heat-treated at 150 ° C. for 10 minutes in a nitrogen atmosphere. Next, P3HT (manufactured by Prectronics: regioregular poly-3-hexylthiophene) and PCBM (manufactured by Frontier Carbon Co., Ltd .: 6,6-phenyl-C61-butyric acid methyl ester) are added to 3.0% by mass of chlorobenzene. A liquid mixed at 1: 0.8 was prepared so that the film thickness was 100 nm while being filtered through a filter, and the film was allowed to stand at room temperature and dried. Subsequently, a heat treatment was performed at 150 ° C. for 15 minutes to form a photoelectric conversion layer.

Next, the substrate on which the series of functional layers is formed is moved into a vacuum deposition apparatus chamber, the inside of the vacuum deposition apparatus is depressurized to 1 × 10 ⁻⁴ Pa or less, and then fluorinated at a deposition rate of 0.01 nm / second. Laminate 0.6 nm of lithium, and then continue to deposit 100 nm of Al metal at a deposition rate of 0.2 nm / sec through a shadow mask with a width of 2 mm (vaporization is performed so that the light receiving part is 2 × 2 mm). A second electrode was formed. The obtained organic photoelectric conversion element was moved to a nitrogen chamber, and the barrier film samples 1 to 13 on which no element was formed were faced using the same sample and UV curable resin, and sealed as described below. Processing was performed to prepare organic photoelectric conversion elements 1 to 13 each having a light receiving portion of 2 × 2 mm size.

(Sealing of organic photoelectric conversion elements)
In an environment purged with nitrogen gas (inert gas), the barrier film samples 1 to 13 having elements formed on one side and the same barrier film not formed are sealed on the surface provided with the barrier layer. An epoxy photocurable adhesive was applied as a material. The organic photoelectric conversion elements 1 to 13 after sealing treatment were cured by irradiating UV light from one side of the substrate.

  Using the obtained organic photoelectric conversion element, a solar cell was produced, and the following evaluation was performed to evaluate durability.

<< Production of solar cells and evaluation of energy conversion efficiency >>
Evaluation of the organic photoelectric conversion elements 1-13 obtained above produced each solar cell 1-13 using each element, calculated | required energy conversion efficiency, and evaluated the durability as an element.

For each of the solar cells 1 to 13 is irradiated with light having an intensity of 100 mW / cm ² solar simulator (AM1.5G filter), a superposed mask in which the effective area 4.0 mm ² on the light receiving unit, evaluating the IV characteristics Thus, the short-circuit current density Jsc (mA / cm ² ), the open-circuit voltage Voc (V), and the fill factor FF (%) were measured for each of the four light receiving portions formed on the same element. A four-point average value of the obtained energy conversion efficiency PCE (%) was estimated.

(Formula 1)
PCE (%) = [Jsc (mA / cm ² ) × Voc (V) × FF (%)] / 100 mW / cm ²
The conversion efficiency as the initial cell characteristics of the obtained solar cells 1 to 13 was measured, and then the conversion after the forced deterioration test in which the degree of deterioration in performance over time was stored for 1000 hours in a temperature 60 ° C., humidity 90% RH environment. Five-level rank evaluation was performed based on the efficiency remaining rate.

(5-level rank evaluation)
Ratio of conversion efficiency / initial conversion efficiency after forced degradation test 5: 90% or more 4: 70% or more, less than 90% 3: 50% or more, less than 70% 2: 30% or more, less than 50% 1: less than 30% Note that rank 3 or higher can withstand practical use. The obtained results are shown in Table 1.

  According to the present invention, it is possible to provide a barrier film excellent in durability and efficiency in a very short time, a highly durable organic electronic device using the barrier film, and a method for producing them.

1 base material 2 barrier layer (lower layer)
3 Barrier layer (upper layer)
4 Smooth layer 5 Bleed-out prevention layer

Claims (5)

  A coating solution containing a polysilazane compound and an amine compound is coated on a substrate that does not substantially have a water vapor barrier property, and at least two or more water vapor barrier layers composed of a silicon compound are irradiated by irradiating vacuum ultraviolet light after drying. When forming, a barrier film characterized in that the boiling point of the amine compound contained in the coating solution used on the side closer to the substrate is higher than the boiling point of the amine compound contained in the coating solution used on the side far from the substrate. Manufacturing method.   The method for producing a barrier film according to claim 1, wherein the amine compound has a boiling point higher than that of the coating solvent. However, regarding the boiling point of the amine compound, when two or more amine compounds are used, the boiling point of the amine compound showing the lowest boiling point among the amine compounds used is the boiling point of the amine compound.   A barrier film produced by the method for producing a barrier film according to claim 1.   A method for producing an organic electronic device, comprising sealing an organic photoelectric conversion element through an adhesive using the barrier film according to claim 3.   An organic electronic device manufactured by the manufacturing method according to claim 4.

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